阅读说明：本技术 用于制备烯烃-烯烃醇共聚物的方法 (Process for preparing olefin-olefin alcohol copolymers ) 是由 高榕 郭子芳 赖菁菁 李昕阳 顾元宁 李岩 黄廷杰 于 2020-06-05 设计创作，主要内容包括：本发明涉及一种用于制备烯烃-烯烃醇共聚物的方法及由所述方法制备的烯烃-烯烃醇共聚物。所述方法包括在催化剂、改进剂和任选地链转移剂存在下使烯烃和烯烃醇发生聚合反应,生成烯烃-烯烃醇共聚物,其中使用的催化剂包含式I所示的二亚胺金属配合物。根据本发明的制备方法制得的球形和/或类球形聚合物在工业应用中具有良好的前景。(The present invention relates to a method for preparing an olefin-olefin alcohol copolymer and an olefin-olefin alcohol copolymer prepared by the method. The process comprises polymerizing an olefin and an olefin alcohol in the presence of a catalyst, an improver, and optionally a chain transfer agent to form an olefin-olefin alcohol copolymer, wherein the catalyst used comprises a diimine metal complex of formula I. The spherical and/or spheroidal polymers prepared by the preparation method of the invention have good prospects in industrial application.)

1. A process for preparing an olefin-olefin alcohol copolymer comprising polymerising an olefin and an olefin alcohol in the presence of a catalyst, an improver and optionally a chain transfer agent to produce the olefin-olefin alcohol copolymer,

wherein the catalyst comprises a main catalyst and an optional cocatalyst, and the main catalyst comprises a diimine metal complex shown as a formula I:

in the formula I, R₁And R₂The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r₅-R₈The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r₅-R₈Optionally forming a ring with each other; r₁₂Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.

2. The method of claim 1, wherein R is₁And R₂Selected from substituted or unsubstituted C1-C20 alkyl and/or substituted or unsubstituted C6-C20 aryl, preferably R₁And/or R₂Is a group of formula II:

in the formula II, R¹-R⁵The substituents are the same or different, and are respectively and independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, and C1-C20 alkyl with or without substituentC2-C20 alkynyloxy, substituted or unsubstituted C3-C20 cycloalkoxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, and substituted or unsubstituted C7-C20 alkaryl; r¹-R⁵Optionally forming a ring with each other;

preferably, in formula II, R¹-R⁵The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;

m is selected from nickel and palladium; y is selected from O and S; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent, preferably selected from halogen, C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent; r₁₂Is selected from C1-C20 alkyl with or without substituent, preferably C1-C10 alkyl with or without substituent, more preferably C1-C6 alkyl with or without substituent.

3. A process according to claim 1 or 2, wherein the diimine metal complex is of formula III:

in the formula III, R¹-R¹¹The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, and substituentOptionally substituted C2-C20 alkenyl, optionally substituted C2-C20 alkynyl, optionally substituted C3-C20 cycloalkyl, optionally substituted C1-C20 alkoxy, optionally substituted C2-C20 alkenyloxy, optionally substituted C2-C20 alkynyloxy, optionally substituted C3-C20 cycloalkoxy, optionally substituted C6-C20 aryl, optionally substituted C7-C20 aralkyl, and optionally substituted C7-C20 alkaryl,

m, X, Y, R in formula III₁₂Have the same definition as formula I.

4. The method of any one of claims 1-3, wherein R is¹-R¹¹The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;

preferably, R¹-R¹¹Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

5. A process according to any one of claims 1 to 4, characterised in that the substituents are selected from halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy; the substituents are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy;

preferably, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3, 3-dimethylbutyl;

preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3, 3-dimethylbutoxy,

preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.

6. A process according to any one of claims 1 to 5, characterised in that the diimine metal complex is selected from one or more of the following complexes:

1) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

2) a diimine metal complex of formula III wherein R¹＝R³Ethyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

3) a diimine metal complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

4) a diimine metal complex of formula III wherein R¹-R³Methyl, R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

5) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝Br，R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

6) a diimine metal complex of formula III wherein R¹＝R³＝F，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

7) a diimine metal complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

8) a diimine metal complex of formula III wherein R¹＝R³＝Br，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

9) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

10) a diimine metal complex of formula III wherein R¹＝R³Ethyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

11) a diimine metal complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

12) a diimine metal complex of formula III wherein R¹-R³Methyl, R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

13) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝Br，R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

14) a diimine metal complex of formula III wherein R¹＝R³＝F，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

15) a diimine metal complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

16) a diimine metal complex of formula III wherein R¹＝R³＝Br，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

17) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

18) a diimine metal complex of formula III wherein R¹＝R³Ethyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

19) a diimine metal complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

20) a diimine metal complex of formula III wherein R¹-R³Methyl, R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

21) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝Br，R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

22) a diimine metal complex of formula III wherein R¹＝R³＝F，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

23) a diimine metal complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

24) a diimine metal complex of formula III wherein R¹＝R³＝Br，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, and X ═ Br.

