CN111116803A - Preparation method of olefin-unsaturated carboxylic acid copolymer - Google Patents
Preparation method of olefin-unsaturated carboxylic acid copolymer Download PDFInfo
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- CN111116803A CN111116803A CN201811288657.7A CN201811288657A CN111116803A CN 111116803 A CN111116803 A CN 111116803A CN 201811288657 A CN201811288657 A CN 201811288657A CN 111116803 A CN111116803 A CN 111116803A
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Abstract
The invention discloses a method for preparing olefin-unsaturated carboxylic acid copolymer, which comprises the steps of contacting olefin and unsaturated carboxylic acid shown in formula I with catalyst and optional chain transfer agent in the presence of alkane solvent to react to generate the copolymer,
in the formula I, L1-L3 are respectively and independently selected from H or C1‑C30Alkyl, L4 is C with pendant groups1‑C30An alkylene group; said C is1‑C30Alkyl is optionally substituted with a substituent. The copolymer prepared by the method provided by the invention has good form and good prospect in industrial application.
Description
Technical Field
The present invention relates to a process for producing 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.
The more mature method for preparing the copolymer containing polar groups mainly comprises a copolymerization method and a grafting method. Copolymerization methods mostly use high-pressure radical polymerization to promote the copolymerization of olefins with polar group-containing olefin monomers. 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 invention provides a preparation method of an olefin-unsaturated carboxylic acid copolymer, which can prepare a copolymer containing spherical and/or spheroidal polymers through polymerization of olefin and unsaturated carboxylic acid, does not need subsequent granulation processing, has good appearance of the polymers, and has good industrial application prospect.
According to a first aspect of the present invention, there is provided a process for producing an olefin-unsaturated carboxylic acid copolymer, comprising contacting an olefin and an unsaturated carboxylic acid represented by formula i with a catalyst and optionally a chain transfer agent in the presence of an alkane solvent to produce the copolymer;
in the formula I, L1-L3 are respectively and independently selected from H or C1-C30Alkyl, L4 is C with pendant groups1-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 carboxyl.
According to a preferred embodiment of the present invention, the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is a metal complex represented by formula II:
in the formula II，R1-R10Each independently selected from H, halogen, C1-C24Saturated or unsaturated hydrocarbon groups and C1-C24Saturated or unsaturated hydrocarbyloxy radicals, R1-R3、R9、R10Optionally form a ring with each other, R4-R8Optionally forming a ring with each other; r1-R4Each independently selected from H, halogen, saturated or unsaturated hydrocarbyl and substituted saturated or unsaturated hydrocarbyl, R1-R4Optionally forming a ring with each other; m is a group VIII metal; x is selected from one or more of halogen, saturated or unsaturated alkyl and saturated or unsaturated alkoxy; n is an integer satisfying the valence of M.
According to a preferred embodiment of the invention, the side 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 carboxyl.
According to a preferred embodiment of the invention, the side group in L4 is selected from halogen, C6-C20Aryl radical, C1-C20Alkyl, carboxy substituted C1-C20Alkyl and alkoxy substituted C1-C20One or more of alkyl groups. Preferably, the side group is selected from halogen, C6-C20Aryl radical, C1-C10Alkyl, carboxy substituted C1-C10Alkyl and alkoxy substituted C1-C10One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C1-C6Alkyl and carboxy substituted C1-C6One or more of alkyl, said C1-C6The alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and,T-butyl, pentyl and hexyl.
According to a preferred embodiment of the invention, in formula I, L1 and L2 are H, and L3 is H or C1-C30Alkyl, L4 is C with pendant groups1-C30Alkylene radical of the formula C1-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 carboxyl.
According to a preferred embodiment of the invention, in formula I, L1 and L2 are H, L3 is H, C1-C10Alkyl or halogen substituted C1-C10Alkyl, preferably L3 is H or C1-C10An alkyl group; l4 is C with pendant groups1-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 I, L1 and L2 are H, and L3 is H or C1-C6An alkyl group; l4 is C with pendant groups1-C10An alkylene group.
