JPH047385A - Reversible phase transition material - Google Patents
Reversible phase transition materialInfo
- Publication number
- JPH047385A JPH047385A JP2109152A JP10915290A JPH047385A JP H047385 A JPH047385 A JP H047385A JP 2109152 A JP2109152 A JP 2109152A JP 10915290 A JP10915290 A JP 10915290A JP H047385 A JPH047385 A JP H047385A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- phase transition
- reversible phase
- vinyl monomer
- alkyl
- 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
- 230000002441 reversible effect Effects 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title abstract description 20
- 230000007704 transition Effects 0.000 title abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012782 phase change material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 4
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- -1 group Chemical group 0.000 description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 4
- 239000012769 display material Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000003983 crown ethers Chemical group 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical class CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
- GQRWGIWRQMNZNT-UHFFFAOYSA-N 2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadecane Chemical group O1CCOCCOCCOCCOC2CCCCC21 GQRWGIWRQMNZNT-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- JKCQOMAQPUYHPL-UHFFFAOYSA-N dibenzo-21-crown-7 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 JKCQOMAQPUYHPL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- FIBUWQFQYAAXHD-UHFFFAOYSA-N n-cyclopropyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1CC1 FIBUWQFQYAAXHD-UHFFFAOYSA-N 0.000 description 1
- ZOTWHNWBICCBPC-UHFFFAOYSA-N n-ethyl-n-methylprop-2-enamide Chemical compound CCN(C)C(=O)C=C ZOTWHNWBICCBPC-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035440 response to pH Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規な可逆的相転移材料、さらに詳しくは、表
示材料、センサ材料、薬物の放出制御材料などとして有
用な特定の化学物質に高感度で感応して可逆的に相転移
を起こす高分子材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel reversible phase change material, more specifically, a material with high sensitivity to specific chemical substances useful as a display material, a sensor material, a controlled release material for drugs, etc. It relates to polymeric materials that undergo a reversible phase transition upon response.
従来の技術
特定の化学物質に感応して可逆的に状態変化を起こす高
分子材料は、表示材料、センサ材料、薬物の放出制御材
料などに利用することができる。BACKGROUND OF THE INVENTION Polymer materials that undergo a reversible state change in response to specific chemical substances can be used as display materials, sensor materials, drug release control materials, and the like.
例えば、ｐＨに感応して状態変化を起こす高分子材料と
しては、メチルビニルエーテルと無水マレイン酸との共
重合体、ボリヒニルアルコール／ポリアクリル酸／ポリ
アリルアミン複合膜、ポリアクリルアミドなどの他にリ
ポソーム、マイクロカプセル構成材料なとが知られてお
り〔「高分子新素材便覧」第３３２ページ（１９８９年
発行）、「高分子」第３６巻、第３５４ページ（１９８
７年）、 「フィジカル・レビュールターズ（Ｐｈｙｓ
ｉｃａｌ Ｒｅｖｉｅｗ Ｌｅｔｔｅｒｓ）Ｊ第４５巻
、第１６３６ページ（１９８０年）、「マクロモレキュ
ルズ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）Ｊ第１７巻、第
１６９２ページ（１９８４年）、「ジャーナル・オブ・
アメリカン・ケミカル・ソサエティ（Ｊ、Ａｍｅｒ、Ｃ
ｈｅｍ、５ｏｃ）Ｊ第１０６巻、第８０６５ページ（１
９８４年）〕、これらの高分子材料は、主として薬物の
放出制御や人工筋肉などへの応用を目的として研究が進
められている。For example, polymer materials that change their state in response to pH include copolymers of methyl vinyl ether and maleic anhydride, polyhinyl alcohol/polyacrylic acid/polyallylamine composite membranes, polyacrylamide, and liposomes. , microcapsule constituent materials are known [``Handbook of New Polymer Materials'', page 332 (published in 1989), ``Polymer'' Vol. 36, page 354 (198
7th year), “Physical Review Luthers (Physical Reviewers)
ical Review Letters J Vol. 45, p. 1636 (1980), "Macromolecules J Vol. 17, p. 1692 (1984), "Journal of
American Chemical Society (J, Amer, C
hem, 5oc) J Volume 106, Page 8065 (1
(984)], research on these polymeric materials is being advanced mainly for the purpose of controlling the release of drugs and applying them to artificial muscles.
