Coordination precipitation polymerization method for olefin polymerization and polyolefin

Abstract

The present invention relates to the technical field of polyolefin, and discloses a coordination precipitation polymerization method for olefin polymerization and polyolefin, the method comprises: mixing an olefin monomer, a catalyst and an auxiliary agent, and carrying out a polymerization reaction, the olefin monomer contains a non-polar monomer and a polar monomer; the non-polar monomer is selected from one or more than two of ethylene, alpha-olefin and internal olefin; the polar monomer is selected from one or more than two of enol, unsaturated carboxylic acid and unsaturated carboxylic ester; the catalyst is selected from a mono-metallocene front transition metal complex shown in the formula (I), the loading technological process of the catalyst can be omitted, polymerization and self-forming of the olefin homogeneous catalyst are achieved, and polyolefin with good particle morphology is prepared. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the technical field of polyolefins, and in particular to a coordination precipitation polymerization method for olefin polymerization and polyolefins. Background Art

[0002] Polyolefin products are inexpensive, have excellent performance and a wide range of applications. Olefin polymerization catalysts and polymerization processes are the core of polyolefin technology. From the perspective of the development of olefin polymerization catalysts, there are two main aspects: (1) Developing catalysts that can prepare polyolefin resins with special properties or better performance, such as metallocene catalysts and non-metallocene late transition metal catalysts; (2) On the basis of further improving catalyst performance, simplifying catalyst preparation processes, reducing catalyst costs, and developing environmentally friendly technologies to improve efficiency and enhance competitiveness. Before the 1980s, the focus of polyethylene catalyst research was on pursuing catalyst efficiency. After nearly 30 years of efforts, the catalytic efficiency of polyethylene catalysts has increased by orders of magnitude, thereby simplifying the production process of polyolefins and reducing energy and material consumption. Ziegler-Natta catalysts have been around for nearly 60 years. Although polyolefin catalysts such as metallocenes and non-metallocenes have emerged during this period, there are many problems in their industrialization, such as expensive co-catalysts and difficulties in loading the main catalyst. In recent years, olefin polymerization catalyst products have emerged in an endless stream at home and abroad, and catalyst stability and polymerization catalytic activity have also been continuously improved. However, there are still deficiencies in hydrogen sensitivity, control of catalyst particle regularity and particle size distribution. Current research is still focused on developing spherical or quasi-spherical supported catalysts with simple process, good hydrogen sensitivity and uniform particle size distribution.

[0003] Common polymerization processes in the polyolefin industry include slurry, gas phase, and bulk polymerization, and the catalysts used are mostly supported catalysts. The polymerized monomers are inserted and complex-grown on the supported catalyst to prepare granular polymer particles. The stability of the catalyst in the device and the morphology of the polymer depend to a large extent on the particle morphology, particle strength, and particle size distribution of the catalyst. Therefore, the catalyst loading technology plays a vital role in the olefin polymerization effect.

[0004] In his book Principles of Polymerization, Odian pointed out that precipitation polymerization is a polymerization process in which the polymerization reaction starts from a homogeneous system but can be quickly converted into a heterogeneous system. Usually, precipitation polymerization occurs in a solution of monomers or monomers and solvents, and the formed polymer precipitates out because it is insoluble in the reaction medium. In recent years, precipitation polymerization has aroused widespread research interest because it can obtain polymer microsphere particles with pure surfaces. However, precipitation polymerization is mostly used in free radical polymerization reactions. If precipitation polymerization can be combined with co-coordination polymerization, in a commonly used solvent for coordination polymerization, by controlling the polymerization reaction process, it is possible to directly prepare polymer particles with good particle morphology from non-loaded transition metal complexes through precipitation polymerization, which has good application prospects. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems of complicated catalyst loading process and polymer deashing and granulation post-treatment procedures in the prior art, and to provide a coordination precipitation polymerization method and polyolefin for olefin polymerization. The method controls the polymerization reaction process to realize direct preparation of polyolefin with good particle morphology by precipitation polymerization of olefin monomers under the action of monocyclopentadienyl pre-transition metal complexes, thereby eliminating the complicated catalyst loading process, greatly simplifying the preparation process of the main catalyst, having low equipment requirements, low energy consumption and low environmental pollution.

[0006] In order to achieve the above object, the present invention provides a coordination precipitation polymerization method for olefin polymerization, which comprises mixing olefin monomers, catalysts and additives to carry out polymerization reaction; the olefin monomers contain non-polar monomers and polar monomers; the non-polar monomers are selected from one or more of ethylene, α-olefins and internal olefins; the polar monomers are selected from one or more of ene alcohols, unsaturated carboxylic acids and unsaturated carboxylic acid esters; the catalyst is selected from a monocyclopentadienyl transition metal complex represented by formula (I),

[0007]

[0008] Wherein, M is selected from Group IVB metals; R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon group; X is selected from halogen, C1-C10 hydrocarbon group, n is 1 or 2; L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, substituted or unsubstituted fluorenyl; R1 is OR 21 R 22 , where R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 , R22 They are connected with O to form a ring or ring system, and m is 0 or 1.

[0009] Preferably, the monocyclopentadienyl early transition metal complex is selected from the following complexes,

[0010] Complex 1: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0011] Complex 2: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0012] Complex 3: A complex represented by formula (I), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0013] Complex 4: A complex represented by formula (I), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0014] Complex 5: A complex represented by formula (I), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0015] Complex 6: A complex represented by formula (I), wherein M is Ti, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0016] Complex 7: A complex represented by formula (I), wherein M is Ti, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0017] Complex 8: A complex represented by formula (I), wherein M is Ti, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0018] Complex 9: A complex represented by formula (I), wherein M is Ti, L1 is phenyl-indenyl, and R 11 -R15 is H, X is Cl, n=2, m=0;

[0019] Complex 10: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0020] Complex 11: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0021] Complex 12: A complex represented by formula (I), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0022] Complex 13: A complex represented by formula (I), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0023] Complex 14: A complex represented by formula (I), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0024] Complex 15: A complex represented by formula (I), wherein M is Ti, L1 is indenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0025] Complex 16: A complex represented by formula (I), wherein M is Ti, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0026] Complex 17: A complex represented by formula (I), wherein M is Ti, L1 is fluorenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0027] Complex 18: A complex represented by formula (I), wherein M is Ti, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0028] Complex 19: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0029] Complex 20: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0030] Complex 21: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0031] Complex 22: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0032] Complex 23: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0033] Complex 24: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0034] Complex 25: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0035] Complex 26: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0036] Complex 27: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0037] Complex 28: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0038] Complex 29: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0039] Complex 30: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0040] Complex 31: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0041] Complex 32: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0042] Complex 33: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0043] Complex 34: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0044] Complex 35: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0045] Complex 36: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0046] Complex 37: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0047] Complex 38: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0048] Complex 39: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0049] Complex 40: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0050] Complex 41: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0051] Complex 42: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0052] Complex 43: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0053] Complex 44: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0054] Complex 45: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0055] Complex 46: A complex represented by formula (I), wherein M is Hf, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0056] Complex 47: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0057] Complex 48: A complex represented by formula (I), wherein M is Hf, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0058] Complex 49: A complex represented by formula (I), wherein M is Hf, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0059] Complex 50: A complex represented by formula (I), wherein M is Hf, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0060] Complex 51: A complex represented by formula (I), wherein M is Hf, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0061] Complex 52: A complex represented by formula (I), wherein M is Hf, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0062] Complex 53: A complex represented by formula (I), wherein M is Hf, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0063] Complex 54: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0064] Complex 55: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0065] Complex 56: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0066] Complex 57: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0067] Complex 58: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0068] Complex 59: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0069] Complex 60: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, m=0;

[0070] Complex 61: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is CH2C6H5, n=2, m=0;

[0071] Complex 62: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0072] Complex 63: A complex represented by formula (I), wherein M is Hf, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0073] Complex 64: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, m=0;

[0074] Complex 65: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is CH2C6H5, n=2, m=0.

[0075] Preferably, the enol is selected from the monomers represented by formula (G1),

[0076]

[0077] Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, and L4 is selected from a C1-C30 alkylene group having a side group.

[0078] Preferably, the coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2 is characterized in that the unsaturated carboxylic acid is selected from the monomer represented by formula (G2),

[0079]

[0080] Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, and L4 is selected from a C1-C30 alkylene group having a side group.

[0081] Preferably, the unsaturated carboxylic acid ester is selected from the monomers represented by formula (G3),

[0082]

[0083] Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, L4 is selected from a C1-C30 alkylene group having a side group, and L6 is selected from a C1-C30 alkyl group.

[0084] Preferably, the auxiliary agent is selected from one or more of an organoaluminum compound, an organoboron compound and an organosilicon compound.

[0085] Preferably, the organoaluminum compound is AlR n X 1 3-n ; wherein R is selected from H, C1-C20 saturated or unsaturated hydrocarbon group and C1-C20 saturated or unsaturated hydrocarbonoxy group, preferably C1-C20 alkyl group, C1-C20 alkoxy group, C7-C20 aralkyl group or C6-C20 aryl group; X 1 is selected from halogen, preferably chlorine or bromine; <n≤3。

[0086] Preferably, the organic boron compound is an aromatic boron and / or a borate.

[0087] Preferably, the aromatic hydrocarbon boron is selected from substituted or unsubstituted phenyl boron, preferably tris(pentafluorophenyl)boron.

[0088] Preferably, the borate is selected from N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl tetrakis(pentafluorophenyl)borate.

[0089] Preferably, the organosilicon compound is an alkyl silicon compound.

[0090] Preferably, the general formula of the alkyl silicon compound is SiH1H2H3H4, wherein H1 is selected from C1-C10 alkyl, and H2, H3 and H4 are each independently selected from C1-C10 alkyl or halogen.

