Coordination precipitation polymerization method for olefin polymerization and obtained polyolefin

Abstract

The present invention discloses a coordination precipitation polymerization method for olefin polymerization and the obtained polyolefin, the method comprising: mixing raw materials including olefin monomers, catalysts, auxiliary agents, modifiers and solvents, and reacting; wherein the catalyst is selected from at least one of the transition metal complexes shown in formula (I) and the transition metal complexes shown in formula (II). The method does not require subsequent processing such as granulation, and can directly obtain spherical and / or quasi-spherical polymers, and the polymers have good morphology, so the method of the present invention has good industrial application prospects.

Description

Technical Field

[0001] The invention belongs to the field of high molecular polymer preparation, in particular to olefin polymerization, and in particular to olefin coordination precipitation polymerization. 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 attracted 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 and coordinative polymerization can be combined, in a common solvent for coordination polymerization, by controlling the polymerization process, the non-loaded transition metal complex can be directly prepared by precipitation polymerization method with good particle morphology, that is, coordination precipitation polymerization method, this method can not only avoid the complicated catalyst loading process, but also greatly simplify the polymer deashing and granulation post-treatment process, which can inject new blood into olefin polymerization technology. Summary of the invention

[0005] In order to overcome the problems existing in the prior art, the present invention provides a coordination precipitation polymerization method for olefin polymerization and the obtained polyolefin. During the polymerization process, the entire polymerization system (such as comonomer structure, catalyst and modifier, etc.) is adjusted to achieve the direct preparation of spherical or spherical polymer particles by catalyzing olefin polymerization with a non-supported transition metal catalyst. The present invention greatly simplifies the preparation process of the main catalyst, the polymer particles have good morphology, low equipment requirements, low energy consumption, and low environmental pollution.

[0006] One of the purposes of the present invention is to provide a coordination precipitation polymerization method for olefin polymerization, comprising: mixing raw materials including olefin monomers, catalysts, additives, modifiers and solvents, and reacting;

[0007] Wherein, the catalyst is selected from at least one of the transition metal complex represented by formula (I) and the transition metal complex represented by formula (II):

[0008]

[0009] In formula (I), R1 and R2 are each independently selected from one of substituted or unsubstituted C1-C30 hydrocarbon groups; R3 and R4 are each independently selected from one of hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon groups, substituted or unsubstituted C1-C20 hydrocarbonoxy groups, and adjacent R3 and R4 are optionally interconnected to form a ring or ring system; M is selected from one of Group VIII metals; X is selected from one of halogen, substituted or unsubstituted C1-C10 hydrocarbon groups, substituted or unsubstituted C1-C10 hydrocarbonoxy groups, and repeated Xs are the same or different;

[0010] In formula (II), R1 and R2 are each independently selected from one of C1-C30 hydrocarbon groups with or without substitution, and repeated R1 or R2 are the same or different; R3 and R4 are each independently selected from one of hydrogen, halogen, hydroxyl, C1-C20 hydrocarbon groups with or without substitution, and C1-C20 alkoxy groups with or without substitution, and adjacent R3 and R4 are optionally connected to each other to form a ring or ring system, and repeated R3 or R4 are the same or different; R 11 is selected from one of C1-C20 hydrocarbon groups with or without substitution, and the repeated R 11 the same or different; Y is selected from one of the non-metal atoms of Group VIA, and repeated Ys are the same or different; M is selected from one of the metals of Group VIII, and repeated Ms are the same or different; X is selected from one of the halogen, C1-C10 hydrocarbon groups with or without substitution, and C1-C10 hydrocarbonoxy groups with or without substitution, and repeated Xs are the same or different.

[0011] The present invention provides a novel coordination precipitation polymerization method, that is, before the reaction monomers are polymerized, the system is a uniform reaction solution, and the polymer is self-formed to prepare quasi-spherical or spherical polymers. The polymerization method can avoid the catalyst loading process and directly use a homogeneous catalyst to catalyze the polymerization to prepare quasi-spherical or spherical polymer particles.

[0012] In a preferred embodiment, R1 in formula (I), R2 in formula (I), R1 in formula (II), and R2 in formula (II) are each independently selected from a C1-C20 alkyl group containing or not containing a substituent, or a C6-C20 aryl group containing or not containing a substituent; R3 in formula (I), R4 in formula (I), R3 in formula (II), and R4 in formula (II) are each independently selected from a hydrogen, a halogen, a hydroxyl, a C1-C20 hydrocarbon group containing or not containing a substituent, or a C1-C20 alkoxy group containing or not containing a substituent, Adjacent R3 and R4 are optionally interconnected to form a ring or ring system; M in formula (I) and M in formula (II) are each independently selected from nickel or palladium; Y in formula (II) is selected from oxygen or sulfur; X in formula (I) and X in formula (II) are each independently selected from halogen, C1-C10 alkyl with or without substituents, C1-C10 alkoxy with or without substituents, preferably independently selected from halogen, C1-C6 alkyl with or without substituents and C1-C6 alkoxy with or without substituents; R in formula (II) 11 One selected from substituted or unsubstituted C1-C20 alkyl groups, preferably one selected from substituted or unsubstituted C1-C10 alkyl groups, more preferably one selected from substituted or unsubstituted C1-C6 alkyl groups.

[0013] In a further preferred embodiment, R1 in formula (I), R2 in formula (I), R1 in formula (II), and R2 in formula (II) are each independently a group as shown in formula A:

[0014]

[0015] In formula (A), R 1 -R 5 each independently selected from the group consisting of hydrogen, halogen, hydroxyl, a C1-C20 alkyl group which may be substituted or unsubstituted, a C2-C20 alkenyl group which may be substituted or unsubstituted, a C2-C20 alkynyl group which may be substituted or unsubstituted, a C1-C20 alkoxy group which may be substituted or unsubstituted, a C2-C20 alkenyloxy group which may be substituted or unsubstituted, a C2-C20 alkynyloxy group which may be substituted or unsubstituted, a C6-C20 aryl group which may be substituted or unsubstituted, a C6-C20 aryloxy group which may be substituted or unsubstituted, a C7-C20 aralkyl group which may be substituted or unsubstituted, a C7-C20 aralkyloxy group which may be substituted or unsubstituted, a C7-C20 alkaryl group which may be substituted or unsubstituted, and R 1 -R 5 optionally linked to each other to form a ring or ring system;

[0016] In a further preferred embodiment, R1 in formula (I), R2 in formula (I), R1 in formula (II), and R2 in formula (II) are each independently a group as shown in formula A. In formula (A), R 1 -R 5 Each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyl The invention can be selected from the group consisting of an oxy group, a substituted or unsubstituted C3-C10 cycloalkyloxy group, a substituted or unsubstituted C6-C15 aryl group, a substituted or unsubstituted C6-C15 aryloxy group, a substituted or unsubstituted C7-C15 aralkyl group, a substituted or unsubstituted C7-C15 aralkyloxy group, a substituted or unsubstituted C7-C15 alkaryl group, and a substituted or unsubstituted C7-C15 alkaryloxy group.

[0017] In a preferred embodiment, R3 in formula (I), R4 in formula (I), R3 in formula (II), and R4 in formula (II) are each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substitution, C2-C20 alkenyl with or without substitution, C2-C20 alkynyl with or without substitution, C1-C20 alkoxy with or without substitution, C2-C at least one of a C2-C20 alkenyloxy group, a substituted or unsubstituted C2-C20 alkynyloxy group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C7-C20 aralkyloxy group, a substituted or unsubstituted C7-C20 alkaryl group, and a substituted or unsubstituted C7-C20 alkaryloxy group;

[0018] In a further preferred embodiment, R3 in formula (I), R4 in formula (I), R3 in formula (II), and R4 in formula (II) are each independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substitution, C2-C10 alkenyl with or without substitution, C2-C10 alkynyl with or without substitution, C3-C10 cycloalkyl with or without substitution, C1-C10 alkoxy with or without substitution, C2-C10 cycloalkyl with or without substitution, C1-C10 alkoxy with or without substitution, C2-C10 cycloalkyl with or without substitution, C3 ... at least one of a C2-C10 alkenyloxy group, a substituted or unsubstituted C2-C10 alkynyloxy group, a substituted or unsubstituted C3-C10 cycloalkyloxy group, a substituted or unsubstituted C6-C15 aryl group, a substituted or unsubstituted C6-C15 aryloxy group, a substituted or unsubstituted C7-C15 aralkyl group, a substituted or unsubstituted C7-C15 aralkyloxy group, a substituted or unsubstituted C7-C15 alkaryl group, and a substituted or unsubstituted C7-C15 alkaryloxy group;

[0019] In a further preferred embodiment, R3 in formula (I), R4 in formula (I), R3 in formula (II), and R4 in formula (II) are each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, and more preferably independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen;

[0020] In a preferred embodiment, the transition metal complex represented by formula (I) is selected from at least one of formula (Ia) to formula (Ic):

[0021]

[0022] In Formula (Ia) to Formula (Ic), R 1 -R 5 Each is independently selected from hydrogen, halogen, C1-C6 alkyl with or without substitution, C1-C6 alkoxy with or without substitution; M is nickel or palladium; X is independently selected from halogen; R3 and R4 have the same definitions as in formula (I); in formula (Ib), R5-R 10 Each is independently selected from one of hydrogen, halogen, C1-C6 alkyl, and C1-C6 alkoxy; in formula (Ic), R5-R8 are each independently selected from one of hydrogen, halogen, C1-C6 alkyl, and C1-C6 alkoxy.

[0023] In a preferred embodiment, the transition metal complex represented by formula (II) is selected from at least one of formula (IIa) and formula (IIb):

[0024]

[0025] In formula (IIa), R 1 -R 5 Each is independently selected from hydrogen, halogen, C1-C6 alkyl with or without substitution, C1-C6 alkoxy with or without substitution; R5-R 10 Each is independently selected from one of hydrogen, halogen, C1-C6 alkyl and C1-C6 alkoxy; M is nickel; Y is O; X is selected from halogen; R 11 One selected from C1-C6 alkyl groups which may be substituted or unsubstituted.

[0026] In formula (IIb), R 1 -R 5 R5-R8 are each independently selected from one of hydrogen, halogen, C1-C6 alkyl with or without substitution, C1-C6 alkoxy with or without substitution; R5-R8 are each independently selected from one of hydrogen, halogen, hydroxyl, C1-C20 hydrocarbon with or without substitution, and R5-R8 are optionally connected to each other to form a ring or ring system; R 11 is selected from one of C1-C20 hydrocarbon groups with or without substitution; Y is independently selected from one of VIA group non-metal atoms; M is independently selected from one of VIII group metals; X is independently selected from one of halogen, C1-C10 hydrocarbon groups with or without substitution, and C1-C10 hydrocarbonoxy groups with or without substitution.

