JPH0376707A - Production of functional polymer - Google Patents
Production of functional polymerInfo
- Publication number
- JPH0376707A JPH0376707A JP21451889A JP21451889A JPH0376707A JP H0376707 A JPH0376707 A JP H0376707A JP 21451889 A JP21451889 A JP 21451889A JP 21451889 A JP21451889 A JP 21451889A JP H0376707 A JPH0376707 A JP H0376707A
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- polymer
- group
- side chain
- sulfonic ester
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920001002 functional polymer Polymers 0.000 title claims description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 7
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 13
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002130 sulfonic acid ester group Chemical group 0.000 claims description 2
- -1 styrene) Chemical class 0.000 abstract description 10
- 150000002148 esters Chemical class 0.000 abstract description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229920001477 hydrophilic polymer Polymers 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 229940114081 cinnamate Drugs 0.000 abstract description 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 3
- 229930195729 fatty acid Natural products 0.000 abstract 3
- 239000000194 fatty acid Substances 0.000 abstract 3
- 150000004665 fatty acids Chemical class 0.000 abstract 3
- 125000004185 ester group Chemical group 0.000 abstract 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract 1
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNNTVWFUEVZBLE-UHFFFAOYSA-N (1-methyl-2h-benzo[e][1,3]benzothiazol-2-yl)-phenylmethanone Chemical compound S1C2=CC=C3C=CC=CC3=C2N(C)C1C(=O)C1=CC=CC=C1 DNNTVWFUEVZBLE-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-KBXRYBNXSA-N (2e,4e)-5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)\C=C\C=C\C1=CC=CC=C1 FEIQOMCWGDNMHM-KBXRYBNXSA-N 0.000 description 1
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 1
- CDUQMGQIHYISOP-RMKNXTFCSA-N (e)-2-cyano-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C\C1=CC=CC=C1 CDUQMGQIHYISOP-RMKNXTFCSA-N 0.000 description 1
- ZCJLOOJRNPHKAV-ONEGZZNKSA-N (e)-3-(furan-2-yl)prop-2-enoic acid Chemical compound OC(=O)\C=C\C1=CC=CO1 ZCJLOOJRNPHKAV-ONEGZZNKSA-N 0.000 description 1
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-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
- AAHIANQEIRNOIH-UHFFFAOYSA-N 2-(butylamino)ethane-1,1-diol Chemical compound CCCCNCC(O)O AAHIANQEIRNOIH-UHFFFAOYSA-N 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-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
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 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
- MAABLZJEPOZZEJ-UHFFFAOYSA-N 2-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=CS1 MAABLZJEPOZZEJ-UHFFFAOYSA-N 0.000 description 1
- WKCYFSZDBICRKL-UHFFFAOYSA-N 3-(diethylamino)propan-1-ol Chemical compound CCN(CC)CCCO WKCYFSZDBICRKL-UHFFFAOYSA-N 0.000 description 1
- WPXMLUUYWNHQOR-UHFFFAOYSA-N 3-naphthalen-1-ylprop-2-enoic acid Chemical compound C1=CC=C2C(C=CC(=O)O)=CC=CC2=C1 WPXMLUUYWNHQOR-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UJROAYFTMKEHAO-UHFFFAOYSA-N C(#N)C(=C(C(=O)O)C=1SC=CC1)C=C Chemical compound C(#N)C(=C(C(=O)O)C=1SC=CC1)C=C UJROAYFTMKEHAO-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N cinnamyl alcohol Chemical compound OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N cinnamylideneacetic acid Natural products OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- PWNDYKKNXVKQJO-UHFFFAOYSA-N n',n'-dibutylethane-1,2-diamine Chemical compound CCCCN(CCN)CCCC PWNDYKKNXVKQJO-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- IRNCDKLDJPXBOD-UHFFFAOYSA-N n',n'-dimethyl-n-phenylmethanediamine Chemical compound CN(C)CNC1=CC=CC=C1 IRNCDKLDJPXBOD-UHFFFAOYSA-N 0.000 description 1
- MKPFJMOHYMWVHT-UHFFFAOYSA-N n,2,2-triethylbutan-1-amine Chemical compound CCNCC(CC)(CC)CC MKPFJMOHYMWVHT-UHFFFAOYSA-N 0.000 description 1
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 description 1
- IAWXHEPLJXAMSG-UHFFFAOYSA-N pent-2-en-1-amine Chemical compound CCC=CCN IAWXHEPLJXAMSG-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000005314 unsaturated fatty acid group Chemical class 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
(発明の分野)
本発明は機能性高分子、特に不飽和脂肪酸誘導体を側鎖
に持つ親水性高分子の製法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a method for producing functional polymers, particularly hydrophilic polymers having unsaturated fatty acid derivatives in their side chains.
