METHOD FOR PREPARING OLEFIN-POLAR MONOMER COPOLYMER

Abstract

A method for preparing an olefin-olefinic alcohol copolymer and an olefin-olefinic alcohol copolymer prepared by the method are provided. The catalyst used in the method for preparing the olefin-olefinic alcohol copolymer has a diimine metal complex as shown in Formula I.

##STR00001##

Claims

1. A method for preparing an olefin-polar monomer copolymer, comprising copolymerizing an olefin and a polar monomer in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-polar monomer copolymer, wherein, the catalyst comprises a main catalyst and optionally a cocatalyst, the main catalyst comprises a diimine-metal complex represented by Formula I: ##STR00032## wherein, R.sub.1 and R.sub.2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q; R.sub.3 and R.sub.4 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without a substituent Q, and adjacent R.sub.3 and R.sub.4 groups are optionally joined to form a ring or ring system; each R.sub.11 is independently a C1-C20 hydrocarbyl with or without a substituent Q; each Y is independently a Group VIA non-metal atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without a substituent Q and C1-C10 hydrocarbyloxy with or without a substituent Q, or an amino-imine metal complex represented by Formula I′ ##STR00033## wherein, R.sub.1 and R.sub.2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q; each R.sub.3 is independently selected from the group consisting of hydrogen and C1-C20 hydrocarbyl with or without a substituent Q; R.sub.5 to R.sub.8 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, and C1-C20 hydrocarbyl with or without a substituent Q, and R.sub.5 to R.sub.8 groups are optionally joined to form a ring or ring system; each R.sub.12 is independently a C1-C20 hydrocarbyl with or without a substituent Q; each Y is independently a Group VIA non-metal atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without a substituent Q and C1-C10 hydrocarbyloxy with or without a substituent Q, preferably, the polar monomer is a vinyl monomer carrying one or more hydroxy groups and/or one or more carboxy group.

2. The method as claimed in claim 1, having at least one of the following features: the polar monomer is a vinyl monomer carrying one or more hydroxy groups, or the polar monomer is a vinyl monomer carrying one or more carboxy groups; the main catalyst comprises a diimine metal complex represented by Formula Ib: ##STR00034## wherein, R.sub.1 and R.sub.2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q; R.sub.5-R.sub.8 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without a substituent Q, and R.sub.5-R.sub.8 are optionally joined to form a ring or ring system; each R.sub.12 is independently a C1-C20 hydrocarbyl with or without a substituent Q; each Y is independently a Group VIA nonmetal atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without a substituent Q and C1-C10 hydrocarbyloxy with or without a substituent Q.

3. The method as claimed in claim 2, having at least one of the following features: R.sub.1 and R.sub.2 are independently selected from the group consisting of C1-C20 alkyl with or without a substituent Q and C6-C20 aryl with or without a substituent Q, preferably R.sub.1 and/or R.sub.2 are/is a group represented by Formula A: ##STR00035## wherein R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q, and R.sup.1-R.sup.5 are optionally joined to form a ring or ring system; preferably, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; each M is independently selected from the group consisting of nickel and palladium; each Y is independently selected from the group consisting of O and S; each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without a substituent Q and C1-C10 alkoxy with or without a substituent Q, preferably from the group consisting of halogen, C1-C6 alkyl with or without a substituent Q and C1-C6 alkoxy with or without a substituent Q; each R.sub.12 is independently a C1-C20 alkyl with or without a substituent Q, preferably a C1-C10 alkyl with or without a substituent Q, and more preferably a C1-C6 alkyl with or without a substituent Q; and the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy, preferably from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy; preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl; preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy, iso-hexoxy and 3,3-dimethylbutoxy.

4. The method as claimed in claim 2, wherein the diimine metal complex is represented by Formula IIIb: ##STR00036## wherein, R.sup.1-R.sup.11 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q, M, X, Y and R.sub.12 are as defined in claim 2.

5. The method as claimed in claim 2, wherein in the diimine metal complex, R.sup.1-R.sup.11 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; preferably, R.sup.1-R.sup.11 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

6. The method as claimed in claim 2, wherein the diimine metal complex is selected from the group consisting of: 1) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 2) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 3) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 4) the diimine metal complex represented by Formula III, wherein R.sup.1-R.sup.3=methyl, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 5) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=methyl, R.sup.2=Br, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 6) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=F, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 7) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=Cl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 8) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=Br, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 9) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 10) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 11) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 12) the diimine metal complex represented by Formula III, wherein R.sup.1-R.sup.3=methyl, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 13) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=methyl, R.sup.2=Br, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 14) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=F, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 15) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=Cl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 16) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=Br, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; 17) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 18) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 19) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 20) the diimine metal complex represented by Formula III, wherein R.sup.1-R.sup.3=methyl, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 21) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=methyl, R.sup.2=Br, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 22) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=F, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 23) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=Cl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; 24) the diimine metal complex represented by Formula III, wherein R.sup.1=R.sup.3=Br, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=bromomethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br.

7. The method as claimed in claim 1, having at least one of the following features: the polar monomer is a vinyl monomer carrying one or more hydroxy groups, or the polar monomer is a vinyl monomer carrying one or more carboxy groups; the main catalyst comprises a diimine metal complex represented by Formula Ic: ##STR00037## wherein, R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without a substituent Q and C1-C20 hydrocarbyloxy with or without a substituent Q, and R.sub.21-R.sub.24 are optionally joined to form a ring or ring system; R.sub.1, R.sub.2, R.sub.11, Y, M and X are as defined in claim 1.

8. The method as claimed in claim 7, having at least one of the following features: R.sub.1 and R.sub.2 are independently selected from the group consisting of C1-C20 alkyl with or without a substituent Q and C6-C20 aryl with or without a substituent Q, preferably R.sub.1 and/or R.sub.2 are/is a group represented by Formula A: ##STR00038## wherein, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q, and R.sup.1-R.sup.5 are optionally joined to form a ring or ring system; preferably, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; each M is independently selected from the group consisting of nickel and palladium; each Y is independently selected from the group consisting of O and S; each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without a substituent Q and C1-C10 alkoxy with or without a substituent Q, preferably from the group consisting of halogen, C1-C6 alkyl with or without a substituent Q and C1-C6 alkoxy with or without a substituent Q; each R.sub.11 is independently a C1-C20 alkyl with or without a substituent Q, preferably a C1-C10 alkyl with or without a substituent Q, more preferably a C1-C6 alkyl with or without a substituent Q; and the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy, preferably from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy, preferably, the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl; preferably, the C1-C6 alkoxy is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy, iso-hexoxy and 3,3-dimethylbutoxy.

9. The method as claimed in claim 7, wherein the diimine metal complex has a structure represented by Formula IIIc: ##STR00039## wherein, R.sup.1-R.sup.10, R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkoxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q, and R.sup.1-R.sup.10 are optionally joined to form a ring or ring system, R.sub.21-R.sub.24 are optionally joined to form a ring or ring system; R.sub.11, Y, M and X are as defined in claim 7.

10. The method as claimed in claim 7, wherein in the diimine metal complex, R.sup.1-R.sup.10, R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; preferably, R.sup.1-R.sup.10, R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

11. The method as claimed in claim 7, wherein the diimine metal complex is selected from the group consisting of: 1) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 2) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 3) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 4) the complex represented by Formula IIIc, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 5) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 6) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 7) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 8) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 9) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 10) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 11) the complex represented by Formula IIIc, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 12) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 13) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 14) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 15) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 16) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 17) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 18) the complex represented by Formula IIIc, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 19) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 20) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 21) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 22) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 23) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 24) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 25) the complex represented by Formula IIIc, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 26) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 27) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 28) the complex represented by Formula IIIc, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.23=R.sub.24=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; ##STR00040## 29) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 30) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 31) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 32) the complex represented by Formula (IIIc′), wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 33) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 34) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 35) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 36) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 37) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 38) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 39) the complex represented by Formula (IIIc′), wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 40) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 41) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 42) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 43) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 44) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 45) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 46) the complex represented by Formula (IIIc′), wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 47) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 48) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 49 The complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 50) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 51) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 52) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 53) the complex represented by Formula (IIIc′), wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 54) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 55) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 56) the complex represented by Formula (IIIc′), wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2R.sub.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.11=isobutyl, M=Ni, Y=O, X=Br.

12. The method as claimed in claim 1, wherein the polar monomer is a vinyl monomer carrying one or more hydroxy groups, or the polar monomer is a vinyl monomer carrying one or more carboxy groups, and wherein the main catalyst comprises the amino-imine metal complex represented by Formula I′.

13. The method as claimed in claim 12, wherein the amino-imine metal complex has at least one of the following features: R.sub.1 and R.sub.2 are independently selected from the group consisting of C1-C20 alkyl with or without a substituent Q and C6-C20 aryl with or without a substituent Q, preferably R.sub.1 and/or R.sub.2 are/is a group represented by Formula A: ##STR00041## wherein, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkyloxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q, and R.sup.1-R.sup.5 are optionally joined to form a ring or ring system; preferably, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; each M is independently selected from the group consisting of nickel and palladium; each Y is independently selected from the group consisting of O and S; each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without a substituent Q and C1-C10 alkoxy with or without a substituent Q, preferably from the group consisting of halogen, C1-C6 alkyl with or without a substituent Q and C1-C6 alkoxy with or without a substituent Q; each R.sub.12 is independently a C1-C20 alkyl with or without a substituent Q, preferably a C1-C10 alkyl with or without a substituent Q, more preferably a C1-C6 alkyl with or without a substituent Q; each R.sub.3 is selected from the group consisting of C1-C20 alkyl with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q and C7-C20 alkaryl with or without a substituent Q; preferably, each R.sub.3 is selected from the group consisting of C1-C10 alkyl with or without a substituent Q, C6-C10 aryl with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q and C7-C15 alkaryl with or without a substituent Q; and more preferably, each R.sub.3 is a C1-C6 alkyl with or without a substituent Q; the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy, preferably from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy; preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl; preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy.

14. The method as claimed in claim 12, wherein the amino-imine metal complex is represented by Formula III′: ##STR00042## wherein, R.sup.1-R.sup.11 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkyloxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q; R.sub.3, R.sub.12, Y, M and X are as defined in claim 12.

15. The method as claimed in claim 14, wherein in the amino-imine metal complex, R.sup.1-R.sup.11 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; preferably, R.sup.1-R.sup.11 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, and more preferably from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

16. The method as claimed in claim 12, wherein the amino-imine metal complex is selected from the group consisting of: the complex represented by Formula III′, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=methyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=methyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=methyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=methyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=methyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=methyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=i-Pr, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1-R.sup.3=methyl, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1-R.sup.3=methyl, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=Br, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=R.sub.3=CH.sub.3, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=Br, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=F, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=Cl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=Br, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=ethyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1-R.sup.3=methyl, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=Br, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=methyl, R.sub.3=isopropyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=F, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=isopropyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=Cl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=isopropyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=Br, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=isopropyl, R.sub.12=isobutyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=CH.sub.3, R.sup.11=bromomethyl, R.sub.3=isopropyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=ethyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=CH.sub.3, R.sup.11=CH.sub.2Br, R.sub.3=isopropyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=isopropyl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=CH.sub.3, R.sup.11=CH.sub.2Br, R.sub.3=ethyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1-R.sup.3=methyl, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=CH.sub.3, R.sup.11=CH.sub.2Br, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=methyl, R.sup.2=Br, R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sub.3=ethyl, R.sup.11=CH.sub.2Br, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=F, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=CH.sub.2Br, R.sub.3=isobutyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=Cl, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=CH.sub.2Br, R.sub.3=isobutyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br; the complex represented by Formula III′, wherein R.sup.1=R.sup.3=Br, R.sup.2=R.sup.4-R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=methyl, R.sup.11=CH.sub.2Br, R.sub.3=isobutyl, R.sub.12=ethyl, M=Ni, Y=O, X=Br.

