CN111116810A - Preparation method of olefin-olefin alcohol copolymer - Google Patents
Preparation method of olefin-olefin alcohol copolymer Download PDFInfo
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- CN111116810A CN111116810A CN201811291006.3A CN201811291006A CN111116810A CN 111116810 A CN111116810 A CN 111116810A CN 201811291006 A CN201811291006 A CN 201811291006A CN 111116810 A CN111116810 A CN 111116810A
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Abstract
The invention provides a preparation method of an olefin-olefin alcohol copolymer, which comprises the following steps: 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, preferably selected from halogen, C1‑C10Alkyl radical, C1‑C10Alkoxy radical, C6‑C10One or more of aryl, cyano and hydroxyl. The prepared copolymer has good shape and good prospect in industrial application.
Description
Technical Field
The invention relates to the field of preparation of copolymers, in particular 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 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
In view of the problems in the prior art, the present invention aims to provide a method for preparing an olefin-unsaturated carboxylic acid copolymer, wherein the method provided by the present invention can be used for directly obtaining a copolymer containing spherical and/or spheroidal polymers through polymerization of olefin and olefin alcohol without subsequent processing such as granulation, and the polymer has good appearance and good industrial application prospect.
In one aspect, the present invention provides 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 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 hydroxy;
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-R4Are the same or different and are each independently selected from C1-C30Hydrocarbyl and heterohydrocarbyl radicals, R1-R4Optionally forming a ring with each other; r5Selected from H, C1-C10Alkyl radical, C2-C10An alkenyl group; r6Is an electron donating ligand; r5And R6Optionally interconnected; a is selected from arylene, monocyclic heteroarylene, C3-C10Cycloalkylene radical, C2-C8Alkenylene and C3-C10Cycloalkenylene; m is a group VIII metal; x-Is a counterion to the cationic organometallic compound.
According to the invention, in the formula II, R1-R4Are the same or different and are each independently selected from C1-C20Hydrocarbyl and C1-C20Heterohydrocarbyl radicals, R1-R4Optionally forming a ring with each other; preferably, R1-R4Are the same or different and are each independently selected from C1-C10Hydrocarbyl and C1-C10Heterohydrocarbyl radicals, R1-R4Optionally forming a ring with each other; more preferably, R1-R4Are the same or different and are each independently selected from C1-C6Hydrocarbyl and C1-C6Heterohydrocarbyl radicals, R1-R4Optionally form a ring with each other, wherein hydrocarbyl means alkyl, alkenyl and alkynyl, preferably alkyl.
In some preferred embodiments of the invention, in formula I, L1 and L2 are H, and L3 is 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 hydroxyl.
In some preferred embodiments of the invention, in formula I, L1 and L2 are H, and L3 is H, C1-C10Alkyl or halogen substitutionC of (A)1-C10Alkyl, 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 or a substituted alkylene group,
the number of carbons n of the Cn alkylene group refers to the number of C's in the linear chain, not including the number of C's in the pendant group, e.g., isopropylidene (-CH)2-CH(CH3) -) is referred to herein as C with a pendant group (methyl)2An alkylene group.
In some preferred embodiments of the present invention, the pendant 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 C1-10One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C1-C6Alkyl and hydroxy substituted C1-C6One or more of alkyl, said C1-C6Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl.
According to the invention, the alkene alcohol may be a linear or branched alkene alcohol, and may be an alkene alcohol containing cycloalkyl, cycloalkylalkyl, aryl, alkylaryl, arylalkyl groups. Preferably, the alkene alcohol is substituted or unsubstituted C3-C30Alkene alcohols, said "substituted C3-C30The alkene alcohol "means" C3-C30The hydrogen atom or the carbon atom in the alkene alcohol "is substituted with a halogen atom, an oxygen atom, a sulfur atom or a nitrogen atom. More preferably, the alkene alcohol is C6-C20The terminal alkenyl alkene alcohol of (1).
In some preferred embodiments of the present invention, specific examples of the alkene alcohols 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, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2, 3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2, 5-dimethyl-1-hepten-4-ol, 2, 6-dimethyl-7-octen-2-ol, 2-hydroxy-2, 4, 5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-6-heptene, 2-hydroxy, 3-methyl-3-hydroxy-7-octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl-3-hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1, 2-dihydroxy-7-octene, 2, 6-dimethyl-2, 6-dihydroxy-7-octene, 2, 6-dimethyl-2, 3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, mixtures thereof, and mixtures thereof, 2-methyl-2-hydroxy-3, 5-dichloro-7-octene, 3, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3, 5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2, 3-diol, and 2, 6-dimethyl-7-octen-2, 6-diol.
