CN115353586A - Preparation method of linear copolymer - Google Patents
Preparation method of linear copolymer Download PDFInfo
- Publication number
- CN115353586A CN115353586A CN202211176252.0A CN202211176252A CN115353586A CN 115353586 A CN115353586 A CN 115353586A CN 202211176252 A CN202211176252 A CN 202211176252A CN 115353586 A CN115353586 A CN 115353586A
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- Prior art keywords
- solvent
- conjugated diene
- ethyl
- butyl
- reaction
- Prior art date
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- 229920005684 linear copolymer Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 150000001993 dienes Chemical class 0.000 claims abstract description 62
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 239000002904 solvent Substances 0.000 claims abstract description 57
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 26
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 229920005603 alternating copolymer Polymers 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
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- 238000003756 stirring Methods 0.000 claims description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 9
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
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- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 8
- -1 azo compound Chemical class 0.000 claims description 8
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 0.000 claims description 6
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 claims description 6
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 claims description 6
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 5
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- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 4
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 claims description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 claims description 3
- MLLAPOCBLWUFAP-UHFFFAOYSA-N 3-Methylbutyl benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1 MLLAPOCBLWUFAP-UHFFFAOYSA-N 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
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- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
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- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical class CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- APPOKADJQUIAHP-UHFFFAOYSA-N hexa-2,4-diene Chemical class CC=CC=CC APPOKADJQUIAHP-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000021178 picnic Nutrition 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a process for the preparation of linear copolymers by a precipitation polymerization process to obtain linear copolymers of a conjugated diene and an electron accepting monomer by carrying out the polymerization reaction using a suitable solvent system, a suitable feeding method and in the presence of a suitable initiator at a suitable temperature.
Description
Technical Field
The invention belongs to the field of polymer preparation methods, and particularly relates to a preparation method of a linear copolymer.
Background
Maleic anhydride is a typical electron accepting monomer. The conjugated diene-maleic anhydride copolymer is an important high molecular material and is widely applied to the fields of latex paint, modifier of adhesive, dispersant of pigment, compatilizer of rubber and plastic and the like.
The current focus of research on conjugated diene-maleic anhydride copolymers is the grafting of maleic anhydride (Mah) onto homopolymers and copolymers of conjugated dienes. For example, in non-patent document 1, the graft reaction between polybutadiene and maleic anhydride is carried out at a high temperature (180 to 200 ℃) for 4 to 5 hours. In non-patent document 2, maleic anhydride graft modification of polybutadiene is performed in a solution using xylene as a solvent and benzoyl peroxide as an initiator.
The preparation method of the conjugated diene-maleic anhydride copolymer at present mainly adopts free radical polymerization, and a small amount of the conjugated diene-maleic anhydride copolymer adopts coordination polymerization. Free radical polymerization is currently the predominant method for preparing conjugated diene-maleic anhydride copolymers. For example, in non-patent document 3, a maleic anhydride/isoprene alternating copolymer in which the diene structure is a high cis-1,4-structure is obtained at 80 ℃ using cyclohexanone as a solvent.
In patent documents 1 to 5, a linear copolymer of a conjugated diene and maleic anhydride is prepared by using an initiator such as dibenzoyl peroxide, azobisisobutyronitrile, or lauroyl peroxide and selecting a polar solvent such as tetrahydrofuran, dioxane, acetone, or N, N-dimethylformamide at 60 to 150 ℃.
In non-patent document 4, nd (naph) 3 -AlEt 3 A catalytic system, toluene/dioxane is used as a mixed solvent, the set temperature is 5 ℃, and the maleic anhydride-isoprene alternating copolymer is prepared after 2h of reaction. In non-patent document 5, fe (acac) is a bimetallic system 3 -Al(i-Bu) 3 As a catalyst, toluene/dioxane is used as a mixed solvent, the temperature is set to be 20 ℃, and the maleic anhydride-isoprene copolymer is prepared after 2h of reaction.
Patent document 6 discloses a self-stabilized precipitation polymerization method for producing a crosslinked copolymer of a conjugated diene and maleic anhydride, which is insoluble in acetone, tetrahydrofuran, and N, N-dimethylformamide, by reacting an initiator such as dibenzoyl peroxide, azobisisobutyronitrile, and lauroyl peroxide at 50 to 90 ℃ for 0.5 to 73 hours and selecting a solvent such as isoamyl acetate, butyl acetate, and ethyl butyrate.
