An ultrahigh molecular weight polyolefin and a method for preparing the same

Abstract

This invention discloses an ultra-high molecular weight polyolefin and its preparation method. The ultra-high molecular weight polyolefin has a weight-average molecular weight higher than 500,000 and a melting point greater than or equal to 100°C. The preparation method includes: polymerizing a non-polar olefin monomer with a polar olefin monomer in the presence of a catalyst composition, a solvent, and a modifier. The catalyst composition includes a main catalyst, wherein the main catalyst is selected from at least one of the metal complexes shown in formula (1). This invention achieves the synthesis of ultra-high molecular weight polyolefins by employing a special catalyst and adjusting the monomer structure.

Description

[0001] This invention belongs to the field of polymers, and particularly relates to olefin polymerization, especially to ultra-high molecular weight polyolefins. Background Technology

[0002] With the ever-increasing demand for lightweight, high-performance materials, the application range of composite materials, especially fiber-reinforced composite materials, is expanding rapidly. Fiber-reinforced composite materials have replaced metal alloys and are widely used in important structural components in the aerospace and automotive fields. Ultra-high molecular weight polyethylene (UHMWPE) fiber, as a third-generation high-performance fiber, possesses advantages such as lightweight, high strength, high modulus, and impact resistance, making it an ideal reinforcing material for polymer-based composite materials. It is widely used in ballistic protection, aerospace, defense, battery separators, transportation, and medical equipment. Although widely accepted in composite material manufacturing, its low surface energy, non-polarity, and inertness limit the application range of UHMWPE. Therefore, surface modification to prepare UHMWPE with excellent surface properties is of great significance.

[0003] Currently, there are two main methods for improving the surface of UHMWPE: physical methods and chemical methods. Physical methods include plasma treatment, corona treatment, and chemical oxidation etching, while chemical methods include chemical grafting. These modification methods mainly aim to improve adhesion by increasing the specific surface area, the number of surface active groups, and surface wettability of UHMWPE. However, in existing technologies, plasma and irradiation methods for modifying fiber surfaces require sophisticated equipment and are not easy to implement in continuous production; chemical oxidation methods require large amounts of strong acids and alkalis, which can easily cause environmental pollution; and polydopamine (PDA) coating methods have disadvantages such as weak inter-PDA (non-covalent) interactions, easy shedding of polar groups, few active groups, and unsatisfactory surface wettability.

[0004] Copolymerization modification refers to the addition of functional comonomers during ethylene polymerization to alter the molecular chain structure and improve its interfacial properties. Pre-transition metal catalysts exhibit poor tolerance to polar groups, while post-transition metal catalysts demonstrate superior tolerance to polar functional groups. However, post-transition metal catalysts suffer from poor thermal stability and inadequate stereochemical control, resulting in polymers with low molecular weights and high branching content, making them unsuitable for fiber materials.

[0005] Therefore, it is necessary to develop a new type of ultra-high molecular weight polyethylene (UHMWPE) material with low production cost, environmental friendliness, structural stability, and high content of surface active groups, so as to expand the application of UHMWPE in the field of high-end composite materials. Summary of the Invention

[0006] To overcome the problems existing in the prior art, this invention provides an ultra-high molecular weight polyolefin and its preparation method. By employing a special catalyst and adjusting the monomer structure, ultra-high molecular weight polyolefins are synthesized.

[0007] One of the objectives of this invention is to provide an ultra-high molecular weight polyolefin with a weight-average molecular weight greater than 500,000 and a melting point greater than or equal to 100°C.

[0008] In a preferred embodiment, the polyolefin comprises the structural unit shown in formula (i), the structural unit shown in formula (ii), and a derivative structure of the optional structural unit shown in formula (ii):

[0009]

[0010] In formula (i), L1'-L4' are each independently selected from H, and C1-C30 alkyl groups with or without substituents; in formula (ii), L1-L3 are each independently selected from H, and C1-C30 alkyl groups with or without substituents, L4 is selected from C1-C30 alkylene groups with or without side groups, and Pg is selected from hydroxyl, carboxyl, carboxylic acid ester, and carboxylate.

[0011] Preferably:

[0012] In formula (i), the substituents in L1'-L4' are selected from nonpolar substituents, preferably from C1-C10 alkyl or C6-C10 aryl; in formula (ii), the substituents in L1-L3 are selected from one or more of halogens, C1-C10 alkyls, C1-C10 alkoxys, C6-C10 aryl, cyano, and hydroxyl; more preferably, the substituents in L1-L3 are selected from one or more of C1-C6 alkyls, halogens, and C1-C6 alkoxys.

[0013] Preferably:

[0014] In formula (ii), the side group in L4 is selected from one of halogen, C6-C20 aryl with or without substituents, C1-C20 alkyl with or without substituents, and C1-C20 alkoxy with or without substituents. Preferably, the substituent is selected from one of halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, and hydroxyl.

[0015] In a preferred embodiment, the molar content of the structural unit represented by formula (ii) in the polyolefin is 0.01 to 20 mol%, preferably 0.01 to 10 mol%, for example, 0.01 mol%, 0.05 mol%, 0.1 mol%, 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, and 8 mol%.

[0016] In this invention, when Pg represents a carboxylate in formula (ii), it is selected from one of group IA, IIA, IIIA or IIB metal carboxylates.

[0017] In a preferred embodiment, the polyolefin is a spherical and / or near-spherical polymer with an average particle size of 0.02 to 50.0 mm, preferably 0.05 to 50.0 mm.

[0018] A second objective of this invention is to provide a method for preparing the ultra-high molecular weight polyolefin described in one objective of this invention, comprising: polymerizing a nonpolar olefin monomer with a polar olefin monomer in the presence of a catalyst composition, a solvent, and a modifier, wherein the catalyst composition includes a main catalyst, and the main catalyst is selected from at least one of the metal complexes shown in formula (1):

[0019]

[0020] In formula (1), R1-R5 are each independently selected from hydrogen, hydrocarbon group, hydrocarbon group, halogen, aryl or aryl group, and R1-R5 are optionally connected to each other in a ring; M is selected from group IVA metals; X is selected from halogen, hydrocarbon group or hydrocarbon group; L is a monovalent anion ligand with a group 15 element as the coordinating atom; m is an integer from 1 to 3.

[0021] In a preferred embodiment, the nonpolar olefin monomer is selected from at least one of the olefin monomers shown in formula (I):

[0022]

[0023] In formula (I), L1'-L4' are each independently selected from H, and from C1-C30 alkyl groups with or without substituents.

[0024] In a further preferred embodiment, in formula (I), L1'-L3' are selected from H, and L4' is selected from one of C1-C10 alkyl groups with or without substituents.

[0025] In a further preferred embodiment, in formula (I), the substituents in L1'-L4' are selected from nonpolar substituents, preferably from C1-C10 alkyl or C6-C10 aryl groups.

[0026] In a preferred embodiment, the polar olefin monomer is selected from at least one of enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters. Preferably, the enol, unsaturated carboxylic acid, and unsaturated carboxylic acid ester are each independently selected from at least one of the monomers shown in formula (II), wherein Pg is selected from hydroxyl, carboxyl, or carboxylic acid ester groups respectively.