(従来技術〉
親水性高分子の製法としては、種々の方法があり、カル
ボキシ基、スルフォ基もしくは四級塩を側鎖に持つもの
の検討例が多い。例えば、特開昭49−98490.4
9−111991.49−85822.53−6394
.59−79246に詳しい。(Prior art) There are various methods for producing hydrophilic polymers, and there are many examples of studies that have carboxy groups, sulfo groups, or quaternary salts in the side chains.For example, JP-A No. 49-98490.4
9-111991.49-85822.53-6394
.. 59-79246 for details.
然し、これらの従来技術における製法では、高分子、特
に不飽和脂肪酸誘導体の如く官能基を持つ高分子の製法
としては、いくつかの問題があった。例えば、反応性が
低い、官能基の導入率が上がらない、副反応がおきやす
い、ゲル化を生じやすい、原料が高価である等である。However, these conventional production methods have some problems when it comes to producing polymers, especially polymers with functional groups such as unsaturated fatty acid derivatives. For example, the reactivity is low, the introduction rate of functional groups is not increased, side reactions are likely to occur, gelation is likely to occur, raw materials are expensive, etc.
本発明者等は、これらのてんに着目して、新規な製法を
開発したものである。The inventors of the present invention have developed a new manufacturing method by paying attention to these ingredients.
(発明の目的〉
本発明の目的は、入手が容易でかつ反応性の高い化合物
を巧みに用いる事による機能性高分子の製法を提供する
ものである。(Object of the Invention) The object of the present invention is to provide a method for producing a functional polymer by skillfully using easily available and highly reactive compounds.
(発明の樋底)
本発明の目的は、側鎖に芳香族スルフォン酸エステル基
を有する単独若しくは共重合体と脂肪族三級アミノ基を
有する不飽和脂肪酸誘導体を反応させることを特徴とす
る機能性高分子の製法を開発することにより達成された
。(Gutter Bottom of the Invention) The purpose of the present invention is to provide a function characterized by reacting a homopolymer or a copolymer having an aromatic sulfonic acid ester group in the side chain with an unsaturated fatty acid derivative having an aliphatic tertiary amino group. This achievement was achieved by developing a method for producing synthetic polymers.
本発明において、芳香族とは、置換基をゆうしていても
よいアリールを示す、置換基はアルキル、ハロゲン、ア
ルコキシ、置換アルキル等から選ばれる。好ましいのは
、人手と反応性の点から、べンゼン若しくはトルエンで
ある。特に、トルエンスルフォン酸エステルが好マシい
。In the present invention, aromatic refers to aryl which may have a substituent, and the substituent is selected from alkyl, halogen, alkoxy, substituted alkyl, and the like. Benzene or toluene is preferred from the viewpoint of manpower and reactivity. In particular, toluene sulfonic acid ester is better.
主鎖とこのエステルの間には、アミド、エステル、エー
テルあるいは芳香環等から選ばれた、炭素原子数20以
下の二価の基を有していてよい。 芳香族スルフォン酸
エステルは、トルエンスルフォニルクロリドとアルコー
ルとの反応により、容易に得られる。アルコール部分と
しては、酢酸ビニルの単独又は共重合体の鹸化によるも
の、ヒドロキシ基を持つ(メタ)アクリレートもしくは
(メタ)アクリルアミドの単独又は共重合体、ヒドロキ
シメチルスチレンの単独又は共重合体、ヒドロキシエチ
ルビニルエーテルの単独又は共重合体等がある。此等に
ついて先に述べた特許にもくわしい。共重合のモノマー
としては、置換基をゆうしていてもよい、スチレン、(
メタ)アクリレート、アクリルアミドなどがある。別の
jL−−トとして、芳香族スルフォン酸エステルをもつ
モノマーを単独又は共重合させるものがある。例えば、
トルエンスルフォニルオキシチル(メタ)アクリレート
、レート、トルエンスルフォニルオキシプロピル(メタ
)アクリルアミド、トルエンスルフォニルオキシメチル
スチレンなどは、本発明においても、好都合にもちいら
れる。これらについては、本発明者等が既に、提唱済で
ある。A divalent group having 20 or less carbon atoms selected from amides, esters, ethers, aromatic rings, etc. may be present between the main chain and the ester. Aromatic sulfonic acid esters can be easily obtained by reacting toluenesulfonyl chloride with alcohol. The alcohol moiety is obtained by saponification of vinyl acetate alone or a copolymer, (meth)acrylate or (meth)acrylamide alone or copolymer having a hydroxy group, hydroxymethylstyrene alone or a copolymer, hydroxyethyl There are vinyl ether homopolymers or copolymers. Please refer to the patents mentioned above for details on this subject. As monomers for copolymerization, styrene, (
Examples include meth)acrylate and acrylamide. Another example is one in which a monomer having an aromatic sulfonic acid ester is monopolymerized or copolymerized. for example,
Toluenesulfonyloxytyl (meth)acrylate, toluenesulfonyloxypropyl (meth)acrylamide, toluenesulfonyloxymethylstyrene, etc. are advantageously used in the present invention. These have already been proposed by the present inventors.