The cited documents are:
non-patent literature:
non-patent document 1: hexuan, xuewangman, etc. "research on grafting liquid polybutadiene with an electronic monomer", anhui chemical, 1998, no. 3, pages 32 to 34;
non-patent document 2: nihon, lixudong, et al, "study of low relative molecular weight trans-polybutadiene grafted electron-accepting monomers", elastomers, 2004, no. 5, 11-15;
non-patent document 3: trivedi, B.M.Culbertson, maleic Anhydride, plenum Press, new York,1982, pp.344;
non-patent document 4: picnic, zhanyifeng, etc. "rare earth catalyzed isoprene-electron accepting monomer alternate copolymerization", journal of higher school chemistry, 2001, 6 th, pages 1049-1052;
non-patent document 5: huanjianghua, yangkofang, etc. "Fe (acac) 3 -Al(i-Bu) 3 Research on the copolymerization of an electron-accepting monomer and isoprene, 2006, 1 st stage, pages 36 to 39 of Polymer science and engineering.
Patent documents:
patent document 1: US 3491068A;
patent document 2: US 3773727A;
patent document 3: CA 848513A;
patent document 4: CA 852293A;
patent document 5: CA 867843A;
patent document 6: CN 101781387A.
Disclosure of Invention
Problems to be solved by the invention
The series of methods in patent documents 1 to 5 is solution polymerization, and the post-treatment process is complicated and expensive. The methods of non-patent documents 4 and 5 use solvents that are highly toxic and require the introduction of metal catalysts, and the catalytic systems are complicated and expensive. Patent document 6 discloses a crosslinked copolymer which is insoluble in solvents such as acetone, tetrahydrofuran, and N, N-dimethylformamide.
Therefore, in the copolymerization method of conjugated diene and electron accepting monomer in the prior art, the preparation of the linear copolymer is usually carried out by metal catalysis and solution polymerization, which increases the difficulty for the purification treatment and practical application of the subsequent polymer, increases the economic cost and aggravates the environmental pollution. The copolymers obtained in the precipitation polymerization process tend to form crosslinked systems, which limits subsequent applications.
Therefore, it is highly desirable to develop a method for preparing a linear copolymer of conjugated diene and electron accepting monomer, which does not require the use of a catalyst, is easy to post-treat the polymer, is low in cost, and is environmentally friendly.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the above-mentioned technical problems and found that a linear copolymer of a conjugated diene and an electron accepting monomer can be prepared by a precipitation polymerization method using a suitable solvent system, a suitable feeding method and carrying out a polymerization reaction at a suitable temperature in the presence of a suitable initiator.
Specifically, the present invention solves the problems of the present invention by the following means.
[1] A process for the preparation of a linear copolymer, comprising the steps of:
at the reaction temperature, adding the conjugated diene solution into the electron-accepting monomer solution within the feeding time to carry out polymerization reaction;
wherein the reaction temperature is 90-170 ℃, and the charging time is more than 0.1 hour;
the electron accepting monomer solution comprises an electron accepting monomer and a solvent A, wherein the solvent A is organic alkanoate, and the electron accepting monomer is one or more selected from maleic anhydride, itaconic anhydride and derivatives thereof;
the conjugated diene solution comprises conjugated diene, a solvent B and an initiator, wherein the solvent B is a polar solvent containing oxygen atoms in molecules, and the half-life period of the initiator at the reaction temperature is less than 3 hours.
[2] The production method according to [1], wherein the addition is a batch addition or a continuous addition, and the batch addition is a step of adding the conjugated diene solution to the electron-accepting monomer solution in 4 or more times.
[3] The production process according to [1] or [2], characterized in that the conjugated diene is one or more selected from conjugated dienes having 4 to 60 carbon atoms, which preferably has a structure represented by the following formula (1):
in the formula (1), R and R 1 、R 2 、R 3 Represent, identically or differently, hydrogen, halogen, alkyl, alkoxy or aryl, wherein the alkyl and alkoxy groups independently of one another have from 1 to 40, preferably from 1 to 20, more preferably from 1 to 8, carbon atoms and the aryl group has from 4 to 40, preferably from 6 to 20, carbon atoms;
more preferably, the conjugated diene is one or more selected from optionally mono-or poly-substituted butadiene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 4-hexadiene, wherein the substituents are independently one or more selected from halogen, C1-C10 alkyl, C1-C10 alkoxy and phenyl.
[4] The production method according to [1] or [2], characterized in that the organic alkanoic acid ester has a structure represented by the following formula (2):
in the formula (2), R 4 Is a hydrogen atom, a C1-C5 alkyl group, a phenyl group or a benzyl group, R 5 Is C1-C5 alkyl, phenyl or benzyl;
preferably, the organic alkanoic acid ester is one or more selected from the group consisting of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.