[0091] Preferably, when the auxiliary agent contains an organic aluminum compound, the molar ratio of the amount of aluminum element in the organic aluminum compound to the amount of M element in the catalyst is (10-10000000):1.

[0092] Preferably, when the auxiliary agent contains an organic boron compound, the molar ratio of the amount of the boron element in the organic boron compound to the amount of the M element in the catalyst is (0.1-1000):1.

[0093] Preferably, when the auxiliary agent contains an organosilicon compound, the molar ratio of the amount of silicon element in the organosilicon compound to the amount of M element in the catalyst is (10-10000000):1.

[0094] Preferably, when the auxiliary agent is a combination of an organic aluminum compound, an organic boron compound and an organic silicon compound, the molar ratio of the total amount of aluminum, boron and silicon in the auxiliary agent to the amount of M element in the catalyst is (10-11000000):1.

[0095] Preferably, the polymerization reaction is carried out in the presence of a solvent.

[0096] Preferably, the solvent is selected from one or more of alkanes, halogenated alkanes and aromatic hydrocarbons.

[0097] Preferably, the alkane is selected from one or more of C3-C20 alkanes.

[0098] Preferably, the general formula of the halogenated alkane is R 1 X 2 n2 R 2 X 3 m2 , where X 2 and X 3 Each is independently selected from halogen, m2+n2≥1, R 1 is selected from C1-C10 alkyl or alkenyl, R 2 Selected from C1-C10 alkylene or alkenylene.

[0099] Preferably, the general formula of the aromatic hydrocarbon is R 4 -Ph-R 3 , where R 3 and R 4 Each is independently selected from hydrogen, phenyl and C1-C10 alkane.

[0100] Preferably, the polymerization reaction conditions include: temperature of -50 to 180° C. and time of 10 to 200 min.

[0101] The second aspect of the present invention provides a polyolefin prepared by the above-mentioned coordination precipitation polymerization method for olefin polymerization, wherein the shape of the polyolefin is spherical or quasi-spherical.

[0102] Preferably, the average particle size of the polyolefin is 0.02-50 mm.

[0103] Preferably, the weight average molecular weight of the polyolefin is 10,000-800,000.

[0104] Preferably, the molecular weight distribution index of the polyolefin is ≤10.

[0105] Preferably, the melting point of the polyolefin is 90-140°C.

[0106] Compared with the prior art, the present invention has the following beneficial effects:

[0107] (1) In the coordination precipitation polymerization method for olefin polymerization described in the present invention, before the olefin monomer is polymerized, the system is a uniform reaction solution, and the monoclinic pre-transition metal complex does not need to be loaded on an inorganic or organic carrier. By controlling the polymerization process, the polyolefin is precipitated from the system, and the polyolefin is self-formed to prepare spherical or quasi-spherical polyolefins. Therefore, the present invention can avoid the catalyst loading process flow, realize the self-formation of olefin homogeneous catalyst polymerization, and prepare olefin polymers with good particle morphology;

[0108] (2) The coordination precipitation polymerization method for olefin polymerization described in the present invention can prepare spherical or quasi-spherical polar polyolefins with polar groups and a relatively high melting point, that is, polar groups can be introduced into the polyolefin chain, thereby improving the interfacial compatibility of the polyolefin while retaining its crystallization properties;

[0109] (3) The coordination precipitation polymerization method for olefin polymerization described in the present invention does not require subsequent processing such as granulation, and can directly obtain spherical or quasi-spherical polyolefins, which greatly simplifies the preparation process of the main catalyst, has low equipment requirements, low energy consumption, and low environmental pollution. Therefore, the present invention has good industrial application prospects;

[0110] (4) The coordination precipitation polymerization method for olefin polymerization of the present invention directly prepares spherical or quasi-spherical polyolefins with good morphology by selecting the monocyclopentadienyl transition metal complex, olefin monomer and appropriate reaction conditions. The obtained polyolefin is not easy to scale in the reactor and is convenient for transportation.

[0111] (5) The coordination precipitation polymerization method for olefin polymerization described in the present invention can catalyze the polymerization reaction of olefin monomers with high activity, greatly simplify the process flow, and reduce production costs. DETAILED DESCRIPTION

[0112] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0113] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0114] The present invention provides a coordination precipitation polymerization method for olefin polymerization, which comprises mixing olefin monomers, a catalyst and an auxiliary agent to carry out a polymerization reaction; the olefin monomers contain non-polar monomers and polar monomers; the non-polar monomers are selected from one or more of ethylene, α-olefins and internal olefins; the polar monomers are selected from one or more of ene alcohols, unsaturated carboxylic acids and unsaturated carboxylic acid esters; the catalyst is selected from a monocyclopentadienyl transition metal complex represented by formula (I),

[0115]

[0116] Wherein, M is selected from Group IVB metals; R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon group; X is selected from halogen, C1-C10 hydrocarbon group, n is 1 or 2; L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, substituted or unsubstituted fluorenyl; R1 is OR 21 R 22 , where R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 , R 22 They are connected with O to form a ring or ring system, and m is 0 or 1.

[0117] In a preferred aspect of the present invention, in formula (I), M is selected from titanium, zirconium and hafnium.

[0118] In the preferred embodiment of the present invention, in formula (I), R 11 -R 15Each is independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C6-C15 aryl.

[0119] In a preferred embodiment of the present invention, in formula (I), X is selected from halogen, C1-C8 hydrocarbon group (such as C1-C6 alkyl group).

[0120] In the present invention, in formula (I), n is 1 or 2, indicating that the number of X groups connected to the metal M is n. In a preferred embodiment, n is 1.

[0121] In the present invention, in formula (I), L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, substituted or unsubstituted fluorenyl. In a preferred case, L1 group is selected from cyclopentadienyl, methyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,2,4-trimethyl-cyclopentadienyl, 1,2,3,4-tetramethyl-cyclopentadienyl, pentamethylcyclopentadienyl, n-butyl-cyclopentadienyl, tert-butyl-cyclopentadienyl, isobutyl-cyclopentadienyl, indenyl, butyl-indenyl, 1-methyl-indenyl, 2-methyl-indenyl, 1-phenyl-indenyl, trihydro-indenyl and fluorenyl.

[0122] In the present invention, in formula (I), R1 is OR 21 R 22 , where R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 , R 22 In a preferred embodiment, R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C6 hydrocarbon groups, and R 21 , R 22 They are connected to each other with O to form a five-membered ring or a six-membered ring. In a further preferred case, R1 is tetrahydrofuran (C4H8O), 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, 2,2-dimethyltetrahydrofuran, and the like.

[0123] In the present invention, in formula (I), m may be 0 or 1. When m is 0, it means that the R1 group does not exist.

[0124] In the present invention, the "substituted" in "substituted or unsubstituted" refers to containing substituents, and the substituents here can be selected from halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.

[0125] In the present invention, the alkyl group (such as C1-C6 alkyl group or C1-C10 alkyl group) can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl and 3,3-dimethylbutyl.

[0126] In the present invention, the alkoxy group (such as C1-C6 alkoxy group) can be selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3,3-dimethylbutoxy.

[0127] In the present invention, the aryl group (such as a C6-C8 aryl group, a C6-C15 aryl group or a C6-C20 aryl group) may be selected from a phenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a dimethylphenyl group and a vinylphenyl group.

[0128] In the present invention, the halogen is selected from fluorine, chlorine, bromine and iodine.

[0129] In a more preferred embodiment, the monocyclopentadienyl transition metal complex is selected from the following complexes:

[0130] Complex 1: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0131] Complex 2: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0132] Complex 3: A complex represented by formula (I), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0133] Complex 4: A complex represented by formula (I), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0134] Complex 5: A complex represented by formula (I), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0135] Complex 6: A complex represented by formula (I), wherein M is Ti, L1 is indenyl, and R 11 -R15 is H, X is Cl, n=2, m=0;

[0136] Complex 7: A complex represented by formula (I), wherein M is Ti, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0137] Complex 8: A complex represented by formula (I), wherein M is Ti, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0138] Complex 9: A complex represented by formula (I), wherein M is Ti, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0139] Complex 10: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0140] Complex 11: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0141] Complex 12: A complex represented by formula (I), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0142] Complex 13: A complex represented by formula (I), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0143] Complex 14: A complex represented by formula (I), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0144] Complex 15: A complex represented by formula (I), wherein M is Ti, L1 is indenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0145] Complex 16: A complex represented by formula (I), wherein M is Ti, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0146] Complex 17: A complex represented by formula (I), wherein M is Ti, L1 is fluorenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0147] Complex 18: A complex represented by formula (I), wherein M is Ti, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0;

[0148] Complex 19: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0149] Complex 20: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0150] Complex 21: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0151] Complex 22: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0152] Complex 23: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0153] Complex 24: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0154] Complex 25: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0155] Complex 26: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0156] Complex 27: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0157] Complex 28: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0158] Complex 29: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0159] Complex 30: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0160] Complex 31: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0161] Complex 32: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0162] Complex 33: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0163] Complex 34: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0164] Complex 35: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0165] Complex 36: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0166] Complex 37: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0167] Complex 38: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0168] Complex 39: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0169] Complex 40: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0170] Complex 41: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0171] Complex 42: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0172] Complex 43: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0173] Complex 44: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0174] Complex 45: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0175] Complex 46: A complex represented by formula (I), wherein M is Hf, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0176] Complex 47: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0177] Complex 48: A complex represented by formula (I), wherein M is Hf, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0178] Complex 49: A complex represented by formula (I), wherein M is Hf, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0179] Complex 50: A complex represented by formula (I), wherein M is Hf, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0180] Complex 51: A complex represented by formula (I), wherein M is Hf, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0181] Complex 52: A complex represented by formula (I), wherein M is Hf, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0182] Complex 53: A complex represented by formula (I), wherein M is Hf, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0183] Complex 54: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0184] Complex 55: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0185] Complex 56: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, R1 is tetrahydrofuran, m=1;

[0186] Complex 57: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1;

[0187] Complex 58: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0188] Complex 59: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0189] Complex 60: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, m=0;

[0190] Complex 61: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is CH2C6H5, n=2, m=0;

[0191] Complex 62: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0192] Complex 63: A complex represented by formula (I), wherein M is Hf, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0;

[0193] Complex 64: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, m=0;

[0194] Complex 65: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is CH2C6H5, n=2, m=0.

