JP2023169604A - Method for producing polymer - Google Patents
Method for producing polymer Download PDFInfo
- Publication number
- JP2023169604A JP2023169604A JP2022080826A JP2022080826A JP2023169604A JP 2023169604 A JP2023169604 A JP 2023169604A JP 2022080826 A JP2022080826 A JP 2022080826A JP 2022080826 A JP2022080826 A JP 2022080826A JP 2023169604 A JP2023169604 A JP 2023169604A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- acrylate
- unsaturated bond
- units
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 229920001577 copolymer Polymers 0.000 claims abstract description 97
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 37
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 26
- 238000007112 amidation reaction Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 18
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000178 monomer Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 4
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- -1 hydroxy, amino Chemical group 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 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 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- ASVKKRLMJCWVQF-UHFFFAOYSA-N 3-buten-1-amine Chemical compound NCCC=C ASVKKRLMJCWVQF-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- BUNYBPVXEKRSGY-UHFFFAOYSA-N buta-1,3-dien-1-amine Chemical compound NC=CC=C BUNYBPVXEKRSGY-UHFFFAOYSA-N 0.000 description 1
- LNDKRVOOYMEYTC-UHFFFAOYSA-N buta-1,3-dien-1-ol Chemical compound OC=CC=C LNDKRVOOYMEYTC-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ポリマーの生産方法に関する。 The present invention relates to a method for producing polymers.
不飽和結合を側鎖に有するポリマーは、機能性材料として有用である。例えば、特許文献１では、炭素間二重結合を側鎖に有するポリマーを活性エネルギー線硬化型樹脂として利用している。 Polymers having unsaturated bonds in their side chains are useful as functional materials. For example, in Patent Document 1, a polymer having a carbon-carbon double bond in a side chain is used as an active energy ray-curable resin.
ポリマーに付加価値を付与すべく、不飽和結合をポリマーの側鎖に導入することが求められている。しかし、側鎖に不飽和結合を有するモノマーは架橋反応や重合阻害反応を起こすため、モノマーの重合反応によって不飽和結合を側鎖に有するポリマーを選択的に得ることは難しい。
特許文献１では、エポキシ基含有共重合体を得た後にその共重合体のエポキシ基と、短鎖不飽和カルボン酸および長鎖不飽和カルボン酸を反応させ、不飽和結合をポリマーの側鎖に導入している。そのため、合成工程が煩雑である。
本発明は、不飽和結合を側鎖に有するポリマーを簡便に生産できる生産方法を提供する。
In order to add value to polymers, it is desired to introduce unsaturated bonds into the side chains of polymers. However, since monomers having unsaturated bonds in their side chains cause crosslinking reactions and polymerization inhibition reactions, it is difficult to selectively obtain polymers having unsaturated bonds in their side chains through polymerization reactions of monomers.
In Patent Document 1, after obtaining an epoxy group-containing copolymer, the epoxy group of the copolymer is reacted with a short-chain unsaturated carboxylic acid and a long-chain unsaturated carboxylic acid to form an unsaturated bond in the side chain of the polymer. It has been introduced. Therefore, the synthesis process is complicated.
The present invention provides a production method that can easily produce a polymer having an unsaturated bond in a side chain.
本発明は、下記の態様を有する。
［１］グアニジン有機触媒の存在下で、アクリレートに基づく単位を有する共重合体（Ａ）と不飽和結合含有アルコール（ｂ１）との間でエステル交換反応を行い、不飽和結合を側鎖に有する共重合体（Ｂ１）を得る、ポリマーの生産方法。
［２］グアニジン有機触媒の存在下で、アクリレートに基づく単位を有する共重合体（Ａ）と不飽和結合含有アミン（ｂ２）との間でアミド化反応を行い、不飽和結合を側鎖に有する共重合体（Ｂ２）を得る、ポリマーの生産方法。
［３］前記アクリレートに基づく単位の割合が、前記共重合体（Ａ）の全構成単位に対して１０～８０質量％である、［１］または［２］の生産方法。
［４］前記共重合体（Ａ）の数平均分子量が、３００００以上である、［１］～［３］のいずれかの生産方法。
［５］前記共重合体（Ａ）のガラス転移点が、１０℃以上である、［１］～［４］のいずれかの生産方法。
［６］前記共重合体（Ａ）が、メチルアクリレートに基づく単位とメチルメタクリレートに基づく単位とを有する共重合体、ｎ－ブチルアクリレートに基づく単位とメチルメタクリレートに基づく単位とを有する共重合体およびメチルアクリレートに基づく単位とエチレンに基づく単位とを有する共重合体からなる群から選ばれる少なくとも１種である、［１］～［５］のいずれかの生産方法。
The present invention has the following aspects.
[1] In the presence of a guanidine organic catalyst, a transesterification reaction is carried out between the copolymer (A) having units based on acrylate and the unsaturated bond-containing alcohol (b1), and the unsaturated bond is present in the side chain. A method for producing a polymer to obtain a copolymer (B1).
[2] In the presence of a guanidine organic catalyst, an amidation reaction is carried out between the copolymer (A) having units based on acrylate and the unsaturated bond-containing amine (b2), and the unsaturated bond is present in the side chain. A method for producing a polymer to obtain a copolymer (B2).
[3] The production method according to [1] or [2], wherein the proportion of the acrylate-based units is 10 to 80% by mass based on the total constitutional units of the copolymer (A).
[4] The production method according to any one of [1] to [3], wherein the copolymer (A) has a number average molecular weight of 30,000 or more.
[5] The production method according to any one of [1] to [4], wherein the copolymer (A) has a glass transition point of 10° C. or higher.
[6] The copolymer (A) is a copolymer having a unit based on methyl acrylate and a unit based on methyl methacrylate, a copolymer having a unit based on n-butyl acrylate and a unit based on methyl methacrylate, and The production method according to any one of [1] to [5], wherein the copolymer is at least one selected from the group consisting of copolymers having units based on methyl acrylate and units based on ethylene.
