CN111116780B - Preparation method of olefin-olefin alcohol copolymer - Google Patents
Preparation method of olefin-olefin alcohol copolymer Download PDFInfo
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- CN111116780B CN111116780B CN201811290872.0A CN201811290872A CN111116780B CN 111116780 B CN111116780 B CN 111116780B CN 201811290872 A CN201811290872 A CN 201811290872A CN 111116780 B CN111116780 B CN 111116780B
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Abstract
The invention discloses a preparation method of an olefin-olefin alcohol copolymer, which comprises the steps of carrying out contact reaction on olefin and olefin alcohol shown as a formula I, a catalyst and an optional chain transfer agent in the presence of an alkane solvent to obtain 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 invention relates to a preparation method of an olefin-olefin alcohol copolymer.
Background
The polyolefin product has low price, excellent performance and wide application range. Under the condition of keeping the original excellent physical and chemical properties of the polyolefin, polar groups are introduced into polyolefin molecular chains by a chemical synthesis method, so that the chemical inertness, the printing property, the wettability and the compatibility with other materials can be improved, and new characteristics which are not possessed by raw materials are endowed. High pressure free radical polymerization is currently used commercially to promote direct copolymerization of olefins with polar monomers, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, and ethylene-acrylic acid copolymers. Although the polar comonomer can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.
Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is a novel high molecular material integrating the processability of ethylene polymer and the gas barrier property of vinyl alcohol polymer, is one of three barrier resins industrially produced in the world at present, and is widely used for packaging food, medical solution and other products. Since vinyl alcohol cannot exist independently in the form of monomer, it is usually prepared by alcoholysis of ethylene-vinyl acetate copolymer by radical polymerization, but the alcoholysis process requires the use of a large amount of solvent, and the final saponification product contains a large amount of impurities such as acetic acid and alkali metal salt, and requires a large amount of water for washing.
As a preparation technology of polymers at normal temperature and normal pressure, coordination catalytic copolymerization has attracted extensive attention due to its remarkable effects in reducing energy consumption, improving reaction efficiency and the like. The catalyst participates in the reaction process, so that the activation energy of the copolymerization reaction of the olefin monomer and the polar monomer is greatly reduced, and the functional polymer with higher molecular weight can be obtained at lower temperature and pressure. Currently, only a few documents report the use of transition metal complexes to catalyze the copolymerization of olefins and unsaturated alcohols. However, in the prior art, the polymer obtained by any method is a viscous massive solid, so that the polymer is easily scaled in polymerization equipment, and the transportation, solvent removal, granulation and the like of the polymer are difficult.
Disclosure of Invention
The invention provides a preparation method of olefin-olefin alcohol copolymer, which directly obtains spherical and/or spheroidal polymers through polymerization of olefin and olefin alcohol without subsequent processing such as granulation, and the polymers have good appearance and good industrial application prospect.
According to a first aspect of the present invention, there is provided a process for the preparation of an alkene-alkene alcohol copolymer comprising contacting an alkene and an alkene alcohol of formula i with a catalyst and optionally a chain transfer agent in the presence of an alkane solvent to form 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 hydroxy;
the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is a metal complex shown as a 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 hydroxyl.
According to a preferred embodiment of the invention, the side group in L4 is selected from halogen, 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-C10One or more of alkyl, and further preferably, the side group in L4 is selected from halogen, phenyl, C1-C6Alkyl and hydroxy substituted C1-C6One or more of alkyl, said C1-C6Alkyl includes methylEthyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-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 hydroxyl.