[0027] In a preferred embodiment, the substituent is selected from halogen, hydroxyl, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated C1-C10 alkoxy, preferably selected from one of halogen, hydroxyl, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy or halogenated C1-C6 alkoxy.

[0028] For example: the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl or 3,3-dimethylbutyl; the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentyl, n-hexyl, isohexyl or 3,3-dimethylbutoxy; the halogen is selected from fluorine, chlorine, bromine or iodine.

[0029] In a preferred embodiment, the olefin monomer is selected from any one or more of formulas (i) to (viii): (i) ethylene; (ii) propylene; (iii) α-olefins and internal olefins; (iv) C4-C20 dienes; (v) olefins; (vi) unsaturated carboxylic acids; (vii) unsaturated carboxylic acid esters; (viii) terminal olefin silanes / siloxanes.

[0030] It is worth noting that the method of the present invention can be used for the polymerization of internal olefins (non-α-olefins). The internal olefin in the present invention 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 cis-2-C4, trans-2-C4, or a mixture of one or more isomers. The terminal olefin is an olefin whose double bond is at the terminal position, for example, butene is 1-C4.

[0031] The (iii) α-olefin and internal olefin described in the present invention refer to olefins without polar groups, and the (iii) α-olefin and internal olefin do not belong to the (iv) C4-C20 diene, and do not contain hydroxyl, carboxyl, carboxylate, silane / siloxane groups. The (iv) C4-C20 diene described in the present invention does not contain hydroxyl, (vi) carboxyl, (vii) carboxylate, (viii) silane / siloxane groups. That is, the (iii) α-olefin and internal olefin described in the present invention are different from the (iv) C4-C20 diene, (v) enol, (vi) unsaturated carboxylic acid, (vii) unsaturated carboxylic acid ester and (viii) terminal alkenyl silane / siloxane; the (iv) C4-C20 diene described in the present invention is different from the (v) enol, (vi) unsaturated carboxylic acid, (vii) unsaturated carboxylic acid ester and (viii) terminal alkenyl silane / siloxane.

[0032] In a further preferred embodiment, the enol, unsaturated carboxylic acid, unsaturated carboxylic acid ester, terminal alkenyl silane / siloxane (olefin with polar group) are each independently selected from at least one of the monomers represented by formula G:

[0033]

[0034] Wherein, in formula G, L1-L3 are each independently selected from H, a C1-C30 alkyl group with or without a substituent, L4 is selected from a C1-C30 alkylene group with or without a side group, and Pg is respectively selected from a hydroxyl group, a carboxyl group, a carboxylate group, and a silane group / siloxane group.

[0035] Preferably, in formula G, L1 and L2 are H, L3 is H, one of a C1-C30 alkyl group with or without a substituent, and L4 is one of a C1-C30 alkylene group with or without a side group;

[0036] More preferably, in formula G, L1 and L2 are H, L3 is one of H and a C1-C20 alkyl group with or without a substituent, and L4 is a C1-C20 alkylene group with or without a side group;

[0037] More preferably, L1 and L2 are H, L3 is selected from H, a C1-C10 alkyl group with or without a substituent, and L4 is selected from a C1-C10 alkylene group with or without a side group, preferably a C1-C6 alkylene group with or without a side group;

[0038] In formula G, 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; more preferably, the substituents in L1-L3 are selected from one or more of C1-C6 alkyl, halogen, and C1-C6 alkoxy.

[0039] In formula G, 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.

[0040] Preferably, the side groups in L4 are selected from halogen, C6-C20 aryl, C1-C20 alkyl, hydroxy-substituted C1-C20 alkyl or alkoxy-substituted C1-C20 alkyl. More preferably, the side groups in L4 are selected from halogen, C6-C20 aryl, C1-C10 alkyl, hydroxy-substituted C1-C10 alkyl and alkoxy-substituted C1-C10 alkyl; more preferably, the side groups in L4 are selected from halogen, phenyl, C1-C6 alkyl and hydroxy-substituted C1-C6 alkyl. Examples of the C1-C6 alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl.

[0041] In the present invention, the carbon number of the alkylene group refers to the number of C in the straight chain, excluding the number of C in the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to herein as a C2 alkylene group with a side group (methyl).

[0042] In some embodiments of the present invention, the enol is one or more selected from the group consisting of the alkene alcohols represented by formula G1:

[0043]

[0044] In formula G1, L1-L3 are each independently selected from H, a C1-C30 alkyl group with or without a substituent, and L4 is selected from a C1-C30 alkylene group with or without a side group;

[0045] In some embodiments of the present invention, the unsaturated carboxylic acid is one or more selected from the unsaturated carboxylic acids represented by formula G2:

[0046]

[0047] In formula G2, L1-L3 are each independently selected from H, a C1-C30 alkyl group with or without a substituent, and L4 is selected from a C1-C30 alkylene group with or without a side group.

[0048] 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 G3:

[0049]

[0050] In formula G3, L1-L3 are each independently selected from H, a C1-C30 alkyl group with or without a substituent, L4 is selected from a C1-C30 alkylene group with or without a side group, and L5 is selected from a C1-C30 alkyl group with or without a substituent.

[0051] Preferably, in formula G3, L5 is a C1-C20 alkyl group; more preferably a C1-C10 alkyl group, and even more preferably a C1-C6 alkyl group.

[0052] In some embodiments of the present invention, the terminal alkenyl silane / siloxane is selected from one or more of the terminal alkenyl silane / siloxanes represented by formula G4:

[0053]

[0054] In formula G4, L1-L3 are independently selected from H, a C1-C30 alkyl group with or without substituents, L4 is a C1-C30 alkylene group with or without side groups, and R'1-R'3 are each independently selected from halogen, a C1-C10 alkyl group with or without substituents, and a C1-C10 alkoxy group with or without substituents.

[0055] Preferably, in formula G1, G2, G3 or G4, L1 and L2 are H; L3 is one of H and C1-C30 alkyl with or without substituents, preferably one of H and C1-C20 alkyl with or without substituents, more preferably one of H and C1-C10 alkyl with or without substituents; L4 is one of C1-C30 alkylene with or without side groups, preferably one of C1-C20 alkylene with or without side groups, more preferably one of C1-C10 alkylene with or without side groups, more preferably one of C1-C60 alkylene with or without side groups.

[0056] For example, the substituent is selected from halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C10 aryl, cyano or hydroxy.

[0057] More preferably, in formula G1, G2, G3 or G4, L1 and L2 are H; L3 is one of H, C1-C10 alkyl, alkyl or halogen-substituted C1-C10 alkyl, preferably one of H and C1-C10 alkyl; L4 is one of C1-C20 alkylene with or without side groups, preferably C1~C20 alkylene with side groups, more preferably C1-C10 alkylene with side groups.

[0058] Most preferably, in formula G1, G2, G3 or G4, L1 and L2 are H, L3 is one of H and C1-C6 alkyl; and L4 is a C1-C10 alkylene group containing a side group.

[0059] According to a preferred embodiment of the present invention, in formula G3, L5 is a C1-C20 alkyl group; more preferably a C1-C10 alkyl group, and more preferably a C1-C6 alkyl group.

[0060] In the present invention, the carbon number n of the Cn alkylene group refers to the number of Cs in the straight chain, and does not include the number of Cs in the side group. For example, isopropylidene (-CH2-CH(CH3)-) is referred to as a C2 alkylene group with a side group (methyl) in this article.

[0061] In a preferred embodiment, 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-hexane ene, 3-butene-2-ol, 3-methyl-5-hexene-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-octene-2,3-diol, 2,6-dimethyl-7-octene-2,6-diol.

[0062] In a preferred embodiment, 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-hexene 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 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.

[0063] 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-pentenoate, 2-vinyl-4-methyl-4-pentanoic acid methyl ester, 2,2-dimethyl-3-butenoic acid ethyl ester, 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-vinylhexanoic 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-dimethyl ethyl)-5-hexenoate, ethyl 3-methyl-2-oxo-5-hexenoate, methyl 2-vinyl-3,3-dimethyl-5-hexanoate, methyl-β-vinyl benzopropionate, 3-methyl-5-hexenoate, methyl 2-propyl-6-hexenoate, methyl 2-methyl-6-hexenoate, ethyl 2-methyl-6-hexenoate, ethyl 2-methyl-6-hexenoate, methyl 2,2-dimethyl 6-hexenoate, ethyl 2,4-dimethyl 6-hexenoate, ethyl 2-propyl-6-hexenoate, ethyl 2,2-dimethyl 6-hexenoate, 1,3-dimethyl 2-(4-penten-1-yl)malonate, 2-methyl-1,1-dimethylethyl ester, tert-butyl 2-methyl-3-butenoate, ethyl 2-isopropyl-3-butenoate, methyl 2-isobutyl-4-pentenoate, methyl 2,2-dimethyl-4-pentenoate, methyl 3,3-dimethyl-4-pentenoate, ethyl 3,3-dimethyl-4-pentenoate, ethyl 2,2-dimethyl-4-pentenoate, methyl 2-n-propyl-4-pentenoate, methyl 2-isopropyl-4-pentenoate, isobutyl 2-methyl-4-pentenoate, diethyl allylmalonate, dimethyl allylmalonate, allylsuccinic anhydride, ethyl 2-methyl-4-pentenoate, 2-methyl-4- Methyl pentenoate, methyl 3-methyl-4-pentenoate, methyl 3-ethyl-4-pentenoate, isobutyl 3-methyl-4-pentenoate, ethyl 2-(tert-butyl)-4-pentenoate, 3-allyldihydrofuran-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-hexenoate, methyl 2,4-dimethyl-9-decenoate.

