CN111116804B

CN111116804B - Preparation method of olefin-olefin alcohol copolymer

Info

Publication number: CN111116804B
Application number: CN201811288798.9A
Authority: CN
Inventors: 高榕; 郭子芳; 周俊领; 张师军; 张晓帆; 李岩; 林洁; 傅捷; 马冬
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2018-10-31
Filing date: 2018-10-31
Publication date: 2022-11-18
Anticipated expiration: 2038-10-31
Also published as: CN111116804A

Abstract

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, 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 C ₁ ‑C ₃₀ Alkyl, L4 is C with pendant groups ₁ ‑C ₃₀ An alkylene group; said C is ₁ ‑C ₃₀ Alkyl is optionally substituted by a substituent, preferably selected from halogen, C ₁ ‑C ₁₀ Alkyl radical, C ₁ ‑C ₁₀ Alkoxy radical, C ₆ ‑C ₁₀ One or more of aryl, cyano and hydroxyl. The prepared copolymer has good shape and good prospect in industrial application.

Description

Preparation method of olefin-olefin alcohol copolymer

Technical Field

The invention relates to the field of preparation of copolymers, and particularly 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 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 olefin monomers containing polar groups. Although polar monomers can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the process 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, which can directly obtain a copolymer containing spherical and/or spheroidal polymers through polymerization of olefin and olefin alcohol without subsequent processing such as granulation, and 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 C ₁ -C ₃₀ Alkyl, L4 is C with pendant groups ₁ -C ₃₀ An alkylene group; said C is ₁ -C ₃₀ Alkyl is optionally substituted by a substituent, preferably selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl, cyano and hydroxy;

the catalyst is selected from metal complexes shown in a formula II:

in the formula II, M is a metal in a VIII group; r is _n Each R in (A) is independently selected from H, halogen, O, N, P, C ₁ -C ₃₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₃₀ (ii) hydrocarbyl, each R optionally forming a ring with each other, n =0-4; r ₁ 、R ₂ Each independently selected from H, halogen, O, N, P and C ₁ -C ₃₀ A hydrocarbyl group; r ₃ Selected from H, halogen, O, P, C _1- C ₃₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₃₀ A hydrocarbyl group; r ₄ Is C containing at least one element selected from O, N, P and S ₁ -C ₃₀ A compound is provided.

In a preferred embodiment of the inventionIn the formula I, L1 and L2 are H, and L3 is H or C ₁ -C ₃₀ Alkyl, L4 is C with pendant groups ₁ -C ₃₀ An alkylene group; said C is ₁ -C ₃₀ Alkyl is optionally substituted by a substituent, preferably selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl, cyano and hydroxyl. .

In a preferred embodiment of the invention, in the formula I, L1 and L2 are H, and L3 is H, C ₁ -C ₁₀ Alkyl or halogen substituted C ₁ -C ₁₀ Alkyl, preferably L3 is H or C ₁ -C ₁₀ An alkyl group; l4 is C with pendant groups ₁ -C ₂₀ Alkylene, e.g. L4, being methylene with pendant groups, ethylene with pendant groups, propylene with pendant groups, butylene with pendant groups, C with pendant groups ₅ Alkylene, C having pendant groups ₆ Alkylene, C having pendant groups ₇ Alkylene, C having pendant groups ₈ Alkylene, C having pendant groups ₉ Alkylene, C having pendant groups ₁₀ Alkylene, C having pendant groups ₁₂ Alkylene, C having pendant groups ₁₄ Alkylene, C having pendant groups ₁₈ Alkylene, C having pendant groups ₂₀ Alkylene, preferably C, having pendant groups ₁ -C ₁₀ An alkylene group.

According to a preferred embodiment of the invention, in formula I, L1 and L2 are H, L3 is H or C1-C6 alkyl; l4 is a C1-C10 alkylene group having a pendant 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(CH ₃ ) -) are referred to herein as C2 alkylene having a pendant group (methyl).

