CN113754817A - 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 PDFInfo
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- CN113754817A CN113754817A CN202010506738.0A CN202010506738A CN113754817A CN 113754817 A CN113754817 A CN 113754817A CN 202010506738 A CN202010506738 A CN 202010506738A CN 113754817 A CN113754817 A CN 113754817A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
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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
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 polar comonomer can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.
Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is a novel high molecular material integrating the processability of ethylene polymer and the gas barrier property of vinyl alcohol polymer, is one of three barrier resins industrially produced in the world at present, and is widely used for packaging food, medical solution and other products. Since vinyl alcohol cannot exist independently in the form of monomer, it is usually prepared by alcoholysis of ethylene-vinyl acetate copolymer by radical polymerization, but the alcoholysis process requires the use of a large amount of solvent, and the final saponification product contains a large amount of impurities such as acetic acid and alkali metal salt, and requires a large amount of water for washing.
CN109843948A reports a process for the preparation of 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 polymer has good appearance and 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:
in the formula I, R1And R2The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r5-R7The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r5-R7Optionally forming a ring with each other; r11Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.
According to some embodiments of the invention, R1And R2Selected from containing or not containing substituentsAnd/or a substituted or unsubstituted C6-C20 aryl group.
According to some embodiments of the invention, R1And/or R2Is a group of formula A:
in the formula A, R1-R5The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent; r1-R5Optionally forming a ring with each other.
According to some embodiments of the invention, R in formula A1-R5The aryl group is selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent.
According to some embodiments of the invention, M is selected from nickel and palladium.
According to some embodiments of the invention, Y is selected from O and S.
According to some embodiments of the invention, X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, and substituted or unsubstituted C1-C10 alkoxy, preferably from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy.
According to some embodiments of the invention, R11Is selected from C1-C20 alkyl with or without substituent, preferably C1-C10 alkyl with or without substituent, more preferably C1-C6 alkyl with or without substituent.
According to some embodiments of the invention, the diimine metal complex is of formula II:
in the formula II, R5-R10The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent, and C7-C20 alkaryl with or without substituent,
r in the formula II1、R2M, X, Y and R11Have the same definition as formula I.
According to some embodiments of the invention, R5-R10The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C1 with or without substituent0 cycloalkyl, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent, and C7-C15 alkaryl with or without substituent.
According to some embodiments of the invention, R5-R10Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.
According to some embodiments of the invention, the substituent is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy; the substituents are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.
According to some embodiments of the invention, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3, 3-dimethylbutyl.
According to some embodiments of the invention, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3, 3-dimethylbutoxy.
According to some embodiments of the invention, the halogen is selected from fluorine, chlorine, bromine and iodine.
According to some embodiments of the invention, the diimine metal complex is represented by formula III:
according to some embodiments of the invention, in formula III,R1-R5selected from hydrogen, halogen, C1-C6 alkyl with or without substituent, and C1-C6 alkoxy with or without substituent; r5-R10Selected from hydrogen, halogen, C1-C6 alkyl and C1-C6 alkoxy; m is selected from nickel; y is selected from O; x is selected from halogen; r11Is selected from C1-C6 alkyl containing substituent or not containing substituent.
According to some embodiments of the invention, the diimine metal complex is selected from one or more of the following complexes:
1) a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
2) A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
3) A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
4) A complex of formula III wherein R1-R3＝Me，R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
5) A complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
6) A complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
7) A complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
8) A complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
9) A complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
10) A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
11) A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
12) A complex of formula III wherein R1-R3＝Me，R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
13) A complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
14) A complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
15) A complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
16) A complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
17) A complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
18) a complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
19) a complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
20) a complex of formula III wherein R1-R3＝Me，R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
21) a complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
22) a complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
23) a complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
24) a complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
25) a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
26) A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
27) A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
28) A complex of formula III wherein R1-R3＝Me，R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
29) A complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
30) A complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
31) A complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
32) A complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br。
According to some embodiments of the invention, the alkene alcohol is selected from one or more of the alkene alcohols represented by formula G:
in the formula G, L1-L3Each independently selected from H and C with or without substituent1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group.
According to some embodiments of the invention, the copolymer has a content of structural units derived from the alkene alcohol represented by formula G of 0.4 to 10.0 mol%.
According to some embodiments of the invention, in formula G, L1And L2Is H.
