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

Abstract

The present invention provides a copolymer of an olefin and an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative, said copolymer being 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. A copolymer of olefin and unsaturated carboxylic acid or unsaturated carboxylic acid derivative, comprising a spherical and/or spherical-like polymer, at least part of the spherical and/or spherical-like polymer having a cavity therein.

2. The copolymer according to claim 1, 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, ##STR00008## wherein in Formula I, L1-L3 each are 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 derivative of Formula I being a IIA, IIIA or IIB Group metal salt of Formula I, the C.sub.1-C.sub.30 alkyl 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, cyano group and carboxyl; and preferably, the side group in L4 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.

3. The copolymer according to claim 1, wherein a density of the spherical and/or spherical-like polymer is 0.3000-0.8500 g/cm.sup.3, preferably 0.4000-0.7500 g/cm.sup.3, and the density is measured by using GB/T6463-2009.

4. The copolymer according to claim 1, wherein an average particle size of the spherical and/or spherical-like polymer is 0.1-50.0 mm, preferably 0.5-20.0 mm.

5. The copolymer according to claim 1, wherein a volume of the cavity in the spherical and/or spherical-like polymer having a cavity therein is 5-99%, preferably 30-95%, more preferably 50-90%, of a volume of the spherical and/or spherical-like polymer.

6. The copolymer according to claim 1, 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 %, preferably 0.4-10.0 mol % .

7. The copolymer according to claim 1, wherein a number-average molecular weight of the copolymer is 5000-200000, preferably 15000-150000.

8. 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 or halogen-substituted C.sub.1-C.sub.10 alkyl, L4 is C.sub.1-C.sub.10 alkylene having a side group which is preferably 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.

9. A preparation method for the copolymer according to claim 1, 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; ##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 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.

10. The preparation method according to claim 9, wherein the main catalyst is selected from at least one metal complex shown in 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.

11. The preparation method according to claim 9, 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.

12. The preparation method according to claim 9, 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 or C.sub.1-C.sub.24 hydrocarbyloxy, R.sup.1-R.sup.3, R.sup.9, and R.sup.10 optionally forming a ring to each other, R.sup.4-R.sup.6, R.sup.7, and R.sup.8 optionally forming a ring to each other; and M, X and n have the same definitions as those in Formula III and Formula IV.

13. The preparation method according to claim 12, 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.

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

15. 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 the organic boron compound is selected from the group consisting of aryl boron and borate.

16. The preparation method according to claim 9, wherein a concentration of the main catalyst in a 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 main catalyst is (10-10000000):1; and when the co-catalyst is the organic boron compound, a molar ratio of boron in the co-catalyst and M in the main catalyst is (0.1-1000):1.

17. 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, and a molar ratio of the chain transfer agent and M in the main catalyst is (0.1-2000):1

18. The preparation method according to claim 9, wherein a molar ratio of the unsaturated carboxylic acid shown in Formula II or the unsaturated carboxylic acid derivative shown in 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 in a range from 50 C. to 50 C. and a reaction time of 10-200 min.

20. A foaming material comprising a copolymer according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0077] 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:

[0078] FIG. 1 is an electron micrograph of a spherical and/or spherical-like polymer obtained in Example 2 of the present invention.

[0079] 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

[0080] The present disclosure is described in detail in conjunction with examples below, but the present disclosure is not limited by the following examples.

[0081] The results of the present invention were characterized by the following manners.

[0082] Before the measurement, the polymer was subject to a washing treatment with an acid solution, a content of metal in the polymer50 ppm.

[0083] 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.

[0084] 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: 3Plgel 10 m M1ED-B 3007.5 nm).

[0085] 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.

[0086] 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.

[0087] A particle size of the spherical and/or spherical-like polymers was tested by using ASTM D1921.

EXAMPLE 1

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.6 mg) of complex al, 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)

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.6 mg) of complex al, 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)

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.6 mg) of complex al, 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

[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 mol (1.5 mg) of complex bl, 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

[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 mol (1.5 mg) of complex bl, 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

[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 mol (1.4 mg) of complex cl, 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

[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 mol (1.6 mg) of complex al, 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

[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 2.5 mol (1.6 mg) of complex al, 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

[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 hexane was injected into the polymerization system, and meanwhile 5.0 mol (3.2 mg) of complex al, 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

[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 toluene was injected into the polymerization system, and meanwhile 2.5 mol (1.6 mg) of complex al, 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

[0105] 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 mol (1.6 mg) of complex al, 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 there are Polymerization spherical and/or Average particle size Activity Mn Comonomer Melting spherical-like of the spherical and/or Serial 10.sup.6g/mol (ten Content Point polymers in the Density.sup.a Density.sup.b spherical-like polymers Number Complex Ni/h thousand) (mol %) ( C.) copolymer (g .Math. cm.sup.3) (g .Math. 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.

[0106] 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.