17. The method as claimed in claim 12, wherein the amino-imine metal complex has a structure represented by Formula IV′: ##STR00043## wherein, R.sub.1 and R.sub.2 are each independently a C1-C30 hydrocarbyl with or without a substituent Q; R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 hydrocarbyl with or without a substituent Q and C1-C20 hydrocarbyloxy with or without a substituent Q, and R.sub.21-R.sub.24 are optionally joined to form a ring or ring system, preferably a substituted or unsubstituted benzene ring; each R.sub.5 is independently selected from the group consisting of hydrogen and C1-C20 hydrocarbyl with or without a substituent Q; each R.sub.11 is independently a C1-C20 hydrocarbyl with or without a substituent Q; each Y is independently a Group VIA nonmetal atom; each M is independently a Group VIII metal; each X is independently selected from the group consisting of halogen, C1-C10 hydrocarbyl with or without a substituent Q and C1-C10 hydrocarbyloxy with or without a substituent Q.

18. The method as claimed in claim 17, wherein the amino-imine metal complex has at least one of the following features: R.sub.1 and R.sub.2 are independently selected from the group consisting of C1-C20 alkyl with or without a substituent Q and C6-C20 aryl with or without a substituent Q, preferably R.sub.1 and/or R.sub.2 are/is a group represented by Formula A: ##STR00044## wherein, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 aralkyloxy with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q, and R.sup.1-R.sup.5 are optionally joined to form a ring or ring system; preferably, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; more preferably, R.sup.1-R.sup.5 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C6 alkyl with or without a substituent Q, C2-C6 alkenyl with or without a substituent Q, C2-C6 alkynyl with or without a substituent Q, C1-C6 alkoxy with or without a substituent Q, C2-C6 alkenyloxy with or without a substituent Q, C2-C6 alkynyloxy with or without a substituent Q, C6-C10 aryl with or without a substituent Q, C7-C10 aralkyl group with or without a substituent Q, C7-C10 alkaryl with or without a substituent Q, C6-C10 aryloxy with or without a substituent Q, C7-C10 aralkyloxy with or without a substituent Q, and C7-C10 alkaryloxy with or without a substituent Q; each M is independently selected from the group consisting of nickel and palladium; each Y is independently selected from the group consisting of O and S; each X is independently selected from the group consisting of halogen, C1-C10 alkyl with or without a substituent Q and C1-C10 alkoxy with or without a substituent Q, preferably from the group consisting of halogen, C1-C6 alkyl with or without a substituent Q and C1-C6 alkoxy with or without a substituent Q; each R.sub.1 is independently a C1-C20 alkyl with or without a substituent Q, preferably a C1-C10 alkyl with or without a substituent Q, and more preferably a C1-C6 alkyl with or without a substituent Q; each R.sub.5 is independently selected from the group consisting of C1-C20 alkyl with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q and C7-C20 alkaryl with or without a substituent Q; preferably, each R.sub.5 is independently selected from the group consisting of C1-C10 alkyl with or without a substituent Q, C6-C10 aryl with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q and C7-C15 alkaryl with or without a substituent Q, and more preferably each R.sub.5 is a C1-C6 alkyl with or without a substituent Q; and the substituent Q is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy, preferably from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy; preferably, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl; preferably, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexyloxy, isohexyloxy and 3,3-dimethylbutoxy; preferably, the halogen is selected from fluorine, chlorine, bromine and iodine; R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without a substituent Q, C2-C20 alkenyl with or without a substituent Q, C2-C20 alkynyl with or without a substituent Q, C1-C20 alkoxy with or without a substituent Q, C2-C20 alkenoxy with or without a substituent Q, C2-C20 alkynoxy with or without a substituent Q, C6-C20 aryl with or without a substituent Q, C7-C20 aralkyl with or without a substituent Q, C7-C20 alkaryl with or without a substituent Q, C6-C20 aryloxy with or without a substituent Q, C7-C20 aralkyloxy with or without a substituent Q and C7-C20 alkaryloxy with or without a substituent Q, and R.sub.21-R.sub.24 are optionally joined to form a ring or ring system; preferably, R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without a substituent Q, C2-C10 alkenyl with or without a substituent Q, C2-C10 alkynyl with or without a substituent Q, C1-C10 alkoxy with or without a substituent Q, C2-C10 alkenoxy with or without a substituent Q, C2-C10 alkynoxy with or without a substituent Q, C6-C15 aryl with or without a substituent Q, C7-C15 aralkyl with or without a substituent Q, C7-C15 alkaryl with or without a substituent Q, C6-C15 aryloxy with or without a substituent Q, C7-C15 aralkoxy with or without a substituent Q and C7-C15 alkaryloxy with or without a substituent Q; more preferably, R.sub.21-R.sub.24 are each independently selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from the group consisting of hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

19. The method as claimed in claim 17, wherein the amino-imine metal complex has a structure represented by Formula IV′A: ##STR00045## wherein R.sub.31-R.sub.34 have the same meanings as R.sub.21-R.sub.24 in Formula IV′, preferably R.sub.33 and R.sub.34 are hydrogen, and R.sub.1, R.sub.2, R.sub.5, Rn, Y, M and X are as defined for Formula IV′ in claim 17.

20. The method as claimed in claim 17, wherein the amino-imine metal complex is represented by the following Formula V or V′: ##STR00046## wherein the individual symbols are as defined above, preferably, the amino-imine metal complex is selected from the group consisting of: 1) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 2) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 3) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 4) the complex represented by Formula V, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 5) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 6) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 7) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 8) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 9) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 10) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 11) the complex represented by Formula V, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 12) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 13) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 14) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=R.sub.11=ethyl, M=Ni, Y=O, X=Br; 15) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 16) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 17) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 18) the complex represented by Formula V, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.1=isobutyl, M=Ni, Y=O, X=Br; 19) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 20) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 21) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 22) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=ethyl, M=Ni, Y=O, X=Br; 23) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=ethyl, M=Ni, Y=O, X=Br; 24) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=ethyl, M=Ni, Y=O, X=Br; 25) the complex represented by Formula V, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 26) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=ethyl, M=Ni, Y=O, X=Br; 27) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=ethyl, M=Ni, Y=O, X=Br; 28) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=ethyl, M=Ni, Y=O, X=Br; 29) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=isobutyl, M=Ni, Y=O, X=Br; 30) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.1=isobutyl, M=Ni, Y=O, X=Br; 31) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 32) the complex represented by Formula V, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 33) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 34) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 35) the complex represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.22=H, R.sub.21=t-butyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 29) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 30) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 31) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 32) the complex represented by Formula V′, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 33) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 34) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 35) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=ethyl, M=Ni, Y=O, X=Br; 36) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 37) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 38) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 39) the complex represented by Formula V′, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 40) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 41) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 42) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 43) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 44) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 45) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 46) the complex represented by Formula V′, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 47) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 48) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 49) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 50) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=isopropyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=R.sub.11=ethyl, R.sub.5=CH.sub.3, M=Ni, Y=O, X=Br; 51) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=ethyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 52) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=methyl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 53) the complex represented by Formula V′, wherein R.sup.1-R.sup.6=methyl, R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 54) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Br, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 55) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Cl, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br; 56) the complex represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=F, R.sup.2=R.sup.5=R.sup.7-R.sup.10=H, R.sub.31=R.sub.32=ethyl, R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br.

21. The method as claimed in claim 1, having at least one of the following features: the olefin is an olefin, preferably an α-olefin, having 2 to 16 carbon atoms, the polar monomer is one or more of olefinic alcohols represented by Formula G: ##STR00047## wherein, L.sub.1-L.sub.3 are each independently selected from the group consisting of H and C1-C30 alkyl with or without a substituent, L.sub.4 is a C.sub.1-C.sub.30 alkylene optionally having a pendant group; preferably, in the copolymer, the content of the structure units derived from the olefinic alcohol represented by Formula G is from 0.4 to 10.0 mol %; preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.30 alkyl, L.sub.4 is a C.sub.1-C.sub.30 alkylene having a pendant group; more preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.20 alkyl, L.sub.4 is a C.sub.1-C.sub.20 alkylene having a pendant group; still more preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.10 alkyl, L.sub.4 is a C.sub.1-C.sub.10 alkylene having a pendant group; still more preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.10 alkyl, L.sub.4 is a C.sub.1-C.sub.6 alkylene having a pendant group.

22. The method as claimed in claim 21, wherein the substituent in L.sub.1-L.sub.3 is one or more selected from the group consisting of halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.10 aryl, cyano and hydroxy; more preferably the substituent in L.sub.1-L.sub.3 is one or more selected from the group consisting of C1-C6 alkyl, halogen and C1-C6 alkoxy; the pendant group in L.sub.4 is one or more selected from the group consisting of halogen, C.sub.6-C.sub.20 aryl, C.sub.1-C.sub.20 alkyl and C.sub.1-C.sub.20 alkoxy, the C.sub.6-C.sub.20 aryl, C.sub.1-C.sub.20 alkyl and C.sub.1-C.sub.20 alkoxy being optionally substituted by a substituent, which is preferably one or more selected from the group consisting of halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.10 aryl and hydroxy.

23. The method as claimed in claim 1, having at least one of the following features: the olefin is an olefin, preferably an α-olefin, having 2-16 carbon atoms, the polar monomer is an unsaturated carboxylic acid represented by Formula G′: ##STR00048## wherein, L.sub.1-L.sub.3 are each independently selected from the group consisting of H and C1-C30 alkyl with or without a substituent, L.sub.4 is a C.sub.1-C.sub.30 alkylene having a pendant group; preferably, in the copolymer, the content of the structure units derived from the unsaturated carboxylic acid represented by Formula G′ is from 0.2 to 15.0 mol %, and more preferably from 0.7 to 10.0 mol %; preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.30 alkyl, L.sub.4 is a C.sub.1-C.sub.30 alkylene having a pendant group; more preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.20 alkyl, L.sub.4 is a C.sub.1-C.sub.20 alkylene having a pendant group; still more preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.10 alkyl, L.sub.4 is a C.sub.1-C.sub.10 alkylene having a pendant group; still more preferably, L.sub.1 and L.sub.2 are H, L.sub.3 is H or a C.sub.1-C.sub.10 alkyl, L.sub.4 is a C.sub.1-C.sub.6 alkylene having a pendant group.

24. The method as claimed in claim 23, characterized in that the substituent in L.sub.1-L.sub.3 is one or more selected from the group consisting of halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.10 aryl, cyano and hydroxy; and more preferably the substituent in L.sub.1-L.sub.3 is one or more selected from the group consisting of C.sub.1-C.sub.6 alkyl, halogen and C.sub.1-C.sub.6 alkoxy; the pendant group in L.sub.4 is one or more selected from the group consisting of halogen, C.sub.6-C.sub.20 aryl, C.sub.1-C.sub.20 alkyl and C.sub.1-C.sub.20 alkoxy, the C.sub.6-C.sub.20 aryl, C.sub.1-C.sub.20 alkyl and C.sub.1-C.sub.20 alkoxy being optionally substituted by a substituent, which is preferably one or more selected from the group consisting of halogen, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkoxy, C.sub.6-C.sub.10 aryl and hydroxy.