[0027]

[0028] In formula (II), L1-L3 are each independently selected from H, and from C1-C30 alkyl groups with or without substituents, and L4 is selected from C1-C30 alkylene groups with or without side groups.

[0029] In a further preferred embodiment, in formula (II), the substituents in L1-L3 are each independently selected from one or more of halogens, C1-C10 alkyl groups, C1-C10 alkoxy groups, C6-C10 aryl groups, cyano groups, and hydroxyl groups; preferably, in formula (II), the substituents in L1-L3 are selected from one or more of C1-C6 alkyl groups, halogens, and C1-C6 alkoxy groups;

[0030] In a further preferred embodiment, in formula (II), the side group in L4 is selected from one of halogen, C6-C20 aryl with or without substituents, C1-C20 alkyl with or without substituents, and C1-C20 alkoxy with or without substituents. Preferably, the substituent is selected from one of halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, and hydroxyl.

[0031] In a preferred embodiment, in formula (II), L1 and L2 are H, L3 is H, a C1-C30 alkyl group with or without substituents, and L4 is a C1-C30 alkylene group with or without side groups; preferably, in formula (II), L1 and L2 are H, L3 is H, a C1-C20 alkyl group with or without substituents, and L4 is a C1-C20 alkylene group with or without side groups.

[0032] In a further preferred embodiment, the side group in L4 is selected from halogens, C6-C20 aryl groups, C1-C20 alkyl groups, hydroxy-substituted C1-C20 alkyl groups, or alkoxy-substituted C1-C20 alkyl groups; preferably, the side group in L4 is selected from halogens, C6-C20 aryl groups, C1-C10 alkyl groups, hydroxy-substituted C1-C10 alkyl groups, and alkoxy-substituted C1-C10 alkyl groups; more preferably, the side group in L4 is selected from halogens, phenyl groups, C1-C6 alkyl groups, and hydroxy-substituted C1-C6 alkyl groups.

[0033] In this invention, examples of the C1-C6 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, and hexyl.

[0034] In this invention, the number of carbon atoms in the alkylene group refers to the number of carbon atoms on the straight chain, excluding the number of carbon atoms on the side groups. For example, isopropylene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group with a side group (methyl).

[0035] In some embodiments of the present invention, the enol is one or more selected from the olefin alcohols represented by formula (II-1):

[0036]

[0037] In formula (II-1), L1-L3 are each independently selected from H, C1-C30 alkyl groups with or without substituents, and L4 is selected from C1-C30 alkylene groups with or without side groups;

[0038] In some embodiments of the present invention, the unsaturated carboxylic acid is one or more selected from the unsaturated carboxylic acids of formula (II-2):

[0039]

[0040] In formula (II-2), L1-L3 are each independently selected from H, and from C1-C30 alkyl groups with or without substituents, and L4 is selected from C1-C30 alkylene groups with or without side groups.

[0041] In some embodiments of the present invention, the unsaturated carboxylic acid ester is selected from one or more of the unsaturated carboxylic acid esters represented by formula (II3):

[0042]

[0043] In formula (II-3), L1-L3 are each independently selected from H, and from C1-C30 alkyl groups with or without substituents, L4 is selected from C1-C30 alkylene groups with or without side groups, and L5 is selected from C1-C30 alkyl groups with or without substituents.

[0044] Preferably, in formula (II-3), L5 is a C1-C20 alkyl group; more preferably, it is a C1-C10 alkyl group, and even more preferably, it is a C1-C6 alkyl group.

[0045] Preferably, in formulas (II-1), (II-2), and (II-3), L1 and L2 are H; L3 is H, a C1-C30 alkyl group with or without substituents, preferably H, a C1-C20 alkyl group with or without substituents, more preferably H, a C1-C10 alkyl group with or without substituents; L4 is a C1-C30 alkylene group with or without side groups, preferably a C1-C20 alkylene group with or without side groups, more preferably a C1-C10 alkylene group with or without side groups, and even more preferably a C1-C6 alkylene group with or without side groups.

[0046] For example, the substituent is selected from halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, cyano or hydroxyl.

[0047] More preferably, in formulas (II-1), (II-2), and (II-3), L1 and L2 are H; L3 is one of H, C1-C10 alkyl, alkyl, or halogen-substituted C1-C10 alkyl, preferably one of H or C1-C10 alkyl; L4 is one of C1-C20 alkylene with or without side groups, preferably a C1-C20 alkylene with side groups, more preferably a C1-C10 alkylene with side groups.

[0048] Most preferably, in formulas (II-1), (II-2), and (II-3), L1 and L2 are H, L3 is H or one of C1-C6 alkyl groups, and L4 is a C1-C10 alkylene group containing a side group.

[0049] In this invention, the number n of carbon atoms in Cn alkylene refers to the number of carbon atoms in the straight chain, excluding the number of carbon atoms in the side groups. For example, isopropylene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene with a side group (methyl).

[0050] In a preferred embodiment, the enol is selected from at least one of the following compounds: 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1,1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2,2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2,4-dimethyl-4-penten-2-ol, 4-enyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5- Hexene, 1-allylcyclohexanol, 2,3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-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-hepten-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.

[0051] In a preferred embodiment, the unsaturated carboxylic acid is selected from at least one of the following compounds: 2-methyl-4-pentenoic acid, 3-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-heptenoic acid, 2-ethyl-6-heptenoic acid, 2-propyl-6-heptenoic acid, 2,3-dimethyl-6-heptenoic acid, 2,4-dimethyl-6-heptenoic acid, 2,2-dimethyl-6-heptenoic acid, 2-isopropyl-5-methyl-6-heptenoic 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-heptenic acid, 2,2-diethyl-6-heptenic acid, 2-methyl-7-octenic acid, 2-ethyl-7-octenic acid, 2-propyl-7-octenic acid, 2,3-dimethyl-7-octenic acid, 2,4-dimethyl-7-octenic acid, 2,2-dimethyl-7-octenic acid, 2-isopropyl-5-methyl-7-octenic acid, 2-isopropyl-7-octenic acid, 2,3,4-trimethyl-7-octenic acid, 2-methyl-2-ethyl-7-octenic acid, 2-(1-methylpropyl)-7-octenic acid, 2,2,3-trimethyl-7-octenic acid, 2,2-diethyl-7-octenic 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.