The carbon number of the alkylene group means the number of C's in the linear chain, not including the number of C's in the side group, e.g., 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 formula i 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-, 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, 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-ethyl-7-octenoic acid, 2-propyl-7-octenoic acid, 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, 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, R1-R4Each independently selected from H, halogen and C1-C20Saturated or unsaturated hydrocarbon radicals, R1-R4Optionally forming a ring with each other.
According to a preferred embodiment of the invention, in formula II, R1-R10Each independently selected fromH. Halogen, C1-C24Saturated or unsaturated hydrocarbon groups and C1-C24Saturated or unsaturated hydrocarbyloxy
According to a preferred embodiment of the invention, in formula II, R1-R10Each independently selected from H, halogen, C1-C24Alkyl and C1-C24An alkoxy group.
According to a preferred embodiment of the invention, in formula II, R1-R10Each independently selected from H, C1-C10Alkyl and C1-C10Alkoxy, preferably selected from H, C1-C6Alkyl and C1-C6An alkoxy group; such as H, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, methoxy, ethoxy and propoxy; further preferably, R1-R6Each independently selected from H and C1-C6Alkyl radical, R7-R10Is H, e.g. R1-R6Each independently selected from H, methyl, ethyl, n-propyl, isopropyl and butyl, R7-R10Is H.
According to a preferred embodiment of the invention, M is a group viii metal; x is selected from halogen and C1-C10One or more of alkyl; n is an integer satisfying the valence of M. Preferably, M is a group VIII metal and X is selected from halogens, preferably bromine and/or chlorine.
According to a preferred embodiment of the present invention, the procatalyst is a metal complex represented by formula iii:
in the formula III, R1-R10Have the same definitions as in formula II;
R21、R22the same or different, each independently selected from H, halogen, saturated or unsaturated hydrocarbyl and substituted saturated or unsaturated hydrocarbyl, preferably selected from H, halogen, C1-C10Saturated or unsaturated hydrocarbon radicals or C1-C10Saturated or unsaturatedA saturated hydrocarbyloxy group; r21、R22Optionally annulated to each other, M is a group VIII metal, preferably nickel; x, which are identical or different, are chosen from halogen, saturated or unsaturated hydrocarbon radicals and saturated or unsaturated hydrocarbonoxy radicals, preferably halogen and C1-10 alkyl radicals; n is an integer satisfying the valence of M.
In some embodiments of the invention, R21、R22Are the same or different and are each independently selected from H or C1-C6Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, and butyl. In some embodiments of the invention, R is21、R22Together with the C to which it is attached, form a benzene ring.
According to a preferred embodiment of the invention, in formulae ii and iii, M is nickel.
According to a preferred embodiment of the invention, said X is a halogen, preferably Br or Cl.
According to a preferred embodiment of the present invention, the metal complex represented by the formula II is prepared by the following method:
step S1, contacting the diimine compound shown in the formula iii with lithium aluminum hydride to react to obtain the ligand shown in the formula i,
in formulae i and iii, R1-R10And R1-R4Have the same definitions as in formula II;
step S2, coordination of the ligand of formula i with MXn or a derivative of MXn to give a metal complex of formula II, M, X and n having the same definitions as in formula II.
According to a preferred embodiment of the invention, said MXn comprises nickel halides, such as nickel bromide and nickel chloride, and the derivatives of MXn comprise 1, 2-dimethoxyethane nickel bromide or 1, 2-dimethoxyethane nickel chloride.
According to a preferred embodiment of the present invention, when the metal complex has a structure represented by formula iii, the method for preparing the metal complex comprises:
step S1-1, contacting the diimine compound shown in formula iv with lithium aluminum hydride for reaction to obtain a ligand shown in formula ii,
in formulae ii and iv, R1-R10And R21、R22Has the same definition as in formula III;
step S2-1, coordination reaction of ligand represented by formula ii with MXn or MXn derivative to obtain metal complex represented by formula III, M, X and n having the same definition as in formula II.
According to a preferred embodiment of the present invention, in step S1 or step S-1, the molar ratio of lithium aluminum hydride to the diimine compound is 2.0 to 6.0: 1;
according to a preferred embodiment of the present invention, in step S1 or step S-1, the conditions of the contact reaction include: the temperature is 20-120 ℃, and/or the time is 2-24 hours.