25. The method as claimed in claim 1, wherein the cocatalyst is selected from the group consisting of organoaluminum compounds and organoboron compounds; the organoaluminum compounds are selected from the group consisting of alkylaluminoxanes, aluminum alkyls and alkyl aluminum halides; the organoboron compounds are selected from the group consisting of aromatic hydrocarbyl boron compounds and borates; the chain transfer agent is selected from the group consisting of aluminum alkyls, magnesium alkyls, boron alkyls and zinc alkyls; preferably, when the cocatalyst is the organoaluminum compound, a molar ratio of aluminum in the cocatalyst to M in the diimine metal complex is (10-107):1, preferably (10-100000):1, and more preferably (100-10000):1; when the cocatalyst is the organoboron compound, a molar ratio of boron in the cocatalyst to M in the diimine metal complex is (0.1-1000):1, and preferably (0.1-500):1; and a molar ratio of the chain transfer agent to M in the diimine metal complex is (0.1-5000):1, and preferably (1.0-1,000):1.

26. An olefin-polar monomer copolymer prepared by the method as claimed in claim 1, which is of spherical and/or spherical-like shape, and/or which has a particle diameter of from 0.1 to 50 mm.

Description

DESCRIPTION OF THE DRAWINGS

[0301] FIG. 1 is a structural unit diagram of the nickel complex Ni1 of Example 1 of the invention (for clarity, hydrogen atoms, dichloromethane solvent molecules and atoms for symmetry operations are not marked).

[0302] FIG. 2 is a photograph of the spherical and/or spherical-like polymer obtained in Example 2 of the invention.

[0303] FIG. 3 is a photograph of the olefin-unsaturated carboxylic acid polymer obtained in Example 20 of the invention.

[0304] FIG. 4 is a photograph of the spherical and/or spherical-like polymer obtained in Example 70 of the invention.

EXAMPLES

[0305] The present invention will be described in detail below in conjunction with examples and drawings, but it should be understood that the examples and drawings are used only to exemplarily illustrate the present invention, and do not constitute any limitation on the protection scope of the present invention. All reasonable alterations and combinations included in the scope of the inventive concept of the present invention fall into the protection scope of the present invention.

[0306] The analytical characterization instruments used in the present invention are as follows:

[0307] Prior to measurement, the polymer sample is washed with a dilute acid solution to make the metal content in the polymer ≤50 ppm.

[0308] 1. Nuclear magnetic resonance instrument for determining the structure of complex ligand: Bruker DMX 300 (300 MHz), with tetramethyl silicon (TMS) as the internal standard, measured at 25° C.

[0309] 2. Analysis of comonomer content of polymer (the content of structural units derived from the olefinic alcohol represented by Formula G): measured through .sup.13C NMR spectra recorded on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer, using a 10 mm PASEX 13 probe, with the polymer sample being dissolved in 1,2,4-trichlorobenzene at 120° C.

[0310] 3. Analysis of comonomer content of copolymer (the content of structural units derived from the unsaturated carboxylic acid represented by Formula G′): measured through .sup.13C NMR spectra recorded on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer, using a 10 mm PASEX 13 probe, with the polymer sample being dissolved in deuterated tetrachloroethane at 130° C.

[0311] 4. Molecular weight and molecular weight distribution PDI (PDI=Mw/Mn) of polymer: PL-GPC220 chromatograph, with trichlorobenzene as solvent, measured at 150° C. (standards: PS; flow rate: 1.0 mL/min; Column: 3×PLgel 10 um M1×ED-B 300×7.5 nm).

[0312] 5. Activity measurement method: gravimetric method, with activity being expressed as polymer weight (g)/nickel (mol)×2.

[0313] The structure of the complexes involved in the following Examples 1-35 is shown by Formula

##STR00020##

Example 1

[0314] 1) Preparation of Ligand L.sub.1:

[0315] Under nitrogen atmosphere, 2,6-diethylaniline (2.0 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 h. The reaction product was neutralized with aqueous sodium hydroxide solution and extracted with dichloromethane, and combined organic layers were dried over anhydrous magnesium sulfate and concentrated. The residues were then subjected to a column chromatography to afford yellow ligand L.sub.1. Yield: 69.2%. .sup.1H-NMR (CDCl.sub.3): δ6.94-6.92 (m, 6H, C.sub.Ar—CH.sub.3), 2.56-2.51 (m, 4H, C.sub.Ar—CH.sub.3), 2.36-2.31 (m, 4H, C.sub.Ar—CH.sub.3), 1.82-1.78 (m, 4H, CH.sub.2), 1.54 (m, 1H), 1.24-1.18 (m, 12H), 1.09 (s, 3H, CH.sub.3), 0.94 (m, 6H, CH.sub.3).

[0316] 2) Preparation of complex Ni.sub.1 (represented by structural Formula IIIb, wherein R.sup.1, R.sup.3 are ethyl; R.sup.2, R.sup.4-R.sup.7, R.sup.10 are hydrogen; R.sup.8, R.sup.9 and R.sup.11 are methyl; R.sub.12 is ethyl; M is nickel, Y is O, and X is Br):

[0317] A solution of 0.277 g (0.9 mmol) of (DMVE)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.258 g (0.6 mmol) of ligand L.sub.1 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.1 as brownish-red powdery solids. Yield: 78.2%. Elemental analysis (calculated for C.sub.64H.sub.90Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 47.96; H, 5.66; N, 3.50; experimental value (%): C, 47.48; H, 6.00; N, 3.26.

[0318] 3) Polymerization:

[0319] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time, 8.0 mg (5.0 mol) of the complex Ni.sub.1, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm.

[0320] The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 2

[0321] Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 1, except that 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

[0322] FIG. 2 shows a photograph of the spherical and/or spherical-like polymer prepared in this Example.

Example 3

[0323] Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 2, except that the polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 4

[0324] Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 2, except that 0.5 mL of diethyl zinc (1 mol/L solution in hexane) was further added together with the catalyst. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 5

[0325] Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 4, except that 2 times quantity of the diethylzinc (i.e., 1.0 mL diethylzinc (1 mol/L solution in hexane)) was used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 6

[0326] Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 1, except that 3.33 times quantity of the 2-methyl-2-hydroxy-7-octene (i.e., 50 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene) and 3.33 times quantity of AlEt.sub.3 (i.e., 50 mL of AlEt.sub.3 (1.0 mol/L solution in hexane)) were used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 7

[0327] Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 1, except that 6.67 times quantity of the 2-methyl-2-hydroxy-7-octene (i.e., 100 mmol (17.0 mL) of 2-methyl-2-hydroxy-7-octene) and 6.67 times quantity of the AlEt.sub.3 (i.e., 100 mL of AlEt.sub.3 (1.0 mol/L solution in hexane)) were used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 8

[0328] 1) Preparation of ligand L.sub.2:

[0329] Under nitrogen atmosphere, 2,6-diisopropylaniline (2.4 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the reaction mixture was refluxed for 6 h. The reaction product was neutralized with aqueous sodium hydroxide solution and extracted with dichloromethane, and combined organic layers were dried over anhydrous magnesium sulfate and concentrated. The residues were then subjected to a column chromatography to afford yellow ligand L.sub.2. Yield: 41.3%. .sup.1H NMR (300 MHz, CDCl3), δ (ppm): 7.06-6.81 (m, 6H, Ar—H), 2.88 (m, 4H, CH(CH.sub.3).sub.2), 2.36 (m, 1H,), 1.86 (m, 4H, CH.sub.2), 1.24 (d, 24H, CH(CH.sub.3).sub.2), 0.96 (s, 6H, CH.sub.3), 0.77 (s, 3H, CH.sub.3).

[0330] 2) Preparation of complex Ni.sub.2 (represented by structural Formula IIb, wherein R.sup.1, R.sup.3 are isopropyl; R.sup.2, R.sup.4-R.sup.7, R.sup.10 are hydrogen; R.sup.8, R.sup.9 and R.sup.11 are methyl; R.sub.12 is ethyl; M is nickel, Y is O, and X is Br):

[0331] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.291 g (0.6 mmol) of ligand L.sub.2 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.2 as brownish-red powdery solids. Yield: 74.0%. Elemental analysis (calculated for C.sub.72H.sub.106Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 50.42; H, 6.23; N, 3.27; experimental value (%): C, 50.28; H, 6.42; N, 3.18.

[0332] 3) Polymerization:

[0333] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time, 8.6 mg (5.0 mol) of the complex Ni.sub.2, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 9

[0334] Copolymerization of ethylene and 2-methyl-2-hydroxy-7-octene was carried out according to the polymerization procedure described in Example 8, except that the polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 10

[0335] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 8, except that 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol was used as a comonomer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 11

[0336] 1) Preparation of complex Ni.sub.3 (represented by structural Formula IIb, wherein R.sup.1, R.sup.3 are isopropyl; R.sup.2, R.sup.4-R.sup.7, R.sup.10 are hydrogen; R.sup.8, R.sup.9 and R.sup.11 are methyl; R.sub.12 is isobutyl; M is nickel, Y is O, and X is Br):

[0337] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in 2-methyl-1-propanol (10 mL) was added slowly dropwise to a solution of 0.291 g (0.6 mmol) of ligand L.sub.2 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.3 as brownish-red powdery solids. Yield: 76.0%. Elemental analysis (calculated for C.sub.76H.sub.114Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 51.54; H, 6.49; N, 3.16; experimental value (%): C, 51.28; H, 6.82; N, 3.19.

[0338] 2) Polymerization:

[0339] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.9 mg (5.0 mol) of the complex Ni.sub.3, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm.

[0340] The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 12

[0341] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 11, except that 30 mmol (4.5 mL) of 4-methyl-1-hepten-4-ol as a comonomer was used. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 13

[0342] 1) Preparation of ligand L.sub.3:

[0343] Under nitrogen atmosphere, 2,4,6-trimethyl-aniline (1.7 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 h. The reaction product was neutralized with aqueous sodium hydroxide solution, extracted with dichloromethane, dried, and concentrated, and then subjected to a column chromatography to afford yellow ligand L.sub.3 in a yield of 62.5%. THNMR (300 MHz, CDCl.sub.3), δ (ppm) [with an isomer ratio of 1.2:1]: major isomer: 6.72 (s, 4H, Ar—H), 2.26-2.13 (m, 12H, C.sub.Ar—CH.sub.3), 1.87 (s, 6H, C.sub.Ar—CH.sub.3), 1.79 (m, 4H, CH.sub.2), 1.42 (m, 1H), 1.26 (s, 3H, CH.sub.3), 1.07 (s, 6H, CH.sub.3); minor isomer: 6.67 (s, 4H, Ar—H), 2.09-2.01 (m, 12H, C.sub.Ar—CH.sub.3), 1.85 (s, 6H, C.sub.Ar—CH.sub.3), 1.79 (m, 4H, CH.sub.2), 1.40 (m, 1H), 1.26 (s, 3H, CH.sub.3), 0.94 (s, 6H, CH.sub.3).

[0344] 2) Preparation of Complex Ni.sub.4 (Represented by the Structural Formula IIIb, Wherein R.sup.1-R.sup.3 are Methyl, R.sup.4-R.sup.7 and R.sup.10 are Hydrogen, R.sup.8, R.sup.9 and R.sup.11 are Methyl, R.sub.12 is Ethyl, M is Nickel, Y is O, and X is Br):

[0345] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.240 g (0.6 mmol) of ligand L.sub.3 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.4 as brownish-red powdery solids in a yield of 78.6%. Elemental analysis (calculated for C.sub.60H.sub.82Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 46.59; H, 5.34; N, 3.62; experimental value (%): C, 46.24; H, 5.67; N, 3.21.