[0052] In a preferred embodiment, 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-pentanoate, methyl 2-vinyl-4-methyl-4-pentanoate, methyl 2,2-dimethyl-3-butenoate, ethyl 2-hydroxy-2-methyl-3- Methyl butenoate, 2-methyl-3-butenoate isobutyl ester, 2-(1-methylethyl)-3-butenoate ethyl ester, 2,2,3-trimethyl-3-butenoate methyl ester, 2-vinylhexanoate ethyl ester, 2-ethyl-2-methyl-3-butenoate methyl ester, 3-methyl-5-hexenoate methyl ester, 4-methyl-5-hexenoate methyl ester, 4-methyl-5-hexenoate ethyl ester, 2-methyl-6-heptenoate methyl ester, 2,4-dimethyl-5-hexenoate methyl ester, 2-ethyl-5-hexenoate methyl ester, 3-methyl-5-hexenoate methyl ester, 4-methyl-5-hexenoate methyl ester, 2-ethyl-4-pentenoate methyl ester, 2-propyl-4-pentenoate methyl ester, 2-propyl-5- Methyl hexanoate, methyl 2-propyl-4-pentenoate, methyl 2-butyl-5-hexenoate, methyl 3-vinylhexanoate, methyl 2-(2-propen-1-yl)-4-pentanoate, methyl 2-(3-buten-1-yl)-5-hexenoate, methyl 3,3-dimethyl-5-hexenoate, ethyl 3-propyl-5-hexenoate, ethyl 3,3-dimethyl-5-hexenoate, methyl 3,4,4-trimethyl-5-hexenoate, ethyl 3-(1,1-dimethylethyl)-5-hexenoate, ethyl 3-methyl-2-oxo-5-hexenoate, 2-Vinyl-3,3-dimethyl-5-hexanoate, methyl-β-vinylbenzopropionate, methyl 3-methyl-5-hexenoate, methyl 2-propyl-6-heptenoate, methyl 2-methyl-6-heptenoate, ethyl 2-methyl-6-heptenoate, methyl 2,2-dimethyl-6-heptenoate, ethyl 2,4-dimethyl-6-heptenoate, ethyl 2-propyl-6-heptenoate, ethyl 2,2-dimethyl-6-heptenoate, 1,3-dimethyl 2-(4-penten-1-yl)malonic acid, 6-heptenoic acid-2-methyl-1,1-Dimethyl ethyl 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, allyl malonate diethyl ester, allyl malonate dimethyl ester, allyl succinic anhydride, 2-methyl-4-pentenoic acid ethyl ester, 2-methyl-4-pentenoic acid methyl ester, 3- Methyl methyl-4-pentenoate, methyl 3-ethyl-4-pentenoate, isobutyl 3-methyl-4-pentenoate, ethyl 2-(tert-butyl)-4-pentenoate, 3-allyl dihydrofuran-2(3H)-one, methyl 2-(dimethylamino)-2-methylpent-4-enoate, methyl 3-methyl-4-pentenoate, methyl 2-methyl-5-hexenoate, methyl 2,2-dimethyl-5-hexenoate, ethyl 2,2-dimethyl-5-hexenoate, benzyl 2-methyl-5-hexenoate, methyl 4,4-dimethyl-6-heptenoate, methyl 2,4-dimethyl-9-decenoate.

[0053] In a preferred embodiment, the main catalyst is selected from at least one of the transition metal complexes shown in formula (2) and formula (3), preferably from at least one of the transition metal complexes shown in formula (2):

[0054]

[0055] In formula (2), R1-R7 are each independently selected from hydrogen, C1-C30 hydrocarbon groups or halogens, preferably from C1-C20 alkyl groups, C2-C20 alkenyl groups or halogens, and R1-R5 are optionally linked to each other in a ring; X1 is selected from halogens, C1-C6 alkyl groups or benzyl groups; M is selected from titanium, zirconium or hafnium.

[0056] In equation (3), R1~R5, R7~R 11 Each R1 to R5 is independently selected from hydrogen, C1-C30 hydrocarbon groups, preferably from C1-C20 alkyl groups, C2-C20 alkenyl groups, or halogens; R1 to R5 are optionally linked in pairs to form a ring; R 7 ~R 11 Optionally, they are linked together in pairs to form a ring; M is selected from titanium, zirconium, or hafnium; X1 is selected from oxygen, sulfur, alkylene group, or alkyleneoxy group; X2 and X3 are each independently selected from halogen, C1-C6 alkyl, or benzyl.

[0057] In a further preferred embodiment, the main catalyst is selected from at least one of the complexes shown in formula (2A):

[0058]

[0059] In equation (2A), R6, R7, R 11 -R 17 Each is independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, or halogen, and R 11 -R 17 Optionally, they are linked together in pairs to form a ring; X1 is selected from halogen, C1-C6 alkyl or benzyl, and M is selected from titanium, zirconium or hafnium.

[0060] In a preferred embodiment, the catalyst composition further includes an auxiliary agent selected from at least one of organoaluminum compounds, organoboron compounds, and organosilicon compounds, preferably from at least one of organoaluminum compounds and organoboron compounds.

[0061] In a preferred embodiment, the organoaluminum compound is selected from alkylaluminoxanes or compounds with the general formula AlR. n X 1 3-n Organoaluminum compounds; general formula AlR n X 1 3-n In this context, R represents H and C1-C. 20 Saturated or unsaturated hydrocarbon groups or C1-C 20 Saturated or unsaturated hydroxyl groups, preferably C1-C 20 Alkyl, C1-C 20 Alkoxy, C7-C 20 Aryl or C6-C 20 Aryl; X 1 It is a halogen, preferably chlorine or bromine; 0 <n≤3;

[0062] In a further preferred embodiment, the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, dichloroethylaluminum, methylaluminoxane (MAO), and modified methylaluminoxane (MMAO); more preferably, the organoaluminum compound is methylaluminoxane (MAO).

[0063] In a preferred embodiment, the organoboron compound is selected from at least one of aromatic boron and borate; preferably, the aromatic boron is selected from substituted or unsubstituted phenylboron, preferably tris(pentafluorophenyl)boron; and / or, the borate is selected from at least one of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate and triphenylmethyl tetra(pentafluorophenyl)borate.

[0064] In a preferred embodiment, the organosilicon compound is selected from the general formula SiR. m X n The alkylsilicon compound shown has the general formula SiR m X n In this context, R is selected from C1-C10 alkyl groups, repeated R may be the same or different, X is selected from halogens, m≥1, and m+n=4.

[0065] In a preferred embodiment, the organosilicon compound is selected from the general formula SiR. m X n The alkylsilane compound shown has the general formula SiR m X n In this context, R is selected from C1-C10 alkyl groups, repeated R may be the same or different, X is selected from halogens, m≥1, and m+n=4;

[0066] In a further preferred embodiment, the organosilicon compound is selected from at least one of trimethylchlorosilane, dichlorodimethylsilane, propyldimethylchlorosilane, dichloroethylmethylsilane, tert-butyldimethylchlorosilane, diisopropylchlorosilane, trichloroethylsilane, chloromethyldimethylchlorosilane, ditert-butylchlorosilane, dichloro(methyl)propylsilane, methyltrichlorosilane, and trichloroethylsilane.

[0067] In a preferred embodiment, the ratio of the total molar amount of aluminum, boron, and silicon in the additive to the molar amount of M in the main catalyst is (10-11000000):1, preferably (10-200000):1.

[0068] In a further preferred embodiment, when the additive contains an organoaluminum compound, the molar ratio of aluminum in the organoaluminum compound to M in the catalyst is (10-10000000):1, preferably (10-100000):1, and more preferably (100-10000):1.

[0069] For example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, or 10000000:1 or any value in between.

[0070] In a further preferred embodiment, when the auxiliary contains an organoboron compound, the molar ratio of boron in the organoboron compound to M in the catalyst is (0.1-1000):1, preferably (0.1-500):1.