また、カルシウムイオンに応答するマイクロカプセルの
例も報告されている〔「ジャーナル・オブ・アメリカン
・ケミカル・ソサエティ（Ｊ、Ａｍｅｒ 、Ｃｈｅｍ。Examples of microcapsules that respond to calcium ions have also been reported [Journal of the American Chemical Society (J, Amer, Chem.
Ｓｏｃ、 ）Ｊ第１０６巻、第４６９６ページ（１９８
４年）〕。Soc, ) J Volume 106, Page 4696 (198
4th year)].
しかしなから、これらの可逆的相転移高分子材料は、イ
オンなどの化学物質に対する選択性が十分ではなく、ま
た、該化学物質の濃度に対する応答性にも問題かあり、
現在のところほとんど実用化に至っていないのが実状で
ある。However, these reversible phase change polymer materials do not have sufficient selectivity for chemical substances such as ions, and also have problems in their responsiveness to the concentration of the chemical substances.
The reality is that it has hardly been put into practical use at present.
発明か解決しようとする課題
本発明は、イオン種選択性やイオン濃度感応性に優れ、
例えば表示材料、センサ材料、薬物の放出制御材料など
として有用な可逆的相転移材料を提供することを目的と
してなされたものである。Problems to be Solved by the Invention The present invention has excellent ion species selectivity and ion concentration sensitivity.
The purpose of this invention is to provide a reversible phase change material useful as, for example, a display material, a sensor material, a drug release control material, and the like.
課題を解決するための手段
本発明者らは前記の好ましい性質を有する可逆的相転移
材料を開発すべく鋭意研究を重ねた結果、分子内に機能
性置換基を有する特定の共重合体と水との組成物から成
る材料により、その目的を達成しうろことを見い出し、
この知見に基づいて本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive research to develop a reversible phase change material having the above-mentioned preferable properties. By using a material composed of a composition of
Based on this knowledge, we have completed the present invention.
すなわち、本発明は、Ｎ−アルキルアクリルアミド又は
Ｎ−アルキルメタクリルアミド単位と機能性置換基をも
つビニルモノマー単位とから構成される分子量１０００
０〜２０００００の共重合体と水との組成物から成る可
逆的相転移材料を提供するものである。That is, the present invention is directed to a compound having a molecular weight of 1000 and consisting of an N-alkylacrylamide or N-alkylmethacrylamide unit and a vinyl monomer unit having a functional substituent.
The present invention provides a reversible phase change material comprising a composition of a copolymer of 0 to 200,000 and water.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の可逆的相転移材料はＮ−アルキルアクリルアミ
ド又はＮ−アルキルメタクリルアミド単位と機能性置換
基をもつビニルモノマー単位とから構成された共重合体
と水との組成物から成るものであって、該共重合体は（
１）Ｎ−アルキルアクリルアミド又はＮ−アルキルメタ
クリルアミドと機能性置換基又はその前駆体をもつビニ
ルモノマーとの共重合反応による方法、又は（２）ポリ
（Ｎ−アルキルアクリルアミド）又はポリ（Ｎ−アルキ
ルメタクリルアミド）の高分子反応による方法によって
製造することができる。The reversible phase change material of the present invention is composed of a copolymer composed of N-alkylacrylamide or N-alkylmethacrylamide units and vinyl monomer units having functional substituents, and water. , the copolymer is (
1) A method based on a copolymerization reaction of N-alkylacrylamide or N-alkylmethacrylamide with a vinyl monomer having a functional substituent or its precursor, or (2) Poly(N-alkylacrylamide) or poly(N-alkyl It can be produced by a polymer reaction method using (methacrylamide).
