CN113754819B

CN113754819B - Method for preparing olefin copolymer with carboxyl

Info

Publication number: CN113754819B
Application number: CN202010507490.XA
Authority: CN
Inventors: 高榕; 郭子芳; 张晓帆; 赖菁菁; 李昕阳; 周俊领; 刘东兵; 顾元宁; 安京燕
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: 2020-06-05
Filing date: 2020-06-05
Publication date: 2023-04-11
Anticipated expiration: 2040-06-05
Also published as: CN113754819A

Abstract

The present invention relates to a method for preparing an olefin copolymer having a carboxyl group and an olefin copolymer having a carboxyl group prepared by the method. The preparation method comprises the step of carrying out polymerization reaction on olefin and unsaturated carboxylic acid in the presence of a catalyst, a modifier and an optional chain transfer agent to generate the olefin copolymer with carboxyl, wherein the catalyst used comprises a diimine metal complex shown in a formula I. The spherical and/or spheroidal polymer can be obtained by the preparation method of the invention, and has good prospect in industrial application.

Description

Method for preparing olefin copolymer with carboxyl

Technical Field

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

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. At present, only a few documents report that transition metal complexes are used for catalyzing the copolymerization of olefins and unsaturated carboxylic acids, and most of the transition metal complexes are mononuclear metal complexes. For example, CN111116801a discloses a preparation method of an olefin-unsaturated carboxylic acid, wherein the catalyst used comprises a complex as shown in the following:

disclosure of Invention

It is an object of the present invention to provide a novel process for producing an olefin copolymer having a carboxyl group (i.e., 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 producing an olefin copolymer having a carboxyl group, which comprises subjecting an olefin and an unsaturated carboxylic acid to polymerization reaction in the presence of a catalyst, optionally a chain transfer agent, and an improver to produce an 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, R ₁ And R ₂ The same or different, independently selected from C1-C30 alkyl containing substituent or not containing substituent; r ₅ -R ₇ The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r ₅ -R ₇ Optionally forming a ring with each other; r ₁₁ Selected from C1-C20 alkyl containing substituent or not containing substituent; y is selected from nonmetal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl containing substituent or not containing substituent and C1-C10 alkoxy containing substituent or not containing substituent.

According to some embodiments of the invention, R ₁ And R ₂ Is selected from C1-C20 alkyl containing substituent or not containing substituent and/or C6-C20 aryl containing substituent or not containing substituent.

According to some embodiments of the invention, R ₁ And/or R ₂ Is a group of formula A:

in the formula A, R ¹ -R ⁵ The same or different, each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-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; r ¹ -R ⁵ Optionally forming a ring with each other.

According to some embodiments of the invention, R in formula A ¹ -R ⁵ The 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, 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, C1-C10 alkyl with or without substituent, and C1-C10 alkoxy with or without substituent, preferably from the group consisting of halogen, C1-C6 alkyl with or without substituent, and C1-C6 alkoxy with or without substituent.

According to some embodiments of the invention, R ₁₁ Is 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, R ₅ -R ₁₀ The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl containing substituent or not, C2-C20 alkenyl containing substituent or not, and C2-C20 alkenyl containing substituent or notSubstituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-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,

r in the formula II ₁ 、R ₂ M, X, Y and R ₁₁ Have the same definition as formula I.

According to some embodiments of the invention, R ₅ -R ₁₀ The same or different, each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 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.

According to some embodiments of the invention, R ₅ -R ₁₀ Each 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 the group consisting of 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 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 III ¹ -R ⁵ Selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy; r ₅ -R ₁₀ Selected 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; r ₁₁ Selected from C1-C6 alkyl containing or not containing substituents.