[0195] In the present invention, the method for preparing the above-mentioned monocyclopentadienyl transition metal complex comprises the following steps:

[0196] (1) reacting the compound represented by formula (II) with the compound represented by formula (III) to obtain a ligand represented by formula (IV);

[0197] (2) reacting the ligand with a hydrogen extraction agent, and then reacting with an M metal compound, wherein the metal M in the M metal compound is selected from Group IVB metals, and the M metal compound comprises at least one of a substituted or unsubstituted cyclopentadienyl, a substituted or unsubstituted indenyl, a tetrahydroindenyl, and a substituted or unsubstituted fluorenyl.

[0198]

[0199] Among them, R 11 -R 15 The definition of is the same as described above.

[0200] In the method described in the present invention, the compound represented by formula (II) may be in S form and / or R form.

[0201] In a preferred case, the transition metal M in the M metal compound is selected from titanium, zirconium and hafnium. Further preferably, the M metal compound is selected from cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, methyl-cyclopentadienyl titanium trichloride, n-butyl-cyclopentadienyl titanium trichloride, tert-butyl-cyclopentadienyl titanium trichloride, indenyl titanium trichloride, fluorenyl titanium trichloride, butyl-indenyl-titanium trichloride, 1-methyl-indenyl titanium trichloride, 2-methyl-indenyl titanium trichloride, 1-phenyl-indenyl-titanium trichloride, cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trichloride, methyl-cyclopentadienyl zirconium trichloride, 1,3-dimethyl-cyclopentadienyl-zirconium trichloride, 1,2,4-trimethyl-cyclopentadienyl-zirconium trichloride, n-butyl-cyclopentadienyl zirconium trichloride, tert-butyl-cyclopentadienyl trichloride. Zirconium chloride, indenyl zirconium trichloride, fluorenyl zirconium trichloride, butyl-indenyl-zirconium trichloride, 1-methyl-indenyl zirconium trichloride, 2-methyl-indenyl zirconium trichloride, 1-phenyl-indenyl-zirconium trichloride, cyclopentadienyl-1,2-dimethoxy-ethyl-zirconium trichloride, cyclopentadienyl hafnium trichloride, pentamethylcyclopentadienyl hafnium trichloride, methyl-cyclopentadienyl trichloride At least one of hafnium trichloride, 1,2,3,4-tetramethyl-cyclopentadienyl-hafnium trichloride, n-butyl-cyclopentadienyl hafnium trichloride, tert-butyl-cyclopentadienyl hafnium trichloride, isobutyl-cyclopentadienyl hafnium trichloride, indenyl hafnium trichloride, fluorenyl hafnium trichloride, trihydro-indenyl-hafnium trichloride and cyclopentadienyl-1,2-dimethoxy-ethyl-hafnium trichloride.

[0202] In a preferred embodiment, the hydrogen extraction agent is selected from at least one of NaH, KH, n-butyl lithium and methyl lithium.

[0203] In a specific embodiment, the preparation process of step (1) comprises: in a protective gas (such as nitrogen) atmosphere, dissolving the compound represented by formula (II) in anhydrous ether, adding a hydrogen extraction agent (such as n-butyl lithium) at room temperature, stirring at room temperature, adding tetrahydrofuran, and further stirring the obtained black solution containing the precipitate; then adding the compound represented by formula (III), stirring at room temperature, and adding NH4Cl aqueous solution to quench; then extracting the organic phase with ethyl acetate, drying the obtained organic phase with anhydrous sodium sulfate, and recrystallizing with dichloromethane / hexane to obtain a yellow crystalline compound; then adding methanol and concentrated hydrochloric acid, reflux reaction, removing the organic solvent after the reaction is completed, dissolving the product in ethyl acetate, adding NaHCO3 aqueous solution to neutralize, extracting the organic phase, and then drying, filtering, concentrating, and column chromatography in sequence to obtain the ligand represented by formula (IV).

[0204] In a specific embodiment, the preparation process of step (2) comprises: in a protective gas (such as nitrogen) atmosphere, dissolving the ligand obtained in step (1) in tetrahydrofuran, adding an excess of a hydrogen extraction agent (such as NaH, KH, etc.), stirring at room temperature, filtering to remove the hydrogen extraction agent, then adding a tetrahydrofuran solution of the M metal compound, reacting at room temperature overnight, draining the solvent, adding dichloromethane to dissolve, filtering to remove the filter cake, concentrating the filtrate, adding heptane for recrystallization, and obtaining the monocyclopentadienyl early transition metal complex of the present invention.

[0205] In the present invention, the α-olefin is selected from one or more of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.

[0206] In the present invention, the internal olefin refers to an olefin whose double bond is not at the terminal position. The internal olefin of an olefin can be a mixture of multiple isomers or a single internal olefin. For example, butene can be 1-C4, cis-2-C4, trans-2-C4 and isobutylene, or a mixture of one or more isomers. The catalyst structure and the composition of the mixed olefins have a certain influence on the structure and properties of the polymer product.

[0207] In the present invention, the enol is selected from the monomers represented by formula (G1),

[0208]

[0209] Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, and L4 is selected from a C1-C30 alkylene group having a side group.

[0210] In the present invention, in formula (G1), L5 and L2 are H, L3 is H or C1-C30 alkyl, and L4 is a C1-C30 alkylene group having a side group. Preferably, L5 and L2 are H; L3 is H or a C1-C10 alkyl group or a halogen-substituted C1-C10 alkyl group, preferably H or a C1-C10 alkyl group; L4 is a C1-C20 alkylene group having a side group, preferably a C1-C10 alkylene group having a side group. In a further preferred case, L5 and L2 are H, L3 is H or a C1-C6 alkyl group, and L4 is a C1-C6 alkylene group having a side group. The carbon number of the alkylene group refers to the number of Cs on the straight chain, and does not include the number of Cs on the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group having a side group (methyl).

[0211] In the present invention, in formula (G1), the side group is selected from one of halogen, C6-C20 aryl with or without substituents, and C1-C20 alkyl with or without substituents; preferably, the substituent is selected from one of halogen, C1-C10 alkyl, and C6-C10 aryl.

[0212] Preferably, in formula (G1), the side group is selected from halogen, phenyl or C1-C6 alkyl. Examples of the C1-C6 alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl or hexyl.

[0213] In the present invention, the enol is selected from at least one of the following compounds: 2-methyl-3-butene-1-ol, 2-ethyl-3-butene-1-ol, 1,1-diphenyl-3-butene-1-ol, 2-methyl-3-butene-2-ol, 2,2-dimethyl-3-butene-1-ol, 3-methyl-1-pentene-3-ol, 2,4-dimethyl-4-pentene-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-pentene-2-ol, 2-methyl-4-pentene-2-ol, 2-phenyl-4-pentene-2-ol, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-butene-1-ol, 2-hydroxy-5-hexene, 3-butene-2-ol, 2-methyl-4-pentene-2-ol, 2-phenyl-4-pentene-2-ol, 2-allylhexafluoroisopropan ...1-ol, 2-methyl-3-butene-2-ol, 2-methyl-3-butene-1-ol, 3-methyl-1-pentene-3-ol, 2,4-dimethyl-4-pentene-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-pentene-2-ol, 2-methyl-4-pentene-2-ol, 2-phenyl-4-pentene-2-ol, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-butene-1-ol, 3- 2-Methyl-2-hydroxy-5-hexene, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2,3-dimethyl-2-hydroxy-5-hexene, 1-heptene-4-ol, 4-methyl-1-heptene-4-ol, 4-n-propyl-1-heptene-4-ol, 6-heptene-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2,5-dimethyl -1-heptene-4-ol, 2,6-dimethyl-7-octen-2-ol, 2-hydroxy-2,4,5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 3-methyl-3-hydroxy-7-octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl-3-hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1,2-dihydroxy-7-octene, 2,6-dimethyl-2,6 -dihydroxy-7-octene, 2,6-dimethyl-2,3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, 2-methyl-2-hydroxy-3,5-dichloro-7-octene, 3,4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3,5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2,3-diol, 2,6-dimethyl-7-octen-2,6-diol.

[0214] In the present invention, the coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2 is characterized in that the unsaturated carboxylic acid is selected from the monomer represented by formula (G2),

[0215]

[0216] Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, and L4 is selected from a C1-C30 alkylene group having a side group.

[0217] In the present invention, in formula (G2), L5 and L2 are H, L3 is H or C1-C30 alkyl, and L4 is a C1-C30 alkylene group having a side group. Preferably, L5 and L2 are H; L3 is H or a C1-C10 alkyl group or a halogen-substituted C1-C10 alkyl group, preferably H or a C1-C10 alkyl group; L4 is a C1-C20 alkylene group having a side group, preferably a C1-C10 alkylene group having a side group. In a further preferred case, L5 and L2 are H, L3 is H or a C1-C6 alkyl group, and L4 is a C1-C6 alkylene group having a side group. The carbon number of the alkylene group refers to the number of Cs on the straight chain, and does not include the number of Cs on the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group having a side group (methyl).

