COPOLYMER OF OLEFIN AND UNSATURATED CARBOXYLIC ACID OR UNSATURATED CARBOXYLIC ACID DERIVATIVE

Abstract

A preparation method for a copolymer includes the step(s) of contacting an olefin and an unsaturated carboxylic acid shown in Formula II or a derivative of the unsaturated carboxylic acid shown in Formula II with a catalyst and optionally a chain transfer agent for reaction in the presence of an alkane solvent to obtain the copolymer. The copolymer is a spherical and/or spherical-like copolymer.

Claims

1. A preparation method for a copolymer, comprising: contacting an olefin and an unsaturated carboxylic acid shown in Formula II or a derivative of the unsaturated carboxylic acid shown in Formula II with a catalyst and optionally a chain transfer agent for reaction in the presence of an alkane solvent to obtain the copolymer, ##STR00008## ##STR00009## wherein in Formula II, each of L1, L2, and L3 is independently selected from the group consisting of H and C.sub.1-C.sub.30 alkyl, and L4 is a C.sub.1-C.sub.30 alkylene having a side group selected from the group consisting of C.sub.6-C.sub.20 aryl, C.sub.1-C.sub.20 alkyl, and C.sub.1-C.sub.20 alkoxy, and wherein the catalyst comprises a main catalyst and a co-catalyst, and the main catalyst is selected from at least one metal complex shown in Formula III: ##STR00010## wherein in Formula III, R.sub.9 and R.sub.10 are identical to or different from each other, and each are independently selected from substituted or unsubstituted hydrocarbyl; R.sub.2 and R.sub.3 are identical to or different from each other, each are independently selected from the group consisting of H, halogen, and substituted or unsubstituted hydrocarbyl, and R.sub.2 and R.sub.3 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 alkyl; and n is an integer that meets an M valence state.

2. The preparation method according to claim 1, wherein the main catalyst is a metal complex of Formula IV: ##STR00011## wherein in Formula IV, R.sub.9, R.sub.10, M, X, and n have the same definitions as those in Formula III; and R.sub.5-R.sub.8 are identical to or different from each other, each independently selected from the group consisting of H, halogen, and substituted or unsubstituted C.sub.1-C.sub.20 hydrocarbyl, and R.sub.5-R.sub.8 optionally form a ring with each other.

3. The preparation method according to claim 1, wherein in Formula IV, R.sub.9 and R.sub.10 each are independently selected from the group consisting of substituted or unsubstituted C.sub.6-C.sub.30 aryl or substituted and unsubstituted C.sub.7-C.sub.30 aralkyl; and R.sub.5-R.sub.8 are identical to or different from each other, each independently selected from the group consisting of H and C.sub.1-C.sub.20 hydrocarbyl, and R.sub.5-R.sub.8 optionally form a ring with each other.

4. The preparation method according to claim 1, wherein the main catalyst is selected from at least one metal complex shown in Formula V: ##STR00012## wherein in Formula V, R.sup.1-R.sup.10 are identical to or different from each other, and each are independently selected from the group consisting of hydrogen, 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 form a ring, R.sup.4-R.sup.6, R.sup.7, and R.sup.8 optionally form a ring; and M, X and n have the same definitions as those in Formula III and Formula IV.

5. The preparation method according to claim 4, wherein in Formula V, 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 are independently selected from the group consisting of H and C.sub.1-C.sub.3 alkyl.

6. The preparation method according to claim 1, wherein the M is nickel.

7. The preparation method according to claim 1, 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 the organic boron compound is selected from the group consisting of aryl boron and borate.

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

9. The preparation method according to claim 1, wherein the chain transfer agent is one or more selected from the group consisting of aluminum alkyl, magnesium alkyl, and zinc alkyl, and a molar ratio of the chain transfer agent and M in the main catalyst is (0.1-2000):1.

10. The preparation method according to claim 1, wherein a molar ratio of the unsaturated carboxylic acid shown in Formula II or the unsaturated carboxylic acid derivative shown in Formula II is 0.01-6000 mmol/L.

