CN112745428B - A kind of preparation method of olefin-olefin alcohol copolymer - Google Patents

Abstract

The present invention relates to a preparation method of an olefin-olefin alcohol copolymer and an olefin-olefin alcohol copolymer prepared by the method. The catalyst used in the preparation method of the olefin-olefin alcohol copolymer comprises the aminoimine complex shown in formula I. The spherical and/or spherical-like polymers prepared according to the preparation method of the present invention have good prospects in industrial applications.

Description

A kind of preparation method of olefin-olefin alcohol copolymer

technical field

The invention belongs to the field of high molecular polymer preparation, in particular to a preparation method of an olefin-olefin alcohol copolymer.

Background technique

Polyolefin products are inexpensive, excellent in performance and have a wide range of applications. Under the condition of retaining the original excellent physical and chemical properties of polyolefin, the introduction of polar groups into the molecular chain of polyolefin through chemical synthesis can improve its chemical inertness, printing and dyeing properties, wettability and compatibility with other materials properties, giving it new properties that its raw materials do not possess. At present, high-pressure free radical polymerization is mostly used in industry to promote the direct copolymerization of olefins and polar monomers, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, and ethylene-acrylic acid copolymers. Although high-pressure free radical copolymerization can directly introduce copolymerized polar monomers into the polyolefin chain, this method requires high temperature and high pressure conditions, high energy consumption, and expensive equipment.

Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is a new type of polymer material that integrates the processability of ethylene polymers and the gas barrier properties of vinyl alcohol polymers. It is one of the three major barrier resins industrially produced in the world. One, it is widely used in packaging food, medical solutions and other products. Since vinyl alcohol cannot exist independently in the form of monomers, it is usually prepared by free radical polymerization of ethylene-vinyl acetate, and the copolymer is obtained by alcoholysis reaction. However, a large amount of solvent needs to be used in the alcoholysis process, and the final The saponification product contains a large amount of impurities such as acetic acid and alkali metal salts, and requires a large amount of water for washing.

Coordination-catalyzed copolymerization, as a polymer preparation technology at room temperature and pressure, has received extensive attention due to its significant role in reducing energy consumption and improving reaction efficiency. The participation of the catalyst in the reaction process greatly reduces the activation energy of the copolymerization reaction of olefin monomers and polar monomers, which is beneficial to obtain functional polymers with higher molecular weight at lower temperature and pressure. Currently, only a few literatures report the use of transition metal complexes to catalyze the copolymerization of olefins with unsaturated alcohols. However, in the prior art, no matter what method is used to carry out the polymerization, the polymer obtained is a viscous bulk solid, which is easy to scale in the polymerization equipment, which brings difficulties to the transportation, solvent removal, and granulation of the polymer.

SUMMARY OF THE INVENTION

One of the objectives of the present invention is to overcome the deficiencies of the prior art and provide a preparation method of an olefin-olefin alcohol copolymer. The catalyst used in the method provided by the present invention contains a novel trinuclear complex. Spherical and/or quasi-spherical polymers can be directly obtained by the method of the present invention, and the polymers have good morphology and good industrial application prospects.

In a first aspect, the present invention provides a method for preparing an olefin-olefin alcohol copolymer, which comprises polymerizing an olefin and an olefin alcohol in the presence of a catalyst and optionally a chain transfer agent to generate the olefin-olefin alcohol copolymer ,

Wherein, the catalyst includes a main catalyst and an optional co-catalyst, and the main catalyst includes an aminoimine complex as shown in formula I:

In formula I, R ₁ and R ₂ are the same or different, and are independently selected from C1-C30 hydrocarbon groups with or without substituents; R ₂₁ -R ₂₄ are the same or different, and are independently selected from hydrogen, halogen, hydroxyl, Substituted or unsubstituted C1-C20 hydrocarbyl and substituted or unsubstituted C1-C20 hydrocarbyloxy; R ₂₁ -R ₂₄ optionally form a ring with each other, preferably R ₂₁ and R ₂₂ form benzene Ring, the benzene ring may have a substituent; R ₅ is selected from hydrogen and C1-C20 hydrocarbon group with or without substituent; R ₁₁ is selected from C1-C20 hydrocarbon group with or without substituent; Y is selected from non-metal atoms of Group VIA; M is a metal of Group VIII; X is selected from halogen, C1-C10 hydrocarbyl with or without substituents, and C1-C10 hydrocarbyloxy with or without substituents.

According to some embodiments of the present invention, R ₁ and R ₂ are selected from substituted or unsubstituted C1-C20 alkyl groups and or substituted or unsubstituted C6-C20 aryl groups, preferably, R ₁ and/or R ₂ are groups of formula A:

In formula A, R ¹ -R ⁵ are the same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2- with or without substituent C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy , C2-C20 alkynyloxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent, C7-C20 with substituent substituted or unsubstituted C7-C20 alkaryl, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C7-C20 aralkoxy and substituted or Unsubstituted C7-C20 alkaryloxy; R ¹ -R ⁵ optionally form rings with each other.

According to some embodiments of the present invention, in formula A, R ¹ -R ⁵ are the same or different, and each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyloxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7 -C15 aralkyl, substituted or unsubstituted C7-C15 alkaryl, substituted or unsubstituted C6-C15 aryloxy, substituted or unsubstituted C7-C15 aryl Alkoxy and substituted or unsubstituted C7-C15 alkaryloxy groups.

According to some embodiments of the present invention, R ¹ -R ⁵ are the same or different, each independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C2-C6 alkynyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted C2- C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C7-C10 aralkane substituted or unsubstituted C7-C10 alkaryl, substituted or unsubstituted C6-C10 aryloxy, substituted or unsubstituted C7-C10 aralkoxy and Substituted or unsubstituted C7-C10 alkaryloxy.