本発明によれば、不飽和結合を側鎖に有するポリマーを簡便に生産できる生産方法が提供される。 According to the present invention, a production method that can easily produce a polymer having an unsaturated bond in a side chain is provided.
本明細書において式（１）で表される化合物を化合物（１）と記す。他の式で表される化合物も同様に記す。
本明細書における以下の用語の意味は以下の通りである。
数平均分子量、ガラス転移点は、実施例に記載の方法によって求められる値である。
数値範囲を示す「～」は、その前後に記載された数値を下限値および上限値として含むことを意味する。
In this specification, the compound represented by formula (1) is referred to as compound (1). Compounds represented by other formulas are also described in the same manner.
The meanings of the following terms in this specification are as follows.
The number average molecular weight and glass transition point are values determined by the method described in Examples.
"~" indicating a numerical range means that the numerical values written before and after it are included as lower and upper limits.
＜第１の態様＞
本発明の第１の態様に係るポリマーの生産方法では、グアニジン有機触媒の存在下で、アクリレートに基づく単位を有する共重合体（Ａ）と、不飽和結合含有アルコール（ｂ１）との間でエステル交換反応を行い、不飽和結合を側鎖に有する共重合体（Ｂ１）を得る。
<First aspect>
In the method for producing a polymer according to the first aspect of the present invention, an ester is formed between a copolymer (A) having units based on acrylate and an unsaturated bond-containing alcohol (b1) in the presence of a guanidine organic catalyst. An exchange reaction is performed to obtain a copolymer (B1) having an unsaturated bond in the side chain.
（共重合体（Ａ））
共重合体（Ａ）は、アクリレートに基づく単位（以下、「アクリレート単位（ａ１）」と記す。）を有する。共重合体（Ａ）は、２種以上のアクリレート単位（ａ１）を有する共重合体であってもよく；アクリレート単位（ａ１）と、アクリレート以外の他のモノマーに基づく単位（以下、「他のモノマー単位（ａ２）」と記す。）と、を有する共重合体であってもよい。また、共重合体（Ａ）は１種を単独で用いてもよく、２種以上を併用してもよい。
(Copolymer (A))
The copolymer (A) has units based on acrylate (hereinafter referred to as "acrylate units (a1)"). The copolymer (A) may be a copolymer having two or more types of acrylate units (a1); acrylate units (a1) and units based on other monomers other than acrylate (hereinafter referred to as "other"). It may be a copolymer having a monomer unit (a2). Moreover, one type of copolymer (A) may be used alone, or two or more types may be used in combination.
アクリレートは、ヒドロキシ基、アミノ基およびエポキシ基を含有しないアクリル酸エステルである。例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸イソプロピル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸イソアミル、アクリル酸ヘキシル、アクリル酸２－エチルヘキシル、アクリル酸オクチル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸イソステアリル、アクリル酸ヘキサデシル、アクリル酸ノニル、アクリル酸イソノニル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸シクロヘキシル、アクリル酸テトラヒドロフルフリル、アクリル酸イソボルニル、アクリル酸３，５，５－トリメチルシクロヘキシル、アクリル酸ジシクロペンタニル、アクリル酸ジシクロペンテニル、アクリル酸ジシクロペンテニルオキシエチル、テルペンアクリレートおよびその誘導体、水添ロジンアクリレートおよびその誘導体、アクリル酸ドコシル、アクリル酸フェニル、アクリル酸２－メトキシエチルが挙げられる。ただし、アクリレートはこれらの例示に何ら限定されない。
アクリレートは１種を単独で用いてもよく、２種以上を併用してもよい。
Acrylates are acrylic acid esters that do not contain hydroxy, amino and epoxy groups. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, acrylic acid Lauryl, stearyl acrylate, isostearyl acrylate, hexadecyl acrylate, nonyl acrylate, isononyl acrylate, phenyl acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 3,5 acrylate , 5-trimethylcyclohexyl, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, terpene acrylate and its derivatives, hydrogenated rosin acrylate and its derivatives, docosyl acrylate, phenyl acrylate, acrylic Examples include 2-methoxyethyl acid. However, acrylates are not limited to these examples.
One type of acrylate may be used alone, or two or more types may be used in combination.
他のモノマーは、アクリレートと共重合可能なモノマーであれば特に限定されない。例えば、エチレン、プロピレン、メタクリレート、スチレンおよびその誘導体、アクリロニトリルが挙げられる。ただし、他のモノマーはこれらの例示に何ら限定されない。
他のモノマーは１種を単独で用いてもよく、２種以上を併用してもよい。
Other monomers are not particularly limited as long as they are monomers copolymerizable with acrylate. Examples include ethylene, propylene, methacrylate, styrene and its derivatives, and acrylonitrile. However, other monomers are not limited to these examples.
One type of other monomers may be used alone, or two or more types may be used in combination.
共重合体（Ａ）としては、下記の共重合体（Ａ１）、共重合体（Ａ２）および共重合体（Ａ３）からなる群から選ばれる少なくとも１種が好ましい。
共重合体（Ａ１）：メチルアクリレートに基づく単位とメチルメタクリレートに基づく単位とを有する共重合体、
共重合体（Ａ２）：ｎ－ブチルアクリレートに基づく単位とメチルメタクリレートに基づく単位とを有する共重合体
共重合体（Ａ３）：メチルアクリレートに基づく単位とエチレンに基づく単位とを有する共重合体。
As the copolymer (A), at least one selected from the group consisting of the following copolymer (A1), copolymer (A2) and copolymer (A3) is preferable.
Copolymer (A1): a copolymer having units based on methyl acrylate and units based on methyl methacrylate,
Copolymer (A2): A copolymer having a unit based on n-butyl acrylate and a unit based on methyl methacrylate. Copolymer (A3): A copolymer having a unit based on methyl acrylate and a unit based on ethylene.