[0346] 3) Polymerization:

[0347] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 7.7 mg (5 μmol) of the complex Ni.sub.4 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 1 below.

Example 14

[0348] 1) Preparation of Ligand L.sub.4:

[0349] Under nitrogen atmosphere, 2,6-dimethyl-4-bromo-aniline (2.45 g, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and the system was cooled to room temperature. Camphorquinone (0.831 g, 5 mmol) was added, and the system was refluxed for 6 h. The reaction product was neutralized with aqueous sodium hydroxide solution, extracted with dichloromethane, dried and concentrated, and then subjected to a column chromatography to afford yellow ligand L.sub.4 in a yield of 60.7%. THNMR (300 MHz, CDCl.sub.3), δ (ppm) [with an isomer ratio of 1.1:1]: major isomer: 7.05 (s, 4H, Ar—H), 2.18 (m, 12H, C.sub.Ar—CH.sub.3), 1.85 (m, 4H, CH.sub.2), 1.37 (m, 1H), 1.26 (s, 3H, CH.sub.3), 1.06 (s, 6H, CH.sub.3); minor isomer: 7.02 (s, 4H, Ar—H), 2.04 (m, 12H, C.sub.Ar—CH.sub.3), 1.85 (m, 4H, CH.sub.2), 1.37 (m, 1H), 1.26 (s, 3H, CH.sub.3), 0.96 (s, 6H, CH.sub.3).

[0350] 2) Preparation of Complex Ni.sub.5 (Represented by the Structural Formula IIIb, Wherein R.sup.1 and R.sup.3 are Methyl, R.sup.2 is Bromine, R.sup.4-R.sup.7 and R.sup.10 are Hydrogen, R.sup.8, R.sup.9 and R.sup.11 are Methyl, R.sub.12 is Ethyl, M is Nickel, Y is O, and X is Br):

[0351] A solution of 0.278 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.318 g (0.6 mmol) of ligand L.sub.4 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.5 as brownish-red powdery solids in a yield of 74.1%. Elemental analysis (calculated for C.sub.56H.sub.70Br.sub.10N.sub.4Ni.sub.3O.sub.2): C, 37.24; H, 3.91; N, 3.10; experimental value (%): C, 37.38; H, 4.30; N, 3.03.

[0352] 3) Polymerization:

[0353] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 9.0 mg (5 μmol) of the complex Ni.sub.5 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 1 below.

Example 15

[0354] 1) Preparation of ligand L.sub.5:

[0355] Under nitrogen atmosphere, 2,6-diisopropyl-aniline (2.30 ml, 12 mmol) was dissolved in 20 ml of toluene, and 12 ml of trimethylaluminum (1.0M, 12 mmol) was added dropwise at room temperature. The reaction was refluxed for 2 hours, and the system was cooled to room temperature. Dione (1.225 g, 5 mmol) was added, and the system was refluxed for 6 h. The reaction product was neutralized with aqueous sodium hydroxide solution, extracted with dichloromethane, dried and concentrated, and then subjected to a column chromatography to afford yellow ligand L.sub.5 in a yield of 62.7%. .sup.1H NMR (300 MHz, CDCl.sub.3), δ (ppm): 7.05-6.83 (m, 6H, Ar—H), 3.30 (m, 2H, CH.sub.2), 2.80 (m, 4H, CH(CH.sub.3).sub.2), 1.55 (m, 1H), 1.83 (m, 4H, CH.sub.2), 1.26 (d, 24H, CH(CH.sub.3).sub.2), 0.99 (s, 6H, CH.sub.3).

[0356] 2) Preparation of Complex Ni.sub.6 (Represented by the Structural Formula IIIb, Wherein R.sup.1 and R.sup.3 are Isopropyl, R.sup.2, R.sup.4-R.sup.7 and R.sup.10 are Hydrogen, R.sup.8 and R.sup.9 are Methyl, R.sup.11 is CH.sub.2Br, R.sub.12 is Ethyl, M is Nickel, Y is O, and X is Br):

[0357] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.338 g (0.6 mmol) of ligand L.sub.5 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.6 as brownish-red powdery solids in a yield of 80.2%. Elemental analysis (calculated for C.sub.72H.sub.104Br.sub.8N.sub.4Ni.sub.3O.sub.2): C, 46.17; H, 5.60; N, 2.99; experimental value (%): C, 46.24; H, 5.80; N, 3.13.

[0358] 3) Polymerization:

[0359] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 9.4 mg (5 μmol) of the complex Ni.sub.6 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 1 below.

Example 16

[0360] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 2, except that 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution) was used instead of the MAO. The results are shown in Table 1 below.

Example 17

[0361] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.0 mg (5.0 mol) of the complex Ni.sub.1, 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm.

[0362] The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 1 below.

Example 18

[0363] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 2, except that 500 mL of toluene was used instead of the hexane. The results are shown in Table 1 below.

Comparative Example 1

[0364] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 1, except that 15 μmol of Comparative Catalyst A was used.

##STR00021##

Comparative Example 2

[0365] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 1, except that 15 μmol of Comparative Catalyst B was used.

##STR00022##

TABLE-US-00001 TABLE 1 Whether is there spherical or Polymerization spherical-like Spherical Activity Alcohol polymer particle 10.sup.6 g .Math. mol.sup.−1 Mw content particles in the diameter No. Complex (Ni) .Math. h.sup.−1 (×10.sup.4) PDI (mol %) copolymer? (mm) Example 1 Ni.sub.1 20.2 34.4 2.02 0.67 Yes 3.5 Example 2 Ni.sub.1 26.7 48.2 1.92 1.37 Yes 3.8 Example 3 Ni.sub.1 21.7 20.2 1.98 1.21 No Example 4 Ni.sub.1 15.2 32.4 1.90 1.14 Yes 2.8 Example 5 Ni.sub.1 12.4 21.7 1.95 1.03 Yes 2.1 Example 6 Ni.sub.1 28.2 58.2 1.98 2.03 Yes 2.9 Example 7 Ni.sub.1 15.7 62.4 2.03 3.84 Yes 2.2 Example 8 Ni.sub.2 21.4 62.7 1.96 1.02 Yes 3.8 Example 9 Ni.sub.2 20.3 31.6 2.02 0.96 No Example 10 Ni.sub.2 11.7 20.6 2.02 0.98 Yes 3.6 Example 11 Ni.sub.3 16.4 51.2 2.01 0.94 Yes 3.4 Example 12 Ni.sub.3 13.3 42.7 2.04 0.93 Yes 3.2 Example 13 Ni.sub.4 33.2 13.4 2.01 1.48 Yes 2.8 Example 14 Ni.sub.5 35.1 14.9 1.98 1.46 Yes 2.9 Example 15 Ni.sub.6 18.4 40.3 2.02 0.94 Yes 3.0 Example 16 Ni.sub.1 24.2 43.3 2.04 1.36 Yes 3.3 Example 17 Ni.sub.1 18.2 37.8 2.08 1.52 No Example 18 Ni.sub.1 24.1 44.3 2.02 1.36 No Comp. Ex. 1 A 15.2 36.3 2.32 0.97 Yes 3.4 Comp. Ex. 2 B 3.41 64.3 2.35 0.92 No

Example 19

[0366] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.0 mg (5.0 mol) of the complex Ni.sub.1, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 20

[0367] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 19, except that 2 times quantity of 2,2-dimethyl-7-octenoic acid and 2 times quantity of AlEt.sub.3 were used. The results are shown in Table 1 below. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 21

[0368] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 22

[0369] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 0.5 mL of diethylzinc (1 mol/L solution in hexane) was further added together with the catalyst. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 23

[0370] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 1.0 mL of diethylzinc (1 mol/L solution in hexane) was further added together with the catalyst. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 24

[0371] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 19, except that 3.33 times quantity (i.e., 50 mmol (8.51 g)) of 2,2-dimethyl-7-octenoic acid and 3.33 times quantity (i.e., 50 mL) of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 25

[0372] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 19, except that 6.67 times quantity (i.e., 100 mmol (17.02 g)) of 2,2-dimethyl-7-octenoic acid and 6.67 times quantity (i.e., 100 mL) of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 26

[0373] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.6 mg (5 mol) of the complex Ni.sub.2, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 27

[0374] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.6 mg (5 mol) of the complex Ni.sub.2, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 28

[0375] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.6 mg (5 mol) of the complex Ni.sub.2, 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 29

[0376] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 8.9 mg (5 μmol) of the complex Ni.sub.3 was used as a catalyst. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 30

[0377] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 7.7 mg (5 μmol) of the complex Ni.sub.4 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 2 below.

Example 31

[0378] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 9.0 mg (5 μmol) of the complex Ni.sub.5 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 20° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 2 below.

Example 32

[0379] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 9.4 mg (5 μmol) of the complex Ni.sub.6 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 50° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 2 below.

Example 33

[0380] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution) was used instead of MAO. The results are shown in Table 2 below.

Example 34

[0381] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 20, except that 30 mmol (5.53 g) of 10-undecenoic acid was used as a comonomer. The polymerization activity and polymer performance parameters are shown in Table 2 below.

Example 35

[0382] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 2, except that 500 mL of toluene was used instead of the hexane. The polymerization activity and polymer performance parameters are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Whether is there spherical and/or spherical- like Polymerization polymer Activity Comonomer particles 10.sup.6 g .Math. mol.sup.−1 Mn content in the No. Complex (Ni)h.sup.−1 (×10.sup.4) (mol %) copolymer? Example Ni.sub.1 15.3 14.2 0.78 Yes 19 Example Ni.sub.1 17.2 16.3 1.24 Yes 20 Example Ni.sub.1 16.2 9.3 1.02 No 21 Example Ni.sub.1 11.7 10.4 1.21 Yes 22 Example Ni.sub.1 9.3 8.4 1.17 Yes 23 Example Ni.sub.1 20.7 18.4 2.02 Yes 24 Example Ni.sub.1 16.3 16.2 3.72 Yes 25 Example Ni.sub.2 15.8 20.6 1.17 Yes 26 Example Ni.sub.2 11.3 16.4 1.02 No 27 Example Ni.sub.2 15.2 18.9 1.15 Yes 28 Example Ni.sub.3 11.3 10.4 1.01 Yes 29 Example Ni.sub.4 21.7 8.4 1.53 Yes 30 Example Ni.sub.5 13.2 6.3 1.40 Yes 31 Example Ni.sub.6 14.2 17.3 1.02 Yes 32 Example Ni.sub.1 15.4 14.7 1.21 Yes 33 Example Ni.sub.1 14.1 13.0 1.13 No 34 Example Ni.sub.1 17.0 15.4 1.23 No 35

[0383] It can be seen from Table 2 that when the catalyst of the present invention catalyzes the copolymerization of ethylene and an unsaturated carboxylic acid, it exhibits higher polymerization activity, and the resulting polymer has a higher molecular weight. The catalyst of the present invention can have a copolymerization activity of up to 21.7×10.sup.6 g.Math.mol.sup.−1(Ni).Math.h.sup.−1, and the molecular weight of the polymer can be adjusted in a wide range by the addition of a chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0384] The following structural Formulae of ligands and complexes are mentioned in Example 36-68:

##STR00023##

Example 36

[0385] 1) Ligand L.sub.11 (represented by the structural Formula B, wherein R.sup.1, R.sup.3, R.sup.4, and R.sup.6 are isopropyl, R.sup.2, R.sup.5, R.sup.7-R.sup.10, R.sub.21, and R.sub.22 are hydrogen) was prepared by following the literature Organometallics, 2013, 32, 2291-2299.

