CN112745426A - Process for preparing olefin-olefin alcohol copolymers - Google Patents
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Abstract
The present invention relates to a method for preparing an olefin-olefin alcohol copolymer and an olefin-olefin alcohol copolymer prepared by the method. The catalyst used in the method for preparing an olefin-olefin alcohol copolymer includes a diimine metal complex represented by formula I. The preparation method can prepare 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 method for preparing an olefin-olefin alcohol copolymer.
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.
As a preparation technology of polymers at normal temperature and normal pressure, coordination catalytic copolymerization has attracted extensive attention due to its remarkable effects in reducing energy consumption, improving reaction efficiency and the like. The catalyst participates in the reaction process, so that the activation energy of the copolymerization reaction of the olefin monomer and the polar monomer is greatly reduced, and the functional polymer with higher molecular weight can be obtained at lower temperature and pressure. Currently, only a few documents report the use of transition metal complexes to catalyze the copolymerization of olefins and unsaturated alcohols. However, in the prior art, the polymer obtained by any method is a viscous massive solid, so that the polymer is easily scaled in polymerization equipment, and the transportation, solvent removal, granulation and the like of the polymer are difficult.
Disclosure of Invention
The process for preparing an olefin-olefin alcohol copolymer provided by the present invention uses a novel trinuclear metal complex-containing catalyst. The catalyst is not reported, therefore, the technical problem solved by the invention is to provide a novel preparation method of olefin-olefin alcohol copolymer. The method can directly obtain the polymer containing spherical and/or spheroidal, and 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-olefin alcohol copolymer comprising polymerising an olefin and an olefin alcohol in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-olefin alcohol copolymer,
wherein the catalyst comprises a main catalyst and an optional cocatalyst, the main catalyst comprises an amino imine metal complex shown as a formula I,
in the formula I, R1And R2The same or different, independently selectedA C1-C30 hydrocarbon group containing a substituent or not containing a substituent; r3Selected from hydrogen and substituted or unsubstituted C1-C20 hydrocarbyl; r5-R8The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r5-R8Optionally forming a ring with each other; r12Selected 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 substituted or unsubstituted C1-C20 alkyl and/or substituted or unsubstituted C6-C20 aryl, preferably R1And/or R2Is a group of formula II:
in the formula II, 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 II, R1-R5The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituentA 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 alkaryl group.
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, R12Is 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, R3Is selected from C1-C20 alkyl with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent.
According to some embodiments of the invention, R3Selected from the group consisting of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C7-C15 aralkyl, and substituted or unsubstituted C7-C15 alkaryl, more preferably, R3Is selected from C1-C6 alkyl with or without substituent, such as methyl, ethyl, propyl or butyl.
According to some embodiments of the invention, the aminoimine metal complex is represented by formula III:
in the formula III, R1-R11The 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;
R3、R12y, M and X have the same definitions as formula I.
According to some embodiments of the invention, R1-R11The 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, R1-R11Each 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.
Exemplary C1-C6 alkyl groups in accordance with the present invention include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3, 3-dimethylbutyl.
Exemplary C1-C6 alkoxy groups according to the present invention are selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3, 3-dimethylbutoxy.
Exemplary halogens according to the present invention are selected from fluorine, chlorine, bromine and iodine.