7. The process according to any one of claims 1 to 6, wherein the olefin comprises an olefin having 2 to 16 carbon atoms, preferably the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms, and/or the olefinic alcohol is selected from one or more olefinic alcohols of formula G:

in the formula G, L₁-L₃Each independently selected from H and C with or without substituent₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group;

preferably, the copolymer has a content of structural units derived from the olefin alcohol represented by the formula G of 0.4 to 10.0 mol%;

preferably, L₁And L₂Is H, L₃Is H or C₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group;

more preferably, L₁And L₂Is H, L₃Is H or C₁-C₂₀Alkyl radical, L₄Is C having a pendant group₁-C₂₀An alkylene group;

still more preferably, L₁And L₂Is H, L₃Is H or C₁-C₁₀Alkyl radical, L₄Is C having a pendant group₁-C₁₀An alkylene group;

further preferably, L₁And L₂Is H, L₃Is H or C₁-C₁₀Alkyl radical, L₄Is C having a pendant group₁-C₆An alkylene group.

8. The method of claim 7, wherein L is₁-L₃Wherein said substituents are selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical、C₆-C₁₀One or more of aryl, cyano and hydroxy; more preferably L₁-L₃Wherein the substituent is selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy;

the side group in L4 is selected from halogen and C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀One or more of alkoxy, said C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl and hydroxyl.

9. A process according to any one of claims 1 to 8, characterised in that the cocatalyst is selected from organoaluminium compounds and/or organoboron compounds; the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate; the chain transfer agent is selected from one or more of alkyl aluminum, alkyl magnesium, alkyl boron and alkyl zinc;

the improver comprises halogenated hydrocarbon, preferably, the halogenated hydrocarbon is selected from halogenated hydrocarbon of C1-C15, preferably halogenated alkane of C1-C15, more preferably halogenated alkane of C1-C10, and further preferably halogenated alkane of C1-C6;

preferably, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine metal complex is (10-10)⁷):1, preferably (10-100000) 1, more preferably (100-; when the cocatalyst is an organic boron compound, the molar ratio of boron in the cocatalyst to M in the diimine metal complex is (0.1-1000):1, preferably (0.1-500): 1; the molar ratio of the chain transfer agent to M in the diimine metal complex is (0.1-5000) to 1, preferably (1.0-1000) to 1;

preferably, the volume ratio of the solvent used for the polymerization to the modifier is (1-5000):1, preferably (1.0-500): 1.

10. An olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 9, which is spherical and/or spheroidal, and/or which has a particle size of from 0.1 to 50 mm.

11. Use of an olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 9 or the olefin-olefin alcohol copolymer of claim 10 as a polyolefin material.

Technical Field

The invention belongs to the field of preparation of high molecular polymers, and particularly relates to a method for preparing an olefin-olefin alcohol copolymer.

Background

The polyolefin product has low price, excellent performance and wide application range. Under the condition of keeping the original excellent physical and chemical properties of the polyolefin, polar groups are introduced into polyolefin molecular chains by a chemical synthesis method, so that the chemical inertness, the printing property, the wettability and the compatibility with other materials can be improved, and new characteristics which are not possessed by raw materials are endowed. High pressure free radical polymerization is currently used commercially to promote direct copolymerization of olefins with polar monomers, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, and ethylene-acrylic acid copolymers. Although the polar comonomer can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.

Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is a novel high molecular material integrating the processability of ethylene polymer and the gas barrier property of vinyl alcohol polymer, is one of three barrier resins industrially produced in the world at present, and is widely used for packaging food, medical solution and other products. Since vinyl alcohol cannot exist independently in the form of monomer, it is usually prepared by alcoholysis of ethylene-vinyl acetate copolymer by radical polymerization, but the alcoholysis process requires the use of a large amount of solvent, and the final saponification product contains a large amount of impurities such as acetic acid and alkali metal salt, and requires a large amount of water for washing.

As a preparation technology of polymers at normal temperature and normal pressure, coordination catalytic copolymerization has attracted extensive attention due to its remarkable effects in reducing energy consumption, improving reaction efficiency and the like. The catalyst participates in the reaction process, so that the activation energy of the copolymerization reaction of the olefin monomer and the polar monomer is greatly reduced, and the functional polymer with higher molecular weight can be obtained at lower temperature and pressure. Currently, only a few documents report the use of transition metal complexes to catalyze the copolymerization of olefins and unsaturated alcohols. For example, CN109694438A discloses a process for the polymerization of olefins to olefinic alcohols wherein the procatalyst used is a mononuclear transition metal complex.