According to a preferred embodiment of the invention, in formula I, L1 and L2 are H, L3 is H, C1-C10Alkyl or C1-C10Haloalkyl, preferably L3 is H or C1-C10An alkyl group; l4 is C with pendant groups1-C20Alkylene, e.g. L4, is methylene having pendant groups, ethylene having pendant groups, propylene having pendant groups, butylene having pendant groups, C having pendant groups5Alkylene, 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 olefinic alcohol represented by formula I include, but are not limited to: 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2, 4-dimethyl-4-penten-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-methyl-3-buten-2-ol, 2-methyl-4-penten-2-ol, 2-methyl-3-buten-ol, 2-methyl-4-penten-2-ol, 2-methyl-4-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-2-ol, and mixtures thereof, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2, 3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2, 5-dimethyl-1-hepten-4-ol, 2, 6-dimethyl-7-octen-2-ol, 2-hydroxy-2, 4, 5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-6-heptene, 2-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-2-heptene, 2-methyl-2-1-heptene, 2-methyl-2-4-methyl-6-heptene, 2-methyl-4-heptene, 2-1-octene, 2-octene, 2-heptene, 2-octene, 2-one, 3-methyl-3-hydroxy-7-octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl-3-hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1, 2-dihydroxy-7-octene, 2, 6-dimethyl-2, 6-dihydroxy-7-octene, 2, 6-dimethyl-2, 3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, mixtures thereof, and mixtures thereof, 2-methyl-2-hydroxy-3, 5-dichloro-7-octene, 3, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3, 5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2, 3-diol, and 2, 6-dimethyl-7-octen-2, 6-diol.
According to 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 from H, halogen, C1-C24Saturated or unsaturated hydrocarbon groups and C1-C24Saturated or unsaturated hydrocarbyloxy groups.
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.
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.
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-C10A saturated or unsaturated 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-C10An alkyl group; 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 halides, such as 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, 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 is an olefin having 2 to 16 carbon atoms, in some embodiments of the invention the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms. In other embodiments of the present invention, the olefin is C3-C16A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or has 3 to 16Alpha-olefins of 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 alkene alcohol represented by 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 olefin alcohol is pre-treated with a dehydroactive hydrogen, preferably with a co-catalyst or chain transfer agent as described above, to remove hydroxyl active hydrogen from the olefin alcohol. Preferably, the molar ratio of hydroxyl groups in the alkene alcohol to co-catalyst or chain transfer agent during pretreatment is from 10:1 to 1: 10.
According to a preferred embodiment of the invention, the reaction is carried out in the absence of water and oxygen.
According to a preferred embodiment of the invention, the conditions of the reaction include: the temperature of the reaction is-50 ℃ to 50 ℃, preferably-20 ℃ to 50 ℃, more preferably 0 ℃ to 50 ℃, and can be, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ and any value therebetween; and/or the reaction time is 10-200min, preferably 20-60 min. In the present invention, the reaction pressure is not particularly limited as long as the monomer can be subjected to coordination copolymerization. When the olefin is ethylene, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50atm, from the viewpoint of cost reduction and simplification of the polymerization process.
In the present invention, the "reaction system" is meant to include the totality of solvent, olefin alcohol monomer, catalyst, and optionally chain transfer agent.
The olefin-olefin alcohol copolymer produced by the above production method, which comprises a spherical and/or spheroidal polymer.
According to a preferred embodiment of the invention, the copolymer has a cavity inside at least part of the 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, the volume of the hollow cavity in the spherical and/or spheroidal polymer having a hollow cavity therein is 5 to 99% of the volume of the spherical and/or spheroidal polymer, for example, may be 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and any value therebetween, preferably 30 to 95%, more preferably 50 to 90%.
According to a preferred embodiment of the present invention, in the olefin-olefin alcohol copolymer, the content of the structural unit derived from the olefin alcohol represented by the formula I is 0.4 to 30.0 mol%, and for example, may be 0.4 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 5.0 mol%, 8.0 mol%, 10.0 mol%, 15.0 mol%, 20.0 mol%, 25.0 mol%, 30.0 mol% and any value therebetween, preferably 0.7 to 10.0 mol%.
According to a preferred embodiment of the present invention, the weight average molecular weight of the olefin-olefin alcohol copolymer is 3000-500000, preferably 5000-400000.
According to a preferred embodiment of the present invention, the olefin-olefin alcohol copolymer has a molecular weight distribution of 4.0 or less, and for example, may be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and any value therebetween, and preferably, the molecular weight distribution is 1.0 to 4.0.
In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.
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 still another aspect of the present invention, there is provided a use of the olefin-olefin alcohol copolymer as a foamed polyolefin material.
According to the preparation method of the olefin-olefin alcohol copolymer, the spherical and/or spheroidal polymer with good form is directly prepared by selecting the olefin alcohol monomer and the catalyst for reaction 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.