前記機能性置換基は、化学物質と特異的に反応又は相互
作用して共重合体と水との組成物に可逆的な相変化をも
たらす基であって、このようなものとしては、例えばカ
ルボキシル基、ピリジル基、大環状ポリエーテル基など
が挙げられる。The functional substituent is a group that specifically reacts or interacts with a chemical substance to bring about a reversible phase change in the composition of the copolymer and water, and examples of such groups include carboxyl, group, pyridyl group, macrocyclic polyether group, etc.
前記（１）の共重合反応によって、該共重合体を製造す
るのに用いられるＮ−アルキルアクリルアミドやＮ−ア
ルキルメタクリルアミドとしては、例えばＮ−エチルア
クリルアミド、Ｎ −ｎ−プロピルアクリルアミド、Ｎ
−ｎ−プロピルメタクリルアミド、Ｎ−イソプロピルア
クリルアミド、Ｎ−イソプロピルメタクリルアミド、Ｎ
−シクロプロピルアクリルアミド、Ｎ−シクロプロピル
メタクリルアミド、Ｎ−エチル−Ｎ−メチルアクリルア
ミド、Ｎ、Ｎ−ジエチルアクリルアミド、Ｎ−アクリル
ピロリジン、Ｎ−アクリルピペリジンなどを挙げること
ができる。これらのＮ−アルキルアクリルアミドやＮ−
アルキルメタクリルアミドは１種用いてもよいし、２種
以上を組み合わせて用いてもよい。Examples of the N-alkylacrylamide and N-alkylmethacrylamide used to produce the copolymer by the copolymerization reaction in (1) include N-ethylacrylamide, N-n-propylacrylamide, and N-alkylmethacrylamide.
-n-propylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N
Examples include -cyclopropylacrylamide, N-cyclopropylmethacrylamide, N-ethyl-N-methylacrylamide, N,N-diethylacrylamide, N-acrylpyrrolidine, and N-acrylpiperidine. These N-alkylacrylamides and N-
One type of alkyl methacrylamide may be used, or two or more types may be used in combination.
一方、前記の機能性置換基又はその前駆体をもつビニル
モノマーとしては、例えば無水マレイン厳や、２−ビニ
ルピリジン、３−ビニルピリジン、４−ビニルピリジン
などのビニルピリジン類及びクラウンエーテル残基を有
するアクリルアミド誘導体、メタクリルアミド誘導体、
アクリル酸エステル誘導体、メタクリル酸エステル誘導
体、スチレン誘導体などが用いられる。該クラウンエー
テル残基としては、シクロへキシル−１５−クラウン−
５、シクロへキシル−１８−クラウン−６、ベンゾ−１
８−クラウン−６、ジベンゾ−１８−クラウン−６、ジ
ベンゾ−２１−クラウン−７などの残基が挙げられる。On the other hand, examples of the vinyl monomer having the above-mentioned functional substituent or its precursor include maleic anhydride, vinylpyridines such as 2-vinylpyridine, 3-vinylpyridine, and 4-vinylpyridine, and crown ether residues. Acrylamide derivatives, methacrylamide derivatives,
Acrylic ester derivatives, methacrylic ester derivatives, styrene derivatives, etc. are used. The crown ether residue is cyclohexyl-15-crown-
5, cyclohexyl-18-crown-6, benzo-1
Examples include residues such as 8-crown-6, dibenzo-18-crown-6, and dibenzo-21-crown-7.
これらのビニルモノマーは１種用いてもよいし、２種以
上を組み合わせて用いてもよい。These vinyl monomers may be used alone or in combination of two or more.