重合の手法については、底置に詳しい。Regarding the polymerization method, please refer to the bottom of this page for details.
WIR◆5orenson’ Preparat iw
e Methods of PolymerCh
emistry”、J−BrandrupPolyme
r Handbook″Wiley& 5ons
など。WIR◆5orenson' Preparation iw
e Methods of PolymerCh
emistry”, J-Brandrup Polyme
r Handbook"Wiley&5ons
Such.
単独又は共重合体は一般的には、ラジカル重合反応によ
りえられる。アゾ化合物、過酸化物、レドックス系など
はこのましい一例である。Homopolymers or copolymers are generally obtained by radical polymerization reactions. Preferred examples include azo compounds, peroxides, and redox compounds.
脂肪族三級アミノ基をゆうする不飽和脂肪酸誘導体につ
いて述べる。Unsaturated fatty acid derivatives containing aliphatic tertiary amino groups will be described.
脂肪族三級アミノ基としては、アルキルまたはアラルキ
ルから選ばれたふたつと、少なくともひとつの不飽和脂
肪酸で置換したアルキルとからなる三級アミンをいう。The aliphatic tertiary amino group refers to a tertiary amine consisting of two selected from alkyl or aralkyl and an alkyl substituted with at least one unsaturated fatty acid.
アルキルまたはアラルキルは置換基として、不飽和脂肪
酸誘導体、不飽和結合などを有していてよい。ジメチル
アミノ、ジエチルアミノ、ジブチルアミノ、メチルベン
ジルアミノ、エチルプロパルギルアミノ、ジアリルアミ
ノ、アリルエチルアミノ、ジベンジルアミノ、N−ヒド
ロキシプロピルエチルアミノ、N−アクリロキシエチル
アミノ、ジヒドロキシエチルアミノ、モルフォリノ、ピ
ペラジノ等は三級アミン残基として好ましい。Alkyl or aralkyl may have an unsaturated fatty acid derivative, an unsaturated bond, etc. as a substituent. Dimethylamino, diethylamino, dibutylamino, methylbenzylamino, ethylpropargylamino, diallylamino, allylethylamino, dibenzylamino, N-hydroxypropylethylamino, N-acryloxyethylamino, dihydroxyethylamino, morpholino, piperazino, etc. Preferred as a tertiary amine residue.
不飽和脂肪酸としては、ベータナフチルアクリル酸、ア
クリル酸、メタアクリル酸、桂皮酸、チエニルアクリル
酸、フリルアクリル酸、p−エトキシカルボニル桂皮酸
、アルファシアノ桂皮酸、ソルビン酸、クロトン酸、ジ
メチル無水マレイン酸、無水マレイン酸、シンナミリデ
ン酢酸、シアノチエニルペンタジェン酸などがある。Unsaturated fatty acids include beta-naphthyl acrylic acid, acrylic acid, methacrylic acid, cinnamic acid, thienyl acrylic acid, furyl acrylic acid, p-ethoxycarbonyl cinnamic acid, alpha-cyanocinnamic acid, sorbic acid, crotonic acid, dimethyl maleic anhydride. Examples include maleic anhydride, cinnamylideneacetic acid, and cyanothienylpentadienoic acid.