[5] The production method according to [1] or [2], characterized in that the polar solvent containing an oxygen atom in a molecule is one or more selected from a ketone solvent, an ester solvent, an ether solvent and an amide solvent; preferably one or more selected from the group consisting of acetone, cyclohexanone, butanone, ethyl acetate, ethyl butyrate, dioxane, tetrahydrofuran, N-dimethylformamide, dipropyl ether, dibutyl ether, dimethyl ether of ethylene glycol or dimethyl ether of diethylene glycol, methyl tert-butyl ether, and derivatives thereof; more preferably one or more selected from tetrahydrofuran, acetone, dioxane.
[6] The production method according to [1] or [2], characterized in that the half-life of the initiator at the reaction temperature is 2 hours or less, preferably 1 hour or less, more preferably 0.5 hour or less; the initiator is preferably one or more selected from organic peroxides and azo compounds, the organic peroxide is preferably dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; the azo compound is preferably azobisisobutyronitrile, azobisisoheptonitrile; the amount of the initiator is 0.01 to 10% by mass, preferably 1.2 to 3.2% by mass, based on the conjugated diene.
[7] The production process according to [1] or [2], characterized in that the molar ratio of the electron accepting monomer to the conjugated diene in the reaction system is 5:1 to 1:1, the total mass concentration of the conjugated diene and the electron accepting monomer in the reaction system is 0.6 to 50%, preferably 1 to 40%, more preferably 2 to 30%.
[8] The process according to item [1] or item [2], wherein after the completion of the addition of the conjugated diene solution, the mass of the solvent A in the reaction system is 25% to 75% relative to the total mass of the solvent A and the solvent B.
[9] The production method according to [1] or [2], characterized in that the polymerization reaction is carried out under stirring; the polymerization reaction is carried out in an inert atmosphere; the reaction temperature is 90-120 ℃; the reaction time is 0.1 to 48 hours, preferably 0.2 to 10 hours, more preferably 0.5 to 8 hours; the production method further comprises a step of separating the obtained polymer from the reaction system, preferably by centrifugation or filtration.
[10] A linear copolymer obtained by the production method according to any one of [1] to [9], which is an alternating copolymer having a cis-1, 4-diene content of 75% or more and a gel fraction of 10% or less.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymerization method is precipitation polymerization, the obtained polymer has a clean surface, the separation and purification operations of the polymer are simple, the cost is low, and the method is environment-friendly.
The polymer obtained by the method is a linear alternating copolymer, can be dissolved in strong polar solvents such as acetone, tetrahydrofuran, N-dimethylformamide and the like, and has wide application prospect.
Drawings
FIG. 1 shows a butadiene-maleic anhydride linear alternating copolymer obtained in example 1 1 H-NMR spectrum;
FIG. 2 is an IR spectrum of a butadiene-maleic anhydride linear alternating copolymer obtained in example 1;
FIG. 3 is a photograph of the reaction system after the polymerization reaction in example 1 was completed;
FIG. 4 is a photograph showing a solubility test of the butadiene-maleic anhydride linear alternating copolymer obtained in example 1;
FIG. 5 is a photograph of a butadiene-maleic anhydride linear alternating copolymer obtained in example 1.
Detailed Description
< terms and definitions >
In the present specification, the term "alkyl" includes straight-chain, branched-chain or cyclic alkyl groups unless explicitly stated otherwise.
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end points of numerical values a and B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the use of "optionally" or "optional" means that certain materials, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and "%" used means weight or mass% unless otherwise specified.
Reference throughout this specification to "a preferred embodiment," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< method for producing Linear copolymer >
The object of the present invention is to provide a process for the preparation of a linear copolymer comprising the steps of:
at the reaction temperature, adding the conjugated diene solution into the electron accepting monomer solution for polymerization reaction within the feeding time;
wherein the reaction temperature is 90-170 ℃, and the charging time is more than 0.1 hour;
the electron accepting monomer solution comprises an electron accepting monomer and a solvent A, wherein the solvent A is organic alkanoate, and the electron accepting monomer is one or more selected from maleic anhydride, itaconic anhydride and derivatives thereof;
the conjugated diene solution comprises conjugated diene, a solvent B and an initiator, wherein the solvent B is a polar solvent containing oxygen atoms in molecules, and the half life of the initiator at the reaction temperature is less than 3 hours.
