JPS6366211A - Dihydroxyl group-containing condensible macromonomer - Google Patents
Dihydroxyl group-containing condensible macromonomerInfo
- Publication number
- JPS6366211A JPS6366211A JP61209305A JP20930586A JPS6366211A JP S6366211 A JPS6366211 A JP S6366211A JP 61209305 A JP61209305 A JP 61209305A JP 20930586 A JP20930586 A JP 20930586A JP S6366211 A JPS6366211 A JP S6366211A
- Authority
- JP
- Japan
- Prior art keywords
- group
- macromonomer
- formula
- formulas
- mercaptohydroxyl
- 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.)
- Granted
Links
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- -1 mercaptohydroxyl compound Chemical class 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 4
- 125000005170 cycloalkyloxycarbonyl group Chemical group 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002348 vinylic group Chemical group 0.000 abstract 2
- RRCCWYJNLXYHMI-UHFFFAOYSA-N sulfanylmethanediol Chemical compound OC(O)S RRCCWYJNLXYHMI-UHFFFAOYSA-N 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229940035024 thioglycerol Drugs 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- RMCCONIRBZIDTH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 1,3-dioxo-2-benzofuran-5-carboxylate Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 RMCCONIRBZIDTH-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 description 1
- VHJHZYSXJKREEE-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl prop-2-enoate Chemical compound FC(F)C(F)(F)COC(=O)C=C VHJHZYSXJKREEE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- VYSBIWBURKYGPB-UHFFFAOYSA-N 2-sulfanylpropane-1,2-diol Chemical compound CC(O)(S)CO VYSBIWBURKYGPB-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- YOQPKXIRWPWFIE-UHFFFAOYSA-N ctk4c8335 Chemical compound CC(=C)C(=O)OCCOP(=O)=O YOQPKXIRWPWFIE-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はジヒドロキジル基含有縮合性マクロモノマー、
更に詳しくは、ビニルポリマー鎖の末端にヒドロキシル
基２個を持つオリゴマーであって、特にある種の櫛型ポ
リマー、すなわち上記ヒドロキシル基を介して生成する
ポリウレタンやポリエステルを主鎖とし、ビニルポリマ
ーを側鎖とする櫛型ポリマーの中間体として有用な新規
マクロモノマーおよびその製造法に関する。なお、当該
マクロモノマーから得られる櫛型ポリマーは、接着性も
しくは密着性付与剤、相溶化剤、界面活性剤として機能
しうる。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to dihydroxyl group-containing condensable macromonomers,
More specifically, it is an oligomer having two hydroxyl groups at the end of a vinyl polymer chain, and in particular, a type of comb-shaped polymer, that is, a main chain of polyurethane or polyester formed through the above-mentioned hydroxyl groups, and a vinyl polymer on the side. This invention relates to a novel macromonomer useful as an intermediate for comb-shaped polymer chains and a method for producing the same. Note that the comb-shaped polymer obtained from the macromonomer can function as an adhesive or adhesion imparting agent, a compatibilizer, and a surfactant.
鳩木坏叛ζ解決ずべき問題、張
近年、ポリマー合成の分野において、従来の機械的強度
や耐熱性などの要求機能に加えて付加価値の高い高分子
材料の出現が望まれ、かかる多様化したニーズに伴い、
機能性を有オろ様々なグラフトポリマー、ブロックポリ
マー、櫛型ポリマーが合成されつつある。たとえば、連
鎖移動剤としてヂオグリコール酸の存在下メチルメタク
リレートを重合させて末端カルボン酸のオリゴマーをｉ
す、更にグリンジルメタクリレートを付加反応させて、
末端に重合−性二重結合を持ったマクロモノマーを合成
し、かかるマクロモノマーを適当なコモノマーとラジカ
ル共重合させてグラフトポリマーを得る方法が知られて
いる（日本接着協会誌、Ｖｏ１１７、Ｎｏ、９．３７１
〜３７６頁、１９８１年参照）。しかして、このように
マクロモノマーを介して所望のグラフトポリマーを得る
ことができるが、マクロモノマー自体の反応が多段階に
わたり複雑であったり、目的グラフトポリマーの収率が
悪かったり、更にコスト的にも高くつくなどの欠点があ
った。Problems to be solved, Zhang In recent years, in the field of polymer synthesis, there has been a desire for the emergence of high-value-added polymeric materials in addition to the conventional required functions such as mechanical strength and heat resistance, and this diversification has increased. With the needs of
Graft polymers, block polymers, and comb polymers with various functionalities are being synthesized. For example, methyl methacrylate is polymerized in the presence of diglycolic acid as a chain transfer agent to form oligomers of terminal carboxylic acids.