According to some embodiments of the invention, in formula G, L3Is H or C1-C30An alkyl group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C30An alkylene group.
According to some embodiments of the invention, in formula G, L3Is H or C1-C20An alkyl group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C20An alkylene group.
According to some embodiments of the invention, in formula G, L3Is H or C1-C10An alkyl group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C10An alkylene group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C6An alkylene group.
According to some embodiments of the invention, L1-L3Wherein said substituents are selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl, cyano and hydroxyl.
According to some embodiments of the invention, L1-L3Wherein the substituent is selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy.
According to some embodiments of the invention, the pendant group in L4 is selected from halogen, C6-C20Aryl radical, C1-C20Alkyl and C1-C20One or more of alkoxy, said C6-C20Aryl radical, C1-C20Alkyl and C1-C20Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl and hydroxyl.
According to a preferred embodiment of the invention, said L4The side group in (A) is selected from halogen and C6-C20Aryl radical, C1-C20Alkyl, hydroxy substituted C1-C20Alkyl and alkoxy substituted C1-C20One or more of alkyl; preferably, the side group is selected from halogen, C6-C20Aryl radical, C1-C10Alkyl, hydroxy substituted C1-C10Alkyl and alkoxy substituted C1-10One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C1-C6Alkyl and hydroxy substituted C1-C6One or more of alkyl, said C1-C6Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl.
According to a preferred embodiment of the invention, in formula G, L1And L2Is H, L3Is H or C1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group; said C is1-C30Alkyl is optionally substituted by a substituent, preferably selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl, cyano and hydroxyl.
According to a preferred embodiment of the invention, in formula G, L1And L2Is H, L3Is H, C1-C10Alkyl or halogen substituted C1-C10Alkyl, preferably L3Is H or C1-C10An alkyl group; l is4Is C having a pendant group1-C20Alkylene radicals, e.g. L4Is methylene with side group, ethylene with side group, propylene with side group, butylene with side group, C with side group5Alkylene, C having pendant groups6Alkylene, C having pendant groups7Alkylene, C having pendant groups8Alkylene, C having pendant groups9Alkylene, C having pendant groups10Alkylene, C having pendant groups12Alkylene, C having pendant groups14Alkylene, C having pendant groups18Alkylene, C having pendant groups20Alkylene, preferably C, having pendant groups1-C10An alkylene group.
According to a preferred embodiment of the invention, in formula G, L1And L2Is H, L3Is H or C1-6An alkyl group; l is4Is C having a pendant group1-C10An alkylene group.
In the present invention, the carbon number n of the Cn alkylene group means the number of C's in the linear chain, excluding the number of C's in the pendant group, and is, for example, isopropylidene (-CH)2-CH(CH3) -) is referred to herein as C with a pendant group (methyl)2An alkylene group.
According to a preferred embodiment of the present invention, specific examples of the alkene alcohol represented by formula G include, but are not limited to: -2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2, 4-dimethyl-4-penten-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-methyl-3-buten-2-ol, 2-methyl-4-penten-2-ol, 2-methyl-2-penten-ol, 2-methyl-4-penten-2-ol, 2-yl-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-2-ol, and mixtures thereof, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2, 3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2, 5-dimethyl-1-hepten-4-ol, 2, 6-dimethyl-7-octen-2-ol, 2-hydroxy-2, 4, 5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-6-heptene, 2-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-2-heptene, 2-methyl-2-1-heptene, 2-methyl-2-4-methyl-6-heptene, 2-methyl-4-heptene, 2-1-octene, 2-octene, 2-heptene, 2-octene, 2-one, 3-methyl-3-hydroxy-7-octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl-3-hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1, 2-dihydroxy-7-octene, 2, 6-dimethyl-2, 6-dihydroxy-7-octene, 2, 6-dimethyl-2, 3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, mixtures thereof, and mixtures thereof, 2-methyl-2-hydroxy-3, 5-dichloro-7-octene, 3, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3, 5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2, 3-diol, and 2, 6-dimethyl-7-octen-2, 6-diol.
According to an embodiment of the invention, the modifier comprises a halogenated hydrocarbon.
According to an embodiment of the invention, the halogenated hydrocarbon is selected from C1-C15The halogenated hydrocarbon of (1).
According to an embodiment of the invention, the halogenated hydrocarbon is selected from C1-C10The halogenated alkane of (1).