共重合体（Ａ）は２種以上のアクリレート単位（ａ１）を有する共重合体であってもよいが、共重合体（Ａ）が他のモノマー単位（ａ２）を有する場合、アクリレート単位（ａ１）の割合は共重合体（Ａ）の全構成単位に対して５～９９質量％が好ましく、１０～８０質量％がより好ましい。アクリレート単位（ａ１）の割合が前記数値範囲内の下限値以上であると、より多くの不飽和結合を側鎖に有する共重合体が得られやすい。アクリレート単位（ａ１）の割合が前記数値範囲内の上限値以下であると、不飽和結合を側鎖に有する共重合体の収率が向上しやすい。 The copolymer (A) may be a copolymer having two or more types of acrylate units (a1), but when the copolymer (A) has another monomer unit (a2), the acrylate unit (a1) ) is preferably 5 to 99% by mass, more preferably 10 to 80% by mass, based on the total constitutional units of copolymer (A). When the proportion of acrylate units (a1) is at least the lower limit within the above numerical range, a copolymer having more unsaturated bonds in its side chains can be easily obtained. When the proportion of acrylate units (a1) is below the upper limit within the above numerical range, the yield of the copolymer having an unsaturated bond in the side chain tends to improve.
共重合体（Ａ）が他のモノマー単位（ａ２）を有する場合、他のモノマー単位（ａ２）の割合は共重合体（Ａ）の全構成単位に対して１～９５質量％が好ましく、２０～９０質量％がより好ましい。他のモノマー単位（ａ２）の割合が前記数値範囲内の下限値以上であると、不飽和結合を側鎖に有する共重合体の収率が向上しやすい。他のモノマー単位（ａ２）の割合が前記数値範囲内の上限値以下であると、より多くの不飽和結合を側鎖に有する共重合体が得られやすい。 When the copolymer (A) has another monomer unit (a2), the proportion of the other monomer unit (a2) is preferably 1 to 95% by mass based on the total constitutional units of the copolymer (A), and 20 More preferably 90% by mass. When the proportion of other monomer units (a2) is at least the lower limit within the above numerical range, the yield of the copolymer having an unsaturated bond in its side chain tends to improve. When the proportion of other monomer units (a2) is below the upper limit within the above numerical range, a copolymer having more unsaturated bonds in the side chain can be easily obtained.
共重合体（Ａ）の数平均分子量は３００００以上が好ましく、３００００～５０００００がより好ましく、３００００～２０００００がさらに好ましい。共重合体（Ａ）の数平均分子量が３００００以上であると、反応後に得られる共重合体を成型材料、粘接着剤等の用途に適用しやすい。共重合体（Ａ）の数平均分子量が前記数値範囲内の上限値以下であると、反応後に得られる共重合体を塗料等の用途に適用しやすい。 The number average molecular weight of the copolymer (A) is preferably 30,000 or more, more preferably 30,000 to 500,000, and even more preferably 30,000 to 200,000. When the number average molecular weight of the copolymer (A) is 30,000 or more, the copolymer obtained after the reaction can be easily applied to applications such as molding materials and adhesives. When the number average molecular weight of the copolymer (A) is less than or equal to the upper limit within the above numerical range, the copolymer obtained after the reaction can be easily applied to applications such as paints.
前記共重合体（Ａ）のガラス転移点は１０℃以上が好ましく、１０～１５０℃がより好ましく、１０℃～１２０℃がさらに好ましい。ガラス転移点が複数存在する場合は、最も温度の高いガラス転移点を共重合体（Ａ）のガラス転移点とする。共重合体（Ａ）のガラス転移点が１０℃以上であると、反応後に得られる共重合体を成型材料等の用途に適用しやすい。共重合体（Ａ）のガラス転移点が前記数値範囲内の上限値以下であると、反応後に得られる共重合体を塗料、粘接着剤等の用途に適用しやすい。 The glass transition point of the copolymer (A) is preferably 10°C or higher, more preferably 10 to 150°C, even more preferably 10 to 120°C. When there are multiple glass transition points, the glass transition point with the highest temperature is defined as the glass transition point of the copolymer (A). When the glass transition point of the copolymer (A) is 10° C. or higher, the copolymer obtained after the reaction can be easily applied to uses such as molding materials. When the glass transition point of the copolymer (A) is below the upper limit within the above numerical range, the copolymer obtained after the reaction can be easily applied to applications such as paints and adhesives.
（不飽和結合含有アルコール（ｂ１））
不飽和結合含有アルコール（ｂ１）は、不飽和結合を有する１価の炭化水素基を有するアルコールである。不飽和結合の数は特に限定されず、１個でも複数個でもよい。
不飽和結合含有アルコール（ｂ１）としては、例えば、アリルアルコール、３－ブテン－１－オール、４－ペンテン－１－オール、１，３－ブタジエン－１－オール、フルフリルアルコール、ゲラニオール、リナロール、ネロール、シトロネロールが挙げられる。ただし、不飽和結合含有アルコール（ｂ１）はこれらの例示に何ら限定されない。
不飽和結合含有アルコール（ｂ１）は１種を単独で用いてもよく、２種以上を併用してもよい。
(Unsaturated bond-containing alcohol (b1))
The unsaturated bond-containing alcohol (b1) is an alcohol having a monovalent hydrocarbon group having an unsaturated bond. The number of unsaturated bonds is not particularly limited, and may be one or more.
Examples of the unsaturated bond-containing alcohol (b1) include allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 1,3-butadien-1-ol, furfuryl alcohol, geraniol, linalool, Examples include nerol and citronellol. However, the unsaturated bond-containing alcohol (b1) is not limited to these examples at all.
The unsaturated bond-containing alcohol (b1) may be used alone or in combination of two or more.
