CN112745420A

CN112745420A - Method for preparing olefin-unsaturated carboxylic acid copolymer

Info

Publication number: CN112745420A
Application number: CN201911048989.2A
Authority: CN
Inventors: 高榕; 郭子芳; 李昕阳; 林洁; 赖菁菁; 刘东兵; 顾元宁; 周俊领; 黄廷杰
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2021-05-04
Anticipated expiration: 2039-10-31
Also published as: CN112745420B

Abstract

The present invention relates to a method for preparing an olefin-unsaturated carboxylic acid copolymer and an olefin-unsaturated carboxylic acid copolymer prepared by the method. The catalyst used in the preparation method of the olefin-unsaturated carboxylic acid copolymer comprises a diimine metal complex shown in formula I. Spherical and/or spheroidal polymers can be obtained by preferred embodiments of the preparation process of the invention, with good prospects in industrial applications.

Description

Method for preparing olefin-unsaturated carboxylic acid copolymer

Technical Field

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

Background

The polyolefin product has low price, excellent performance and wide application range. Under the condition of keeping the excellent physical and chemical properties of the original 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. Although polar monomers can be directly introduced into polyolefin chains 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.

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 carboxylic acids. However, in the prior art, no matter which method is adopted for polymerization reaction, the obtained polymer is viscous massive solid, and is easy to scale in polymerization equipment, thereby bringing difficulties to the transportation, solvent removal, granulation and the like of the polymer.

Disclosure of Invention

It is an object of the present invention to provide a novel process for producing an olefin-unsaturated carboxylic acid copolymer. Furthermore, the spherical and/or spheroidal polymer can be directly obtained by the method, the polymer has good appearance and good industrial application prospect.

In a first aspect, the present invention provides a process for preparing an olefin-unsaturated carboxylic acid copolymer, which comprises polymerizing an olefin and an unsaturated carboxylic acid in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-unsaturated carboxylic acid 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-R₇The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r₅-R₇Optionally forming a ring with each other; r₁₁Selected 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 R₂Is selected from C1-C20 alkyl with or without substituent and/or C6-C20 aryl with or without substituent.

According to some embodiments of the invention, R₁And/or R₂Is a group of formula A:

in the formula A, 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 A¹-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, R₁₁Is 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 of formula II:

in the formula II, R₅-R₁₀The 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, R in formula II₁、R₂M, X, Y and R₁₁Have the same definition as formula I.

According to some embodiments of the invention, R₅-R₁₀The two are same or different and are respectively and 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, and C3-C10 cycloalkyl with or without substituentOptionally substituted C2-C10 alkynyloxy, optionally substituted C3-C10 cycloalkoxy, optionally substituted C6-C15 aryl, optionally substituted C7-C15 aralkyl, and optionally substituted C7-C15 alkaryl.

According to some embodiments of the invention, R₅-R₁₀Each 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, and 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 and 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 represented by formula III:

according to some embodiments of the invention, R in formula III¹-R⁵Selected from hydrogen, halogen, C1-C6 alkyl with or without substituent and with or without substituentC1-C6 alkoxy of (1); r₅-R₁₀Selected from hydrogen, halogen, C1-C6 alkyl and C1-C6 alkoxy; m is selected from nickel; y is selected from O; x is selected from halogen; r₁₁Is selected from C1-C6 alkyl containing substituent or not containing substituent.