[0218] In the present invention, in formula (G2), the side group is selected from one of halogen, C6-C20 aryl with or without substituents, and C1-C20 alkyl with or without substituents; preferably, the substituent is selected from one of halogen, C1-C10 alkyl, and C6-C10 aryl.

[0219] Preferably, in formula (G2), the side group is selected from halogen, phenyl or C1-C6 alkyl. Examples of the C1-C6 alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl or hexyl.

[0220] In the present invention, the unsaturated carboxylic acid is selected from at least one of the following compounds: 2-methyl-4-pentenoic acid, 2,3-dimethyl-4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2,2,3-trimethyl-4-pentenoic acid, 2,3,3-trimethyl-4-pentenoic acid, 2-ethyl-3-methyl-4-pentenoic acid, 2-(2-methylpropyl)-4-pentenoic acid, 2,2-diethyl-4-pentenoic acid, 2-methyl-2-ethyl-4-pentenoic acid, 2,2,3,3-tetramethyl-4-pentenoic acid, 2-methyl-5-hexenoic acid, 2- ethyl-5-hexenoic acid, 2-propyl-5-hexenoic acid, 2,3-dimethyl-5-hexenoic acid, 2,2-dimethyl-5-hexenoic acid, 2-isopropyl-5-hexenoic acid, 2-methyl-2-ethyl-5-hexenoic acid, 2-(1-methylpropyl)-5-hexenoic acid, 2,2,3-trimethyl-5-hexenoic acid, 2,2-diethyl-5-hexenoic acid, 2-methyl-6-hexenoic acid, 2-ethyl-6-hexenoic acid, 2-propyl-6-hexenoic acid, 2,3-dimethyl-6-hexenoic acid, 2,4-dimethyl-6-hexenoic acid, 2,2-dimethyl-6-hexenoic acid, 2-isopropyl-5-methyl-6-hexenoic acid, 2 -isopropyl-6-heptenoic acid, 2,3,4-trimethyl-6-heptenoic acid, 2-methyl-2-ethyl-6-heptenoic acid, 2-(1-methylpropyl)-6-heptenoic acid, 2,2,3-trimethyl-6-heptenoic acid, 2,2-diethyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-ethyl-7-octenoic acid, 2-propyl-7-octenoic acid, 2,3-dimethyl-7-octenoic acid, 2,4-dimethyl-7-octenoic acid, 2,2-dimethyl-7-octenoic acid, 2-isopropyl-5-methyl-7-octenoic acid, 2-isopropyl-7-octenoic acid, 2,3,4-trimethyl-7-octenoic acid, 2-methyl- 2-ethyl-7-octenoic acid, 2-(1-methylpropyl)-7-octenoic acid, 2,2,3-trimethyl-7-octenoic acid, 2,2-diethyl-7-octenoic acid, 2-methyl-8-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl-8-nonenoic acid, 2,3-dimethyl-8-nonenoic acid, 2,4-dimethyl-8-nonenoic acid, 2,2-dimethyl-8-nonenoic acid, 2,2-diethyl-8-nonenoic acid, 2-isopropyl-5-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2,3-dimethyl-9-decenoic acid, 2,4-dimethyl-9-decenoic acid, 2-methyl-10-undecenoic acid.

[0221] In the present invention, the unsaturated carboxylic acid ester is selected from the monomers represented by formula (G3),

[0222]

[0223] Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, L4 is selected from a C1-C30 alkylene group having a side group, and L6 is selected from a C1-C30 alkyl group.

[0224] In the present invention, in formula (G3), L5 and L2 are H, L3 is H or C1-C30 alkyl, and L4 is a C1-C30 alkylene group having a side group. Preferably, L5 and L2 are H, L3 is H or a C1-C10 alkyl group or a halogen-substituted C1-C10 alkyl group, preferably H or a C1-C10 alkyl group; L4 is a C1-C20 alkylene group having a side group, preferably a C1-C10 alkylene group having a side group. In a further preferred case, L5 and L2 are H, L3 is H or a C1-C6 alkyl group, and L4 is a C1-C6 alkylene group having a side group. The carbon number of the alkylene group refers to the number of Cs on the straight chain, and does not include the number of Cs on the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group having a side group (methyl).

[0225] In the present invention, in formula (G3), the side group is selected from one of halogen, C6-C20 aryl group with or without substituent, and C1-C20 alkyl group with or without substituent; preferably, the substituent is selected from one of halogen, C1-C10 alkyl group and C6-C10 aryl group.

[0226] Preferably, in formula (G3), the side group is selected from halogen, phenyl or C1-C6 alkyl. Examples of the C1-C6 alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl or hexyl.

[0227] In the present invention, the unsaturated carboxylic acid ester is selected from at least one of the following compounds: methyl 2-methyl-3-butenoate, methyl 2-methyl-4-pentenoate, ethyl 2-methyl-4-pentenoate, methyl 2,3-dimethyl-4-pentenoate, ethyl 2-methyl-3-butenoate, methyl 2,3-dimethylbutenoate, methyl 2-ethyl-3-butenoate, methyl 2,2-dimethyl-3-butenoate, methyl 2-methyl-3-methylenepentenoate, ethyl 2,3-dimethyl-3-butenoate, methyl 2-vinylhexanoate, ethyl 2-ethyl-3-butenoate, methyl-2-vinyl-3-pentenoate, methyl 2-vinyl-4-methyl-4-pentenoate, methyl 2,2-dimethyl-3-butenoate 2-Hydroxy-2-methyl-3-butenoic acid methyl ester, 2-methyl-3-butenoic acid isobutyl ester, 2-(1-methylethyl)-3-butenoic acid ethyl ester, 2,2,3-trimethyl-3-butenoic acid methyl ester, 2-vinylhexanoic acid ethyl ester, 2-ethyl-2-methyl-3-butenoic acid methyl ester, 3-methyl-5-hexenoic acid methyl ester, 4-methyl-5-hexenoic acid methyl ester, 4-methyl-5-hexenoic acid ethyl ester, 2-methyl-6-heptenoic acid methyl ester, 2,4-dimethyl-5-hexenoic acid methyl ester, 2-ethyl-5-hexenoic acid methyl ester, 3-methyl-5-hexenoic acid methyl ester, 4-methyl-5-hexenoic acid methyl ester, 2-ethyl-4-pentenoic acid methyl ester, 2-propyl-4-pentenoic acid methyl ester, 2 -propyl-5-hexenoic acid methyl ester, 2-propyl-4-pentenoic acid methyl ester, 2-butyl-5-hexenoic acid methyl ester, 3-vinyl hexanoic acid methyl ester, 2-(2-propen-1-yl)-4-pentanoic acid methyl ester, 2-(3-buten-1-yl)-5-hexenoic acid methyl ester, 3,3-dimethyl-5-hexenoic acid methyl ester, 3-propyl-5-hexenoic acid ethyl ester, 3,3-dimethyl-5-hexenoic acid ethyl ester, 3,4,4-trimethyl-5-hexenoic acid methyl ester, 3-(1,1-dimethylethyl)-5-hexenoic acid ethyl ester, 3-methyl-2-oxo-5-hexenoic acid ethyl ester, 2-vinyl-3,3-dimethyl-5-hexanoic acid methyl ester, methyl-β-vinylbenzopropionic acid ester, 3-methyl-5-hexenoic acid Benzyl ester, 2-propyl-6-heptenoic acid methyl ester, 2-methyl-6-heptenoic acid methyl ester, 2-methyl-6-heptenoic acid ethyl ester, 2,2-dimethyl-6-heptenoic acid methyl ester, 2,4-dimethyl-6-heptenoic acid ethyl ester, 2-propyl-6-heptenoic acid ethyl ester, 2,2-dimethyl-6-heptenoic acid ethyl ester, 2-(4-penten-1-yl)malonic acid 1,3-dimethyl ester, 6-heptenoic acid-2-methyl-1,1-dimethylethyl ester, 2-methyl-3-butenoic acid tert-butyl ester, 2-isopropyl-3-butenoic acid ethyl ester, 2-isobutyl-4-pentenoic acid methyl ester, 2,2-dimethyl-4-pentenoic acid methyl ester, 3,3-dimethyl-4-pentenoic acid methyl ester, 3,3-dimethyl-4-pentenoic acid ethyl ester, 2,2-dimethyl-4-pentenoic acid ethyl ester, 2-n-propyl-4-pentenoic acid methyl ester, 2-isopropyl-4-pentenoic acid methyl ester, 2-methyl-4-pentenoic acid isobutyl ester, allylmalonate diethyl ester, allylmalonate dimethyl ester, allylsuccinic anhydride, 2-methyl-4-pentenoic acid ethyl ester, 2-methyl-4-pentenoic acid methyl ester, 3-methyl-4-pentenoic acid methyl ester, 3-ethyl-4-pentenoic acid methyl ester, 3-methyl-4-pentenoic acid isobutyl ester, 2-(tert- butyl)-4-pentenoic acid ethyl ester, 3-allyldihydrofuran-2(3H)-one, 2-(dimethylamino)-2-methylpent-4-enoic acid methyl ester, 3-methyl-4-pentenoic acid methyl ester, 2-methyl-5-hexenoic acid methyl ester, 2,2-dimethyl-5-hexenoic acid methyl ester, 2,2-dimethyl-5-hexenoic acid ethyl ester, 2-methyl-5-hexenoic acid benzyl ester, 4,4-dimethyl-6-heptenoic acid methyl ester, 2,4-dimethyl-9-decenoic acid methyl ester.

[0228] In the present invention, the auxiliary agent is selected from one or more of an organoaluminum compound, an organoboron compound and an organosilicon compound.