In a preferred embodiment of the present invention, the side group in L4 is selected from halogen, C ₆ -C ₂₀ Aryl radical, C ₁ -C ₂₀ Alkyl, hydroxy substituted C ₁ -C ₂₀ Alkyl and alkoxy substituted C ₁ -C ₂₀ One or more of alkyl; preferably, said pendant groupSelected from halogen, C ₆ -C ₂₀ Aryl radical, C ₁ -C ₁₀ Alkyl, hydroxy substituted C ₁ -C ₁₀ Alkyl and alkoxy substituted C _1-10 One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C ₁ -C ₆ Alkyl and hydroxy substituted C ₁ -C ₆ One or more of alkyl, said C ₁ -C ₆ Alkyl 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 C ₃ -C ₃₀ Alkene alcohols of said "substituted C ₃ -C ₃₀ By alkene alcohol "is meant" C ₃ -C ₃₀ The 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 a C6-C20 terminal alkene alcohol.

In a preferred embodiment of the present invention, specific examples of the olefinic alcohol represented by formula I include, but are not limited to: <xnotran> 2- -3- -1- ,2- -3- -1- ,1,1- -3- -1- ,2- -3- -2- ,2,2- -3- -1- ,3- -1- -3- ,2,4- -4- -2- ,4- -2- ,4- -4- -2- ,2- -4- -2- ,2- -4- -2- ,2- ,2- -5- ,3- -2- ,3- -5- -3- ,2- -2- -5- ,1- ,2,3- -2- -5- ,1- -4- ,4- -1- -4- ,4- -1- -4- ,6- -3- ,2- -2- -6- ,5- -2- -6- , </xnotran> 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, 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-3-7-octene, 2, 6-dimethyl-2-hydroxy-7-octene, 2, 3-dimethyl-7-octene, 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 a preferred embodiment of the invention, in formula ii, M is nickel or palladium; r is _n Each R in (A) is independently selected from H, halogen and C ₁ -C ₃₀ (ii) hydrocarbyl, each R optionally forming a ring with each other, n =1-4; r is ₁ 、R ₂ Each independently selected from C ₁ -C ₃₀ A hydrocarbyl group; r ₃ Is selected from C ₁ -C ₃₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₃₀ A hydrocarbyl group; r ₄ Is C containing at least one element selected from O, N, P and S ₁ -C ₂₀ A compound is provided.

According to the invention, in formula II, M is nickel or palladium; r _n Each R in (A) is independently selected from H, halogen and C ₁ -C ₂₀ (ii) hydrocarbyl, each R optionally forming a ring with each other, n =1-4; r is ₁ 、R ₂ Each independently selected from C ₁ -C ₂₀ A hydrocarbyl group; r is ₃ Is selected from C ₁ -C ₂₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₂₀ A hydrocarbyl group; r ₄ Is C containing at least one element selected from O, N, P and S ₁ -C ₁₅ A compound is provided.

According to the invention, in formula II, M is nickel or palladium; r _n Each R in (A) is independently selected from H, halogen and C ₁ -C ₁₀ Hydrocarbyl, each R optionally forming a ring with each other, n =1-4; r is ₁ 、R ₂ Each independently selected from C ₁ -C ₁₀ A hydrocarbyl group; r is ₃ Is selected from C ₁ -C ₁₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₁₀ A hydrocarbyl group; r is ₄ Is C containing at least one element selected from O, N, P and S ₁ -C ₁₀ A compound is provided.

According to the invention, in formula II, M is nickel or palladium; r is _n Each R in (A) is independently selected from H, halogen and C ₁ -C ₆ (ii) hydrocarbyl, each R optionally forming a ring with each other, n =1-4; r is ₁ 、R ₂ Each independently selected from C ₁ -C ₆ A hydrocarbyl group; r ₃ Is selected from C ₁ -C ₆ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₆ A hydrocarbyl group; r ₄ Is C containing at least one element selected from O, N, P and S ₁ -C ₆ A compound is provided.

According to the invention, the term "halogen" means F, cl, br, I and At, in the present invention Cl or Br being preferred.

According to the present invention, the term "hydrocarbyl" refers to alkyl, alkenyl and alkynyl groups, and in the present invention, alkyl groups are preferred.

According to the invention, the metal complex shown in the formula II can be prepared by a preparation method disclosed in literatures Organometallic,2016,35,1472-1479, ACS Catal.2017,7,1308-1312, organometallic,2017,36,2338-2344, and relevant contents disclosed in the literatures can be fully incorporated into the invention for reference, and are not described again.