[0064] In a preferred embodiment, the terminal alkenyl silane / siloxane is selected from at least one of the following compounds: trimethyl (1-methyl-2-propylene-1-yl) silane, trimethyl (1-methyl-3-butene-1-yl) silane, (1-ethyl-2-propylene-1-yl) trimethyl silane, trimethyl (1,1,2,2-tetramethyl-3-butene-1-yl) silane, [1-(trimethylsilyl)-3-butene-1-yl] benzene, methoxydimethyl (1-methyl-2-propylene-1-yl) silane, chloro-5-hexene-1-yl dimethyl silane, 2-(trimethylsilyl)-4-pentene-1-ol, vinyl dimethyl (1-methylethyl) silane 、(Chloromethyl)dimethyl-2-propene-1-ylsilane, 5-hexen-1-yltrimethylsilane, hexyldimethyl-2-propene-1-ylsilane, dichlorohexyl-2-propene-1-ylsilane, dichloro-5-hexen-1-ylmethylsilane, 4-(trimethylsilyl)-1-butene, (chloromethyl)dimethyl(1-methyl-2-propene-1-yl)silane, 5-hexen-1-yldimethoxymethylsilane, triethyl(3-methyl-4-penten-1-yl)silane, diethylmethyl(2-methyl-3-buten-1-yl)silane, allyltriethylsilane, methoxydimethyl(1-methyl-2-propene-1-yl)silane, 7-octenyl trichlorosilane, chlorodimethyl (1-methyl-2-propene-1-yl) silane, 3-butene-1-yl methoxydimethyl silane, 3-butene-1-yl chlorodimethyl silane, allyl (tert-butyl) dimethyl silane, trichloro-10-undecen-1-yl silane, (7-oct-1-yl) trimethoxy silane, allyl trimethoxy silane, 3-butenyl triethoxy silane, trimethoxy-10-undecen-1-yl silane, dimethoxymethyl-2-propene-1-yl silane, 6-tert-butyldimethylsiloxy-1-hexene, (1,1-dimethylethyl) dimethyl [(1-methyl-2-propene-1-yl) oxy] silane, 1-(trimethylsilyl) -4-penten-1-ol, 5-(trimethylsilyl)-1-penten-3-ol, 3-(3-buten-1-yldimethylsilyl)-1-propanol, 1-(trimethylsilyl)-3-buten-1-ol, 1-(trimethylsilyl)-2-propen-1-ol, 1-(dimethyl-2-propen-1-ylsilyl)-2-propanol, 3-trimethylsilyl-4-pentenoic acid methyl ester, 2-acrylate (trimethylsilyl) methyl ester, triethoxy(2-methyl-3-buten-1-yl)silane, styreneethyltrimethoxysilane, 1-vinyl-4-[2-(triethoxysilyl)ethyl]benzene, 1-vinyl-4-[2-(trimethoxysilyl)ethyl]benzene.

[0065] Among them, the spherical polar polyolefins with polar groups and high melting points can be prepared by using the method of the present invention, that is, polar groups can be introduced into the polyolefin chain to improve the interfacial compatibility of the polyolefin while retaining its crystallization performance.

[0066] In a preferred embodiment, the auxiliary agent is selected from at least one of organoaluminum compounds, organoboron compounds, and organosilicon compounds, preferably from at least one of organoaluminum compounds and organoboron compounds.

[0067] In a further preferred embodiment, the organoaluminum compound is selected from alkylaluminoxanes or organoaluminum compounds (alkylaluminum or alkylaluminum halides) of the general formula AlR n X 1 3-n In the general formula AlR n X 1 3-n R is a saturated or unsaturated hydrocarbon group of H, C1-C 20 or a saturated or unsaturated hydrocarbon oxy group of C1-C 20 preferably C1-C 20 alkyl, C1-C 20 alkoxy, C7-C 20 aralkyl or C6-C 20 aryl; X 1 is a halogen, preferably chlorine or bromine; 0 < n ≤ 3. Preferably, the organoaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, dichloroethylaluminum, dichloroisobutylaluminum, sesquiethylaluminum chloride, dichloroethylaluminum, methylaluminoxane (MAO), and modified methylaluminoxane (MMAO); more preferably, the organoaluminum compound is methylaluminoxane (MAO).

[0068] In a further preferred embodiment, the organoboron compound is selected from at least one of arylborons and borates; preferably, the arylboron is selected from substituted or unsubstituted phenylborons, preferably tris(pentafluorophenyl)boron; and / or the borate is selected from at least one of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and triphenylmethyl tetrakis(pentafluorophenyl)borate.

[0069] In a further preferred embodiment, the organosilicon compound is selected from alkylsilicon compounds represented by the general formula SiR’ m1 X 2 n1 In the general formula SiR’ m1 X 2 n1 R’ is selected from alkyl groups of C1-C10, the repeated R’ are the same or different, X 2Selected from halogen, m1≥1, and m1+n1=4; preferably, the organosilicon compound is selected from at least one of trimethylchlorosilane, dichlorodimethylsilane, propyldimethylchlorosilane, dichloroethylmethylsilane, tert-butyldimethylchlorosilane, diisopropylchlorosilane, trichloroethylsilane, chloromethyldimethylchlorosilane, di-tert-butylchlorosilane, dichloro(methyl)propylsilane, methyltrichlorosilane and trichloroethylsilane.

[0070] 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 catalyst is (10-11000000):1, preferably (10-200000):1, for example, 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.

[0071] In a further preferred embodiment, when the auxiliary agent 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.

[0072] For example, when the auxiliary agent contains an organic aluminum compound, the molar ratio of aluminum in the organic aluminum compound to M in the catalyst is 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 or 10000000:1 or any value therebetween.

[0073] In a further preferred embodiment, when the auxiliary agent contains an organic boron compound, the molar ratio of boron in the organic boron compound to M in the catalyst is (0.1-1000):1, preferably (0.1-500):1.

[0074] For example, when the auxiliary agent contains an organoaluminum 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 therebetween.

[0075] In a further preferred embodiment, when the auxiliary agent 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, for example, 10:1, 20:1, 50:1, 100:1, 500:1, 1000:1, 1500:1, 2000:1, 5000:1, 10000:1, 100000:1, 1000000:1.

[0076] In a preferred embodiment, the solvent is selected from alkane solvents.

[0077] In a further preferred embodiment, the alkane solvent is selected from one or more C3-C20 alkanes, preferably one or more C3-C10 alkanes.

[0078] For example, the solvent may be selected from one or more of butane, isobutane, pentane, hexane, heptane, octane, and cyclohexane, preferably one or more of hexane, heptane, and cyclohexane.

[0079] In a preferred embodiment:

[0080] When the monomer is selected from at least one of (i) ethylene, (ii) propylene, (iii) α-olefins and internal olefins, (iv) C4-C20 dienes, (vii) unsaturated carboxylic acid esters, and (viii) terminal olefin silanes / siloxanes, the modifier is selected from at least one of halogenated alkanes, organic paraffins, monoether organic solvents, diether organic solvents, polyether organic solvents, and cyclic organic solvents;

[0081] or,

[0082] When the monomer is selected from at least one of (v) enol and (vi) unsaturated carboxylic acid, the modifier is selected from at least one of organic paraffin, monoether organic solvent, diether organic solvent, polyether organic solvent and cyclic organic solvent, or the modifier is selected from at least one of organic paraffin, monoether organic solvent, diether organic solvent, polyether organic solvent and cyclic organic solvent.

[0083] Preferably, the halogenated alkane is selected from the formula R1'X 3 n2 R2'X 4 m2 At least one of the compounds shown, wherein X 3 , X 4Each is independently selected from halogen, m2+n2≥1, R1' is selected from C1-C10 alkyl or alkenyl, R2' is selected from C1-C10 alkylene or alkenylene; and / or, the monoether organic solvent is selected from at least one of the compounds represented by the formula R5'-O-R6', wherein R5' and R6' are independently selected from C1-C10 alkyl, R5' and R6' are optionally cyclized; and / or, the diether organic solvent is selected from at least one of the compounds represented by the formula R7'OR8'OR9', wherein R7' and R9' are independently selected from C1-C10 alkyl, R7' and R9' are optionally cyclized, and R8' is selected from C1-C10 alkylene; and / or, the polyether organic solvent is selected from the formula R 10 '-(OR 11 ') x -OR 12 ', where R 10 '、R 12 ' are each independently selected from C1-C10 alkyl groups, R 11 ' is selected from C1-C10 alkylene, x≥2; and / or, the cyclic organic solvent is selected from at least one of dioxane, tetrahydrofuran, tetralin, pyridine and cyclohexane.

[0084] More preferably, the halogenated alkane is selected from at least one of chloroform, dichloromethane, dichloroethane, dichloropropane, trichloroethylene, and carbon tetrachloride; and / or, the monoether organic solvent is selected from at least one of diethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether; and / or, the diether organic solvent is selected from 2,2-dimethoxypropane, dioxane, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, diethyl cellosolve, 2-methoxyethoxymethyl chloride, tert-butyl glycidyl ether, 2-(chloromethyl)-1, At least one of 4-dioxane, 2-(chloromethyl)-1,4-dioxane, 2-(methoxymethyl)tetrahydrofuran, and 2,6-dioxaspiro[3,3]heptane; and / or, the polyether organic solvent is selected from at least one of diethylene glycol dimethyl ether, 3,3-dimethoxyoxetane, epoxy acrolein diethyl acetal, diethylene glycol methyl ethyl ether, 1,1-diethoxy-2-methoxyethane, 4,4-dimethoxytetrahydro-4H-pyran, and 1,1,3,3-tetramethoxypropane.

[0085] Preferably the modifier is different from the solvent.

[0086] In a preferred embodiment, the concentration of the 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.

[0087] For example, the concentration of the 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 therebetween.

[0088] In a preferred embodiment, the concentration of the 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.

[0089] For example, the concentration of the catalyst in the polymerization system can be 0.00001mmol / L, 0.00005mmol / L, 0.0001mmol / L, 0.0005mmol / L, 0.001mmol / L, 0.005mmol / L, 0.01mmol / L, 0.05mmol / L, 0.1mmol / L, 0.2mmol / L, 0.3mmol / L, 0.4mmol / L, 0.5mmol / L, 0.8mmol / L, 1mmol / L, 5mmol / L, 8mmol / L, 10mmol / L, 20mmol / L, 30mmol / L, 50mmol / L, 70mmol / L, 80mmol / L or 100mmol / L or any value therebetween.

[0090] 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.

[0091] For example, 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.

[0092] In a preferred embodiment, the reaction conditions include: a reaction temperature of -50°C to 100°C, preferably -20 to 60°C, more preferably 0 to 80°C, for example, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, and any value therebetween; 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.

[0093] In the present invention, there is no particular restriction on the reaction pressure, as long as the monomer can undergo coordination copolymerization. When the olefin is ethylene, from the perspective of reducing costs and simplifying the polymerization process, in the reactor, the ethylene pressure is preferably 1 to 1000 atm, more preferably 1 to 200 atm, and more preferably 1 to 50 atm.

[0094] According to a preferred embodiment of the present invention, the reaction is carried out under anhydrous and oxygen-free conditions.

[0095] The method of the present invention can be a precipitation polymerization method for polymerizing ethylene or at least one olefin monomer of 3 to 18 carbon atoms in a homogeneous solution, wherein the polymerization or copolymerization is carried out in the presence of a non-supported catalyst, and spherical or spherical polymer particles are prepared by polymerization self-forming. Furthermore, the method of the present invention catalyzes olefin polymerization under the action of a catalyst to directly prepare a spherical or spherical polyolefin product with a particle size greater than 20 μm, a weight average molecular weight of 50,000 to 3 million, and a melting point of 90 to 140°C.

[0096] A second object of the present invention is to provide a polymer obtained by the method described in one of the objects of the present invention, which is a spherical or quasi-spherical polymer.