Disclosure of Invention

In a first aspect, the present invention provides a process for the preparation of an olefin-olefin alcohol copolymer comprising polymerising an olefin and an olefin alcohol in the presence of a catalyst, an improver, optionally a chain transfer agent, to produce the olefin-olefin alcohol copolymer,

wherein the catalyst comprises a main catalyst and an optional cocatalyst, and the main catalyst comprises a diimine metal complex shown as a formula I:

in the formula I, R₁And R₂The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r₅-R₈The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r₅-R₈Optionally forming a ring with each other; r₁₂Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.

According to some embodiments of the invention, R₁And R₂Selected from substituted or unsubstituted C1-C20 alkyl and or substituted or unsubstituted C6-C20 aryl, preferably R₁And/or R₂Is a group of formula II:

in the formula II, R¹-R⁵The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent; r¹-R⁵Optionally forming a ring with each other.

According to some embodiments of the invention, R in formula II¹-R⁵The aryl group is selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent.

According to some embodiments of the invention, M is selected from nickel and palladium.

According to some embodiments of the invention, Y is selected from O and S.

According to some embodiments of the invention, X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, and substituted or unsubstituted C1-C10 alkoxy, preferably from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy.

According to some embodiments of the invention, R₁₂Is selected from C1-C20 alkyl with or without substituent, preferably C1-C10 alkyl with or without substituent, more preferably C1-C6 alkyl with or without substituent.

According to some embodiments of the invention, the diimine metal complex is represented by formula III:

in the formula III, R¹-R¹¹The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent, and C7-C20 alkaryl with or without substituent, M, X, Y, R-C20 alkenyl with or without substituent in formula III₁₂Have the same definition as formula I.

According to some embodiments of the invention, R¹-R¹¹The substituents are selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent, and CC7-C15 alkylaryl.

According to some embodiments of the invention, R¹-R¹¹Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

According to some embodiments of the invention, the substituent is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy; the substituents are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy;

according to some embodiments of the invention, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3, 3-dimethylbutyl;

according to some embodiments of the invention, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3, 3-dimethylbutoxy.

According to some embodiments of the invention, the halogen is selected from fluorine, chlorine, bromine and iodine.

According to some embodiments of the invention, the diimine metal complex is selected from one or more of the following complexes:

1) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

2) a diimine metal complex of formula III wherein R¹＝R³Ethyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M-Ni, Y-O, X＝Br；

3) A diimine metal complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

4) a diimine metal complex of formula III wherein R¹-R³Methyl, R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

5) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝Br，R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

6) a diimine metal complex of formula III wherein R¹＝R³＝F，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

7) a diimine metal complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

8) a diimine metal complex of formula III wherein R¹＝R³＝Br，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

9) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

10) a diimine metal complex of formula III wherein R¹＝R³Ethyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

11) a diimine metal complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

12) a diimine metal complex of formula III wherein R¹-R³Methyl, R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

13) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝Br，R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

14) a diimine metal complex of formula III wherein R¹＝R³＝F，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

15) a diimine metal complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

16) a diimine metal complex of formula III wherein R¹＝R³＝Br，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹＝R¹¹Methyl, R₁₂Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

17) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

18) a diimine metal complex of formula III wherein R¹＝R³Ethyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

19) a diimine metal complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

20) a diimine metal complex of formula III wherein R¹-R³Methyl, R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

21) a diimine metal complex of formula III wherein R¹＝R³Methyl, R²＝Br，R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

22) a diimine metal complex of formula III wherein R¹＝R³＝F，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M-Ni, Y-O，X＝Br；

23) A diimine metal complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, X ═ Br;

24) a diimine metal complex of formula III wherein R¹＝R³＝Br，R²＝R⁴-R⁷＝R¹⁰＝H，R⁸＝R⁹Methyl, R¹¹Bromomethyl, R₁₂Ethyl, M ═ Ni, Y ═ O, and X ═ Br.

According to some embodiments of the invention, the alkene alcohol is selected from one or more of the alkene alcohols represented by formula G:

in the formula G, L₁-L₃Each independently selected from H and C with or without substituent₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group.

According to some embodiments of the invention, the copolymer has a content of structural units derived from the alkene alcohol represented by formula G of 0.4 to 10.0 mol%.

According to some embodiments of the invention, in formula G, L₁And L₂Is H.

According to some embodiments of the invention, in formula G, L₃Is H or C₁-C₃₀An alkyl group.

According to some embodiments of the invention, in formula G, L₄Is C having a pendant group₁-C₃₀An alkylene group.