[0386] 2) Preparation of complex Ni.sub.11 (represented by the structural Formula IIIc, wherein R.sup.1, R.sup.3, R.sup.4, and R.sup.6 are isopropyl, R.sup.2, R.sup.5, R.sup.7-R.sup.10, R.sub.21, and R.sub.22 are hydrogen, R.sub.1 is ethyl, M is nickel, Y is O, and X is Br): A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.332 g (0.6 mmol) of ligand L.sub.11 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.11 as brownish-red powdery solids in a yield of 78.2%. Elemental analysis (calculated for C.sub.84H.sub.98Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 54.50; H, 5.34; N, 3.03; experimental value (%): C, 54.38; H, 5.72; N, 3.16.

[0387] 3) Polymerization:

[0388] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 37

[0389] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 38

[0390] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 37, except that the polymerization temperature was 60° C. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 39

[0391] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), 0.5 mL of diethylzinc (1 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 40

[0392] Ethylene copolymerization was carried out according to the polymerization procedure described in Example 39, except that 2 times quantity (1.0 mL) of diethylzinc (1 mol/L solution in hexane) was used. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 41

[0393] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 50 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 50 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 42

[0394] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 100 mmol (17.0 mL) of 2-methyl-2-hydroxy-7-octene, 100 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 43

[0395] ##STR00024##

[0396] 1) Ligand L.sub.12 (represented by the structural Formula B, wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.6 are ethyl, R.sup.2, R.sup.5, R.sup.7-R.sup.10 and R.sub.22 are hydrogen, and R.sub.21 is tert-butyl) was prepared by following the Patent CN106397264 as follows. Compound A (2.7 g, 7.8 mmol) and 2,6-diethylaniline (3.0 ml, 17.4 mmol) were refluxed in the presence of p-toluenesulfonic acid (0.02 g) as a catalyst in 100 mL of toluene for 1 day, and then the solvent was filtered off. The residue was dissolved in dichloromethane and then separated by over-basic alumina column chromatography with petroleum ether/ethyl acetate (20:1) as an eluant, with the second fraction being the target product. After removing the solvent, a yellow solid product was obtained at a yield of 81%. .sup.1H NMR (CDCl3, 6, ppm): 1.06 (t, 12H, J=7.0 Hz), 1.19 ppm (s, 18H), 2.20 (dd, 8H, J=7.0 Hz), 4.70 (s, 2H), 7.04 (m, 10H), 7.13 (s, 2H).

[0397] 2) Preparation of complex Ni.sub.12 (represented by the structural Formula IIIc, wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.6 are ethyl, R.sup.2, R.sup.5, R.sup.7-R.sup.10 and R.sub.22 are hydrogen, R.sub.21 is tert-butyl, R.sub.11 is ethyl, M is nickel, Y is O, and X is Br):

[0398] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.365 g (0.6 mmol) of ligand L.sub.2 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.12 as brownish-red powdery solids in a yield of 82.0%. Elemental analysis (calculated for C.sub.92H.sub.114Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 56.28; H, 5.85; N, 2.85; experimental value (%): C, 56.43; H, 6.12; N, 3.08.

[0399] 3) Polymerization:

[0400] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.8 mg (5 mol) of the complex Ni.sub.12, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 44

[0401] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.8 mg (5 mol) of the complex Ni.sub.12, 30 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 45

[0402] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.8 mg (5 mol) of the complex Ni.sub.12, 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 46

[0403] 1) Preparation of ligand L.sub.13 (represented by the structural Formula B, wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.6 are methyl, R.sup.2 and R.sup.5 are bromine, R.sup.7-R.sup.10 and R.sub.22 are hydrogen, R.sub.21 is t-butyl): Compound A (1.77 g, 5.1 mmol) and 2,6-dimethyl-4-bromo-aniline (2.3 g, 11.3 mmol) were refluxed, in the presence of p-toluenesulfonic acid (0.02 g) as a catalyst, in 100 mL of toluene for 1 day. The solvent was filtered off, and the residue was dissolved in dichloromethane and separated by column chromatography with petroleum ether/ethyl acetate as an eluant, to afford L.sub.13 as yellow solids in a yield of 78%. 1H NMR (CDCl3, 6, ppm): 1.84 (s, 12H), 1.19 ppm (s, 18H), 4.70 (s, 2H), 7.04 (8H), 7.12 (s, 2H).

[0404] 2) Preparation of Complex Ni.sub.13 (Represented by the Structural Formula IIIc, Wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.6 are Methyl, R.sup.2 and R.sup.5 are Bromine, R.sup.7-R.sup.10 and R.sub.22 are Hydrogen, R.sub.21 is Tert-Butyl, R.sub.11 is Ethyl, M is Nickel, Y is O, and X is Br):

[0405] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.426 g (0.6 mmol) of ligand L.sub.13 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.13 as brownish-red powdery solids in a yield of 82.0%. Elemental analysis (calculated for C.sub.84H.sub.94Br.sub.10N.sub.4Ni.sub.3O.sub.2): C, 46.56; H, 4.37; N, 2.59; experimental value (%): C, 46.43; H, 4.72; N, 2.98.

[0406] 3) Polymerization:

[0407] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 10.8 mg (5 mol) of the complex Ni.sub.13, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 47

[0408] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 10.8 mg (5 mol) of the complex Ni.sub.13, 30 mmol (4.5 mL) of 4-methyl-1-heptene-4-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/L solution in toluene) were added. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 48

[0409] 1) Preparation of Complex Ni.sub.14 (Represented by the Structural Formula IIIc, Wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.6 are Ethyl, R.sup.2, R.sup.5, R.sup.7-R.sup.10 and R.sub.22 are Hydrogen, R.sub.21 is Tert-Butyl, R.sub.11 is Isobutyl, M is Nickel, Y is O, and X is Br)

[0410] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in 2-methyl-1-propanol (10 mL) was added slowly dropwise to a solution of 0.365 g (0.6 mmol) of ligand L.sub.12 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.14 as brownish-red powdery solids in a yield of 83.0%. Elemental analysis (calculated for C.sub.96H.sub.122Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 57.09; H, 6.09; N, 2.77; experimental value (%): C, 57.24; H, 6.32; N, 3.04.

[0411] 2) Polymerization:

[0412] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 10.1 mg (5 μmol) of the complex Ni.sub.14 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 3 below.

Example 49

[0413] ##STR00025##

[0414] 1) Ligand L.sub.19 was prepared by following the method disclosed in patent application CN201510462932.2 and by using the compound B as a raw material.

[0415] 2) Preparation of complex Ni.sub.15 (represented by Formula IIIc′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Et, R.sup.2=R.sup.5=R.sup.7-R.sup.10=R.sub.31=R.sub.32=H, R.sub.11=Et, M=Ni, Y=O, X=Br):

##STR00026##

[0416] A solution of 0.277 g (0.9 mmol) of (DME)NiBr.sub.2 in ethanol (10 mL) was added slowly dropwise to a solution of 0.358 g (0.6 mmol) of ligand L.sub.19 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni.sub.15 as brownish-red powdery solids in a yield of 84.3%. Elemental analysis (calculated for C.sub.92H.sub.90Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 56.98; H, 4.68; N, 2.89; experimental value (%): C, 56.78; H, 4.62; N, 3.18.

[0417] 3) Polymerization:

[0418] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 9.7 mg (5 μmol) of the complex Ni.sub.15 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 3 below.

Example 50

[0419] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were added thereto, followed by the addition of 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution). The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 51

[0420] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

Example 52

[0421] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of toluene was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 3 below.

TABLE-US-00003 TABLE 3 Whether is there Polymerization spherical and/or Activity Alcohol spherical-like 10.sup.6 g .Math. mol.sup.−1 Mw content polymer particles No. Complex (Ni) .Math. h.sup.−1 (×10.sup.4) PDI (mol %) in the copolymer? Example 36 Ni.sub.11 3.03 63.2 2.13 0.64 Yes Example 37 Ni.sub.11 4.12 68.2 2.11 1.27 Yes Example 38 Ni.sub.11 2.37 22.5 2.23 1.08 No Example 39 Ni.sub.11 2.64 48.3 2.08 1.04 Yes Example 40 Ni.sub.11 1.92 31.7 2.02 0.96 Yes Example 41 Ni.sub.11 4.94 71.3 2.04 2.01 Yes Example 42 Ni.sub.11 2.12 74.0 2.05 3.71 Yes Example 43 Ni.sub.12 1.96 16.2 2.32 1.33 Yes Example 44 Ni.sub.12 1.27 8.4 2.36 1.00 No Example 45 Ni.sub.12 1.15 13.8 2.24 1.16 Yes Example 46 Ni.sub.13 2.24 6.3 2.42 1.38 Yes Example 47 Ni.sub.13 2.41 6.8 2.31 1.36 Yes Example 48 Ni.sub.14 1.53 15.6 2.14 1.17 Yes Example 49 Ni.sub.15 2.36 17.3 2.10 1.24 Yes Example 50 Ni.sub.11 3.76 63.2 2.27 1.26 Yes Example 51 Ni.sub.11 4.42 73.1 2.02 1.26 No Example 52 Ni.sub.11 4.13 67.0 2.12 1.27 No

[0422] It can be seen from Table 3 that the catalyst of the present invention exhibits higher polymerization activity when catalyzing the copolymerization of ethylene and an enol, and the resulting polymer has a higher molecular weight. The catalyst of the invention can have a copolymerization activity of up to 4.94×10.sup.6 g.Math.mol.sup.−1(Ni).Math.h.sup.−1. The molecular weight of the polymer can be adjusted in a wide range by the addition of a chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

Example 53

[0423] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

Example 54

[0424] Ethylene copolymerization was carried out according to the procedure described in Example 53, except that 2 times quantity (30 mmol (5.10 g)) of 2,2-dimethyl-7-octenoic acid and 2 times quantity (30 mL) of AlEt.sub.3 were used. The results are shown in Table 4 below.

Example 55

[0425] Ethylene copolymerization was carried out according to the procedure described in Example 54, except that polymerization temperature was 60° C. The results are shown in Table 4 below.

Example 56

[0426] Ethylene copolymerization was carried out according to the procedure described in Example 54, except that 0.5 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 4 below.

Example 57

[0427] Ethylene copolymerization was carried out according to the procedure described in Example 54, except that 1.0 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 4 below.

Example 58

[0428] Ethylene copolymerization was carried out according to the procedure described in Example 53, except that 3.33 times quantity (50 mmol (8.51 g)) of 2,2-dimethyl-7-octenoic acid and 3.33 times quantity (50 mL) of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 4 below.

Example 59

[0429] Ethylene copolymerization was carried out according to the procedure described in Example 53, except that 6.67 times quantity of 2,2-dimethyl-7-octenoic acid and 6.67 times quantity of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 4 below.

Example 60

[0430] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.8 mg (5 mol) of the complex Ni.sub.12, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

Example 61

[0431] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.8 mg (5 mol) of the complex Ni.sub.12, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

Example 62

[0432] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.8 mg (5 mol) of the complex Ni.sub.12, 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

Example 63

[0433] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 10.8 mg (5 mol) of the complex Ni.sub.13, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

Example 64

[0434] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 10.1 mg (5 μmol) of the complex Ni.sub.14 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 4 below.