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 R ¹ ＝R ³ = isopropyl, R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

2) A complex of formula III, wherein R ¹ ＝R ³ ＝Et，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

3) A complex of formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

4) A complex of formula III wherein R ¹ -R ³ ＝Me，R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

5) A complex of formula III, wherein R ¹ ＝R ³ ＝Me，R ² ＝Br,R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

6) A complex of formula III wherein R ¹ ＝R ³ ＝Br，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

7) A complex of formula III wherein R ¹ ＝R ³ ＝Cl，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

8) A complex of formula III wherein R ¹ ＝R ³ ＝F，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

9) A complex of formula III wherein R ¹ ＝R ³ = isopropyl, R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

10A complex of the formula III wherein R ¹ ＝R ³ ＝Et，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

11 A complex of the formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

12 A complex of the formula III wherein R ¹ -R ³ ＝Me，R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

13 A complex of the formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝Br,R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

14 A complex of the formula III wherein R ¹ ＝R ³ ＝Br，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

15 A complex of the formula III wherein R ¹ ＝R ³ ＝Cl，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

16 A complex of the formula III wherein R ¹ ＝R ³ ＝F，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

17 A complex of the formula III wherein R ¹ ＝R ³ = isopropyl, R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

18 A complex of the formula III wherein R ¹ ＝R ³ ＝Et，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

19 A complex of the formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

20 A complex of the formula III wherein R ¹ -R ³ ＝Me，R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

21 A complex of the formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝Br,R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

22 A complex of the formula III wherein R ¹ ＝R ³ ＝Br，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

23 A complex of the formula III wherein R ¹ ＝R ³ ＝Cl，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

24 A complex of the formula III wherein R ¹ ＝R ³ ＝F，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ = isobutyl, M = Ni, Y = O, X = Br;

25 A complex of the formula III wherein R ¹ ＝R ³ = isopropyl, R ² ＝R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

26 A complex of the formula III wherein R ¹ ＝R ³ ＝Et，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

27 A complex of the formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

28 A complex of the formula III wherein R ¹ -R ³ ＝Me，R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

29 A complex of the formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝Br,R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

30 A complex of the formula III wherein R ¹ ＝R ³ ＝Br，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

31 A complex of the formula III wherein R ¹ ＝R ³ ＝Cl，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝Et，M＝Ni，Y＝O，X＝Br；

32 A complex of the formula III wherein R ¹ ＝R ³ ＝F，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ ＝R ₆ ＝R ₉ ＝R ₁₀ ＝H，R ₇ ＝R ₈ ＝Me,R ₁₁ ＝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, L ₁ -L ₃ Each independently selected from H and C with or without substituent ₁ -C ₃₀ An alkyl group, a carboxyl group,L ₄ is C having a pendant group ₁ -C ₃₀ An 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 15.0mol%, more preferably 0.7 to 10.0mol%.

According to some embodiments of the invention, L in formula G ₁ And L ₂ Is H.

According to some embodiments of the invention, in formula G, L ₃ Is H or C ₁ -C ₃₀ An alkyl group.

According to some embodiments of the invention, in formula G, L ₄ Is C having a pendant group ₁ -C ₃₀ An alkylene group.

According to some embodiments of the invention, in formula G, L ₃ Is H or C ₁ -C ₂₀ An alkyl group.

According to some embodiments of the invention, in formula G, L ₄ Is C having a pendant group ₁ -C ₂₀ An alkylene group.

According to some embodiments of the invention, in formula G, L ₃ Is H or C ₁ -C ₁₀ An alkyl group.

According to some embodiments of the invention, L in formula G ₄ Is C having pendant groups ₁ -C ₁₀ An alkylene group.

According to some embodiments of the invention, L in formula G ₄ Is C having a pendant group ₁ -C ₆ An alkylene group.

According to some embodiments of the invention, L ₁ -L ₃ Wherein said substituent is selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl, cyano and hydroxyl.