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, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, diethylaluminum sesquichlorideAluminum chlorohydrate, 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 is an olefin having from 2 to 16 carbon atoms, in some embodiments of the invention the olefin is ethylene or α -ene having from 3 to 16 carbon atomsA hydrocarbon. In other embodiments of the present invention, the olefin is C3-C16Preferably, the olefin is ethylene or an α -olefin having 3 to 16 carbon atoms, more preferably ethylene or C2-C10α -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 represented by the formula I 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 alkane solvent is selected from C3-C20One or more of the alkanes, 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 unsaturated carboxylic acid is previously subjected to an active hydrogen removal pretreatment, preferably, the unsaturated carboxylic acid is pretreated using the above-mentioned co-catalyst or chain transfer agent to remove active hydrogen in the unsaturated carboxylic acid. Preferably, the molar ratio of carboxyl groups in the unsaturated carboxylic acid to co-catalyst or chain transfer agent during the 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 olefin-unsaturated carboxylic acid copolymer produced by the above production method, which comprises a spherical and/or spheroidal polymer.
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 i 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 number average molecular weight of the olefin-unsaturated carboxylic acid copolymer is 30000-200000, preferably 5000-100000.
According to a preferred embodiment of the present invention, the molecular weight distribution of the ethylenically unsaturated carboxylic acid copolymer is 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.
In the present invention, the term "substituted" used to define an alkene or an alkane means that the C or H atom in the alkene or the alkane is optionally substituted with a group of halogen, saturated or unsaturated hydrocarbon group, oxo (-O-), hetero atom containing one or more of oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium and tin atom.
According to the preparation method of the olefin-unsaturated carboxylic acid copolymer, the unsaturated carboxylic acid monomer and the catalyst for reaction are selected, and a proper polymerization process is adopted, so that the spherical and/or spheroidal polymer with a good form is obtained through the copolymerization of the olefin and the unsaturated carboxylic acid, the subsequent processing processes such as granulation and the like are not needed, the obtained polymerization product is not easy to scale in a reactor, the transportation is convenient, the process flow is reduced, and the preparation method has a good prospect in industrial application.
Drawings
FIG. 1 is a photograph of a copolymer 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 an internal standard, was used to determine the structure of the ligands at 25 ℃.
Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the polymer: 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).
Comonomer content of the polymer (structural units derived from the unsaturated carboxylic acid represented by formula I): the polymer samples were dissolved in deuterated tetrachloroethane at 130 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX 13 probe for analytical testing using 13C NMR spectroscopy.
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 iv, wherein R is1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H；
A2 is an alpha-diimine compound of formula iv, wherein R is1＝R2＝R3＝R4＝R5＝R6＝Me，R7＝R8＝R9＝R10＝R21＝R22＝H；
A3 is an alpha-diimine compound of formula iv, wherein R is1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H；
A4 is an alpha-diimine compound represented by the following formula a:
ligand L1 is a diamine compound of formula ii, wherein R1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H；
Ligand L2 is of formula iiIn which R is1＝R2＝R3＝R4＝R5＝R6＝Me，R7＝R8＝R9＝R10＝R21＝R22＝H；
Ligand L3 is a diamine compound of formula ii, wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22＝H；
Ligand L4 is a diamine compound shown in formula b,
the complex 1 is a complex shown as a formula III, wherein R1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22H, M is nickel, X ═ Br;
the complex 2 is a complex shown as a formula III, wherein R1＝R2＝R3＝R4＝R5＝R6＝Me，R7＝R8＝R9＝R10＝R21＝R22H, M is nickel, X ═ Br;
the complex 3 is a complex shown as a formula III, wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22H, M is nickel, X ═ Br;
the complex 4 is a complex shown as a formula III, wherein R1＝R3＝R4＝R6＝iPr，R2＝R5＝R7＝R8＝R9＝R10＝R21＝R22H, M is nickel, X ═ Cl;
the complex 5 is a complex shown as the following formula c,
example 1
1) Preparation of the ligand:
after 14.42g (8mmol) of the alpha-diimine compound, 50ml of tetrahydrofuran and 0.61g (16mmol) of lithium aluminum hydride were sequentially added thereto, and the mixture was stirred at 60 ℃ for 6 hours. After cooling, the reaction was quenched with aqueous sodium hydroxide, and the organic phase was extracted with ethyl acetate, dried, filtered and recrystallized to give ligand L1 as colorless crystals in 63% yield.1HNMR(CDCl3，300MHz)7.02-7.23(m,14H),4.03(s,2H,NH),3.75(m,2H),3.04(m,2H),2.88(m,4H,CH(CH3)2),1.19(d,24H,CH3).
