Olefin-olefinic alcohol copolymer, and preparation method therefor

Abstract

The invention provides an olefin-olefinic alcohol copolymer and a preparation method thereof, said copolymer comprising a spherical and/or spherical-like polymer. The copolymer provided by the invention exhibits a good morphology and has good prospects in industrial use.

Claims

1. An olefin-olefinic alcohol copolymer, comprising a plurality of polymeric particles, wherein one or more of the plurality of polymeric particle is spherical in shape and has a cavity therein, wherein the copolymer comprises a structural unit derived from olefin and a structural unit of Formula I: ##STR00008## wherein, in Formula I, L1-L3 each is independently selected from the group consisting of H and C.sub.1-C.sub.30 alkyl, and L4 is C.sub.1-C.sub.30 alkylene having a side group, the C.sub.1-C.sub.30 alkyl being optionally substituted by a substituent.

2. The copolymer according to claim 1, wherein the structural unit of Formula I is derived from an olefinic alcohol selected from a group consisting of 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1,1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2,2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2,4-dimethyl-4-penten-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, hexafluoroisopropanol, 2-hydroxyl-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl hydroxyl-5-hexene, 1-allylcyclohexanol, 2,3-dimethyl-2-hydroxyl-5-hexene, 1-heptylen-4-ol, 4-methyl-1-heptylen-4-ol, 4-n-propyl-1-heptyl-4-ol, 6-heptylen-3-ol, 2-methyl-2-hydroxyl heptylene, 5-methyl-2-hydroxyl-6-heptylene, 2-hydroxyl-3-methyl-6-heptylene, 2-hydroxyl ethyl-6-heptylene, 2-hydroxyl-4-methyl-6-heptylene, 2-hydroxyl-5-methyl-6-heptylene, 2,5-dimethyl-1-heptylen-4-ol, 2,6-dimethyl-7-octylene-2-ol, 2-hydroxyl-2,4,5-trimethyl-6-heptylene, 2-methyl-3-hydroxyl-7-octylene, 3-methyl-3-hydroxyl-6-heptylene, 2-methyl-2-hydroxyl-7-octylene, 3-methyl-3-hydroxyl-7-octylene, 4-methyl-2-hydroxyl-7-octylene, 4-methyl-3-hydroxyl-7-octylene, 5-methyl-3-hydroxyl-7-octylene, 6-methyl-3-hydroxyl-7-octylene, 3-ethyl-3-hydroxyl-7-octylene, 1,2-dihydroxyl-7-octylene, 2,6-dimethyl-2,6-dihydroxyl-7-octylene, 2,6-dimethyl-2,3-dihydroxyl-7-octylene, 2-methyl-2-hydroxyl-3-chloro-7-octylene, 2-methyl-2-hydroxyl-3,5-dichloro-7-octylene, 3,4-dimethyl-4-hydroxyl-8-nonylene, 4-methyl-4-hydroxyl-8-nonylene, 4-ethyl-4-hydroxyl-8-nonylene, 4-propyl-4-hydroxyl-8-nonylene, 7-octylene-2-ol, 3,5-dichloro-2-methyl-7-octylen-2-ol, 3-chloro-2-methyl-7-octylen-2,3-diol, and 2,6-dimethyl-7-octylen-2,6-diol.

3. The copolymer according to claim 1, wherein a density of the polymeric particles is 0.3000-0.7500 g/cm.sup.3, measured according to GB/T6343-2009.

4. The copolymer according to claim 1, wherein an average particle size of the plurality of polymeric particles is 0.1-50.0 mm, and/or a volume of the cavity in each polymeric particle is 5-99% of a volume of the polymeric particle.

5. The copolymer according to claim 1, wherein each polymeric particle comprises a plurality of microsphere particles, and based on a total weight of the copolymer, a content of the plurality of microsphere particles is 5-70 wt %.

6. The copolymer according to claim 5, wherein an average particle size of the microsphere particles is 0.1-5.0 μm.

7. The copolymer according to claim 1, wherein, in the copolymer, a content of the structural unit derived from the olefinic alcohol of Formula I is 0.4-30.0 mol %.

8. The copolymer according to claim 1, wherein the structural unit derived from olefin is selected from the group consisting of a structural unit derived from C.sub.2-C.sub.16 α-olefin and a structural unit derived from C.sub.3-C.sub.16 cycloolefin.