[0097] In a preferred embodiment, the density of the spherical and / or quasi-spherical polymer is 0.3000-0.8500 g / cm 3 , for example, it can be 0.3000 g / cm 3 , 0.3500g / cm 3 , 0.4000g / cm 3 , 0.4500g / cm 3 , 0.5000g / cm 3 , 0.5500g / cm 3 , 0.6000g / cm 3 、0.6500g / cm 3 , 0.7000g / cm 3 , 0.7500g / cm3 , 0.8000g / cm 3 , 0.8500g / cm 3 And any value therebetween, preferably 0.4000-0.7500 g / cm 3 , the density is measured using the method in GB / T6463-2009.

[0098] In a preferred embodiment, the average particle size of the spherical and / or quasi-spherical polymers 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 therebetween, preferably 0.2 to 20.0 mm.

[0099] In a preferred embodiment, the melting point of the polymer is 90-140°C, for example 90°C, 95°C, 100°C, 105°C, 110°C, 120°C, 125°C, 130°C, 135°C, 140°C and any value therebetween.

[0100] In a preferred embodiment, the density of the polymer is 0.4000-0.8500 g / cm 3 , preferably 0.4500~0.7500g / cm 3 ; and / or, the weight average molecular weight of the polymer is 50,000 to 3,000,000, preferably 80,000 to 2,000,000.

[0101] In a preferred embodiment, the molecular weight distribution of the polymer is ≤20.0, for example, it can be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 6.0, 8.0, 10.0, 12.0, 14.0, 16.0, 18.0 and any value therebetween, preferably, the molecular weight distribution is 2.0-15.0.

[0102] In the present invention:

[0103] Alkyl refers to straight chain alkyl, branched chain alkyl or cycloalkyl. 20 Alkyl refers to C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl or C6-C 20Examples 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, vinylphenyl.

[0104] Alkenyl refers to straight chain alkenyl, branched chain alkenyl or cycloalkenyl. 20 Alkenyl refers to C1-C 20 Straight chain alkenyl, C3-C 20 Branched alkenyl or C3-C 20 Examples of alkenyl groups include, but are not limited to, vinyl, allyl, and butenyl.

[0105] C7-C 20 Examples of aralkyl groups include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl, and phenyl-t-butyl.

[0106] The endpoints and any values ​​of the scope disclosed in the present invention are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, the endpoint values ​​of each scope, the endpoint values ​​of each scope 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 regarded as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be regarded as specifically disclosed in this article.

[0107] Compared with the prior art, the present invention has the following beneficial effects:

[0108] (1) The method of the present invention uses a novel coordination precipitation polymerization method. This polymerization method has not been reported. Therefore, the technical problem solved by the present invention is to eliminate the catalyst loading process flow and realize the self-forming preparation of olefin polymers with good particle morphology by homogeneous catalyst polymerization;

[0109] (2) The method of the present invention does not require subsequent processing such as granulation, and can directly obtain spherical and / or quasi-spherical polymers with good morphology. Therefore, the method of the present invention has good industrial application prospects;

[0110] (3) Furthermore, in the method of the present invention, by selecting the transition metal complex, olefin monomer, modifier and appropriate reaction conditions, a spherical and / or quasi-spherical polymer with good morphology is directly prepared, and the obtained polymer product is not easy to scale in the reactor and is convenient to transport. DETAILED DESCRIPTION

[0111] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0112] It should also be noted that the various specific technical features described in the following specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0113] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0114] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0115] The analytical characterization instruments used in the present invention are as follows:

[0116] The polymer was washed with a dilute acid solution before measurement to ensure that the metal content in the polymer was ≤50 ppm.

[0117] 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.

[0118] 2. Comonomer content of copolymer (derived from the structural unit shown in formula G): 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.

[0119] 3. Molecular weight and molecular weight distribution PDI (PDI = Mw / Mn) of the polymer: measured at 150°C using PL-GPC220 with trichlorobenzene as solvent (standard sample: PS, flow rate: 1.0 mL / min, column: 3×Plgel10um M1×ED-B 300×7.5 nm).

[0120] 4. Activity measurement method: gravimetric analysis. Activity is expressed as polymer weight (g) / metal complex (mol)×2.

[0121] All ligands in the examples and Ni5, Ni9, Ni 10 、Ni 16 、Ni 17 It can be purchased directly or prepared by the method disclosed in the prior art.

[0122] Example 1

[0123] The preparation of complex Ni1 refers to Example 1 in patent CN112745359.

[0124] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130℃ for 6h, and vacuum was evacuated while hot and replaced with N2 gas 3 times. 450mL of heptane, 50mL of 1,2-dichloroethane, 20mL of cyclohexane, 50mmol (10mL) of 2,6-dimethyl-7-octen-2-ol, 50mL of AlEt3 (1.0mol / L hexane solution), 2.0mL of MAO (1.53mol / L toluene solution) were injected into the polymerization system, and 2.0mg (1.5μmol) of complex Ni1 was added at 30℃, maintaining an ethylene pressure of 10atm, and stirring the reaction for 30min. Finally, it was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. The polymerization activity was 6.37×10 6 g·mol -1 (Ni)·h -1 The molecular weight of the obtained polymer is 186,000, the molecular weight distribution is 2.21, the hydroxyl content in the polymer is 1.95 mol%, the melting point of the polymer is 120.4°C, the average particle size of the spherical polymer in the obtained polymer is 3.20 mm, and the yield of the spherical polymer is 61%.

[0125] Example 2

[0126] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130℃ for 6h, evacuated while hot and replaced with N2 gas three times. 400mL of cyclohexane and 100mL of dichloroethane, 30mmol (4.0mL) of 3,3-dimethyl-4-pentenoic acid, 30mL of AlEt3 (1.0mol / L hexane solution), 0.6mL of AlMe3 (1.0mol / L heptane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate were injected into the polymerization system, and 2.0mg (1.5μmol) of complex Ni1 was added at 30℃, maintaining an ethylene pressure of 10atm, and stirring the reaction for 30min. Finally, it was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. The polymerization activity was 7.43×10 6 g·mol -1 (Ni)·h -1 The molecular weight of the obtained polymer is 174,000, the molecular weight distribution is 2.18, the hydroxyl content in the polymer is 0.98 mol%, the melting point of the polymer is 122.4°C, the average particle size of the spherical polymer in the obtained polymer is 3.00 mm, and the yield of the spherical polymer is 63%.

[0127] Example 3

[0128] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130℃ for 2h, evacuated while hot and replaced with N2 gas three times. 400mL of hexane, 100mL of 1,2-dichloroethane, 4.7mL (30mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 30mL of AliBu3 (1.0mol / L hexane solution), 0.6mL of AlMe3 (1.0mol / L heptane solution), 3.1mg (6.0μmol) of tris(pentafluorophenyl)borane, and 2.0mg (1.5μmol) of complex Ni1 were added into the polymerization system. The ethylene pressure was maintained at 10atm at 30℃ and the reaction was stirred for 30min. Finally, the reaction was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 6.83×10 6 g·mol -1 (Ni)·h -1 The molecular weight of the obtained polymer was 167,000, the molecular weight distribution was 2.24, the unsaturated carboxylic acid ester content in the polymer was 0.74 mol%, the melting point of the polymer was 119.3°C, the average particle size of the spherical polymer in the obtained polymer was 3.4 mm, and the yield of the spherical polymer was 60%.

[0129] Example 4

[0130] A 7mL 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 gas three times. 4.0mL of heptane, 100μL of ether, 50μL (0.24mmol) 3-trimethylsilyl-4-pentenoic acid methyl ester, 124μL AliBu3 (95%), 50μL AlMe3 (0.1mol / L heptane solution), 50.0μL (1.0mmol / L toluene solution) tetrakis(pentafluorophenyl)borate triphenylmethyl salt were injected into the polymerization system, and 12.5μL (1.0mmol / L toluene solution) of complex Ni1 was added. At 30°C, the ethylene pressure was maintained at 10atm and the reaction was stirred for 30min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 2.31×10 6 g·mol -1 (Ni)·h -1 , the weight average molecular weight is 128,000, the molecular weight distribution is 3.34, the polymerization melting point is 116.0°C, the Si monomer molar content is 3.20%. The average particle size of the spherical polymer is 0.62 mm, and the yield of the spherical polymer is 62%.

[0131] Example 5

[0132]

[0133] An ethanol solution (10 mL) containing 0.277 g (0.9 mmol) (DME) NiBr2 was slowly added dropwise to a dichloromethane solution (10 mL) containing 0.209 g (0.6 mmol) ligand L2, stirred at room temperature for 6 h, and anhydrous ether was added to precipitate. The filter cake was filtered and washed with anhydrous ether, and then vacuum dried to obtain a yellow powdery solid Ni2. The yield was 72.0%. Elemental analysis (C 52 H 74 Br6N4Ni3O2): C, 43.29; H, 5.17; N, 3.88; Exp. value (%): C, 43.31; H, 5.52; N, 3.65.

[0134] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130℃ for 2h, vacuumed while hot and replaced with N2 gas three times. 450mL of hexane, 50mL of 2,2-dichloropropane, 4.7mL (30mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 30mL of AliBu3 (1.0mol / L hexane solution), 0.5mL of AlMe3 (1.0mol / L heptane solution), 4.0mg (5.0μmol) of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate were injected into the polymerization system, and 1.0mL (1.25mmol / L) of complex Ni2 was added at 30℃, maintaining an ethylene pressure of 10atm, and stirring the reaction for 30min. Finally, it was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. The polymerization activity and performance parameters of the polymer are shown in Table 1. The polymerization activity is 7.42×10 6 g·mol -1 (Ni)·h -1 The molecular weight of the obtained polymer was 377,000, the molecular weight distribution was 2.32, the content of unsaturated carboxylic acid ester in the polymer was 0.88 mol%, the melting point of the polymer was 114.6 ° C, the average particle size of the spherical polymer in the obtained polymer was 1.0 mm, and the yield of the spherical polymer was 60%

[0135] Example 6

[0136]

[0137] The preparation of complex Ni3 refers to Example 12 in patent CN112745359A.

[0138] A 7mL stainless steel glass-lined polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 2h, vacuumed while hot and replaced with N2 gas 3 times. 4.0mL of heptane, 100μL of dioxane, 100μL (0.58mmol) 2-isopropyl-4-pentenoic acid methyl ester, 146μL AliBu3 (95%, 0.58mmol), 50μL AlMe3 (0.1mol / L heptane solution), 50μL (1.0mmol / L toluene solution) tris (pentafluorophenyl) borane, 12.5μL (0.01mol / L toluene solution) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were injected into the polymerization system, and 12.5μL (1.0mmol / L toluene solution) complex Ni3 was added at the same time. At 30°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred for 30min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 3.02×10 6 g·mol -1 (Ni)·h -1The molecular weight of the obtained polymer was 184,000, the molecular weight distribution was 2.30, the content of unsaturated carboxylic acid ester in the polymer was 0.78 mol%, the melting point of the polymer was 119.3°C, the average particle size of the spherical polymer in the obtained polymer was 0.61 mm, and the yield of the spherical polymer was 61%.