According to a preferred embodiment of the present invention, the concentration of the 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 0.5mmol/L.

According to the present invention, the olefin is an olefin having from 2 to 16 carbon atoms, and in some embodiments of the invention, the olefin is ethylene or an alpha-olefin having from 3 to 16 carbon atoms. In other embodiments of the present invention, the olefin is a C3-C16 cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having from 3 to 16 carbon atoms, more preferably ethylene or a C2-C10 alpha-olefin, for example, 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 catalyst is (0.1-2000): 1, e.g., 0.1.

According to the invention, the alkane solvent is selected from one or more of C3-C20 alkanes, for example, may be selected from one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexane, preferably from 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 olefinic alcohol to the organoaluminum compound or chain transfer agent during pretreatment is 10.

According to the invention, the organoaluminium compound is selected from alkylaluminoxanes or compounds of general formula AlR _n X ¹ _3-n With an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlR _n X ¹ _3-n In the formula, R is H or C ₁ -C ₂₀ Or C is a hydrocarbon group ₁ -C ₂₀ Hydrocarbyloxy, preferably C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Alkoxy radical, C ₇ -C ₂₀ Aralkyl radicals or C ₆ -C ₂₀ An aryl group; x ¹ Is 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 a preferred embodiment of the present invention, the reaction conditions include: the reaction temperature is-50 ℃ to 200 ℃, preferably-20 ℃ to 100 ℃, more preferably 0 ℃ to 100 ℃, and most preferably 30 ℃ to 100 ℃, for example, 0 ℃,10 ℃,20 ℃,30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃,100 ℃, 110 ℃, 120 ℃,130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and any value in between; and/or the reaction time is 10min-200min, preferably 20min-60min.

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 invention, the at least partially spherical and/or spheroidal polymer has a cavity inside.

According to the present invention, the olefin-olefin alcohol copolymer does not contain a carboxylic acid and an alkali metal salt.

According to the present invention, the volume of the cavity in the spherical and/or spheroidal polymer having a cavity therein is 1 to 99%, preferably 5 to 95%, more preferably 30 to 95%, and most preferably 50 to 90% of the volume of the spherical and/or spheroidal polymer, and for example, may be 1%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and any value therebetween.

According to the invention, the spherical and/or spheroidal polymer having a cavity inside is a polymer having a core-shell structure, wherein the cavity is a core and the polymer layer covering the cavity is a shell.

In a preferred embodiment of the invention, the spherical and/or spheroidal polymer has a density of 0.880g/cm ³ -0.940g/cm ³ For example, it may be 0.880g/cm ³ 、0.890g/cm ³ 、0.900g/cm ³ 、0.910g/cm ³ 、0.920g/cm ³ 、0.930g/cm ³ 、0.940g/cm ³ And any value in between, the density being measured using the method of GB/T6463-2009.

In a preferred embodiment of the invention, the spherical and/or spheroidal polymer has 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 20.0mm.

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 invention, the spherical and/or spheroidal polymer has a number-average molecular weight of 1000 to 300000, preferably 2000 to 100000; 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 olefin-olefin alcohol copolymer has a number average molecular weight of 1000 to 300000, for example 1000, 3000, 5000, 10000, 20000, 50000, 100000, 150000, 200000, 250000, 300000 and any value in between, preferably a number average molecular weight of 2000 to 100000.

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 ℃, 140 ℃ and any value therebetween.

In a preferred embodiment of the invention, the content of structural units derived from the alkene alcohol of the formula I in the copolymer is from 0.4 to 15.0mol%, for example 0.4mol%, 0.5mol%, 0.7mol%, 0.8mol%, 1.0mol%, 1.5mol%, 2.0mol%, 5.0mol%, 8.0mol%, 10.0mol%, 12.0mol%, 15.0mol% and any value in between, preferably from 0.5 to 13.0mol%.

In the present invention, the term "substituted or unsubstituted" as used to define an alkene or alkane, etc., means that the C or H atoms in the alkene or alkane are optionally substituted with one or more of halogen, hydrocarbyl, oxo (-O-), groups 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 is as follows:

alcohol content in the copolymer (content of structural units derived from the olefin alcohol represented by formula II): by using ¹³ The C 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, and analytically measuring.