Example 65

[0435] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 9.7 mg (5 μmol) of the complex Ni.sub.15 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 20° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 4 below.

Example 66

[0436] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were added thereto, followed by the addition of 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution). The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

Example 67

[0437] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (5.53 g) of 10-undecenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

Example 68

[0438] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of toluene was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni.sub.11, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 4 below.

TABLE-US-00004 TABLE 4 Whether is there spherical and/or spherical- like Polymerization polymer Activity Comonomer particles 10.sup.6 g .Math. mol.sup.−1 Mn content in the No. Complex (Ni)h.sup.−1 (×10.sup.4) (mol %) copolymer? Example Ni.sub.11 1.54 18.4 0.72 Yes 53 Example Ni.sub.11 1.86 22.1 1.10 Yes 54 Example Ni.sub.11 1.12 10.3 0.92 No 55 Example Ni.sub.11 1.20 13.4 1.04 Yes 56 Example Ni.sub.11 0.98 8.4 1.01 Yes 57 Example Ni.sub.11 2.12 24.4 1.98 Yes 58 Example Ni.sub.11 1.63 19.2 3.20 Yes 59 Example Ni.sub.12 1.13 12.6 1.14 Yes 60 Example Ni.sub.12 1.20 13.4 2.02 No 61 Example Ni.sub.12 1.22 12.9 1.15 Yes 62 Example Ni.sub.13 2.42 8.4 1.41 Yes 63 Example Ni.sub.14 1.06 10.7 1.10 Yes 64 Example Ni.sub.15 1.37 14.4 1.14 Yes 65 Example Ni.sub.11 1.70 21.4 1.06 Yes 66 Example Ni.sub.11 1.35 20.2 1.10 No 67 Example Ni.sub.11 1.38 20.4 1.09 No 68

[0439] It can be seen from Table 4 that when the catalyst of the present invention catalyzes the copolymerization of ethylene and an unsaturated carboxylic acid, it exhibits higher polymerization activity, and the resulting polymer has a higher molecular weight. The catalyst of the present invention can have a copolymerization activity of up to 2.42×10.sup.6 g.Math.mol.sup.−(Ni).Math.h.sup.−1, and the molecular weight of the polymer can be adjusted in a wide range by the addition of a chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0440] The compounds of the following structural Formulae are mentioned in the following examples:

##STR00027##

[0441] Diimine Compound A21: α-diimine compound represented by Formula VI, wherein R.sup.1=R.sup.3=Me, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3;

[0442] Diimine Compound A22: α-diimine compound represented by Formula VI, wherein R.sup.1=R.sup.3=iPr, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3;

[0443] Ligand L.sub.21: amino-imine compound represented by Formula V, wherein R.sup.1=R.sup.3=Me, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3;

[0444] Ligand L.sub.22: amino-imine compound represented by Formula V, wherein R.sup.1=R.sup.3=iPr, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3; R.sub.3=CH.sub.3;

[0445] Ligand L.sub.23: amino-imine compound represented by Formula V, wherein R.sup.1=R.sup.3=iPr, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3; R.sub.3=Et;

[0446] Complex Ni.sub.21: complex represented by Formula III, wherein R.sup.1=R.sup.3=Me, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3, R.sub.3=CH.sub.3, R.sub.12=Et, M=Ni, Y=O, X=Br;

[0447] Complex Ni.sub.22: complex represented by Formula III, wherein R.sup.1=R.sup.3=iPr, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3; R.sub.3=CH.sub.3, R.sub.12=Et, M=Ni, Y=O, X=Br;

[0448] Complex Ni.sub.23: complex represented by Formula III, wherein R.sup.1=R.sup.3=iPr, R.sup.2=R.sup.4=R.sup.5=R.sup.6=R.sup.7=R.sup.10=H, R.sup.8=R.sup.9=R.sup.11=CH.sub.3; R.sub.3=Et, R.sub.12=Et, M=Ni, Y=O, X=Br.

Example 69

[0449] 1) Preparation of Ligand L.sub.21:

[0450] 1.5 mL of 2,6-dimethylaniline (12 mmol) was reacted with 57 ml of 1M trimethylaluminum in toluene under refluxing for 3 h. Then, camphorquinone (1.05 g, 5 mmol) was added thereto, and the reaction mixture was refluxed for 8 hours. After cooling, the reaction was terminated with sodium hydroxide/ice water, the reaction mixture was extracted with ethyl acetate, and organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography with petroleum ether/ethyl acetate as an eluent to obtain ligand L.sub.21 as colorless crystals in a yield of 70.2%. .sup.1HNMR δ(ppm) 7.00-6.89 (m, 6H, Ar—H), 3.57 (s, 1H, NH), 2.18 (s, 6H, C.sub.Ar—CH.sub.3), 2.05 (s, 6H, CH.sub.3), 1.74 (m, 4H, CH.sub.2), 1.44 (s, 3H, CH.sub.3), 1.35 (m, 1H), 1.21 (s, 3H, C H.sub.3), 1.01 (s, 3H, CH.sub.3), 0.87 (s, 3H, CH.sub.3).

[0451] 2) Preparation of Complex Ni21:

[0452] A solution of (DME)NiBr.sub.2 (277 mg, 0.9 mmol) in ethanol (10 mL) was added dropwise to a solution of ligand L.sub.21 (233 mg, 0.6 mmol) in dichloromethane (10 mL), and the resulting mixture was stirred at room temperature for 6 h, with precipitants being generated. After filtering, the filter cake was washed with diethyl ether and dried to afford red powdery solids in a yield of 70%. Elemental analysis (calculated for C.sub.58H.sub.22Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 45.75; H, 5.43; N, 3.68; experimental value (%): C, 45.56; H, 5.83; N, 3.46.

[0453] 3) Polymerization:

[0454] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 70

[0455] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

[0456] FIG. 4 shows a photograph of the spherical and/or spherical-like polymer prepared in this example.

Example 71

[0457] Ethylene copolymerization was carried out according to the procedure described in Example 70, except that polymerization temperature was 60° C. The results are shown in Table 5 below.

Example 72

[0458] Ethylene copolymerization was carried out according to the procedure described in Example 70, except that 0.5 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 5 below.

Example 73

[0459] Ethylene copolymerization was carried out according to the procedure described in Example 70, except that 1.0 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 5 below.

Example 74

[0460] Ethylene copolymerization was carried out according to the procedure described in Example 69, except that 3.33 times quantity (50 mmol (8.5 mL)) of 2-methyl-2-hydroxy-7-octene and 3.33 times quantity (50 mL) of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 5 below.

Example 75

[0461] Ethylene copolymerization was carried out according to the procedure described in Example 69, except that 6.67 times quantity of 2-methyl-2-hydroxy-7-octene and 6.67 times quantity of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 5 below.

Example 76

[0462] 1) Preparation of Ligand L.sub.22:

[0463] To a reaction flask were successively charged with 3.88 g (8 mmol) of α-diimine compound A22, 30 ml of toluene, and 1M trimethylaluminum (16 ml, 16 mmol), and the contents were allowed to react under reflux for 8 hours. The reaction was terminated with sodium hydroxide/ice water and extracted with ethyl acetate, and organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography with petroleum ether/ethyl acetate as an eluent to obtain ligand L.sub.22 as colorless crystals in a yield of 84.2%. .sup.1HNMR δ(ppm) 7.19-7.06 (m, 6H, Ar—H), 3.42 (s, 1H, NH), 2.98 (m, 2H, CH(CH.sub.3).sub.2), 2.88 (m, 2H, CH(CH.sub.3).sub.2), 2.32 (m, 1H), 1.81 (m, 4H, CH.sub.2), 1.50 (s, 3H, CH.sub.3), 1.21 (m, 24H, CH.sub.3), 0.92 (s, 3H, CH.sub.3), 0.75 (s, 3H, CH.sub.3), 0.72 (s, 3H, CH.sub.3).

[0464] 2) Preparation of Complex Ni.sub.22:

[0465] A solution of (DME)NiBr.sub.2 (277 mg, 0.9 mmol) in ethanol (10 mL) was added dropwise to a solution of ligand L.sub.22 (300 mg, 0.6 mmol) in dichloromethane (10 mL), and the resulting mixture was stirred at room temperature for 6 h, with precipitants being generated. After filtering, the filter cake was washed with diethyl ether and dried to afford red powdery solids in a yield of 78%. Elemental analysis (calculated for C.sub.74H.sub.114Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 50.87; H, 6.58; N, 3.21; experimental value (%): C, 50.57; H, 6.73; N, 3.04.

[0466] 3) Polymerization:

[0467] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.7 mg (5 mol) of the complex Ni.sub.22, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 77

[0468] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.7 mg (5 mol) of the complex Ni.sub.22, 30 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 78

[0469] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.7 mg (5 mol) of the complex Ni.sub.22, 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 79

[0470] 1) Preparation of Ligand L.sub.23:

[0471] To a reaction flask were successively charged with 3.88 g (8 mmol) of α-diimine compound A22, 30 ml of diethyl ether, and 2M diethylzinc (4 ml, 8 mmol), and the contents were stirred at room temperature for 3 hours. The reaction was terminated with ice water, the reaction mixture was extracted with ethyl acetate, and organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography with petroleum ether/ethyl acetate as an eluent to obtain ligand L.sub.23 as colorless crystals with a yield of 52.1%. .sup.1HNMR δ(ppm) 7.17-7.06 (m, 6H, Ar—H), 4.44 (s, 1H, NH), 2.98 (m, 2H, CH(CH.sub.3).sub.2), 2.87 (m, 2H, CH(CH.sub.3).sub.2), 2.33 (m, 1H), 1.86 (m, 2H, CH.sub.2), 1.81 (m, 4H, CH.sub.2), 1.21 (m, 24H, CH.sub.3), 1.08 (t, 3H, CH.sub.3), 0.93 (s, 3H, CH.sub.3), 0.75 (s, 3H, CH.sub.3), 0.72 (s, 3H, CH.sub.3).

[0472] 2) Preparation of Complex Ni.sub.23:

[0473] A solution of (DME)NiBr.sub.2 (277 mg, 0.9 mmol) in ethanol (10 mL) was added dropwise to a solution of ligand L.sub.23 (309 mg, 0.6 mmol) in dichloromethane (10 mL), and the resulting mixture was stirred at room temperature for 6 h, with precipitants being generated. After filtering, the filter cake was washed with diethyl ether and dried to afford red powdery solids in a yield of 72%. Elemental analysis (calculated for C.sub.76H.sub.118Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 51.42; H, 6.70; N, 3.16; experimental value (%): C, 51.29; H, 6.98; N, 3.04.

[0474] 3) Polymerization:

[0475] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.9 mg (5 mol) of the complex Ni.sub.23, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 80

[0476] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.9 mg (5 mol) of the complex Ni.sub.23, 30 mmol (4.5 mL) of 4-methyl-1-hepten-4-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 81

[0477] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were added thereto, followed by the addition of 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution). The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 82

[0478] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

Example 83

[0479] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of toluene was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.2, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 w % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 5 below.