According to some embodiments of the invention, L ₁ -L ₃ Wherein 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, C ₆ -C ₂₀ Aryl radical, C ₁ -C ₂₀ Alkyl and C ₁ -C ₂₀ One or more of alkoxy, said C ₆ -C ₂₀ Aryl radical, C ₁ -C ₂₀ Alkyl and C ₁ -C ₂₀ Alkoxy is optionally substituted with a substituent, preferably selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl and hydroxyl.

According to a preferred embodiment of the invention, said L ₄ The side group in (A) is selected from halogen and C ₆ -C ₂₀ Aryl radical, C ₁ -C ₂₀ Alkyl, hydroxy-substituted C ₁ -C ₂₀ Alkyl and alkoxy substituted C ₁ -C ₂₀ One or more of alkyl; preferably, the side group is selected from halogen, C ₆ -C ₂₀ Aryl radical, C ₁ -C ₁₀ Alkyl, hydroxy-substituted C ₁ -C ₁₀ Alkyl and alkoxy substituted C _1-10 One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C ₁ -C ₆ Alkyl and hydroxy substituted C ₁ -C ₆ One or more of alkyl, said C ₁ -C ₆ Alkyl 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, L ₁ And L ₂ Is H, L ₃ Is H or C ₁ -C ₃₀ Alkyl radical, L ₄ Is C having a pendant group ₁ -C ₃₀ An alkylene group; said C is ₁ -C ₃₀ Alkyl is optionally substituted by a substituent, preferably selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl, cyano and hydroxyl.

According to a preferred embodiment of the invention, in formula G, L ₁ And L ₂ Is H, L ₃ Is H, C ₁ -C ₁₀ Alkyl or halogen substituted C ₁ -C ₁₀ Alkyl, preferably L ₃ Is H or C ₁ -C ₁₀ An alkyl group; l is a radical of an alcohol ₄ Is C having a pendant group ₁ -C ₂₀ Alkylene radicals, e.g. L ₄ Is methylene with side group, ethylene with side group, propylene with side group, butylene with side group, C with side group ₅ Alkylene, C having pendant groups ₆ Alkylene, C having pendant groups ₇ Alkylene, C having pendant groups ₈ Alkylene, C having pendant groups ₉ Alkylene, C having pendant groups ₁₀ Alkylene, C having pendant groups ₁₂ Alkylene, C having pendant groups ₁₄ Alkylene, C having pendant groups ₁₈ Alkylene, C having pendant groups ₂₀ Alkylene, preferably C, having pendant groups ₁ -C ₁₀ An alkylene group.

According to a preferred embodiment of the invention, in formula G, L ₁ And L ₂ Is H, L ₃ Is H or C _1-6 An alkyl group; l is a radical of an alcohol ₄ Is C having a pendant group ₁ -C ₁₀ An 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(CH ₃ ) -) is referred to herein as C with a pendant group (methyl) ₂ An 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, 2,2-dimethyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2,2,3-trimethyl-4-pentenoic acid, 2,3,3-trimethyl-4-pentenoic acid, 2-ethyl-3-methyl-4-pentenoic acid, 2- (2-methylpropyl) -4-pentenoic acid, 2,2-diethyl-4-pentenoic acid, 2-methyl-2-ethyl-4-pentenoic acid, 2,2,3,3-tetramethyl-4-pentenoic acid, 2-methyl-5-hexenoic acid 2-ethyl-5-hexenoic acid, 2-propyl-5-hexenoic acid, 2,3-dimethyl-5-hexenoic acid, 2,2-dimethyl-5-hexenoic acid, 2-isopropyl-5-hexenoic acid, 2-methyl-2-ethyl-5-hexenoic acid, 2- (1-methylpropyl) -5-hexenoic acid, 2,2,3-trimethyl-5-hexenoic acid, 2,2-diethyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-ethyl-6-heptenoic acid, 2-propyl-6-heptenoic acid, 2,3-dimethyl-6-heptenoic acid, a, 2,4-dimethyl-6-heptenoic acid, 2,2-dimethyl-6-heptenoic acid, 2-isopropyl-5-methyl-6-heptenoic acid, 2-isopropyl-6-heptenoic acid, 2,3,4-trimethyl-6-heptenoic acid, 2-methyl-2-ethyl-6-heptenoic acid, 2- (1-methylpropyl) -6-heptenoic acid, 2,2,3-trimethyl-6-heptenoic acid, 2,2-diethyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-ethyl-7-octenoic acid, 2-propyl-7-octenoic acid, 2,3-dimethyl-7-octenoic acid 2,4-dimethyl-7-octenoic acid, 2,2-dimethyl-7-octenoic acid, 2-isopropyl-5-methyl-7-octenoic acid, 2-isopropyl-7-octenoic acid, 2,3,4-trimethyl-7-octenoic acid, 2-methyl-2-ethyl-7-octenoic acid, 2- (1-methylpropyl) -7-octenoic acid, 2,2,3-trimethyl-7-octenoic acid, 2,2-diethyl-7-octenoic acid, 2-methyl-8-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl-8-nonenoic acid, 2,3-dimethyl-8-nonenoic acid, 2,4-dimethyl-8-nonenoic acid, 2,2-dimethyl-8-nonenoic acid, 2,2-diethyl-8-nonenoic acid, 2-isopropyl-5-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2,3-dimethyl-9-decenoic acid, 2,4-dimethyl-9-decenoic acid, or 2-methyl-10-undecenic acid.