脂肪族三級アミノ基と不飽和脂肪酸との結合は炭素原子
数12以下の、エーテル、エステル、アミド、ウレイド
、ウレア等を有していてよい、二価の基が好ましい。四
級塩形成反応を妨げない範囲において、ハロゲン原子、
ヒドロキシ基、ジアルキルアミノアリール基などを有し
ていてよい。The bond between the aliphatic tertiary amino group and the unsaturated fatty acid is preferably a divalent group having 12 or less carbon atoms and which may have ether, ester, amide, ureido, urea, etc. Halogen atoms, as long as they do not interfere with the quaternary salt formation reaction.
It may have a hydroxy group, a dialkylaminoaryl group, etc.
原料の入手の点からは、不飽和脂肪酸のハライド好まし
くはクロライドと、上述のアミン残基をもつ、アルコー
ルとの反応がこのましい。From the viewpoint of availability of raw materials, it is preferable to react a halide, preferably a chloride, of an unsaturated fatty acid with an alcohol having the above-mentioned amine residue.
ジエチルアミノエタノール、ジメチルアミノエタノール
、ジヒドロキシエチルブチルアミン、N−ヒドロキシエ
チルモルフォリン、エチルアリルアミン、ジエチルプロ
パノールアミン、ジメチルアミノメチルベンジルアルコ
ール、ジエチルアミノメチルシンナミルアルコール等は
好ましい一例である。また別の製法として、上述のアミ
ン残基を持つアミンと不飽和脂肪酸、またはそのエステ
ル、クロライドとのアミド化反応によるものがある。Preferred examples include diethylaminoethanol, dimethylaminoethanol, dihydroxyethylbutylamine, N-hydroxyethylmorpholine, ethylallylamine, diethylpropanolamine, dimethylaminomethylbenzyl alcohol, and diethylaminomethylcinnamyl alcohol. Another production method involves an amidation reaction between the above-mentioned amine having an amine residue and an unsaturated fatty acid, or an ester or chloride thereof.
アミノプロピルジエチルアミン、アミノエチルモルフォ
リン、アミノエチルジブチルアミン、トリエチルジエチ
ルアミン、ジメチルアミノメチルアニリン、アミノブチ
ルジェタノールアミンなどは、好ましい一例である。
アミド化、エステル化にさいし
ては、塩基を触媒に用いることがのぞましい。苛性ソー
ダ、苛性加重、ピリジン、トリエチルアミン等はこのま
しい。また、極性溶剤の使用もこのましい。Preferred examples include aminopropyldiethylamine, aminoethylmorpholine, aminoethyldibutylamine, triethyldiethylamine, dimethylaminomethylaniline, and aminobutyljetanolamine.
In amidation and esterification, it is preferable to use a base as a catalyst. Caustic soda, caustic loading, pyridine, triethylamine and the like are preferred. It is also preferable to use a polar solvent.
本発明の機能性高分子は重合ユニットあたり一つ以上の
不飽和脂肪酸誘導体と四級塩の部分をもちうるので、媒
染効果がたがい、硬化・架橋が早く、然も確実且つ親水
性なので、アルカリ水処理、含水溶剤処理などを利用し
た画像形成に好都合に利用できる利点をもつ。そのよう
な用途での使用例はすでにくわしい。J−Kosar″
L1ght 5ensitive Systems
角田”感光性樹脂”特開平1−105944等。Since the functional polymer of the present invention can have one or more unsaturated fatty acid derivatives and quaternary salt moieties per polymerization unit, it has a mordant effect, cures and crosslinks quickly, and is reliably and hydrophilic. It has the advantage that it can be conveniently used for image formation using water treatment, water-containing solvent treatment, etc. Examples of use in such applications are already detailed. J-Kosar''
L1ght 5intensive Systems
Tsunoda "Photosensitive Resin" JP-A-1-105944, etc.
以下に実施例をあげ、本発明を詳しく述べる。The present invention will be described in detail with reference to Examples below.
実施例 1.2
MEKlooml、ヒドロキシエチルアクリレート0・
1モル、ブチルメタアクリレート0・1モルおよび触媒
量のアゾビスイソブチロニトリルを用いて、定法にした
がい窒素ガスを通じながら65度ないし78度に6・5
時間掻き混ぜて共重合体をえた。コンバージョンはほぼ
定量的であった。スルフオラン50m1.0・1モルの
トルエンスルフォニルクロライドをくわえ攪拌した。次
に、50度以下で、トリエチルアミン0・3モルを滴下
した。副生ずる塩酸塩をのぞき、生じたトシルオキシ基
をゆうするポリマーを、メタノールをもちいてjl離し
た。乾燥重量から求めた、反応率は、定量的であった。Example 1.2 MEKrooml, hydroxyethyl acrylate 0.