According to an embodiment of the invention, the halogenated hydrocarbon is selected from C1-C6The halogenated alkane of (1).
According to a preferred embodiment of the invention, the halogenated hydrocarbon is methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, 1,1, 2-trichloroethane, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, 1,1,1, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 2-chloropropane, chloro-n-propane, 1, 3-dichloropropane, 1,1, 2-trichloropropane, 1,1,2,2,3, 3-hexachloropropane, 1,1,1,2,2,3, 3-heptachloropropane, 1-chlorobutane, chloro-tert-butane, 1, 4-dichlorobutane, 1, 2-dichloroisobutane, 1,1, 2-trichloro-2-methylpropane, 1,2,3, 4-tetrachlorobutane, 1-chloropentane, 2-chloro-2-methylbutane, 1-chloro-3-methylbutane, 1-chloro-2, 2-dimethylpropane, 1-chloro-2-methylbutane, 1, 5-dichloropentane, 2, 2-dimethyl-1, 3-dichloropropane, 1,1,1- (trichloromethyl) ethane, tetrachloro-pentanes.
According to a preferred embodiment of the 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 AlRnX1 3-nWith an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlRnX1 3-nWherein R is H, C1-C20Saturated or unsaturated hydrocarbon radicals or C1-C20Saturated or unsaturated hydrocarbyloxy radicals, preferably C1-C20Alkyl radical, C1-C20Alkoxy radical, C7-C20Aralkyl or C6-C20An aryl group; x1Is halogen, preferably chlorine or bromine; 0<n is less than or equal to 3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminumTri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compound is Methylaluminoxane (MAO).
According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
According to a preferred embodiment of the present invention, the concentration of the main catalyst in the reaction system is 0.00001 to 100mmol/L, for example, 0.00001mmol/L, 0.00005mmol/L, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.3mmol/L, 0.5mmol/L, 0.8mmol/L, 1mmol/L, 5mmol/L, 8mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 80mmol/L, 100mmol/L and any value therebetween, preferably 0.0001 to 1mmol/L, more preferably 0.001 to 0.5 mmol/L.
According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (10-10000000):1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1 and any value therebetween, preferably (10-100000):1, more preferably (100-10000): 1; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the procatalyst is (0.1-1000):1, e.g., 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 4:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, and any value therebetween, preferably (0.1-500): 1.
According to a preferred embodiment of the invention, saidOlefins include olefins having from 2 to 16 carbon atoms, and in some embodiments of the invention, the olefins include ethylene or alpha olefins having from 3 to 16 carbon atoms. In other embodiments of the present invention, the olefin is C3-C16A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms, more preferably ethylene or C2-C10Alpha-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene and octene.
According to a preferred embodiment of the present invention, the concentration of the 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 invention, the molar ratio of the chain transfer agent to M in the procatalyst is (0.1-2000: 1, e.g. 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 600:1, 800:1, 1000:1, 2000:1 and any value in between, preferably (10-600: 1).
According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent. According to a preferred embodiment of the invention, the alkane solvent is selected from C3-C20One or more alkanes, preferably selected from C3-C10Alkanes, for example, may be selected from one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexaneAnd more, preferably one or more of hexane, heptane and cyclohexane.
According to a preferred embodiment of the invention, the volume ratio of solvent to modifier used for the polymerization is (1-5000):1, preferably (1.0-500): 1. For example, 1:1, 2:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 600:1, 800:1, 1000:1, 2000:1, and any value in between, preferably (1.0-500): 1.
According to a preferred embodiment of the present invention, the 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 from 10:1 to 1: 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 20-60 min. In the present invention, the reaction pressure is not particularly limited as long as the monomer can be subjected to coordination copolymerization. When the olefin is ethylene, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50atm, from the viewpoint of cost reduction and simplification of the polymerization process. In the present invention, the "reaction system" refers to the whole formed by including the solvent, the olefin alcohol monomer, the catalyst, optionally the chain transfer agent and the modifier.
The invention also provides an olefin-olefin alcohol copolymer prepared by the preparation method, which comprises spherical and/or spheroidal polymers.
According to a preferred embodiment of the invention, the spherical and/or spheroidal polymers have an average particle size of 0.1 to 50.0mm, for example 0.1mm, 0.5mm, 1.0mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value in between, preferably 0.5 to 20.0 mm.