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

According to an embodiment of the invention, the modifier comprises a halogenated hydrocarbon.

According to an embodiment of the invention, the halogenated hydrocarbon is selected from C ₁ -C ₁₅ The halogenated hydrocarbon of (1).

According to an embodiment of the invention, the halogenated hydrocarbon is selected from C ₁ -C ₁₀ The halogenated hydrocarbon of (1).

According to an embodiment of the invention, the halogenated hydrocarbon is selected from C ₁ -C ₆ The halogenated hydrocarbon of (1).

According to an embodiment of the invention, the halogenated hydrocarbon is selected from C ₁ -C ₁₅ The halogenated alkane of (4).

According to an embodiment of the invention, the halogenated hydrocarbon is selected from C ₁ -C ₁₀ The halogenated alkane of (1).

According to an embodiment of the invention, the halogenated hydrocarbon is selected from C ₁ -C ₆ The halogenated alkane of (1).

According to a preferred embodiment of the invention, the halohydrocarbon comprises methyl chloride, methylene chloride, chloroform, ethyl chloride, 1,2-dichloroethane, 1,1-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, 6262 zxft 62-dichlorobutane, 1,2-dichloroisobutane, 1,1,2-trichloro-2-methylpropane, 3838 z3838-tetrachlorobutane, 1-chloropentane, 2-chlorobutane, 651-dimethyl-5795-dimethyl-trichloropropane, 3495-trichloromethane, 3495-dichloropropane, 3495-tetrachloroethane, or a mixture thereof.

According to a preferred embodiment of the invention, the organoaluminium compound is selected from alkylaluminoxanes or compounds of general formula AlR _n X ¹ _3-n With an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlR _n X ¹ _3-n Wherein R is H, C ₁ -C ₂₀ Saturated or unsaturated hydrocarbon radicals or C ₁ -C ₂₀ Saturated or unsaturated hydrocarbyloxy radicals, preferably C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Alkoxy radical, C ₇ -C ₂₀ Aralkyl radicals or C ₆ -C ₂₀ An aryl group; x ¹ Is halogen, preferably chlorine or bromine; 0<n is less than or equal to 3. Specific examples of the organoaluminum compounds 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 0.5mmol/L.

According to a preferred embodiment of the invention, when the cocatalyst is an organoaluminium compound, the molar ratio of aluminium in the cocatalyst to M in the procatalyst is (10-10000000): 1, such as 10; 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.

According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent selected from C ₃ -C ₂₀ One or more alkanes, preferably selected from C ₃ -C ₁₀ The 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.