9. A preparation method for the olefin-olefinic alcohol copolymer according to claim 1, comprising contacting an olefin and an olefinic alcohol of Formula II with a catalyst and optionally a chain transfer agent for reaction in the presence of an alkane solvent in a reaction system to obtain the copolymer: ##STR00009## wherein, in Formula II, definitions of L1-L4 are the same as the definitions of L1-L4 in Formula I; and the catalyst comprises a first catalyst and a co-catalyst, wherein the first catalyst is one or more metal complex of Formula III: ##STR00010## wherein, in Formula III, R.sub.9 and R.sub.10 each is independently selected from the group consisting of H, halogen, and substituted or unsubstituted hydrocarbyl, and optionally form a ring with each other; M is a Group VIII metal; X is one or more selected from the group consisting of halogen, hydrocarbyl, and hydrocarbyloxy; and n is an integer that meets an M valence state.

10. The preparation method according to claim 9, wherein, in Formula III, R.sub.9 and R.sub.10 each is independently selected from the group consisting of substituted or unsubstituted C.sub.6-C.sub.30 aryl and substituted or unsubstituted C.sub.7-C.sub.30 aralkyl; R.sub.5-R.sub.8 are identical to or different from each other, each is independently selected from the group consisting of H and C.sub.1-C.sub.20 hydrocarbyl, and optionally form a ring with each other; M is a Group VIII metal; X is one or more selected from the group consisting of halogen and C.sub.1-C.sub.10 hydrocarbyl; and n is an integer that meets an M valence state.

11. The preparation method according to claim 9, wherein the catalyst is selected from at least one metal complex shown in Formula IV: ##STR00011## wherein, in Formula IV, R.sup.1-R.sup.10 are identical to or different from each other, and each is independently selected from the group consisting of H, halogen, C.sub.1-C.sub.24 hydrocarbyl, and C.sub.1-C.sub.24 hydrocarbyloxy, R.sup.1-R.sup.3, R.sup.9, and R.sup.10 optionally forming a ring, R.sup.4-R.sup.6, R.sup.7, and R.sup.8 optionally forming a ring; and M, X, and n have the same definitions as those in Formula III.

12. The preparation method according to claim 11, wherein, in Formula IV, R.sup.7-R.sup.10 are H, and R.sup.1-R.sup.6 are identical to or different from each other and each is independently selected from the group consisting of H and C.sub.1-C.sub.6 alkyl.

13. The preparation method according to claim 9, wherein the M is nickel.

14. The preparation method according to claim 9, wherein the co-catalyst is selected from the group consisting of an organic aluminum compound and an organic boron compound; the organic aluminum compound is one or more selected from the group consisting of alkyl aluminoxane, alkylaluminum, and alkylaluminum halides; and/or the organic boron compound is selected from the group consisting of arylboron and borate.

15. The preparation method according to claim 9, wherein a concentration of the first catalyst in the reaction system is 0.00001-100 mmol/L; when the co-catalyst is the organic aluminum compound, a molar ratio of aluminum in the co-catalyst and M in the first catalyst is 10:1 to 10000000:1; and when the co-catalyst is the organic boron compound, a molar ratio of boron in the co-catalyst and M in the first catalyst is 0.1:1 to 1000:1.

16. The preparation method according to claim 9, wherein the chain transfer agent is one or more selected from the group consisting of aluminum alkyl, magnesium alkyl, and zinc alkyl.

17. The preparation method according to claim 9, wherein a molar ratio of the chain transfer agent and M in the first catalyst is 0.1:1 to 2000:1.

18. The preparation method according to claim 9, wherein a concentration of the olefinic alcohol monomer of Formula II in the reaction system is 0.01-6000 mmol/L.

19. The preparation method according to claim 9, wherein reaction conditions comprise: a reaction temperature ranging from −50° C. to 50° C., and/or a reaction time of 10-200 min.

20. A foaming polyolefin material comprising the copolymer according to claim 1.

21. The copolymer according to claim 1, wherein, in Formula I, L1 and L2 are H, L3 is selected from the group consisting of H, C.sub.1-C.sub.10 alkyl, and C.sub.1-C.sub.10 alkyl substituted by halogen, L4 is a C.sub.1-C.sub.10 alkylene having a side group.