According to some embodiments of the invention, the diimine metal complex is selected from the group consisting of:

1) a complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

2) A complex of formula III wherein R¹＝R³＝Et，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

3) A complex of formula III wherein R¹＝R³＝Me，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

4) A complex of formula III wherein R¹-R³＝Me，R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

5) A complex of formula III wherein R¹＝R³＝Me，R²＝Br,R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

6) A complex of formula III wherein R¹＝R³＝Br，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

7) A complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

8) A complex of formula III, whereinR¹＝R³＝F，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

9) A complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

10) A complex of formula III wherein R¹＝R³＝Et，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

11) A complex of formula III wherein R¹＝R³＝Me，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

12) A complex of formula III wherein R¹-R³＝Me，R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

13) A complex of formula III wherein R¹＝R³＝Me，R²＝Br,R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

14) A complex of formula III wherein R¹＝R³＝Br，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

15) A complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

16) A complex of formula III wherein R¹＝R³＝F，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

17) A complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

18) a complex of formula III wherein R¹＝R³＝Et，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

19) a complex of formula III wherein R¹＝R³＝Me，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

20) a complex of formula III wherein R¹-R³＝Me，R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

21) a complex of formula III wherein R¹＝R³＝Me，R²＝Br,R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

22) a complex of formula III wherein R¹＝R³＝Br，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

23) a complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

24) a complex of formula III wherein R¹＝R³＝F，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

25) a complex of formula III wherein R¹＝R³Is isopropyl, R²＝R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

26) A complex of formula III wherein R¹＝R³＝Et，R²＝R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

27) A complex of formula III wherein R¹＝R³＝Me，R²＝R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

28) A complex of formula III wherein R¹-R³＝Me，R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

29) A complex of formula III wherein R¹＝R³＝Me，R²＝Br,R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

30) A complex of formula III wherein R¹＝R³＝Br，R²＝R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

31) A complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

32) A complex of formula III wherein R¹＝R³＝F，R²＝R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

According to some embodiments of the invention, the unsaturated carboxylic acid is selected from one or more of the unsaturated carboxylic acids 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 present invention, the content of the structural unit derived from the unsaturated carboxylic acid represented by the formula G in the copolymer is 0.2 to 15.0 mol%, more preferably 0.7 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, L₄Is C having a pendant group₁-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 substituted C_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-C₆The alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, and isopropylButyl, t-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-C₁₀An alkylene group.

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 unsaturated carboxylic acid represented by the formula G include, but are not limited to: 2-methyl-4-pentenoic acid, 2, 3-dimethyl-4-pentenoic acid, 2-dimethyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 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-diethyl-4-pentenoic acid, 2-methyl-2-ethyl-4-pentenoic acid, 2,3, 3-tetramethyl-4-pentenoic acid, 2-methyl-, 2-methyl-5-hexenoic acid, 2-ethyl-5-hexenoic acid, 2-propyl-5-hexenoic acid, 2, 3-dimethyl-5-hexenoic acid, 2-dimethyl-5-hexenoic acid, 2-isopropyl-5-hexenoic acid, 2-methyl-2-ethyl-5-hexenoic acid, 2- (1-methylpropyl) -5-hexenoic acid, 2, 3-trimethyl-5-hexenoic acid, 2-diethyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-ethyl-6-heptenoic acid, 2-propyl-6-heptenoic acid, 2, 3-dimethyl-6-heptenoic acid, 2-ethyl-5-hexenoic acid, 2-methyl-5-hexenoic acid, 2-ethyl-5-hexenoic, 2, 4-dimethyl-6-heptenoic acid, 2-dimethyl-6-heptenoic acid, 2-isopropyl-5-methyl-6-heptenoic acid, 2-isopropyl-6-heptenoic acid, 2,3, 4-trimethyl-6-heptenoic acid, 2-methyl-2-ethyl-6-heptenoic acid, 2- (1-methylpropyl) -6-heptenoic acid, 2, 3-trimethyl-6-heptenoic acid, 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-methyl-6-heptenoic acid, 2-ethyl-7-octenoic acid, 2-propyl-7-octenoic acid, 2, 4-dimethyl-7-octenoic acid, 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, 3-trimethyl-7-octenoic acid, 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-methyl-7-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl, 2, 4-dimethyl-8-nonenoic acid, 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, or 2-methyl-10-undecenoic acid.