According to a preferred embodiment of the present invention, in the olefin-olefin alcohol copolymer, the content of the structural unit derived from the olefin alcohol represented by the formula G is 0.4 to 30.0 mol%, and for example, may be 0.4 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 5.0 mol%, 8.0 mol%, 10.0 mol%, 15.0 mol%, 20.0 mol%, 25.0 mol%, 30.0 mol% and any value therebetween, preferably 0.7 to 10.0 mol%.
According to a preferred embodiment of the present invention, the weight average molecular weight of the olefin-olefin alcohol copolymer is 30000-500000, preferably 50000-400000.
According to a preferred embodiment of the present invention, the olefin-olefin alcohol copolymer has a molecular weight distribution of 4.0 or less, and for example, may be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and any value therebetween, and preferably, the molecular weight distribution is 1.0 to 4.0.
In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.
According to still another aspect of the present invention, there is provided a use of the olefin-olefin alcohol copolymer as a polyolefin material.
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 herein1、R2、R3、R4、R5、R1-R10、R11、R5X, M, A, Y, etc., have the same definitions in each general formula or structural formula unless otherwise specified.
In the present invention, C1-C20Alkyl is C1-C20Straight chain alkyl or C3-C20Branched alkyl groups of (a), including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
C3-C20Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C6-C20Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.
C2-C20Alkenyl means C1-C20Linear alkenyl of (A) or (C)3-C20Including but not limited to: vinyl, allyl, butenyl.
C7-C20Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl and phenyl-tert-butyl.
C7-C20Examples 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:
1HNMR nuclear magnetic resonance apparatus: bruker DMX 300(300MHz), 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 using13C NMR spectroscopy was carried out by dissolving a polymer sample in 1,2, 4-trichlorobenzene at 120 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX 13 probe.
Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the copolymer: measured at 150 ℃ using PL-GPC220 in trichlorobenzene (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).
The activity measurement method comprises the following steps: weight of polymer (g)/nickel (mol). times.2.
Example 1
Preparation of Complex Ni1
Will contain 0.277g (0.9mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.233g (0.6mmol) of ligand L1In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni1. Yield: 78.2 percent. Elemental analysis (C)60H58Br6N4Ni3O2): c, 47.33; h, 3.84; n, 3.68; experimental values (%): c, 47.38; h, 4.00; and N, 3.46.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. mu. mol) of complex Ni1, 10mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L in hexane), 6.5mL of MAO (1.53mol/L in toluene)Solution), ethylene pressure of 10atm was maintained at 30 deg.c, and the reaction was stirred for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 2
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. mu. mol) of complex Ni1, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 3
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane while adding 7.6mg (5. mu. mol) of complex Ni1, 100mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 4
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane while adding 7.6mg (5. mu. mol) of complex Ni1, 200mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. Polymerization Activity and Polymer Property parameters are given in the table1 is shown.
Example 5
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. mu. mol) of complex Ni1, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 1.0mL diethyl zinc (1mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ for 30min while maintaining an ethylene pressure of 10 atm. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 6
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane while adding 7.6mg (5. mu. mol) of complex Ni1, 50mL of 1, 2-dichloroethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 7
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane while adding 7.6mg (5. mu. mol) of complex Ni1, 50mL of dichloromethane, 50mmol (8.5mL) of 2-methyl-2-hydroxy-7-octene, 50mL of AlEt3(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 8
Preparation of Complex Ni2
Will contain 0.277g (0.9mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.300g (0.6mmol) of ligand L2In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain a brownish red powdery solid Ni 2. The yield was 74.0%. Elemental analysis (C)76H90Br6N4Ni3O2): c, 52.25; h, 5.19; n, 3.21; experimental values (%): c, 52.48; h, 5.52; and N, 3.10.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane, while adding 8.7mg (5. mu. mol) of complex Ni2, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 9
Preparation of Complex Ni3
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution of 2-methyl-1-propanol (10mL) containing 0.300g (0.6mmol) of ligand L2In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain a brownish red powdery solid Ni 3. The yield is74.0 percent. Elemental analysis (C)80H98Br6N4Ni3O2): c, 53.29; h, 5.48; n, 3.11; experimental values (%): c, 53.28; h, 5.82; and N, 3.29.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane, while adding 9.0mg (5. mu. mol) of complex Ni3, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 10
Preparation of Complex Ni4
Will contain 0.277g (0.9mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.389g (0.6mmol) of ligand L3In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain a brownish red powdery solid Ni 4. The yield was 74.1%. Elemental analysis (C)52H34Br14N4Ni3O2): c, 30.59; h, 1.68; n, 2.74; experimental values (%): c, 30.72; h, 1.97; and N, 2.48.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 500mL of hexane were injected and simultaneously 10.2mg (5. mu. mol) of complex Ni4, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53mol/L in toluene). At 30 deg.C, keepThe reaction was stirred vigorously for 30min, maintaining an ethylene pressure of 10 atm. The polymer was obtained by neutralizing with a 10 wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.