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 C ₃ -C ₁₆ A 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 C ₂ -C ₁₀ Alpha-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, for example, 0.1.

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 cocatalyst during the pretreatment is 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 comprise: 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 20-60min. 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, the improver 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 20.0mm.

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 30.0mol%, and for example, may be 0.4mol%, 0.5mol%, 0.7mol%, 0.8mol%, 1.0mol%, 1.5mol%, 2.0mol%, 5.0mol%, 8.0mol%, 10.0mol%, 15.0mol%, 20.0mol%, 25.0mol%, 30.0mol% and any value therebetween, preferably 0.7 to 10.0mol%.

According to a preferred embodiment of the present invention, the weight average molecular weight of the olefin-unsaturated carboxylic acid copolymer is 30000 to 500000, preferably 50000 to 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 of equal volume 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 producing an olefin copolymer having a carboxyl group (i.e., 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.

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

Symbols such as R used in different formulae or structural formulae herein ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ 、R ₁ -R ₁₀ 、R ₁₁ 、R ₅ X, M, A, Y and the like, have the same definitions in each general formula or structural formula unless otherwise specified.

In the present invention, C ₁ -C ₂₀ Alkyl is C ₁ -C ₂₀ Straight chain alkyl or C ₃ -C ₂₀ 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.

C ₃ -C ₂₀ Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

C ₆ -C ₂₀ Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.

C ₂ -C ₂₀ Alkenyl means C ₁ -C ₂₀ Linear alkenyl of (A) or (C) ₃ -C ₂₀ Including but not limited to: vinyl, allyl, butenyl.

C ₇ -C ₂₀ Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl and phenyl-tert-butyl.

C ₇ -C ₂₀ Examples of alkaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl groups.

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 is as follows:

¹ HNMR nuclear magnetic resonance apparatus: bruker DMX 300 (300 MHz) with Tetramethylsilicon (TMS) as inner partStandard, the structure of the ligand of the complex was tested at 25 ℃.

Comonomer content of the polymer (content of structural units derived from the unsaturated carboxylic acid represented by formula G): by using ¹³ C 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 PASEXX 13 probe.

Molecular weight and molecular weight distribution PDI (PDI = Mw/Mn) of the copolymer: using PL-GPC220, in trichlorobenzene as a solvent, at 150 ℃ for determination (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 1 um M1 XED-B300X 7.5 nm).

Method of activity measurement: weight of polymer (g)/nickel (mol). Times.2.

Example 1

Complex Ni ₁ Preparation of

Will contain 0.277g (0.9 mmol) of (DME) NiBr ₂ Was slowly added dropwise to a solution containing 0.233g (0.6 mmol) of the ligand L in ethanol (10 mL) ₁ In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, 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 Ni ₁ . Yield: 78.2 percent. Elemental analysis (C) ₆₀ H ₅₈ Br ₆ N ₄ Ni ₃ O ₂ ): 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 N ₂ Replace qi for 3 times. 500mL of hexane was injected into the polymerization system, while adding 7.6mg (5. Mu. Mol) of complex Ni1, 10mL of dichloromethane, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atmAnd (3) 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system while 7.6mg (5. Mu. Mol) of complex Ni was added ₁ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL of MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system while 7.6mg (5. Mu. Mol) of complex Ni was added ₁ 100mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL MAO (1.53 mol/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 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. Mu. Mol) of complex Ni was added ₁ 200mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL of MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralization with a 10wt% 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. Mu. Mol) of complex Ni was added ₁ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 1.0mL diethyl zinc (1 mol/L hexane solution), 6.5mL MAO (1.53 mol/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 10wt% 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. Mu. Mol) of complex Ni was added ₁ 50mL of 1, 2-dichloroethane, 30mmol (5.10 g) 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL of MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. Mu. Mol) of complex Ni was added ₁ 50mL of methylene chloride, 50mmol (8.51 g) of 2,2-dimethyl-7-octenoic acid, 50mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL of MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 8