Further, by addition reaction with Grindyl methacrylate,
A known method is to synthesize a macromonomer having a polymerizable double bond at the end and radical copolymerize the macromonomer with a suitable comonomer to obtain a graft polymer (Japan Adhesive Association Journal, Vol. 117, No. 9.371
376, 1981). Although it is possible to obtain a desired graft polymer using a macromonomer in this way, the reaction of the macromonomer itself is complex and involves multiple steps, the yield of the desired graft polymer is poor, and the cost is high. It also had drawbacks such as being expensive.
本発明者らは、機能性を有するポリマーの中間体として
有用なマクロモノマーを創製するため鋭意研究を進めた
結果、連鎖移動剤として２個のヒドロキシル基を含有す
るメルカプト化合物を用い、これとビニル系モノマーを
光重合すれば、末端にヒドロキシル基２個を持つ縮合性
のマクロモノマーを簡易かつ低コストで得ることができ
、これをジイソシアネートやジカルボン酸と縮重合する
ことにより、機能性を有する新規な櫛型ポリマーが得ら
れることを見出し、本発明を完成するに至った。As a result of intensive research to create a macromonomer useful as an intermediate for functional polymers, the present inventors used a mercapto compound containing two hydroxyl groups as a chain transfer agent, and combined this with vinyl By photopolymerizing these monomers, a condensable macromonomer with two hydroxyl groups at the end can be obtained easily and at low cost. By condensing and polymerizing this with diisocyanate or dicarboxylic acid, new functional monomers can be obtained. The present inventors have discovered that a comb-shaped polymer can be obtained, and have completed the present invention.
発明の構成と効果
すなわち、本発明は、式：
％式％
［］
１式中、Ｒ’ 、Ｒ’およびＲ３は同一もしくは異なっ
て、単結合または炭素数１〜４のアルキレン基、Ｒ４は
水素または炭素数１〜４のアルキル基、Ｒ５は水素また
はメチル基、Ｘはアルキルオキシカルボニル基、置換ア
ルキルオキシカルボニル基、シクロアルキルオキシカル
ボニル基またはフェニル基、およびｎは１〜１万の整数
である］で示されるジヒドロキジル基含有縮合性マクロ
モノマー、並びに式・
Ｒ’−０Ｈ
Ｒ９−Ｒ３−（、−Ｒ’ ［ＩＩ］Ｒ’−
ＯＨ
のメルカプトヒドロキシル化合物と、式：ＣＨ２＝Ｃ−
Ｘ ［］Ｔｆ］のビニル系モノマ
ーを光照射により重合させることから成る上記式［１］
のジヒドロキジル基含有縮合性マクロモノマーの製造法
を提供するものである。Structure and Effects of the Invention Namely, the present invention is based on the formula: %Formula% [] In the formula, R', R' and R3 are the same or different and are a single bond or an alkylene group having 1 to 4 carbon atoms, and R4 is hydrogen. or an alkyl group having 1 to 4 carbon atoms; R5 is hydrogen or a methyl group; ] A dihydroxyl group-containing condensable macromonomer represented by the formula:
A mercaptohydroxyl compound of OH and the formula: CH2=C-
The above formula [1] consisting of polymerizing a vinyl monomer of X[]Tf] by light irradiation
The present invention provides a method for producing a dihydroxyl group-containing condensable macromonomer.