According to some embodiments of the invention, in formula G, L₃Is H or C₁-C₂₀An alkyl group.

According to some embodiments of the invention, in formula G, L₄To have a sideC of radical₁-C₂₀An alkylene group.

According to some embodiments of the invention, in formula G, L₃Is H or C₁-C₁₀An alkyl group.

According to some embodiments of the invention, in formula G, L₄Is C having a pendant group₁-C₁₀An alkylene group.

According to some embodiments of the invention, in formula G, L₄Is C having a pendant group₁-C₆An alkylene group.

According to some embodiments of the invention, L₁-L₃Wherein said substituents are selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl, cyano and hydroxyl.

According to some embodiments of the invention, L₁-L₃Wherein the substituent is selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy.

According to some embodiments of the invention, the pendant group in L4 is selected from halogen, C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀One or more of alkoxy, said C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl and C₁-C₂₀Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl and hydroxyl.

According to a preferred embodiment of the invention, said L₄The side group in (A) is selected from halogen and C₆-C₂₀Aryl radical, C₁-C₂₀Alkyl, hydroxy substituted C₁-C₂₀Alkyl and alkoxy substituted C₁-C₂₀One or more of alkyl; preferably, the side group is selected from halogen, C₆-C₂₀Aryl radical, C₁-C₁₀Alkyl, hydroxy substituted C₁-C₁₀Alkyl and alkoxy substitutedC_1-10One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C₁-C₆Alkyl and hydroxy substituted C₁-C₆One or more of alkyl, said C₁-C₆Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl.

According to a preferred embodiment of the invention, in formula G, L₁And L₂Is H, L₃Is H or C₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group; said C is₁-C₃₀Alkyl is optionally substituted by a substituent, preferably selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl, cyano and hydroxyl.

According to a preferred embodiment of the invention, in formula G, L₁And L₂Is H, L₃Is H, C₁-C₁₀Alkyl or halogen substituted C₁-C₁₀Alkyl, preferably L₃Is H or C₁-C₁₀An alkyl group; l is₄Is C having a pendant group₁-C₂₀Alkylene radicals, e.g. L₄Is methylene with side group, ethylene with side group, propylene with side group, butylene with side group, C with side group₅Alkylene, C having pendant groups₆Alkylene, C having pendant groups₇Alkylene, C having pendant groups₈Alkylene, C having pendant groups₉Alkylene, C having pendant groups₁₀Alkylene, C having pendant groups₁₂Alkylene, C having pendant groups₁₄Alkylene, C having pendant groups₁₈Alkylene, C having pendant groups₂₀Alkylene, preferably C, having pendant groups₁-C₁₀An alkylene group.

According to a preferred embodiment of the invention, in formula G, L₁And L₂Is H, L₃Is H or C_1-6An alkyl group; l is₄Is C having a pendant group₁-C₁₀Alkylene radical。

In the present invention, the carbon number n of the Cn alkylene group means the number of C's in the linear chain, excluding the number of C's in the pendant group, and is, for example, isopropylidene (-CH)₂-CH(CH₃) -) is referred to herein as C with a pendant group (methyl)₂An alkylene group.

According to a preferred embodiment of the present invention, specific examples of the alkene alcohol represented by formula G include, but are not limited to: 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2, 4-dimethyl-4-penten-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-methyl-3-buten-2-ol, 2-methyl-4-penten-2-ol, 2-methyl-3-buten-ol, 2-methyl-4-penten-2-ol, 2-methyl-4-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-2-ol, and mixtures thereof, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2, 3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2, 5-dimethyl-1-hepten-4-ol, 2, 6-dimethyl-7-octen-2-ol, 2-hydroxy-2, 4, 5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-6-heptene, 2-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-2-heptene, 2-methyl-2-1-heptene, 2-methyl-2-4-methyl-6-heptene, 2-methyl-4-heptene, 2-1-octene, 2-octene, 2-heptene, 2-octene, 2-one, 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, mixtures thereof, and mixtures thereof, 2-methyl-2-hydroxy-3, 5-dichloro-7-octene, 3, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3, 5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2, 3-diol, and 2, 6-dimethyl-7-octen-2, 6-diol.

According to a preferred embodiment of the invention, the cocatalyst is chosen from organoaluminum compounds and/or organoboron compounds.

According to a preferred embodiment of the invention, the organoaluminium compound is selected from alkylaluminoxanes or compounds of general formula AlR_nX¹ _3-nWith an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlR_nX¹ _3-nWherein R is H, C₁-C₂₀Saturated or unsaturated hydrocarbon radicals or C₁-C₂₀Saturated or unsaturated hydrocarbyloxy radicals, preferably C₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy radical, C₇-C₂₀Aralkyl or C₆-C₂₀An aryl group; x¹Is halogen, preferably chlorine or bromine; 0<n is less than or equal to 3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compound is Methylaluminoxane (MAO).