TABLE-US-00005 TABLE 5 Whether is there Polymerization spherical and/or Activity Alcohol spherical-like 10.sup.6 g .Math. mol.sup.−1 Mw content polymer particles No. Complex (Ni) .Math. h.sup.−1 (×10.sup.4) PDI (mol %) in the copolymer? Example 69 Ni21 2.72 18.4 1.72 0.71 Yes Example 70 Ni21 3.02 20.1 1.68 1.14 Yes Example 71 Ni21 1.03 6.4 1.60 0.93 No Example 72 Ni21 1.63 12.0 1.50 1.02 Yes Example 73 Ni21 1.07 7.6 1.12 0.96 Yes Example 74 Ni21 2.96 20.8 1.73 1.42 Yes Example 75 Ni21 1.54 21.7 1.86 2.37 Yes Example 76 Ni22 5.17 38.6 1.57 1.02 Yes Example 77 Ni22 4.12 14.6 1.77 0.92 No Example 78 Ni22 4.33 33.1 1.64 1.01 Yes Example 79 Ni23 2.12 18.3 1.67 0.99 Yes Example 80 Ni23 2.07 16.4 1.70 1.02 Yes Example 81 Ni21 2.76 18.3 1.65 1.11 Yes Example 82 Ni21 3.12 21.6 1.66 1.12 No Example 83 Ni21 3.04 19.6 1.65 1.15 No

[0480] It can be seen from Table 5 that when the catalyst of the present invention catalyzes the copolymerization of ethylene and an enol, it exhibits higher polymerization activity, and the resulting polymer has a higher molecular weight. The catalyst of the present invention can have a copolymerization activity of up to 5.17×10.sup.6 g.Math.mol.sup.−i(Ni).Math.h.sup.−1, and the molecular weight of the polymer can be adjusted in a wide range by the addition of a chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

Example 84

[0481] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/l solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 85

[0482] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/l solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 86

[0483] Ethylene copolymerization was carried out according to the procedure described in Example 85, except that polymerization temperature was 60° C. The results are shown in Table 6 below.

Example 87

[0484] Ethylene copolymerization was carried out according to the procedure described in Example 85, except that 0.5 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 6 below.

Example 88

[0485] Ethylene copolymerization was carried out according to the procedure described in Example 85, except that 1.0 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 6 below.

Example 89

[0486] Ethylene copolymerization was carried out according to the procedure described in Example 84, except that 3.33 times quantity (50 mmol (8.51 g)) of 2,2-dimethyl-7-octenoic acid and 3.33 times quantity (50 mL) of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 6 below.

Example 90

[0487] Ethylene copolymerization was carried out according to the procedure described in Example 84, except that 6.67 times quantity of 2,2-dimethyl-7-octenoic acid and 6.67 times quantity of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 6 below.

Example 91

[0488] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.7 mg (5 mol) of the complex Ni.sub.22, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 92

[0489] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.7 mg (5 mol) of the complex Ni.sub.22, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 93

[0490] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.7 mg (5 mol) of the complex Ni.sub.22, 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 94

[0491] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.9 mg (5 mol) of the complex Ni.sub.23, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 95

[0492] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.9 mg (5 mol) of the complex Ni.sub.23, 30 mmol (4.26 g) of 2-isopropyl-4-pentenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 96

[0493] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were added thereto, followed by the addition of 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution). The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 97

[0494] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 7.6 mg (5 mol) of the complex Ni.sub.21, 30 mmol (5.53 g) of 10-undecenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

Example 98

[0495] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of toluene was charged into the autoclave, and at the same time 7.6 mg (5 μmol) of the complex Ni.sub.2, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/l solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 6 below.

TABLE-US-00006 TABLE 6 Whether is there spherical and/or spherical- like Polymerization polymer Activity Comonomer particles 10.sup.6 g .Math. mol.sup.−1 Mn content in the No. Complex (Ni) .Math. h.sup.−1 (×10.sup.4) (mol %) copolymer? Example Ni21 1.96 5.12 0.67 Yes 84 Example Ni21 2.02 5.43 1.10 Yes 85 Example Ni21 1.33 2.52 0.96 No 86 Example Ni21 1.52 2.72 1.02 Yes 87 Example Ni21 1.00 1.63 0.97 Yes 88 Example Ni21 2.12 6.33 1.44 Yes 89 Example Ni21 1.23 5.10 2.72 Yes 90 Example Ni22 4.52 14.7 1.13 Yes 91 Example Ni22 4.17 8.6 0.93 No 92 Example Ni22 4.07 13.3 1.13 Yes 93 Example Ni23 2.32 9.3 1.07 Yes 94 Example Ni23 1.21 5.4 0.96 Yes 95 Example Ni21 1.97 5.36 1.09 Yes 96 Example Ni21 2.07 5.53 1.11 No 97 Example Ni21 2.04 5.36 1.10 No 98

[0496] It can be seen from Table 6 that when the catalyst of the present invention catalyzes the copolymerization of ethylene and an unsaturated carboxylic acid, it exhibits higher polymerization activity, and the resulting polymer has a higher molecular weight. The catalyst of the present invention can have a copolymerization activity of up to 4.52×10.sup.6 g.Math.mol.sup.−1(Ni).Math.h.sup.−1, and the molecular weight of the polymer can be adjusted in a wide range by the addition of a chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0497] The following compounds, ligands and complexes are mentioned in the following examples:

##STR00028##

[0498] Diimine Compound A31: α-diimine compound represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=CH.sub.3, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H;

[0499] Diimine Compound A32: α-diimine compound represented by Formula V, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=i-Pr, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H;

[0500] Diimine Compound A33: α-diimine compound represented by Formula V′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Me, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.31=R.sub.32=H;

##STR00029##

[0501] Ligand L31: amino-imine compound represented by Formula VI, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=CH.sub.3, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3;

[0502] Ligand L32: amino-imine compound represented by Formula VI, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=i-Pr, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3;

[0503] Ligand L33: amino-imine compound represented by Formula VI, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=CH.sub.3, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=Et;

[0504] Ligand L34: amino-imine compound represented by Formula VI′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=Me, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.31=R.sub.32=H, R.sub.5=CH.sub.3;

##STR00030##

[0505] Complex Ni31: complex represented by Formula II, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=CH.sub.3, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H, R.sub.5=CH.sub.3, R.sub.11=Et, M=Ni, Y=O, X=Br;

[0506] Complex Ni32: complex represented by Formula II, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=iPr, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H; R.sub.5=CH.sub.3, R.sub.11=Et, M=Ni, Y=O, X=Br;

[0507] Complex Ni33: complex represented by Formula II, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=iPr, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H; R.sub.5=CH.sub.3, R.sub.11=isobutyl, M=Ni, Y=O, X=Br;

[0508] Complex Ni34: complex represented by Formula II, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=CH.sub.3, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.21=R.sub.22=H; R.sub.5=Et, R.sub.11=Et, M=Ni, Y=O, X=Br;

[0509] Complex Ni35: complex represented by Formula II′, wherein R.sup.1=R.sup.3=R.sup.4=R.sup.6=CH.sub.3, R.sup.2=R.sup.5=R.sup.7=R.sup.8=R.sup.9=R.sup.10=R.sub.31=R.sub.32=H; R.sub.5=Me, R.sub.1=Et, M=Ni, Y=O, X=Br.

Example 99

[0510] 1) Preparation of Ligand L31:

[0511] To a reaction flask were successively charged with 3.52 g (8 mmol) of α-diimine compound A1, 30 ml of toluene, and 1M trimethylaluminum (16 mL, 16 mmol), and the reaction mixture was refluxed for 8 hours. The reaction was terminated with sodium hydroxide/ice water, the reaction mixture was extracted with ethyl acetate, and organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography with petroleum ether/ethyl acetate as an eluent to obtain ligand L31 as colorless crystals with a yield of 85.2%. .sup.1HNMR δ(ppm) 7.23-6.88 (m, 14H), 4.84 (s, 1H), 4.73 (s, 1H), 3.85 (s, 1H, NH), 2.02 (s, 3H, CH.sub.3), 1.87 (s, 6H, CH.sub.3), 1.75 (s, 6H, CH.sub.3).

[0512] 2) Preparation of complex Ni31:

[0513] 10 mL solution of (DME)NiBr.sub.2 (277 mg, 0.9 mmol) in ethanol was added dropwise to 10 mL solution of ligand L31 (274 mg, 0.6 mmol) in dichloromethane, and the resulting mixture was stirred at room temperature for 6 h, with precipitants being generated. After filtering, the filter cake was washed with diethyl ether and dried to afford red powdery solids in a yield of 74%. Elemental analysis (calculated for C.sub.70H.sub.74Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 50.68; H, 4.50; N, 3.38; experimental value (%): C, 50.53; H, 4.73; N, 3.21.

[0514] 3) After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 100

[0515] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 101

[0516] Ethylene copolymerization was carried out according to the procedure described in Example 100, except that polymerization temperature was 60° C. The results are shown in Table 7 below.

Example 102

[0517] Ethylene copolymerization was carried out according to the procedure described in Example 100, except that 0.5 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 7 below.

Example 103

[0518] Ethylene copolymerization was carried out according to the procedure described in Example 100, except that 1.0 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 7 below.

Example 104

[0519] Ethylene copolymerization was carried out according to the procedure described in Example 99, except that 3.33 times quantity of 2-methyl-2-hydroxy-7-octene and 3.33 times quantity of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 7 below.

Example 105

[0520] Ethylene copolymerization was carried out according to the procedure described in Example 99, except that 6.67 times quantity of 2-methyl-2-hydroxy-7-octene and 6.67 times quantity of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 7 below.

Example 106

[0521] 1) Preparation of Ligand L32:

[0522] To a reaction flask were successively charged with 4.42 g (8 mmol) of α-diimine compound A32, 30 ml of toluene, and 1M trimethylaluminum (16 mL, 16 mmol), and the reaction mixture was refluxed for 8 hours. The reaction was terminated with sodium hydroxide/ice water, the reaction mixture was extracted with ethyl acetate, and organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography with petroleum ether/ethyl acetate as an eluent to obtain ligand L32 as colorless crystals in a yield of 76.2%. .sup.1HNMR δ(ppm) 7.21-6.95 (m, 14H), 4.96 (s, 1H), 4.87 (s, 1H), 3.85 (s, 1H, NH), 2.51 (m, 4H, CH(CH.sub.3).sub.2), 2.02 (s, 3H, CH.sub.3), 1.18 (d, 3H, CH.sub.3), 1.11 (d, 3H, CH.sub.3), 1.05 (d, 6H, CH.sub.3), 0.98 (d, 6H, CH.sub.3), 0.60 (d, 6H, CH.sub.3).

[0523] 2) Preparation of Complex Ni32:

[0524] 10 mL solution of (DME)NiBr.sub.2 (277 mg, 0.9 mmol) in ethanol was added dropwise to 10 mL solution of ligand L2 (341 mg, 0.6 mmol) in dichloromethane, and the resulting mixture was stirred at room temperature for 6 h, with precipitants being generated. After filtering, the filter cake was washed with diethyl ether and dried to afford red powdery solids in a yield of 76%. Elemental analysis (calculated for C.sub.86H.sub.106Br.sub.6N.sub.4Ni3O.sub.2): C, 54.85; H, 5.67; N, 2.97; experimental value (%): C, 54.61; H, 5.73; N, 3.14.