Example 11
Preparation of Complex Ni5
Will contain 0.277g (0.9mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.249g (0.6mmol) of ligand L in ethanol (10mL)4In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain a brownish red powdery solid Ni 5. The yield was 84.3%. Elemental analysis (C)64H66Br6N4Ni3O2): c, 48.69; h, 4.21; n, 3.55; experimental values (%): c, 48.54; h, 4.47; and N, 3.21.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 500mL of hexane were injected and at the same time 7.9mg (5. mu. mol) of complex Ni5, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53mol/L in toluene). The reaction was vigorously stirred at 30min with keeping the ethylene pressure at 10atm at 30 ℃. The polymer was obtained by neutralizing with a 10 wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.
Example 12
Complex Ni6Preparation of
Will contain 0.277g (0.9mmol) of (DME) NiBr2Was slowly added dropwise to a solution containing 0.317g (0.6mmol) of ligand L5In dichloromethane solutionIn solution (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and drying in vacuum to obtain a brownish red powdery solid Ni 6. The yield was 75.2%. Elemental analysis (C)80H98Br6N4Ni3O2): c, 53.29; h, 5.48; n, 3.11; experimental values (%): c, 53.62; h, 5.87; and N, 3.00.
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6hrs, vacuumizing while it is hot, and adding N2Replace qi for 3 times. 500mL of hexane were injected and simultaneously 9.0mg (5. mu. mol) of complex Ni6, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L in hexane), 6.5ml of Methylaluminoxane (MAO) (1.53mol/L in toluene). The reaction was vigorously stirred at 30min with keeping the ethylene pressure at 10atm at 30 ℃. The polymer was obtained by neutralizing with a 10 wt% hydrochloric acid acidified ethanol solution, and the results are shown in Table 1.
Example 13
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane, while adding 7.6mg (5. mu. mol) of complex Ni1, 50mL of dichloromethane, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 15mL of a toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (1mmol/L toluene solution) was added, and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 14 (comparative)
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. mu. mol) of complex Ni1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L in hexane), 6.5mL of MAO (1.53mol/L in toluene)Solution), ethylene pressure of 10atm was maintained at 30 deg.c, and the reaction was stirred for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
TABLE 1
As can be seen from Table 1, the catalyst used in the present invention exhibits higher polymerization activity when it catalyzes the copolymerization of ethylene 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 controlled within a wide range according to the addition of the chain transfer agent.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A process for preparing an olefin copolymer having polar groups, which comprises polymerizing 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:
in the formula I, R1And R2The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r5-R7The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r5-R7Optionally forming a ring with each other; r11Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.
2. The method of claim 1, wherein R is1And R2Selected from substituted or unsubstituted C1-C20 alkyl and or substituted or unsubstituted C6-C20 aryl, preferably R1And/or R2Is a group of formula A:
in the formula A, R1-R5The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent; r1-R5Optionally forming a ring with each other;
preferably, in formula A, R1-R5Are the same or different and are 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 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;
m is selected from nickel and palladium; y is selected from O and S; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent, preferably selected from halogen, C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent; r11Is selected from C1-C20 alkyl with or without substituent, preferably C1-C10 alkyl with or without substituent, more preferably C1-C6 alkyl with or without substituent.
3. A process according to claim 1 or 2, wherein the diimine metal complex is of formula II:
in the formula II, R5-R10The substituents are respectively and independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, and C8926-C20 alkynyloxy with or without substituentOr C7-C20 aralkyl having no substituent and C7-C20 alkaryl having no substituent or having no substituent,
r in the formula II1、R2M, X, Y and R11Have the same definition as formula I.
4. The method of any one of claims 1-3, wherein R is5-R10The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;
preferably, R5-R10Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.