[0229] In the present invention, when the auxiliary agent contains an organic aluminum compound, the organic aluminum compound is AlR n X 1 3-n ; wherein R is selected from H, C1-C20 saturated or unsaturated hydrocarbon group and C1-C20 saturated or unsaturated hydrocarbonoxy group, preferably C1-C20 alkyl group, C1-C20 alkoxy group, C7-C20 aralkyl group or C6-C20 aryl group; X 1 is selected from halogen, preferably chlorine or bromine; <n≤3。

[0230] In the present invention, the C1-C20 alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl or 4-n-butylcyclohexyl; the C1-C20 alkoxy group may be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isopentyloxy or tert-pentyloxy; the C7-C20 aralkyl group may be phenylmethyl, phenylethyl, phenyl n-propyl, phenyl isopropyl, phenyl n-butyl or phenyl tert-butyl; the C6-C20 aryl group may be phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl or vinylphenyl.

[0231] Preferably, the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum (AliBu3), tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogenate, diisobutylaluminum monohydrogenate, diethylaluminum monochloride (AlEt2Cl), diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane (MAO) and modified methylaluminoxane (MMAO).

[0232] In a further preferred embodiment, the organoaluminum compound is methylaluminoxane (MAO).

[0233] In the present invention, when the auxiliary agent contains an organic boron compound, the organic boron compound is an aromatic boron and / or a borate.

[0234] In the present invention, when the organic boron compound is an aromatic boron, the aromatic boron is selected from substituted or unsubstituted phenyl boron, preferably tris(pentafluorophenyl)boron.

[0235] In the present invention, when the organic boron compound is a borate, the borate is selected from N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl tetrakis(pentafluorophenyl)borate.

[0236] In the present invention, when the auxiliary agent contains an organic silicon compound, the organic silicon compound is an alkyl silicon compound.

[0237] In the present invention, the general formula of the alkyl silicon compound is SiH1H2H3H4, wherein H1 is selected from C1-C10 alkyl, and H2, H3 and H4 are each independently selected from C1-C10 alkyl or halogen.

[0238] In a preferred embodiment, the alkyl silicon compound is selected from one or more of trimethylchlorosilane, dichlorodimethylsilane, propyldimethylchlorosilane, dichloroethylmethylsilane, tert-butyldimethylchlorosilane, diisopropylchlorosilane, trichloroethylsilane, chloromethyldimethylchlorosilane, di-tert-butylchlorosilane, dichloro(methyl)propylsilane, methyltrichlorosilane and trichloroethylsilane.

[0239] In the present invention, when the auxiliary agent contains an organoaluminum compound, the molar ratio of the amount of aluminum element in the organoaluminum compound to the amount of M element in the catalyst is (10-10000000): 1, preferably (10-100000): 1, and more preferably (100-10000): 1. Specifically, the molar ratio of the amount of aluminum element in the organoaluminum compound to the amount of M element in the catalyst can be 100: 1, 200: 1, 300: 1, 500: 1, 700: 1, 800: 1, 1000: 1, 2000: 1, 3000: 1, 5000: 1 or 10000: 1.

[0240] In the present invention, when the auxiliary agent contains an organic boron compound, the molar ratio of the amount of the boron element in the organic boron compound to the amount of the M element in the catalyst is (0.1-1000): 1, preferably (0.1-500): 1. Specifically, the molar ratio of the amount of the boron element in the organic boron compound to the amount of the M element in the catalyst can be 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1 or 500:1.

[0241] In the present invention, when the auxiliary agent contains an organosilicon compound, the molar ratio of the amount of silicon element in the organosilicon compound to the amount of M element in the catalyst is (10-10000000): 1, preferably (10-200000): 1. Specifically, the molar ratio of the amount of silicon element in the organosilicon compound to the amount of M element in the catalyst can be 10: 1, 20: 1, 50: 1, 100: 1, 500: 1, 1000: 1, 1500: 1, 2000: 1, 5000: 1, 10000: 1, 100000: 1, 200000: 1.

[0242] In the present invention, when the auxiliary agent is a combination of an organic aluminum compound, an organic boron compound and an organic silicon compound, the molar ratio of the total amount of aluminum, boron and silicon in the auxiliary agent to the amount of M element in the catalyst is (10-11000000): 1, preferably (10-200000): 1. Specifically, the molar ratio of the total amount of aluminum, boron and silicon in the auxiliary agent to the amount of M element in the catalyst can be 10: 1, 20: 1, 50: 1, 100: 1, 500: 1, 1000: 1, 1500: 1, 2000: 1, 5000: 1, 10000: 1, 100000: 1, 150000: 1 or 200000: 1.

[0243] In the present invention, the polymerization reaction is carried out in the presence of a solvent.

[0244] In a preferred embodiment, the solvent is selected from one or more of alkanes, halogenated alkanes and aromatic hydrocarbons.

[0245] In the present invention, the alkane is selected from one or more of C3-C20 alkanes, preferably one or more of C3-C10 alkanes, further preferably one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexane, and further preferably one or more of hexane, heptane and cyclohexane.

[0246] In the present invention, the general formula of the halogenated alkane is R 1 X 2 n2 R 2 X 3 m2 , where X 2 and X 3 Each is independently selected from halogen, m2+n2≥1, R 1 is selected from C1-C10 alkyl or alkenyl, R 2 is selected from C1-C10 alkylene or alkenylene. The alkenyl refers to a straight chain alkenyl, a branched chain alkenyl or a cycloalkenyl, and specifically, the alkenyl is vinyl, allyl or butenyl.

[0247] In a preferred embodiment, the halogenated alkane is selected from one or more of chloroform, dichloromethane, dichloroethane, dichloropropane and trichloroethylene.

[0248] In the present invention, the general formula of the aromatic hydrocarbon is R 4 -Ph-R 3 , where R 3 and R 4 Each is independently selected from hydrogen, phenyl and C1-C10 alkane, and Ph represents a benzene ring.

[0249] In a preferred embodiment, the aromatic hydrocarbon is selected from one or more of pentylbenzene, ethylbenzene, xylene, toluene and benzene.

[0250] Preferably, the polymerization reaction is carried out under anhydrous and oxygen-free conditions.

[0251] In the present invention, the non-polar monomer having a carbon number of ≤3 is generally a gas, and its amount is adjusted by controlling the pressure of the reaction system. In some specific embodiments, the amount of the non-polar monomer is such that the pressure of the reaction system is 1-20 atm, preferably 5-15 atm. Specifically, when the non-polar monomer is ethylene, the ethylene pressure in the reaction system is 1-20 atm, preferably 5-15 atm, and specifically can be 5 atm, 8 atm, 10 atm, 11 atm, 12 atm, 13 atm, 14 atm or 15 atm.

[0252] In the present invention, the pressure refers to absolute pressure.

[0253] In the present invention, the polar monomer is generally a liquid, and its amount is regulated by controlling the concentration of the polar monomer in the liquid raw material. In some specific embodiments, the concentration of the polar monomer in the liquid raw material (usually including a polar monomer, a catalyst, an auxiliary agent and a solvent) is 0.01-6000mmol / L, preferably 0.1-1000mmol / L, and more preferably 1-500mmol / L. Specifically, the concentration of the polar monomer in the polymerization raw material can be 1mmol / L, 50mmol / L, 100mmol / L, 150mmol / L, 200mmol / L, 250mmol / L, 300mmol / L, 350mmol / L, 400mmol / L, 450mmol / L or 500mmol / L.

[0254] In the present invention, the concentration of the catalyst in the liquid raw material is 0.00001-100mmol / L, preferably 0.0001-1mmol / L, more preferably 0.001-0.5mmol / L. More preferably, it is 0.002-0.1mmol / L. Specifically, the concentration of the catalyst in the liquid raw material can be 0.002mmol / L, 0.004mmol / L, 0.006mmol / L, 0.008mmol / L, 0.01mmol / L, 0.02mmol / L, 0.04mmol / L, 0.06mmol / L, 0.08mmol / L or 0.1mmol / L.

[0255] In the present invention, the polymerization reaction conditions include: temperature of -50 to 180° C. and time of 10 to 200 min.

[0256] Preferably, the polymerization reaction temperature is -20 to 100°C, more preferably 20-100°C, specifically, the polymerization reaction temperature may be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C; the polymerization reaction time is 20-60min, specifically, the polymerization reaction time may be 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min.

[0257] The second aspect of the present invention provides a polyolefin prepared by the above-mentioned coordination precipitation polymerization method for olefin polymerization, wherein the shape of the polyolefin is spherical or quasi-spherical; the average particle size of the polyolefin is 0.02-50 mm, preferably 0.05-50 mm, and further preferably 0.2-20 mm. Specifically, the average particle size of the spherical or quasi-spherical polymer can be 0.2 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 3 mm, 5 mm, 8 mm, 10 mm, 15 mm or 20 mm.

[0258] In the present invention, the weight average molecular weight of the polyolefin is 10,000-800,000, preferably 10,000-500,000. Specifically, the molecular weight of the polyolefin may be 10,000, 20,000, 30,000, 40,000 or 50,000.

[0259] In the present invention, the molecular weight distribution index of the polyolefin is ≤10, preferably 1.5-10. Specifically, the molecular weight distribution index of the polyolefin may be 1.5, 2, 2.5, 3, 3.5, 4, 6, 8 or 10.

[0260] In the present invention, the molecular weight distribution index represents M w / M n .

[0261] In the present invention, the melting point of the polyolefin is 90-140° C. Specifically, the melting point of the polyolefin may be 90° C., 100° C., 110° C., 120° C., 125° C., 130° C., 135° C. or 140° C.

[0262] In the present invention, the density of the polyolefin is 0.3-0.85 g / cm 3 , preferably 0.4-0.75g / cm 3 Specifically, the density of the spherical or quasi-spherical polymer may be 0.4 g / cm 3 , 0.45g / cm 3 , 0.5g / cm 3 , 0.55g / cm 3 , 0.6g / cm 3 , 0.65g / cm 3 , 0.7g / cm 3 , 0.75g / cm 3 .