11. The preparation method according to claim 1, wherein the reaction is carried out at a reaction temperature in a range from −50° C. to 50° C. and a reaction time of 10-200 min.

12. The preparation method according to claim 1, wherein the copolymer is in the form of a spherical and/or spherical-like particles, at least part of the spherical and/or spherical-like particles of copolymer have a cavity therein, preferably, wherein a volume of the cavity in the number of the spherical and/or spherical-like particles of copolymer having a cavity therein is 5-99% of a volume of the spherical and/or spherical-like particles of copolymer.

13. The preparation method according to claim 12, wherein the spherical and/or spherical-like particles of copolymer has a density of is 0.3000-0.8500 g/cm.sup.3, measured according to GB/T6343-2009.

14. The preparation method according to claim 12, wherein an average particle size of the spherical and/or spherical-like particles of copolymer is 0.1-50.0 mm.

15. The preparation method according to claim 12, wherein, in the copolymer, a content of the structural unit of Formula I or the structural unit of the derivative of Formula I is 0.2-15.0 mol %.

16. The preparation method according to claim 1, wherein the copolymer a number-average molecular weight of 5000-200000.

17. The preparation method according to claim 12, 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 halogen-substituted C.sub.1-C.sub.10 alkyl, L4 is a C.sub.1-C.sub.10 alkylene having a side group that is one or more selected from the group consisting of C.sub.6-C.sub.10 aryl and C.sub.1-C.sub.10 alkyl.

18. The preparation method according to claim 12, wherein the copolymer comprises a structural unit derived from olefin and a structural unit of Formula I or a structural unit of a derivative of Formula I, ##STR00013## wherein, in Formula I, each of L1, L2, and L3 is independently selected from the group consisting of H and C.sub.1-C.sub.30 alkyl, and L4 is a C.sub.1-C.sub.30 alkylene having a side group selected from the group consisting of C.sub.6-C.sub.20 aryl, C.sub.1-C.sub.20 alkyl, and C.sub.1-C.sub.20 alkoxy, and the derivative of Formula I is a IIA, IIIA or IIB Group metal salt of Formula I.

19. The preparation method according to claim 18, wherein, in Formula I, the C.sub.1-C.sub.30 alkyl has one or more substituents 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 group, and carboxyl.

20. A foaming material comprising a copolymer prepared according to the preparation method of claim 12.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0076] The accompanying drawings are provided for further understanding to the present disclosure, constitute one part of the description, are used for explaining the present disclosure together with embodiments of the present disclosure, and do not constitute limitation to the present disclosure. In the drawings:

[0077] FIG. 1 is an electron micrograph of a spherical and/or spherical-like polymer obtained in Example 2 of the present invention.

[0078] 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.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0079] The present disclosure is described in detail in conjunction with examples below, but the present disclosure is not limited by the following examples.

[0080] The results of the present invention were characterized by the following manners.

[0081] Before the measurement, the polymer was subject to a washing treatment with an acid solution, a content of metal in the polymer≤50 ppm.

[0082] A content of comonomers in the copolymer (the structural unit of the unsaturated carboxylic acid shown in Formula I or the structural unit of the derivative of the unsaturated carboxylic acid shown in Formula I) was measured by using .sup.13C NMR spectrum, 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 deuterated tetrachloroethane at 130° C. and analysis and testing.

[0083] A molecular weight 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).

[0084] 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 is 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.

[0085] A density of the polymer was tested by using GB/T1033-1986 and GB/T6463-2009 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/T6463-2009, 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.

[0086] A particle size of the spherical and/or spherical-like polymers was tested by using ASTM D1921.