本発明において用いるメルカプトヒドロキシル化合物［
ｎ］としては、たとえば１−メルカプト−１，１−メ（
１）タンジオール［なお、メ（１）タンとはメタンまた
はエタンを指称する］、２−メルカプト−１，２−プロ
パンジオール、２−メルカプト−２−メ（１）チル−１
，３−プロパンジオール［なお、メ（１）デルとはメチ
ルまたはエチルを指称する、以下同様］、３−メルカプ
ト−１，２−プロパンジオール、１−メル プｌ−−２
、２−プロパンジオール、２−メルカプトメ（１）チル
−１，３−プロパンジオール、２−メルカプトメ（１）
チル−２−メ（１）チル−１，３−プロパンジオール等
が挙げられ、これらの１種または２種以上を使用に供す
る。使用量は通常、ビニル系モノマー１００部（重量部
、以下同様）に対して０．０１−１０部の範囲で選定す
ればよい。Mercaptohydroxyl compound used in the present invention [
n], for example, 1-mercapto-1,1-me(
1) Tanediol [meth(1)thane refers to methane or ethane], 2-mercapto-1,2-propanediol, 2-mercapto-2-meth(1)thyl-1
, 3-propanediol [Me (1) del refers to methyl or ethyl, the same applies hereinafter], 3-mercapto-1,2-propanediol, 1-mer-propanediol
, 2-propanediol, 2-mercaptome (1) thyl-1,3-propanediol, 2-mercaptome (1)
Examples include thyl-2-me(1) thyl-1,3-propanediol, and one or more of these may be used. The amount used is usually selected within the range of 0.01 to 10 parts per 100 parts (parts by weight, hereinafter the same) of the vinyl monomer.
本発明において用いるビニル系モノマー［ＩＩＩ］とし
てはビニル基、ビニレン基、ビニリデン基を有するモノ
マーを指称し、具体的にはたとえばエチルアクリレート
、プロピルアクリレート、 ｎ−ブチルアクリレート、
イソブチルアクリレート、アミルアクリレート、ヘキシ
ルアクリレート、２−エチルヘキノルアクリレート、シ
クロへキシルアクリレート、ｎ−オクヂルアクリレート
、メチルアクリレート、グリシジルアクリレート、２−
ヒドロキシエチルアクリレート、２−ヒドロキシプロピ
ルアクリレート、メチルメタクリレート、エチルメタク
リレート、ｎ−ブチルアクリレート、イソブチルアクリ
レート、２−エチルへキシルメタクリレート、ラウリル
メタクリレート、トリデノルメタクリレート、ヘンシル
メタクリレート、シクロへキシルメタクリレート、テト
ラヒドロフルフリルメタクリレート、グリシジルアクリ
レート、２−メトキシエチルメタクリレート、２−エト
キシエチルメタクリレート、２，２，３．３−テトラフ
ルオロプロピルアクリレート、オクタフルオロペンデル
アクリレート、オクタフルオロペンチルメタクリレート
等が挙げられ、これらの１種または２種以上を使用に供
する。また必要に応じ、これらのビニル系モノマーの共
重合モノマーとして、無水マレイン酸、酢酸ビニル、４
−ＭＥＴＡ（４−メタクリロキシエチルトリメリット酸
無水物）、ＨＥＭＡＰ（アシッドホスホオキシエチルメ
タクリレート）、メタクリル酸、アクリル酸、プロピオ
ン酸ビニル、パーサティック酸ビニル（商品名ベオバ、
シェル化学製）、塩化ビニル、アクリロニトリル、アク
リル酸アミド、Ｎ−メチロールアクリル酸アミド、ビニ
ルピリジン、ビニルピロリドン、ブタジェン、スチレン
等の１種または２種以上を使用されてもよい。The vinyl monomer [III] used in the present invention refers to a monomer having a vinyl group, a vinylene group, or a vinylidene group, and specifically includes, for example, ethyl acrylate, propyl acrylate, n-butyl acrylate,
Isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-ocdyl acrylate, methyl acrylate, glycidyl acrylate, 2-
Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridenol methacrylate, hensyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl Examples include methacrylate, glycidyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2,2,3.3-tetrafluoropropyl acrylate, octafluoropendel acrylate, octafluoropentyl methacrylate, etc., and one or two of these Use seeds or more. If necessary, as copolymerization monomers of these vinyl monomers, maleic anhydride, vinyl acetate,
-META (4-methacryloxyethyl trimellitic anhydride), HEMAP (acid phosphooxyethyl methacrylate), methacrylic acid, acrylic acid, vinyl propionate, vinyl persate (trade name Beoba,
(manufactured by Shell Chemical), vinyl chloride, acrylonitrile, acrylamide, N-methylolacrylamide, vinylpyridine, vinylpyrrolidone, butadiene, styrene, etc., or one or more of them may be used.