Complex Ni ₂ Preparation of (2)

The mixture containing 0.277g (0.9 mmol) of (DME) NiBr ₂ Was slowly added dropwise to a solution containing 0.300g (0.6 mmol) of the ligand L ₂ In 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 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 Ni ₂ . The yield was 74.0%. Elemental analysis (C) ₇₆ H ₉₀ Br ₆ N ₄ Ni ₃ O ₂ ): 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.7mg (5. Mu. Mol) of complex Ni was added ₂ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL of MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 9

Complex Ni ₃ Preparation of

Will contain 0.277g (0.9 mmol) of (DME) NiBr ₂ To a solution of 2-methyl-1-propanol (10 mL) containing 0.300g (0.6 mmol) of ligand L ₂ Dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtainSolid Ni in the form of brownish red powder ₃ . The yield was 74.0%. Elemental analysis (C) ₈₀ H ₉₈ Br ₆ N ₄ Ni ₃ O ₂ ): 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 N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 9.0mg (5. Mu. Mol) of complex Ni was added ₃ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL of MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralization with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 10

Complex Ni ₄ Preparation of

Will contain 0.277g (0.9 mmol) of (DME) NiBr ₂ Was slowly added dropwise to a solution containing 0.389g (0.6 mmol) of ligand L ₃ In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain brownish red powdery solid Ni ₄ . The yield was 74.1%. Elemental analysis (C) ₅₂ H ₃₄ Br ₁₄ N ₄ Ni ₃ O ₂ ): 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 N ₂ Replace qi for 3 times. 500ml of hexane were injected and 10.2mg (5. Mu. Mol) of complex Ni were added simultaneously ₄ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0mAn ol/L solution in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53 mol/L solution 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 10wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.

Example 11

Complex Ni ₅ Preparation of

The mixture containing 0.277g (0.9 mmol) of (DME) NiBr ₂ Was slowly added dropwise to a solution containing 0.249g (0.6 mmol) of the ligand L in ethanol (10 mL) ₄ In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, 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 Ni ₅ . The yield was 84.3%.78.6 percent. Elemental analysis (C) ₆₄ H ₆₆ Br ₆ N ₄ Ni ₃ O ₂ ): 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 N ₂ Replace qi for 3 times. 500ml of hexane were injected and 7.9mg (5. Mu. Mol) of complex Ni were added simultaneously ₅ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53 mol/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 neutralization with a 10wt% ethanol solution acidified with hydrochloric acid, and the results are shown in Table 1.

Example 12

Complex Ni ₆ Preparation of

The mixture containing 0.277g (0.9 mmol) of (DME) NiBr ₂ To a solution containing 0.317g (0.6 mmol) of ligand L was slowly added dropwise ₅ Dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain brownish red powdery solid Ni ₆ . The yield was 75.2%. Elemental analysis (C) ₈₀ H ₉₈ Br ₆ N ₄ Ni ₃ O ₂ ): c,53.29; h,5.48; n,3.11; experimental values (%): c,53.62; h,5.87; 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 N ₂ Replace 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 added ₆ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53 mol/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 10wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.

Example 13

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N ₂ Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. Mu. Mol) of complex Ni was added ₁ 50mL of methylene chloride, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 15mL of a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1 mmol/L toluene solution) was added, and the reaction was stirred at 30 ℃ for 30 minutes while maintaining an ethylene pressure of 10 atm. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.

Example 14

Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N ₂ Gas replacement 3Next, the process is carried out. 500mL of hexane was injected into the polymerization system, while adding 7.6mg (5. Mu. Mol) of complex Ni1, 30mmol (5.10 g) of 2,2-dimethyl-7-octenoic acid, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5mL of MAO (1.53 mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30min. Finally, the polymer was obtained by neutralizing the mixture with a 10wt% 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, when the modifier is added, the catalyst of the present invention catalyzes the copolymerization of ethylene and unsaturated carboxylic acid, and shows higher polymerization activity, and the content of spherical polymers in the obtained polymer is increased. The molecular weight of the polymer can be controlled within a wide range according to the addition of the chain transfer agent.