According to some embodiments of the present invention, exemplary aminoimine metal complexes include, but are not limited to:
a complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12Et, M ═ Ni, Y ═ O, X ═ Br; a complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12Et, M ═ Ni, Y ═ O, X ═ Br; a complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝i-Pr，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1-R3＝Me，R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1-R3＝Me，R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3Is a nailRadical, R2＝Br，R4-R7＝R10＝H，R8＝R9＝R11＝R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3Methyl, R2＝Br，R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝F，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Cl，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Br，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3Methyl, R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Ethyl, R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1-R3Methyl, R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Methyl, R2＝Br，R4-R7＝R10＝H，R8＝R9＝R11Methyl, R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝F，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Cl，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Br，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
complexes of formula IIIWherein R is1＝R3Methyl, R2＝R4-R7＝R10＝H，R8＝R9＝CH3，R11Bromomethyl, R3Is isopropyl, R12Ethyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Et，R2＝R4-R7＝R10＝H，R8＝R9＝CH3，R11＝CH2Br，R3Is isopropyl, R12Ethyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4-R7＝R10＝H，R8＝R9＝CH3，R11＝CH2Br，R3Ethyl, R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1-R3＝Me，R4-R7＝R10＝H，R8＝R9＝CH3，R11＝CH2Br，R12Ethyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Me，R2＝Br，R4-R7＝R10＝H，R8＝R9＝Me，R3＝Et，R11＝CH2Br，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝F，R2＝R4-R7＝R10＝H，R8＝R9＝Me，R11＝CH2Br，R3Not butyl, R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Cl，R2＝R4-R7＝R10＝H，R8＝R9＝Me，R11＝CH2Br，R3Not butyl, R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Br，R2＝R4-R7＝R10＝H，R8＝R9＝Me，R11＝CH2Br，R3Not butyl, R12＝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, e.g., isopropylidene(-CH2-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, 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, 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 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 formulaAlRnX1 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, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compound is Methylaluminoxane (MAO).
According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
According to a preferred embodiment of the present invention, the concentration of the main catalyst in the reaction system is 0.00001 to 100mmol/L, for example, 0.00001mmol/L, 0.00005mmol/L, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.3mmol/L, 0.5mmol/L, 0.8mmol/L, 1mmol/L, 5mmol/L, 8mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 80mmol/L, 100mmol/L and any value therebetween, preferably 0.0001 to 1mmol/L, more preferably 0.001 to 0.5 mmol/L.
According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (10-10000000):1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1 and any value therebetween, preferably (10-100000):1, more preferably (100-10000): 1; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the procatalyst is (0.1-1000):1, e.g., 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 4:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, and any value therebetween, preferably (0.1-500): 1.
According to a preferred embodiment of the invention, the olefin comprises an olefin having 2 to 16 carbon atoms, and in some embodiments of the invention, the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms. In other embodiments of the present invention, the olefin is C3-C16A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms, more preferably ethylene or C2-C10Alpha-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene and octene.
According to a preferred embodiment of the present invention, the concentration of the 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 selected from C3-C20One or more alkanes, preferably selected from C3-C10The alkane, for example, may be selected from one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexane, preferably one or more of hexane, heptane and cyclohexane.
According to a preferred embodiment of the present invention, the olefin alcohol is pre-treated with a dehydroactive hydrogen, preferably with a co-catalyst or chain transfer agent as described above, to remove hydroxyl active hydrogen from the olefin alcohol. Preferably, the molar ratio of hydroxyl groups in the alkene alcohol to co-catalyst or chain transfer agent during pretreatment is from 10:1 to 1: 10.
According to a preferred embodiment of the invention, the reaction is carried out in the absence of water and oxygen.
According to a preferred embodiment of the invention, the conditions of the reaction include: the temperature of the reaction is-50 ℃ to 50 ℃, preferably-20 ℃ to 50 ℃, more preferably 0 ℃ to 50 ℃, and can be, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃,50 ℃ and any value therebetween; and/or the reaction time is 10-200min, preferably 20-60 min. In the present invention, the reaction pressure is not particularly limited as long as the monomer can be subjected to coordination copolymerization. When the olefin is ethylene, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50atm, from the viewpoint of cost reduction and simplification of the polymerization process.
In the present invention, the "reaction system" is meant to include the totality of solvent, olefin alcohol monomer, catalyst, and optionally chain transfer agent.
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.
Furthermore, in the preparation method of the olefin-olefin alcohol copolymer provided by the invention, the spherical and/or spheroidal polymers with good shapes are directly prepared by selecting the olefin alcohol monomer for reaction, the catalyst and a proper polymerization process without subsequent processing steps such as granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.
Further, compared with the existing industrial process for preparing 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.
Drawings
FIG. 1 is a photograph of a spherical and/or spheroidal polymer obtained in example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The analytical characterization instrument used in the present invention was as follows:
1HNMR nuclear magnetic resonance apparatus: bruker DMX 300(300MHz), Tetramethylsilicon (TMS) as 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.