22. The copolymer according to claim 21, wherein the side group is one or more selected from the group consisting of halogen, C.sub.6-C.sub.10 aryl, and C.sub.1-C.sub.10 alkyl.

23. The copolymer according to claim 1, wherein a volume of the cavity in the spherical polymer having a cavity therein is 30-95%.

24. The copolymer according to claim 1, wherein, in the copolymer, a content of the structural unit derived from the olefinic alcohol of Formula I is 0.7-10.0 mol %.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The accompanying drawings are provided for further understanding to the present invention, constitute one part of the description, are used for explaining the present invention together with embodiments of the present invention, and do not constitute limitation to the present invention. In the drawings:

(2) FIG. 1 is an electron micrograph of a spherical and/or spherical-like polymer obtained in Example 2 of the present invention;

(3) FIG. 2 is an electron micrograph of a cross-section of a spherical and/or spherical-like polymer having a cavity therein obtained in Example 2 of the present invention;

(4) FIG. 3 is an electron micrograph of an outer surface of the spherical and/or spherical-like polymer having a cavity therein obtained in Example 2 of the present invention; and

(5) FIG. 4 is an electron micrograph of an inner surface of the spherical and/or spherical-like polymer having a cavity therein obtained in Example 2 of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(6) The present invention is described in detail in conjunction with examples below, but the present invention is not limited by the following examples.

(7) The results of the present invention were characterized by the following manners.

(8) A content of alcohol in the copolymer (a content of the structural unit derived from the olefinic alcohol shown in Formula I) was measured by using .sup.13C NMR, on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer, with a 10 mm PASEX 13 probe, through dissolution of a polymer sample with 1,2,4-trichlorobenzene at 120° C. and analysis and testing.

(9) A molecular weight and a molecular weight distribution PDI (PDI=Mw/Mn) of the copolymer was measured by using PL-GPC220, with the trichlorobenzene as the solvent at 150° C. (standard sample: PS; flow velocity: 1.0 mL/min; and column: 3×Plgel 10 um M1×ED-B 300×7.5 nm).

(10) A melting point of the copolymer was tested by using the differential scanning calorimetry (DSC). A sample of 10 mg was placed in a crucible, and was measured at a Pekin Elmer DSC 8500 differential scanning calorimeter. Under a nitrogen atmosphere, the temperature was increased from 0° C. to 180° C. at an increasing rate of 10° C./min and maintained for 1 min, and decreased to 10° C. at a rate of 10° C./min and maintained for 3 min. After that, the temperature was increased to 180° C. at the increasing rate of 10° C./min, and scanning data during the second temperature increasing was recorded.

(11) A density of the polymer was tested by using GB/T1033-1986 and GB/T6343-2009 respectively. When the testing was performed by using GB/T1033-1986, the test object was randomly selected from the copolymerization product. In the case that the testing was performed by using GB/T6343-2009, the test object was randomly selected from the spherical and/or spherical-like polymers when the copolymer contains spherical and/or spherical-like polymers, and the test object was randomly selected from the copolymerization product when the copolymer did not contain spherical and/or spherical-like polymers.

(12) A particle size of the spherical and/or spherical-like polymers was tested by using ASTM D1921.

(13) Structures of complex h and complex g are shown in Formula h and Formula g.

(14) ##STR00007##

Example 1

(15) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 15 mmol (2.5 mL) of 2-methyl-2-hydroxyl-7-octene, 15 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 2

(16) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, and 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 3 (Comparison)

(17) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 60° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 4

(18) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), 0.25 mL of diethylzinc (1 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 5

(19) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), 0.5 mL of diethylzinc (1 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 6 (Comparison)

(20) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 80° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 7

(21) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 50 mmol (8.5 mL) of 2-methyl-2-hydroxyl-7-octene, 50 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 8

(22) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 100 mmol (17.0 mL) of 2-methyl-2-hydroxyl-7-octene, 100 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 9

(23) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 10

(24) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.5 mg) of complex b1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 11

(25) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.5 mg) of complex b1, 50 mmol (8.5 mL) of 2-methyl-2-hydroxyl-7-octene, 50 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 12

(26) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.5 mg) of complex b1, 30 mmol (4.5 mL) of 4-methyl-1-heptylen-4-ol, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 13

(27) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.4 mg) of complex c1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 14

(28) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution) were added; and 2.5 mL of toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1 mmol/L toluene solution) was added, making Ni/B=1. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 15