（グアニジン有機触媒）
グアニジン有機触媒は、共重合体（Ａ）と不飽和結合含有アルコール（ｂ１）との間のエステル交換反応において触媒として機能する。本発明においてはグアニジン有機触媒を使用するため、エステル交換反応による変換率が向上する。
(guanidine organic catalyst)
The guanidine organic catalyst functions as a catalyst in the transesterification reaction between the copolymer (A) and the unsaturated bond-containing alcohol (b1). In the present invention, since a guanidine organic catalyst is used, the conversion rate by transesterification is improved.
グアニジン有機触媒としては、例えば、下記の化合物（１）、化合物（２）、化合物（３）、化合物（４）が挙げられる。 Examples of the guanidine organic catalyst include the following compound (1), compound (2), compound (3), and compound (4).
なかでも、グアニジン有機触媒としては化合物（１）、すなわち、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン（ＴＢＤ）が好ましい。 Among these, compound (1), ie, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), is preferred as the guanidine organic catalyst.
（エステル交換反応）
第１の態様においては、アクリレート単位（ａ１）と不飽和結合含有アルコール（ｂ１）との間でエステル交換反応が起きる。アクリレート単位（ａ１）を－（ＣＨ２ＣＨ（Ｃ（＝Ｏ）Ｏ－Ｒａ１））－で表し、不飽和結合含有アルコール（ｂ１）をＲｂ１－ＯＨで表すとき、Ｒａ１とＲｂ１との間でエステル交換反応が起きる（Ｒｂ１は不飽和結合を有する１価の有機基である。）。結果、共重合体（Ａ１）のアクリレート単位（ａ１）のうち、少なくとも一部のＲａ１がＲｂ１に変換される。そのため、エステル結合を介して不飽和結合含有基が側鎖に結合した共重合体（Ｂ１）が得られる。
共重合体（Ｂ１）は、共重合体（Ａ１）のアクリレート単位（ａ１）のすべてがエステル交換反応したものでもよく、アクリレート単位（ａ１）の一部がエステル交換反応したものでもよい。
(ester exchange reaction)
In the first embodiment, a transesterification reaction occurs between the acrylate unit (a1) and the unsaturated bond-containing alcohol (b1). When the acrylate unit (a1) is represented by -(CH 2 CH (C(=O)O-R a1 ))- and the unsaturated bond-containing alcohol (b1) is represented by R b1 -OH, R a1 and R b1 A transesterification reaction occurs between (R b1 is a monovalent organic group having an unsaturated bond). As a result, at least a portion of R a1 of the acrylate units (a1) of the copolymer (A1) is converted to R b1 . Therefore, a copolymer (B1) in which an unsaturated bond-containing group is bonded to a side chain via an ester bond is obtained.
The copolymer (B1) may be one in which all of the acrylate units (a1) of the copolymer (A1) undergo a transesterification reaction, or may be one in which a part of the acrylate units (a1) undergo a transesterification reaction.
エステル交換反応の反応温度は特に限定されないが、例えば、７０～２００℃が好ましい。エステル交換反応の反応温度が前記数値範囲内の下限値以上であると、エステル交換反応の変換率が向上しやすい。エステル交換反応の反応温度が前記数値範囲内の上限値以下であると、触媒の分解が抑制される。 The reaction temperature for the transesterification reaction is not particularly limited, but is preferably, for example, 70 to 200°C. When the reaction temperature of the transesterification reaction is equal to or higher than the lower limit within the above numerical range, the conversion rate of the transesterification reaction tends to improve. When the reaction temperature of the transesterification reaction is below the upper limit within the above numerical range, decomposition of the catalyst is suppressed.
エステル交換反応の反応時間は特に限定されないが、例えば、０．５～２４時間が好ましい。エステル交換反応の反応時間が前記数値範囲内の下限値以上であると、エステル交換反応の変換率が向上しやすい。エステル交換反応の反応時間が前記数値範囲内の上限値以下であると、生産性が向上しやすい。 The reaction time for the transesterification reaction is not particularly limited, but is preferably 0.5 to 24 hours, for example. When the reaction time of the transesterification reaction is equal to or longer than the lower limit within the above numerical range, the conversion rate of the transesterification reaction tends to improve. When the reaction time of the transesterification reaction is less than or equal to the upper limit within the above numerical range, productivity tends to improve.
エステル交換反応は溶媒中で行ってもよく、溶媒を用いずに行ってもよい。溶媒は、エステル交換反応に不活性な化合物であればよく、特に限定されない。また、不飽和結合含有アルコール（ｂ１）を溶媒として用いてもよい。
溶媒としては、例えば、トルエン、キシレン等の芳香族炭化水素；Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリル等の極性溶媒が挙げられる。溶媒は１種を単独で用いてもよく、２種以上を併用してもよい。
The transesterification reaction may be performed in a solvent or without using a solvent. The solvent is not particularly limited as long as it is a compound inert to the transesterification reaction. Further, an unsaturated bond-containing alcohol (b1) may be used as a solvent.
Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, and acetonitrile. One type of solvent may be used alone, or two or more types may be used in combination.
エステル交換反応を行う際、反応によって生成されるアルコール類を取り除く目的でモレキュラーシーブを加えてもよい。モレキュラーシーブの使用量は共重合体（Ａ１）に対して、５～５０質量％が好ましく、１０～３０質量％がより好ましい。モレキュラーシーブの使用量が前記数値範囲内の下限値以上であるとエステル交換反応の変換率が向上しやすい。モレキュラーシーブの使用量が前記数値範囲内の上限値以下であると、反応溶液を撹拌しやすい。 When carrying out the transesterification reaction, a molecular sieve may be added for the purpose of removing alcohols produced by the reaction. The amount of molecular sieve used is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the copolymer (A1). When the amount of molecular sieve used is at least the lower limit within the above numerical range, the conversion rate of the transesterification reaction tends to improve. When the amount of molecular sieve used is below the upper limit within the above numerical range, it is easy to stir the reaction solution.