For the purpose of conciseness and clarity in the examples, the ligands and complexes are illustrated below:
a1 is an alpha-diimine compound of formula VI, wherein R is1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3；
A2 is an alpha-diimine compound of formula VI, wherein R is1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3；
Ligand L1 is an aminoimine compound of formula V, wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3；
Ligand L2 is an aminoimine compound of formula V, wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3；R3＝CH3；
Ligand L3 is an aminoimine compound of formula V, wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3；R3＝Et；
The complex Ni1 is a complex shown as a formula III, wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
The complex Ni2 is a complex shown as a formula III, wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3；R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
The complex Ni3 is a complex shown as a formula III, wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3；R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br。
Example 1
1) Preparation of ligand L1:
1.5ml of 2, 6-dimethylaniline (12mmol) was reacted with 57ml of 1M trimethylaluminum in toluene, after refluxing for 3h camphorquinone (1.05g, 5mmol) was added, the reaction was refluxed for 8 h, cooled, then quenched with sodium hydroxide/ice water, extracted with ethyl acetate, the organic phases were combined, dried over anhydrous magnesium sulfate and the product was chromatographed over a petroleum ether/ethyl acetate column to give ligand L1 as a colorless crystal in 70.2% yield.1HNMRδ(ppm)7.00-6.89(m,6H,Ar-H),3.57(s,1H,NH),2.18(s,6H,CAr-CH3),2.05(s,6H,CH3),1.74(m,4H,CH2),1.44(s,3H,CH3),1.35(m,1H),1.21(s,3H,C H3),1.01(s,3H,CH3),0.87(s,3H,CH3).
2) Preparation of complex Ni 1:10 ml of (DME) NiBr2(277mg,0.9mmol) in ethanol (10mL) was added dropwise to a solution of ligand L1(233mg,0.6mmol) in dichloromethane (10mL) at room temperature for 6 hours, and the precipitate was precipitated, filtered, washed with ether and dried to give a yellow powder solid in 70% yield. Elemental analysis (C)58H82Br6N4Ni3O2): c, 45.75; h, 5.43; n, 3.68; experimental values (%): c, 45.56; h, 5.83; and N, 3.46.
3) Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. mu. mol) of complex Ni1, 15mmol (2.5mL) of 2-methyl-2-hydroxy-7-octene, 15mL of AlEt3(1.0mol/L in hexane), 6.5mL of Methylaluminoxane (MAO) (1.53mol/L in toluene), at 30 ℃,the reaction was stirred for 30min while maintaining the 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 2
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. mu. mol) of complex Ni1, 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.
FIG. 1 shows a photograph of the spherical and/or spheroidal polymer produced in this example.
Example 3
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. mu. mol) of complex Ni1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 60 ℃ under 10atm of ethylene pressure for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 4
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. mu. mol) of complex Ni1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 0.5mL diethyl zinc (1mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under 10atm of ethylene pressure for 30 min. Finally, the ethanol solution is acidified by 10 wt% hydrochloric acidAnd neutralizing to obtain the polymer. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 5
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.6mg (5. mu. mol) of complex Ni1, 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. 500mL of hexane was charged to the polymerization system while adding 7.6mg (5. mu. mol) of complex Ni1, 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 7
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was charged to the polymerization system while adding 7.6mg (5. mu. mol) of complex Ni1, 100mmol (17.0mL) of 2-methyl-2-hydroxy-7-octene, 100mL 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
1) Preparation of ligand L2:
alpha-diimine compound A23.88g (8mmol), sequentially adding 30ml of toluene and 1M trimethylaluminum (16ml and 16mmol), refluxing for 8 hours, stopping the reaction by using sodium hydroxide/ice water, extracting with ethyl acetate, combining organic phases, drying by using anhydrous magnesium sulfate, and carrying out column chromatography on the product by using petroleum ether/ethyl acetate to obtain colorless crystal ligand L2, wherein the yield is 84.2%.1HNMRδ(ppm)7.19-7.06(m,6H,Ar-H),3.42(s,1H,NH),2.98(m,2H,CH(CH3)2),2.88(m,2H,CH(CH3)2),2.32(m,1H),1.81(m,4H,CH2),1.50(s,3H,CH3),1.21(m,24H,CH3),0.92(s,3H,CH3),0.75(s,3H,CH3),0.72(s,3H,CH3).
