CN112745424B - Method for preparing olefin-unsaturated carboxylic acid copolymer - Google Patents
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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Abstract
The present invention relates to a method for preparing an olefin-unsaturated carboxylic acid copolymer and an olefin-unsaturated carboxylic acid copolymer prepared by the method. The catalyst used in the method for preparing the olefin-unsaturated carboxylic acid copolymer comprises a diimine complex shown in formula I. The spherical and/or spheroidal polymers prepared by the preparation method of the invention have good prospects 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-unsaturated carboxylic acid copolymer.
Background
The polyolefin product has low price, excellent performance and wide application range. Under the condition of keeping the excellent physical and chemical properties of the original polyolefin, polar groups are introduced into polyolefin molecular chains by a chemical synthesis method, so that the chemical inertness, the printing property, the wettability and the compatibility with other materials can be improved, and new characteristics which are not possessed by raw materials are endowed. Although polar monomers can be directly introduced into polyolefin chains by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.
As a preparation technology of polymers at normal temperature and normal pressure, coordination catalytic copolymerization has attracted extensive attention due to its remarkable effects in reducing energy consumption, improving reaction efficiency and the like. The catalyst participates in the reaction process, so that the activation energy of the copolymerization reaction of the olefin monomer and the polar monomer is greatly reduced, and the functional polymer with higher molecular weight can be obtained at lower temperature and pressure. Currently, only a few documents report the use of transition metal complexes to catalyze the copolymerization of olefins and unsaturated carboxylic acids. However, in the prior art, no matter which method is adopted for polymerization reaction, the obtained polymer is viscous massive solid, and is easy to scale in polymerization equipment, thereby bringing difficulties to the transportation, solvent removal, granulation and the like of the polymer.
Disclosure of Invention
The preparation method of the olefin-unsaturated carboxylic acid copolymer provided by the invention uses a novel catalyst containing trinuclear metal complexes. The catalyst is not reported, therefore, the technical problem solved by the invention is to provide a novel preparation method of olefin-unsaturated carboxylic acid copolymer. 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 preparing an olefin-unsaturated carboxylic acid copolymer, which comprises polymerizing an olefin and an unsaturated carboxylic acid in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-unsaturated carboxylic acid copolymer,
the catalyst comprises a main catalyst and an optional cocatalyst, wherein the main catalyst comprises a diimine 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; r21-R24The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl containing substituent or not containing substituent, and C1-C20 alkoxy containing substituent or not containing substituent; r21-R24Optionally forming a ring with each other; r11Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from group VIAA metal atom; 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. R1And R2Is selected from C1-C20 alkyl with or without substituent and/or C6-C20 aryl 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 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 substituents are the same or different, and are respectively and 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, and C2-C10 alkynyloxy with or without substituentC3-C10 cycloalkoxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl, and substituted or unsubstituted C7-C15 alkaryl.
According to some embodiments of the invention, M is selected from nickel and palladium.
According to some embodiments of the invention, Y is selected from O and S.
According to some embodiments of the invention, X is selected from the group consisting of halogen, 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 complex has a structure represented by formula II:
wherein R is1-R10、R21-R24The two substituents are the same or different and are respectively and independently selected from hydrogen, 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 C1-C20 aryl with or without substituentA substituted C7-C20 aralkyl group, a substituted or unsubstituted C7-C20 alkaryl group and a halogen, and R1-R10Optionally form a ring with each other, R21-R24Optionally forming a ring with each other.
R11Y, M and X have the same definitions as formula I.
According to some embodiments of the invention, R1-R10、R21-R24The 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-R10、R21-R24The same or different, are each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, 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 diimine complex of formula I has a substructure of formula IIA:
wherein R is31-R34And R in the formula I21-R24Having the same definition, preferably, R33And R34Is hydrogen;
R11y, M and X have the same definitions as formula I.
According to some embodiments of the invention, R31-R34The same or different, each is independently selected from hydrogen, 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, C7-C20 alkylaryl with or without substituent, and halogen.
According to some embodiments of the invention, R31-R34Each 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 alkylaryl with or without substituent. According to some embodiments of the invention, R31-R34The same or different, are each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.
According to some embodiments of the invention, the substituent is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy; the substituents are preferably selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.