2) Preparation of Complex 1:10 ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a solution of 10ml of ligand L1(501mg,0.9mmol) in dichloromethane, and stirred at room temperature for 6 hours to precipitate, which was washed with ether for filtration and dried to give a red powdery solid in a yield of 80%. Elemental analysis (C)40H48Br2N2Ni): c, 61.97; h, 6.24; n, 3.61; experimental values (%): c, 62.25; h, 6.53; and N, 3.72.
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 charged to the polymerization system while 7.8mg (10. mu. mol) of complex 1, 15mmol (2.55g) of 2, 2-dimethyl-7-octenoic acid, 15mL 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 neutralization with 5 vol% ethanol 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 7.8mg (10. mu.M) was added simultaneouslymol) Complex 1, 30mmol (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 neutralization with 5 vol% ethanol 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 charged to the polymerization system while 7.8mg (10. mu. mol) of complex 1, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralization with 5 vol% ethanol 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 charged to the polymerization system while 7.8mg (10. mu. mol) of complex 1, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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 polymer was obtained by neutralization with 5 vol% ethanol 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 charged to the polymerization system while 7.8mg (10. mu. mol) of complex 1, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 30mL of AlEt3(1.0mol/L in hexane), 1.0mL of diethylzinc (1mol/L in hexane), 6.5mL of MAO (1.53mol/L in toluene), at 30 deg.C,the reaction was stirred for 30min while maintaining the ethylene pressure of 10 atm. Finally, the polymer was obtained by neutralization with 5 vol% ethanol 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 7.8mg (10. mu. mol) of complex 1, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 80 ℃ under 10atm of ethylene pressure for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% ethanol 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 7.8mg (10. mu. mol) of complex 1, 50mmol (8.51g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 8
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, and 7.8mg (10. mu. mol) of complex 1, 100mmol (17.02g) of 2, 2-dimethyl-7-octenoic acid, 100mL of AlEt3(1.0mol/L hexane solution), 3mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 9
1) Preparation of the ligand:
after 23.75g (8mmol) of the alpha-diimine compound, 50ml of tetrahydrofuran and 0.61g (16mmol) of lithium aluminum hydride were sequentially added thereto, and the mixture was stirred at 60 ℃ for 6 hours. After cooling, the reaction was quenched with aqueous sodium hydroxide, and the organic phase was extracted with ethyl acetate, dried, filtered and recrystallized to give ligand L2 as colorless crystals in 82% yield.1HNMR(CDCl3，300MHz)6.97-7.23(m,12H),4.04(s,2H,NH),3.76(m,2H),3.05(m,2H),1.84(s,6H,CH3),1.73(s,12H,CH3).
2) Preparation of Complex 2: 10ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a solution of 10ml of ligand L2(425mg,0.9mmol) in dichloromethane, and stirred at room temperature for 6 hours to precipitate, which was washed with ether for filtration and dried to give a red powdery solid in a yield of 85%. Elemental analysis (C)34H36Br2N2Ni): c, 59.08; h, 5.25; n, 4.05; experimental values (%): c, 59.17; h, 5.42; n, 4.14.