2) Preparation of complex Ni 2: 10ml of (DME) NiBr2(277mg,0.9mmol) in ethanol (10mL) was added dropwise to a solution of ligand L2(300mg,0.6mmol) in dichloromethane (10mL) at room temperature for 6 hours, and the precipitate was precipitated, filtered, washed with ether and dried to give a red powder solid in 78% yield. Elemental analysis (C)74H114Br6N4Ni3O2): c, 50.87; h, 6.58; n, 3.21; experimental values (%): c, 50.57; h, 6.73; and N, 3.04.
3) Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.7mg (5. mu. mol) of complex Ni2, 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
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.7mg (5. mu. mol) of complex Ni2, 30mmol (8.5mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L of hexane)Solution), 6.5mL of MAO (1.53mol/L in toluene), and the reaction was stirred at 60 ℃ 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 10
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was charged to the polymerization system while adding 8.7mg (5. mu. mol) of complex Ni2, 30mmol (4.1mL) of 3-methyl-5-hexen-3-ol, 30mL of AlEt-3-ol3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction mixture was stirred at 30 ℃ under 10atm of ethylene pressure for 60 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 11
1) Preparation of ligand L3:
alpha-diimine compound A23.88g (8mmol), sequentially adding 30ml of diethyl ether and 2M diethyl zinc (4ml, 8mmol), stirring at normal temperature for 3 hours, terminating the reaction with ice water, extracting with ethyl acetate, combining organic phases, drying with anhydrous magnesium sulfate, and separating the product by petroleum ether/ethyl acetate column chromatography to obtain colorless crystal ligand L3 with the yield of 52.1%.1HNMRδ(ppm)7.17-7.06(m,6H,Ar-H),4.44(s,1H,NH),2.98(m,2H,CH(CH3)2),2.87(m,2H,CH(CH3)2),2.33(m,1H),1.86(m,2H,CH2),1.81(m,4H,CH2),1.21(m,24H,CH3),1.08(t,3H,CH3),0.93(s,3H,CH3),0.75(s,3H,CH3),0.72(s,3H,CH3).
2) Preparation of complex Ni 3: 10ml of (DME) NiBr2(277mg,0.9mmol) in ethanol (10mL) was added dropwise to a solution of ligand L3(309mg,0.6mmol) in dichloromethane (10mL) at room temperature and stirred for 6 hours to precipitate, which was filtered, washed with ether and dried to give a red powder solid in a yield of 72%. Elemental analysis (C)76H118Br6N4Ni3O2)：C,51.42；H,6.70；N,3.16；Experimental values (%): c, 51.29; h, 6.98; and N, 3.04.
3) Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.9mg (5. mu. mol) of complex Ni3, 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 12
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 8.9mg (5. mu. mol) of complex Ni3, 30mmol (4.5mL) of 4-methyl-1-hepten-4-ol, 30mL of AlEt-4-ol were added3(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 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. 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 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
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 injected into the polymerization system, while 7.6mg (5. mu. mol) of complex Ni1, 30mmol (6.0mL) of 10-undecen-1-ol, 30mL of AlEt-1-ol were added3(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 15
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of toluene was charged to the polymerization system while adding 7.6mg (5. mu. mol) of complex Ni1, 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.
TABLE 1
As can be seen from Table 1, the catalyst of the present invention exhibits higher polymerization activity when it catalyzes the copolymerization of ethylene and an alkenyl alcohol, and the resulting polymer has higher molecular weight. The copolymerization activity of the catalyst can reach 5.17 x 10at most6g·mol-1(Ni)·h-1. The molecular weight of the polymer can be controlled within a wide range according to the addition of the chain transfer agent. In addition, by regulating and controlling the polymerization conditions, a copolymerization product with good particle morphology can be prepared.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A process for preparing an olefin-olefin alcohol copolymer comprising polymerizing an olefin and an olefin alcohol in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-olefin alcohol copolymer,
the catalyst comprises a main catalyst and an optional cocatalyst, wherein the main catalyst comprises an amino imine 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; r3Selected from hydrogen and substituted or unsubstituted C1-C20 hydrocarbyl; r5-R8The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r5-R8Optionally forming a ring with each other; r12Selected 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 aminoimine metal complex of claim 1, wherein R is1And R2Selected from containing substituents or not containing substituentsSubstituted C1-C20 alkyl and/or substituted or unsubstituted C6-C20 aryl, preferably R1And/or R2Is a group of formula II:
in the formula II, 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 II, R1-R5The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;
m is selected from nickel andpalladium; 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; r12Is 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;
R3selected from the group consisting of substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, and substituted or unsubstituted C7-C20 alkaryl;
preferably, R3Selected from the group consisting of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C7-C15 aralkyl, and substituted or unsubstituted C7-C15 alkaryl, more preferably, R3Is selected from C1-C6 alkyl with or without substituent, such as methyl, ethyl, propyl or butyl.