（第１の態様の作用機序）
以上一例を用いて説明した一実施形態においては、グアニジン有機触媒の存在下で、共重合体（Ａ）と不飽和結合含有アルコール（ｂ１）との間でエステル交換反応を行うため、不飽和結合を側鎖に有する共重合体（Ｂ１）を選択的に生産でき、また、簡便に生産できる。また、本実施形態に係る生産方法は、特許文献１のような複雑な合成工程を要しない。不飽和結合含有アルコール（ｂ１）の分子量の制御によって、共重合体（Ｂ１）の分子量を制御できるため、特許文献１に比べ、不飽和結合導入後の分子量を大きくすることもでき、また、小さくすることもでき、側鎖の長さを制御しやすい。また、不飽和結合導入後にＯＨ基が残存しにくいため、表面自由エネルギーの制御も容易である。そして、不飽和結合含有アルコール（ｂ１）は豊富な種類があるため、様々な不飽和結合を導入でき、ポリマーの構造の自由度が高いという利点もある。
(Mechanism of action of the first aspect)
In one embodiment described using one example above, in order to carry out the transesterification reaction between the copolymer (A) and the unsaturated bond-containing alcohol (b1) in the presence of a guanidine organic catalyst, the unsaturated bond The copolymer (B1) having this in its side chain can be produced selectively and easily. Furthermore, the production method according to the present embodiment does not require a complicated synthesis process as in Patent Document 1. The molecular weight of the copolymer (B1) can be controlled by controlling the molecular weight of the unsaturated bond-containing alcohol (b1), so compared to Patent Document 1, the molecular weight after introducing the unsaturated bond can be increased, and the molecular weight can be reduced. It is also possible to easily control the length of the side chain. Furthermore, since OH groups are unlikely to remain after the introduction of unsaturated bonds, surface free energy can be easily controlled. Furthermore, since there are a wide variety of unsaturated bond-containing alcohols (b1), various unsaturated bonds can be introduced, which has the advantage of having a high degree of freedom in polymer structure.
＜第２の態様＞
本発明の第２の態様に係るポリマーの生産方法では、グアニジン有機触媒の存在下で、アクリレート単位（ａ１）を有する共重合体（Ａ）と、不飽和結合含有アミン（ｂ２）との間でアミド化反応を行い、不飽和結合を側鎖に有する共重合体（Ｂ２）を得る。
共重合体（Ａ）の詳細および好ましい態様は、第１の態様において説明した内容と同じである。
<Second aspect>
In the method for producing a polymer according to the second aspect of the present invention, in the presence of a guanidine organic catalyst, a copolymer (A) having an acrylate unit (a1) and an unsaturated bond-containing amine (b2) are produced. An amidation reaction is performed to obtain a copolymer (B2) having an unsaturated bond in the side chain.
Details and preferred embodiments of the copolymer (A) are the same as those explained in the first embodiment.
（不飽和結合含有アミン（ｂ２））
不飽和結合含有アミン（ｂ２）は、不飽和結合を有する１価の炭化水素基を有するアミンである。不飽和結合の数は特に限定されず、１個でも複数個でもよい。
不飽和結合含有アミン（ｂ２）としては、例えば、アリルアミン、３－ブテン－１－アミン、４－ペンテン－１－アミン、１，３－ブタジエン－１－アミンが挙げられる。ただし、不飽和結合含有アミン（ｂ２）はこれらの例示に何ら限定されない。
不飽和結合含有アミン（ｂ２）は１種を単独で用いてもよく、２種以上を併用してもよい。
(Unsaturated bond-containing amine (b2))
The unsaturated bond-containing amine (b2) is an amine having a monovalent hydrocarbon group having an unsaturated bond. The number of unsaturated bonds is not particularly limited, and may be one or more.
Examples of the unsaturated bond-containing amine (b2) include allylamine, 3-buten-1-amine, 4-penten-1-amine, and 1,3-butadien-1-amine. However, the unsaturated bond-containing amine (b2) is not limited to these examples.
The unsaturated bond-containing amine (b2) may be used alone or in combination of two or more.
（グアニジン有機触媒）
第２の態様においてグアニジン有機触媒は、共重合体（Ａ）と不飽和結合含有アミン（ｂ２）との間のアミド化反応において触媒として機能する。グアニジン有機触媒の詳細および好ましい態様は、第１の態様において説明した内容と同じである。第２の態様においては、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン（ＴＢＤ）を使用することで、アミド化反応による収率が高くなる。
(guanidine organic catalyst)
In the second embodiment, the guanidine organic catalyst functions as a catalyst in the amidation reaction between the copolymer (A) and the unsaturated bond-containing amine (b2). The details and preferred embodiments of the guanidine organic catalyst are the same as those explained in the first embodiment. In the second embodiment, the use of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) increases the yield of the amidation reaction.
（アミド化反応）
第２の態様においては、アクリレート単位（ａ１）と不飽和結合含有アミン（ｂ２）との間でアミド化反応が起きる。アクリレート単位（ａ１）を－（ＣＨ２ＣＨ（Ｃ（＝Ｏ）Ｏ－Ｒａ１））－で表し、不飽和結合含有アミン（ｂ２）をＮ（Ｒｂ２）（Ｒｂ３）Ｈで表すとき、Ｒａ１とＲｂ２、Ｒｂ３との間でアミド化反応が起きる（Ｒｂ２、Ｒｂ３はそれぞれ独立に、不飽和結合を有する１価の有機基または水素原子であり、同時に水素原子ではない。）。結果、共重合体（Ａ１）のアクリレート単位（ａ１）のうち、少なくとも一部のＲａ１がＲｂ２またはＲｂ３に変換される。そのため、アミド結合を介して不飽和結合含有基が側鎖に結合した共重合体（Ｂ２）が得られる。
共重合体（Ｂ２）は、共重合体（Ａ１）のアクリレート単位（ａ１）のすべてがアミド化反応したものでもよく、アクリレート単位（ａ１）の一部がアミド化反応したものでもよい。
(amidation reaction)
In the second embodiment, an amidation reaction occurs between the acrylate unit (a1) and the unsaturated bond-containing amine (b2). When the acrylate unit (a1) is represented by -(CH 2 CH (C(=O)O-R a1 ))-, and the unsaturated bond-containing amine (b2) is represented by N(R b2 ) (R b3 )H, An amidation reaction occurs between R a1 and R b2 and R b3 (R b2 and R b3 are each independently a monovalent organic group having an unsaturated bond or a hydrogen atom, and are not hydrogen atoms at the same time. ). As a result, at least a portion of R a1 of the acrylate units (a1) of the copolymer (A1) is converted to R b2 or R b3 . Therefore, a copolymer (B2) in which an unsaturated bond-containing group is bonded to a side chain via an amide bond is obtained.