According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.

According to an embodiment of the invention, said modifier comprises a halogenated hydrocarbon, preferably said halogenated hydrocarbon is selected from C₁-C₁₅The halogenated hydrocarbon of (1).

According to a preferred embodiment of the invention, the modifier comprises a halogenated alkane of C1 to C15, more preferably a halogenated alkane of C1 to C10, even more preferably a halogenated alkane of C1 to C6.

According to a preferred embodiment of the invention, the improver comprises methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, 1,1, 2-trichloroethane, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, 1,1,1, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 2-chloropropane, chloro-n-propane, 1, 3-dichloropropane, 1,1, 2-trichloropropane, 1,1,2,2,3, 3-hexachloropropane, 1,1,1,2,2,3, 3-heptachloropropane, 1-chlorobutane, chloro-tert-butane, 1, 4-dichlorobutane, 1, 2-dichloroisobutane, 1,1, 2-trichloro-2-methylpropane, 1,2,3, 4-tetrachlorobutane, 1-chloropentane, 2-chloro-2-methylbutane, 1-chloro-3-methylbutane, 1-chloro-2, 2-dimethylpropane, 1-chloro-2-methylbutane, 1, 5-dichloropentane, 2, 2-dimethyl-1, 3-dichloropropane, 1,1,1- (trichloromethyl) ethane, tetrachloro-pentanes.

According to a preferred embodiment of the present invention, the concentration of the main catalyst in the reaction system is 0.00001 to 100mmol/L, for example, 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, 0.3mmol/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, 100mmol/L and any value therebetween, preferably 0.0001 to 1mmol/L, more preferably 0.001 to 0.5 mmol/L.

According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (10-10000000):1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1 and any value therebetween, preferably (10-100000):1, more preferably (100-10000): 1; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the procatalyst is (0.1-1000):1, e.g., 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 4:1, 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, preferably (0.1-500): 1.

According to a preferred embodiment of the invention, the olefin comprises an olefin having from 2 to 16 carbon atoms, in some embodiments of the invention the olefin comprises ethylene or has from 3 to 16Alpha-olefins of carbon atoms. In other embodiments of the present invention, the olefin is C₃-C₁₆A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms, more preferably ethylene or C₂-C₁₀Alpha-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene and octene.

According to a preferred embodiment of the present invention, the concentration of the olefin alcohol monomer represented by the formula G in the reaction system is 0.01 to 6000mmol/L, preferably 0.1 to 1000mmol/L, more preferably 1 to 500mmol/L, and may be, for example, 1mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 90mmol/L, 100mmol/L, 200mmol/L, 300mmol/L, 400mmol/L, 500mmol/L and any value therebetween.

According to a preferred embodiment of the present invention, the chain transfer agent is selected from one or more of aluminum alkyls, magnesium alkyls, boron alkyls and zinc alkyls.

According to a preferred embodiment of the invention, the chain transfer agent is a trialkylaluminum and/or a dialkylzinc, preferably one or more selected from the group consisting of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc and diethylzinc.

According to a preferred embodiment of the invention, the molar ratio of the chain transfer agent to M in the procatalyst is (0.1-2000: 1, e.g. 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, 600:1, 800:1, 1000:1, 2000:1 and any value in between, preferably (10-600: 1).

According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent. According to a preferred embodiment of the invention, the alkane solvent is selected from C₃-C₂₀One or more alkanes, preferably selected from C₃-C₁₀The alkane, for example, 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.

According to a preferred embodiment of the invention, the volume ratio of solvent to modifier used for the polymerization is (1-5000):1, preferably (1.0-500): 1. For example, 1:1, 2:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 600:1, 800:1, 1000:1, 2000:1, and any value in between, preferably (1.0-500): 1.

According to a preferred embodiment of the present invention, the olefin alcohol is pre-treated with a dehydroactive hydrogen, preferably with a co-catalyst or chain transfer agent as described above, to remove hydroxyl active hydrogen from the olefin alcohol. Preferably, the molar ratio of hydroxyl groups in the alkene alcohol to co-catalyst or chain transfer agent during pretreatment is from 10:1 to 1: 10.

According to a preferred embodiment of the invention, the reaction is carried out in the absence of water and oxygen.