3. The aminoimine metal complex of claim 1 or 2, wherein the aminoimine metal complex is of formula III:
in the formula III, R1-R11The 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, and CC6-C20 aryl containing substituent groups, C7-C20 aralkyl containing substituent groups or not containing substituent groups and C7-C20 alkaryl containing substituent groups or not containing substituent groups;
R3、R12y, M and X have the same definitions as formula I.
4. The aminoimine metal complex of any one of claims 1 to 3, wherein R is1-R11The 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, R1-R11Each 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. An aminoimine metal complex according to any of claims 1 to 4, wherein 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, 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, 3, 3-dimethylbutoxy;
preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.
6. Aminoimine metal complex according to any of claims 1 to 5, selected from one or more of the following complexes:
a complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Me，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12Me, M ═ Ni, Y ═ O, X ═ Br; a complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝iPr，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Et，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Me，R2＝R4＝R5＝R6＝R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝i-Pr，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1-R3＝Me，R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1-R3＝Me，R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3Methyl, R2＝Br，R4-R7＝R10＝H，R8＝R9＝R11＝R3＝CH3，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3Methyl, R2＝Br，R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝F，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Cl，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Br，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3Methyl, R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝Et，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Ethyl, R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1-R3Methyl, R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3＝CH3，R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Methyl, R2＝Br，R4-R7＝R10＝H，R8＝R9＝R11Methyl, R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝F，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Cl，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Br，R2＝R4-R7＝R10＝H，R8＝R9＝R11＝CH3，R3Is isopropyl, R12Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Methyl, R2＝R4-R7＝R10＝H，R8＝R9＝CH3，R11Bromomethyl, R3Is isopropyl, R12Ethyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Et，R2＝R4-R7＝R10＝H，R8＝R9＝CH3，R11＝CH2Br，R3Is isopropyl, R12Ethyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3Is isopropyl, R2＝R4-R7＝R10＝H，R8＝R9＝CH3，R11＝CH2Br，R3Ethyl, R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1-R3＝Me，R4-R7＝R10＝H，R8＝R9＝CH3，R11＝CH2Br，R12Ethyl, M ═ Ni, Y ═ O, X ═ Br;
a complex of formula III wherein R1＝R3＝Me，R2＝Br，R4-R7＝R10＝H，R8＝R9＝Me，R3＝Et，R11＝CH2Br，R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝F，R2＝R4-R7＝R10＝H，R8＝R9＝Me，R11＝CH2Br，R3Not butyl, R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Cl，R2＝R4-R7＝R10＝H，R8＝R9＝Me，R11＝CH2Br，R3Not butyl, R12＝Et，M＝Ni，Y＝O，X＝Br；
A complex of formula III wherein R1＝R3＝Br，R2＝R4-R7＝R10＝H，R8＝R9＝Me，R11＝CH2Br，R3Not butyl, R12＝Et，M＝Ni，Y＝O，X＝Br。
7. The process according to any one of claims 1 to 6, wherein the olefin comprises an olefin having 2 to 16 carbon atoms, preferably the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms, and/or the 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;
the side group in L4 is selected from halogen and C6-C20Aryl radical, C1-C20Alkyl and C1-C20One or more of alkoxy, said C6-C20Aryl radical, C1-C20Alkyl and C1-C20Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl and hydroxyl.