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 charged to the polymerization system while 6.9mg (10. mu. mol) of complex 2, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralization with 5 vol% ethanol 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 6.9mg (10. mu. mol) of complex 2, 50mmol (8.51g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralizing with 5 vol% hydrochloric acid acidified ethanol solution to obtain polymerA compound (I) is provided. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 11
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 6.9mg (10. mu. mol) of complex 2, 30mmol (4.69g) of 2, 2-dimethyl-6-heptenoic acid and 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 neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 12
Synthesis of alpha-diamine ligand L3
3.52g (8mmol) of the alpha-diimine compound A3 was placed in a 100ml three-necked flask equipped with a reflux condenser, and then 50ml of tetrahydrofuran and 0.61g (16mmol) of lithium aluminum hydride were sequentially added thereto, followed by stirring at 60 ℃ for 6 hours. After cooling, the reaction was quenched with aqueous sodium hydroxide, and the organic phase was extracted with ethyl acetate, dried, filtered and recrystallized to give ligand L3 as colorless crystals in 82% yield.1HNMR(CDCl3，300MHz)6.94-7.21(m,14H),4.04(s,2H,NH),3.76(m,2H),3.06(m,2H),1.75(s,12H,CH3).
2) Preparation of Complex 3: 10ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a solution of 10ml of ligand L3(400mg,0.9mmol) in dichloromethane, and stirred at room temperature for 6 hours, to precipitate, which was washed with ether by filtration and dried to give a red powdery solid in a yield of 87%. Elemental analysis (C)32H32Br2N2Ni): c, 57.96; h, 4.86; n, 4.22; experimental values (%): c, 58.14; h, 4.98; and N, 4.31.
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 charged to the polymerization system while 6.6mg (10. mu. mol) of complex 3, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 30mL of AlEt3(1.0mol/L in hexane), 6.5mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% ethanol 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 charged to the polymerization system while 6.6mg (10. mu. mol) of complex 3, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralization with 5 vol% ethanol 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 charged to the polymerization system while 6.6mg (10. mu. mol) of complex 3, 30mmol (4.26g) of 2-isopropyl-4-pentenoic acid, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and 30mi0n was stirred at 30 ℃ under 10atm ethylene pressure. Finally, the polymer was obtained by neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 15
Preparation of Complex 4: 10ml of (DME) NiCl2(198mg,0.9mmol) of dichloromethane solution was added dropwise to a solution of 10ml ligand L1(501mg,0.9mmol) in dichloromethane, stirred at room temperature for 6 hours, the precipitate precipitated, filtered, washed with ether and dried to give a red powder solid with a yield of 81%. Elemental analysis (C)40H48Cl2N2Ni): c, 69.99; h, 7.05; n, 4.08; experimental values (%): c, 70.15; h, 7.38; n, 4.22.
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 6.9mg (10. mu. mol) of complex 4, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 16
1) Preparation of the ligand:
after 44.32g (8mmol) of the alpha-diimine compound, 50ml of tetrahydrofuran and 0.61g (16mmol) of lithium aluminum hydride were sequentially added thereto, and the mixture was stirred at 60 ℃ for 6 hours. After cooling, the reaction was quenched with aqueous sodium hydroxide, and the organic phase was extracted with ethyl acetate, dried, filtered and recrystallized to yield colorless crystals as ligand L4 in 84% yield.1HNMR(CDCl3，300MHz)1HNMRδ(ppm)6.94-7.88(m,18H),4.08(s,2H,NH),3.82(m,2H),3.08(m,2H),1.73(s,12H,CH3).
2) Preparation of Complex 5: 10ml of (DME) NiBr2(277mg,0.9mmol) of a dichloromethane solution was added dropwise to a solution of 10ml of ligand L4(490mg,0.9mmol) in dichloromethane, and stirred at room temperature for 6 hours to precipitate, which was washed with ether for filtration and dried to give a red powdery solid in a yield of 80%. Elemental analysis (C)40H36Br2N2Ni): c, 62.95; h, 4.75; n, 3.67; experimental values (%): c, 63.17; h, 5.24; n, 3.43.