Molecular weight and molecular weight distribution PDI (PDI = Mw/Mn) of the copolymer: using PL-GPC220, with trichlorobenzene as a solvent, at 150 ℃ for measurement (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 Pekin Elmer 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 polymerization vessel equipped with mechanical stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced with nitrogen 3 times. 500mL of hexane was injected into the polymerization system, and 13.2mg (20. Mu. Mol) of complex 1 represented by the formula (1), 5.1mL (30 mmol) of 2-methyl-2-hydroxy-7-octene was added simultaneously，30mL AlEt ₃ (1.0 mol/L hexane solution), and the reaction was carried out at 25 ℃ under an ethylene pressure of 10atm with stirring for 30min. 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 poured into the polymerization system, and 13.2mg (20. Mu. Mol) of complex 1 represented by the formula (1), 5.1mL (30 mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt ₃ (1.0 mol/L hexane solution), 0.5mL diethyl zinc (1 mol/L hexane solution), at 25 ℃, keeping 10atm of ethylene pressure, stirring and reacting for 30min. 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

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 poured into the polymerization system, and 13.2mg (20. Mu. Mol) of complex 1 represented by the formula (1), 5.1mL (30 mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt ₃ (1.0 mol/L hexane solution), and the reaction was carried out at 80 ℃ under an ethylene pressure of 10atm with stirring for 30min. 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. Into the polymerization system was charged 500mL of hexane, while adding 19.0mg (20. Mu. Mol) of complex 2 represented by the formula (2), 5.1mL (30 mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt ₃ (1.0 mol/L hexane solution) at 25 deg.C and maintaining ethylene pressure of 10atmThe reaction was stirred for 30min. 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 adding 19.0mg (20. Mu. Mol) of complex 2 represented by the formula (2), 5.1mL (30 mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt ₃ (1.0 mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an 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

A1L stainless steel polymerization vessel equipped with mechanical stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced with nitrogen 3 times. 500mL of hexane was charged into the polymerization system, and at the same time, 17.2mg (20. Mu. Mol) of complex 3 represented by the formula (3), 5.1mL (30 mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt ₃ (1.0 mol/L hexane solution), and the reaction was stirred at 25 ℃ for 30min while maintaining an 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 7

A1L stainless steel polymerization vessel equipped with mechanical stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced with nitrogen 3 times. Into the polymerization system was charged 500mL of hexane, while 13.2mg (20. Mu. Mol) of the complex 4 represented by the formula (4), 5.1mL (30 mmol) of 2-methyl-2-hydroxy-7-octene, 30mL of AlEt ₃ (1.0mAn ol/L hexane solution), and the reaction was carried out at 80 ℃ under an ethylene pressure of 10atm with stirring for 30min. 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

A1L stainless steel polymerization vessel equipped with mechanical stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced with nitrogen 3 times. Into the polymerization system was charged 500mL of hexane, while 13.0mg (20. Mu. Mol) of complex 5 represented by the formula (5), 17.1mL (100 mmol) of 2-methyl-2-hydroxy-7-octene, 100mL of AlEt ₃ (1.0 mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an 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.

Comparative example 1

A1L stainless steel polymerization vessel equipped with mechanical stirring was dried continuously at 130 ℃ for 6 hours, evacuated while hot and replaced with nitrogen 3 times. Into the polymerization system was charged 500mL of hexane, while 13.2mg (20. Mu. Mol) of complex 1 represented by the formula (1), 30mmol (6.0 mL) of 10-undecen-1-ol, 30mL of AlEt-1-ol ₃ (1.0 mol/L hexane solution), and the reaction was stirred at 80 ℃ for 30min while maintaining an 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.