Using 1 mol of butyl methacrylate, 0.1 mol of butyl methacrylate, and a catalytic amount of azobisisobutyronitrile, the mixture was heated to 6.5°C from 65°C to 78°C while passing nitrogen gas according to the usual method.
After stirring for a while, a copolymer was obtained. The conversion was almost quantitative. 1.0.1 mol of toluenesulfonyl chloride was added to 50ml of sulfolane and stirred. Next, 0.3 mol of triethylamine was added dropwise at a temperature below 50 degrees. Except for the by-produced hydrochloride, the resulting polymer containing tosyloxy groups was separated using methanol. The reaction rate determined from the dry weight was quantitative.
こウシて、トルエンスルフォニルオキシエチルアクリレ
ートとブチルメタアクリレートとの共重合体をえた。重
合体lとよぶ。As a result, a copolymer of toluenesulfonyloxyethyl acrylate and butyl methacrylate was obtained. It is called polymer l.
DMFIQmlに、4gの重合体1を秤りとり溶解し、
ジメチルアミノエチルシンナメイト0・01モルを加え
て、60度に50分間保持した。Weigh and dissolve 4 g of polymer 1 in DMFIQml,
0.01 mol of dimethylaminoethyl cinnamate was added and the mixture was maintained at 60 degrees for 50 minutes.
生じた四級塩ポリマーを酢酸エチル/ヘキサンから沈澱
させ分離した。(実施例1)
上と同様な操作を、ジエチルアミノプロビルシンナムア
ミドを用いて行った。(実施例2)(参考例)
実施例1・2で得られた側鎖に、不飽和脂肪酸誘導体部
分と四級環部分を持つ機能性ポリマーのそれぞれに、8
パーセントの増感剤(N−メチルベンゾイルナフトチア
ゾリン)を加え、DMFに溶解した。これを、電解処理
したアルミ版に、乾燥後の厚みが2ミクロンになるよう
に、dip−coatした。400W高圧水銀ランプを
用いて30cmの距離から、2分間照射した。露光部分
は、溶剤でリンスしてもはがれなかった。The resulting quaternary salt polymer was precipitated from ethyl acetate/hexane and isolated. (Example 1) A similar operation as above was performed using diethylaminoprobyl cinnamamide. (Example 2) (Reference example) Each of the functional polymers having an unsaturated fatty acid derivative moiety and a quaternary ring moiety in the side chain obtained in Examples 1 and 2 contained 8
% sensitizer (N-methylbenzoylnaphthothiazoline) was added and dissolved in DMF. This was dip-coated onto an electrolytically treated aluminum plate so that the thickness after drying was 2 microns. Irradiation was performed for 2 minutes from a distance of 30 cm using a 400W high-pressure mercury lamp. The exposed areas did not come off even after rinsing with solvent.
Claims (1)
くは共重合体と脂肪族三級アミノ基を有する不飽和脂肪
酸誘導体を反応させる事を特徴とする機能性高分子の製
法A method for producing a functional polymer characterized by reacting a single or copolymer having an aromatic sulfonic acid ester group in its side chain with an unsaturated fatty acid derivative having an aliphatic tertiary amino group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21451889A JPH0376707A (en) | 1989-08-21 | 1989-08-21 | Production of functional polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21451889A JPH0376707A (en) | 1989-08-21 | 1989-08-21 | Production of functional polymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0376707A true JPH0376707A (en) | 1991-04-02 |
Family
ID=16657052
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21451889A Pending JPH0376707A (en) | 1989-08-21 | 1989-08-21 | Production of functional polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0376707A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2351498A (en) * | 1999-06-26 | 2001-01-03 | Hyundai Electronics Ind | Benzenesulphonyloxyalkyl (meth)acrylate polymers |
-
1989
- 1989-08-21 JP JP21451889A patent/JPH0376707A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2351498A (en) * | 1999-06-26 | 2001-01-03 | Hyundai Electronics Ind | Benzenesulphonyloxyalkyl (meth)acrylate polymers |
GB2351498B (en) * | 1999-06-26 | 2004-09-08 | Hyundai Electronics Ind | Organic anti-reflective polymer and preparation thereof |
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