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 in relation to an exemplary embodiment, and it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made 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 copolymer having a carboxyl group, which comprises polymerizing an olefin and an unsaturated carboxylic acid in the presence of a catalyst, an improver and optionally a chain transfer agent to produce an olefin-unsaturated carboxylic acid copolymer,

wherein the modifier comprises a halogenated hydrocarbon;

the unsaturated carboxylic acid is selected from one or more unsaturated carboxylic acids shown in a formula G:

in the formula G, L ₁ -L ₃ Each independently selected from H and C with or without substituent ₁ -C ₃₀ Alkyl radical, L ₄ Is C having a pendant group ₁ -C ₃₀ An alkylene group;

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

in the formula II, R ₅ -R ₁₀ The same or different, each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-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;

in the formula II, R ₁ And R ₂ The same or different, are independently selected from the group shown in formula A:

in the formula A, R ¹ -R ⁵ The same or different, each independently selected from hydrogen, halogen, hydroxyl, and the group containingA substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20 alkenyloxy group, a substituted or unsubstituted C2-C20 alkynyloxy group, a substituted or unsubstituted C3-C20 cycloalkoxy group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 aralkyl group, and a substituted or unsubstituted C7-C20 alkaryl group; r ¹ -R ⁵ Optionally forming a ring with each other;

in the formula II, R ₁₁ Selected from C1-C20 alkyl containing substituent or not containing substituent; m is selected from nickel and palladium; y is selected from O and S; x is selected from halogen, C1-C10 alkyl containing substituent or not containing substituent and C1-C10 alkoxy containing substituent or not containing substituent.

2. The method of claim 1, wherein R in formula A ¹ -R ⁵ The 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, 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.

3. The method according to claim 1, wherein in formula II, X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, and substituted or unsubstituted C1-C10 alkoxy; r ₁₁ Selected from C1-C20 alkyl containing or not containing substituent.

4. The method according to claim 3, wherein in formula II, X is selected from the group consisting of halogen, C1-C6 alkyl with or without substituent, and C1-C6 alkoxy with or without substituent;

and/or R ₁₁ Selected from C1-C10 alkyl containing or not containing substituent.

5. The method of claim 4, wherein R is in formula II ₁₁ Selected from C1-C6 alkyl containing substituent or not containing substituent.

6. The method of claim 1, wherein in formula II, R ₅ -R ₁₀ The same or different, each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 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.

7. The method of claim 6, wherein R in formula II ₅ -R ₁₀ Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen.

8. The method of claim 7, wherein R is in formula II ₅ -R ₁₀ Each independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

9. The method of any one of claims 1-8, wherein in formula II and formula a, 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.

10. The method of claim 9, wherein in formula II and formula a, the substituent is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy.

11. The method of claim 10, wherein the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3,3-dimethylbutyl;

and/or 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;

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

12. The method of claim 1, wherein the diimine metal complex is of formula III:

in the formula III, R ¹ -R ⁵ Selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy; r is ₅ -R ₁₀ Selected 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; r ₁₁ Selected from C1-C6 alkyl containing or not containing substituents.

13. The method of claim 12, wherein the diimine metal complex is selected from the group consisting of:

2) A complex of formula III wherein R ¹ ＝R ³ ＝Et，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

5) A complex of formula III wherein R ¹ ＝R ³ ＝Me，R ² ＝Br,R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

7) A complex of formula III, wherein R ¹ ＝R ³ ＝Cl，R ² ＝R ⁴ ＝R ⁵ ＝R ₅ -R ₁₀ ＝H，R ₁₁ ＝Me，M＝Ni，Y＝O，X＝Br；

14. The method of any one of claims 1-8, 10-13, wherein the olefin comprises an olefin having 2-16 carbon atoms;

and/or, in the copolymer, the content of the structural unit derived from the unsaturated carboxylic acid represented by the formula G is 0.2 to 15.0mol%.