[0263] In the present invention, the density is measured using the method in GB / T6343-2009.

[0264] In the present invention, according to the coordination precipitation polymerization method, non-polar monomers and polar monomers undergo polymerization reaction in the presence of a non-loaded catalyst to prepare spherical or spherical polymer particles. This method not only eliminates the complicated catalyst loading process, but also greatly simplifies the polymer deashing and granulation post-treatment procedures, which can inject new blood into olefin polymerization technology.

[0265] The coordination precipitation polymerization method for olefin polymerization and polyolefin of the present invention are further described by examples. The examples are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given, but the protection scope of the present invention is not limited to the following examples.

[0266] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all commercially available.

[0267] The polymer was washed with a dilute acid solution before measurement to ensure that the metal content in the polymer was ≤50 ppm.

[0268] The analytical characterization instruments used in the present invention are as follows:

[0269] 1. Nuclear magnetic resonance instrument: Bruker DMX 300 (300 MHz), tetramethylsilane (TMS) as internal standard, used to test the structure of complex ligands at 25°C.

[0270] 2. Comonomer content of copolymer: 13 C NMR spectra were measured on a 400 MHz Bruker Avance 400 NMR spectrometer using a 10 mm PASEX 13 probe and the polymer samples were dissolved in deuterated tetrachloroethane at 130°C for analysis.

[0271] 3. Molecular weight and molecular weight distribution index PDI (PDI = M w / M n ): PL-GPC220 was used with trichlorobenzene as solvent and the measurement was performed at 150°C (standard sample: PS, flow rate: 1.0 mL / min, column: 3×Plgel 10um M1×ED-B300×7.5 nm).

[0272] 4. Activity measurement method: gravimetric analysis. The calculation method of polymerization activity is: polymerization activity = polymerization

[0273] Weight of metal complex (g) / metal complex (mol) × 60 / polymerization time (min).

[0274] 5. Polymer density test method: refer to GBT 6343-2009 method test.

[0275] Example 1

[0276] Complex 20: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, and m=1.

[0277] In a nitrogen atmosphere, the compound represented by formula (II) (11.23 g, 30 mmol, S type) was dissolved in anhydrous ether (150 mL), and n-butyl lithium solution (2.5 M, 36 mL, 90 mmol) was added dropwise at room temperature, stirred at room temperature for 4 h, tetrahydrofuran (150 mL) was added, and the obtained black solution containing the precipitate was further stirred for 1 h; dicyclohexylphosphine chloride (90 mmol, 19.2 mL) was added at 0°C, stirred at room temperature for 1 h, and then NH4Cl aqueous solution (5 mL) was added to quench; the organic phase was extracted with ethyl acetate, and the obtained organic phase was dried over anhydrous sodium sulfate; methanol (100 mL) and 5 mL of concentrated hydrochloric acid were added, and the reaction was refluxed for 16 h. After the reaction was completed, TLC was used to track; the organic solvent was removed, the product was dissolved in ethyl acetate, and NaHCO3 aqueous solution was added for neutralization, the organic phase was extracted, dried over anhydrous MgSO4, filtered, concentrated, and column chromatography (dichloromethane as solvent) was performed to obtain ligand I1 with a yield of 42%; 1 H NMR (400MHz, CDCl3): δ=1.15-1.38(m, 20H), 1.67-1.84(m, 16H), 1.89-2.00(m, 4H), 2.15(t, 2H) ), 2.25(t, 2H), 6.53(d, 2H), 7.10(d, 2H), 7.25(t, 2H), 7.33(t, 2H), 7.88(d, 2H), 8.03(s, 2H); 31 P NMR (162MHz, CDCl3): δ = -20.21 (s); High-resolution mass spectrometry test: Theoretical calculated value is: 679.38, measured value is: 679.30;

[0278] In a nitrogen atmosphere, ligand I1 (0.68 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 h. NaH was filtered out. A tetrahydrofuran solution (-78°C) of pentamethylcyclopentadienylzirconium trichloride (0.666 g, 2 mmol) was added dropwise. The mixture was reacted overnight at room temperature. The solvent was drained, and dichloromethane (40 mL) was added to dissolve the mixture. The filter cake was removed by filtration, and the filtrate was concentrated. Heptane was added for recrystallization to obtain a white complex 20 with a yield of 78%. Elemental analysis test: C 72 H 100Cl4O4P2Zr2: Theoretical calculation value: C, 61.08; H, 7.12; Test value: C, 61.23; H, 7.40;

[0279] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 for 3 times, 500mL of heptane, 30mmol (6.0mL) of 2,6-dimethyl-7-octen-2-ol, 36mL of AliBu3 (1.0mol / L n-pentane solution), 3.5mL of MAO (1.53mol / L toluene solution) were injected into the polymerization system, and 3.6mg (2.5μmol) of complex 20 was added at the same time. The ethylene pressure was maintained at 10atm at 30°C and the reaction was stirred for 30min. Finally, the reaction was neutralized with 10wt% hydrochloric acid-acidified ethanol solution to obtain polyolefin A1. The polymerization activity of polyolefin A1 was 5.23×10 5 g·mol -1 ·h -1 The weight average molecular weight of polyolefin A1 is 142000, the molecular weight distribution index of polyolefin A1 is 3.3, the molar content of hydroxyl groups in polyolefin A1 is 1.12%, the melting point of polyolefin A1 is 121.1°C, the average particle size of spherical polymers in polyolefin A1 is 2.05 mm, and the density of polyolefin A1 is 0.562 g / cm 3 , the yield of spherical polymer in polyolefin A1 was 64%.

[0280] Example 2

[0281] Complex 20: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0282] The preparation method and preparation process of complex 20 in this embodiment are the same as those of complex 20 in Example 1;

[0283] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 for 3 times; 500mL of pentane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 36mL of AliBu3 (1.0mol / L hexane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 3.5mg (2.6μmol) of complex 20 was added at 30°C, maintaining an ethylene pressure of 10atm, and stirring for 30min; finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyolefin A2; the polymerization activity of polyolefin A2 was 7.78×10 5g·mol -1 ·h -1 The weight average molecular weight of polyolefin A2 is 184000, the molecular weight distribution index of polyolefin A2 is 3.12, the molar content of carboxyl groups in polyolefin A2 is 1.20%, the melting point of polyolefin A2 is 127.1°C, the average particle size of spherical polymers in polyolefin A2 is 1.88 mm, and the density of polyolefin A2 is 0.741 g / cm 3 , the yield of spherical polymer in polyolefin A2 was 65%.

[0284] Example 3

[0285] Complex 20: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0286] The preparation method and preparation process of complex 20 in this embodiment are the same as those of complex 20 in Example 1;

[0287] A 7 mL stainless steel glass-lined polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 2 h, evacuated while hot and replaced with N2 for 3 times; 3.0 mL of pentane, 0.5 mL (3.1 mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 1.10 mL of AliBu3 (3.0 mol / L hexane solution), 0.4 mL of triphenylmethyl tetrakis(pentafluorophenyl)borate (3.0 mmol / L dichloromethane solution) were injected into the polymerization system, and 0.1 mL of complex 20 (3.0 mmol / L dichloromethane solution) was added. The reaction was stirred at 20°C while maintaining an ethylene pressure of 10 atm for 20 min; finally, the reaction was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin A3; the polymerization activity of polyolefin A3 was 2.24×10 5 g·mol -1 ·h -1 The weight average molecular weight of polyolefin A3 is 104000, the molecular weight distribution index of polyolefin A3 is 3.21, the molar content of ester groups in polyolefin A3 is 2.02%, the average particle size of the spherical polymer in polyolefin A3 is 0.43 mm, and the yield of the spherical polymer in polyolefin A3 is 62%.

[0288] Example 4

[0289] Complex 20: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0290] The preparation method and preparation process of complex 20 in this embodiment are the same as those of complex 20 in Example 1;

[0291] A 7 mL stainless steel glass-lined polymerization kettle equipped with mechanical stirring was dried continuously at 130° C. for 2 h, evacuated while hot and replaced with N2 for 3 times; 4.0 mL of heptane, 600 μL (3.86 mmol) of 2-octene, 100 μL of AliBu3 (0.1 mol / L heptane solution), 60.0 μL of triphenylmethyl tetrakis(pentafluorophenyl)borate (1.0 mmol / L dichloromethane solution) were injected into the polymerization system, and 50 μL of complex 20 (1.0 mmol / L dichloromethane solution) was added, and the reaction was stirred at 60° C. while maintaining an ethylene pressure of 10 atm for 30 min; finally, the reaction was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain polyolefin A4; the polymerization activity of polyolefin A4 was 6.89×10 5 g·mol -1 ·h -1 The weight average molecular weight of polyolefin A4 is 89000, the molecular weight distribution index of polyolefin A4 is 3.1, the melting point of polyolefin A4 is 120.0°C, the average particle size of the spherical polymer in polyolefin A4 is 0.60 mm, and the yield of the spherical polymer in polyolefin A4 is 54%.