前記Ｎ−アルキルアクリルアミドやＮ−アルキルメタク
リルアミドと機能性置換基又はその前駆体をもつビニル
モノマーとの共重合反応には、通常のラジカル重合方法
が用いられるが、操作が容易な点で、溶液重合法を用い
ることが好ましい。重合溶媒としては、例えばベンゼン
、トルエン、テトラヒドロフラン、ジオキサンなどが用
いられ、重合開始剤としては、通常のラジカル重合開始
剤、例えばベンゾイルパーオキシド、２．２−アゾビス
イソブチロニトリルなどが用いられる。重合温度は通常
５０〜８０℃の範囲で選ばれ、重合時間は３０分ないし
６時間径度で十分である。また必要に店じ、重合系中に
少量の架橋剤を加えてもよい。For the copolymerization reaction of the N-alkylacrylamide or N-alkylmethacrylamide with the vinyl monomer having a functional substituent or its precursor, an ordinary radical polymerization method is used, but from the viewpoint of ease of operation, it is preferable to use a solution method. Preferably, polymerization methods are used. As the polymerization solvent, for example, benzene, toluene, tetrahydrofuran, dioxane, etc. are used, and as the polymerization initiator, ordinary radical polymerization initiators such as benzoyl peroxide, 2,2-azobisisobutyronitrile, etc. are used. . The polymerization temperature is usually selected within the range of 50 to 80°C, and a polymerization time of 30 minutes to 6 hours is sufficient. If necessary, a small amount of crosslinking agent may be added to the polymerization system.
この架橋剤としては、例えばメチレンビスアクリルアミ
ド、エチレンジメタクリレートなどを用いることができ
る。As this crosslinking agent, for example, methylene bisacrylamide, ethylene dimethacrylate, etc. can be used.
前記（２）のポリ（Ｎ−アルキルアクリルアミド）又は
ポリ（Ｎ−アルキルメタクリルアミド）の高分子反応に
よって該共重合体を製造する方法においては、前記（１
）の方法で例示したＮ−アルキルアクリルアミド又はＮ
−アルキルメタクリルアミドを同様にして重合させポリ
（Ｎ−アルキルアクリルアミド）又はポリ（Ｎ−アルキ
ルメタクリドアミド）を得たのち、加水分解してアミド
基の一部を機能性官能基のカルボキシル基に変え、必要
ならばこのカルボキシル基を用いて通常のエステル結合
生成反応により他の機能性官能基を導入することにより
、所望の共重合体を得ることができる。この場合、該共
重合体は、共重合反応によらなくとも、Ｎ−アルキルア
クリルアミドとアクリル酸若しくはアクリル酸エステル
との共重合体、又はＮ−アルキルメタクリルアミドとメ
タクリル酸若しくはメタクリル酸エステルとの共重合体
の構造となる。In the method for producing the copolymer by a polymer reaction of poly(N-alkylacrylamide) or poly(N-alkylmethacrylamide) in the above (2), the above (1)
) N-alkylacrylamide or N
- Polymerize alkylmethacrylamide in the same manner to obtain poly(N-alkylacrylamide) or poly(N-alkylmethacrylamide), and then hydrolyze it to convert some of the amide groups into carboxyl groups of functional groups. If necessary, the desired copolymer can be obtained by introducing other functional groups using this carboxyl group through a conventional ester bond forming reaction. In this case, the copolymer may be a copolymer of N-alkylacrylamide and acrylic acid or acrylic ester, or a copolymer of N-alkylmethacrylamide and methacrylic acid or methacrylic ester, even if it does not involve a copolymerization reaction. It has a polymer structure.
このようにして機能性官能基か導入された共重合体は、
その分子量か１０，０００〜２００，０００の範囲にあ
ることが必要であり、この範囲を逸脱すると本発明の目
的が十分に達せられない。The copolymer into which functional groups have been introduced in this way is
It is necessary that the molecular weight is in the range of 10,000 to 200,000; if it deviates from this range, the object of the present invention cannot be fully achieved.
また、この共重合体中の該機能性官能基の含有量は、通
常帆１〜１０モル％の範囲で選ばれる。Further, the content of the functional group in this copolymer is usually selected within the range of 1 to 10 mol%.