15. The process of claim 14, wherein the olefin comprises ethylene or an alpha-olefin having from 3 to 16 carbon atoms;

and/or, in the copolymer, the content of the structural unit derived from the unsaturated carboxylic acid represented by the formula G is 0.7 to 10.0mol%.

16. The method of claim 14, wherein in formula G, L is ₁ And L ₂ Is H, L ₃ Is H or C ₁ -C ₃₀ Alkyl radical, L ₄ Is C having a pendant group ₁ -C ₃₀ An alkylene group.

17. The method of claim 14, wherein in formula G, L is ₁ And L ₂ Is H, L ₃ Is H or C ₁ -C ₂₀ Alkyl radical, L ₄ Is C having pendant groups ₁ -C ₂₀ An alkylene group.

18. The method of claim 14, wherein in formula G, L is ₁ And L ₂ Is H, L ₃ Is H or C ₁ -C ₁₀ Alkyl radical, L ₄ Is C having a pendant group ₁ -C ₁₀ An alkylene group.

19. The method of claim 14, wherein in formula G, L ₁ And L ₂ Is H, L ₃ Is H or C ₁ -C ₁₀ Alkyl radical, L ₄ Is C having a pendant group ₁ -C ₆ An alkylene group.

20. The method of claim 14, whichCharacterized in that in the formula G, L ₁ -L ₃ Wherein said substituents are selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl, cyano and hydroxy;

L ₄ wherein the side group is selected from halogen, C ₆ -C ₂₀ Aryl radical, C ₁ -C ₂₀ Alkyl and C ₁ -C ₂₀ One or more of alkoxy, said C ₆ -C ₂₀ Aryl radical, C ₁ -C ₂₀ Alkyl and C ₁ -C ₂₀ Alkoxy is optionally substituted with a substituent.

21. The method of claim 20, wherein in formula G, L ₁ -L ₃ Wherein the substituents are selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy;

and/or, L ₄ Wherein said substituents are selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl and hydroxyl.

22. The method of any one of claims 1-8, 10-13, 15-21, wherein the co-catalyst is selected from an organoaluminum compound and/or an organoboron compound; 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; the halogenated hydrocarbon in the improver is selected from halogenated hydrocarbons of C1-C15.

23. The method of claim 22, wherein the halogenated hydrocarbon in the modifier is selected from the group consisting of C1-C10 halogenated hydrocarbons;

and/or, 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; when saidWhen 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; the molar ratio of the chain transfer agent to M in the diimine metal complex is (0.1-5000): 1; the volume ratio of the solvent used for polymerization to the improver is (1-5000): 1.

24. The method of claim 23, wherein the halogenated hydrocarbon in the modifier is selected from the group consisting of C1-C10 halogenated alkanes;

and/or, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine metal complex is (10-100000: 1;

and/or, when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the diimine metal complex is (0.1-500): 1;

and/or the molar ratio of the chain transfer agent to M in the diimine metal complex is (1.0-1000): 1;

and/or the volume ratio of the solvent used for polymerization to the improver is (1.0-500): 1.

25. The process of claim 24, wherein when the co-catalyst is an organoaluminum compound, the molar ratio of aluminum in the co-catalyst to M in the diimine metal complex is (100-10000): 1.

26. An olefin copolymer having a carboxyl group, which is prepared according to the method of any one of claims 1 to 25, is spherical and/or spheroidal, and/or has a particle diameter of 0.1 to 50mm.

27. Use of the olefin copolymer having a carboxyl group prepared according to the method of any one of claims 1 to 25 or the olefin copolymer having a carboxyl group of claim 26 as a polyolefin material.