[0071] For example, when the auxiliary contains an organoboron compound, the molar ratio of boron in the organoboron compound to M in the catalyst is 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, 500:1, 700:1, 800:1, 1000:1, and any value between them.

[0072] In a further preferred embodiment, when the additive contains an organosilicon compound, the molar ratio of silicon in the organosilicon compound to M in the catalyst is (10-10000000):1, preferably (10-200000):1.

[0073] In a preferred embodiment, the solvent is selected from hydrocarbon solvents.

[0074] In a further preferred embodiment, the hydrocarbon solvent is selected from one or more of C3-C20 alkanes or aromatics, preferably from one or more of C3-C10 alkanes.

[0075] For example, the solvent may be selected from one or more of butane, isobutane, pentane, hexane, heptane, and octane.

[0076] In a preferred embodiment, the modifier is selected from at least one of haloalkanes, organic paraffins, and aromatic organic solvents.

[0077] In a further preferred embodiment, the haloalkane is selected from formula R 1 X 2 n2 R 2 X 3 m2 At least one of the compounds shown, wherein X 2 X 3 Each is independently selected from halogens, m2+n2≥1, R 1 Selected from C1-C10 alkyl or alkenyl groups, R 2 Selected from C1-C10 alkylene or alkenylene groups; and / or, the aromatic organic solvent is selected from R 4 -Ph-R 3 Where Ph represents a benzene ring, and R 3 R 4 Each is independently selected from alkanes, phenyl groups, or hydrogens from C1 to C10.

[0078] In a further preferred embodiment, the haloalkane is selected from at least one of chloroform, dichloromethane, dichloroethane, dichloropropane, and trichloroethylene; and / or, the aromatic organic solvent is selected from at least one of pentylbenzene, ethylbenzene, xylene, toluene, and benzene.

[0079] In a preferred embodiment, the volume ratio of the solvent to the modifier is 1:100 to 100:1, preferably 1:20 to 20:1, more preferably (1 to 20):1, for example (3 to 10):1.

[0080] For example, when the raw material contains the modifier, the volume ratio of the solvent to the modifier is 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 14:1, 16:1, 18:1 or 20:1.

[0081] When the raw material contains a modifier, the yield of spherical polymers can be significantly improved.

[0082] In a preferred embodiment, the total concentration of the nonpolar olefin monomer and the polar olefin monomer in the raw material is 0.01-6000 mmol / L, preferably 0.1-1000 mmol / L, and more preferably 1-500 mmol / L.

[0083] For example, the concentrations of the nonpolar olefin monomer and the polar olefin monomer in the polymerization system can be 1 mmol / L, 10 mmol / L, 20 mmol / L, 30 mmol / L, 50 mmol / L, 70 mmol / L, 90 mmol / L, 100 mmol / L, 200 mmol / L, 300 mmol / L, 400 mmol / L, or 500 mmol / L, or any value between them.

[0084] In a preferred embodiment, based on 100% of the total molar amount of the nonpolar olefin monomer and the polar olefin monomer, the molar amount of the polar olefin monomer is 0.01 to 20 mol%, preferably 0.01 to 10 mol%.

[0085] In a preferred embodiment, the concentration of the main catalyst in the raw material is 0.00001-100 mmol / L, preferably 0.0001-1 mmol / L, and more preferably 0.001-0.5 mmol / L.

[0086] For example, the concentration of the catalyst in the polymerization system can be 0.00001 mmol / L, 0.00005 mmol / L, 0.0001 mmol / L, 0.0005 mmol / L, 0.001 mmol / L, 0.005 mmol / L, 0.01 mmol / L, 0.05 mmol / L, 0.1 mmol / L, 0.2 mmol / L, 0.3 mmol / L, 0.4 mmol / L, 0.5 mmol / L, 0.8 mmol / L, 1 mmol / L, 5 mmol / L, 8 mmol / L, 10 mmol / L, 20 mmol / L, 30 mmol / L, 50 mmol / L, 70 mmol / L, 80 mmol / L, or 100 mmol / L, or any value between them.

[0087] In a preferred embodiment, the polymerization conditions include: a polymerization temperature of -50°C to 180°C, preferably -20°C to 100°C, more preferably 20°C to 100°C, for example, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, and any value between them; and / or a reaction time of 10 to 200 min, preferably 20 to 60 min, for example, 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 150 min, or 200 min.

[0088] In this invention, there is no particular limitation on the reaction pressure, as long as it allows the monomers to undergo coordination copolymerization. When the olefin is ethylene, from the perspective of reducing costs and simplifying the polymerization process, the pressure of ethylene in the reactor is preferably 1 to 1000 atm, more preferably 1 to 200 atm, and even more preferably 1 to 50 atm.

[0089] According to a preferred embodiment of the present invention, the reaction is carried out under anhydrous and oxygen-free conditions.

[0090] A third objective of this invention is to provide a polyolefin obtained by the preparation method described in the second objective of this invention.

[0091] In a preferred embodiment, the polyolefin is spherical or near-spherical, and the average particle size of the spherical and / or near-spherical polymer is 0.02 to 50.0 mm, preferably 0.05 to 50.0 mm, for example, it can be 0.02 mm, 0.05 mm, 0.1 mm, 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, 3.0 mm, 5.0 mm, 8.0 mm, 10.0 mm, 15.0 mm, 20.0 mm, 25.0 mm, 30.0 mm, 35.0 mm, 40.0 mm, 45.0 mm, 50.0 mm and any value between them, preferably 0.2 to 20.0 mm.

[0092] In a preferred embodiment, the polymer has a melting point greater than or equal to 100°C, preferably 100-140°C, for example 100°C, 105°C, 110°C, 120°C, 125°C, 130°C, 135°C and any value between them.

[0093] In a preferred embodiment, the polyolefin has a weight-average molecular weight greater than 500,000.

[0094] In a further preferred embodiment, the weight-average molecular weight of the polymer is 500,000 to 10,000,000, preferably 500,000 to 8,000,000, and more preferably 500,000 to 5,000,000.

[0095] In this invention:

[0096] Alkyl groups refer to straight-chain alkyl groups, branched alkyl groups, or cycloalkyl groups. For example, C1-C 20 Alkyl refers to C1-C 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl or C6-C 20 Aryl. Examples of straight-chain or branched alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl; C3-C 20 Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl; C6-C 20 Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, and vinylphenyl.

[0097] Alkenyl groups refer to straight-chain alkenyl groups, branched alkenyl groups, or cycloalkenyl groups. For example, C2-C... 20 Alkenyl refers to C1-C20 Straight-chain alkenyl, C3-C 20 Branched alkenyl or C3-C 20 Cycloalkenyl groups. Examples of alkenyl groups include, but are not limited to: vinyl, allyl, and butenyl.

[0098] C7-C 20 Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl-tert-butyl.

[0099] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of various ranges, the endpoint values ​​of various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0100] Compared with the prior art, the present invention has the following beneficial effects:

[0101] (1) This invention can prepare polyolefins with extremely high polarity and ultra-high molecular weight. However, the existing technology of copolymerizing non-polar olefin monomers (such as ethylene) with polar olefin monomers using transition metal complexes produces polar polyethylene with low weight average molecular weight, or hyperbranched polar polyethylene. There are no reports on crystalline, ultra-high molecular weight polyethylene with high melting point (melting point ≥ 100℃).