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

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

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

According to some embodiments of the present invention, R ₁₁ is selected from substituted or unsubstituted C1-C20 alkyl, preferably substituted or unsubstituted C1-C10 alkyl, more preferably substituted or C1-C6 alkyl without substituents.

According to some embodiments of the present invention, R ₅ is selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl group and C7-C20 alkaryl group with or without substituent group; preferably, R ₅ is selected from C1-C10 alkyl group with or without substituent group, with substituent group or Unsubstituted C6-C10 aryl, substituted or unsubstituted C7-C15 aralkyl and substituted or unsubstituted C7 _- C15 alkaryl, more preferably, R From substituted or unsubstituted C1-C6 alkyl such as methyl, ethyl, propyl or butyl.

According to some embodiments of the present invention, R ₂₁ -R ₂₄ are the same or different, and are each 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 C1-C20 alkoxy, substituted or unsubstituted C2- C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkane substituted or unsubstituted C7-C20 alkaryl, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C7-C20 aralkoxy and Substituted or unsubstituted C7-C20 alkaryloxy; R ₂₁ -R ₂₄ optionally form a ring with each other.

According to some embodiments of the present invention, R ₂₁ -R ₂₄ are the same or different, each 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 C1-C10 alkoxy, substituted or unsubstituted C2- C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyloxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkane substituted or unsubstituted C7-C15 alkaryl, substituted or unsubstituted C6-C15 aryloxy, substituted or unsubstituted C7-C15 aralkoxy and Substituted or unsubstituted C7-C15 alkaryloxy.

According to some embodiments of the present invention, R ₂₁ -R ₂₄ are the same or different, each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1 -C10 alkoxy and halogen, more preferably selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.

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

According to some embodiments of the present invention, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, n-pentoxy , isopentyloxy, n-hexyloxy, isohexyloxy, 3,3-dimethylbutoxy.

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

According to some embodiments of the present invention, the structure of the aminoimine complex is shown in the substructure of formula IA:

Wherein, R ₃₁ -R ₃₄ have the same definitions as R ₂₂ -R ₂₄ in formula I, preferably, R ₃₃ and R ₃₄ are hydrogen.

According to some embodiments of the present invention, the aminoimine complex is shown in formula II:

Examples of aminoimine complexes represented by formula II include, but are not limited to:

1) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

2) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

3) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

4) The complex represented by formula II, wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O , X=Br;

5) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

6) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

7) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

8) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =R ₁₁ =Et, M=Ni, Y=O, X=Br;

9) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =R ₁₁ = Et, M=Ni, Y=O, X=Br;

10) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =R ₁₁ = Et, M=Ni, Y=O, X=Br;

11) The complex represented by formula II, wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =R ₁₁ =Et, M=Ni, Y=O, X= Br;

12) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =R ₁₁ = Et, M=Ni, Y=O, X=Br;

13) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =R ₁₁ = Et, M=Ni, Y=O, X=Br;

14) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =R ₁₁ = Et, M=Ni, Y=O, X=Br;

15) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

16) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

17) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

18) The complex represented by formula II, wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M =Ni,Y =O, X=Br;

19) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

20) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

21) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

22) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

23) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

24) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

25) The complex represented by formula II, wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =Et, M =Ni , Y=O, X=Br;

26) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

27) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

28) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

29) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

30) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

31) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

32) The complex represented by formula II, wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =isobutyl, M =Ni, Y=O, X=Br;

33) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

34) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

35) The complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₂₂ =H, R ₂₁ =tert-butyl, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

29) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

30) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

31) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

32) The complex represented by formula (II'), wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M =Ni, Y=O, X=Br;

33) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

34) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

35) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

36) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

37) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

38) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

39) The complex represented by formula (II'), wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ =CH ₃ , R ₁₁ =isobutyl, M= Ni, Y=O, X=Br;

40) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

41) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

42) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ = CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

43) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =HR ₃₁ =R ₃₂ =R ₁₁ = Et, R ₅ =CH ₃ , M=Ni, Y=O, X=Br;

44) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =R ₁₁ = Et, R ₅ =CH ₃ , M=Ni, Y=O, X=Br;

45) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =R ₁₁ = Et, R ₅ =CH ₃ , M=Ni, Y=O, X=Br;

46) The complex represented by formula (II'), wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =R ₁₁ =Et, R ₅ =CH ₃ , M =Ni, Y=O, X=Br;

47) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =R ₁₁ = Et, R ₅ =CH ₃ , M=Ni, Y=O, X=Br;

48) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =R ₁₁ = Et, R ₅ =CH ₃ , M=Ni, Y=O, X=Br;

49 The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =R ₁₁ =Et , R ₅ =CH ₃ , M=Ni, Y=O, X=Br;

50) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =isopropyl, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =R ₁₁ =Et, R ₅ =CH ₃ , M=Ni, Y=O, X=Br;

51) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Et, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =Et, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

52) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =Et, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

53) The complex represented by formula (II'), wherein R ¹ -R ⁶ =Me, R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =Et, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

54) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Br, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =Et, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

55) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =Cl, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =Et, R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

56) The complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =F, R ² =R ⁵ =R ⁷ -R ¹⁰ =H, R ₃₁ =R ₃₂ =Et, R ₅ = _CH3 , _R11 =isobutyl, M=Ni, Y=O, X=Br.

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

In formula G, L ₁ -L ₃ are each independently selected from H and C ₁ -C ₃₀ alkyl groups with or without substituents, and L ₄ is C ₁ -C ₃₀ alkylene groups with pendant groups.

According to some embodiments of the present invention, the content of the structural unit derived from the olefin alcohol represented by formula G in the copolymer is 0.4-10.0 mol%.

According to some embodiments of the present invention, in formula G, L ₁ and L ₂ are H.