本発明に係るジヒドロキジル基含有縮合性マクロモノマ
ー［Ｉ］は、以下の手順に従って製造することができる
。The dihydroxyl group-containing condensable macromonomer [I] according to the present invention can be produced according to the following procedure.
上記ビニル系モノマー［Ｉ］に所定割合のメルカブトヒ
ドロキシル化合物［］Ｉ］を配合し、光照射により重合
させる。この重合は無溶媒でも溶液重合でもよい。この
ように光重合を採用することにより通常の熱重合に比し
、以下の如き利点が奏せられる。A predetermined proportion of the mercabutohydroxyl compound [I] is blended with the vinyl monomer [I] and polymerized by light irradiation. This polymerization may be carried out without a solvent or in a solution. By employing photopolymerization in this manner, the following advantages can be achieved compared to ordinary thermal polymerization.
ｌ）ラジカル開始剤（ジアゾ化合物、過酸化物）が不要
ｉｉ）収率が高い
山）末端に官能基がより確実に導入されるｉｖ）これら
の理由からコストダウンが計れるかかる光重合によって
、末端にヒドロキシル基２個を有する本発明の縮合性マ
クロモノマー［Ｔ］が得られる。l) No need for radical initiators (diazo compounds, peroxides) ii) High yields) Functional groups are introduced more reliably at the ends iv) Cost reductions can be achieved for these reasons. The condensable macromonomer [T] of the present invention having two hydroxyl groups is obtained.
本発明の縮合性マクロモノマー［Ｉ］は、最終目的であ
る櫛型ポリマーの中間体として有用である。The condensable macromonomer [I] of the present invention is useful as an intermediate for a comb-shaped polymer, which is the final objective.
すなわち、当該縮合性マクロモノマー［１］をジカルボ
ン酸、ジイソシアネートなどを用い、要すれば縮重合触
媒の存在下で、縮重合させて、たとえばジカルボン酸の
場合、式：
■
（−Ｃ−Ｒ’ −Ｃ−はジカルボン酸残基）の単位、ジ
イソシアネートの場合、式：％式％
（−Ｃ−Ｎ−Ｒ″−Ｎ−Ｃ−はジイソシアネートＩＩ
ｌ ｌ ＩＩＯＨＨＯ
残基）
の単位から成る櫛型ポリマーが製造される。That is, the condensable macromonomer [1] is subjected to condensation polymerization using a dicarboxylic acid, diisocyanate, etc., if necessary in the presence of a condensation polymerization catalyst. For example, in the case of a dicarboxylic acid, the formula: -C- is a unit of dicarboxylic acid residue), in the case of diisocyanate, the formula: % formula % (-C-N-R″-N-C- is diisocyanate II
A comb polymer consisting of units of l l IIOHHO residues is produced.
次に実施例を挙げて、本発明をより具体的に説明する。Next, the present invention will be explained in more detail with reference to Examples.