[0102] (2) The technical problem solved by the present invention is to prepare high polarity and ultra-high molecular weight polyethylene by selecting appropriate transition metal complexes to catalyze the copolymerization of non-polar olefin monomers (such as ethylene) with polar olefin monomers.

[0103] (3) Further, in the method of the present invention, by selecting the transition metal complex, olefin monomer and suitable reaction conditions, high polarity and ultra-high molecular weight polyethylene with good particle morphology is directly prepared.

[0104] (4) It can eliminate the catalyst loading process and realize the self-forming preparation of olefin polymers with good particle morphology by homogeneous catalyst polymerization. Detailed Implementation

[0105] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0106] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0107] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0108] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0109] The analytical and characterization instruments used in this invention are as follows:

[0110] The polymer was washed with a dilute acid solution before measurement to ensure that the metal content in the polymer was ≤50ppm.

[0111] 1. Nuclear magnetic resonance spectrometer: Bruker DMX 300 (300MHz), tetramethylsilicon (TMS) as internal standard, used to test the structure of complex ligands at 25℃.

[0112] 2. Comonomer content of the copolymer (derived from the structural unit shown in formula G): using... 13 The analysis was performed using C NMR spectroscopy on a 400MHz Bruker Avance 400 NMR spectrometer, with a 10mm PASEX 13 probe, at 130°C by dissolving the polymer sample in deuterated tetrachloroethane.

[0113] 3. Molecular weight and molecular weight distribution PDI (PDI = Mw / Mn): The molecular weight and molecular weight distribution of the polymer were determined using a PL-GPC220 with trichlorobenzene as the solvent at 150℃ (standard: PS, flow rate: 1.0 mL / min, column: 3×Plgel 10um M1×ED-B 300×7.5nm).

[0114] 4. Activity measurement method: gravimetric analysis. Activity is expressed as polymer weight (g) / metal complex (mol) × 2.

[0115] Example 1

[0116]

[0117] The synthesis of complex A is described in reference Chem. Commun., 2004, 876–877. Complex A was obtained by reacting compound 1 with an equimolar amount of Cp*TiCl3 for 72 h, with a yield of 90%. 1 HNMR:δ H (400MHz, CDCl3)6.48(2H,s,NCH),2.09(15H,s,CCH3);1.66(18H,s,CCH3).δ C (400MHz, CDCl3)145.8(s,NCN),125.9(s,C5Me5),109.6(NCH),58.8(CMe),29.9(CMe), 12.9(C5Me5).

[0118] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of n-pentane, 50 mL of dichloromethane, 30 mmol (6.0 mL) of 2,6-dimethyl-7-octen-2-ol, 36 mL of AliBu3 (1.0 mol / L n-pentane solution), and 3.5 mL of MAO (1.53 mol / L toluene solution) were added to the polymerization system, along with 2.2 mg (5 μmol) of complex A. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 8.72 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a weight-average molecular weight of 693,000, a molecular weight distribution of 4.13, a hydroxyl content of 0.73 mol%, a melting point of 134.2 °C, an average particle size of spherical polymers of 3.10 mm, and a yield of spherical polymers of 60%.

[0119] Example 2

[0120] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of hexane, 100 mL of 1,2-dichloroethane, 30 mmol (4.0 mL) of 3,3-dimethyl-4-pentenoic acid, 36 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 2.2 mg (5 μmol) of complex A. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 6.27 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a molecular weight of 674,000, a molecular weight distribution of 4.21, a carboxyl content of 0.77 mol%, a melting point of 133.6 °C, an average particle size of 2.70 mm for spherical polymers, and a yield of 63% for spherical polymers.

[0121] Example 3

[0122] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 450 mL of hexane, 50 mL of 2,2-dichloropropane, 50 mmol (6.7 mL) of 3,3-dimethyl-4-pentenoic acid, 62 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 2.2 mg (5 μmol) of complex A. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 5.32 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a molecular weight of 679,000, a molecular weight distribution of 4.34, a carboxyl content of 1.21 mol%, a melting point of 125.2 °C, an average particle size of spherical polymers of 2.90 mm, and a yield of spherical polymers of 69%.

[0123] Example 4

[0124] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. 4.0 mL of heptane, 500 μL of dichloromethane, 50 μL (0.31 mmol) of methyl 3,3-dimethyl-4-pentenoate, 160 μL of AliBu3 (95%), and 60.0 μL (1.0 mmol / L toluene solution) of triphenylmethyl tetratetra(pentafluorophenyl)borate were added to the polymerization system. 50 μL (1.0 mmol / L toluene solution) of complex A was added, and the reaction was carried out at 30 °C with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 1.82 × 10⁻⁶. 6 g·mol -1 ·h -1 The weight-average molecular weight is 637,000, the molecular weight distribution is 4.47, the polymerization melting point is 135.4℃, and the ester molar content in the polymer is 0.61%. The average particle size of the near-spherical polymer is 0.65 mm, and the yield of the spherical polymer is 60%.

[0125] Example 5

[0126] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400mL of hexane, 100mL of chlorocyclohexane, 50mmol (6.7mL) of 3,3-dimethyl-4-pentenoic acid, 62mL of AliBu3 (1.0mol / L hexane solution), and 4.8mg (6.0μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 2.2mg (5μmol) of complex A. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 minutes to obtain the polymer. Without hydrochloric acid acidification, it was found to be ultra-high molecular weight polyethylene containing aluminum carboxylate groups, with a polymerization activity of 4.84 × 10⁻⁶. 5 g·mol -1 ·h -1 The polymer was treated again with hydrochloric acid and ethanol, and washed three times with ethanol. The resulting polymer had a weight-average molecular weight of 607,000, a polymerization melting point of 126.2℃, and a carboxyl molar content of 1.20%. The average particle size of the near-spherical polymer was 2.90 mm, and the yield of the spherical polymer was 68%.

[0127] Example 6

[0128]

[0129] The synthesis of complex B is described in reference Chem. Commun., 2004, 876–877. Complex B was obtained by reacting compound 1 with an equimolar amount of InTiCl3 for 72 h, with a yield of 88%. 1 HNMR:δ H (400MHz, CDC13)7.70(2H,dd,J=4.0),7.32(2H,dd,J=4.0),6.88(1H,t,t=4.0),6.52(2H,s,NCH),6.40(2H,d,J=4.4),1.75(18H,s,CCH3).δ C (400MHz, CDCl3)128.7,128.4, 126.0,125.3,125.1,115.8,112.2,109.6(NCH),106.5,59.0,29.7,29.4.

[0130] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 2 hours, and then evacuated while hot and purged three times with N2 gas. 400mL of hexane, 100mL of dichloromethane, 30mmol (4.1mL) of 3-methyl-5-hexen-3-ol, 32mL of AliBu3 (1.0mol / L hexane solution), and 4.8mg (6.0μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added, along with 2.1mg (5μmol) of complex B. The reaction was carried out at 30℃ with a 10atm ethylene pressure and vigorous stirring for 30min. The mixture was neutralized with 10wt% hydrochloric acid-acidified ethanol solution to obtain the polymer, with a polymerization activity of 7.34×10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight was 638,000, the molecular weight distribution was 3.37, the molar content of hydroxyl monomers was 0.84%, the average particle size of the spherical polymers was 3.3 mm, and the yield of spherical polymers was 69%.