Example 1

[0087] 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 N2 gas for 3 times. 500 mL of hexane was injected into the polymerization system, and meanwhile 2.5 μmol (1.6 mg) of complex a1, 15 mmol (2.55 g) of 2,2-dimethyl-7-octenoic acid, 15 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0088] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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)

[0089] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (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 20% 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

[0090] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), 0.25 mL diethylzinc (1 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0091] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), 0.5 mL diethylzinc (1 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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)

[0092] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (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 20% 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

[0093] 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 a1, 50 mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0094] 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 a1, 100 mmol (17.02 g) of 2,2-dimethyl-7-octenoic acid, 100 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0095] 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 a1, 30 mmol (4.69 g) of 2,2-dimethyl-7-heptenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0096] 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 a1, 30 mmol (4.26 g) of 2-isopropyl-4-pentenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0097] 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 (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 60 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0098] 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 (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 60 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0099] 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 (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0100] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution) were added; and 2.5 mL of toluene solution containing 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 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0101] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of AlEt.sub.2Cl (2 mmol/L hexane solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0102] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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

[0103] 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 a1, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 1% 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

[0104] 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 a1, 30 mmol (5.53 g) of 10-undecylenic acid, 30 mL of AlEt.sub.3 (1.0 mol/L of hexane solution), and 3 mL of methylaluminoxane (MAO) (1.53 mol/L toluene solution) were added. The reaction was performed for 30 min by stirring at 30° C. and at an ethylene pressure of 10 atm. Finally, an ethanol solution acidified with 20% 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.

TABLE-US-00001 TABLE 1 Whether Average there are particle spherical size of the and/or spherical spherical- and/or Polymerization like spherical- Activity Mn Comonomer Melting polymers Density.sup.a Density.sup.b like Serial 10.sup.6 g/mol (ten Content Point in the (g .Math. (g .Math. polymers Number Complex Ni/h thousand) (mol %) (° C.) copolymer cm.sup.−3) cm.sup.−3) (mm) Example 1 a1 11.2 10.4 0.52 117.3 Yes 0.965 0.672 1.4 Example 2 a1 15.8 11.7 0.94 119.8 Yes 0.975 0.675 1.2 Example 3 a1 14.7 7.1 0.91  60.2 No 0.952 0.940 — Example 4 a1 9.4 8.0 0.93 118.0 Yes 0.975 0.672 1.1 Example 5 a1 7.6 6.1 0.94 118.4 Yes 0.975 0.672 1.0 Example 6 a1 8.8 2.8 0.72 — No 0.924 0.912 — Example 7 a1 18.6 12.8 1.73 120.1 Yes 0.980 0.677 1.2 Example 8 a1 12.4 11.2 3.33 119.8 Yes 0.984 0.678 1.0 Example 9 a1 14.5 12.0 0.94 120.2 Yes 0.976 0.726 0.7 Example 10 a1 11.7 8.3 0.92 118.9 Yes 0.974 0.768 1.1 Example 11 b1 18.6 5.9 1.02 122.3 Yes 0.980 0.705 0.8 Example 12 b1 21.6 6.8 2.07 123.4 Yes 0.986 0.710 0.7 Example 13 c1 14.4 11.8 0.92 119.1 Yes 0.975 0.674 1.3 Example 14 a1 13.1 10.7 1.04 119.2 Yes 0.975 0.675 1.1 Example 15 a1 8.4 6.7 0.73 119.0 Yes 0.975 Nd 0.8 Example 16 a1 14.2 6.3 0.92 119.7 Yes 0.975 0.650 2.5 Comparative a1 16.7 11.8 0.96 119.8 No 0.975 0.958 — Example 1 Comparative a1 15.7 10.7 0.83 119.4 No 0.975 0.964 — Example 2 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.

[0105] It should be noted that the embodiments described above are only used to explain the present disclosure, and do not constitute any limitation to the present disclosure. The present disclosure 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 disclosure within the scope of the claims of the present disclosure according to provisions, and revisions can be made to the present disclosure without departing from the scope and spirit of the present disclosure. Although the present disclosure described relates to specific methods, materials, and embodiments, it does not mean that the present disclosure is limited to the specific examples disclosed herein, but rather the present disclosure can be extended to all other methods and applications having the same function.