[0292] Example 5

[0293] Complex 2: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0294] The preparation method and preparation process of ligand I1 in this embodiment are the same as those of ligand I1 in embodiment 1;

[0295] In a nitrogen atmosphere, ligand I1 (0.68 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 h, and NaH was removed by filtration; a tetrahydrofuran solution of pentamethylcyclopentadienyltitanium trichloride (0.578 g, 2 mmol) was added dropwise, and the mixture was reacted overnight at room temperature, the solvent was drained, and dichloromethane (40 mL) was added to dissolve the mixture, the filter cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain an orange complex 2 with a yield of 76%; elemental analysis tested complex 2 (C 64 H 84 Cl4O2P2Ti2): Theoretical calculated values ​​are: C, 64.88; H, 7.15; Test values ​​are: C, 64.92; H, 7.43;

[0296] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 for 3 times; 500mL of pentane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 36mL of AliBu3 (1.0mol / L hexane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 3.0mg (2.5μmol) of complex 2 was added at the same time. The ethylene pressure was maintained at 10atm at 30°C and the reaction was stirred for 30min; finally, the reaction was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyolefin A5; the polymerization activity of polyolefin A5 was 1.21×10 5 g·mol -1 ·h -1 The weight average molecular weight of polyolefin A5 is 171000, the molecular weight distribution index of polyolefin A5 is 3.52, the molar content of carboxyl groups in polyolefin A5 is 1.16%, the melting point of polyolefin A5 is 125.3°C, the average particle size of spherical polymers in polyolefin A5 is 1.25 mm, and the density of polyolefin A5 is 0.732 g / cm 3 , the yield of spherical polymer in polyolefin A5 was 60%.

[0297] Example 6

[0298] Complex 2: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0299] The preparation method and preparation process of complex 2 in this embodiment are the same as those of complex 2 in Example 5;

[0300] A 7 mL stainless steel glass-lined polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 2 h, evacuated while hot and replaced with N2 for 3 times; 3.0 mL of pentane, 0.5 mL (3.1 mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 1.1 mL of AliBu3 (3.0 mol / L hexane solution), 0.5 mL of triphenylmethyl tetrakis(pentafluorophenyl)borate (3.0 mmol / L dichloromethane solution) were injected into the polymerization system, and 0.1 mL of complex 2 (3.0 mmol / L dichloromethane solution) was added, and the ethylene pressure was maintained at 10 atm at 20°C, and the reaction was stirred for 10 min; finally, the reaction was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain polyolefin A6; the polymerization activity of polyolefin A6 was 0.84×10 5 g·mol -1 ·h -1The weight average molecular weight of polyolefin A6 is 80,000, the molecular weight distribution index of polyolefin A6 is 3.13, the molar content of ester groups in polyolefin A6 is 2.01%, the average particle size of the spherical polymer in polyolefin A6 is 0.43 mm, and the yield of the spherical polymer in polyolefin A6 is 62%.

[0301] Example 7

[0302] Complex 47: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0303] The preparation method and preparation process of ligand I1 in this embodiment are the same as those of ligand I1 in embodiment 1;

[0304] In a nitrogen atmosphere, ligand I1 (0.68 g, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 h. NaH was filtered out. A tetrahydrofuran solution (-78°C) of pentamethylcyclopentadienyl hafnium trichloride (0.840 g, 2 mmol) was added dropwise. The mixture was reacted at room temperature overnight. The solvent was drained, and dichloromethane (40 mL) was added to dissolve the mixture. The filter cake was removed by filtration. The filtrate was concentrated, and heptane was added for recrystallization to obtain a white complex 47 with a yield of 81%. Elemental analysis of complex 47 (C 64 H 84 Cl4Hf2O2P2): Theoretical calculated values ​​are: C, 53.16; H, 5.86; Test values ​​are: C, 53.22; H, 5.98;

[0305] A 7 mL stainless steel glass-lined polymerization kettle equipped with mechanical stirring was dried continuously at 130° C. for 2 h, evacuated while hot and replaced with N2 gas three times; 4.0 mL of heptane, 600 μL of 2-octene, 100 μL of AliBu3 (0.1 mol / L heptane solution), 60.0 μL of triphenylmethyl tetrakis(pentafluorophenyl)borate (1.0 mmol / L dichloromethane solution) were injected into the polymerization system, and 50 μL of complex 47 (1.0 mmol / L dichloromethane solution) was added. The reaction was stirred at 60° C. and maintained at an ethylene pressure of 10 atm for 30 min. Finally, the reaction was neutralized with an ethanol solution acidified with 10 wt % hydrochloric acid to obtain polyolefin A7. The polymerization activity of polyolefin A7 was 3.72×10 5 g·mol -1 ·h -1The weight average molecular weight of polyolefin A7 is 1014000, the molecular weight distribution index of polyolefin A7 is 3.3, the melting point of polyolefin A7 is 112.7°C, the average particle size of the spherical polymer in polyolefin A7 is 0.53 mm, and the yield of the spherical polymer in polyolefin A7 is 55%.

[0306] Example 8

[0307] Complex 47: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0;

[0308] The preparation method and preparation process of complex 47 in this example are the same as those of complex 47 in Example 7;

[0309] A 1L stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2h, evacuated while hot and replaced with N2 for 3 times, 400mL of pentane, 14.3mL (90mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 100mL of AliBu3 (1.0mol / L hexane solution), 3.3mL of MAO (1.53mol / L) were injected into the polymerization system, 3.5mg (2.5μmol) of complex 47 was added, and the reaction was stirred for 10min at 25°C while maintaining an ethylene pressure of 10atm. Finally, the reaction was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyolefin A8. The polymerization activity of polyolefin A8 was 2.02×10 5 g·mol -1 ·h -1 The weight average molecular weight of polyolefin A8 is 862000, the molecular weight distribution index of polyolefin A8 is 3.34, the molar content of ester groups in polyolefin A8 is 1.21%, the average particle size of the spherical polymer in polyolefin A8 is 3.04 mm, and the yield of the spherical polymer in polyolefin A8 is 64%.

[0310] Example 9

[0311] Complex 54: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1;

[0312] In a nitrogen atmosphere, the compound represented by formula (II) (3.74 g, 10 mmol, S type) was dissolved in tetrahydrofuran (50 mL), and n-butyl lithium solution (14 mL, 33 mmol) was added dropwise at -78 ° C. The reaction gradually returned to room temperature and continued to stir for 4 h to obtain a white precipitate; bis[5-methyl-2-(1-methylethyl)cyclohexyl]-phosphine chloride (30 mmol, 10.35 g) was evenly dispersed in 10 mL of ether, and added dropwise to the original reaction system under an ice-water bath, and the temperature was slowly raised to room temperature and stirred overnight; quenched with water, the organic phase was extracted with ether, the obtained organic phase was concentrated, and the frozen cycle was deoxygenated. 5 mL of concentrated hydrochloric acid was added under a nitrogen atmosphere to react for 5 h. After the reaction was completed, TLC was used to track the reaction; NaHCO3 aqueous solution was added for neutralization, quenched with water, the organic phase was extracted with ether, dried over anhydrous MgSO4, filtered, concentrated, and column chromatography was performed to obtain ligand I2 with a yield of 33%; 1 H NMR (400MHz, CDCl3): δ = 0.34 (d, 6H), 0.50 (m, 2H), 0.88 (m, 20H), 0.95 (m, 18H), 1.05 (m, 2H), 1.20 (m, 4H), 1.37 (m, 4H), 1.54 (m, 6H), 1.67 ( m, 2H), 1.78 (m, 2H), 1.91 (m, 6H), 2.12 (m, 2H), 2.82 (m, 2H), 6.52 (d, 2H), 7.08 (d, 2H), 7.23 (t, 2H), 7.32 (t, 2H), 7.88 (d, 2H), 8.02 (s, 2H);

[0313] In a nitrogen atmosphere, ligand I2 (0.90, 1 mmol) was dissolved in tetrahydrofuran, excess NaH (0.072 g, 3 mmol) was added, and the mixture was stirred at room temperature for 10 h. NaH was filtered out, and a tetrahydrofuran solution (-78°C) of pentamethylcyclopentadienylzirconium trichloride (0.666 g, 2 mmol) was added dropwise. The mixture was reacted at room temperature overnight, the solvent was drained, and dichloromethane (40 mL) was added to dissolve the mixture. The filter cake was removed by filtration, the filtrate was concentrated, and heptane was added for recrystallization to obtain a white complex 54 with a yield of 73%. The complex 54 (C 88 H 132 Cl4O4P2Zr2): Theoretical calculated values ​​are: C, 64.44; H, 8.11; Test values ​​are: C, 64.33; H, 8.31;

[0314] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 for 3 times; 500mL of pentane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 36mL of AliBu3 (1.0mol / L hexane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 4.8mg (2.5μmol) of complex 54 was added at the same time. The reaction was stirred at 30°C and maintained at 10atm of ethylene pressure for 30min; finally, the reaction was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain polyolefin A9; the polymerization activity of polyolefin A9 was 6.23×10 5 g·mol -1 ·h -1 The weight average molecular weight of polyolefin A9 is 152000, the molecular weight distribution index of polyolefin A9 is 3.24, the molar content of carboxyl groups in polyolefin A9 is 1.12%, the melting point of polyolefin A9 is 126.1°C, the average particle size of spherical polymers in polyolefin A9 is 1.33 mm, and the density of polyolefin A9 is 0.683 g / cm 3 , the yield of spherical polymer in polyolefin A9 was 62%.

[0315] Comparative Example 1

[0316] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 for 3 times, 500mL of pentane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 36mL of AliBu3 (1.0mol / L hexane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 3.6mg (5.0μmol) of complex F (synthesis reference Dalton Trans., 2014, 43, 222-230) was added at the same time. The ethylene pressure was maintained at 10atm at 30°C and the reaction was stirred for 20min. Finally, the reaction was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain polyolefin D1. The polymerization activity of polyolefin D1 was 3.32×10 5 g·mol -1 ·h -1 The weight average molecular weight of polyolefin D1 is 82000, the molecular weight distribution index of polyolefin D1 is 3.49, the molar content of carboxyl groups in polyolefin D1 is 1.14%, the average particle size of the spherical polymer in polyolefin D1 is 1.42 mm, and the yield of the spherical polymer in polyolefin D1 is 45%.