According to a preferred embodiment of the invention, the conditions of the reaction include: the temperature of the reaction is-50 ℃ to 50 ℃, preferably-20 ℃ to 50 ℃, more preferably 0 ℃ to 50 ℃, and can be, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃,50 ℃ and any value therebetween; and/or the reaction time is 10-200min, preferably 20-60 min. In the present invention, the reaction pressure is not particularly limited as long as the monomer can be subjected to coordination copolymerization. When the olefin is ethylene, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50atm, from the viewpoint of cost reduction and simplification of the polymerization process.

In the present invention, the "reaction system" refers to the whole formed by the solvent, olefin alcohol monomer, catalyst, modifier and optionally chain transfer agent.

The invention also provides an olefin-olefin alcohol copolymer prepared by the preparation method, which comprises spherical and/or spheroidal polymers.

According to a preferred embodiment of the invention, the spherical and/or spheroidal polymers have an average particle size of 0.1 to 50.0mm, for example 0.1mm, 0.5mm, 1.0mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value in between, preferably 0.5 to 20.0 mm.

According to a preferred embodiment of the present invention, in the olefin-olefin alcohol copolymer, the content of the structural unit derived from the olefin alcohol represented by the formula G is 0.4 to 30.0 mol%, and for example, may be 0.4 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 5.0 mol%, 8.0 mol%, 10.0 mol%, 15.0 mol%, 20.0 mol%, 25.0 mol%, 30.0 mol% and any value therebetween, preferably 0.7 to 10.0 mol%.

According to a preferred embodiment of the present invention, the weight average molecular weight of the olefin-olefin alcohol copolymer is 30000-500000, preferably 50000-400000.

According to a preferred embodiment of the present invention, the olefin-olefin alcohol copolymer has a molecular weight distribution of 4.0 or less, and for example, may be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and any value therebetween, and preferably, the molecular weight distribution is 1.0 to 4.0.

In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.

According to still another aspect of the present invention, there is provided a use of the olefin-olefin alcohol copolymer as a polyolefin material.

Symbols such as R used in different formulae or structural formulae herein¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R₁₂、R₃X, M, A, Y, etc., have the same definitions in each general formula or structural formula unless otherwise specified.

In the present invention, C₁-C₂₀Alkyl is C₁-C₂₀Straight chain alkyl or C₃-C₂₀Branched alkyl groups of (a), including but 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-C₂₀Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

C₆-C₂₀Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.

C₂-C₂₀Alkenyl means C₁-C₂₀Linear alkenyl of (A) or (C)₃-C₂₀Including but not limited to: vinyl, allyl, butenyl.

C₇-C₂₀Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl and phenyl-tert-butyl.

C₇-C₂₀Examples of alkaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl groups.

The process for preparing an olefin-olefin alcohol copolymer provided by the present invention uses a novel trinuclear metal complex-containing catalyst. The catalyst is not reported, therefore, the technical problem solved by the invention is to provide a novel preparation method of olefin-olefin alcohol copolymer.

Furthermore, in the preparation method of the olefin-olefin alcohol copolymer provided by the invention, the spherical and/or spheroidal polymers with good shapes are directly prepared by selecting the olefin alcohol monomer for reaction, the catalyst and a proper polymerization process without subsequent processing steps such as granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.

Further, compared with the existing industrial process for preparing olefin-olefin alcohol copolymers, the method for preparing olefin-olefin alcohol copolymers provided by the invention omits the step of saponification reaction, and has simpler preparation process.

Furthermore, the modifier introduced in the invention can effectively improve the balling effect of the polymer.

Detailed Description

The present invention is described in detail with reference to the following examples, but it should be understood that the examples are only for illustrative purposes and are not intended to limit the scope of the present invention. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.

The analytical characterization instrument used in the present invention was as follows:

1. nuclear magnetic resonance apparatus: bruker DMX 300(300MHz), Tetramethylsilicon (TMS) as an internal standard, was used to test the structure of the complex ligands at 25 ℃.

2. Comonomer content of the polymer: (content of structural units derived from the olefin alcohol represented by the formula G): by using¹HNMR、¹³C NMR spectroscopy was carried out by dissolving a polymer sample in 1,2, 4-trichlorobenzene at 120 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX 13 probe.

3. Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the polymer: measured at 150 ℃ using PL-GPC220 in trichlorobenzene (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).