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

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

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

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

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

According to some embodiments of the present invention, in formula G, L ₄ is a C ₁ -C ₁₀ alkylene group having a pendant group.

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

According to some embodiments of the present invention, the substituents in L ₁ -L ₃ are selected from halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₁₀ aryl, cyano and one or more of the hydroxyl groups.

According to some embodiments of the present invention, the substituents in L ₁ -L ₃ are selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy.

According to some embodiments of the present invention, the side group in L4 is selected from one or more of halogen, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkoxy, The C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkyl and C ₁ -C ₂₀ alkoxy groups are optionally substituted with substituents, preferably the substituents are selected from halogen, C ₁ -C ₁₀ alkyl , one or more of C ₁ -C ₁₀ alkoxy, C ₆ -C ₁₀ aryl and hydroxyl.

According to a preferred embodiment of the present invention, the side group in L ₄ is selected from halogen, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkyl, hydroxy-substituted C ₁ -C ₂₀ alkyl and alkoxy One or more of substituted C ₁ -C ₂₀ alkyl groups; preferably, the side group is selected from halogen, C ₆ -C ₂₀ aryl, C ₁ -C ₁₀ alkyl, hydroxy substituted C ₁ - One or more of C ₁₀ alkyl and alkoxy substituted C _1-10 alkyl; more preferably, the side group is selected from halogen, phenyl, C ₁ -C ₆ alkyl and hydroxy substituted One or more of C ₁ -C ₆ alkyl groups, the 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 present invention, in formula G, L ₁ and L ₂ are H, L ₃ is H or C ₁ -C ₃₀ alkyl, and L ₄ is C ₁ -C ₃₀ alkylene with side groups; The C ₁ -C ₃₀ alkyl group is optionally substituted with a substituent, preferably the substituent is selected from halogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₁₀ aryl, One or more of cyano and hydroxyl.

According to a preferred embodiment of the present invention, in formula G, L ₁ and L ₂ are 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 alkyl group; L ₄ is C ₁ -C ₂₀ alkylene group with side group, for example L ₄ is methylene group with side group, ethylene group with side group, propylene with side group group, butylene with side group, _C5 alkylene with side group, _C6 alkylene with side group, _C7 alkylene with side group, _C8 alkylene with side group, with side group C ₉ alkylene with side groups, C ₁₀ alkylene with side groups, C ₁₂ alkylene with side groups, C ₁₄ alkylene with side groups, C 18 alkylene with side groups, C ₁₈ alkylene with side groups Pendant C ₂₀ alkylene groups, preferably C ₁ -C ₁₀ alkylene groups with pendant groups.

According to a preferred embodiment of the present invention, in formula G, L ₁ and L ₂ are H, L ₃ is H or C _1-6 alkyl; L ₄ is C ₁ -C ₁₀ alkylene with side groups.

In the present invention, the carbon number n of the Cn alkylene group refers to the number of C on the straight chain, excluding the number of C on the side group, for example, isopropylidene (-CH ₂ -CH(CH ₃ )-) is in the It is referred to herein as a _C2 alkylene group with a pendant (methyl) group.

According to a preferred embodiment of the present invention, specific examples of the alkene alcohol represented by formula G include but are not limited to: 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol , 1,1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2,2-dimethyl-3-buten-1-ol, 3 -Methyl-1-penten-3-ol, 2,4-dimethyl-4-penten-2-ol, 4-enyl-2-pentenol, 4-methyl-4-pentene- 2-ol, 2-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene , 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2,3 -Dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-heptyl-4- Alcohol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6- Heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2,5-di Methyl-1-hepten-4-ol, 2,6-dimethyl-7-octen-2-ol, 2-hydroxy-2,4,5-trimethyl-6-heptene, 2- Methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 3-methyl-3-hydroxy-7 -Octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl -3-Hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1,2-dihydroxy-7-octene, 2,6-dimethyl-2,6-dihydroxy -7-octene, 2,6-dimethyl-2,3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, 2-methyl-2 -Hydroxy-3,5-dichloro-7-octene, 3,4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl -4-Hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3,5-dichloro-2-methyl-7-octene- 2-ol, 3-chloro-2-methyl-7-octene-2,3-diol, and 2,6-dimethyl-7-octene-2,6-diol.

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

According to a preferred embodiment of the present invention, the organoaluminum compound is selected from the group consisting of alkylaluminoxanes or organoaluminum compounds (alkylaluminum or alkylaluminum halides) of general formula AlR _n X ¹ _3-n , general formula AlR In _n X ¹ _3-n , R is H, C ₁ -C ₂₀ saturated or unsaturated hydrocarbon group or C ₁ -C ₂₀ saturated or unsaturated hydrocarbon oxy group, preferably C ₁ -C ₂₀ alkyl group, C 1 -C 20 alkyl group, C 1 -C 20 saturated or unsaturated hydrocarbon group ₁ -C ₂₀ alkoxy group, C ₇ -C ₂₀ aralkyl group or C ₆ -C ₂₀ aryl group; X ¹ is halogen, preferably chlorine or bromine; 0<n≤3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisohydridohydrogenaluminum Butyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, sesquiethyl aluminum chloride, dichloroethyl aluminum, methylaluminoxane (MAO) and modified methylaluminoxane ( MMAO). Preferably, the organoaluminum compound is methylaluminoxane (MAO).

According to a preferred embodiment of the present invention, the organoboron compound is selected from aromatic boron and/or borates. The aromatic hydrocarbyl boron is preferably substituted or unsubstituted phenylboron, 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 0.00001-100mmol/L, for example, 0.00001mmol/L, 0.00005mmol/L, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L 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 between them, preferably 0.0001-1mmol/L, more preferably 0.001-0.5mmol/L L.

