CN113754817B - Method for preparing olefin copolymer with polar group and product thereof - Google Patents

Method for preparing olefin copolymer with polar group and product thereof Download PDF

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CN113754817B
CN113754817B CN202010506738.0A CN202010506738A CN113754817B CN 113754817 B CN113754817 B CN 113754817B CN 202010506738 A CN202010506738 A CN 202010506738A CN 113754817 B CN113754817 B CN 113754817B
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CN113754817A (en
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高榕
郭子芳
赖菁菁
李昕阳
顾元宁
李岩
马冬
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/03Multinuclear procatalyst, i.e. containing two or more metals, being different or not

Abstract

The present invention relates to a method for preparing an olefin copolymer having a polar group and an olefin-olefin alcohol copolymer prepared by the method. In the preparation method, olefin and olefin alcohol are polymerized in the presence of a catalyst, a modifier and an optional chain transfer agent, wherein the catalyst used is a diimine metal complex shown in a formula I. The preparation method can obtain spherical and/or spheroidal polymers and has good prospect in industrial application.

Description

Method for preparing olefin copolymer with polar group and product thereof
Technical Field
The invention belongs to the field of preparation of high molecular polymers, and particularly relates to a preparation method of an olefin copolymer with polar groups and a product thereof.
Background
The polyolefin product has low price, excellent performance and wide application range. Under the condition of keeping the original excellent physical and chemical properties of the polyolefin, polar groups are introduced into polyolefin molecular chains by a chemical synthesis method, so that the chemical inertness, the printing property, the wettability and the compatibility with other materials can be improved, and new characteristics which are not possessed by raw materials are endowed. High pressure free radical polymerization is currently used commercially to promote direct copolymerization of olefins with polar monomers, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, and ethylene-acrylic acid copolymers. Although the introduction of the copolymerized polar monomer into the polyolefin chain can be directly carried out by high-pressure radical copolymerization, the process requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.
Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is a novel high molecular material integrating the processability of ethylene polymer and the gas barrier property of vinyl alcohol polymer, is one of three barrier resins industrially produced in the world at present, and is widely used for packaging food, medical solution and other products. Since vinyl alcohol cannot exist independently in the form of monomer, it is usually prepared by alcoholysis of ethylene-vinyl acetate copolymer by radical polymerization, but the alcoholysis process requires the use of a large amount of solvent, and the final saponification product contains a large amount of impurities such as acetic acid and alkali metal salt, and requires a large amount of water for washing.
CN109843948A reports a process for preparing a copolymer comprising the step of copolymerizing at least one first type of olefin monomer with at least one second type of functionalized olefin monomer under suitable reaction conditions using a catalyst system comprising: i) A single site catalyst or catalyst precursor comprising a metal selected from Ti3+ or Cr3 +; ii) a cocatalyst; iii) Optionally a scavenger.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel preparation method of an olefin copolymer with polar groups. Furthermore, the spherical and/or spheroidal polymer can be directly obtained by the method, the morphology of the polymer is good, and the method has a good industrial application prospect.
In a first aspect, the present invention provides a process for the preparation of an olefin copolymer having polar groups, which comprises polymerising an olefin and an olefin alcohol in the presence of a catalyst, an improver and optionally a chain transfer agent to produce an olefin-olefin alcohol copolymer,
wherein the catalyst comprises a main catalyst and an optional cocatalyst, and the main catalyst comprises a diimine metal complex shown as a formula I:
Figure BDA0002526797910000021
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 non-metal 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 or not containing substituent and/or C6-C20 aryl containing or not containing substituent.
According to some embodiments of the invention, R 1 And/or R 2 Is a group of formula A:
Figure BDA0002526797910000022
in the formula A, R 1 -R 5 The same or different, and the same or different, each independently selected from the group consisting of hydrogen, halogen, hydroxy, 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, and,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, 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, 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:
Figure BDA0002526797910000031
in the formula II, R 5 -R 10 The same or different, each is independently selected from the group consisting of hydrogen, halogen, hydroxy, 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 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:
Figure BDA0002526797910000051
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 the group consisting of 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 is 11 Selected from C1-C6 alkyl containing or not containing substituents.
According to some embodiments of the invention, the diimine metal complexes are selected from one or more of the following complexes:
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 Formula I)II of the complex, 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 alkene alcohol is selected from one or more of the alkene alcohols represented by formula G:
Figure BDA0002526797910000071
Figure BDA0002526797910000081
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.
According to some embodiments of the invention, the copolymer has a content of structural units derived from the alkene alcohol represented by formula G of 0.4 to 10.0mol%.
According to some embodiments of the invention, in formula G, L 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, L in formula G 4 Is C having a pendant group 1 -C 20 An alkylene group.