The preparation method of the invention realizes the precipitation polymerization reaction of the conjugated diene and the electron accepting monomer by selecting a proper solvent system, a proper feeding method and in the presence of a proper temperature and a proper initiator. The polymer precipitate obtained by the precipitation polymerization system of the invention has clean surface, and can be separated to obtain the solid product of the copolymer by centrifugation or filtration, wherein the polymer precipitate is a linear alternating copolymer of conjugated diene and electron accepting monomer, and can be dissolved in strong polar solvents such as acetone, tetrahydrofuran, N-dimethylformamide and the like.
The preparation process of the present invention will be described in detail below in terms of monomers, solvent systems, methods of feeding, initiators, reaction conditions, and the like, respectively.
Monomer
The monomers in the preparation process of the present invention include conjugated diolefin and electron accepting monomers, and optionally other monomers.
The conjugated diene used in the present invention is not particularly limited, and may be any conjugated diene capable of being copolymerized with an electron accepting monomer in the art.
In one embodiment, the electron accepting monomer is one or more selected from the group consisting of maleic anhydride, itaconic anhydride, and derivatives thereof. Electron accepting monomers have in common that the carbon-carbon double bond is linked to one or more electron withdrawing groups and therefore have similar properties in polymerizing with the conjugated diene. Examples of electron accepting monomers include, but are not limited to, maleic anhydride, itaconic anhydride, and esters, imides, amides derivatives of maleic anhydride and itaconic anhydride, and the like.
In one embodiment, the conjugated diene is one or more selected from conjugated dienes having 4 to 60 carbon atoms, preferably 4 to 40 carbon atoms, more preferably 4 to 20 carbon atoms, and still more preferably 4 to 10 carbon atoms.
In a preferred embodiment, the conjugated diene has the structure shown in the following formula (1):
in the formula (1), R and R 1 、R 2 、R 3 Represent, identically or differently, hydrogen, halogen, alkyl, alkoxy or aryl, wherein the alkyl and alkoxy groups independently of one another have from 1 to 40, preferably from 1 to 20, more preferably from 1 to 8, carbon atoms and the aryl group has from 4 to 40, preferably from 6 to 20, carbon atoms.
Preferably, in formula (1), R 1 、R 2 、R 3 The same or different represent hydrogen, halogen, C1-C5 alkyl, phenyl, alkylphenyl; the C1-C5 alkyl groups are more preferably methyl, ethyl, propyl, butyl and pentyl; the alkylphenyl group is preferably a benzyl group, a dimethylphenyl group, an ethylphenyl group, a diethylphenyl group or the like.
In a more preferred embodiment, the conjugated diene is one or more selected from optionally mono-or poly-substituted butadienes, 1, 3-pentadienes, 1, 3-hexadienes and 2, 4-hexadienes, wherein the substituents are independently from each other one or more selected from halogen, C1-C10 alkyl, C1-C10 alkoxy and phenyl.
In a more specific embodiment, the conjugated diene is one or more selected from the group consisting of butadiene, isoprene, 2-chloro-1, 3-butadiene, 2, 3-dichlorobutadiene, 2, 3-dimethylbutadiene, piperylene, 2, 4-hexadiene, 2-methyl-1, 3-pentadiene, 2-ethyl-1, 3-butadiene, 2-propyl-1, 3-butadiene, 2-phenyl-1, 3-butadiene, 3-methyl-1, 3-pentadiene, 2-methyl-1, 3-hexadiene, 1-methoxy-1, 3-butadiene.
In one embodiment, the molar ratio of electron accepting monomer to conjugated diene in the reaction system is 5:1 to 1:5, preferably 1.2:1 to 1:1.
in one embodiment, the total mass concentration of the conjugated diene and the electron accepting monomer in the reaction system is from 0.6 to 50%, preferably from 1 to 40%, more preferably from 2 to 30%.
In the present specification, the "reaction system" refers to a system composed of an electron accepting monomer solution and a conjugated diene solution.
Solvent system
In the present specification, the "solvent system" is composed of a solvent a and a solvent B. The solvent A, the solvent B and the solvent system have good dissolving effect on the electron-accepting monomer, the conjugated diene monomer and the initiator, so as to ensure that the reaction system is a homogeneous system before reaction. Meanwhile, the copolymer generated by the polymerization reaction cannot be dissolved by the solvent system, so that the macromolecular chain can be precipitated from the solvent system after reaching a certain critical length.
The preparation process of the present invention also optionally comprises a step of dissolving the electron accepting monomer in the solvent a, for example adding the electron accepting monomer to the solvent a and optionally stirring and/or heating to completely dissolve it.