According to a preferred embodiment of the present invention, when the co-catalyst is an organoaluminum compound, the molar ratio of aluminum in the co-catalyst to M in the main catalyst is (10-10,000,000):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 between them, preferably (10-100000):1, more preferably (100-10000):1; when the cocatalyst is organoboron compound, the molar ratio of boron in the cocatalyst to M in the main catalyst is (0.1-1000):1, for example, 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 between them, preferably (0.1-500):1.

According to preferred embodiments of the present invention, the olefins include olefins having 2-16 carbon atoms, and in some embodiments of the present invention, the olefins include ethylene or alpha-olefins having 3-16 carbon atoms. In other embodiments of the present invention, the olefin is a C ₃ -C ₁₆ cyclic olefin, preferably a 5-membered ring or a 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3-16 carbon atoms, more preferably ethylene or a C ₂ -C ₁₀ alpha-olefin, eg ethylene, propylene, butene, pentene, hexene , heptene and octene.

According to a preferred embodiment of the present invention, the concentration of the alkene alcohol monomer represented by formula G in the reaction system is 0.01-6000 mmol/L, preferably 0.1-1000 mmol/L, more preferably 1-500 mmol/L, for example, it can be 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 their any value in between.

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

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

According to a preferred embodiment of the present invention, the molar ratio of the chain transfer agent to M in the main catalyst is (0.1-2000):1, for example, 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 present invention, the polymerization is carried out in an alkane solvent, the alkane solvent is selected from one or more of C ₃ -C ₂₀ alkanes, preferably selected from C ₃ -C ₁₀ alkanes, for example, it can be One or more selected from 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 alkene alcohol is pretreated by deactivation hydrogenation, preferably, the alkene alcohol is pretreated by using the above-mentioned cocatalyst or chain transfer agent to remove the reactive hydroxyl groups in the alkene alcohol hydrogen. Preferably, in the pretreatment process, the molar ratio of the hydroxyl group in the alkene alcohol to the cocatalyst or the chain transfer agent is 10:1-1:10.

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

According to a preferred embodiment of the present invention, the reaction conditions include: the temperature of the reaction is -50°C-50°C, preferably -20-50°C, more preferably 0-50°C, such as 0°C, 10°C, 20°C , 30°C, 40°C, 50°C and any value therebetween; and/or, the reaction time is 10-200 min, preferably 20-60 min. In the present invention, the pressure of the reaction is not particularly limited as long as the monomer can undergo the coordination copolymerization reaction. When the olefin is ethylene, from the viewpoint of reducing cost and simplifying the polymerization process, in the reactor, the pressure of ethylene is preferably 1-1000 atm, more preferably 1-200 atm, more preferably 1-50 atm. In the present invention, the "reaction system" refers to the whole formed by including solvent, olefin, olefin alcohol monomer, catalyst and optionally chain transfer agent.

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

According to a preferred embodiment of the present invention, the spherical and/or spherical-like polymer has an average particle size of 0.1-50.0 mm, such as 0.1 mm, 0.5 mm, 1.0 mm, 2.0 mm, 3.0 mm, 5.0 mm, 8.0 mm mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value therebetween, preferably 0.5-20.0mm.

According to a preferred embodiment of the present invention, in the olefin-olefin alcohol copolymer, the content of the structural unit derived from the olefin alcohol represented by formula G is 0.4-30.0 mol %, for example, it can be 0.4 mol %, 0.5 mol % , 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 their Any value between, preferably 0.7-10.0 mol%.

According to a preferred embodiment of the present invention, the weight average molecular weight of the olefin-olefin alcohol copolymer is 30,000-500,000, preferably 50,000-400,000.

According to a preferred embodiment of the present invention, the molecular weight distribution of the olefin-olefin alcohol copolymer is less than or equal to 4.0. Preferably, the molecular weight distribution is 1.0-4.0.

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

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

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

Further, in the preparation method of the olefin-olefin alcohol copolymer provided by the present invention, by selecting the reacted olefin alcohol monomer, a catalyst and a suitable polymerization process, a spherical shape with good shape is directly prepared without subsequent processing steps such as granulation. and/or quasi-spherical polymer, the obtained polymer product is not easy to scale in the reactor and is convenient for transportation.

Further, the method for preparing olefin-olefin alcohol copolymer provided by the present invention saves the step of saponification reaction compared with the process for preparing olefin-olefin alcohol copolymer used in the existing industry, and the preparation process is simpler.

Description of drawings

Figure 1 is a photograph of the spherical and/or spherical-like polymer obtained in Example 2 of the present invention.

Detailed ways

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

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

¹ HNMR nuclear magnetic resonance apparatus: Bruker DMX 300 (300MHz), tetramethylsilicon (TMS) as the internal standard, used to test the structure of the complex ligand at 25°C.

Comonomer content of the polymer (content of structural units derived from alkene alcohols of formula G): determined using ¹³ CNMR spectroscopy on a 400 MHz Bruker Avance 400 nuclear magnetic resonance spectrometer using a 10 mm PASEX 13 probe at 120 The polymer sample was dissolved in 1,2,4-trichlorobenzene at ℃, and the result was obtained by analysis and test.

The molecular weight and molecular weight distribution PDI of the copolymer (PDI=Mw/Mn): PL-GPC220 was used, and trichlorobenzene was used as solvent, and measured at 150 °C (standard sample: PS, flow rate: 1.0 mL/min, column: 3× Plgel 10um M1×ED-B 300×7.5nm).

Activity measurement method: polymer weight (g)/nickel (mol)×2.