According to some embodiments of the invention, L in formula G 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 a pendant group 1 -C 10 An alkylene group.
According to some embodiments of the invention, in formula G, L 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 said substituents are selected from the group consisting of C1-C6 alkyl, halogen and C1-C6 alkoxyOne or more of (a).
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 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 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 present invention, in the 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 4 Is C having pendant groups 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 4 Is C having a pendant group 1 -C 10 An alkylene group.
In the present invention, the carbon number n of Cn alkylene means the number of C's in a linear chain, not including the number of C's in a pendant group, e.g., isopropylidene (-CH) 2 -CH(CH 3 ) -) is referred to herein as C having a pendant group (methyl) 2 An alkylene group.
According to a preferred embodiment of the present invention, specific examples of the alkene alcohol represented by formula G include, but are not limited to: <xnotran> -2- -3- -1- ,2- -3- -1- ,1,1- -3- -1- ,2- -3- -2- ,2,2- -3- -1- ,3- -1- -3- ,2,4- -4- -2- ,4- -2- ,4- -4- -2- ,2- -4- -2- ,2- -4- -2- ,2- ,2- -5- ,3- -2- ,3- -5- -3- ,2- -2- -5- ,1- ,2,3- -2- -5- ,1- -4- ,4- -1- -4- ,4- -1- -4- ,6- -3- ,2- -2- -6- ,5- -2- -6- , </xnotran> 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2, 5-dimethyl-1-hepten-4-ol, 2, 6-dimethyl-7-octen-2-ol, 2-hydroxy-2, 4, 5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 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-3-7-octene, 2, 6-dimethyl-2-hydroxy-7-octene, 2, 3-dimethyl-7-octene, 2-methyl-2-hydroxy-3, 5-dichloro-7-octene, 3, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3, 5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2, 3-diol, and 2, 6-dimethyl-7-octen-2, 6-diol.
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 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).
<xnotran> , , , , ,1,2- ,1,1- ,1,1,2- ,1,1,1- ,1,1,2,2- ,1,1,1,2- , , ,2- , ,1,3- ,1,1,2- ,1,1,2,2,3,3- ,1,1,1,2,2,3,3- ,1- , ,1,4- ,1,2- ,1,1,2- -2- ,1,2,3,4- ,1- ,2- -2- ,1- -3- ,1- -2,2- ,1- -2- ,1,5- ,2,2- -1,3- ,1,1,1- ( ) , . </xnotran>
According to a preferred embodiment of the invention, the cocatalyst is chosen from organoaluminum compounds and/or organoboron compounds.
According to a preferred embodiment of the invention, the organoaluminium compound is selected from alkylaluminoxanes or compounds of general formula AlR n X 1 3-n With an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlR n X 1 3-n In the formula, R is H or 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 present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (10-10000000): 1, 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 preferred embodiments of the present invention, the olefin comprises an olefin having from 2 to 16 carbon atoms, and in some embodiments of the present invention, the olefin comprises ethylene or an alpha-olefin having from 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 olefin alcohol monomer represented by the formula G in the reaction system is 0.01 to 6000mmol/L, preferably 0.1 to 1000mmol/L, more preferably 1 to 500mmol/L, and may be, for example, 1mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 90mmol/L, 100mmol/L, 200mmol/L, 300mmol/L, 400mmol/L, 500mmol/L and any value therebetween.
According to a preferred embodiment of the present invention, the chain transfer agent is selected from one or more of aluminum alkyls, magnesium alkyls 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 present invention, the molar ratio of the chain transfer agent to M in the procatalyst is (0.1-2000): 1, e.g., 0.1.
According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent. According to a preferred embodiment of the invention, the alkane solvent is selected from 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.
According to a preferred embodiment of the present invention, the olefinic alcohol is pre-treated with a dehydroactive hydrogen, preferably with the use of a cocatalyst as described above, to remove hydroxyl active hydrogen from the olefinic alcohol. Preferably, the molar ratio of hydroxyl groups in the alkene alcohol to co-catalyst during pretreatment is 10.
According to a preferred embodiment of the present invention, the polymerization reaction is carried out under anhydrous and oxygen-free conditions.
According to a preferred embodiment of the present invention, the conditions of the polymerization reaction include: the temperature of the reaction is-50 ℃ to-50 ℃, preferably-20 ℃ to 50 ℃, more preferably 0 ℃ to 50 ℃, and can be, for example, 0 ℃,10 ℃, 20 ℃,30 ℃, 40 ℃,50 ℃ and any value therebetween; and/or the reaction time is 10-200min, preferably 20-60min. 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 viewpoints of reducing the cost and simplifying the polymerization process. In the present invention, the "reaction system" refers to the whole formed by including the solvent, the olefin alcohol monomer, the catalyst, optionally the chain transfer agent and the modifier.
The invention also provides the olefin-olefin alcohol copolymer prepared by the preparation method, which comprises spherical and/or spheroidal polymers.
According to a preferred embodiment of the invention, the spherical and/or spheroidal polymers have an average particle size of 0.1 to 50.0mm, for example 0.1mm, 0.5mm, 1.0mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value in between, preferably 0.5 to 20.0mm.
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 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-olefin alcohol copolymer is 30000-500000, preferably 50000-400000.
According to a preferred embodiment of the present invention, the olefin-olefin alcohol copolymer has a molecular weight distribution of 4.0 or less, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and any value therebetween, and preferably, a molecular weight distribution of 1.0 to 4.0.
In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.
According to still another aspect of the present invention, there is provided a use of the olefin-olefin alcohol copolymer as a polyolefin material.
The preparation method of the olefin copolymer with polar groups uses a novel catalyst containing trinuclear metal complexes. The catalyst has not been reported, therefore, the technical problem solved by the invention is to provide a novel preparation method of olefin copolymer (i.e. olefin-olefin alcohol copolymer) with polar groups.