[0131] Example 7

[0132] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. 3.0 mL of heptane, 1.0 mL of dichloromethane, 0.5 mL (2.66 mmol) of 2,6-dimethyl-7-octen-2-ol, 1.0 mL of AliBu3 (95%), and 60.0 μL (1.0 mmol / L toluene solution) of triphenylmethyl tetra(pentafluorophenyl)borate were added to the polymerization system. 50 μL (1.0 mmol / L toluene solution) of complex B was added, and the reaction was carried out at 30 °C with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 4.37 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight is 1.245 million, the molecular weight distribution is 14.1%, the polymerization melting point is 132.3℃, and the molar content of hydroxyl monomers is 1.65%. The average particle size of the near-spherical polymer is 1.00 mm, and the yield of the spherical polymer is 68%.

[0133] Example 8

[0134] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of n-pentane, 50 mL of dichloromethane, 30 mmol (6.0 mL) of 2,6-dimethyl-7-octen-2-ol, 36 mL of AliBu3 (1.0 mol / L n-pentane solution), and 3.5 mL of MAO (1.53 mol / L toluene solution) were added to the polymerization system, along with 2.1 mg (5 μmol) of complex B. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 7.87 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a weight-average molecular weight of 894,000, a molecular weight distribution of 5.41, a hydroxyl content of 0.65 mol%, a melting point of 135.9 °C, an average particle size of spherical polymers of 3.40 mm, and a yield of spherical polymers of 69%.

[0135] Example 9

[0136] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. 3.0 mL of heptane, 1.0 mL of dichloromethane, 0.20 g (1.17 mmol) of 2,2-dimethyl-7-octenic acid, 450 μL of AliBu3 (95%), and 60.0 μL (1.0 mmol / L toluene solution) of triphenylmethyl tetra(pentafluorophenyl)borate were added to the polymerization system. 50 μL (1.0 mmol / L toluene solution) of complex B was added, and the reaction was carried out at 30 °C with an ethylene pressure of 20 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 5.27 × 10⁻⁶. 6 g·mol -1 ·h -1 The viscosity-average molecular weight was 4.78 million, the polymerization melting point was 134.5℃, and the carboxyl molar content was 0.32%, as measured by ASTM D4020-2018. The average particle size of the near-spherical polymer was 0.73 mm, and the yield of the spherical polymer was 70%.

[0137] Example 10

[0138] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 2 hours, and then evacuated while hot and purged three times with N2 gas. 450 mL of heptane, 50 mL of dichloroethane, 30 mmol (4.0 mL) of 2,2-dimethyl-4-pentenoic acid, 30 mL of AlEt3 (1.0 mol / L hexane solution), 0.6 mL of AlEt3 (1.0 mol / L heptane solution), and 3.1 mg (6.0 μmol) of tris(pentafluorophenyl)borane were added to the polymerization system, along with 2.1 mg (5 μmol) of complex B. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 7.43 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight was 1.822 million, the molecular weight distribution was 5.1, the carboxyl molar content was 0.67%, the average particle size of the spherical polymers was 3.2 mm, and the yield of spherical polymers was 68%.

[0139] Example 11

[0140] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. 3.0 mL of heptane, 1.0 mL of dichloromethane, 50 μL (0.31 mmol) of methyl 3,3-dimethyl-4-pentenoate, 160 μL of AliBu3 (95%), and 60.0 μL (1.0 mmol / L toluene solution) of triphenylmethyl tetratetra(pentafluorophenyl)borate were added to the polymerization system. 50 μL (1.0 mmol / L toluene solution) of complex B was added, and the reaction was carried out at 30 °C with an ethylene pressure of 15 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 1.65 × 10⁻⁶. 6 g·mol -1 ·h -1 The weight-average molecular weight is 1.276 million, the molecular weight distribution is 3.82, the polymerization melting point is 134.9℃, and the ester molar content in the polymer is 0.57%. The average particle size of the near-spherical polymer is 0.87 mm, and the yield of the spherical polymer is 65%.

[0141] Example 12

[0142] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. The polymerization system was then injected with 3.5 mL of heptane, 500 μL of carbon tetrachloride, 100 μL (0.58 mmol) of methyl 2-isopropyl-4-pentenoate, 220 μL of AliBu3 (95%), 60 μL (1.0 mmol / L toluene solution) of tris(pentafluorophenyl)borane, and 12.5 μL (0.01 mol / L toluene solution) of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate. Simultaneously, 50 μL (1.0 mmol / L toluene solution) of complex B was added. The reaction was carried out at 30 °C with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with 10 wt% hydrochloric acid-acidified ethanol solution to obtain the polymer. The polymerization activity was 6.72 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a molecular weight of 653,000 and a molecular weight distribution of 3.46. NMR analysis revealed that the unsaturated carboxylic acid ester content in the polymer was 0.85 mol%, the polymer melting point was 133.4℃, and the particle size of the spherical polymer was 0.89 mm. The yield of the spherical polymer was 65%.

[0143] Example 13

[0144]

[0145] For the synthesis of complex C, refer to Dalton Trans., 2006, 459–467.

[0146] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of hexane, 100 mL of chlorocyclohexane, 30 mmol (6.0 mL) of 2,6-dimethyl-7-octen-2-ol, 36 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 2.9 mg (5 μmol) of complex C. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 3.24 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a molecular weight of 1.186 million, a molecular weight distribution of 5.10, a hydroxyl content of 0.78 mol%, a melting point of 133.8℃, an average particle size of 1.72 mm for the near-spherical polymer, and a yield of 60% for the spherical polymer.

[0147] Example 14

[0148] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of hexane, 100 mL of dichloroethane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenic acid, 36 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 2.9 mg (5 μmol) of complex C. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 4.36 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a molecular weight of 757,000, a molecular weight distribution of 6.44, a carboxyl content of 0.73 mol%, a melting point of 134.7 °C, and an average particle size of 1.93 mm for the spherical polymers. The yield of the spherical polymers was 62%.

[0149] Example 15

[0150] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. 3.5 mL of heptane, 500 μL of dichloromethane, 100 μL (0.58 mmol) of isobutyl 2-methyl-3-butenoate, 230 μL of AliBu3 (95%), and 60.0 μL (1.0 mmol / L toluene solution) of triphenylmethyl tetra(pentafluorophenyl)borate were added to the polymerization system. 50 μL (1.0 mmol / L toluene solution) of complex C was added, and the reaction was carried out at 30 °C with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 3.12 × 10⁻⁶. 5 g·mol -1 ·h -1 The weight-average molecular weight is 1.075 million, the molecular weight distribution is 6.52, the polymerization melting point is 132.8℃, and the ester molar content in the polymer is 0.64%. The average particle size of the near-spherical polymer is 0.65 mm. The yield of the spherical polymer is 60%.

[0151] Example 16

[0152]

[0153] For the synthesis of complex D, refer to Organometallics, 1998, 17, 2152-2154.