According to some embodiments of the invention, the C1-C6 alkyl 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, 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, exemplary complexes include, but are not limited to:
1) a complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
2) A complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
3) A complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
4) A complex of formula II wherein R1-R6=Me,R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
5) A complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
6) A complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
7) A complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
8) A complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R21=R22=
R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
9) a complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
10) a complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
11) a complex of formula II wherein R1-R6=Me,R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
12) a complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
13) a complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
14) a complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
15) a complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
16) A complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
17) A complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
18) A complex of formula II wherein R1-R6=Me,R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
19) A complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
20) A complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
21) A complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
22) A complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
23) a complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
24) a complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
25) a complex of formula II wherein R1-R6=Me,R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
26) a complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
27) a complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
28) a complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
29) a complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
30) A complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
31) A complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
32) A complex of formula (II') wherein R1-R6=Me,R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
33) A complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
34) A complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
35) A complex of formula (II') wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
36) A complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M Ni, YO,X=Br;
37) A complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
38) a complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
39) a complex of formula (II') wherein R1-R6=Me,R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
40) a complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
41) a complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
42) a complex of formula (II') wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
43) a complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=H R31=R32=R11=Et,M=Ni,Y=O,X=Br;
44) A complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
45) A complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
46) A complex of formula (II') wherein R1-R6=Me,R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
47) A complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
48) A complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
49 of the formula (II'), wherein R1=R3=R4=R6=F,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
50) A complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
51) A complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
52) a complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
53) a complex of formula (II') wherein R1-R6=Me,R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
54) a complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
55) a complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
56) a complex of formula (II') wherein R1=R3=R4=R6=F,R2=R5=R7-R10=H,R31=R32=Et,R11I.e., isobutyl, M ═ Ni, Y ═ O, and X ═ Br.
According to some embodiments of the invention, the unsaturated carboxylic acid is selected from one or more of the unsaturated carboxylic acids represented by formula G:
in the formula G,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 present invention, the content of the structural unit derived from the unsaturated carboxylic acid represented by the formula G in the copolymer is 0.2 to 15.0 mol%, more preferably 0.7 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 unsaturated carboxylic acid represented by the formula G include, but are not limited to: 2-methyl-4-pentenoic acid, 2, 3-dimethyl-4-pentenoic acid, 2-dimethyl-4-pentenoic acid, 2-ethyl-4-pentenoic acid, 2-isopropyl-4-pentenoic acid, 2, 3-trimethyl-4-pentenoic acid, 2,3, 3-trimethyl-4-pentenoic acid, 2-ethyl-3-methyl-4-pentenoic acid, 2- (2-methylpropyl) -4-pentenoic acid, 2-diethyl-4-pentenoic acid, 2-methyl-2-ethyl-4-pentenoic acid, 2,3, 3-tetramethyl-4-pentenoic acid, 2-methyl-4-pentenoic acid, 2-methyl-pentenoic acid, 2-methyl-pentenoic acid, 2-methyl-4-pentenoic acid, 2-methyl-pentenoic acid, 2, 2-methyl-5-hexenoic acid, 2-ethyl-5-hexenoic acid, 2-propyl-5-hexenoic acid, 2, 3-dimethyl-5-hexenoic acid, 2-dimethyl-5-hexenoic acid, 2-isopropyl-5-hexenoic acid, 2-methyl-2-ethyl-5-hexenoic acid, 2- (1-methylpropyl) -5-hexenoic acid, 2, 3-trimethyl-5-hexenoic acid, 2-diethyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-ethyl-6-heptenoic acid, 2-propyl-6-heptenoic acid, 2, 3-dimethyl-6-heptenoic acid, 2-ethyl-5-hexenoic acid, 2-methyl-5-hexenoic acid, 2-ethyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-hexenoic acid, 2-methyl-5-hexenoic acid, 2-ethyl-hexenoic acid, 2-5-hexenoic acid, 2-methyl-5-hexenoic acid, 2-methyl-hexenoic acid, 2-methyl-5-hexenoic acid, 2-5-hexenoic acid, 2-methyl-6-hexenoic acid, 2-6-5-hexenoic acid, 2-6-hexenoic acid, 2-ethyl-6-hexenoic acid, 2-6-methyl-hexenoic acid, 2-methyl-hexenoic acid, 2-hexenoic, 2, 4-dimethyl-6-heptenoic acid, 2-dimethyl-6-heptenoic acid, 2-isopropyl-5-methyl-6-heptenoic acid, 2-isopropyl-6-heptenoic acid, 2,3, 4-trimethyl-6-heptenoic acid, 2-methyl-2-ethyl-6-heptenoic acid, 2- (1-methylpropyl) -6-heptenoic acid, 2, 3-trimethyl-6-heptenoic acid, 2-diethyl-6-heptenoic acid, 2-methyl-7-octenoic acid, 2-ethyl-7-octenoic acid, 2-propyl-7-octenoic acid, 2, 3-dimethyl-7-octenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-4-6-heptenoic acid, 2-6-heptenoic acid, 2-methyl-6-heptenoic acid, 2-4-methyl-heptenoic acid, 2-4-6-heptenoic acid, 2-6-4-heptenoic acid, 2-methyl-heptenoic acid, 2-4-6-heptenoic acid, 2-6-heptenoic acid, 2-4-6-heptenoic acid, 2-4-heptenoic acid, 2-methyl-heptenoic acid, 2-4-heptenoic acid, 2-4-6-methyl-heptenoic acid, 2-4-heptenoic acid, 2-4-methyl-heptenoic acid, 2-ethyl-heptenoic acid, 2-methyl-heptenoic acid, 2-4-ethyl-heptenoic, 2, 4-dimethyl-7-octenoic acid, 2-dimethyl-7-octenoic acid, 2-isopropyl-5-methyl-7-octenoic acid, 2-isopropyl-7-octenoic acid, 2,3, 4-trimethyl-7-octenoic acid, 2-methyl-2-ethyl-7-octenoic acid, 2- (1-methylpropyl) -7-octenoic acid, 2, 3-trimethyl-7-octenoic acid, 2-diethyl-7-octenoic acid, 2-methyl-8-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl-8-nonenoic acid, 2, 3-dimethyl-8-nonenoic acid, 2-methyl-7-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-propyl-8-nonenoic acid, 2, 3-dimethyl-8-nonenoic acid, 2-methyl-7-nonenoic acid, 2-methyl-nonenoic acid, 2-ethyl-8-nonenoic acid, 2-methyl-nonenoic acid, 2, and, 2, 4-dimethyl-8-nonenoic acid, 2-diethyl-8-nonenoic acid, 2-isopropyl-5-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2, 3-dimethyl-9-decenoic acid, 2, 4-dimethyl-9-decenoic acid, or 2-methyl-10-undecenoic acid.
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, triisobutylaluminum, tri-n-hexylaluminum, trioctylAlkylaluminum, 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 olefins having from 2 to 16 carbonsAtomic olefins, in some embodiments of the present invention, 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 unsaturated carboxylic acid monomer represented by the formula G in the reaction system is 0.01 to 6000mmol/L, preferably 0.1 to 1000mmol/L, more preferably 1 to 500mmol/L, and may be, for example, 1mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 90mmol/L, 100mmol/L, 200mmol/L, 300mmol/L, 400mmol/L, 500mmol/L and any value therebetween.
According to a preferred embodiment of the present invention, the chain transfer agent is selected from one or more of aluminum alkyls, magnesium alkyls and zinc alkyls.
According to a preferred embodiment of the invention, the chain transfer agent is a trialkylaluminum and/or a dialkylzinc, preferably one or more selected from the group consisting of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc and diethylzinc.
According to a preferred embodiment of the invention, the molar ratio of the chain transfer agent to M in the procatalyst is (0.1-2000: 1, 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 cyclohexaneAnd (4) a plurality of.
According to a preferred embodiment of the present invention, the unsaturated carboxylic acid is pre-treated with a dehydroactive hydrogen, preferably, the unsaturated carboxylic acid is pre-treated with a co-catalyst or a chain transfer agent as described above to remove the hydroxyl active hydrogen in the unsaturated carboxylic acid. Preferably, the molar ratio of hydroxyl groups in the unsaturated carboxylic acid 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" refers to the whole formed by the solvent, the olefin, the unsaturated carboxylic acid monomer, the catalyst and the optional chain transfer agent.
The present invention also provides an olefin-unsaturated carboxylic acid copolymer comprising a spherical and/or spheroidal polymer, which is produced by the above production method.
According to a preferred embodiment of the invention, the spherical and/or spheroidal polymers have an average particle size of 0.1 to 50.0mm, for example 0.1mm, 0.5mm, 1.0mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value in between, preferably 0.5 to 20.0 mm.