The solvent a used in the preparation method of the present invention is an organic alkanoate, which is one or more selected from compounds having a structure represented by the following formula (2):
in the formula (2), R 4 Is a hydrogen atom, a C1-C5 alkyl group, a phenyl group or a benzyl group, R 5 Is C1-C5 alkyl, phenyl or benzyl.
Preferably, R is taken in combination from the aspects of polarity, solubility parameter and viscosity 4 Is a C1-C5 alkyl group such as methyl, ethyl, propyl, butyl, pentyl, isopentyl, and the like. R is 5 Preferably methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, pentyl, isopentyl, phenyl, benzyl, etc.
In specific embodiments, the organic alkanoic acid ester is one or more selected from the group consisting of ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.
The preparation process of the present invention also optionally comprises a step of dissolving the conjugated diene and the initiator in the solvent B, for example adding the conjugated diene and the initiator to the solvent B and optionally stirring and/or heating to completely dissolve them.
The solvent B is a polar solvent containing oxygen atoms in molecules, and the polar solvent containing oxygen atoms in molecules is one or more selected from ketone, ester, ether and amide solvents; preferably one or more selected from the group consisting of acetone, cyclohexanone, butanone, ethyl acetate, ethyl butyrate, dioxane, tetrahydrofuran, N-dimethylformamide, dipropyl ether, dibutyl ether, dimethyl ether of ethylene glycol or dimethyl ether of diethylene glycol, methyl tert-butyl ether, and derivatives thereof; more preferably one or more selected from tetrahydrofuran, acetone, dioxane.
In one embodiment, solvent a and solvent B may be the same or different.
In one embodiment, the content of solvent a is between 25% and 75% by mass, preferably between 25 and 65% by mass, relative to the total mass of the solvent system.
Charging method
In the preparation method of the invention, the conjugated diene solution is added into the electron accepting monomer solution in batches or continuously during the feeding time for polymerization reaction. The inventors have found that by this stepwise feeding of the invention, linear copolymers of conjugated diolefins and electron accepting monomers can be obtained.
In the embodiment of the batchwise addition, the conjugated diene solution may be added to the electron accepting monomer solution in a plurality of times, for example, 4 times or more, for example, 6 times or more, 8 times or more, 10 times or more, within the addition time, the amount of the conjugated diene solution added in each time may be the same or different, and the interval time between the two adjacent additions may be the same or different.
In the continuous feeding embodiment, the conjugated diene solution may be continuously fed to the electron accepting monomer solution over a feeding time, and the feeding rate may be constant or may be varied.
In the production method of the present invention, the charging time is usually 0.1 hour or more. From the viewpoint of production efficiency, the charging time is usually 20 hours or less, preferably 15 hours or less, more preferably 10 hours or less, for example, 8 hours or less or 7 hours or less.
Initiator
In the production method of the present invention, the half-life of the initiator used at the reaction temperature is 3 hours or less, preferably 2 hours or less, more preferably 1 hour or less, and most preferably 0.5 hour or less. The rapid decomposition of the initiator is beneficial to the production efficiency and the stability of the product batch, and more importantly, the yield of the linear polymer is improved and the gel rate is reduced.
The present invention is not particularly limited with respect to the kind of the initiator, and it may be any initiator suitable for copolymerization of the conjugated diene and the electron accepting monomer in the art, such as a conventional thermal decomposition type initiator.
In one embodiment, the initiator is preferably one or more selected from the group consisting of organic peroxides, preferably dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; the azo compound is preferably azobisisobutyronitrile or azobisisoheptonitrile.
In one embodiment, the initiator is present in an amount of 0.01 to 10%, preferably 1.2 to 3.2%, relative to the mass of the conjugated diene.
Reaction conditions
In the preparation method of the invention, the reaction temperature is 90-170 ℃, preferably 90-120 ℃.
In the production method of the present invention, the polymerization reaction may be carried out with or without stirring.
In the production method of the present invention, the polymerization reaction is preferably carried out in an inert atmosphere, for example, an atmosphere of nitrogen or argon, to ensure an oxygen-free environment, but the reaction may be carried out in an atmosphere containing air or oxygen.
In the production method of the present invention, the reaction time may be 0.1 to 48 hours, preferably 0.2 to 10 hours, and more preferably 0.5 to 8 hours.
In one embodiment, the production method of the present invention further comprises a step of separating the obtained polymer from the reaction system, preferably by centrifugation or filtration.
In one embodiment, the preparation method of the present invention further comprises a step of purifying, drying, etc. the obtained polymer.