In order to express the ligands and complexes concisely and clearly in the examples, the descriptions are as follows:

The diimine compound A1 is an α-diimine compound represented by formula V, wherein R ¹ =R ³ =R ⁴ =R ⁶ =CH ₃ , R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₂₁ =R ₂₂ =H;

The diimine compound A2 is an α-diimine compound represented by formula V, wherein R ¹ =R ³ =R ⁴ =R ⁶ =i-Pr, R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ = R ¹⁰ =R ₂₁ =R ₂₂ =H;

The diimine compound A3 is an α-diimine compound represented by formula V', wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₃₁ =R ₃₂ =H;

Ligand L1 is an aminoimine compound represented by formula VI, wherein R ¹ =R ³ =R ⁴ =R ⁶ =CH ₃ , R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ ;

Ligand L2 is an aminoimine compound represented by formula VI, wherein R ¹ =R ³ =R ⁴ =R ⁶ =i-Pr, R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ = R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ ;

Ligand L3 is an aminoimine compound represented by formula VI, wherein R ¹ =R ³ =R ⁴ =R ⁶ =CH ₃ , R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =Et;

Ligand L4 is an aminoimine compound represented by formula VI', wherein R ¹ =R ³ =R ⁴ =R ⁶ =Me, R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₃₁ =R ₃₂ =H, R ₅ =CH ₃ ;

The complex Ni1 is a complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =CH ₃ , R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₂₁ =R ₂₂ =H, R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

The complex Ni2 is a complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =iPr, R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₂₁ =R ₂₂ =H; R ₅ =CH ₃ , R ₁₁ =Et, M=Ni, Y=O, X=Br;

The complex Ni3 is a complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =iPr, R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₂₁ =R ₂₂ =H; R ₅ =CH ₃ , R ₁₁ =isobutyl, M=Ni, Y=O, X=Br;

The complex Ni4 is a complex represented by formula II, wherein R ¹ =R ³ =R ⁴ =R ⁶ =CH ₃ , R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₂₁ =R ₂₂ =H; R ₅ =Et, R ₁₁ =Et, M=Ni, Y=O, X=Br;

The complex Ni5 is a complex represented by formula (II'), wherein R ¹ =R ³ =R ⁴ =R ⁶ =CH ₃ , R ² =R ⁵ =R ⁷ =R ⁸ =R ⁹ =R ¹⁰ =R ₃₁ = _R32 =H _; R5=Me, _R11 =Et, M=Ni, Y=O, X=Br.

Example 1

1) Preparation of ligand L1:

ɑ-diimine compound A1 3.52g (8mmol), successively added 30ml toluene, 1M trimethylaluminum (16ml, 16mmol), refluxed for 8 hours, terminated the reaction with sodium hydroxide/ice water, extracted with ethyl acetate, combined The organic phase was dried over anhydrous magnesium sulfate, and the product was separated by petroleum ether/ethyl acetate column chromatography to obtain the colorless crystal ligand L1 with a yield of 85.2%. ¹ HNMRδ(ppm) 7.23-6.88(m, 14H), 4.84(s, 1H), 4.73(s, 1H), 3.85(s, 1H, NH), 2.02(s, 3H, CH ₃ ), 1.87(s , 6H, CH ₃ ), 1.75(s, 6H, CH ₃ ).

2) Preparation of complex Ni1: 10 ml of (DME) NiBr ₂ (277 mg, 0.9 mmol) in ethanol was added dropwise to a dichloromethane solution of 10 ml of ligand L1 (274 mg, 0.6 mmol), stirred at room temperature for 6 hours, and precipitated. The precipitate was filtered, washed with ether and dried to give a red powder solid in 74% yield. Elemental analysis (C ₇₀ H ₇₄ Br ₆ N ₄ Ni ₃ O ₂ ): C, 50.68; H, 4.50; N, 3.38; found (%): C, 50.53; H, 4.73; N, 3.21.

3) The 1L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 6h, vacuumized while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 15 mmol (2.5 mL) of 2-methyl-2-hydroxy-7-octene, 15 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 2

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 3

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 60° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 4

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 0.5 mL of diethyl zinc (1 mol/L hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 5

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 1.0 mL of diethylzinc (1 mol/L hexane solution), 6.5 mL MAO (1.53 mol/L toluene solution), at 30 °C, maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 6

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 50 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 50 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 7

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 100 mmol (17.0 mL) of 2-methyl-2-hydroxy-7-octene, 100 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 8

1) Preparation of ligand L2:

ɑ-diimine compound A2 4.42g (8mmol), successively added 30ml toluene, 1M trimethylaluminum (16ml, 16mmol), refluxed for 8 hours, terminated the reaction with sodium hydroxide/ice water, extracted with ethyl acetate, combined The organic phase was dried over anhydrous magnesium sulfate, and the product was separated by petroleum ether/ethyl acetate column chromatography to obtain the colorless crystal ligand L2 with a yield of 76.2%. ¹ HNMRδ(ppm) 7.21-6.95(m, 14H), 4.96(s, 1H), 4.87(s, 1H), 3.85(s, 1H, NH), 2.51(m, 4H, CH(CH ₃ ) ₂ ) , 2.02(s, 3H, CH ₃ ), 1.18(d, 3H, CH ₃ ), 1.11(d, 3H, CH ₃ ), 1.05(d, 6H, CH ₃ ), 0.98(d, 6H, CH ₃ ) ,0.60(d,6H,CH ₃ ).

2) Preparation of complex Ni2: 10ml of (DME) _NiBr2 (277mg, 0.9mmol) in ethanol was added dropwise to 10ml of Ligand L2 (341mg, 0.6mmol) in dichloromethane solution, stirred at room temperature for 6 hours, and precipitated. The precipitate was filtered, washed with ether and dried to give a red powder solid in 76% yield. Elemental analysis (C ₈₆ H ₁₀₆ Br ₆ N ₄ Ni ₃ O ₂ ): C, 54.85; H, 5.67; N, 2.97; found (%): C, 54.61; H, 5.73; N, 3.14.