−１１＝
実施例１
ブチルアクリレート１００ｇおよび３−メルカプｌ−１
，２−プロパンジオール（チオグリセロール）Ｉｇをコ
ルベンに入れ、窒素雰囲気下、撹拌しながら系を約５０
℃に保持し、ＵＶ（東芝５ＨＬ−１００）を照射しなが
ら光重合を行う。約６時間後に縮合性マクロモノマーを
得る。重量変化法（１０５℃、４時間）で求めた収率は
１００％であった。ゲルパーミェーションクロマトグラ
フィー（ＧＰＣ）により数平均分子量が１．ＩｘｌＯ’
であった。-11= Example 1 100 g of butyl acrylate and 3-mercap l-1
, 2-propanediol (thioglycerol) Ig was placed in a Kolben, and the system was heated to about 50% while stirring under a nitrogen atmosphere.
℃ and photopolymerization is carried out while irradiating with UV (Toshiba 5HL-100). A condensable macromonomer is obtained after about 6 hours. The yield determined by the weight change method (105°C, 4 hours) was 100%. Gel permeation chromatography (GPC) shows that the number average molecular weight is 1. IxlO'
Met.
実施例２
メチルメタクリレート１００ｇおよびチオグリセロール
１ｇをコルベン中、窒素雰囲気下、撹拌しながら約５０
℃で光重合を行う。約１８時間後に縮合性マクロモノマ
ーを得る。実施例１と同様の方法により、収率９６％、
数平均分子量２． １×１０４であった。Example 2 100 g of methyl methacrylate and 1 g of thioglycerol were mixed in a Kolben under a nitrogen atmosphere with stirring for about 50 g.
Photopolymerization is carried out at °C. After about 18 hours, a condensable macromonomer is obtained. By the same method as Example 1, yield 96%,
Number average molecular weight2. It was 1×104.
実施例３
ブチルアクリレート９．５ｇ、２−ヒドロキソエチルメ
タクリレート０．５ｇおよびチオグリセロールＯ，Ｉｇ
をガラス製重合管に入れ、冷却・脱気後溶封する。これ
を約５０℃の水槽中に入れ、ＵＶを照射して光重合を行
う。約７時間後、内容物を取り出し、実施例１と同様の
方法で調べたところ、収率９８％、数平均分子量１．６
ｘｌＯ’であった。Example 3 9.5 g of butyl acrylate, 0.5 g of 2-hydroxoethyl methacrylate and thioglycerol O,Ig
Put it in a glass polymerization tube, cool it down, degas it, and then melt-seal it. This is placed in a water tank at about 50°C and irradiated with UV to perform photopolymerization. After about 7 hours, the contents were taken out and examined in the same manner as in Example 1. The yield was 98% and the number average molecular weight was 1.6.
It was xlO'.
実施例４
メチルメタクリレート９．５ｇ、２−ヒドロキシエチル
メタクリレー）−０，５ｇおよびチオグリセロールＯ，
Ｉｇを脱気封管して、約５０℃で光重合を行う。約１２
時間後、内容物を取り出し、実施例Ｉと同様な方法で調
べたところ、収率５２％、数平均分子量１．８ＸＩＯ’
であった。Example 4 9.5 g of methyl methacrylate, 0.5 g of 2-hydroxyethyl methacrylate) and thioglycerol O,
Ig is degassed and sealed in a tube, and photopolymerization is carried out at about 50°C. about 12
After a period of time, the contents were taken out and examined in the same manner as in Example I. The yield was 52% and the number average molecular weight was 1.8XIO'.
Met.