5. A process according to any one of claims 1 to 4, characterised in that the substituents are selected from halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy; the substituents are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy;
preferably, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3, 3-dimethylbutyl;
preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3, 3-dimethylbutoxy,
preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.
6. A process according to any one of claims 1 to 5, wherein the diimine metal complex is of formula III:
in the formula III, R1-R5Selected from hydrogen, halogen, C1-C6 alkyl with or without substituent, and C1-C6 alkoxy with or without substituent; r5-R10Selected from hydrogen, halogen, C1-C6 alkyl and C1-C6 alkoxy; m is selected from nickel; y is selected from O; x is selected from halogen; r11Selected from C1-C6 alkyl with or without substituent;
preferably, the diimine metal complex is selected from the group consisting of:
1) a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
2) A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
3) A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
4) A complex of formula III wherein R1-R3＝Me，R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
5) A complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
6) A complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
7) A complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
8) A complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5-R10＝H，R11＝Me，M＝Ni，Y＝O，X＝Br；
9) A complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
10) A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
11) A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
12) A complex of formula III wherein R1-R3＝Me，R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
13) A complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
14) A complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
15) A complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
16) A complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5-R10＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
17) A complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
18) a complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
19) a complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
20) a complex of formula III wherein R1-R3＝Me，R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
21) a complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
22) a complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
23) a complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
24) a complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5-R10＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
25) a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
26) A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
27) A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
28) A complex of formula III wherein R1-R3＝Me，R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
29) A complex of formula III wherein R1＝R3＝Me，R2＝Br,R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
30) A complex of formula III wherein R1＝R3＝Br，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
31) A complex of formula III wherein R1＝R3＝Cl，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br；
32) A complex of formula III wherein R1＝R3＝F，R2＝R4＝R5＝R5＝R6＝R9＝R10＝H，R7＝R8＝Me,R11＝Et，M＝Ni，Y＝O，X＝Br
One or more of (a).
7. The process according to any one of claims 1 to 6, wherein the olefin comprises an olefin having 2 to 16 carbon atoms, preferably the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms, and/or the olefinic alcohol is selected from one or more olefinic alcohols of formula G:
in the formula G, L1-L3Each independently selected from H and C with or without substituent1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group;
preferably, the copolymer has a content of structural units derived from the olefin alcohol represented by the formula G of 0.4 to 10.0 mol%;
preferably, L1And L2Is H, L3Is H or C1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group;
more preferably, L1And L2Is H, L3Is H or C1-C20Alkyl radical, L4Is C having a pendant group1-C20An alkylene group;
still more preferably, L1And L2Is H, L3Is H or C1-C10Alkyl radical, L4Is C having a pendant group1-C10An alkylene group;
further preferably, L1And L2Is H, L3Is H or C1-C10Alkyl radical, L4Is C having a pendant group1-C6An alkylene group.
8. The method of claim 7, wherein L is1-L3Wherein said substituents are selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl, cyano and hydroxy; more preferably L1-L3Wherein the substituent is selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy;
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 by a substituent, preferably selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl and hydroxyl.
9. The process of any one of claims 1 to 8, wherein the cocatalyst is selected from organoaluminum compounds and/or organoboron compounds; the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate; the chain transfer agent is selected from one or more of alkyl aluminum, alkyl magnesium and alkyl zinc; the improver comprises halogenated hydrocarbon, preferably, the halogenated hydrocarbon is C1-C15 halogenated hydrocarbon, preferably C1-C15 halogenated alkane, more preferably C1-C10 halogenated alkane, and further preferably C1-C6 halogenated alkane;
preferably, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine metal complex is (10-10)7):1, preferably (10-100000) 1, more preferably (100-; when the cocatalyst is an organic boron compound, the molar ratio of boron in the cocatalyst to M in the diimine metal complex is (0.1-1000):1, preferably (0.1-500): 1; the molar ratio of the chain transfer agent to M in the diimine metal complex is (0.1-5000) to 1, preferably (1.0-1000) to 1;
preferably, the volume ratio of the solvent used for the polymerization to the modifier is (1-5000):1, preferably (1.0-500): 1.
10. An olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 9, which is spherical and/or spheroidal, and/or which has a particle size of from 0.1 to 50 mm.
11. Use of an olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 9 or the olefin-olefin alcohol copolymer of claim 10 as a polyolefin material.
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