According to a preferred embodiment of the present invention, in the olefin-unsaturated carboxylic acid copolymer, the content of the structural unit derived from the unsaturated carboxylic acid represented by the formula G is 0.4 to 30.0 mol%, 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-unsaturated carboxylic acid copolymer is 30000-500000, preferably 50000-400000.
According to a preferred embodiment of the present invention, the olefin-unsaturated carboxylic acid copolymer has a molecular weight distribution of 4.0 or less, and for example, may be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and any value therebetween, and preferably, the molecular weight distribution is 1.0 to 4.0.
In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere 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-unsaturated carboxylic acid copolymer as a polyolefin material.
The preparation method of the olefin-unsaturated carboxylic acid copolymer provided by the invention uses a novel catalyst containing trinuclear metal complexes. The catalyst is not reported, therefore, the technical problem solved by the invention is to provide a novel preparation method of olefin-unsaturated carboxylic acid copolymer.
Furthermore, in the preparation method of the olefin-unsaturated carboxylic acid copolymer provided by the invention, the spherical and/or spheroidal polymers with good shapes are directly prepared by selecting the reacted unsaturated carboxylic acid monomer, the catalyst and a proper polymerization process without subsequent processing steps such as granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.
Further, compared with the existing industrial process for preparing the olefin-unsaturated carboxylic acid copolymer, the method for preparing the olefin-unsaturated carboxylic acid copolymer provided by the invention omits the step of saponification reaction, and has simpler preparation process.
Symbols such as R used in different formulae or structural formulae herein1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R11、R2、R3、R21-R24X, 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.
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 unsaturated carboxylic acid 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
1) Complex Ni1(R in the formula III)1、R3、R4、R6Is isopropyl, R2、R5、R7-R10、R21、R22Is hydrogen, and R11For ethyl, M is nickel, Y is O, X is Br):
ligand L1(R in the formula B1、R3、R4、R6Is isopropyl, R2、R5、R7-R10、R21、R22Hydrogen) in Organometallics, 2013,32, 2291-.
Will contain 0.277g (0.9mmol) (DME)NiBr2To a solution containing 0.332g (0.6mmol) of ligand L (10ml) was slowly added dropwise1To a dichloromethane 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 vacuum drying to obtain brownish red powdery solid Ni1. Yield: 78.2 percent. Elemental analysis (C)84H98Br6N4Ni3O2): c, 54.50; h, 5.34; n, 3.03; experimental values (%): c, 54.38; h, 5.72; and N, 3.16.
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 9.3mg (5. mu. mol) of complex Ni was added115mmol (2.55g)2, 2-dimethyl-7-octenoic acid, 15mL 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 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 9.3mg (5. mu. mol) of complex Ni was added130mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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. 500mL of hexane was poured into the polymerization system, and 9.3mg (5. mu. mol) of complex Ni was added130mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid,30mL 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 9.3mg (5. mu. mol) of complex Ni was added130mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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 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 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 9.3mg (5. mu. mol) of complex Ni was added130mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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 poured into the polymerization system, and 9.3mg (5. mu. mol) of complex Ni was added150mmol (8.51g)2, 2-dimethyl-7-octenoic acid, 50mL AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), ethylene pressure of 10atm was maintained at 30 ℃ with stirringStirring and reacting 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 poured into the polymerization system, and 9.3mg (5. mu. mol) of complex Ni was added1100mmol (17.02g)2, 2-dimethyl-7-octenoic acid, 100mL 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) Ligand L2Preparation of (R in the structural formula B)1、R3、R4、R6Is ethyl, R2、R5、R7-R10、R22Is hydrogen, R21Is a tertiary butyl group): compound A (2.7g, 7.8mmol) and 2, 6-diethylaniline (3.0mL, 17.4mmol) with p-toluenesulfonic acid as catalyst were refluxed in 100mL of toluene for 1 day, the solvent was removed after filtration, the residue was dissolved in dichloromethane, passed through a basic alumina column, rinsed with petroleum ether/ethyl acetate (20:1), the second stream was 15 product and the solvent was removed to give a yellow solid in 81% yield.1H NMR(CDCl3,δ,ppm):1.06(t,12H,J=7.0Hz),1.19ppm(s,18H),2.20(dd,8H,J=7.0Hz),4.70(s,2H),7.04(m,10H),7.13(s,2H)。
2) Complex Ni2Preparation of (R in the formula III)1、R3、R4、R6Is ethyl, R2、R5、R7-R10、R22Is hydrogen, R21Is tert-butyl, and R11Is aThe M is nickel, the Y is O, and the X is Br)
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.365g (0.6mmol) of ligand L was slowly added dropwise (10ml)2To a dichloromethane 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 vacuum drying to obtain brownish red powdery solid Ni2. The yield was 82.0%. Elemental analysis (C)92H114Br6N4Ni3O2): c, 56.28; h, 5.85; n, 2.85; experimental values (%): c, 56.43; h, 6.12; and N, 3.08.