[0154] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of n-heptane, 100 mL of dichloroethane, 30 mmol (6.0 mL) of 2,6-dimethyl-7-octen-2-ol, 36 mL of AliBu3 (1.0 mol / L n-pentane solution), and 3.5 mL of MAO (1.53 mol / L toluene solution) were added to the polymerization system, along with 2.2 mg (5 μmol) of complex D. The reaction was carried out at 30℃ with an ethylene pressure of 15 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 7.05 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a molecular weight of 504,000, a molecular weight distribution of 5.12, a hydroxyl content of 0.79 mol%, and an average particle size of 3.82 mm for the obtained spherical polymer. The yield of the spherical polymer was 60%.

[0155] Example 17

[0156] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of hexane, 100 mL of dichloromethane, 30 mmol (5.10 g) of 2,2-dimethyl-7-octenic acid, 36 mL of AliBu3 (1.0 mol / L hexane solution), and 4.8 mg (6.0 μmol) of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate were added to the polymerization system, along with 2.2 mg (5 μmol) of complex D. The reaction was carried out at 30℃ with an ethylene pressure of 15 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 8.13 × 10⁻⁶. 5 g·mol -1 ·h -1 The obtained polymer had a molecular weight of 763,000, a molecular weight distribution of 5.54, a carboxyl content of 0.54 mol%, a melting point of 132.5℃, an average particle size of 2.47 mm for spherical polymers, and a yield of 62% for spherical polymers.

[0157] Example 18

[0158] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. 3.0 mL of heptane, 1.0 mL of dichloromethane, 100 μL (0.58 mmol) of isobutyl 2-methyl-3-butenoate, 230 μL of AliBu3 (95%), and 60.0 μL (1.0 mmol / L toluene solution) of triphenylmethyl tetratetra(pentafluorophenyl)borate were added to the polymerization system. 50 μL (1.0 mmol / L toluene solution) of complex D was added, and the reaction was carried out at 30 °C with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 1.82 × 10⁻⁶. 6 g·mol -1 ·h -1 The weight-average molecular weight is 632,000, the molecular weight distribution is 6.34, the polymerization melting point is 129.3℃, and the ester molar content in the polymer is 0.72%. The average particle size of the near-spherical polymer is 0.62 mm. The yield of the spherical polymer is 59%.

[0159] Comparative Example 1

[0160] A 1L stainless steel polymerization reactor equipped with a mechanical stirrer was continuously dried at 130℃ for 6 hours, and then evacuated while hot and purged three times with N2 gas. 400 mL of heptane, 100 mL of dichloroethane, 30 mmol (6.0 mL) of 2,6-dimethyl-7-octen-2-ol, 36 mL of AliBu3 (1.0 mol / L n-pentane solution), and 3.5 mL of MAO (1.53 mol / L toluene solution) were added to the polymerization system. Simultaneously, 2.3 mg (5 μmol) of the complex 3-(2-(methylthio)ethylimino)-1,3-diphenylpropenol-titanium trichloride (synthesis reference: Macromolecules 2013, 46, 2870-2875) was added. The reaction was carried out at 30℃ with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with 10 wt% hydrochloric acid-acidified ethanol solution to obtain the polymer. The polymerization activity was 3.64 × 10⁻⁶. 5 g·mol -1 ·h -1 The resulting polymer had a molecular weight of 348,000 and a molecular weight distribution of 4.49.

[0161] Comparative Example 2

[0162] A 7 mL stainless steel glass-lined polymerization reactor equipped with a mechanical stirrer was continuously dried at 130 °C for 2 h, and then evacuated while hot and purged three times with N2 gas. 3.0 mL of heptane, 500 μL of dichloromethane, 70 μL (0.31 mmol) of methyl 10-undecenoate, 160 μL of AliBu3 (95%), and 60.0 μL (1.0 mmol / L toluene solution) of triphenylmethyl tetratetra(pentafluorophenyl)borate were added to the polymerization system. 50 μL (1.0 mmol / L toluene solution) of complex A was added, and the reaction was carried out at 30 °C with an ethylene pressure of 10 atm and stirred for 30 min. Finally, the mixture was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain the polymer. The polymerization activity was 1.65 × 10⁻⁶. 6 g·mol -1 ·h -1 It has a weight-average molecular weight of 484,000, a molecular weight distribution of 3.73, a polymerization melting point of 113.2℃, and an ester molar content of 0.54%. It is a non-spherical polymer.

[0163] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. An ultra-high molecular weight polyolefin having a weight-average molecular weight greater than 500,000 and a melting point greater than or equal to 100°C; The preparation method of the ultra-high molecular weight polyolefin includes: The nonpolar olefin monomer is polymerized with a polar olefin monomer in the presence of a catalyst composition, a solvent, and a modifier, wherein the catalyst composition includes a main catalyst, and the main catalyst is selected from at least one of the metal complexes shown in formula (1): In formula (1), R1-R5 are each independently selected from hydrogen, hydrocarbon group, hydrocarbon group, halogen, aryl or aryl group, and R1-R5 are optionally connected to each other in a ring; M is selected from group IVA metals; X is selected from halogen, hydrocarbon group or hydrocarbon group; L is a monovalent anion ligand with a group 15 element as the coordinating atom; m is an integer from 1 to 3. The polar olefin monomer is selected from at least one of enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters, wherein each of the enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters is independently selected from at least one of the monomers shown in formula (II), wherein Pg is selected from hydroxyl, carboxyl, or carboxylic acid esters respectively: In formula (II), L1-L3 are each independently selected from H, C1-C30 alkyl groups with or without substituents, and L4 is selected from C1-C30 alkylene groups with side groups; The modifier is selected from at least one of haloalkanes, organic paraffins, and aromatic organic solvents, and the solvent is selected from hydrocarbon solvents.

2. The ultra-high molecular weight polyolefin according to claim 1, characterized in that, The polyolefin includes the structural unit shown in formula (i), the structural unit shown in formula (ii), and derivative structures of the optional structural unit shown in formula (ii): In formula (i), L1'-L4' are each independently selected from H, and C1-C30 alkyl groups with or without substituents; in formula (ii), L1-L3 are each independently selected from H, and C1-C30 alkyl groups with or without substituents, L4 is selected from C1-C30 alkylene groups with or without side groups, and Pg is selected from hydroxyl, carboxyl, carboxylic acid ester, and carboxylate.

3. The ultra-high molecular weight polyolefin according to claim 2, characterized in that, In formula (i), the substituents in L1'-L4' are selected from nonpolar substituents; and / or, In formula (ii), the side group in L4 is selected from one of the following: halogen, C6-C20 aryl with or without substituents, C1-C20 alkyl with or without substituents, and C1-C20 alkoxy with or without substituents; and / or, When Pg represents a carboxylate in formula (ii), it is selected from one of the metal carboxylate groups IA, IIA, IIIA or IIB.

4. The ultra-high molecular weight polyolefin according to claim 2, characterized in that, In formula (i), the substituents in L1'-L4' are selected from C1-C10 alkyl or C6-C10 aryl; in formula (ii), the substituents in L1-L3 are selected from one or more of halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, cyano, and hydroxyl; and / or, In formula (ii), the side group in L4 is selected from one of halogen, C6-C20 aryl with or without substituents, C1-C20 alkyl with or without substituents, and C1-C20 alkoxy with or without substituents, wherein the substituent is selected from one of halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, and hydroxyl.