In a specific embodiment, the preparation method of the present invention comprises the steps of:
adding an electron accepting monomer and a solvent A into a reactor, so that the electron accepting monomer is completely dissolved in the solvent A to form a clear, transparent and homogeneous electron accepting monomer solution;
removing oxygen in the reactor, and heating the electron accepting monomer solution to the reaction temperature;
dissolving conjugated diene and an initiator in a solvent B to obtain a conjugated diene solution;
optionally removing oxygen from the conjugated diene solution;
adding the conjugated diene solution into the electron-accepting monomer solution within the charging time;
carrying out polymerization reaction under the condition of maintaining stirring;
optionally, the solid product obtained after the completion of the reaction is separated from the reaction system by centrifugation or filtration.
Wherein the reactor is preferably equipped with a condenser, a stirrer, a nitrogen blanket and a thermometer; the electron accepting monomer solution may be heated to the reaction temperature by a water or oil bath and maintained during the polymerization reaction; oxygen can be removed by repeated vacuum-inert gas passes.
In the preparation method of the present invention, as the polymerization reaction proceeds, the polymer chain grows to a critical length and precipitates from the solvent system, and a pale yellow/white colloidal copolymer is observed to precipitate.
The present invention accordingly relates to a linear copolymer obtained by the preparation process according to the invention, said linear copolymer being an alternating copolymer having a cis-1, 4-diene content of more than 75% and a gel fraction of less than 10%.
The "gel fraction" described in the present specification can be measured by the method described in the examples section below.
Examples
The present invention will be described in more detail with reference to specific examples. The examples are merely illustrative of the invention and are not to be construed as limiting the invention. Practical application examples of the embodiments are easily grasped and verified by those skilled in the art. If certain changes were made in the light of the present invention, then it would be obvious that such changes would not be covered by the present invention.
Example 1
Under nitrogen protection with stirring, monomeric maleic anhydride (11.81 g) was added to isoamyl acetate (29.8 g) to dissolve thoroughly, and the resulting maleic anhydride solution was stirred continuously and heated to 90 ℃ with water bath heating. Butadiene (6.5 g) and azobisisobutyronitrile (0.14 g) were dissolved in tetrahydrofuran (43.5 g) to obtain a butadiene solution. The obtained butadiene solution was added dropwise at a constant rate to the maleic anhydride solution over a period of 5.5 hours, and after completion of the addition, the reaction was maintained at 90 ℃ for 6 hours. After the completion of the reaction, the reaction system was centrifuged to obtain 10.899g of polymer 1 in a yield of 59.1% and a gel fraction of 1.2%.
As can be seen from FIG. 5, the butadiene-maleic anhydride linear alternating copolymer prepared by the method of the present invention has a white powder sample and good properties.
Examples 2 to 8
Polymers were prepared in a similar manner to example 1, following the starting materials, amounts, reaction conditions, and the like in table 1.
TABLE 1
The abbreviations in table 1 have the following meanings:
and Mah: an electron-accepting monomer;
BD: butadiene;
AIBN: azobisisobutyronitrile;
BPO: benzoyl peroxide;
IAAC: isoamyl acetate;
EB: ethyl butyrate;
BA: butyl acetate;
EH: ethyl heptanoate;
THF: tetrahydrofuran (THF)
Diox: dioxane (dioxane)
AC: acetone (II)
Comparative example 1:
butadiene (0.7505 g) was dissolved in toluene (4.2527 g) with stirring and under nitrogen to give a butadiene/toluene solution. Butadiene/toluene solution, monomeric maleic anhydride (1.3584 g) and dibenzoyl peroxide (0.1496 g) were added to isoamyl acetate (4.1978 g) and dissolved thoroughly, with constant stirring and heated to 95 ℃ with heating in a water bath for 5min. After the reaction was completed, the reaction system was subjected to centrifugal separation to obtain 0.9391g of polymer 9, the yield was 41.6%, and the gel content was 98.1%.
Comparative example 2:
butadiene (0.7519 g) was dissolved in toluene (4.2607 g) with stirring and under nitrogen to give a butadiene/toluene solution. Butadiene/toluene solution, monomeric maleic anhydride (1.3572 g) and azobisisobutyronitrile (0.1470 g) were added to isoamyl acetate (4.1992 g) and dissolved thoroughly, stirred continuously and heated to 95 ℃ with heating in a water bath for 5min. After the completion of the reaction, the reaction system was subjected to centrifugal separation to obtain 0.8275g of Polymer 10, yield 36.6%, gel content 91.0%.