3) Polymerization: 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 9.8mg (5. mu. mol) of complex Ni was added230mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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 9.8mg (5. mu. mol) of complex Ni was added250mmol (8.51g)2, 2-dimethyl-7-octenoic acid, 50mL 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 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. Injection into polymerization systems500mL of hexane, while adding 9.8mg (5. mu. mol) of complex Ni230mmol (4.69g)2, 2-dimethyl-6-heptenoic acid, 30mL AlEt3(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) Ligand L3Preparation of (R in the structural formula B)1、R3、R4、R6Is methyl, R2、R5Is bromine, R7-R10、R22Is hydrogen, R21Is a tertiary butyl group): compound a (1.77g, 5.1mmol) and 2, 6-dimethyl-4-bromo-aniline (2.3g, 11.3mmol) with p-toluenesulfonic acid as catalyst were refluxed in 100mL toluene for 1 day, the solvent was removed after filtration, the residue was dissolved with dichloromethane, passed through a basic alumina column, rinsed with petroleum ether/ethyl acetate (20:1), the second stream was the product, and the solvent was removed to give a yellow solid in 78% yield. 1H NMR (CDCl3,. delta.ppm): 1.84(s, 12H), 1.19ppm (s, 18H), 4.70(s, 2H), 7.04(8H), 7.12(s, 2H).
2) Complex Ni3Preparation of (R in the formula III)1、R3、R4、R6Is methyl, R2、R5Is bromine, R7-R10、R22Is hydrogen, R21Is tert-butyl, and R11Is ethyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.426g (0.6mmol) of ligand L (10ml) was slowly added dropwise3To a dichloromethane 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 vacuum drying to obtain brownish red powdery solid Ni3. The yield was 82.0%. Elemental analysis (C)84H94Br10N4Ni3O2): c, 46.56; h, 4.37; n, 2.59; experiment ofValue (%): c, 46.43; h, 4.72; and N, 2.98.
3) Polymerization: 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 10.8mg (5. mu. mol) of complex Ni was added330mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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
1) Complex Ni4Preparation of (R in the formula III)1、R3、R4、R6Is ethyl, R2、R5、R7-R10、R22Is hydrogen, R21Is tert-butyl, and R11Is isobutyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution of 2-methyl-1-propanol (10ml) containing 0.365g (0.6mmol) of ligand L was slowly added dropwise2To a dichloromethane 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 vacuum drying to obtain brownish red powdery solid Ni4. The yield was 83.0%. Elemental analysis (C)96H122Br6N4Ni3O2): c, 57.09; h, 6.09; n, 2.77; experimental values (%): c, 57.24; h, 6.32; and N, 3.04.
2) Polymerization:
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. 10.1mg (5. mu. mol) of complex Ni are added4Then, vacuum was applied again and ethylene was substituted 3 times. 500mL of hexane, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 30mL of AlEt3(1.0mol/L hexane solution), 6.5ml of methylaluminoxane was further added(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
1) Ligand L4The preparation of (1):
ligand L4See patent CN201510462932.2 for its preparation.
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.358g (0.6mmol) of ligand L (10ml) was slowly added dropwise4To a dichloromethane 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 vacuum drying to obtain brownish red powdery solid Ni5. The yield was 84.3%. Elemental analysis (C)92H90Br6N4Ni3O2): c, 56.98; h, 4.68; n, 2.89; experimental values (%): c, 56.78; h, 4.62; and N, 3.18.