In some preferred embodiments of the invention, R6Selected from pyridine, substituted pyridine, nitrile, ammonia, alkylamine, substituted alkylamine, arylamine or substituted arylamine or a ligand represented by formula III:
in the formula III, W is C or S; z is selected from O, S, NH and NRa(ii) a Y is selected from O, S, NH and NRbAnd Y is optional; r7Selected from substituted OR unsubstituted C1-C10 alkyl, -ORcand-NRd2, wherein Ra、Rb、RcAnd RdEach independently selected from alkyl and aryl.
In some preferred embodiments of the present invention, the procatalyst is selected from the group consisting of metal complexes represented by formula IV:
in the formula IV, R11 is selected from C1-C15Hydrocarbyl and R11 is optional; z is selected from O and NRaWherein R isaIs selected from C2-C15Alkyl or C6-C20Aryl of (a); x is selected from SbF6、BPh4、BArF4、BF4And PF6(ii) a M is palladium.
According to the invention, in formula IV, R11 is optional, and R11 is selected from C1-C10A hydrocarbon group, preferably C1-C6The hydrocarbon group refers to an alkyl group, an alkenyl group and an alkynyl group, and is preferably an alkyl group in the present invention.
According to the invention, in the formula IV, RaIs selected from C2-C6Alkyl or C6-C18Aryl group of (1).
According to the invention, the metal complex shown in the formula IV can be prepared by a preparation method disclosed in the references of ACS Catal.2015,5,5932-.
According to the invention, the cocatalyst can be a cocatalyst commonly used in coordination polymerization of olefins, preferably an organoboron compound.
According to the invention, the organoboron compound is selected from the group consisting of 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 the invention, the molar ratio of boron in the cocatalyst to M in the procatalyst is (0-100):1, for example 0.1:1, 0.2:1, 0.5:1, 0.7:1, 1:1, 1.1:2, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 6:1, 7:1, 8:1, 10:1, 20:1, 50:1, 100:1 and any value in between, preferably (0-50): 1.
According to the present invention, the olefin is an olefin having from 2 to 16 carbon atoms, in some embodiments of the invention the olefin is ethylene or an α -olefin having from 3 to 16 carbon atoms in other embodiments of the invention the olefin is C3-C16A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin isEthylene or α -olefins 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 the present invention, the concentration of the olefin alcohol monomer 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 the invention, the chain transfer agent is selected from one or more of aluminium 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 the invention, the molar ratio of the chain transfer agent to M in the procatalyst is (0.1-2000):1, for example 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 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 the present invention, the olefin alcohol is previously subjected to an active hydrogen removal pretreatment, preferably, an organoaluminum compound or a chain transfer agent is used to pretreat the olefin alcohol to remove hydroxyl active hydrogen in the olefin alcohol. Preferably, the molar ratio of hydroxyl groups in the alkene alcohol to the organoaluminum compound or chain transfer agent during pretreatment is from 10:1 to 1: 10.
According to the invention, the organoaluminium compound is chosen from aluminium alkylsAn alkylene oxide or a compound of the formula AlRnX1 3-nWith an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlRnX1 3-nWherein R is H, C1-C20Or C is a hydrocarbon group1-C20Hydrocarbyloxy, 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 the invention, the reaction is carried out under anhydrous and oxygen-free conditions.
In some preferred embodiments of the invention, the conditions of the reaction include: the reaction temperature is-50 ℃ to 200 ℃, preferably 30 ℃ to 100 ℃, for example, can be 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and any value between them; and/or the reaction time is 10min-200min, preferably 20min-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.
In another aspect of the present invention, there is provided an olefin-olefin alcohol copolymer comprising a spherical and/or spheroidal polymer, which is produced according to the above-mentioned production method.
According to the present invention, the olefin-olefin alcohol copolymer does not contain a carboxylic acid and an alkali metal salt.
In some preferred embodiments of the invention, the spherical and/or spheroidal polymer has a density of 0.880g/cm3-0.940g/cm3For example, it may be 0.880g/cm3、0.890g/cm3、0.900g/cm3、0.910g/cm3、0.920g/cm3、0.930g/cm3、0.940g/cm3And any value in between, the density being measured using the method of GB/T6463-2009.