[0139] Example 7

[0140]

[0141] The preparation of complex Ni4 refers to Example 11 in patent CN112745359A.

[0142] A 7mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130℃ for 2h, evacuated while hot and replaced with N2 gas three times. 3.0mL of heptane, 100μL (0.58mmol) 2-isopropyl-4-pentenoic acid methyl ester, 146μL AliBu3 (95%, 0.58mmol), 50μL AlMe3 (0.1mol / L heptane solution), 5.0μL (0.01mol / L toluene solution) tri(pentafluorophenyl) borane were injected into the polymerization system, and 12.5μL (1.0mmol / L toluene solution) of complex Ni4 was added at 10℃, maintaining an ethylene pressure of 15atm, and stirring for 30min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 6.12×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 964,000, the molecular weight distribution is 3.42, and the unsaturated carboxylic acid ester content in the polymer is 0.55 mol% by nuclear magnetic resonance. The yield of spherical polymer is 56%.

[0143] Example 8

[0144]

[0145] A 7mL 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 gas three times. 4.0mL of heptane, 500μL of dichloromethane, 100μL (0.61mmol) of ethyl 2-methyl-4-pentenoate, 156μL of AliBu3 (95%, 0.61mmol), 50μL of AlMe3 (0.1mol / L heptane solution), 10.0μL (0.01mol / L toluene solution) of tri(pentafluorophenyl)borane, 25.0μL (1.0mmol / L toluene solution) of complex Ni5 were injected into the polymerization system, and 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 a polymer. The polymerization activity was 2.72×10 6 g·mol -1 (Ni)·h -1 The molecular weight of the obtained polymer was 126,000, the molecular weight distribution was 2.27, and the content of unsaturated carboxylic acid ester in the polymer was 0.72 mol% by nuclear magnetic resonance. The average particle size of the spherical polymer in the obtained polymer was 0.57 mm, and the yield of the spherical polymer was 63%.

[0146] Example 9

[0147] A 7mL 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 gas three times. 4.0mL of heptane, 100μL of pyridine, 50μL (0.26mmol) of trimethyl (1-methyl-3-butene-1-yl) silane, 50μL of AlMe3 (0.1mol / L heptane solution), 25μL (2.0mmol / L toluene solution) of tri (pentafluorophenyl) borane were injected into the polymerization system, and 25.0μL (1.0mmol / L toluene solution) of complex Ni5 was added. At 30°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred for 30min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 2.06×10 6 g·mol -1 (Ni)·h -1 , the weight average molecular weight is 64,000, the molecular weight distribution is 3.62, the Si monomer molar content is 2.12%, and the yield of spherical polymer is 58%.

[0148] Example 10

[0149]

[0150] The preparation of complex Ni6 refers to Example 1 in patent CN112745358.

[0151] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130℃ for 2h, evacuated while hot and replaced with N2 gas three times. 400mL of heptane, 100mL of dichloromethane, 20mL of ether, 30mmol (6.0mL) of 2,6-dimethyl-2-hydroxy-7-octene, 30mL of AlEt3 (1.0mol / L hexane solution), 0.6mL of AlMe3 (1.0mol / L heptane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate were injected into the polymerization system, and 2.4mg (1.5μmol) of complex Ni6 was added at 30℃, maintaining an ethylene pressure of 10atm, and stirring the reaction for 30min. Finally, it was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. The polymerization activity was 3.22×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 434,000, the molecular weight distribution is 2.12, the molar content of the enol monomer is 1.22%, the average particle size of the spherical polymer in the obtained polymer is 3.5 mm, and the yield of the spherical polymer is 61%.

[0152] Embodiment 11

[0153] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130℃ for 2h, evacuated while hot and replaced with N2 gas 3 times. 200mL of heptane, 200mL of cyclohexane, 30mmol (4.0mL) of 2,2-dimethyl-4-pentenoic acid, 30mL of AlEt3 (1.0mol / L hexane solution), 0.6mL of AlEt3 (1.0mol / L heptane solution), 3.1mg (6.0μmol) of tri(pentafluorophenyl)borane were injected into the polymerization system, and 2.4mg (1.5μmol) of complex Ni6 was added at 30℃, maintaining an ethylene pressure of 10atm, and stirring the reaction for 30min. Finally, it was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. The polymerization activity was 2.16×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 358,000, the molecular weight distribution is 2.24, the carboxyl molar content is 1.26%, the average particle size of the spherical polymer in the obtained polymer is 3.3 mm, and the yield of the spherical polymer is 68%.

[0154] Example 12

[0155] A 7mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2h, vacuumed while hot and replaced with N2 gas three times. 4.0mL of heptane, 100μL of carbon tetrachloride, 0.50mL (3.16mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 0.57mL of diisopropyldichlorosilane were injected into the polymerization system, stirred for 2h, 60μL of AliBu3 (0.1mol / L heptane solution), 60.0μL (1.0mmol / L toluene solution) of tri(pentafluorophenyl) borane, 15μL (1.0mmol / L toluene solution) of complex Ni6 were added, and the ethylene pressure was maintained at 10atm at 30°C, and the reaction was stirred for 60min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 5.62×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 158,000, the molecular weight distribution is 2.42, the carboxyl molar content is 2.12%, the average particle size of the spherical polymer in the obtained polymer is 1.3 mm, and the yield of the spherical polymer is 69%.

[0156] Embodiment 13

[0157] A 7mL 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 gas three times. 4.0mL of heptane, 100μL of tetrahydrofuran, 100μL of triethoxysilane (2-methyl-3-butenyl) (0.38mmol), 50μL of AlMe3 (0.1mol / L heptane solution), 120μL (1.0mmol / L toluene solution) tri(pentafluorophenyl)borane were injected into the polymerization system, and 15μL (1.0mmol / L toluene solution) of complex Ni6 was added. At 30°C, the ethylene pressure was maintained at 10atm and the reaction was stirred for 30min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 3.46×10 6 g·mol -1 (Ni)·h -1 , the weight average molecular weight is 133,200, the molecular weight distribution is 3.55, the Si monomer molar content is 4.47%, and the yield of spherical polymer is 60%.

[0158] Embodiment 14

[0159]

[0160] The preparation of complex Ni7 refers to Example 13 in patent CN112745358.

[0161] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2 hrs, and vacuumed while hot and replaced with N2 gas three times. 400mL of heptane, 100mL of dichlorohexane, 50mL of cyclohexane, 30mmol (4.1mL) of 3-methyl-5-hexen-3-ol, 30mL of AliBu3 (1.0mol / L hexane solution), 0.6mL of AlEt3 (1.0mol / L heptane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate were injected, and 2.3mg (1.5μmol) of complex Ni7 was added. At 30°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred vigorously for 30min. The polymer was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer with a polymerization activity of 3.62×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 158,000, the molecular weight distribution is 2.27, the molar content of the hydroxyl monomer is 1.32%, the average particle size of the spherical polymer in the obtained polymer is 3.3 mm, and the yield of the spherical polymer is 66%.

[0162] Embodiment 15

[0163] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130℃ for 2hrs, and vacuumed and replaced with N2 gas three times while hot. Then vacuumed and replaced with ethylene three times. 400ml of hexane, 50ml of dichloromethane, 50mL of cyclohexane, 30mmol (5.10g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt3 (1.0mol / L hexane solution), 0.6mL of AlEt3 (1.0mol / L heptane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate were injected, and 2.3mg (1.5μmol) of complex Ni7 was added. The ethylene pressure was maintained at 10atm, and the reaction was stirred vigorously for 30min. It was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. The results are shown in Table 1. The polymerization activity was 2.67×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 173,000, the molecular weight distribution is 2.21, the molar content of the carboxyl monomer is 1.22%, the average particle size of the spherical polymer in the obtained polymer is 3.1 mm, and the yield of the spherical polymer is 65%.

[0164] Example 16

[0165] A 7mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130℃ for 2hrs, evacuated while hot and replaced with N2 gas 3 times. 4.0mL of heptane, 100μL of tetrahydrofuran, 0.500mL (3.16mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 0.57mL of diisopropyldichlorosilane were injected, stirred for 2h, 60μL of AlMe3 (0.1mol / L heptane solution), 60μL (1.0mmol / L toluene solution) of tri(pentafluorophenyl)borane, 60μL (1.0mmol / L toluene solution) of N,N-dimethylanilinium tetra(pentafluorophenyl)borate, and 15μL (1.0mmol / L toluene solution) of complex Ni7 were added. At 30℃, the ethylene pressure was maintained at 10atm, and the reaction was stirred vigorously for 60min. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol solution and the polymerization activity was 7.62×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 153,000, the molecular weight distribution is 2.42, the average particle size of the spherical polymer in the obtained polymer is 1.6 mm, and the yield of the spherical polymer is 65%.

[0166] Embodiment 17

[0167] A 7mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2h, vacuumed while hot and replaced with N2 gas three times. 4.0mL of heptane, 100μL of dichloromethane, 50μL (0.24mmol) 3-trimethylsilyl-4-pentenoic acid methyl ester, 62μL AliBu3 (95%), 50μL AlMe3 (0.1mol / L heptane solution), 12.5μL (0.01mol / L toluene solution) tri(pentafluorophenyl)borane, 12.5μL (0.01mol / L toluene solution) tetrakis(pentafluorophenyl)borate triphenylmethyl salt were injected into the polymerization system, and 12.5μL (1.0mmol / L toluene solution) complex Ni9 was added. At 30°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred for 30min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 3.43×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 133,700, the molecular weight distribution is 4.41, the molar content of Si monomer is 1.34%, the average particle size of the quasi-spherical polymer is 1.14 mm, and the yield of the spherical polymer is 62%.

[0168] Embodiment 18

[0169]

[0170] The preparation of complex Ni8 refers to Example 14 in patent CN112745358.

[0171] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2h, and vacuum was evacuated while hot and replaced with N2 gas three times. 400mL of hexane, 50mL of ether, 30mmol (4.1mL) of 3-methyl-5-hexen-3-ol, 30mL of AlEt3 (1.0mol / L hexane solution), 0.6mL of AlEt3 (1.0mol / L heptane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate were injected, and 2.7mg (1.5μmol) of complex Ni8 was added. At 30°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred vigorously for 30min. The polymer was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid, and the polymerization activity was 4.12×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 173,000, the molecular weight distribution is 2.21, the molar content of the carboxyl monomer is 1.50%, the average particle size of the spherical polymer in the obtained polymer is 3.1 mm, and the yield of the spherical polymer is 64%.