3) The 1L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 6h, vacuumized while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 9.4 mg (5 μmol) of complex Ni 2 , 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 9

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 9.4 mg (5 μmol) of complex Ni 2, 30 mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 60° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 10

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 9.4 mg (5 μmol) of complex Ni 2 , 30 mmol (4.1 mL) of 3-methyl-5-hexen-3-ol, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 60 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 11

A solution of 277 mg (0.9 mmol) of (DME)NiBr2 in ₂ -methyl-1-propanol (10 mL) was slowly added dropwise to a solution of 341 mg (0.6 mmol) of ligand L2 in dichloromethane (10 mL). The color of the solution immediately changed to dark red, and a large amount of precipitate formed. The mixture was stirred at room temperature for 6 h, and then precipitated by adding anhydrous ether. The filter cake was left after filtration, washed with anhydrous ether, and dried in vacuo to obtain a brown-red powdery solid Ni3. The yield was 84.0%. FT-IR (KBr disc, cm ^-1 ) 2969, 1677, 1628, 1462, 1342, 1109, 794, 760. Elemental analysis (C ₉₀ H ₁₁₄ Br ₆ N ₄ Ni ₃ O ₂ ): C, 55.74; H, 5.92; N, 2.89; found (%): C, 56.08; H, 6.12; N, 3.08.

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 9.7 mg (5 μmol) of complex Ni 3 , 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 60 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 12

1) preparation of ligand L3: ɑ-diimine compound A1 3.52g (8mmol), add 30ml ether successively, 2M diethylzinc (4ml, 8mmol) stirs at room temperature for 3 hours, terminates the reaction with ice water, ethyl acetate After extraction, the organic phases were combined, dried over anhydrous magnesium sulfate, and the product was separated by petroleum ether/ethyl acetate column chromatography to obtain the colorless crystalline ligand L3 in a yield of 50.1%. ¹ HNMRδ(ppm) 7.22-6.86(m, 14H), 4.82(s, 1H), 4.73(s, 1H), 3.85(s, 1H, NH), 2.04(m, 2H, CH ₂ CH ₃ ), 1.89 (s, 6H, CH ₃ ), 1.74 (s, 6H, CH ₃ ), 0.89 (t, 3H, CH ₃ ).

2) Preparation of complex Ni4: 10 ml (DME) NiBr ₂ (277 mg, 0.9 mmol) in ethanol was added dropwise to 10 ml of ligand L3 (282 mg, 0.6 mmol) in dichloromethane solution, stirred at room temperature for 6 hours, and precipitated. The precipitate was filtered, washed with ether and dried to give a red powder solid in 73% yield. Elemental analysis (C ₇₂ H ₇₈ Br ₆ N ₄ Ni ₃ O ₂ ): C, 51.26; H, 4.66; N, 3.32; found (%): C, 51.39; H, 4.93; N, 3.24.

3) The 1L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130°C for 6h, vacuumized while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.4 mg (5 μmol) of complex Ni4, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 13

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and simultaneously add 8.4 mg (5 μmol) of complex Ni4, 30 mmol (4.5 mL) of 4-methyl-1-hepten-4-ol, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 14

1) preparation of ligand L4: ɑ-diimine compound A3 4.32g (8mmol), add 30ml toluene successively, 1M trimethylaluminum (16ml, 16mmol) stirs at room temperature for 3 hours, terminates the reaction with ice water, ethyl acetate After extraction, the organic phases were combined, dried over anhydrous magnesium sulfate, and the product was separated by petroleum ether/ethyl acetate column chromatography to obtain the colorless crystal ligand L4 with a yield of 72.1%. ¹ HNMRδ(ppm) 7.68-7.54(m, 8H), 7.37(m, 4H), 7.11-7.04(m, 6H), 5.16(s, 1H), 5.08(s, 1H), 4.05(s, 1H, NH), 1.94 (s, 3H, CH ₃ ), 1.89 (s, 6H, CH ₃ ), 1.73 (s, 6H, CH ₃ ).

2) Preparation of complex Ni5: 10 ml of (DME) NiBr ₂ (277 mg, 0.9 mmol) in ethanol was added dropwise to a solution of 10 ml of ligand L4 (334 mg, 0.6 mmol) in dichloromethane, stirred at room temperature for 6 hours, and precipitated. The precipitate was filtered, washed with ether and dried to give a red powder solid in 72% yield. Elemental analysis (C ₈₆ H ₈₂ Br ₆ N ₄ Ni ₃ O ₂ ): C, 55.56; H, 4.45; N, 3.01; found (%): C, 55.74; H, 4.73; N, 3.14.

3) 10 atm ethylene polymerization: a 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130° C. for 6 hrs, evacuated while hot, and replaced with N gas ₃ times. 9.3 mg (5 [mu]mol) of complex Ni5 were added and then evacuated and replaced 3 times with ethylene. Inject 500 ml of hexane, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L hexane solution), and then add 6.5 ml of methylaluminoxane (MAO ) (1.53 mol/l in toluene). At 60 °C, maintaining the ethylene pressure of 10 atm, the reaction was vigorously stirred for 30 min. Neutralize with 10 wt% hydrochloric acid acidified ethanol solution to obtain polyethylene.