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 organic aluminidingThe compound is selected from alkyl aluminoxane or 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 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 2 to 16 carbon atoms, and in some embodiments of the invention, the olefin comprises ethylene or an alpha-olefin having 3 to 16 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 unsaturated carboxylic acid 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 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 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 present invention, the unsaturated carboxylic acid is pre-treated with a dehydroactive hydrogen, preferably, the unsaturated carboxylic acid is pre-treated with the above-mentioned co-catalyst to remove hydroxyl active hydrogen in the unsaturated carboxylic acid. Preferably, the molar ratio of hydroxyl groups in the unsaturated carboxylic acid to the co-catalyst during the 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, the olefin, the unsaturated carboxylic acid monomer, the catalyst and the optional chain transfer agent.

The present invention also provides an olefin-unsaturated carboxylic acid copolymer comprising a spherical and/or spheroidal polymer, which is produced by the above production method.

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-unsaturated carboxylic acid copolymer, the content of the structural unit derived from the unsaturated carboxylic acid represented by the formula G is 0.4 to 30.0 mol%, 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-unsaturated carboxylic acid copolymer is 30000-500000, preferably 50000-400000.

According to a preferred embodiment of the present invention, the olefin-unsaturated carboxylic acid 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-unsaturated carboxylic acid copolymer as a foamed polyolefin material.

The process for preparing an olefin-unsaturated carboxylic acid 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-unsaturated carboxylic acid copolymer.

Furthermore, in the preparation method of the olefin-unsaturated carboxylic acid copolymer provided by the invention, the spherical and/or spheroidal polymers with good shapes are directly prepared by selecting the reacted unsaturated carboxylic acid monomer, 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 the olefin-unsaturated carboxylic acid copolymer, the method for preparing the olefin-unsaturated carboxylic acid copolymer provided by the invention omits the step of saponification reaction, and has simpler preparation process.

Symbols such as R used in different formulae or structural formulae herein¹、R²、R³、R⁴、R⁵、R₁-R₁₀、R₁₁、R₅X, 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-tertA butyl group.

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

Drawings

FIG. 1 is a photograph of a spherical and/or spheroidal polymer obtained in example 2 of the present invention.

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

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

¹HNMR 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 ℃.

Comonomer content of the polymer (content of structural units derived from the unsaturated carboxylic acid represented by formula G): by using¹³C NMR spectroscopy was carried out by dissolving a sample of the polymer in 1,2, 4-trichlorobenzene at 120 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX13 probe.

Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the copolymer: 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).

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

Example 1

Complex Ni₁Preparation of

Will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.233g (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 the mixture for 6 hours at room temperature,adding anhydrous ether for precipitation. 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)₆₀H₅₈Br₆N₄Ni₃O₂): c, 47.33; h, 3.84; n, 3.68; experimental values (%): c, 47.38; h, 4.00; and N, 3.46.

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 charged to the polymerization system while adding 7.6mg (5. mu. mol) of complex Ni1, 15mmol (2.55g) of 2, 2-dimethyl-7-octenoic acid, 15mL 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

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 7.6mg (5. mu. mol) of complex Ni was added₁30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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

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 7.6mg (5. mu. mol) of complex Ni was added₁30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL AlEt₃(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 60 ℃ under 10atm of ethylene pressure for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. Poly(s) are polymerizedThe reactivity and polymer performance parameters are shown in table 1.

Example 4

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 7.6mg (5. mu. mol) of complex Ni was added₁30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL AlEt₃(1.0mol/L hexane solution), 0.5mL diethyl zinc (1mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under 10atm of ethylene pressure 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 5

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 7.6mg (5. mu. mol) of complex Ni was added₁30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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 6

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 7.6mg (5. mu. mol) of complex Ni was added₁50mmol (8.51g)2, 2-dimethyl-7-octenoic acid, 50mL 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

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 7.6mg (5. mu. mol) of complex Ni was added₁100mmol (17.02g)2, 2-dimethyl-7-octenoic acid, 100mL 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 8

Complex Ni₂Preparation of

Will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.300g (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, 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 Ni₂. The yield was 74.0%. Elemental analysis (C)₇₆H₉₀Br₆N₄Ni₃O₂): c, 52.25; h, 5.19; n, 3.21; experimental values (%): c, 52.48; h, 5.52; and N, 3.10.