[0172] Embodiment 19

[0173] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2 hrs, and vacuumed while hot and replaced with N2 gas 3 times. 450ml of heptane, 50mL of dichloromethane, 50mL of ether, 50mmol (8.5g) of 2,2-dimethyl-7-octenoic acid, 50mL of AlEt3 (1.0mol / L hexane solution) were injected, and then 3.0ml of methylaluminoxane (MAO) (1.53mol / l toluene solution) was added. 2.7mg (1.5μmol) of complex Ni8 was added. At 50°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred vigorously for 30min. It was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer with a polymerization activity of 1.89×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 182,000, the molecular weight distribution is 2.32, the molar content of the carboxyl monomer is 1.51%, the average particle size of the spherical polymer in the obtained polymer is 3.1 mm, and the yield of the spherical polymer is 65%.

[0174] Embodiment 20

[0175]

[0176] A 7mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2hrs, evacuated while hot and replaced with N2 gas three times. 4.0mL of heptane, 500μL of ether, 100μL (0.58mmol) of 2-methyl-3-butenoic acid isobutyl ester, 146μL of AliBu3 (95%), 60μL of AlEt3 (0.1mol / L heptane solution), 60μL (1.0mmol / L toluene solution) of tri(pentafluorophenyl)borane were injected, and 30μL (1.0mmol / L toluene solution) of complex Ni9 was added. At 30°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred vigorously for 30min. The polymer was neutralized with 10wt% hydrochloric acid-acidified ethanol solution to obtain a polymer with a polymerization activity of 1.47×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 282,000, the molecular weight distribution is 2.23, the molar content of the hydroxyl monomer is 0.92%, the average particle size of the spherical polymer in the obtained polymer is 3.0 mm, and the yield of the spherical polymer is 60%.

[0177] Embodiment 21

[0178] A 7mL stainless steel glass-lined polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 2h, evacuated while hot and replaced with N2 gas three times. 4.0mL of heptane, 200μL of pyridine, 100μL of triethoxysilane (2-methyl-3-butenyl) (0.38mmol), 60μL of AlMe3 (0.1mol / L heptane solution), 60μL (1.0mol / L toluene solution) of triphenylmethyl tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 30μL (1.0mmol / L toluene solution) of complex Ni9 was added. At 30°C, the ethylene pressure was maintained at 10atm, and the reaction was stirred for 30min. Finally, it was neutralized with 10wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 6.32×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 82,600, the molecular weight distribution is 3.42, and the molar content of Si monomer is 4.37%. The average particle size of the spherical polymer in the obtained polymer is 1.3 mm, and the yield of the spherical polymer is 66%.

[0179] Embodiment 22

[0180]

[0181] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2h, evacuated while hot and replaced with N2 gas three times. 400mL of heptane, 50mL of 1,6-dichlorohexane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3 (1.0mol / L hexane solution), 0.6mL of AlMe3 (1.0mol / L heptane solution), 5.5mg (6.0μmol) of triphenylmethyl tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 1.9mg (3μmol) of the complex Ni 10 , at 30°C, maintain 10 atm ethylene pressure, stir and react for 30 min. Finally, neutralize with 10 wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The obtained polymer has a polymerization activity of 1.22×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 123,600, the molecular weight distribution is 2.23, the molar content of the hydroxyl monomer is 1.16%, the average particle size of the spherical polymer in the obtained polymer is 3.3 mm, and the yield of the spherical polymer is 60%.

[0182] Embodiment 23

[0183] Complex Ni 11 The preparation method refers to Example 13 in patent CN112745362.

[0184]

[0185] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times. 400mL of heptane, 50mL of chloroform, 50mL of dioxane, 50mmol (10mL) of 2,6-dimethyl-7-octen-2-ol, 50mL of AliBu3 (1.0mol / L hexane solution), 0.6mL of AlMe3 (1.0mol / L heptane solution), 5.5mg (6.0μmol) of triphenylmethyl tetrakis (pentafluorophenyl) borate, and 2.4mg (1.5μmol) of complex Ni were injected into the polymerization system. 11 , at 30°C, maintaining an ethylene pressure of 10 atm, stirring and reacting for 30 min. Finally, neutralizing with 10 wt% hydrochloric acid ethanol solution to obtain a polymer. The polymerization activity was 1.52×10 7 g·mol -1 (Ni)·h -1The weight average molecular weight is 163,300, the molecular weight distribution is 2.20, the molar content of hydroxyl monomer is 1.38%, the average particle size of the spherical polymer in the obtained polymer is 3.2 mm, and the yield of the spherical polymer is 63%.

[0186] Embodiment 24

[0187] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 6 hrs, vacuumed and replaced with N2 gas three times while hot. 400ml of heptane, 100mL of dichloroethane, 50mL of cyclohexane, 30mmol (5.10g) of 2,2-dimethyl-7-octenoic acid, 30mL of AliBu3 (1.0mol / L hexane solution), 0.6mL of AlMe3 (1.0mol / L heptane solution), 4.8mg (6.0μmol) of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 2.4mg (1.5μmol) of the complex Ni were added. 11 At 20°C, the ethylene pressure was maintained at 10 atm and the reaction was stirred vigorously for 30 min. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol solution and the polymerization activity was 1.46×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 153,200, the molecular weight distribution is 2.27, the molar content of the carboxyl monomer is 1.30%, the average particle size of the spherical polymer in the obtained polymer is 3.5 mm, and the yield of the spherical polymer is 66%.

[0188] Embodiment 25

[0189] A 7mL 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 gas three times. 4.0mL of heptane, 500μL of cyclohexane, 100μL (0.64mmol) 3,3-dimethyl-4-pentenoic acid methyl ester, 164μL AliBu3 (95%, 0.64mmol), 60μL triisobutylaluminum (0.1mol / L heptane solution), 120μL (1.0mmol / L toluene solution) tri(pentafluorophenyl) borane, 60μL (1.0mmol / L toluene solution) N,N-dimethylanilinium tetra(pentafluorophenyl) borate were injected into the polymerization system, and 15μL (1.0mmol / L toluene solution) of the complex Ni 11 , at 30°C, maintaining an ethylene pressure of 10 atm, stirring and reacting for 10 min. Finally, neutralizing with 10 wt% hydrochloric acid ethanol solution to obtain a polymer. The polymerization activity was 6.16×10 6 g·mol -1 (Ni)·h -1The weight average molecular weight is 63,100, the molecular weight distribution is 2.52, the molar content of the ester monomer is 0.97%, the average particle size of the spherical polymer in the obtained polymer is 0.82 mm, and the yield of the spherical polymer is 61%.

[0190] Embodiment 26

[0191] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2h, evacuated while hot and replaced with N2 gas three times. 400mL of heptane, 60mL of dichloromethane, 5mL (24.1mmol) of 3-trimethylsilyl-4-pentenoic acid methyl ester, 12.3mL of AliBu3 (95%), 0.6mL of AlMe3 (1.0mol / L heptane solution), 5.5mg (6.0μmol) of triphenylmethyl tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 2.4mg (1.5μmol) of the complex Ni 11 , at 20°C, maintain 10 atm ethylene pressure, stir and react for 30 min. Finally, neutralize with 10 wt% hydrochloric acid ethanol solution to obtain a polymer. The polymerization activity is 5.98×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 84,200, the molecular weight distribution is 3.16, and the molar content of Si monomer is 4.20%. The average particle size of the spherical polymer in the copolymer is 3.3 mm, and the yield of the spherical polymer is 65%.

[0192] Embodiment 27

[0193]

[0194] Complex Ni 12 The preparation of the invention refers to Example 6 in patent CN112745362, except that the ligand L2 of the above formula is used to replace the ligand used in Example 6 in CN112745362.

[0195] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 6h, evacuated while hot and replaced with N2 gas three times. 400mL of heptane, 50mL of dichloroethane, 50mL of cyclohexane, 50mmol (10mL) of 2,6-dimethyl-7-octen-2-ol, 50mL of AliBu3 (1.0mol / L hexane solution), 0.6mL of AlEt3 (1.0mol / L heptane solution), 5.5mg (6.0μmol) of triphenylmethyl tetrakis(pentafluorophenyl)borate, and 2.5mg (1.5μmol) of complex Ni were injected into the polymerization system. 12, at 30°C, maintaining an ethylene pressure of 10 atm, stirring and reacting for 30 min. Finally, neutralizing with 10 wt% hydrochloric acid ethanol solution to obtain a polymer. The polymerization activity was 1.62×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 303,700, the molecular weight distribution is 2.26, the molar content of the hydroxyl monomer is 1.23%, the average particle size of the spherical polymer in the obtained polymer is 3.5 mm, and the yield of the spherical polymer is 61%.

[0196] Embodiment 28

[0197] A 7 mL stainless steel glass-lined polymerization reactor 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, 100 μL of dichlorohexane, 100 μL (0.64 mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 164 μL of AliBu3 (95%, 0.64 mmol), 60 μL of AlMe3 (0.1 mol / L heptane solution), 60 μL (1.0 mmol / L toluene solution) of tris(pentafluorophenyl)borane were injected into the polymerization system, and 15 μL (1.0 mmol / L toluene solution) of the complex Ni 12 , at 30°C, maintaining an ethylene pressure of 10 atm, stirring and reacting for 30 min. Finally, neutralizing with 10 wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 12.36×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 262,100, the molecular weight distribution is 2.41, the molar content of the ester monomer is 0.72%, the average particle size of the spherical polymer in the obtained polymer is 1.1 mm, and the yield of the spherical polymer is 68%.

[0198] Embodiment 29

[0199]

[0200] Complex Ni 13 The preparation reference patent CN112745362 Example 11, the difference is that the ligand L2 in Example 27 of the present invention is used to replace the ligand used in Example 11 of CN112745362.

[0201] A 7mL 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 gas three times. 4.0mL of heptane, 100μL of ether, 100μL (0.58mmol) of 2-methyl-3-butenoic acid isobutyl ester, 146μL of AliBu3 (95%, 0.58mmol), 50μL of AlMe3 (0.1mol / L heptane solution), 12.5μL (0.01mol / L toluene solution) of tri(pentafluorophenyl)borane, 12.5μL (0.01mol / L toluene solution) of triphenylmethyl tetrakis(pentafluorophenyl)borate were injected into the polymerization system, and 12.5μL (1.0mmol / L toluene solution) of the complex Ni 13 , at 30°C, maintaining an ethylene pressure of 20 atm, stirring and reacting for 30 min. Finally, neutralizing with 10 wt% hydrochloric acid acidified ethanol solution to obtain a polymer. The polymerization activity was 2.38×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 973,100, the molecular weight distribution is 2.42, the molar content of the ester monomer is 0.53%, the average particle size of the spherical polymer in the obtained polymer is 1.8 mm, and the yield of the spherical polymer is 63%.

[0202] Embodiment 30

[0203]

[0204] Complex Ni 14 The preparation reference patent CN112745362 Example 12.