Example 15

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L of hexane solution), add 15 mL of N,N-dimethylanilinium tetrakis (pentafluorophenyl) borate toluene solution (1 mmol/L toluene solution), at 30 ° C, keep the ethylene pressure of 10 atm, and stir the reaction for 30 min . Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 16

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of hexane into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 30 mmol (6.0 mL) of 10-undec-1-ol, 30 mL of AlEt ₃ (1.0 mol/L hexane solution), 6.5 mL MAO (1.53 mol/L toluene solution), at 30 °C, maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Example 17

A 1 L stainless steel polymerization kettle equipped with mechanical stirring was continuously dried at 130 °C for 6 h, evacuated while hot, and replaced with N ₂ gas for 3 times. Inject 500 mL of toluene into the polymerization system, and at the same time add 8.3 mg (5 μmol) of complex Ni1, 30 mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30 mL of AlEt ₃ (1.0 mol/L hexane solution) ), 6.5 mL of MAO (1.53 mol/L toluene solution), at 30° C., maintaining an ethylene pressure of 10 atm, and stirring the reaction for 30 min. Finally, it was neutralized with an ethanol solution acidified with 10 wt% hydrochloric acid to obtain a polymer. The polymerization activity and the performance parameters of the polymers are shown in Table 1.

Table 1

As can be seen from Table 1, when the catalyst of the present invention catalyzes the copolymerization of ethylene with enol, it exhibits higher polymerization activity, and the obtained polymer has higher molecular weight. The copolymerization activity of the catalyst of the invention can reach up to 5.27×105g·mol ^-1 (Ni)·h ^-1 . The molecular weight of the polymer can be adjusted within a wide range depending on the addition of the chain transfer agent. In addition, by adjusting the polymerization conditions, a copolymer product with good particle morphology can be obtained.

It should be noted that the above-mentioned embodiments are only used to explain the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but it is to be understood that the words used therein are words of description and explanation, rather than words of limitation. The present invention may be modified within the scope of the claims of the present invention as specified, and may be modified without departing from the scope and spirit of the present invention. Although the invention described herein refers to specific methods, materials and embodiments, it is not intended to be limited to the specific examples disclosed therein, but rather, the invention extends to all other methods and applications having the same function.

Claims (42)

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

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

in the formula I, R₁And R₂Is a group of formula A:

in the formula A, R¹-R⁵The 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, C1-C20 alkoxy with or without substituent, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C7-C20 alkaryl, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C7-C20 aralkyloxy, and substituted or unsubstituted C7-C20 alkaryloxy; r¹-R⁵Optionally forming a ring with each other;

in the formula I, R₂₁-R₂₄The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl containing substituent or not containing substituent, and C1-C20 alkoxy containing substituent or not containing substituent; r₂₁-R₂₄Optionally forming a ring with each other; r₅Selected from hydrogen and substituted or unsubstituted C1-C20 hydrocarbyl; r is₁₁Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.

2. The method of claim 1, wherein R is₂₁And R₂₂Form a benzene ring which may be substitutedHas a substituent.

3. The method of claim 1, wherein R in formula A¹-R⁵The 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, C1-C10 alkoxy with or without substituent, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyloxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl, substituted or unsubstituted C7-C15 alkaryl, substituted or unsubstituted C6-C15 aryloxy, substituted or unsubstituted C7-C15 aralkyloxy and substituted or unsubstituted C7-C15 alkaryloxy.

4. The method of claim 3, wherein R is¹-R⁵The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C6 alkyl with or without substituent, C2-C6 alkenyl with or without substituent, C2-C6 alkynyl with or without substituent, C1-C6 alkoxy with or without substituent, substituted or unsubstituted C2-C6 alkenyloxy, substituted or unsubstituted C2-C6 alkynyloxy, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C7-C10 aralkyl, substituted or unsubstituted C7-C10 alkaryl, substituted or unsubstituted C6-C10 aryloxy, substituted or unsubstituted C7-C10 aralkyloxy and substituted or unsubstituted C7-C10 alkaryloxy.

5. The method of claim 1, wherein M is selected from the group consisting of 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;

R₁₁is selected from self-contained fetchingA substituted or unsubstituted C1-C20 alkyl group;

R₅is selected from C1-C20 alkyl 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.

6. The method of claim 5, wherein X is selected from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy.

7. The method of claim 5, wherein R is₁₁Is C1-C10 alkyl with or without substituent.

8. The method of claim 7, wherein R is₁₁Is C1-C6 alkyl with or without substituent.

9. The method of claim 5, wherein R is₅Is selected from C1-C10 alkyl with or without substituent, C6-C10 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent.

10. The method of claim 9, wherein R is₅Is selected from C1-C6 alkyl containing substituent or not containing substituent.

11. The method of claim 10, wherein R is₅Selected from methyl, ethyl, propyl or butyl.

12. The method of claim 1, wherein R is₂₁-R₂₄The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, and with or without substituentC2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C7-C20 alkaryl, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C7-C20 aralkyloxy, and substituted or unsubstituted C7-C20 alkaryloxy; r₂₁-R₂₄Optionally forming a ring with each other.

13. The method of claim 12, wherein R is₂₁-R₂₄The 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, C1-C10 alkoxy with or without substituent, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyloxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl, substituted or unsubstituted C7-C15 alkaryl, substituted or unsubstituted C6-C15 aryloxy, substituted or unsubstituted C7-C15 aralkyloxy and substituted or unsubstituted C7-C15 alkaryloxy.

14. The method of claim 13, wherein R is₂₁-R₂₄The same or different, are each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen.

15. The method of claim 14, wherein R is₂₁-R₂₄The same or different, are each independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.

16. A method as claimed in any one of claims 1 to 13 wherein said substituents are selected from halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy.

17. The method of claim 16, wherein the substituents are selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy.

18. The method of claim 17, 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, 3, 3-dimethylbutyl.

19. The method of claim 18, wherein the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3, 3-dimethylbutoxy.

20. The method of claim 16, wherein the halogen is selected from the group consisting of fluorine, chlorine, bromine, and iodine.

21. A process according to any one of claims 1 to 15, wherein the aminoimine complex has the substructure according to formula IA:

wherein R is₃₁-R₃₄And R in the formula I₂₁-R₂₄Have the same definition.