(29) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, and 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution) were added; and 3 mL of AlEt.sub.2C.sub.1 (2 mmol/L hexane solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Example 16

(30) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 5.0 μmol (3.2 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Comparative Example 1

(31) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Comparative Example 2

(32) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex h, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Comparative Example 3

(33) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex h, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 60° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Comparative Example 4

(34) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (2.7 mg) of complex g, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Comparative Example 5

(35) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of toluene was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (5.1 mL) of 2-methyl-2-hydroxyl-7-octene, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

Comparative Example 6

(36) An 1 L stainless steel polymerization kettle equipped with a mechanical stirrer was continuously dried for 6 hours at 130° C., evacuated to vacuum while hot, and replaced with N.sub.2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex al, 30 mmol (6.0 mL) of 10-hendecen-1-ol, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of MAO (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 20° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 5% by volume hydrochloric acid was used for neutralization so as to obtain the polymer. Polymerization activity and performance parameters of the polymer are shown in Table 1.

(37) TABLE-US-00001 TABLE 1 Whether there are Average particle size of Polymerization spherical and/or the spherical and/or Activity Mw Alcohol Melting spherical-like spherical-like Serial 10.sup.6 g/mol (ten Content Point polymers in the Density.sup.a Density.sup.b polymers Number Complex Ni/h thousand) PDI (mol %) (° C.) copolymer (g .Math. cm.sup.−3) (g .Math. cm.sup.−3) (mm) Example 1 a1 15.4 35.8 2.17 0.48 123.6 Yes 0.924 0.503 3.4 Example 2 a1 20.4 46.7 2.19 0.93 122.3 Yes 0.923 0.502 3.0 Example 3 a1 16.4 16.1 1.98 0.96 50.2 No 0.882 0.872 — Example 4 a1 14.6 30.3 2.13 0.93 120.2 Yes 0.923 0.503 2.8 Example 5 a1 9.7 20.6 2.14 0.94 120.3 Yes 0.923 0.503 2.8 Example 6 a1 10.4 9.3 2.42 0.83 — No 0.867 0.877 — Example 7 a1 22.7 60.2 2.03 1.82 124.5 Yes 0.924 0.503 2.6 Example 8 a1 12.2 67.7 2.13 3.43 124.8 Yes 0.924 0.502 2.5 Example 9 a1 14.3 22.4 2.16 0.94 116.4 Yes 0.922 0.516 1.7 Example 10 b1 26.6 10.7 2.34 1.06 125.2 Yes 0.926 0.544 2.0 Example 11 b1 27.4 13.3. 2.12 2.21 126.7 Yes 0.926 0.544 1.8 Example 12 b1 17.9 7.2 2.27 0.85 123.4 Yes 0.925 0.541 1.3 Example 13 c1 20.3 46.3 2.04 0.91 122.2 Yes 0.923 0.502 3.1 Example 14 a1 19.8 41.7 2.32 0.94 120.8 Yes 0.923 0.503 2.4 Example 15 a1 8.6 20.2 3.27 0.72 122.1 Yes 0.923 — 1.7 Example 16 a1 18.2 25.4 2.12 0.92 122.1 Yes 0.923 0.484 8.4 Comparative a1 11.7 28.4 2.25 — 121.4 No 0.920 0.916 — Example 1 Comparative h 4.6 42.2 3.48 0.32 117.3 No 0.916 0.908 — Example 2 Comparative h 1.6 13.3 3.14 0.22 44.7 No 0.869 0.844 — Example 3 Comparative g 0.4 3.6 3.37 0.20 106.2 No 0.914 0.901 — Example 4 Comparative a1 21.7 45.4 2.10 0.94 122.3 No 0.923 0.918 — Example 5 Comparative a1 22.6 48.7 2.11 0.98 122.0 No 0.923 0.914 — Example 6 Density.sup.a (g .Math. cm.sup.−3) is tested by using GB/T1033-1986. Density.sup.b (g .Math. cm.sup.−3) is tested by using GB/T6463-2009.

(38) It should be noted that the embodiments described above are only used to explain the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but it should be understood that words used herein are descriptive and explanatory words, not limiting words. Modifications can be made to the present invention within the scope of the claims of the present invention according to provisions, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein, but rather the present invention can be extended to all other methods and applications having the same function.