Further, compared with the existing industrial process for preparing olefin-olefin alcohol copolymers, the method for preparing olefin-olefin alcohol copolymers provided by the invention omits the step of saponification reaction, and has simpler preparation process.
Furthermore, the modifier introduced in the invention can effectively improve the balling effect of the polymer.
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 meanings as defined in the general formulae or structural formulae 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 Branched alkyl groups of (a), including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
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 was as follows:
1 HNMR nuclear magnetic resonance apparatus: bruker DMX 300 (300 MHz), tetramethylsilicon (TMS) as internal standard, was used to test the structure of the complex ligands at 25 ℃.
Comonomer content of the polymer (content of structural units derived from the olefin alcohol represented by formula G): by using 13 C NMR spectroscopy was carried out by dissolving a sample of the polymer in 1,2, 4-trichlorobenzene at 120 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX 13 probe.
Molecular weight and molecular weight distribution PDI of the copolymer (PDI = Mw/Mn): 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).
The activity measurement method comprises the following steps: weight of polymer (g)/nickel (mol). Times.2.
Example 1
Figure BDA0002526797910000141
Preparation of Complex Ni1
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 poured into the polymerization system, and 7.6mg (5. Mu. Mol) of complex Ni1, 10mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously 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 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. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. Mu. Mol) of complex Ni1, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 3
Polymerizing 1L of stainless steel equipped with mechanical stirringThe kettle is continuously dried for 6h at 130 ℃, vacuumized while hot and added with N 2 Replace qi for 3 times. To the polymerization system was charged 500mL of hexane while adding 7.6mg (5. Mu. Mol) of complex Ni1, 100mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 neutralization 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. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. Mu. Mol) of complex Ni1, 200mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. Mu. Mol) of complex Ni1, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 the mixture was addedSubstance Ni1, 50mL 1, 2-dichloroethane, 30mmol (5.1 mL) 2-methyl-2-hydroxy-7-octene, 30mL 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 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 while adding 7.6mg (5. Mu. Mol) of complex Ni1, 50mL of dichloromethane, 50mmol (8.5 mL) of 2-methyl-2-hydroxy-7-octene, 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
Preparation of Complex Ni2
Figure BDA0002526797910000161
Will contain 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 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 the solid Ni2 in the form of brown red powder. 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 it is hot, and adding N 2 Replace qi for 3 times. 500mL of hexane was injected into the polymerization systemAlkane with addition of 8.7mg (5. Mu. Mol) of complex Ni2, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 9
Preparation of Complex Ni3
Figure BDA0002526797910000171
Will contain 0.277g (0.9 mmol) of (DME) NiBr 2 To a solution (10 mL) containing 0.300g (0.6 mmol) of ligand L 2 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 a brownish red powdery solid Ni3. 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. To the polymerization system was charged 500mL of hexane, while adding 9.0mg (5. Mu. Mol) of complex Ni3, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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
Preparation of Complex Ni4
Figure BDA0002526797910000172
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 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 a brownish red powdery solid Ni4. 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, while 10.2mg (5. Mu. Mol) of complex Ni4, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 11
Preparation of Complex Ni5
Figure BDA0002526797910000181
The mixture containing 0.277g (0.9 mmol) of (DME) NiBr 2 To a solution containing 0.249g (0.6 mmol) of the ligand L was slowly added dropwise 4 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 drying in vacuum to obtain a brownish red powdery solid Ni5. The yield was 84.3%. 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, while 7.9mg (5. Mu. Mol) of complex Ni5, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 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 (2)
Figure BDA0002526797910000191
Will contain 0.277g (0.9 mmol) of (DME) NiBr 2 Was slowly added dropwise to a solution containing 0.317g (0.6 mmol) of the ligand L 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 a brownish red powdery solid Ni6. 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; and N,3.00.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N 2 Replace qi for 3 times. 500mL of hexane were injected, while 9.0mg (5. Mu. Mol) of complex Ni6, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 30 ℃ for 30min while maintaining an ethylene pressure of 10 atm. Neutralizing with 10wt% ethanol solution acidified with hydrochloric acid to obtain polymer,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. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. Mu. Mol) of complex Ni1, 50mL of dichloromethane, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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 (comparative)
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while it is 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 Ni1, 30mmol (5.1 mL) of 2-methyl-2-hydroxy-7-octene, 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
Figure BDA0002526797910000201
As can be seen from Table 1, the catalyst used in the present invention exhibits higher polymerization activity when it catalyzes the copolymerization of ethylene and an alkenyl alcohol, and the spherical polymer content in the resulting polymer increases after the modifier is added. The molecular weight of the polymer can be adjusted and controlled in 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 with reference to exemplary embodiments, but 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 (27)