The copolymer (B2) may be one in which all of the acrylate units (a1) of the copolymer (A1) undergo an amidation reaction, or may be one in which a part of the acrylate units (a1) undergo an amidation reaction.
アミド化反応の反応温度は特に限定されないが、例えば、７０～２００℃が好ましい。アミド化反応の反応温度が前記数値範囲内の下限値以上であると、アミド化反応の収率が向上しやすい。アミド化反応の反応温度が前記数値範囲内の上限値以下であると、触媒の分解を抑制しやすい。 The reaction temperature for the amidation reaction is not particularly limited, but is preferably, for example, 70 to 200°C. When the reaction temperature of the amidation reaction is equal to or higher than the lower limit of the above numerical range, the yield of the amidation reaction tends to improve. When the reaction temperature of the amidation reaction is below the upper limit within the above numerical range, decomposition of the catalyst can be easily suppressed.
アミド化反応の反応時間は特に限定されないが、例えば、０．５～２４時間が好ましい。アミド化反応の反応時間が前記数値範囲内の下限値以上であると、アミド化反応の変換率が向上しやすい。アミド化反応の反応時間が前記数値範囲内の上限値以下であると、生産性が向上しやすい。 The reaction time for the amidation reaction is not particularly limited, but is preferably 0.5 to 24 hours, for example. When the reaction time of the amidation reaction is equal to or longer than the lower limit within the above numerical range, the conversion rate of the amidation reaction tends to improve. When the reaction time of the amidation reaction is less than or equal to the upper limit within the above numerical range, productivity tends to improve.
第２の態様においても、アミド化反応は溶媒中で行ってもよく、溶媒を用いずに行ってもよい。溶媒は、アミド化反応に不活性な化合物であればよく、特に限定されない。溶媒の例としては、第１の態様で例示した化合物と同じものが挙げられる。 Also in the second embodiment, the amidation reaction may be performed in a solvent or without using a solvent. The solvent is not particularly limited as long as it is a compound inert to the amidation reaction. Examples of the solvent include the same compounds as those exemplified in the first aspect.
（第２の態様の作用機序）
以上一例を用いて説明した一実施形態においては、グアニジン有機触媒の存在下で、共重合体（Ａ）と不飽和結合含有アミン（ｂ２）との間でアミド化反応を行うため、不飽和結合を側鎖に有する共重合体（Ｂ２）を選択的に生産でき、また、簡便に生産できる。また、本実施形態に係る生産方法は、特許文献１のような複雑な合成工程を要しない。不飽和結合含有アミン（ｂ２）の分子量の制御によって、共重合体（Ｂ２）の分子量を制御できるため、特許文献１に比べ、不飽和結合導入後の分子量を大きくすることもでき、また、小さくすることもでき、側鎖の長さを制御しやすい。そして、不飽和結合含有アミン（ｂ２）は豊富な種類があるため、様々な不飽和結合を導入でき、ポリマーの構造の自由度が高いという利点もある。
(Mechanism of action of second aspect)
In one embodiment described using one example above, in order to carry out an amidation reaction between the copolymer (A) and the unsaturated bond-containing amine (b2) in the presence of a guanidine organic catalyst, the unsaturated bond The copolymer (B2) having this in its side chain can be produced selectively and easily. Furthermore, the production method according to the present embodiment does not require a complicated synthesis process as in Patent Document 1. The molecular weight of the copolymer (B2) can be controlled by controlling the molecular weight of the unsaturated bond-containing amine (b2), so compared to Patent Document 1, the molecular weight after introducing the unsaturated bond can be made larger, and it can also be made smaller. It is also possible to easily control the length of the side chain. Furthermore, since there are a wide variety of unsaturated bond-containing amines (b2), various unsaturated bonds can be introduced, which has the advantage of having a high degree of freedom in polymer structure.
以上一実施形態例を示して一実施形態について説明したが、本発明は本明細書に開示の実施形態例に限定されず、その要旨を変更しない範囲で適宜変更して実施できる。本明細書に開示の実施形態は、その他の様々な形態で実施可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置換、変更が可能である。 Although one embodiment has been described above with reference to one embodiment, the present invention is not limited to the embodiment disclosed in this specification, and can be implemented with appropriate modifications without changing the gist thereof. The embodiments disclosed in this specification can be implemented in various other forms, and various omissions, substitutions, and changes can be made without departing from the gist of the invention.
以下、実施例を挙げて本発明を具体的に説明するが、本発明は以下の記載に限定されない。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following description.
＜略号＞
実施例における略号は以下の通りである。
<Abbreviation>
Abbreviations in Examples are as follows.