5. The ultra-high molecular weight polyolefin according to any one of claims 1 to 4, characterized in that, The molar content of the structural unit represented by formula (ii) in the polyolefin is 0.01 to 20 mol%; and / or, The polyolefin is a spherical and / or near-spherical polymer with an average particle size of 0.02 to 50.0 mm.

6. The ultra-high molecular weight polyolefin according to claim 5, characterized in that, The molar content of the structural unit represented by formula (ii) in the polyolefin is 0.01 to 10 mol%; and / or, The polyolefin is a spherical and / or near-spherical polymer with an average particle size of 0.05 to 50.0 mm.

7. A method for preparing the ultra-high molecular weight polyolefin according to any one of claims 1-6, comprising: The nonpolar olefin monomer is polymerized with a polar olefin monomer in the presence of a catalyst composition, a solvent, and a modifier, wherein the catalyst composition includes a main catalyst, and the main catalyst is selected from at least one of the metal complexes shown in formula (1): In formula (1), R1-R5 are each independently selected from hydrogen, hydrocarbon group, hydrocarbon group, halogen, aryl or aryl group, and R1-R5 are optionally connected to each other in a ring; M is selected from group IVA metals; X is selected from halogen, hydrocarbon group or hydrocarbon group; L is a monovalent anion ligand with a group 15 element as the coordinating atom; m is an integer from 1 to 3. The polar olefin monomer is selected from at least one of enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters, wherein each of the enols, unsaturated carboxylic acids, and unsaturated carboxylic acid esters is independently selected from at least one of the monomers shown in formula (II), wherein Pg is selected from hydroxyl, carboxyl, or carboxylic acid esters respectively: In formula (II), L1-L3 are each independently selected from H, C1-C30 alkyl groups with or without substituents, and L4 is selected from C1-C30 alkylene groups with side groups; The modifier is selected from at least one of haloalkanes, organic paraffins, and aromatic organic solvents, and the solvent is selected from hydrocarbon solvents.

8. The preparation method according to claim 7, characterized in that, The nonpolar olefin monomer is selected from at least one of the olefin monomers shown in formula (I): In formula (I), L1'-L4' are each independently selected from H, and from C1-C30 alkyl groups with or without substituents.

9. The preparation method according to claim 8, characterized in that, In formula (I), L1'-L3' are selected from H, and L4' is selected from one of C1-C10 alkyl groups with or without substituents; and / or, In formula (II), the side group in L4 is selected from one of halogen, C6-C20 aryl with or without substituents, C1-C20 alkyl with or without substituents, and C1-C20 alkoxy with or without substituents.

10. The preparation method according to claim 7, characterized in that, The main catalyst is selected from at least one of the transition metal complexes shown in formula (2) and formula (3): In formula (2), R1-R7 are each independently selected from hydrogen, C1-C30 hydrocarbon groups or halogens; M is selected from titanium, zirconium or hafnium; In equation (3), R1~R5, R7~R 11 Each is independently selected from hydrogen or C1-C30 hydrocarbon groups; R1 to R5 are optionally linked in pairs to form a ring; R 7 ~R 11 Optionally, they are linked together in pairs to form a ring; M is selected from titanium, zirconium, or hafnium; X1 is selected from oxygen, sulfur, alkylene group, or alkyleneoxy group; X2 and X3 are each independently selected from halogen, C1-C6 alkyl, or benzyl.

11. The preparation method according to claim 7, characterized in that, The main catalyst is selected from at least one of the transition metal complexes shown in formula (2): In formula (2), R1-R7 are each independently selected from C1-C20 alkyl, C2-C20 alkenyl or halogen, and R1-R5 are optionally linked to each other in a ring. In equation (3), R1~R5, R7~R 11 Each of the R1 to R5 is independently selected from C1-C20 alkyl, C2-C20 alkenyl or halogen; R1 to R5 are optionally linked in pairs to form a ring.

12. The preparation method according to claim 10, characterized in that, The main catalyst is selected from at least one of the complexes shown in formula (2A): In equation (2A), R6, R7, R 11 -R 17 Each is independently selected from hydrogen, C1-C10 alkyl, C2-C10 alkenyl, or halogen, and R 11 -R 17 Optionally, they are linked together in pairs to form a ring; X1 is selected from halogen, C1-C6 alkyl or benzyl, and M is selected from titanium, zirconium or hafnium.

13. The preparation method according to claim 7, characterized in that, The catalyst composition further includes an auxiliary agent selected from at least one of organoaluminum compounds, organoboron compounds, and organosilicon compounds.

14. The preparation method according to claim 13, characterized in that, The ratio of the total molar amount of aluminum, boron, and silicon in the additive to the molar amount of M in the catalyst is (10-11000000):

1.

15. The preparation method according to claim 13, characterized in that, The ratio of the total molar amount of aluminum, boron, and silicon in the additive to the molar amount of M in the catalyst is (10-200000):

1.

16. The preparation method according to claim 7, characterized in that, The total concentration of the nonpolar olefin monomer and the polar olefin monomer in the feedstock is 0.01-6000 mmol / L; and / or, Based on the total molar amount of the nonpolar olefin monomer and the polar olefin monomer being 100%, the molar amount of the polar olefin monomer is 0.01 to 20 mol%. And / or, The concentration of the main catalyst in the raw material is 0.00001-100 mmol / L.

17. The preparation method according to claim 7, characterized in that, The total concentration of the nonpolar olefin monomer and the polar olefin monomer in the feedstock is 0.1-1000 mmol / L; and / or, Based on the total molar amount of the nonpolar olefin monomer and the polar olefin monomer being 100%, the molar amount of the polar olefin monomer is 0.01 to 10 mol%. And / or, The concentration of the main catalyst in the raw material is 0.0001-1 mmol / L.

18. The preparation method according to claim 7, characterized in that, The total concentration of the nonpolar olefin monomer and the polar olefin monomer in the feedstock is 1-500 mmol / L; and / or, The concentration of the main catalyst in the raw material is 0.001-0.5 mmol / L.

19. The preparation method according to claim 5, characterized in that, The haloalkane is selected from formula R 1 X 2 n2 R 2 X 3 m2 At least one of the compounds shown, wherein X 2 X 3 Each is independently selected from halogens, m2+n2≥1, R 1 Selected from C1-C10 alkyl or alkenyl groups, R 2 Selected from C1-C10 alkylene or alkenylene groups.

20. The preparation method according to any one of claims 7 to 19, characterized in that, The polymerization conditions include: a polymerization temperature of -50°C to 180°C; and / or a reaction time of 10 to 200 min; And / or, The hydrocarbon solvent is selected from one or more of C3-C20 alkanes or aromatics.

21. The preparation method according to any one of claims 7 to 19, characterized in that, The polymerization conditions include: a polymerization temperature of -20℃ to 100℃; and / or a reaction time of 20 to 60 min; and / or, The hydrocarbon solvent is selected from one or more alkanes from C3 to C10.

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