1. A process for preparing an olefin copolymer having polar groups, comprising polymerizing an olefin and an olefin alcohol in the presence of a catalyst, a modifier, and optionally a chain transfer agent to produce an olefin-olefin alcohol copolymer;
wherein the modifier comprises a halogenated hydrocarbon;
the alkene alcohol is selected from one or more of alkene alcohols shown in a formula G:
Figure QLYQS_1
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:
Figure QLYQS_2
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;
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 no substituent and C1-C10 alkoxy containing substituent or no substituent;
in the formula II, R 1 And R 2 The same or different, each independently selected from the group represented by formula A:
Figure QLYQS_3
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.
2. The method of claim 1, wherein R in formula A 1 -R 5 The same or different, each independently selected from hydrogen, halogenA hydroxyl group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyloxy group, a substituted or unsubstituted C2-C10 alkynyloxy group, a substituted or unsubstituted C3-C10 cycloalkoxy group, a substituted or unsubstituted C6-C15 aryl group, a substituted or unsubstituted C7-C15 aralkyl group, and a substituted or unsubstituted C7-C15 alkylaryl group.
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 is 11 Is selected from C1-C20 alkyl containing substituent 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 Is selected from C1-C10 alkyl containing substituent or not containing substituent.
5. The method of claim 4, wherein R in formula II 11 Selected from C1-C6 alkyl containing or not containing substituents.
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, 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, C3-C10 alkenyloxy with or without substituentOptionally substituted C2-C10 alkynyloxy, optionally substituted C3-C10 cycloalkoxy, optionally substituted C6-C15 aryl, optionally substituted C7-C15 aralkyl, and optionally substituted C7-C15 alkaryl.
7. The method of claim 6, wherein R is 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 according to any one of claims 1 to 8, wherein the substituents in formula II and formula a are 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 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 in formula II and formula a.
11. The process according to claim 10, characterized in that said 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 said C1-C6 alkoxy is selected from the group consisting of 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:
Figure QLYQS_4
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 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:
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
One or more of (a).
14. The method of any of claims 1-8, 10-13, wherein the olefin comprises an olefin having 2-16 carbon atoms.
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 olefin alcohol represented by the formula G is 0.4 to 10.0mol%.
16. The method of claim 15, wherein 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.
17. The method of claim 15, wherein in formula G, L 1 And L 2 Is H, L 3 Is H or C 1 -C 20 Alkyl radical, L 4 Is C having a pendant group 1 -C 20 An alkylene group.
18. The method of claim 15, 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 10 An alkylene group.
19. The method of claim 15, 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, wherein in formula G, L is 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 hydroxyl;
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 said substituent is selected from C 1 -C 6 Alkyl, halogen and C 1 -C 6 One or more of alkoxy groups;
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 process of any 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 C1-C15 halogenated hydrocarbon.
23. The method of claim 22, wherein the halogenated hydrocarbon in the modifier is a C1-C15 halogenated alkane;
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 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) to 1;
and/or the volume ratio of the solvent used for polymerization to the modifier is (1-5000): 1.
24. The method of claim 23, wherein the halogenated hydrocarbon in the modifier is a C1-C10 halogenated alkane;
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.
25. The method of claim 24, wherein the halogenated hydrocarbon in the modifier is a C1-C6 halogenated alkane;
and/or, when the cocatalyst is an organic aluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine metal complex is (100-10000): 1.
26. An olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 25, which is spherical and/or spheroidal, and/or which has a particle size of from 0.1 to 50mm.
27. Use of an olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1-25 or the olefin-olefin alcohol copolymer of claim 26 as a polyolefin material.
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