In some preferred embodiments of the invention, the spherical and/or spheroidal polymer has an average particle size of from 0.1mm to 50.0 mm; the number average molecular weight is 3000-300000, preferably 5000-200000; the molecular weight distribution is less than or equal to 4.0, preferably 1.0-4.0; the melting point is 100-140 ℃.
According to the invention, the spherical and/or spheroidal polymers have an average particle size of 0.1mm to 50.0mm, and may for example be 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 0.5mm to 20.0 mm.
In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.
According to the present invention, the number average molecular weight of the olefin-olefin alcohol copolymer is 3000-300000, and may be, for example, 3000, 10000, 50000, 100000, 150000, 200000, 250000, 300000 and any value therebetween, and preferably, the number average molecular weight is 5000 to 200000.
According to 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.
According to the present invention, the melting point of the olefin-olefin alcohol copolymer is 100 ℃ to 140 ℃, for example, 100 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃ and any value therebetween.
In some preferred embodiments of the invention, the content of structural units derived from the alkene alcohol of formula I in the copolymer is from 0.4 to 15.0 mol%, for example, can 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% and any value in between, preferably 0.7 to 10.0 mol%.
In the present invention, the substitution in the phrase "substituted or unsubstituted" used to define an alkene or an alkane, etc., means that the C or H atom in the alkene or the alkane is optionally substituted with one or more of halogen, hydrocarbon group, oxo (-O-), group containing oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium and tin atoms.
In a further aspect, the present invention provides the use of the above 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 for reaction, the catalyst and a proper polymerization process without subsequent processing steps such as granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.
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 shows an electron micrograph of a spherical polymer obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The analytical characterization instrument used in the present invention was as follows:
alcohol content in the copolymer (derived from the structure of the olefin alcohol of formula I)Content of constitutional units): 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).
The melting point of the copolymer was measured using Differential Scanning Calorimetry (DSC): 10mg of the sample was placed in a crucible and measured on a Pekinelmer DSC 8500 differential scanning calorimeter. Raising the temperature from 0 ℃ to 180 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, preserving the heat for l min, reducing the temperature to 0 ℃ at 10 ℃/min, preserving the heat for 3min, then raising the temperature to 180 ℃ at 10 ℃/min, and recording the second heating scanning data.
Example 1
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. 500mL of hexane was charged into the polymerization system, and 32.2mg (20. mu. mol) of complex 1 represented by the formula (1), 2.5mL (15mmol) of 2-methyl-2-hydroxy-7-octene, 15mL of AlEt3(1.0mol/L hexane solution), and the reaction was stirred at 40 ℃ for 30min while maintaining an ethylene pressure of 30 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 2
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. 500mL of hexane was charged into the polymerization system, and 32.2mg (20. mu. mol) of complex 1 represented by the formula (1), 5.1mL (30mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an ethylene pressure of 30 atm. Finally acidifying with 5 vol% hydrochloric acidTo obtain a polymer. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 3
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. 500mL of hexane was charged into the polymerization system, and 32.2mg (20. mu. mol) of complex 1 represented by the formula (1), 5.1mL (30mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), 0.5mL diethyl zinc (1.0mol/L hexane solution), and stirring the mixture at 80 ℃ under 30atm 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
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. 500mL of hexane was charged into the polymerization system, and 29.2mg (2.5. mu. mol) of complex 2 represented by the formula (2), 5.1mL (30mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an ethylene pressure of 30 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 5
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. Into the polymerization system was charged 500mL of hexane, while 16.4mg (20. mu. mol) of complex 3 represented by the formula (3), 5.1mL (30mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an ethylene pressure of 30 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
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. Into the polymerization system was charged 500mL of hexane, while adding 23.1mg (20. mu. mol) of complex 4 represented by the formula (4), 5.1mL (30mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an ethylene pressure of 30 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.
Comparative example 1
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. 500mL of hexane was charged into the polymerization system, and 32.2mg (20. mu. mol) of complex 1 represented by the formula (1), 6.0mL (30mmol) of 10-undecen-1-ol, 30mL of AlEt-1-ol were added simultaneously3(1.0mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an ethylene pressure of 30 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.