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 8.7mg (5. mu. mol) of complex Ni was added₂30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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

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 8.7mg (5. mu. mol) of complex Ni was added₂50mmol (8.51g)2, 2-dimethyl-7-octenoic acid, 50mL AlEt₃(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 60 ℃ under 10atm of ethylene pressure 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 10

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 8.7mg (5. mu. mol) of complex Ni was added₂30mmol (4.69g)2, 2-dimethyl-6-heptenoic acid, 30mL AlEt₃(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under 10atm of ethylene pressure for 60 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 11

Complex Ni₃Preparation of

Will contain 0.277g (0.9mmol) of (DME) NiBr₂To a solution of 2-methyl-1-propanol (10mL) containing 0.300g (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, 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 74.0%. Elemental analysis (C)₈₀H₉₈Br₆N₄Ni₃O₂)：C,53.29；H,5.48; n, 3.11; experimental values (%): c, 53.28; h, 5.82; and N, 3.29.

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 9.0mg (5. mu. mol) of complex Ni was added₃30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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 12

Complex Ni₄Preparation of

Will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.389g (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 Ni₄. The yield was 74.1%. Elemental analysis (C)₅₂H₃₄Br₁₄N₄Ni₃O₂): c, 30.59; h, 1.68; n, 2.74; experimental values (%): c, 30.72; h, 1.97; and N, 2.48.

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. 500ml of hexane were injected and 10.2mg (5. mu. mol) of complex Ni were added simultaneously₄30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL AlEt₃(1.0mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53mol/L in toluene). The reaction was vigorously stirred at 30min with keeping the ethylene pressure at 10atm at 30 ℃. Neutralizing with 10 wt% ethanol solution acidified with hydrochloric acid to obtain polymer,the results are shown in Table 1.

Example 13

Complex Ni₅Preparation of

Will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.249g (0.6mmol) of ligand L in ethanol (10mL)₄In 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 Ni₅. The yield was 84.3%. 78.6 percent. Elemental analysis (C)₆₄H₆₆Br₆N₄Ni₃O₂): c, 48.69; h, 4.21; n, 3.55; experimental values (%): c, 48.54; h, 4.47; and N, 3.21.

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. 500ml of hexane were injected and 7.9mg (5. mu. mol) of complex Ni were added simultaneously₅30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL AlEt₃(1.0mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53mol/L in toluene). The reaction was vigorously stirred at 20 ℃ for 30min while maintaining an ethylene pressure of 10 atm. The polymer was obtained by neutralizing with a 10 wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.

Example 14

Complex Ni₆Preparation of

Will contain 0.277g (0.9mmol) of (DME) NiBr₂Was slowly added dropwise to a solution containing 0.317g (0.6mmol) of ligand L₅In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperatureStirring for 6h, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni₆. The yield was 75.2%. Elemental analysis (C)₈₀H₉₈Br₆N₄Ni₃O₂): c, 53.29; h, 5.48; n, 3.11; experimental values (%): c, 53.62; h, 5.87; and N, 3.00.

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. Then, vacuum was applied and ethylene was substituted 3 times. 500ml of hexane were injected, while 9.0g (5. mu. mol) of complex Ni were added₆30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL AlEt₃(1.0mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53mol/L in toluene). 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 15

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 7.6mg (5. mu. mol) of complex Ni was added₁30mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL AlEt₃(1.0mol/L hexane solution), 15mL of a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1mmol/L toluene solution) was added, and the reaction 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.

Comparative 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 7.6mg (5. mu. mol) of complex Ni was added₁30mmol (5.53g 10-undecenoic acid), 30mL AlEt₃(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atmAnd (3) 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 16

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 toluene was charged to the polymerization system while adding 7.6mg (5. mu. mol) of complex Ni1, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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.