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 charged to the polymerization system while 7.6mg (10. mu. mol) of complex 5, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Comparative example 1
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 7.8mg (10. mu. mol) of complex 1, 30mmol (5.53g of 10-undecylenic acid), 30mL of AlEt 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 neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Comparative 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 toluene was charged to the polymerization system while adding 7.8mg (10. mu. mol) of complex 1, 30mmol (5.10g) of 2, 2-dimethyl-7-octenoic acid, 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 neutralization with 5 vol% ethanol 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 has good thermal stability, shows high polymerization activity even when used for catalyzing the copolymerization of ethylene and unsaturated carboxylic acid at a high temperature, and the obtained polymer has high molecular weight. The copolymerization activity of the catalyst can reach 1.02 x 10 to the maximum5g·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, spherical and/or spheroidal copolymerization products 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 constitute any limitation 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 (10)
1. A method for producing an olefin-unsaturated carboxylic acid copolymer, comprising: in the presence of an alkane solvent, carrying out contact reaction on olefin and unsaturated carboxylic acid shown as a formula I and a catalyst and an optional chain transfer agent to generate the copolymer;
in the formula I, L1-L3 are respectively and independently selected from H or C1-C30Alkyl, L4 is C with pendant groups1-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 carboxyl;
the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is selected from a metal complex shown in a formula II:
in the formula II, R1-R10Each independently selected from H, halogen, C1-C24Saturated or unsaturated hydrocarbon radicals or C1-C24Saturated or unsaturated hydrocarbyloxy radicals, preferably selected from H, C1-C10Alkyl and C1-C10An alkoxy group; r1-R3、R9、R10Optionally form a ring with each other, R4-R8Optionally forming a ring with each other; r1-R4Each independently selected from H, halogen, saturated or unsaturated hydrocarbyl and substituted saturated or unsaturated hydrocarbyl, R1-R4Optionally forming a ring with each other; m is a group VIII metal; x is selected from one or more of halogen, saturated or unsaturated alkyl and saturated or unsaturated alkoxy; n is an integer satisfying the valence of M.
2. The method according to claim 1, wherein the procatalyst is selected from at least one metal complex represented by formula iii:
in the formula III, R1-R10M, X, n have the same definitions as in formula II;
R21、R22the same or different, each independently selected from H, halogen, saturated or unsaturated hydrocarbyl and saturated or unsaturated hydrocarbyloxy, preferably from H, halogen, C1-C10Saturated or unsaturated hydrocarbon radicals or C1-C10A saturated or unsaturated hydrocarbyloxy group; r21、R22Optionally forming a ring with each other.
3. The process according to claim 1 or 2, wherein L1 and L2 are H, and L3 is selected from H, C1-C10Alkyl and C1-C10Haloalkyl, L4 being C having a pendant group1-C10An alkylene group.
4. The method according to any one of claims 1 to 3, wherein the pendant group in L4 is selected from the group consisting of halogen, C6-C20Aryl radical, C1-C20Alkyl and C1-C20One or more of the alkoxy groups, and (C) a group,said C is6-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 carboxyl.
5. The method of any one of claims 1-4, wherein R is1-R6Each independently selected from H, methyl, ethyl, isopropyl, n-propyl, butyl, pentyl and hexyl, R7-R10Is H.
6. The method according to any one of claims 1 to 5, wherein the reaction conditions include: the reaction temperature is-50 ℃, and/or the reaction time is 10-200 min.
7. The method according to any one of claims 1 to 6, wherein the olefin is C2-C16α -olefins.
8. The olefin-unsaturated carboxylic acid copolymer produced by the production process according to any one of claims 1 to 7, which comprises a spherical and/or spheroidal polymer.
9. The copolymer of claim 8, wherein the spherical and/or spheroidal polymers have an average particle size of 0.1 to 50.0 mm.
10. The copolymer according to claim 8 or 9, wherein the content of the structural unit derived from the unsaturated carboxylic acid represented by the formula i in the copolymer is 0.4 to 40.0 mol%, preferably 0.7 to 10.0 mol%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115246902A (en) * | 2021-04-28 | 2022-10-28 | 中国石油化工股份有限公司 | Method for preparing copolymer, copolymer and application |
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| CN115246900B (en) * | 2021-04-28 | 2023-08-15 | 中国石油化工股份有限公司 | Polymer preparation method and polymer |
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