At least part of the spherical and/or spheroidal polymers obtained by the method provided by the invention have cavities inside, and the spherical and/or spheroidal polymers can be used as foaming materials without a foaming process, so that the spherical and/or spheroidal polymers have good prospects in industrial application.
Compared with the existing industrial process for preparing the olefin-olefin alcohol copolymer, the method for preparing the olefin-olefin alcohol copolymer provided by the invention omits the step of saponification reaction, and has simpler preparation process.
Drawings
FIG. 1 is an electron micrograph of a copolymer obtained in example 2 of the present invention.
FIG. 2 is a sectional view of a spherical polymer having a cavity inside, which is 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) and Tetramethylsilicon (TMS) as internal standard, and the internal standard is used for measuring the structure of the ligand of the complex at 25 ℃.
Alcohol content in the copolymer (content of structural units derived from an olefin alcohol represented by formula I): by using13C NMR was measured by dissolving a sample of the polymer in 1,2, 4-trichlorobenzene at 120 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX 13 probe.
Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the copolymer: measured at 150 ℃ using PL-GPC220 and trichlorobenzene as a solvent (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).
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 a diamine compound of formula ii, wherein R1＝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 the dichloromethane solution was added dropwise to a solution of 10ml ligand L1(501mg,0.9mmol) in dichloromethane, and stirred at room temperature for 6 hoursIn time, a precipitate was precipitated, filtered, washed with ether and dried to give a red powder solid with 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 poured into the polymerization system, and 7.8mg (10. mu. mol) of complex 1, 15mmol (2.5mL) of 2-methyl-2-hydroxy-7-octene, 15mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 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. mol) of complex 1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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.
Fig. 1 to 2 show the prepared copolymer and a cross-sectional view of the copolymer, and it can be seen that the resulting spherical polymer has a cavity inside.
Example 3
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.8mg (10. mu. mol) of complex 1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously3(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 use 5The ethanol solution acidified by volume% hydrochloric acid was neutralized to obtain a polymer. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 4
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 7.8mg (10. mu. mol) of complex 1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously3(1.0mol/L hexane solution), 0.5mL diethyl zinc (1mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 poured into the polymerization system, and 7.8mg (10. mu. mol) of complex 1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously3(1.0mol/L hexane solution), 1.0mL diethyl zinc (1mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and stirred at 20 ℃ 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 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 7.8mg (10. mu. mol) of complex 1, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously3(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 adding 7.8mg (10. mu. mol) of complex 1, 50mmol (8.5mL) of 2-methyl-2-hydroxy-7-octene, 50mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 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 (17.0mL) of 2-methyl-2-hydroxy-7-octene, 100mL of AlEt3(1.0mol/L hexane solution), 3mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 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%. Element classificationAnalysis (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 poured into the polymerization system, and 6.9mg (10. mu. mol) of complex 2, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 10
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was charged to the polymerization system while adding 6.9mg (10. mu. mol) of complex 2, 50mmol (8.5mL) of 2-methyl-2-hydroxy-7-octene, 50mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 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 adding 6.9mg (10. mu. mol) of complex 2, 30mmol (4.1mL) of 3-methyl-5-hexen-3-ol, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 12
Synthesis of alpha-diamine ligand L3
Directional dressA100 ml three-necked flask was charged with 3.52g (8mmol) of alpha-diimine compound A3 through 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 poured into the polymerization system, and 6.6mg (10. mu. mol) of complex 3, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 13
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 6.6mg (10. mu. mol) of complex 3, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt were added simultaneously3(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. Polymerization Activity and Polymer Property parameters are given in Table 1As shown.
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 6.6mg (10. mu. mol) of complex 3, 30mmol (4.5mL) of 4-methyl-1-hepten-4-ol, 30mL of AlEt-4-ol were added simultaneously3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and 30mi0n was stirred at 20 ℃ 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, and simultaneously 6.9mg (10. mu. mol) of complex 4, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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 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. Cooling, terminating reaction with sodium hydroxide water solution, extracting organic phase with ethyl acetate, drying, filtering, recrystallizing to obtain colorless crystalThe yield was 84% for ligand L4.1HNMR(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 poured into the polymerization system, and 7.6mg (10. mu. mol) of complex 5, 30mmol (5.1mL) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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.