Comparative example 1

10atm ethylene: 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. 500mL of hexane was poured in, and simultaneously, 9.1mg (15. mu. mol) of comparative catalyst A (the structure is shown in formula 1), 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, and 30mL of AlEt₃(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was vigorously stirred at 30min while maintaining an ethylene pressure of 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.

TABLE 1

As can be seen from Table 1, the catalyst of the present invention exhibits high polymerization activity when it catalyzes the copolymerization of ethylene and an unsaturated carboxylic acid, and the resulting polymer has a high molecular weight. The copolymerization activity of the catalyst can reach 11.3 multiplied by 10 to the maximum⁶g·mol^-1(Ni)·h^-1. Poly(s) are polymerizedThe molecular weight of the compound 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 good particle morphology 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.

Claims

1. A process for producing an olefin-unsaturated carboxylic acid copolymer, which comprises polymerizing an olefin and an unsaturated carboxylic acid in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-unsaturated carboxylic acid copolymer,

in the formula I, R₁And R₂The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r₅-R₇The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r₅-R₇Optionally forming a ring with each other; r₁₁Selected 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 the group consisting of halogen, substituted or unsubstituted C1-C10 hydrocarbyl anda substituted or unsubstituted C1-C10 hydrocarbyloxy group.

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 A:

in the formula A, 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;

preferably, in formula A, 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; r₁₁Is 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 II:

in the formula II, R₅-R₁₀The 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,

r in the formula II₁、R₂M, X, Y and R₁₁Have the same definition as formula I.

4. The method of any one of claims 1-3, wherein R is₅-R₁₀The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C containing with or without substituentSubstituted 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 alkynyloxy, substituted or unsubstituted C3-C10 cycloalkoxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl, and substituted or unsubstituted C7-C15 alkaryl;

preferably, R₅-R₁₀Each 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, and 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 and 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, wherein the diimine metal complex is of formula III:

in the formula III, R¹-R⁵Selected from hydrogen, halogen, C1-C6 alkyl with or without substituent, and C1-C6 alkoxy with or without substituent; r₅-R₁₀Selected from hydrogen, halogen, C1-C6 alkyl and C1-C6 alkoxy; m is selected from nickel; y is selected from O; x is selected from halogen; r₁₁Selected from C1-C6 alkyl with or without substituent;

preferably, the diimine metal complex is selected from the group consisting of:

8) A complex of formula III wherein R¹＝R³＝F，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁＝Me，M＝Ni，Y＝O，X＝Br；

23) a complex of formula III wherein R¹＝R³＝Cl，R²＝R⁴＝R⁵＝R₅-R₁₀＝H，R₁₁Root of Chinese ThymusGroup, M ═ Ni, Y ═ O, X ═ Br;

32) A complex of formula III wherein R¹＝R³＝F，R²＝R⁴＝R⁵＝R₅＝R₆＝R₉＝R₁₀＝H，R₇＝R₈＝Me,R₁₁＝Et，M＝Ni，Y＝O，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 unsaturated carboxylic acid is selected from one or more unsaturated carboxylic acids 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 content of the structural unit derived from the unsaturated carboxylic acid represented by the formula G in the copolymer is 0.2 to 15.0 mol%, more preferably 0.7 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-C₂₀Alkylene oxideA 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. The process of any one of claims 1 to 8, wherein the cocatalyst is selected from organoaluminum 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 and alkyl zinc;

preferably, when the cocatalyst is an organoaluminum compound, the aluminum in the cocatalyst is reacted with the diimmoniumThe molar ratio of M in the amine 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):1, preferably (1.0-1000): 1.

10. The olefin-unsaturated carboxylic acid copolymer prepared according to the method of any one of claims 1 to 9, which is spherical and/or spheroidal, and/or has a particle diameter of 0.1 to 50 mm.

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