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 13.2mg (20. Mu. Mol) of the complex 1 represented by the formula (1) was added thereto, 30mmol (5.1 mL)2-methyl-2-hydroxy-7-octene, 30mL of AlEt ₃ (1.0 mol/L hexane solution), and the reaction was carried out at 80 ℃ under an ethylene pressure of 10atm with stirring for 30min. 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 can catalyze the copolymerization of ethylene and enol with high activity, and the molecular weight of the obtained polymer can be regulated by adding a chain transfer agent. The copolymerization activity of the catalyst can reach 1.25 x 105 g/mol at most ^-1 (M)·h ^-1 . In addition, by regulating and controlling the polymerization conditions, a spherical 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 in relation to an exemplary embodiment, and it is understood that 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

1. A method of making an olefin-olefin alcohol copolymer comprising: in the presence of an alkane solvent, enabling olefin and alkene alcohol shown in a formula I to contact and react with a catalyst and an optional chain transfer agent at the reaction temperature of 10-100 ℃ to obtain the copolymer;

the olefin is ethylene or alpha-olefin with 3-16 carbon atoms;

formula I

In the formula I, L1-L3 are respectively and independently selected from H or C ₁ -C ₃₀ Alkyl radical, said C ₁ -C ₃₀ Alkyl is optionally substituted by a substituent selected from halogen, C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₆ -C ₁₀ One or more of aryl groups; l4 is C having a pendant group ₁ -C ₃₀ Alkylene, the side group in L4 is selected from halogen and C ₆ -C ₂₀ Aryl radical, C ₁ -C ₂₀ Alkyl, hydroxy-substituted C ₁ -C ₂₀ Alkyl and alkoxy substituted C ₁ -C ₂₀ One or more of alkyl;

the catalyst is selected from metal complexes shown in a formula II:

formula II

In the formula II, M is a metal in a VIII group; r is _n Wherein each R is independently selected from H, halogen, O, N, P, C ₁ -C ₃₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₃₀ Hydrocarbyl, each R optionally forming a ring with each other, n =0-4; r is ₁ 、R ₂ Each independently selected from H, halogen, O, N, P and C ₁ -C ₃₀ A hydrocarbyl group; r ₃ Selected from H, halogen, O, P, C ₁ -C ₃₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₃₀ A hydrocarbyl group; r is ₄ Is C containing at least one element selected from O, N, P and S ₁ -C ₃₀ A compound is provided.

2. The process according to claim 1, wherein in the formula I, L1 and L2 are H, and L3 is H or C ₁ -C ₁₀ Alkyl or halogen substituted C ₁ -C ₁₀ Alkyl radical(ii) a L4 is C having a pendant group ₁ -C ₂₀ An alkylene group.

3. The process according to claim 2, wherein in the formula I, L3 is H or C ₁ -C ₁₀ An alkyl group.

4. The method of claim 1, wherein the pendant group in L4 in formula i is selected from the group consisting of halogen, C ₆ -C ₂₀ Aryl radical, C ₁ -C ₁₀ Alkyl, hydroxy-substituted C ₁ -C ₁₀ Alkyl and alkoxy substituted C _1-10 One or more of alkyl groups.

5. The process according to claim 1, wherein in the formula II, M is nickel or palladium; r _n Each R in (A) is independently selected from H, halogen and C containing at least one silicon atom ₁ -C ₃₀ (ii) hydrocarbyl, each R optionally forming a ring with each other, n =1-4; r ₁ 、R ₂ Each independently selected from C ₁ -C ₃₀ A hydrocarbyl group; r ₃ Is selected from C ₁ -C ₃₀ Hydrocarbyl and C containing at least one silicon atom ₁ -C ₃₀ A hydrocarbyl group; r ₄ Is C containing at least one element selected from O, N, P and S ₁ -C ₂₀ A compound is provided.

6. The method of claim 1, wherein the reaction conditions include: the reaction time is 10min-200min.

7. The method of claim 6, wherein the reaction conditions comprise: the reaction time is 20min-60min.

8. The production method according to any one of claims 1 to 7, wherein the obtained olefin-olefin alcohol copolymer comprises a spherical and/or spheroidal polymer.

9. The method of claim 8, wherein the spherical and/or spheroidal polymer has an average particle size of 0.1mm to 50.0mm.

10. The process according to claim 1, wherein the olefin-olefin alcohol copolymer obtained contains a structural unit derived from the olefin alcohol represented by the formula I in an amount of 0.4mol% to 15.0mol%.

11. The method according to claim 10, wherein the structural unit derived from the olefin alcohol represented by the formula i is contained in an amount of 0.5mol% to 13.0mol% in the obtained olefin-olefin alcohol copolymer.