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 injected into the polymerization system, and 7.8mg (10. mu. mol) of complex 1, 30mmol (6.0mL) of 10-undecen-1-ol, 30mL of AlEt-1-ol were added simultaneously3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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.
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 injected into the polymerization system, and 7.8mg (10. mu. mol) of the complex was added1, 30mmol (5.1mL) 2-methyl-2-hydroxy-7-octene, 30mL AlEt3(1.0mol/L hexane solution), 6.5mL MAO (1.53mol/L toluene solution), and the reaction was stirred at 20 ℃ 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.
TABLE 1
As can be seen from Table 1, the catalyst of the present invention has better thermal stability, shows higher polymerization activity even when catalyzing the copolymerization of ethylene and enol at higher temperature, and the obtained polymer has higher molecular weight. The copolymerization activity of the catalyst can reach 1.51 multiplied by 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, 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 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 (15)
1. A method for preparing an olefin-olefin alcohol copolymer, comprising: in the presence of an alkane solvent, carrying out contact reaction on olefin and alkene alcohol shown as a formula I, a catalyst and an optional chain transfer agent to obtain 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 selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy and C6-C10One or more of aryl groups; the side group in L4 is selected from halogen, C6-C20Aryl radical, C1-C20Alkyl and C1-C20One or more of alkoxy groups;
the catalyst comprises a main catalyst and a cocatalyst
In the formula III, R1-R10Each independently selected from H, halogen, C1-C24Alkyl or C1-C24Alkoxy of R1-R3、R9、R10Optionally form a ring with each other, R4-R8Optionally forming a ring with each other;
R21、R22the same or different, each independently selected from H, halogen, C1-C10Alkyl or C1-C10Alkoxy group of (a); r21、R22Optionally forming a ring with each other;
m is a group VIII metal; x is selected from one or more of halogen, alkyl and alkoxy; n is an integer satisfying the valence of M;
the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms;
the reaction temperature is-50 ℃.
2. The process according to claim 1, wherein in the formula III, R is1-R10Each independently selected from H, halogen, C1-C10Alkyl and C1-C10An alkoxy group.
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 of claim 1 or 2, wherein the pendant group in L4 is selected from the group consisting of halogen, C6-C10Aryl radical, C1-C10Alkyl and C1-C10One or more of alkoxy groups.
5. The method according to claim 1 or 2, 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 claim 1 or 2, wherein the reaction time is 10 to 200 min.
7. The process according to claim 1 or 2, wherein the olefin is ethylene or C2-C10Of alpha-olefins.
8. The process according to claim 1 or 2, wherein the olefin is selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene and octene.
9. The olefin-olefin alcohol copolymer produced by the production process as claimed in any one of claims 1 to 8, which comprises a spherical and/or spheroidal polymer, and in which the content of a structural unit derived from the olefin alcohol represented by the formula I is from 0.4 to 30.0 mol%.
10. The copolymer of claim 9 wherein the at least partially spherical and/or spheroidal polymer has a cavity therein.
11. The copolymer according to claim 9 or 10, wherein the spherical and/or spheroidal polymer has an average particle size of 0.1 to 50.0mm, and/or wherein the volume of the cavities in the spherical and/or spheroidal polymer having cavities therein is 5 to 99% of the volume of the spherical and/or spheroidal polymer.
12. The copolymer of claim 11, wherein the volume of the spherical and/or spheroidal polymer cavities having cavities therein is 30 to 95% of the volume of the spherical and/or spheroidal polymer.
13. The copolymer of claim 11, wherein the volume of the spherical and/or spheroidal polymer cavities having cavities therein is 50 to 90% of the volume of the spherical and/or spheroidal polymer.
14. The copolymer according to claim 9 or 10, wherein the content of the structural unit derived from the olefin alcohol represented by the formula i in the copolymer is from 0.7 to 10.0 mol%.
15. Use of the copolymer of any of claims 9 to 14 as a foamed polyolefin material.
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