Comparative example 3:
under the protection of nitrogen and with stirring, monomer maleic anhydride (1.3619 g) is added into isoamyl acetate (4.1996 g) to be fully dissolved, and the obtained maleic anhydride solution is continuously stirred and heated to 122 ℃ by adopting water bath heating. Butadiene (0.7523 g) and dibenzoyl peroxide (0.0145 g) were dissolved in toluene (4.2628 g) to obtain a butadiene solution. The obtained butadiene solution was added dropwise at a constant rate to the maleic anhydride solution over 0.5 hour, and after completion of the addition, the reaction was maintained at 122 ℃ for 1 hour. After the completion of the reaction, the reaction system was subjected to centrifugal separation to obtain 0.7136g of polymer 11, yield 33.0%, gel fraction 72.8%.
Testing and evaluation
1) Nuclear magnetic spectrum
The butadiene-maleic anhydride linear alternating copolymer obtained in example 1 was subjected to a Bruker AV600MHz NMR spectrometer 1 H-NMR measurement, the spectrum is shown in figure 1. As can be seen from FIG. 1, a typical characteristic peak of 1,4 double bonds is at 5.69ppm, a typical characteristic peak of methine maleic anhydride is at 3.21ppm, a characteristic peak of main chain methylene is at 2.60ppm, and the integrated area of each peak strictly follows 1:1:2, indicating that a typical alternating copolymer is obtained for example 1.
2) Infrared spectrogram
The butadiene-maleic anhydride linear alternating copolymer obtained in example 1 was dried in vacuum and then tableted with KBr, followed by infrared measurement on an FTIR670 type infrared spectrometer from Nexus, USA, and the infrared spectrum is shown in FIG. 2. As can be seen from FIG. 2, 2928cm of it -1 Is C-H stretching vibration peak, 1852, 1769cm -1 Is the characteristic peak of the five-membered cyclic anhydride, 1215, 1063cm -1 Is carbonyl CO-O, O-C-C stretching vibration peak, 917cm -1 Is a C-O-C stretching vibration peak, which proves that a maleic anhydride group exists in the polymer chain while 1437cm -1 is-CH 2 Double bond stretching vibration peak of-C = C-, which proves that 1,4 diene structure exists in the main chain of the polymer, and 727cm -1 The peak is a cis-1,4 structure characteristic peak, which proves that the main chain contains a cis-diene structure.
3) Elemental analysis
The butadiene-maleic anhydride linear alternating copolymers obtained in examples 1 and 3 were subjected to elemental analysis using a Vario EL type iii elemental analyzer of germany elemental analysis systems. The test method comprises the following steps: after the copolymer was purified and dried in vacuo, a small amount of the powder was taken, wrapped with a tin boat, and subjected to elemental analysis on an elemental analyzer, the results of which are shown in table 2.
TABLE 2
C element (%) | H element (%) | |
Example 1 | 60.64 | 5.257 |
Example 3 | 60.49 | 5.238 |
Calculation according to the data of table 2 gives a content of maleic anhydride-derived structures (Mah structures) in the polymer of about 50%, which is a typical alternating copolymer.
4) Solubility test
0.5g of the butadiene-maleic anhydride linear alternating copolymer obtained in example 1 was added to 15ml of tetrahydrofuran, and stirred at 25 ℃ for 1 minute, and the dissolution of the polymer was observed as shown in FIG. 4.
As can be seen from fig. 4, the polymer was completely dissolved in tetrahydrofuran, which indicates that the preparation method of the present invention resulted in a polymer having high solubility in polar solvents.
5) Gel fraction test
0.5g of the butadiene-maleic anhydride linear alternating copolymer obtained in example was added to 15ml of tetrahydrofuran, and immersed in 24h at room temperature, 5000rpm/min (20 min), and centrifuged to separate an undissolved portion, which was dried and weighed to obtain the mass of the undissolved portion, and the gel fraction was calculated according to the following formula, and the results are shown in Table 3:
gel fraction = mass of undissolved fraction/initial mass (0.5 g)
TABLE 3
Numbering | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
Gel fraction (%) | 1.2 | 2.7 | 0.2 | 0.0 | 4.6 | 7.0 | 2.0 | 1.0 | 98.1 | 91.0 | 72.8 |
As can be seen from the results in Table 3, the copolymers obtained in examples 1 to 8 had a low gel fraction, indicating a high degree of linearity. In contrast, the copolymers obtained in comparative examples 1 to 3 had a high gel fraction, indicating a high degree of crosslinking.