9. A process according to any one of claims 1 to 8, characterised in that the cocatalyst is selected from organoaluminium compounds and/or organoboron compounds; the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate; the chain transfer agent is selected from one or more of alkyl aluminum, alkyl magnesium and alkyl zinc;
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):1, preferably (1.0-1000): 1.
10. Olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1-9, which is spherical and/or spheroidal, and/or which has a particle size of 0.1-50 mm.
11. Use of an olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 9 as a polyolefin material or of an olefin-olefin alcohol copolymer according to claim 10 as a polyolefin material.
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| CN201911049602.5A CN112745426B (en) | 2019-10-31 | 2019-10-31 | Process for preparing olefin-olefin alcohol copolymers |
| KR1020227018606A KR20220097939A (en) | 2019-10-31 | 2020-10-30 | Method for preparing olefin-polar monomer copolymer |
| BR112022008300A BR112022008300A2 (en) | 2019-10-31 | 2020-10-30 | METHOD FOR PREPARING A POLAR OLEFIN MONOMER COPOLYMER AND POLAR OLEFIN MONOMER COPOLYMER |
| JP2022525809A JP2023500504A (en) | 2019-10-31 | 2020-10-30 | Method for preparing olefin-polar monomer copolymers |
| PCT/CN2020/125433 WO2021083358A1 (en) | 2019-10-31 | 2020-10-30 | Method for preparing olefin-polar monomer copolymer |
| US17/755,542 US20220396646A1 (en) | 2019-10-31 | 2020-10-30 | Method for preparing olefin-polar monomer copolymer |
| EP20880543.2A EP4053174A4 (en) | 2019-10-31 | 2020-10-30 | Method for preparing olefin-polar monomer copolymer |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107162A (en) * | 1993-11-24 | 1995-08-23 | 赫彻斯特股份公司 | Metallocen method for preparation of same and application of same as catalyst |
| WO1995026968A1 (en) * | 1994-03-31 | 1995-10-12 | Boehringer Mannheim Italia S.P.A. | Trinuclear cationic platinum complexes having antitumour activity and pharmaceutical compositions containing them |
| CN1137527A (en) * | 1994-12-28 | 1996-12-11 | 赫彻斯特股份公司 | Metallocene compound and its use as catalyst component |
| US20110021345A1 (en) * | 2006-03-01 | 2011-01-27 | Toyota Jidosha Kabushiki Kaisha | Multiple-metal complex-containing compound and metal complex, and manufacture methods therefor, and exhaust gas purification catalyst manufacture method using the same |
| CN109694436A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-alkene alkoxide polymer and preparation method thereof |
-
2019
- 2019-10-31 CN CN201911049602.5A patent/CN112745426B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107162A (en) * | 1993-11-24 | 1995-08-23 | 赫彻斯特股份公司 | Metallocen method for preparation of same and application of same as catalyst |
| WO1995026968A1 (en) * | 1994-03-31 | 1995-10-12 | Boehringer Mannheim Italia S.P.A. | Trinuclear cationic platinum complexes having antitumour activity and pharmaceutical compositions containing them |
| CN1137527A (en) * | 1994-12-28 | 1996-12-11 | 赫彻斯特股份公司 | Metallocene compound and its use as catalyst component |
| US20110021345A1 (en) * | 2006-03-01 | 2011-01-27 | Toyota Jidosha Kabushiki Kaisha | Multiple-metal complex-containing compound and metal complex, and manufacture methods therefor, and exhaust gas purification catalyst manufacture method using the same |
| CN109694436A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-alkene alkoxide polymer and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| BIJAL KOTTUKKAL BAHULEYAN ET AL.: "Trinuclear Fe(II)/Ni(II) complexes as catalysts for ethylene polymerizations", 《CATALYSIS TODAY》 * |
| DIETER MEINHARD ET AL.: "Activation of Polymerization Catalysts: Synthesis and Characterization of Novel Dinuclear Nickel(I) Diimine Complexes", 《ORGANOMETALLICS》 * |
| GILLES NOEL ET AL.: "Pyrazolate-Based Dinuclear a-Diimine-Type Palladium(II) and Nickel(II) Complexes – a Bimetallic Approach in Olefin", 《ADV. SYNTH. CATAL.》 * |
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