[0317]

[0318] Comparative Example 2

[0319] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 for 3 times, 500mL of pentane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 36mL of AliBu3 (1.0mol / L hexane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 2.6mg (5μmol) of complex N (synthesis reference JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1585-1594) was added at the same time; at 30°C, the ethylene pressure was maintained at 10atm, the reaction was stirred for 30min, and finally neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain polyolefin D2; the polymerization activity of polyolefin D2 was 6.22×10 4 g·mol -1 ·h -1 The weight average molecular weight of polyolefin D2 is 53000, the molecular weight distribution index of polyolefin D2 is 4.12, the molar content of carboxyl groups in polyolefin D2 is 1.02%, the melting point of polyolefin D2 is 133.2°C, and the density of polyolefin D2 is 0.792 g / cm 3 , the yield of spherical polymers in polyolefin D2 was 30%.

[0320]

[0321] In the present invention, compared with the use of the complexes in Comparative Examples 1 and 2, when the transition metal metal complex of the present invention is used as the main catalyst, the obtained polyolefin has higher polymerization activity, and the molecular weight of the obtained polyolefin is significantly higher than the molecular weight of the polyolefin obtained in Comparative Examples 1 and 2. In addition, the coordination precipitation polymerization method for olefin polymerization of the present invention can prepare polar polyolefins with good particle morphology and polar groups.

[0322] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A coordination precipitation polymerization method for olefin polymerization, characterized in that: The method comprises mixing olefin monomers, a catalyst and an auxiliary agent to carry out a polymerization reaction; The olefin monomers contain non-polar monomers and polar monomers; The non-polar monomer is selected from one or more of ethylene, α-olefins and internal olefins; The polar monomer is selected from one or more of enol, unsaturated carboxylic acid and unsaturated carboxylic acid ester; The catalyst is selected from the monocyclopentadienyl transition metal complex shown in formula (I), Wherein, M is selected from Group IVB metals; R 11 -R 15 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon group; X is selected from halogen, C1-C10 hydrocarbon group, n is 1 or 2; L1 is selected from substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, tetrahydroindenyl, substituted or unsubstituted fluorenyl; R1 is OR 21 R 22 , where R 21 and R 22 are each independently selected from substituted or unsubstituted C1-C10 hydrocarbon groups, and R 21 , R 22 They are connected with O to form a ring or ring system, and m is 0 or 1.

2. The coordination precipitation polymerization method for olefin polymerization according to claim 1, characterized in that: The monocyclopentadienyl early transition metal complex is selected from the following complexes, Complex 1: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 2: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 3: A complex represented by formula (I), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 4: A complex represented by formula (I), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 5: A complex represented by formula (I), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 6: A complex represented by formula (I), wherein M is Ti, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 7: A complex represented by formula (I), wherein M is Ti, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 8: A complex represented by formula (I), wherein M is Ti, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 9: A complex represented by formula (I), wherein M is Ti, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 10: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 11: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 12: A complex represented by formula (I), wherein M is Ti, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 13: A complex represented by formula (I), wherein M is Ti, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 14: A complex represented by formula (I), wherein M is Ti, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 15: A complex represented by formula (I), wherein M is Ti, L1 is indenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 16: A complex represented by formula (I), wherein M is Ti, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 17: A complex represented by formula (I), wherein M is Ti, L1 is fluorenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 18: A complex represented by formula (I), wherein M is Ti, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is methyl, n=2, m=0; Complex 19: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 20: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 21: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 22: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 23: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 24: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 25: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 26: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 27: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 28: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 29: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 30: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 31: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 32: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 33: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 34: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 35: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 36: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 37: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 38: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 39: A complex represented by formula (I), wherein M is Zr, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 40: A complex represented by formula (I), wherein M is Zr, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 41: A complex represented by formula (I), wherein M is Zr, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 42: A complex represented by formula (I), wherein M is Zr, L1 is indenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 43: A complex represented by formula (I), wherein M is Zr, L1 is tetrahydroindenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 44: A complex represented by formula (I), wherein M is Zr, L1 is fluorenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 45: A complex represented by formula (I), wherein M is Zr, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 46: A complex represented by formula (I), wherein M is Hf, L1 is cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 47: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 48: A complex represented by formula (I), wherein M is Hf, L1 is 1-methyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 49: A complex represented by formula (I), wherein M is Hf, L1 is 1-n-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 50: A complex represented by formula (I), wherein M is Hf, L1 is 1-tert-butyl-2,4-cyclopentadienyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 51: A complex represented by formula (I), wherein M is Hf, L1 is indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 52: A complex represented by formula (I), wherein M is Hf, L1 is fluorenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 53: A complex represented by formula (I), wherein M is Hf, L1 is phenyl-indenyl, and R 11 -R 15 is H, X is Cl, n=2, m=0; Complex 54: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 55: A complex represented by formula (I), wherein M is Zr, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, R1 is tetrahydrofuran, m=1; Complex 56: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, R1 is tetrahydrofuran, m=1; Complex 57: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is CH2C6H5, n=2, R1 is tetrahydrofuran, m=1; Complex 58: A complex represented by formula (I), wherein M is Ti, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0; Complex 59: A complex represented by formula (I), wherein M is Ti, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0; Complex 60: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, m=0; Complex 61: A complex represented by formula (I), wherein M is Zr, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is CH2C6H5, n=2, m=0; Complex 62: The complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0; Complex 63: A complex represented by formula (I), wherein M is Hf, L1 is cyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 isopropyl, X is Cl, n=2, m=0; Complex 64: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is methyl, n=2, m=0; Complex 65: A complex represented by formula (I), wherein M is Hf, L1 is pentamethylcyclopentadienyl, and R 11 , R 13 and R 14 For H, R 12 is methyl, R 15 is isopropyl, X is CH2C6H5, n=2, m=0.

3. The coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2, characterized in that: The enol is selected from the monomers represented by formula (G1), Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, and L4 is selected from a C1-C30 alkylene group having a side group.

4. The coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2, characterized in that: The unsaturated carboxylic acid is selected from the monomers represented by formula (G2), Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, and L4 is selected from a C1-C30 alkylene group having a side group.

5. The coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2, characterized in that: The unsaturated carboxylic acid ester is selected from the monomers represented by formula (G3), Wherein, L2, L3, and L5 are each independently selected from H or a C1-C30 alkyl group, L4 is selected from a C1-C30 alkylene group having a side group, and L6 is selected from a C1-C30 alkyl group.

6. The coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2, characterized in that: The auxiliary agent is selected from one or more of an organoaluminum compound, an organoboron compound and an organosilicon compound; Preferably, the organoaluminum compound is AlR n X 1 3-n ; wherein R is selected from H, C1-C20 saturated or unsaturated hydrocarbon group and C1-C20 saturated or unsaturated hydrocarbonoxy group, preferably C1-C20 alkyl group, C1-C20 alkoxy group, C7-C20 aralkyl group or C6-C20 aryl group; X 1 is selected from halogen, preferably chlorine or bromine; <n≤3; Preferably, the organic boron compound is an aromatic boron and / or a borate; Preferably, the aromatic hydrocarbon boron is selected from substituted or unsubstituted phenyl boron, preferably tris(pentafluorophenyl)boron; Preferably, the borate is selected from N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and / or triphenylmethyl tetrakis(pentafluorophenyl)borate; Preferably, the organosilicon compound is an alkyl silicon compound; Preferably, the general formula of the alkyl silicon compound is SiH1H2H3H4, wherein H1 is selected from C1-C10 alkyl, and H2, H3 and H4 are each independently selected from C1-C10 alkyl or halogen.

7. The coordination precipitation polymerization method for olefin polymerization according to claim 6, characterized in that: When the auxiliary agent contains an organic aluminum compound, the molar ratio of the amount of aluminum element in the organic aluminum compound to the amount of M element in the catalyst is (10-10000000):1; Preferably, when the auxiliary agent contains an organic boron compound, the molar ratio of the amount of the boron element in the organic boron compound to the amount of the M element in the catalyst is (0.1-1000):1; Preferably, when the auxiliary agent contains an organosilicon compound, the molar ratio of the amount of silicon element in the organosilicon compound to the amount of M element in the catalyst is (10-10000000):1; Preferably, when the auxiliary agent is a combination of an organic aluminum compound, an organic boron compound and an organic silicon compound, the molar ratio of the total amount of aluminum, boron and silicon in the auxiliary agent to the amount of M element in the catalyst is (10-11000000):

1.

8. The coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2, characterized in that: The polymerization reaction is carried out in the presence of a solvent; Preferably, the solvent is selected from one or more of alkanes, halogenated alkanes and aromatic hydrocarbons; Preferably, the alkane is selected from one or more of C3-C20 alkanes; Preferably, the general formula of the halogenated alkane is R 1 X 2 n2 R 2 X 3 m2 , where X 2 and X 3 Each is independently selected from halogen, m2+n2≥1, R 1 is selected from C1-C10 alkyl or alkenyl, R 2 Selected from C1-C10 alkylene or alkenylene; Preferably, the general formula of the aromatic hydrocarbon is R 4 -Ph-R 3 , where R 3 and R 4 Each is independently selected from hydrogen, phenyl and C1-C10 alkane.

9. The coordination precipitation polymerization method for olefin polymerization according to claim 1 or 2, characterized in that: The polymerization reaction conditions include: temperature of -50 to 180° C. and time of 10 to 200 min.

10. The polyolefin prepared by the coordination precipitation polymerization method for olefin polymerization according to any one of claims 1 to 9, characterized in that: The polyolefin is spherical or quasi-spherical in shape; Preferably, the average particle size of the polyolefin is 0.02-50 mm.

11. The polyolefin according to claim 10, characterized in that The weight average molecular weight of the polyolefin is 10000-800000; Preferably, the molecular weight distribution index of the polyolefin is ≤10; Preferably, the melting point of the polyolefin is 90-140°C.

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