[0205] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 6 hrs, evacuated while hot and replaced with N2 gas three times. 400ml of hexane, 100mL of dichloroethane, 50mL of cyclohexane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 36mL of AlHe3 (1.0mol / L hexane solution), 5.5mg (6.0μmol) of triphenylmethyl tetrakis(pentafluorophenyl)borate, and 3.1mg (1.5μmol) of the complex Ni were added. 14 At 30°C, the ethylene pressure was maintained at 10 atm and the reaction was stirred vigorously for 30 min. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol and the polymerization activity was 1.01×10 7 g·mol -1 (Ni)·h -1The weight average molecular weight is 133,400, the molecular weight distribution is 2.20, the molar content of the hydroxyl monomer is 1.20%, the average particle size of the spherical polymer in the obtained polymer is 3.3 mm, and the yield of the spherical polymer is 64%.

[0206] Embodiment 31

[0207] A 7 mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2 hrs, evacuated while hot and replaced with N2 gas three times. 4.0 mL of heptane, 100 μL of ether, 0.10 mL (0.70 mmol) of ethyl 2-methyl-3-butenoate, 178 μL of AliBu3 (95%, 0.70 mmol), 50 μL of AlMe3 (0.1 mol / L heptane solution), 12.5 μL (0.01 mol / L toluene solution) of tri(pentafluorophenyl)borane, 12.5 μL (0.01 mol / L toluene solution) of triphenylmethyl tetrakis(pentafluorophenyl)borate were injected, and 12.5 μL (1.0 mmol / L toluene solution) of the complex Ni 14 At 30°C, the ethylene pressure was maintained at 10 atm and the reaction was stirred vigorously for 30 min. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol solution and the polymerization activity was 1.13×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 123,700, the molecular weight distribution is 2.24, the molar content of the ester monomer is 1.04%, the average particle size of the spherical polymer in the obtained polymer is 0.9 mm, and the yield of the spherical polymer is 60%.

[0208] Embodiment 32

[0209]

[0210] Complex Ni 15 The preparation of the invention refers to Example 14 in patent CN112745362, except that the ligand L4 of the above formula is used to replace the ligand used in Example 14 in CN112745362.

[0211] Slowly drop an ethanol solution (10 mL) containing 0.277 g (0.9 mmol) (DME) NiBr2 into a dichloromethane solution (10 mL) containing 0.284 g (0.6 mmol) ligand L4. The solution immediately turns dark red and a large amount of precipitate is generated. Stir at room temperature for 6 h, add anhydrous ether to precipitate. Filter to obtain a filter cake, wash the filter cake with anhydrous ether, and vacuum dry to obtain a brown-red powder solid Ni 15 The yield was 75.2%. Elemental analysis (C 72 H 82Br6N4Ni3O2): C, 51.14; H, 4.89; N, 3.31; Exp. value (%): C, 50.82; H, 5.12; N, 3.07.

[0212] A 7mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2hrs, evacuated while hot and replaced with N2 gas three times. 4.0mL of heptane, 100μL of dioxane, 0.61mmol (100μL) of ethyl 2-methyl-4-pentenoate, 156μL of AliBu3 (95%, 0.61mmol), 50μL of AlEt3 (0.1mol / L heptane solution), 12.5μL (0.01mol / L toluene solution) of tris(pentafluorophenyl)borane, 12.5μL (0.01mol / L toluene solution) of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, 12.5μL (1.0mmol / L toluene solution) of complex Ni 15 At 30°C, the ethylene pressure was maintained at 10 atm and the reaction was stirred vigorously for 30 min. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol solution and the polymerization activity was 0.93×10 7 g·mol -1 (Ni)·h -1 The weight average molecular weight is 223,400, the molecular weight distribution is 3.21, the molar content of the ester monomer is 1.05%, the average particle size of the spherical polymer in the obtained polymer is 0.8 mm, and the yield of the spherical polymer is 61%.

[0213] Embodiment 33

[0214] A 7 mL stainless steel glass-lined polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2 hrs, evacuated while hot and replaced with N2 gas three times. 4.0 mL of heptane, 100 μL of dichloroethane, 100 μL (0.59 mmol) of allyltrimethoxysilane, 50 μL of AlEt3 (0.1 mol / L heptane solution), 12.5 μL (0.01 mol / L toluene solution) of tris(pentafluorophenyl)borane were injected, and 12.5 μL (1.0 mmol / L toluene solution) of the complex Ni 15 At 30°C, the ethylene pressure was maintained at 10 atm and the reaction was stirred vigorously for 30 min. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol solution and the polymerization activity was 7.32×10 6 g·mol -1 (Ni)·h -1 , the molar content of Si monomer was 3.47%, and the yield of spherical polymer was 57%.

[0215] Embodiment 34

[0216]

[0217] A 1L stainless steel polymerization reactor equipped with mechanical stirring was dried continuously at 130°C for 2h, evacuated while hot and replaced with N2 gas three times. 400ml of heptane, 50mL of dichloroethane, 50mL of cyclohexane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 36mL of AlEt3 (1.0mol / L hexane solution), 6.4mg (12.5μmol) of tris(pentafluorophenyl)borane, and 3.0mg (5μmol) of catalyst Ni were added. 16 At 30°C, the ethylene pressure was maintained at 10 atm and the reaction was stirred vigorously for 30 min. The polymer was neutralized with 10 wt% hydrochloric acid in ethanol and the polymerization activity was 8.13 × 10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 183,400, the molecular weight distribution is 2.61, the molar content of the hydroxyl monomer is 0.89%, the average particle size of the spherical polymer in the obtained polymer is 1.0 mm, and the yield of the spherical polymer is 61%.

[0218] Embodiment 35

[0219]

[0220] A 7mL 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 gas three times. 4.0mL of heptane, 200μL of ether, 100μL (0.64mmol) 3,3-dimethyl-4-pentenoic acid methyl ester, 164μL AliBu3 (95%, 0.64mmol), 60μL triisobutylaluminum (0.1mol / L heptane solution), 120μL (1.0mmol / L toluene solution) tri(pentafluorophenyl) borane, 60μL (1.0mmol / L toluene solution) N,N-dimethylanilinium tetra(pentafluorophenyl) borate were injected into the polymerization system, and 30μL (1.0mmol / L toluene solution) of the complex Ni 17 , at 30°C, maintaining an ethylene pressure of 10 atm, stirring and reacting for 10 min. Finally, neutralizing with 10 wt% hydrochloric acid ethanol solution to obtain a polymer. The polymerization activity was 4.34×10 6 g·mol -1 (Ni)·h -1 The weight average molecular weight is 71,200, the molecular weight distribution is 3.12, the molar content of the ester monomer is 0.90%, the average particle size of the spherical polymer in the obtained polymer is 0.74 mm, and the yield of the spherical polymer is 67%.

[0221] Comparative Example 1

[0222] A 1L stainless steel polymerization kettle equipped with mechanical stirring was dried continuously at 130°C for 2h, vacuumed while hot and replaced with N2 gas three times. 400mL of hexane, 4.7mL (30mmol) of 3,3-dimethyl-4-pentenoic acid methyl ester, 30mL of AliBu3 (1.0mol / L hexane solution), 0.6mL of AlMe3 (1.0mol / L heptane solution), 3.1mg (6.0μmol) of tris(pentafluorophenyl)borane, and 2.0mg (1.5μmol) of complex Ni1 were added into the polymerization system. 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 a polymer. The polymerization activity was 6.83×10 6 g·mol -1 (Ni)·h -1 The molecular weight of the obtained polymer was 167,000, the molecular weight distribution was 2.24, the unsaturated carboxylic acid ester content in the polymer was 0.74 mol%, the melting point of the polymer was 119.3°C, the average particle size of the spherical polymer in the obtained polymer was 3.4 mm, and the yield of the spherical polymer was 51%.

[0223] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

Claims

1. A coordination precipitation polymerization method for olefin polymerization, comprising: Mixing raw materials including monomers, catalysts, additives, modifiers and solvents to react; Wherein, the catalyst is selected from at least one of the transition metal complex represented by formula (I) and the transition metal complex represented by formula (II): Formula (I) Formula (II) In formula (I), R1 and R2 are each independently selected from one of substituted or unsubstituted C1-C30 hydrocarbon groups; R3 and R4 are each independently selected from one of hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 hydrocarbon groups, substituted or unsubstituted C1-C20 hydrocarbonoxy groups, and adjacent R3 and R4 are optionally connected to each other to form a ring or ring system; M is selected from one of Group VIII metals; X is selected from one of halogen, substituted or unsubstituted C1-C10 hydrocarbon groups, substituted or unsubstituted C1-C10 hydrocarbonoxy groups, and repeated Xs are the same or different; In formula (II), R1 and R2 are each independently selected from one of C1-C30 hydrocarbon groups with or without substitution, and repeated R1 or R2 are the same or different; R3 and R4 are each independently selected from one of hydrogen, halogen, hydroxyl, C1-C20 hydrocarbon groups with or without substitution, and C1-C20 alkoxy groups with or without substitution, and adjacent R3 and R4 are optionally connected to each other to form a ring or ring system, and repeated R3 or R4 are the same or different; R 11 is selected from one of C1-C20 hydrocarbon groups with or without substitution, and the repeated R 11 are the same or different; Y is selected from one of the non-metal atoms of Group VIA, and repeated Y is the same or different; M is selected from one of the metals of Group VIII, and repeated M is the same or different; X is selected from halogen, and repeated X is the same or different; The volume ratio of the solvent to the modifier is 1:100 to 100:1; The monomer is selected from any one or more of formulas (i) to (viii): (i) ethylene; (ii) propylene; (iii) α-olefins and internal olefins; (iv) C4-C20 dienes; (v) enols; (vi) unsaturated carboxylic acids; (vii) unsaturated carboxylic acid esters; (viii) terminal silanes / siloxanes; When the monomer is selected from at least one of (i) ethylene, (ii) propylene, (iii) α-olefins and internal olefins, (iv) C4-C20 dienes, (vii) unsaturated carboxylic acid esters, and (viii) terminal olefin silanes / siloxanes, the modifier is selected from at least one of halogenated alkanes, organic paraffins, monoether organic solvents, diether organic solvents, polyether organic solvents, and cyclic organic solvents; or, When the monomer is selected from at least one of (v) enol and (vi) unsaturated carboxylic acid, the modifier is selected from at least one of organic paraffin, monoether organic solvent, diether organic solvent, polyether organic solvent, cyclic organic solvent, or the modifier is selected from at least one of organic paraffin, monoether organic solvent, diether organic solvent, polyether organic solvent, cyclic organic solvent and halogenated hydrocarbons.

2. The coordination precipitation polymerization method according to claim 1, characterized in that: R1 in formula (I), R2 in formula (I), R1 in formula (II), and R2 in formula (II) are each independently selected from a C1-C20 alkyl group with or without a substituent, or a C6-C20 aryl group with or without a substituent; R3 in formula (I), R4 in formula (I), R3 in formula (II), and R4 in formula (II) are each independently selected from a hydrogen, a halogen, a hydroxyl, a C1-C20 hydrocarbon group with or without a substituent, or a C1-C20 hydrocarbonoxy group with or without a substituent, and adjacent R3 and R4 are optionally interconnected to form a ring or a ring system; M in formula (I) and M in formula (II) are each independently selected from nickel or palladium; Y in formula (II) is selected from oxygen or sulfur; X in formula (I) and X in formula (II) are each independently selected from halogen; R in formula (II) 11 One selected from substituted or unsubstituted C1-C20 alkyl groups.