Comparative example 2
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with nitrogen gas 3 times. 500mL of toluene was charged into the polymerization system, and 32.2mg (20. mu. mol) of complex 1 represented by the formula (1), 5.1mL (30mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt3(1.0mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an ethylene pressure of 30 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。
TABLE 1
As can be seen from Table 1, the catalyst of the present invention exhibits higher polymerization activity when it catalyzes the copolymerization of ethylene and enol, and the obtained polymer has higher molecular weight. The copolymerization activity of the catalyst can reach 1.27 multiplied by 10 to the maximum6g·mol-1·h-1. 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 (9)
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 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 hydroxy;
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-R4Are the same or different and are each independently selected from C1-C30Hydrocarbyl and heterohydrocarbyl radicals, R1-R4Optionally forming a ring with each other; r5Selected from H, C1-C10Alkyl radical, C2-C10An alkenyl group; r6Is an electron donating ligand; r5And R6Optionally interconnected; a is selected from arylene, monocyclic heteroarylene, C3-C10Cycloalkylene radical, C2-C8Alkenylene and C3-C10Cycloalkenylene; m is a group VIII metal; x-Is a counterion to the cationic organometallic compound.
2. The process according to claim 1, wherein in the formula I, L1 and L2 are H, and 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-C20An alkylene group; preferably, 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 C1-10One or more of alkyl groups.
3. According to the rightThe process according to claim 1 or 2, wherein R in the formula II6Selected from pyridine, substituted pyridine, alkylamine, substituted alkylamine, arylamine or substituted arylamine or a ligand shown in a formula III:
in the formula III, W is C or S; z is selected from O, S, NH and NRa(ii) a Y is selected from O, S, NH and NRbAnd Y is optional; r7Selected from substituted or unsubstituted C1-C10Alkyl, -ORcand-NRd2, wherein Ra、Rb、RcAnd RdEach independently selected from alkyl and aryl.
4. The method according to any one of claims 1 to 3, wherein the procatalyst is selected from the group consisting of metal complexes represented by formula IV:
in the formula IV, R11Is selected from C1-C15Hydrocarbyl radical and R11Is optionally; z is selected from O and NRaWherein R isaIs selected from C2-C15Alkyl or C6-C20Aryl of (a); x is selected from SbF6、BPh4、BArF4、BF4And PF6(ii) a M is palladium.
5. The method according to any one of claims 1 to 4, wherein the reaction conditions include: the reaction temperature is-50-200 ℃, preferably 30-100 ℃, and/or the reaction time is 10-200 min, preferably 20-60 min.
6. The olefin-olefin alcohol copolymer produced by the production process according to any one of claims 1 to 5, which comprises a spherical and/or spheroidal polymer.
7. The copolymer of claim 6, wherein the spherical and/or spheroidal polymer has an average particle size of 0.1mm to 50.0 mm; the number average molecular weight is 3000-300000, preferably 5000-200000; the molecular weight distribution is less than or equal to 4.0, preferably 1.0-4.0; the melting point is 100-140 ℃.
8. The copolymer according to any one of claims 6 to 7, wherein the content of the structural unit derived from the olefin alcohol represented by the formula I in the copolymer is from 0.4 to 15.0 mol%.
9. Use of the copolymer according to any of claims 6 to 8 as a foamed polyolefin material.
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| CN104271585A (en) * | 2012-05-11 | 2015-01-07 | 国立大学法人东京大学 | Catalyst for synthesizing polyolefins |
| CN105061505A (en) * | 2015-09-16 | 2015-11-18 | 中国科学技术大学 | Catalyst ligand, catalyst, and preparation methods and application thereof |
| US20170137549A1 (en) * | 2014-06-27 | 2017-05-18 | The Trustees Of Princeton University | Transition metal catalysts for olefin polymerization |
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| CN104271585A (en) * | 2012-05-11 | 2015-01-07 | 国立大学法人东京大学 | Catalyst for synthesizing polyolefins |
| US20170137549A1 (en) * | 2014-06-27 | 2017-05-18 | The Trustees Of Princeton University | Transition metal catalysts for olefin polymerization |
| CN105061505A (en) * | 2015-09-16 | 2015-11-18 | 中国科学技术大学 | Catalyst ligand, catalyst, and preparation methods and application thereof |
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| CN116217759A (en) * | 2021-12-03 | 2023-06-06 | 中国石油化工股份有限公司 | Coordination precipitation polymerization method for olefin polymerization and obtained polyolefin |
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