4. The activity measurement method comprises the following steps: weight of polymer (g)/nickel (mol). times.2.

The complex used in the examples has the structure shown in formula III:

example 1

1) Ligand L₁The preparation of (1):

under the protection of nitrogen, 2, 6-diethylaniline (2.0mL,12mmol) is dissolved in 20mL of toluene, 12mL (1.0M,12mmol) of trimethylaluminum is dropped at normal temperature, the reaction is refluxed for 2 hours, the system is cooled to room temperature, camphorquinone (0.831g,5mmol) is added, and the reflux reaction of the system is carried out for 6 hours. Neutralizing the reaction product with sodium hydroxide water solution, extracting with dichloromethane, drying, and separating the column layerThe yellow ligand L is separated out₁The yield was 69.2%.¹H-NMR(CDCl₃):δ6.94-6.92(m,6H,C_Ar-CH₃),2.56-2.51(m,4H,C_Ar-CH₃),2.36-2.31(m,4H,C_Ar-CH₃),1.82-1.78(m,4H,CH₂),1.54(m,1H),1.24-1.18(m,12H),1.09(s,3H,CH₃),0.94(m,6H,CH₃)。

2) Complex Ni₁(R in the formula III)¹、R³Is ethyl, R²、R⁴-R⁷、R¹⁰Is hydrogen, R⁸、R⁹And R¹¹Is methyl, R₁₂For ethyl, M is nickel, Y is O, X is Br):

will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.258g (0.6mmol) of ligand L₁In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni₁. Yield: 78.2 percent. Elemental analysis (C)₆₄H₉₀Br₆N₄Ni₃O₂): c, 47.96; h, 5.66; n, 3.50; experimental values (%): c, 47.48; h, 6.00; and N, 3.26.

3) Polymerization:

continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁10mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 2

This example uses Ni catalyst prepared in example 1₁Description of the preferred embodimentsThe differences between 1 are: the amount of dichloromethane used was 5 times that of example 1. The method comprises the following specific steps:

continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 3

This example uses Ni catalyst prepared in example 1₁The difference from example 1 is that: the amount of dichloromethane used was 10 times that of example 1. The method comprises the following specific steps:

continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁100mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 4

This example uses Ni catalyst prepared in example 1₁The difference from example 1 is that: the amount of dichloromethane used was 20 times that of example 1.

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁200mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L ofHexane solution), 6.5mL of MAO (1.53mol/L in toluene), and the reaction was stirred at 30 ℃ for 30min while maintaining an ethylene pressure of 10 atm. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 5

This example uses Ni catalyst prepared in example 1₁The difference from example 1 is that: 2-methyl-2-hydroxy-7-octene and AlEt₃The amount of (A) was 3.33 times that of example 1.

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁10mL of dichloromethane, 50mmol (8.5mL) of 2-methyl-2-hydroxy-7-octene, 50mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 6

This example uses Ni catalyst prepared in example 1₁The difference from example 2 is that: 50mL1,2 dichloroethane was used instead of dichloromethane.

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁50mL of 1, 2-dichloroethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 7

This example uses Ni catalyst prepared in example 1₁And is andexample 2 differs in that: diethyl zinc was used as chain transfer agent.

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 1.0mL diethyl zinc (1mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ for 30min while maintaining an ethylene pressure of 10 atm. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 8

1) Ligand L₂The preparation of (1):

under the protection of nitrogen, 2, 6-diisopropylaniline (2.4mL,12mmol) is dissolved in 20mL of toluene, 12mL (1.0M,12mmol) of trimethylaluminum is dropped at normal temperature, the reaction is refluxed for 2 hours, the system is cooled to room temperature, camphorquinone (0.831g,5mmol) is added, and the system is refluxed and reacted for 6 hours. Neutralizing the reaction product with sodium hydroxide water solution, extracting with dichloromethane, drying, and performing column chromatography to obtain yellow ligand L₂The yield was 41.3%.¹H NMR(300MHz,CDCl3),δ(ppm):7.06-6.81(m,6H,Ar-H),2.88(m,4H,CH(CH₃)₂),2.36(m,1H,),1.86(m,4H,CH₂),1.24(d,24H,CH(CH₃)₂),0.96(s,6H,CH₃),0.77(s,3H,CH₃)。

2) Complex Ni₂(R in the formula III)¹、R³Is isopropyl, R²、R⁴-R⁷、R¹⁰Is hydrogen, R⁸、R⁹And R¹¹Is methyl, R₁₂For ethyl, M is nickel, Y is O, X is Br):

will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.291g (0.6mmol) of ligand L₂In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, adding anhydrous ether, and precipitatingAnd (4) precipitating. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni₂. The yield was 74.0%. Elemental analysis (C)₇₂H₁₀₆Br₆N₄Ni₃O₂): c, 50.42; h, 6.23; n, 3.27; experimental values (%): c, 50.28; h, 6.42; and N, 3.18.