3. The coordination precipitation polymerization method according to claim 1, characterized in that: X in formula (I) and X in formula (II) are each independently selected from halogen; R in formula (II) 11 One selected from C1-C10 alkyl groups which may be substituted or unsubstituted.

4. The coordination precipitation polymerization method according to claim 1, characterized in that: R in formula (II) 11 One selected from C1-C6 alkyl groups which may be substituted or unsubstituted.

5. The coordination precipitation polymerization method according to claim 1, characterized in that: R1 in formula (I), R2 in formula (I), R1 in formula (II), and R2 in formula (II) are each independently a group represented by formula A: Formula (A) In formula (A), R 1 -R 5 each independently selected from the group consisting of hydrogen, halogen, hydroxyl, a C1-C20 alkyl group which may be substituted or unsubstituted, a C2-C20 alkenyl group which may be substituted or unsubstituted, a C2-C20 alkynyl group which may be substituted or unsubstituted, a C1-C20 alkoxy group which may be substituted or unsubstituted, a C2-C20 alkenyloxy group which may be substituted or unsubstituted, a C2-C20 alkynyloxy group which may be substituted or unsubstituted, a C6-C20 aryl group which may be substituted or unsubstituted, a C6-C20 aryloxy group which may be substituted or unsubstituted, a C7-C20 aralkyl group which may be substituted or unsubstituted, a C7-C20 aralkyloxy group which may be substituted or unsubstituted, a C7-C20 alkaryl group which may be substituted or unsubstituted, and R 1 -R 5 Optionally, they are linked to each other to form a ring or a ring system.

6. The coordination precipitation polymerization method according to claim 1, characterized in that: The transition metal complex represented by formula (I) is selected from at least one of formula (Ia) to formula (Ic): In formula (Ia) to formula (Ic), R 1 -R 5 Each is independently selected from hydrogen, halogen, C1-C6 alkyl with or without substitution, C1-C6 alkoxy with or without substitution; M is nickel or palladium; X is independently selected from halogen; R3 and R4 have the same definitions as in formula (I); in formula (Ib), R5-R 10 Each is independently selected from one of hydrogen, halogen, C1-C6 alkyl, and C1-C6 alkoxy; in formula (Ic), R5-R8 are each independently selected from one of hydrogen, halogen, C1-C6 alkyl, and C1-C6 alkoxy.

7. The coordination precipitation polymerization method according to claim 1, characterized in that: The transition metal complex represented by formula (II) is selected from at least one of formula (IIa) and formula (IIb): In formula (IIa), R 1 -R 5 Each is independently selected from hydrogen, halogen, C1-C6 alkyl with or without substitution, C1-C6 alkoxy with or without substitution; R5-R 10 Each is independently selected from one of hydrogen, halogen, C1-C6 alkyl and C1-C6 alkoxy; M is nickel; Y is O; X is selected from halogen; R 11 One selected from a C1-C6 alkyl group with or without a substituent; In formula (IIb), R 1 -R 5 R5-R8 are each independently selected from one of hydrogen, halogen, C1-C6 alkyl with or without substitution, C1-C6 alkoxy with or without substitution; R5-R8 are each independently selected from one of hydrogen, halogen, hydroxyl, C1-C20 hydrocarbon with or without substitution, and R5-R8 are optionally connected to each other to form a ring or ring system; R 11 is selected from one of C1-C20 hydrocarbon groups with or without substitution; Y is independently selected from one of non-metal atoms of Group VIA; M is independently selected from one of metals of Group VIII; X is independently selected from halogen.

8. The coordination precipitation polymerization method according to claim 1, characterized in that: The enol, unsaturated carboxylic acid, unsaturated carboxylic acid ester, and terminal alkenyl silane / siloxane are each independently selected from at least one of the monomers represented by formula G: Formula G Wherein, in formula G, L1-L3 are each independently selected from H, a C1-C30 alkyl group with or without a substituent, L4 is selected from a C1-C30 alkylene group with or without a side group, and Pg is respectively selected from a hydroxyl group, a carboxyl group, a carboxylate group, and a silane group / siloxane group.

9. The coordination precipitation polymerization method according to claim 8, characterized in that: In formula G, L1 and L2 are H, L3 is H or one of a C1-C30 alkyl group with or without a substituent, and L4 is one of a C1-C30 alkylene group with or without a side group.

10. The coordination precipitation polymerization method according to claim 8, characterized in that: In formula G, L1 and L2 are H, L3 is H or a C1-C20 alkyl group which may or may not be substituted, and L4 is a C1-C20 alkylene group which may or may not have a side group.

11. The coordination precipitation polymerization method according to claim 1, characterized in that: The auxiliary agent is selected from at least one of an organic aluminum compound, an organic boron compound, and an organic silicon compound.

12. The coordination precipitation polymerization method according to claim 11, characterized in that: The organoaluminum compound is selected from alkylaluminoxane or a general formula of AlR n X 1 3-n Organic aluminum compounds, general formula AlR n X 1 3-n In the above formula, R is H, C1-C 20 Saturated or unsaturated hydrocarbon or C1-C 20 Saturated or unsaturated alkoxy group; X 1 is halogen; 0 <n≤3。 13. The coordination precipitation polymerization method according to claim 12, characterized in that: General formula AlR n X 1 3-n In the example, R is C1-C 20 Alkyl, C1-C 20 Alkoxy, C7-C 20 Arylalkyl or C6-C 20 Aryl; X 1 Chlorine or bromine.

14. The coordination precipitation polymerization method according to claim 11, characterized in that: The organic boron compound is selected from at least one of aromatic boron and borate; and / or, The organosilicon compound is selected from the general formula SiR' m1 X 2 n1 The alkyl silicon compound shown has the general formula SiR' m1 X 2 n1 In the formula, R' is selected from a C1-C10 alkyl group, and repeated R's are the same or different, and X 2 Selected from halogen, m1≥1, and m1+n1=4.

15. The coordination precipitation polymerization method according to claim 14, characterized in that: The aromatic hydrocarbon boron is selected from substituted or unsubstituted phenyl boron; and / or, the borate is selected from at least one of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and triphenylmethyl tetrakis(pentafluorophenyl)borate; and / or, The organosilicon compound is selected from at least one of trimethylchlorosilane, dichlorodimethylsilane, propyldimethylchlorosilane, dichloroethylmethylsilane, tert-butyldimethylchlorosilane, diisopropylchlorosilane, trichloroethylsilane, chloromethyldimethylchlorosilane, di-tert-butylchlorosilane, dichloro(methyl)propylsilane, methyltrichlorosilane and trichloroethylsilane.

16. The coordination precipitation polymerization method according to claim 14, characterized in that: The aromatic hydrocarbon boron is tris(pentafluorophenyl)boron.

17. The coordination precipitation polymerization method according to claim 11, 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.

18. The coordination precipitation polymerization method according to claim 11, 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.

19. The coordination precipitation polymerization method according to claim 11, characterized in that: When the auxiliary agent contains an organic aluminum compound, the molar ratio of aluminum in the organic aluminum compound to M in the catalyst is (10-10000000):1; When the auxiliary agent contains an organic boron compound, the molar ratio of boron in the organic boron compound to M in the catalyst is (0.1-1000):1; When the auxiliary agent contains an organosilicon compound, the molar ratio of silicon in the organosilicon compound to M in the catalyst is (10-10000000):

1.

20. The coordination precipitation polymerization method according to claim 11, characterized in that: When the auxiliary agent contains an organic aluminum compound, the molar ratio of aluminum in the organic aluminum compound to M in the catalyst is (10-100000):1; When the auxiliary agent contains an organic boron compound, the molar ratio of boron in the organic boron compound to M in the catalyst is (0.1-500):1; When the auxiliary agent contains an organosilicon compound, the molar ratio of silicon in the organosilicon compound to M in the catalyst is (10-200000):

1.

21. The coordination precipitation polymerization method according to claim 1, characterized in that: The solvent is selected from alkane solvents.

22. The coordination precipitation polymerization method according to claim 21, characterized in that: The alkane solvent is selected from one or more C3-C20 alkanes.

23. The coordination precipitation polymerization method according to claim 21, characterized in that: The alkane solvent is selected from one or more C3-C10 alkanes.

24. The coordination precipitation polymerization method according to claim 1, characterized in that: The halogenated alkane is selected from the formula R1, X 3 n2 R2'X 4 m2 At least one of the compounds shown, wherein X 3 , X 4 Each is independently selected from halogen, m2+n2≥1, R1' is selected from C1-C10 alkyl or alkenyl, R2' is selected from C1-C10 alkylene or alkenylene; and / or, the monoether organic solvent is selected from at least one of the compounds represented by the formula R5'-O-R6', wherein R5' and R6' are independently selected from C1-C10 alkyl, R5' and R6' are optionally cyclized; and / or, the diether organic solvent is selected from at least one of the compounds represented by the formula R7'OR8'OR9', wherein R7' and R9' are independently selected from C1-C10 alkyl, R7' and R9' are optionally cyclized, and R8' is selected from C1-C10 alkylene; and / or, the polyether organic solvent is selected from the formula R 10 '-(OR 11 ') x -OR 12 ', where R 10 '、R 12 ' are each independently selected from C1-C10 alkyl groups, R 11 ' is selected from C1-C10 alkylene, x≥2; and / or, the cyclic organic solvent is selected from at least one of dioxane, tetrahydrofuran, tetralin, pyridine and cyclohexane.

25. The coordination precipitation polymerization method according to any one of claims 1 to 24, characterized in that: The concentration of the monomer in the raw material is 0.01-6000 mmol / L; and / or, The concentration of the catalyst in the raw material is 0.00001-100 mmol / L; and / or, The volume ratio of the solvent to the modifier is 1:20 to 20:

1.

26. The coordination precipitation polymerization method according to claim 25, characterized in that: The concentration of the monomer in the raw material is 0.1-1000 mmol / L; and / or, The concentration of the catalyst in the raw material is 0.0001-1 mmol / L.

27. The coordination precipitation polymerization method according to claim 25, characterized in that: The reaction conditions include: a reaction temperature of -50°C to 100°C; and / or a reaction time of 10 to 200 minutes.

28. The coordination precipitation polymerization method according to claim 27, characterized in that: The reaction conditions include: a reaction temperature of -20 to 60° C.; and / or a reaction time of 20 to 60 min.

29. A polymer obtained by the coordination precipitation polymerization method according to any one of claims 1 to 28, which is a spherical or quasi-spherical polymer.

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