[0525] 3) Polymerization:

[0526] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.4 mg (5 mol) of the complex Ni32, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 107

[0527] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.4 mg (5 mol) of the complex Ni32, 30 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 108

[0528] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.4 mg (5 mol) of the complex Ni32, 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 109

[0529] A solution of 277 mg (0.9 mmol) of (DME)NiBr.sub.2 in 2-methyl-1-propanol (10 mL) was added slowly dropwise to a solution of 341 mg (0.6 mmol) of ligand L32 in dichloromethane (10 mL). The color of the solution immediately changed to deep red, and a large quantity of precipitants was formed. The reaction was stirred at room temperature for 6 h, and then anhydrous diethyl ether was added to perform precipitation. A filtration was performed to afford a filter cake, and the filter cake was washed with anhydrous diethyl ether and dried in vacuum to afford Ni33 as brownish-red powdery solids in a yield of 84.0%. FT-IR (KBr disc, cm.sup.−1) 2969, 1677, 1628, 1462, 1342, 1109, 794, 760. Elemental analysis (calculated for C.sub.90H.sub.114Br.sub.6N.sub.4Ni.sub.3O.sub.2): C, 55.74; H, 5.92; N, 2.89; experimental value (%): C, 56.08; H, 6.12; N, 3.08.

[0530] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.7 mg (5 mol) of the complex Ni33, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 110

[0531] 1) Preparation of Ligand L33:

[0532] To a reaction flask were successively charged with 3.52 g (8 mmol) of α-diimine compound A31, 30 ml of diethyl ether, and 2M diethylzinc (4 mL, 8 mmol), and the reaction mixture was stirred at room temperature for 3 hours. The reaction was terminated with ice water, the reaction mixture was extracted with ethyl acetate, and organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography with petroleum ether/ethyl acetate as an eluent to obtain ligand L33 as colorless crystals in a yield of 50.1%. .sup.1HNMR δ(ppm) 7.22-6.86 (m, 14H), 4.82 (s, 1H), 4.73 (s, 1H), 3.85 (s, 1H, NH), 2.04 (m, 2H, CH.sub.2CH.sub.3), 1.89 (s, 6H, CH.sub.3), 1.74 (s, 6H, CH.sub.3), 0.89 (t, 3H, CH.sub.3).

[0533] 2) Preparation of Complex Ni34:

[0534] 10 mL solution of (DME)NiBr.sub.2 (277 mg, 0.9 mmol) in ethanol was added dropwise to 10 mL solution of ligand L3 (282 mg, 0.6 mmol) in dichloromethane, and the resulting mixture was stirred at room temperature for 6 h, with precipitants being generated. After filtering, the filter cake was washed with diethyl ether and dried to afford red powdery solids in a yield 73%. Elemental analysis (calculated for C.sub.72H.sub.78Br.sub.6N.sub.4Ni3O.sub.2): C, 51.26; H, 4.66; N, 3.32; experimental value (%): C, 51.39; H, 4.93; N, 3.24.

[0535] 3) After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.4 mg (5 mol) of the complex Ni34, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 111

[0536] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.4 mg (5 mol) of the complex Ni34, 30 mmol (4.5 mL) of 4-methyl-1-heptene-4-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 112

[0537] ##STR00031##

[0538] 1) Preparation of Ligand L34:

[0539] To a reaction flask were successively charged with 4.32 g (8 mmol) of α-diimine compound A33, 30 ml of toluene, and 1M trimethylaluminum (16 mL, 16 mmol), and the reaction mixture was stirred at room temperature for 3 hours. The reaction was terminated with ice water, the reaction mixture was extracted with ethyl acetate, and organic phases were combined and dried over anhydrous magnesium sulfate. The product was separated by column chromatography with petroleum ether/ethyl acetate as an eluent to obtain ligand L34 as colorless crystals in a yield of 72.1%. THNMR δ(ppm) 7.68-7.54 (m, 8H), 7.37 (m, 4H), 7.11-7.04 (m, 6H), 5.16 (s, 1H), 5.08 (s, 1H), 4.05 (s, 1H, NH), 1.94 (s, 3H, CH.sub.3), 1.89 (s, 6H, CH.sub.3), 1.73 (s, 6H, CH.sub.3).

[0540] 2) Preparation of Complex Ni35:

[0541] 10 mL solution of (DME)NiBr.sub.2 (277 mg, 0.9 mmol) in ethanol was added dropwise to 10 mL solution of ligand L34 (334 mg, 0.6 mmol) in dichloromethane, and the resulting mixture was stirred at room temperature for 6 h, with precipitants being generated. After filtering, the filter cake was washed with diethyl ether and dried to afford red powdery solids in a yield of 72%. Elemental analysis (calculated for C.sub.86H.sub.82Br.sub.6N.sub.4Ni3O.sub.2): C, 55.56; H, 4.45; N, 3.01; experimental value (%): C, 55.74; H, 4.73; N, 3.14.

[0542] 3) Polymerization:

[0543] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 9.3 mg (5 μmol) of the complex Ni35 was added thereto, followed by evacuating and filling with ethylene to perform replacement 3 times. 500 mL of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were charged into the autoclave, followed by the addition of 6.5 mL of methylaluminoxane (MAO) (1.53 mol/1 solution in toluene). The reaction was vigorously stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The results are shown in Table 7 below.

Example 113

[0544] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane) were added thereto, followed by the addition of 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution). The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 114

[0545] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 30 mmol (6.0 mL) of 10-undecen-1-ol, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

Example 115

[0546] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of toluene was charged into the autoclave, and at the same time 8.3 mg (5 μmol) of the complex Ni31, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 7 below.

TABLE-US-00007 TABLE 7 Whether is there spherical and/or Polymerization spherical-like Activity Alcohol polymer particles 10.sup.5 g .Math. mol.sup.−1 Mw content in the No. Complex (Ni) .Math. h.sup.−1 (×10.sup.4) PDI (mol %) copolymer? Example 99 Ni31 3.66 15.7 1.54 0.78 Yes Example 100 Ni31 3.89 16.8 1.42 1.13 Yes Example 101 Ni31 2.12 10.1 1.96 0.98 No Example 102 Ni31 3.12 11.7 1.24 1.09 Yes Example 103 Ni31 2.37 6.9 1.23 1.06 Yes Example 104 Ni31 4.04 18.9 1.32 1.43 Yes Example 105 Ni31 3.10 14.8 1.40 2.16 Yes Example 106 Ni32 5.27 50.4 1.25 1.02 Yes Example 107 Ni32 3.96 25.7 2.02 0.96 No Example 108 Ni32 4.88 49.2 1.21 1.02 Yes Example 109 Ni33 4.16 41.7 1.23 1.01 Yes Example 110 Ni34 2.02 13.4 1.40 1.10 Yes Example 111 Ni34 2.04 12.7 1.42 1.11 Yes Example 112 Ni35 4.46 18.7 1.38 1.19 Yes Example 113 Ni31 3.64 15.7 1.45 1.13 Yes Example 114 Ni31 3.84 18.7 1.37 1.16 No Example 115 Ni31 3.91 16.7 1.40 1.14 No

[0547] It can be seen from Table 7 that when the catalyst of the present invention catalyzes the copolymerization of ethylene and an enol, it exhibits higher polymerization activity, and the resulting polymer has a higher molecular weight. The catalyst of the present invention can have a copolymerization activity of up to 5.27×10.sup.5 g.Math.mol.sup.−1(Ni).Math.h.sup.−1, and the molecular weight of the polymer can be adjusted in a wide range by the addition of a chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

Example 116

[0548] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/l solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 117

[0549] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/l solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 118

[0550] Ethylene copolymerization was carried out according to the procedure described in Example 117, except that polymerization temperature was 60° C. The results are shown in Table 8 below.

Example 119

[0551] Ethylene copolymerization was carried out according to the procedure described in Example 117, except that 0.5 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 8 below.

Example 120

[0552] Ethylene copolymerization was carried out according to the procedure described in Example 117, except that 1.0 mL of diethylzinc (1 mol/L solution in hexane) was further added into the autoclave. The results are shown in Table 8 below.

Example 121

[0553] Ethylene copolymerization was carried out according to the procedure described in Example 116, except that 3.33 times quantity (50 mmol (8.51 g)) of 2,2-dimethyl-7-octenoic acid and 3.33 times quantity (50 mL) of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 8 below.

Example 122

[0554] Ethylene copolymerization was carried out according to the procedure described in Example 116, except that 6.67 times quantity of 2,2-dimethyl-7-octenoic acid and 6.67 times quantity of AlEt.sub.3 (1.0 mol/L solution in hexane) were used. The results are shown in Table 8 below.

Example 123

[0555] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.4 mg (5 mol) of the complex Ni32, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 124

[0556] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.4 mg (5 mol) of the complex Ni32, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 60° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 125

[0557] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.4 mg (5 mol) of the complex Ni32, 30 mmol (4.69 g) of 2,2-dimethyl-6-heptenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 126

[0558] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.7 mg (5 mol) of the complex Ni33, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 60 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 127

[0559] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.4 mg (5 mol) of the complex Ni34, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 128

[0560] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.4 mg (5 mol) of the complex Ni34, 30 mmol (4.26 g) of 2-isopropyl-4-pentenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 129

[0561] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 9.3 mg (5 mol) of the complex Ni35, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 130

[0562] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 15 mL of a solution of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate in toluene (1 mmol/L toluene solution) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 131

[0563] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of hexane was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 30 mmol (5.53 g) of 10-undecenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

Example 132

[0564] After having been continuously dried at 130° C. for 6 hrs, a 1 L stainless steel polymerization autoclave equipped with mechanical stirring was evacuated while it was hot and then filled with N.sub.2 gas 3 times. 500 mL of toluene was charged into the autoclave, and at the same time 8.3 mg (5 mol) of the complex Ni31, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L solution in hexane), and 6.5 mL of MAO (1.53 mol/1 solution in toluene) were added thereto. The reaction was stirred at 30° C. for 30 minutes, with ethylene pressure being maintained at 10 atm. The reaction mixture was finally neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain a polymer. The polymerization activity and polymer performance parameters are shown in Table 8 below.

TABLE-US-00008 TABLE 8 Whether is there spherical and/or spherical- like Polymerization polymer Activity Comonomer particles 10.sup.5 g .Math. mol.sup.−1 Mn content in the No. Complex (Ni) .Math. h.sup.−1 (×10.sup.4) (mol %) copolymer? Example Ni31 2.67 6.73 0.72 Yes 116 Example Ni31 3.08 7.13 1.16 Yes 117 Example Ni31 2.71 4.64 1.03 No 118 Example Ni31 2.52 5.37 1.09 Yes 119 Example Ni31 1.73 2.86 1.04 Yes 120 Example Ni31 3.32 7.70 1.44 Yes 121 Example Ni31 2.44 6.21 2.38 Yes 122 Example Ni32 4.64 17.26 1.02 Yes 123 Example Ni32 3.27 12.38 0.98 No 124 Example Ni32 4.41 15.82 1.03 Yes 125 Example Ni33 4.07 13.24 1.01 Yes 126 Example Ni34 2.42 4.67 1.02 Yes 127 Example Ni34 2.13 4.24 1.03 Yes 128 Example Ni35 3.68 7.96 1.21 Yes 129 Example Ni31 3.01 7.02 1.14 Yes 130 Example Ni31 3.02 7.14 1.15 No 131 Example Ni31 3.09 7.04 1.15 No 132

[0565] It can be seen from Table 8 that when the catalyst of the present invention catalyzes the copolymerization of ethylene and an unsaturated carboxylic acid, it exhibits higher polymerization activity, and the resulting polymer has a higher molecular weight. The catalyst of the present invention can have a copolymerization activity of up to 4.64×10.sup.5 g.Math.mol.sup.−(Ni).Math.h.sup.−1, and the molecular weight of the polymer can be adjusted in a wide range by the addition of a chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

[0566] It should be noted that the above-described examples are only used to illustrate the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified within the scope of the claims of the present invention as stipulated, and the present invention may be revised without departing from the scope and spirit of the present invention.

[0567] Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.