2) Polymerization: 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. 9.7mg (5. mu. mol) of complex Ni are added5Then, vacuum was applied again and ethylene was substituted 3 times. 500mL of hexane, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 30mL of AlEt3(1.0mol/L hexane solution), 6.5ml of Methylaluminoxane (MAO) (1.53mol/L toluene solution) was added. The reaction was vigorously stirred at 20 ℃ for 30min while 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 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 poured into the polymerization system, and 9.3mg (5 μm) was added simultaneouslyol) Complex Ni130mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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 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 hexane was poured into the polymerization system, and 9.3mg (5. mu. mol) of complex Ni was added130mmol (5.53g 10-undecenoic acid), 30mL 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 16
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 injected into the polymerization system, and 9.3mg (5. mu. mol) of complex Ni was added130mmol (5.10g)2, 2-dimethyl-7-octenoic acid, 30mL 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 high polymerization activity when it catalyzes the copolymerization of ethylene and an unsaturated carboxylic acid, and the resulting polymer has a high molecular weight. The copolymerization activity of the catalyst can reach 2.42 multiplied by 10 to the maximum6g·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 (34)
1. A process for producing an olefin-unsaturated carboxylic acid copolymer, which comprises polymerizing an olefin and an unsaturated carboxylic acid in the presence of a catalyst and optionally a chain transfer agent to produce the olefin-unsaturated carboxylic acid copolymer,
the catalyst comprises a main catalyst and an optional cocatalyst, wherein the main catalyst comprises a diimine complex shown as a formula II:
in the formula II, R1-R10、R21-R24The same or different, each is independently selected from hydrogen, C1-C20 alkyl with or without substituent, and substituent with or without substituentC2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C3-C20 cycloalkoxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C7-C20 alkylaryl, and halogen, and R1-R10Optionally form a ring with each other, R21-R24Optionally 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 M is selected from the group consisting of nickel and palladium; y is selected from O and S; x is selected from halogen, C1-C10 alkyl with or without substituent, and C1-C10 alkoxy with or without substituent;
R11is selected from C1-C20 alkyl containing substituent or not containing substituent.
3. The method of claim 2, wherein X is selected from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy.
4. The method of claim 2, wherein R is11Is selected from C1-C10 alkyl containing substituent or not containing substituent.
5. The method of claim 4, wherein R is11Is selected from C1-C6 alkyl containing substituent or not containing substituent.
6. The method of claim 1Method characterized in that R1-R10、R21-R24The 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.
7. The method of claim 6, wherein R is1-R10、R21-R24The same or different, are each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, and halogen.
8. The method of claim 6, wherein R is1-R10、R21-R24The same or different, are each independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, and halogen.
9. A process according to any one of claims 1 to 6, 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.
10. The method of claim 9, wherein the substituent is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy.
11. The method of claim 10, wherein the C1-C6 alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3, 3-dimethylbutyl.
12. The method of claim 10, wherein the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3, 3-dimethylbutoxy.
13. The method of claim 9, wherein the halogen is selected from the group consisting of fluorine, chlorine, bromine, and iodine.
14. A process according to any one of claims 1 to 8, characterised in that the diimine complexes are selected from one or more of the following complexes:
1) a complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
2) A complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
3) A complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
4) A complex of formula II wherein R1-R6=Me,R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
5) A complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
6) A complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
7) A complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R21=R22=R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
8) A complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
9) a complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
10) a complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
11) a complex of formula II wherein R1-R6=Me,R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
12) a complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
13) a complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
14) a complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R21=R22=R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
15) a complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
16) A complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
17) A complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
18) A complex of formula II wherein R1-R6=Me,R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
19) A complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
20) A complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
21) A complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11=Et,M=Ni,Y=O,X=Br;
22) A complex of formula II wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
23) a complex of formula II wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
24) a complex of formula II wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
25) a complex of formula II wherein R1-R6=Me,R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
26) a complex of formula II wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
27) a complex of formula II wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
28) a complex of formula II wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R22=H,R21Tert-butyl radical, R23=R24=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
29) a complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
30) A complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
31) A complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
32) A complex of formula (II') wherein R1-R6=Me,R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
33) A complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
34) A complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
35) A complex of formula (II') wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R31=R32=H,R11=Et,M=Ni,Y=O,X=Br;
36) A complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
37) a complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
38) a complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
39) a complex of formula (II') wherein R1-R6=Me,R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
40) a complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
41) a complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
42) a complex of formula (II') wherein R1=R3=R4=R6=F,R2=R5=R7-R10=R31=R32=H,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
43) a complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
44) A complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
45) A complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
46) A complex of formula (II') wherein R1-R6=Me,R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
47) A complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
48) A complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
49 of the formula (II'), wherein R1=R3=R4=R6=F,R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
50) A complex of formula (II') wherein R1=R3=R4=R6Is isopropyl, R2=R5=R7-R10=H,R31=R32=R11=Et,M=Ni,Y=O,X=Br;
51) A complex of formula (II') wherein R1=R3=R4=R6=Et,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
52) a complex of formula (II') wherein R1=R3=R4=R6=Me,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
53) a complex of formula (II') wherein R1-R6=Me,R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
54) a complex of formula (II') wherein R1=R3=R4=R6=Br,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
55) a complex of formula (II') wherein R1=R3=R4=R6=Cl,R2=R5=R7-R10=H,R31=R32=Et,R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
56) a complex of formula (II') wherein R1=R3=R4=R6=F,R2=R5=R7-R10=H,R31=R32=Et,R11I.e., isobutyl, M ═ Ni, Y ═ O, and X ═ Br.