Industrial applicability
The preparation method can be widely used for the industrial preparation of the linear copolymer of the conjugated diene and the electron accepting monomer, and the prepared linear copolymer of the conjugated diene and the electron accepting monomer can be widely used in the fields of latex paint, modifier of adhesive, dispersant of pigment, compatilizer of rubber plastic and the like.
Claims (10)
1. A method for preparing a linear copolymer, comprising the steps of:
at the reaction temperature, adding the conjugated diene solution into the electron accepting monomer solution for polymerization reaction within the feeding time;
wherein the reaction temperature is 90-170 ℃, and the charging time is more than 0.1 hour;
the electron accepting monomer solution comprises an electron accepting monomer and a solvent A, wherein the solvent A is organic alkanoate, and the electron accepting monomer is one or more selected from maleic anhydride, itaconic anhydride and derivatives thereof;
the conjugated diene solution comprises conjugated diene, a solvent B and an initiator, wherein the solvent B is a polar solvent containing oxygen atoms in molecules, and the half-life period of the initiator at the reaction temperature is less than 3 hours.
2. The method according to claim 1, wherein the addition is a batch addition or a continuous addition, and the batch addition is a step of adding the conjugated diene solution to the electron-accepting monomer solution in 4 or more divided portions.
3. The process according to claim 1 or 2, wherein the conjugated diene is one or more selected from conjugated dienes having 4 to 60 carbon atoms, and preferably has a structure represented by the following formula (1):
in the formula (1), R and R 1 、R 2 、R 3 Represent, identically or differently, hydrogen, halogen, alkyl, alkoxy or aryl, wherein the alkyl and alkoxy groups independently of one another have from 1 to 40, preferably from 1 to 20, more preferably from 1 to 8, carbon atoms and the aryl group has from 4 to 40, preferably from 6 to 20, carbon atoms;
more preferably, the conjugated diene is one or more selected from optionally mono-or polysubstituted butadiene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 4-hexadiene, wherein the substituents are independently one or more selected from halogen, C1-C10 alkyl, C1-C10 alkoxy and phenyl.
4. The production method according to claim 1 or 2, characterized in that the organic alkanoic acid ester has a structure represented by the following formula (2):
in the formula (2), R 4 Is a hydrogen atom, a C1-C5 alkyl group, a phenyl group or a benzyl group, R 5 Is C1-C5 alkyl, phenyl or benzyl;
preferably, the organic alkanoic acid ester is one or more selected from the group consisting of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate.
5. The production method according to claim 1 or 2, wherein the polar solvent containing an oxygen atom in a molecule is one or more selected from a ketone solvent, an ester solvent, an ether solvent, and an amide solvent; preferably one or more selected from the group consisting of acetone, cyclohexanone, butanone, ethyl acetate, ethyl butyrate, dioxane, tetrahydrofuran, N-dimethylformamide, dipropyl ether, dibutyl ether, dimethyl ether of ethylene glycol or dimethyl ether of diethylene glycol, methyl tert-butyl ether, and derivatives thereof; more preferably one or more selected from tetrahydrofuran, acetone, dioxane.
6. The production method according to claim 1 or 2, characterized in that the half-life of the initiator at the reaction temperature is 2 hours or less, preferably 1 hour or less, more preferably 0.5 hour or less; the initiator is preferably one or more selected from organic peroxides and azo compounds, the organic peroxide is preferably dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; the azo compound is preferably azobisisobutyronitrile, azobisisoheptonitrile; the amount of the initiator is 0.01 to 10% by mass, preferably 1.2 to 3.2% by mass, based on the conjugated diene.
7. The process according to claim 1 or 2, wherein the molar ratio of the electron accepting monomer to the conjugated diene in the reaction system is from 5:1 to 1: the total mass concentration of the conjugated diolefin and the electron accepting monomer in the reaction system is 0.6 to 50%, preferably 1 to 40%, more preferably 2 to 30%.
8. The process according to claim 1 or 2, wherein the mass of the solvent A in the reaction system after the completion of the addition of the conjugated diene solution is 25 to 75% with respect to the total mass of the solvent A and the solvent B.
9. The production method according to claim 1 or 2, characterized in that the polymerization reaction is carried out under stirring; the polymerization reaction is carried out in an inert atmosphere; the reaction temperature is 90-120 ℃; the reaction time is 0.1 to 48 hours, preferably 0.2 to 10 hours, more preferably 0.5 to 8 hours; the production method further comprises a step of separating the resulting polymer from the reaction system, preferably by centrifugation or filtration.
10. The linear copolymer obtained by the production method according to any one of claims 1 to 9, which is an alternating copolymer having a cis-1, 4-diene content of 75% or more and a gel fraction of 10% or less.
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