Claims (1)
なって、単結合または炭素数１〜４のアルキレン基、Ｒ
＾４は水素または炭素数１〜４のアルキル基、Ｒ＾５は
水素またはメチル基、Ｘはアルキルオキシカルボニル基
、置換アルキルオキシカルボニル基、シクロアルキルオ
キシカルボニル基またはフェニル基、およびｎは１〜１
万の整数である］ で示されるジヒドロキシル基含有縮合性マクロモノマー
。 ２、式： ▲数式、化学式、表等があります▼ ［式中、Ｒ＾１、Ｒ＾２およびＲ＾３は同一もしくは異
なって、単結合または炭素数１〜４のアルキレン基、お
よびＲ＾４は水素または炭素数１〜４のアルキル基であ
る］ で示されるメルカプトヒドロキシル化合物と、式： ▲数式、化学式、表等があります▼ ［式中、Ｒ＾５は水素またはメチル基、およびＸはアル
キルオキシカルボニル基、置換アルキルオキシカルボニ
ル基、シクロアルキルオキシカルボニル基またはフェニ
ル基である］ で示されるビニル系モノマーを光照射により重合させて
、式： ▲数式、化学式、表等があります▼ ［式中、ｎは１〜１万の整数、およびＲ＾１、Ｒ＾２、
Ｒ＾３、Ｒ＾４、Ｒ＾５およびＸは前記と同意義］で示
されるジヒドロキシル基含有縮合性マクロモノマーを得
ることを特徴とするジヒドロキシル基含有縮合性マクロ
モノマーの製造法。[Claims] 1. Formulas ▲ Numerical formulas, chemical formulas, tables, etc. group, R
^4 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R^5 is hydrogen or a methyl group, X is an alkyloxycarbonyl group, substituted alkyloxycarbonyl group, cycloalkyloxycarbonyl group, or phenyl group, and n is 1 to 1
is an integer of ten thousand.] A condensable macromonomer containing a dihydroxyl group. 2. Formulas: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1, R^2 and R^3 are the same or different and represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R^ 4 is hydrogen or an alkyl group having 1 to 4 carbon atoms] and the mercaptohydroxyl compound represented by the formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^5 is hydrogen or a methyl group, and is an alkyloxycarbonyl group, a substituted alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, or a phenyl group] By polymerizing the vinyl monomer represented by the following by light irradiation, the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [ In the formula, n is an integer from 1 to 10,000, and R^1, R^2,
A method for producing a dihydroxyl group-containing condensable macromonomer, characterized in that a dihydroxyl group-containing condensable macromonomer is obtained, wherein R^3, R^4, R^5 and X are the same as defined above.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61209305A JPS6366211A (en) | 1986-09-05 | 1986-09-05 | Dihydroxyl group-containing condensible macromonomer |
| US07/090,442 US4818804A (en) | 1986-09-04 | 1987-08-28 | Polycondensable macromonomer from vinyl monomer and mercapto compound |
| DE19873729496 DE3729496A1 (en) | 1986-09-04 | 1987-09-03 | POLYCONDENSIBLE MACROMONOMER AND METHOD FOR THE PRODUCTION THEREOF |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61209305A JPS6366211A (en) | 1986-09-05 | 1986-09-05 | Dihydroxyl group-containing condensible macromonomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6366211A true JPS6366211A (en) | 1988-03-24 |
| JPH0534367B2 JPH0534367B2 (en) | 1993-05-21 |
Family
ID=16570755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61209305A Granted JPS6366211A (en) | 1986-09-04 | 1986-09-05 | Dihydroxyl group-containing condensible macromonomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6366211A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239308A (en) * | 1999-02-24 | 2000-09-05 | Soken Chem & Eng Co Ltd | Acrylic polymer, curing composition, cured product and their use |
| JP2002012621A (en) * | 2000-04-27 | 2002-01-15 | Soken Chem & Eng Co Ltd | Acrylic polymer containing polymerizable unsaturated group at molecular end |
| JP2006117920A (en) * | 2004-09-27 | 2006-05-11 | Sekisui Plastics Co Ltd | Polymer particle having a plurality of pores inside, its manufacturing method, and resin composition containing the polymer particle |
| JP2009155406A (en) * | 2007-12-26 | 2009-07-16 | Toyo Ink Mfg Co Ltd | Curable dispersant, its manufacturing method and pigment composition using the same |