15. The method of any one of claims 1-8, wherein the olefin comprises an olefin having 2-16 carbon atoms.
16. The method of claim 15, wherein the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms.
17. The method according to any one of claims 1 to 8, wherein the unsaturated carboxylic acid is selected from one or more unsaturated carboxylic acids 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.
18. The method according to claim 17, wherein the copolymer contains the structural unit derived from the unsaturated carboxylic acid represented by the formula G in an amount of 0.2 to 15.0 mol%.
19. The method according to claim 17, wherein the copolymer contains the structural unit derived from the unsaturated carboxylic acid represented by the formula G in an amount of 0.7 to 10.0 mol%.
20. The method of claim 17, wherein L is1And L2Is H, L3Is H or C1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group.
21. The method of claim 17, wherein L is1And L2Is H, L3Is H or C1-C20Alkyl radical, L4Is C having a pendant group1-C20An alkylene group.
22. The method of claim 17, wherein L is1And L2Is H,L3Is H or C1-C10Alkyl radical, L4Is C having a pendant group1-C10An alkylene group.
23. The method of claim 17, wherein L is1And L2Is H, L3Is H or C1-C10Alkyl radical, L4Is C having a pendant group1-C6An alkylene group.
24. The method of claim 17, 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;
L4wherein the side group is selected from halogen, C6-C20Aryl radical, C1-C20Alkyl and C1-C20One or more of alkoxy, said C6-C20Aryl radical, C1-C20Alkyl and C1-C20Alkoxy is optionally substituted with a substituent.
25. The method of claim 24, wherein L is1-L3Wherein said substituent is selected from C1-C6Alkyl, halogen and C1-C6One or more of alkoxy groups.
26. The method of claim 24, wherein L is4Wherein said substituents are selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl and hydroxyl.
27. 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.
28. The method as claimed in claim 27, wherein when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine-based complex is 10 to 1071, preparing a catalyst; when the cocatalyst is an organic boron compound, the molar ratio of boron in the cocatalyst to M in the diimine complex is 0.1-1000: 1; the molar ratio of the chain transfer agent to M in the diimine complex is 0.1-5000: 1.
29. The process of claim 28, wherein when the co-catalyst is an organoaluminum compound, the molar ratio of aluminum in the co-catalyst to M in the diimine-based complex is 10-100000: 1.
30. The method as recited in claim 28, wherein when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine-based complex is 100-10000: 1.
31. The method as claimed in claim 28, wherein when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the diimine complex is from 0.1 to 500: 1.
32. The method of claim 28, wherein the molar ratio of the chain transfer agent to M in the diimine complex is from 1.0 to 1000: 1.
33. The olefin-unsaturated carboxylic acid copolymer prepared according to the method of any one of claims 1 to 32, which is spherical and/or spheroidal, and/or has a particle diameter of 0.1 to 50 mm.
34. Use of an olefin-unsaturated carboxylic acid copolymer prepared according to the process of any one of claims 1 to 32 or the olefin-unsaturated carboxylic acid copolymer of claim 33 as a polyolefin material.
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BR112022008300A BR112022008300A2 (en) | 2019-10-31 | 2020-10-30 | METHOD FOR PREPARING A POLAR OLEFIN MONOMER COPOLYMER AND POLAR OLEFIN MONOMER COPOLYMER |
EP20880543.2A EP4053174A4 (en) | 2019-10-31 | 2020-10-30 | Method for preparing olefin-polar 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 |
CA3159659A CA3159659A1 (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 |
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