3) Polymerization:

A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with N2 gas 3 times. 500mL of hexane was poured into the polymerization system, and 8.6mg (5. mu. mol) of complex Ni was added₂20mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 9

1) Ligand L₃The preparation of (1):

under the protection of nitrogen, 2,4, 6-trimethylaniline (1.7mL,12mmol) is dissolved in 20mL of toluene, 12mL of trimethylaluminum (1.0M,12mmol) is dropped at normal temperature, the reaction is refluxed for 2 hours, the system is cooled to room temperature, camphorquinone (0.831g,5mmol) is added, and the system is refluxed and reacted for 6 hours. Neutralizing the reaction product with sodium hydroxide water solution, extracting with dichloromethane, drying, and performing column chromatography to obtain yellow ligand L₃The yield is 62.5 percent.¹HNMR(300MHz,CDCl₃),δ(ppm)[an isomer ratio of1.2:1]:major isomer:6.72(s,4H,Ar-H),2.26-2.13(m,12H,C_Ar-CH₃),1.87(s,6H,C_Ar-CH₃),1.79(m,4H,CH₂),1.42(m,1H),1.26(s,3H,CH₃),1.07(s,6H,CH₃)。Minor isomer:6.67(s,4H,Ar-H),2.09-2.01(m,12H,C_Ar-CH₃),1.85(s,6H,C_Ar-CH₃),1.79(m,4H,CH₂),1.40(m,1H),1.26(s,3H,CH₃),0.94(s,6H,CH₃)。

2) Complex Ni₃(R in the formula III)¹-R³Is methyl, R⁴-R⁷、R¹⁰Is hydrogen, R⁸、R⁹And R¹¹Is methyl, R₁₂For ethyl, M is nickel, Y is O, X is Br):

will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.240g (0.6mmol) of ligand L₃In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni₃. The yield was 78.6%. Elemental analysis (C)₆₀H₈₂Br₆N₄Ni₃O₂): c, 46.59; h, 5.34; n, 3.62; experimental values (%): c, 46.24; h, 5.67; and N, 3.21.

3) Polymerization:

continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N₂Replace qi for 3 times. 7.7mg (5. mu. mol) of complex Ni are added₃20mL of methylene chloride. 500mL of hexane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added. The reaction was vigorously stirred at 30min with keeping the ethylene pressure at 10atm at 30 ℃. The polymer was obtained by neutralizing with a 10 wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.

Example 10

1) Ligand L₄The preparation of (1):

under the protection of nitrogen, 2, 6-dimethyl-4-bromo-aniline (2.45g,12mmol) is dissolved in 20mL of toluene, 12mL (1.0M,12mmol) of trimethylaluminum is dropped at normal temperature, the reaction is refluxed for 2 hours, the system is cooled to room temperature, camphorquinone (0.831g,5mmol) is added, and the system is refluxed for 6 hours. Neutralizing the reaction product with sodium hydroxide water solution, extracting with dichloromethane, drying, and performing column chromatography to obtain yellow ligand L₄The yield is 60.7%.¹HNMR(300MHz,CDCl₃),δ(ppm)[an isomer ratio of 1.1:1]:major isomer:7.05(s,4H,Ar-H),2.18(m,12H,CAr-CH₃),1.85(m,4H,CH₂),1.37(m,1H),1.26(s,3H,CH₃),1.06(s,6H,CH₃).Minor isomer:7.02(s,4H,Ar-H),2.04(m,12H,CAr-CH₃),1.85(m,4H,CH₂),1.37(m,1H),1.26(s,3H,CH₃),0.96(s,6H,CH₃)。

2) Complex Ni₄(R in the formula III)¹、R³Is methyl, R²Is bromine, R⁴-R⁷、R¹⁰Is hydrogen, R⁸、R⁹And R¹¹Is methyl, R₁₂For ethyl, M is nickel, Y is O, X is Br):

will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.318g (0.6mmol) of ligand L₄In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni₄. The yield was 74.1%. Elemental analysis (C)₅₆H₇₀Br₁₀N₄Ni₃O₂): c, 37.24; h, 3.91; n, 3.10; experimental values (%): c, 37.38; h, 4.30; and N, 3.03.

3) Polymerization:

continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N₂Replace qi for 3 times. 9.0mg (5. mu. mol) of complex Ni are added₄20mL of methylene chloride. 500mL of hexane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added. The reaction was vigorously stirred at 30min with keeping the ethylene pressure at 10atm at 30 ℃. The polymer was obtained by neutralizing with a 10 wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.

Example 11 (for comparison)

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N₂Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.0mg (5. mu. mol) of complex Ni was added₁30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

TABLE 1

As can be seen from Table 1, the catalyst used in the present invention exhibits higher polymerization activity when it catalyzes the copolymerization of ethylene with an alkenyl alcohol, and the spherical polymer content in the resulting polymer increases after the addition of the modifier. The molecular weight of the polymer can be controlled within a wide range according to the addition of the chain transfer agent. In addition, by regulating and controlling the polymerization conditions, a copolymerization product with more spherical particles can be prepared.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.