（アクリレート）
・ＭＡ：メチルアクリレート
・ＢＡ：ブチルアクリレート
(acrylate)
・MA: Methyl acrylate ・BA: Butyl acrylate
（メタクリレート）
・ＭＭＡ：メチルメタクリレート
(methacrylate)
・MMA: Methyl methacrylate
（他のモノマー）
・Ｅｔ：エチレン
(other monomers)
・Et: ethylene
（触媒）
・ＴＢＤ：１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン
・ＴＥＡ：トリエチルアミン
(catalyst)
・TBD: 1,5,7-triazabicyclo[4.4.0]dec-5-ene ・TEA: Triethylamine
＜測定方法＞
（Ｍｎ、Ｍｗ）
数平均分子量（Ｍｎ）、質量平均分子量（Ｍｗ）は、ゲル透過クロマトグラフィー（ＧＰＣ）を使用し、ポリメチルメタクリレート（ＰＭＭＡ）の検量線から算出した値である。
具体的にはテトラヒドロフラン５ｍｌに測定対象のポリマー５ｍｇを溶解させ、０．４５μｍフィルターで濾過した溶液をＧＰＣ測定用のサンプルとした。
ゲル浸透クロマトグラフィー測定装置（東ソー社製、製品名「ＨＬＣ－８４２０ＧＰＣ」）に、高分子測定ガードカラム（東ソー社製、製品名「ＴＳＫ－ｇｕａｒｄｃｏｌｕｍｎ ＳＵＰＥＲ Ｈ－Ｈ ４．６ｍｍφ×３５ｍｍ」）と２本の高分子測定カラム（東ソー社製、製品名「ＴＳＫ－ＧＥＬ ＳＵＰＥＲ ＨＭ－Ｈ ６．０ｍｍφ×１５０ｍｍ」）を直列に接続して使用した。
また検出器には示差屈折計（ＲＩ）を用いた。分離カラム温度：４０℃、移動層：テトラヒドロフラン、移動層の流量：０．６ｍＬ／分、サンプル注入量：１０μｌの条件で測定を行った。分子量既知のポリメチルメタクリレート数種類（三菱ケミカル社製品）を標準ポリマーとして、検量線を作成し、ＭｎおよびＭｗを求めた。
<Measurement method>
(Mn, Mw)
The number average molecular weight (Mn) and the mass average molecular weight (Mw) are values calculated from a calibration curve of polymethyl methacrylate (PMMA) using gel permeation chromatography (GPC).
Specifically, 5 mg of the polymer to be measured was dissolved in 5 ml of tetrahydrofuran, and the solution was filtered with a 0.45 μm filter and used as a sample for GPC measurement.
A gel permeation chromatography measurement device (manufactured by Tosoh Corporation, product name "HLC-8420GPC"), a polymer measurement guard column (manufactured by Tosoh Corporation, product name "TSK-guardcolumn SUPER HH 4.6mmφ x 35mm") and 2 A series of polymer measurement columns (manufactured by Tosoh Corporation, product name: "TSK-GEL SUPER HM-H 6.0 mmφ x 150 mm") were used.
Further, a differential refractometer (RI) was used as a detector. The measurement was performed under the following conditions: separation column temperature: 40° C., mobile phase: tetrahydrofuran, mobile phase flow rate: 0.6 mL/min, and sample injection amount: 10 μl. A calibration curve was prepared using several types of polymethyl methacrylate (products of Mitsubishi Chemical Corporation) with known molecular weights as standard polymers, and Mn and Mw were determined.
（ガラス転移点（℃））
ガラス転移点（℃）は、示差走査熱量計（Ｘ－ＤＳＣ７０００，日立ハイテクサイエンス社製）を使用し、－３０～１５０℃まで１０℃／分で昇温し、その後１５０℃から－３０℃まで１０℃／分で降温するサイクルを２度行い、２度目の昇温過程よりガラス転移点（℃）を測定した。
(Glass transition point (℃))
The glass transition point (°C) was measured using a differential scanning calorimeter (X-DSC7000, manufactured by Hitachi High-Tech Science Co., Ltd.) by increasing the temperature from -30 to 150°C at a rate of 10°C/min, and then from 150°C to -30°C. A cycle of decreasing the temperature at a rate of 10° C./min was performed twice, and the glass transition point (° C.) was measured from the second heating process.
（変換率（％））
変換率（％）は下式より算出した。
変換率（％）＝（ｎ１／ｎ０）×１００
式中、ｎ１は、エステル交換反応後のポリマーが有するアルコール由来のアクリレート単位のモル数（ｍｏｌ）であり、ｎ０は、エステル交換反応前のポリマーが有するアクリレート単位のモル数（ｍｏｌ）である。ｎ０およびｎ１は、１ＨＮＭＲより解析して求めた。
(Conversion rate (%))
The conversion rate (%) was calculated from the following formula.
Conversion rate (%) = (n 1 /n 0 ) x 100
In the formula, n1 is the number of moles (mol) of alcohol-derived acrylate units that the polymer has after transesterification, and n0 is the number of moles (mol) of acrylate units that the polymer has before transesterification. be. n 0 and n 1 were determined by analysis using 1 HNMR.
＜ＭＭＡ－ＭＡ共重合体の合成＞
ＭＭＡ：９０質量部とＭＡ：１０質量部をトルエン：１００質量部に加え、開始剤としてアゾビスイソブチロニトリル：０．５質量部を加え、７０℃で５時間攪拌した。その後反応液をヘキサン中で再沈澱することにより、ＭＭＡ－ＭＡ共重合体を得た。熱媒の温度計の計測値を反応温度とした。また、反応液を熱媒に浸漬した時点から熱媒から取り出した時点までの間を反応時間とした。
<Synthesis of MMA-MA copolymer>
90 parts by mass of MMA and 10 parts by mass of MA were added to 100 parts by mass of toluene, 0.5 parts by mass of azobisisobutyronitrile was added as an initiator, and the mixture was stirred at 70°C for 5 hours. Thereafter, the reaction solution was reprecipitated in hexane to obtain an MMA-MA copolymer. The value measured by the thermometer of the heating medium was taken as the reaction temperature. In addition, the reaction time was defined as the period from when the reaction solution was immersed in the heating medium to when it was taken out from the heating medium.