22. According to claim 21The method is characterized in that R₃₃And R₃₄Is hydrogen.

23. The process of any one of claims 1 to 15, wherein the procatalyst comprises one or more of the following complexes:

1) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶Is isopropyl, R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

2) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

3) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

4) A complex of formula II wherein R¹-R⁶＝Me，R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

5) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

6) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

7) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

8) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶Is isopropyl, R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

9) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

10) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

11) A complex of formula II wherein R¹-R⁶＝Me，R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

12) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

13) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

14) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

15) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶Is isopropyl, R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

16) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

17) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

18) a complex of formula II wherein R¹-R⁶＝Me，R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

19) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

20) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

21) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝R₂₁＝R₂₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

22) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶Is isopropyl, R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

23) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Is tert-butyl, R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

24) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

25) A complex of formula II wherein R¹-R⁶＝Me，R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

26) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Is tert-butyl, R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

27) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Is tert-butyl, R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

28) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

29) A complex of formula II wherein R¹＝R³＝R⁴＝R⁶Is ═ isopropyl, R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

30) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

31) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Is tert-butyl, R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

32) a complex of formula II wherein R¹-R⁶＝Me，R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

33) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

34) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

35) a complex of formula II wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝R₂₂＝H，R₂₁Tert-butyl radical, R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

29) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶Is isopropyl, R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

30) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

31) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

32) A complex of formula (II') wherein R¹-R⁶＝Me，R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

33) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

34) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

35) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁＝Et，M＝Ni，Y＝O，X＝Br；

36) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶Is isopropyl, R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

37) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

38) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

39) a complex of formula (II') wherein R¹-R⁶＝Me，R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

40) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

41) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

42) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝R₃₁＝R₃₂＝H，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

43) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶Is isopropyl, R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

44) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

45) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

46) A complex of formula (II') wherein R¹-R⁶＝Me，R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

47) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

48) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

49 of the formula (II'), wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

50) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶Is isopropyl group，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝R₁₁＝Et，R₅＝CH₃，M＝Ni，Y＝O，X＝Br；

51) A complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Et，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝Et，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

52) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Me，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝Et，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

53) a complex of formula (II') wherein R¹-R⁶＝Me，R⁷-R¹⁰＝H，R₃₁＝R₃₂＝Et，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

54) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Br，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝Et，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

55) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝Cl，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝Et，R₅＝CH₃，R₁₁Isobutyl, M ═ Ni, Y ═ O, X ═ Br;

56) a complex of formula (II') wherein R¹＝R³＝R⁴＝R⁶＝F，R²＝R⁵＝R⁷-R¹⁰＝H，R₃₁＝R₃₂＝Et，R₅＝CH₃，R₁₁I.e., isobutyl, M ═ Ni, Y ═ O, and X ═ Br.

24. The method of any one of claims 1-15, wherein the olefin comprises an olefin having 2-16 carbon atoms.

25. The method of claim 24, wherein the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms.

26. The process of any one of claims 1 to 15, wherein the alkene alcohol is selected from one or more alkene alcohols of formula G:

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

27. The method of claim 26, wherein the copolymer has a content of structural units derived from the alkene alcohol of formula G in the range of 0.4 to 10.0 mol%.

28. The method of claim 26, wherein L is₁And L₂Is H, L₃Is H or C₁-C₃₀Alkyl radical, L₄Is C having a pendant group₁-C₃₀An alkylene group.

29. The method of claim 26, wherein L is₁And L₂Is H, L₃Is H or C₁-C₂₀Alkyl radical, L₄Is C having a pendant group₁-C₂₀An alkylene group.

30. The method of claim 26, wherein L is₁And L₂Is H, L₃Is H or C₁-C₁₀Alkyl radical, L₄Is C having a pendant group₁-C₁₀An alkylene group.

31. The method of claim 26, wherein L is₁And L₂Is H, L₃Is H or C₁-C₁₀Alkyl radical, L₄Is C having a pendant group₁-C₆An alkylene group.

32. The method of claim 26, wherein L is₁-L₃Wherein said substituents are selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl, cyano and hydroxyl;

L₄wherein the side group 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 with a substituent.

33. The method of claim 32, wherein L is₁-L₃Wherein said substituent is selected from C₁-C₆Alkyl, halogen and C₁-C₆One or more of alkoxy groups.

34. The method of claim 33, wherein L is₄Wherein said substituents are selected from halogen, C₁-C₁₀Alkyl radical, C₁-C₁₀Alkoxy radical, C₆-C₁₀One or more of aryl and hydroxyl.

35. A process according to any one of claims 1 to 15 characterised in that the cocatalyst is selected from organoaluminium compounds and/or organoboron compounds; the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate; the chain transfer agent is selected from one or more of alkyl aluminum, alkyl magnesium and alkyl zinc.

36. The method as claimed in claim 35, wherein when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the aminoimine-based complex is 10 to 10⁷1, preparing a catalyst; when the cocatalyst is an organic boron compound, the molar ratio of boron in the cocatalyst to M in the amino imine complex is 0.1-1000: 1; the molar ratio of the chain transfer agent to M in the amino imine complex is 0.1-5000: 1.

37. The process of claim 36, wherein when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the aminoimine-based complex is 10-100000: 1.

38. The method as recited in claim 36, wherein when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the aminoimine-based complex is 100-10000: 1.

39. The method of claim 36, wherein when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the aminoimine complex is from 0.1 to 500: 1.

40. The method of claim 36, wherein the molar ratio of the chain transfer agent to M in the aminoimine complex is 1.0 to 1000: 1.

41. An olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 40, which is spherical and/or spheroidal, and/or which has a particle size of from 0.1 to 50 mm.

42. Use of an olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 40 or the olefin-olefin alcohol copolymer of claim 41 as a polyolefin material.

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