| JP2009165910A (en) * | 2008-01-11 | 2009-07-30 | Toyo Ink Mfg Co Ltd | Dispersant, pigment composition using it and pigment dispersion |
| WO2009119546A1 (en) | 2008-03-24 | 2009-10-01 | 東洋インキ製造株式会社 | Dispersant and pigment composition, pigment dispersing substance, and inkjet ink using the dispersant |
| WO2018008610A1 (en) * | 2016-07-08 | 2018-01-11 | 旭硝子株式会社 | Photosensitive composition, method for producing polymer, method for producing photosensitive composition, and method for producing laminate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5962611A (en) * | 1982-10-02 | 1984-04-10 | Daikin Ind Ltd | Fluoroalkyl acrylate polymer |
| JPS6088014A (en) * | 1983-09-20 | 1985-05-17 | レーム・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Radiation sensitive polymer material and manufacture |
| JPS6166726A (en) * | 1984-09-10 | 1986-04-05 | Mitsubishi Kasei Vinyl Co | Surface treatment for molded article of nonrigid vinyl chloride resin |
| JPS62250012A (en) * | 1986-04-22 | 1987-10-30 | Toagosei Chem Ind Co Ltd | Production of polymer having functional group at one terminal |
-
1986
- 1986-09-05 JP JP61209305A patent/JPS6366211A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5962611A (en) * | 1982-10-02 | 1984-04-10 | Daikin Ind Ltd | Fluoroalkyl acrylate polymer |
| JPS6088014A (en) * | 1983-09-20 | 1985-05-17 | レーム・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Radiation sensitive polymer material and manufacture |
| JPS6166726A (en) * | 1984-09-10 | 1986-04-05 | Mitsubishi Kasei Vinyl Co | Surface treatment for molded article of nonrigid vinyl chloride resin |
| JPS62250012A (en) * | 1986-04-22 | 1987-10-30 | Toagosei Chem Ind Co Ltd | Production of polymer having functional group at one terminal |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000239308A (en) * | 1999-02-24 | 2000-09-05 | Soken Chem & Eng Co Ltd | Acrylic polymer, curing composition, cured product and their use |
| JP2002012621A (en) * | 2000-04-27 | 2002-01-15 | Soken Chem & Eng Co Ltd | Acrylic polymer containing polymerizable unsaturated group at molecular end |
| JP2006117920A (en) * | 2004-09-27 | 2006-05-11 | Sekisui Plastics Co Ltd | Polymer particle having a plurality of pores inside, its manufacturing method, and resin composition containing the polymer particle |
| JP4566870B2 (en) * | 2004-09-27 | 2010-10-20 | 積水化成品工業株式会社 | Polymer particles having a plurality of pores therein, a method for producing the same, and a resin composition containing the polymer particles |
| JP2009155406A (en) * | 2007-12-26 | 2009-07-16 | Toyo Ink Mfg Co Ltd | Curable dispersant, its manufacturing method and pigment composition using the same |
| JP2009165910A (en) * | 2008-01-11 | 2009-07-30 | Toyo Ink Mfg Co Ltd | Dispersant, pigment composition using it and pigment dispersion |
| WO2009119546A1 (en) | 2008-03-24 | 2009-10-01 | 東洋インキ製造株式会社 | Dispersant and pigment composition, pigment dispersing substance, and inkjet ink using the dispersant |
| US8344047B2 (en) | 2008-03-24 | 2013-01-01 | Toyo Ink Manufacturing Co., Ltd. | Dispersing agent, and pigment composition, pigment-dispersed product and inkjet ink prepared therefrom |
| WO2018008610A1 (en) * | 2016-07-08 | 2018-01-11 | 旭硝子株式会社 | Photosensitive composition, method for producing polymer, method for producing photosensitive composition, and method for producing laminate |
| JPWO2018008610A1 (en) * | 2016-07-08 | 2019-06-13 | Ａｇｃ株式会社 | PHOTOSENSITIVE COMPOSITION, METHOD FOR PRODUCING POLYMER, METHOD FOR PRODUCING PHOTOSENSITIVE COMPOSITION, METHOD FOR PRODUCING LAMINATE |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0534367B2 (en) | 1993-05-21 |
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