＜実施例１＞
表１に示す組成となるよう、反応器中に共重合体（Ａ）、溶媒のトルエン、不飽和結合含有アルコール（ｂ１）およびＴＢＤ触媒を加え、モレキュラーシーブをさらに加え、１２０℃に加熱し、６時間攪拌した。反応終了後、反応溶液を再沈溶媒（ヘキサン）に滴下し、攪拌することで共重合体（Ｂ１）を得た。
熱媒の温度計の計測値を反応温度とした。また、反応溶液を熱媒に浸漬した時点から熱媒から取り出した時点までの間を反応時間とした。
<Example 1>
To obtain the composition shown in Table 1, the copolymer (A), toluene as a solvent, an unsaturated bond-containing alcohol (b1), and a TBD catalyst were added to a reactor, a molecular sieve was further added, and the mixture was heated to 120°C. Stirred for 6 hours. After the reaction was completed, the reaction solution was added dropwise to a reprecipitation solvent (hexane) and stirred to obtain a copolymer (B1).
The value measured by the thermometer of the heating medium was taken as the reaction temperature. In addition, the reaction time was defined as the period from when the reaction solution was immersed in the heating medium to when it was taken out from the heating medium.
＜実施例２～６、比較例１～３＞
共重合体（Ａ）の組成、不飽和結合含有アルコール（ｂ１）、触媒の使用量、反応温度を表１に示すように変更した以外は実施例１と同じ手法によって実験を行った。
<Examples 2 to 6, Comparative Examples 1 to 3>
An experiment was conducted in the same manner as in Example 1, except that the composition of the copolymer (A), the unsaturated bond-containing alcohol (b1), the amount of catalyst used, and the reaction temperature were changed as shown in Table 1.
各例で使用した共重合体（Ａ）は以下の通りである。
実施例１、４、比較例１：ＭＭＡ－ＭＡ共重合体
実施例２、５、比較例２：クラレ社製品「Ｋｕｒａｒｉｔｙ」
実施例３、６、比較例３：三菱ケミカル社製品「ＲＥＸＰＥＡＲＬ」
The copolymer (A) used in each example is as follows.
Examples 1 and 4, Comparative Example 1: MMA-MA copolymer Examples 2 and 5, Comparative Example 2: Kuraray product "Kurarity"
Examples 3 and 6, Comparative Example 3: Mitsubishi Chemical product “REXPEARL”
ＴＢＤを触媒として使用した実施例１～６では、エステル交換反応が進行し、高い変換率が得られ、不飽和二重結合を有する共重合体が得られた。対してＴＥＡを触媒として使用した比較例１～３では、エステル交換反応が進行しなかった。 In Examples 1 to 6 in which TBD was used as a catalyst, the transesterification reaction proceeded, a high conversion rate was obtained, and a copolymer having unsaturated double bonds was obtained. On the other hand, in Comparative Examples 1 to 3 in which TEA was used as a catalyst, the transesterification reaction did not proceed.
本発明によれば、不飽和結合を側鎖に有するポリマーを簡便に生産できる生産方法が提供される。 According to the present invention, a production method that can easily produce a polymer having an unsaturated bond in a side chain is provided.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022080826A JP2023169604A (en) | 2022-05-17 | 2022-05-17 | Method for producing polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022080826A JP2023169604A (en) | 2022-05-17 | 2022-05-17 | Method for producing polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2023169604A true JP2023169604A (en) | 2023-11-30 |
Family
ID=88924155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022080826A Pending JP2023169604A (en) | 2022-05-17 | 2022-05-17 | Method for producing polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2023169604A (en) |
-
2022
- 2022-05-17 JP JP2022080826A patent/JP2023169604A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100564331B1 (en) | Polymer composition | |
| US11485699B2 (en) | (Meth)acrylic oligomers | |
| JP7069117B2 (en) | Vinyl-based comb-type copolymer | |
| JP6752793B2 (en) | Method for producing copolymer of alkyl methacrylate and maleic anhydride | |
| JP5216744B2 (en) | High heat-resistant acrylic copolymer and method for producing the same | |
| JP2023169604A (en) | Method for producing polymer | |
| CA3030061C (en) | Polyacrylate-polysilane block copolymers | |
| JP2003012719A (en) | Vinyl polymer containing alkenyl group and sulfur atom | |
| JP2023140062A (en) | Copolymer and resin composition | |
| TWI838455B (en) | (Meth)acrylate monomers and polymers containing cyclic carbonate groups | |
| TWI721476B (en) | Vitrimer and preparation method thereof | |
| JP2023511366A (en) | SILICONE ACRYLATE POLYMERS, COPOLYMERS AND RELATED METHODS AND COMPOSITIONS | |
| JP6465634B2 (en) | Polymer containing cyclic amide group | |
| JP2015214614A (en) | Block polymer and production method thereof | |
| JP6618812B2 (en) | 2-Methylene glutarate ester polymer | |
| JPWO2018221564A1 (en) | Adhesive and structure | |
| JPH01254719A (en) | Polysiloxane group-containing polymer | |
| WO2015083744A1 (en) | Cyclic amide group-containing polymer, cyclic amide acrylate-containing composition, and method for producing cyclic amide acrylate | |
| WO2021157668A1 (en) | Polymer compound, method for producing polymer compound, adhesive composition, cured product, method for producing adhesive composition, and method for adjusting adhesive strength | |
| JP6484928B2 (en) | Block polymer and method for producing the same | |
| JP2009001785A (en) | Silane varnish comprising aminosilane and epoxy-functional polyacrylate | |
| Alrefai | Atrp of Bio-Based Methacrylates for Applications in Super Varnishes | |
| JP6805964B2 (en) | (Meta) Acrylic Acid Ester Composition, Its (Co) Polymer and Method for Producing (Co) Polymer | |
| JP6372565B2 (en) | Method for producing block polymer | |
| JP6484927B2 (en) | Block polymer and method for producing the same |