本発明の可逆的相転移材料は、前記のようにして機能性
官能基が導入された共重合体と水との組成物から成るも
のであって、特定の化学物質に感応して、膨潤状態（透
明状態）と凝集状態（白濁状態）の可逆的な相転移が生
じる。The reversible phase change material of the present invention is composed of a copolymer into which a functional group has been introduced as described above and water, and is swollen in response to a specific chemical substance. A reversible phase transition occurs between (transparent state) and agglomerated state (cloudy state).
次に、本発明の可逆的相転移材料の作用について説明す
る。Next, the action of the reversible phase change material of the present invention will be explained.
ポリ（Ｎ−アルキルアクリルアミド）やポリ（Ｎ−アル
キルメタクリルアミド）の水溶液はある特定の温度以上
に加熱すると、非常に狭い温度範囲で相分離することが
知られている。これは１種の相転移現象であり、相転移
点付近においては、系にわずかな摂動が加わることによ
り、系全体の状態は大きく変化し、より安定な状態へ移
行する。It is known that when an aqueous solution of poly(N-alkylacrylamide) or poly(N-alkylmethacrylamide) is heated above a certain temperature, phase separation occurs within a very narrow temperature range. This is a type of phase transition phenomenon, and when a slight perturbation is applied to the system near the phase transition point, the state of the entire system changes significantly and shifts to a more stable state.
第１図は、本発明材料の相転移の１例を示す模式図であ
って、該材料における機能性官能基と特異的に反応若し
くは相互作用して、該材料の相転移を誘起する化学物質
を１１このＩが存在しない場合の該材料におけるポリマ
ーをＡとすると、■が存在しない場合、ポリマーＡは、
温度Ｔａにおいて状態Ｘから状態Ｙへ相転移する。一方
Ｉが存在する場合には、ポリマーＡはＩと反応若しくは
相互作用してポリマーＢとなる。このポリマーＢは温度
Ｔｂにおいて状ＭＡＸから状態Ｙに相転移する。FIG. 1 is a schematic diagram showing one example of phase transition of the material of the present invention, and shows a chemical substance that specifically reacts or interacts with a functional group in the material to induce phase transition of the material. 11 If the polymer in the material when this I does not exist is A, then when ■ does not exist, the polymer A is
A phase transition occurs from state X to state Y at temperature Ta. On the other hand, when I is present, polymer A reacts or interacts with I to form polymer B. This polymer B undergoes a phase transition from state MAX to state Y at temperature Tb.
したがって、Ｔａ（Ｔ （Ｔｂの温度範囲においては、
■の有無により相転移が誘起されることになる。Therefore, in the temperature range of Ta(T(Tb),
A phase transition is induced depending on the presence or absence of (2).
発明の効果
本発明の可逆的相転移材料は、特定のイオン種及び該イ
オンの濃度に鋭敏に応答し、膨潤状態と凝集状態を可逆
的にとりうるので、ｐＨあるいは特定イオンに応答する
投薬システムやイオンセンサの材料として用いることが
できるし、また、白濁状態と透明状態の可逆的変化を利
用して表示材料としても用いることができる。Effects of the Invention The reversible phase change material of the present invention responds sensitively to specific ion species and the concentration of the ions, and can reversibly assume a swollen state and an agglomerated state. It can be used as a material for ion sensors, and can also be used as a display material by utilizing the reversible change between a cloudy state and a transparent state.
実施例
次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
無水マレイン＃７４ｒｎｇ、Ｎ−イングロビルアクリル
アミド２．８３ｇの１ＯｒｎＱベンゼン溶液に開始剤と
して２．２−アゾビスイソブチロニトリル２０ｍ９を加
え、窒素雰囲気下に６０’Ｃ″ｃ１時間がきまぜた。Example 1 20m9 of 2,2-azobisisobutyronitrile was added as an initiator to a 1OrnQ benzene solution containing 74rng anhydrous maleic acid and 2.83g N-inglobil acrylamide, and the mixture was heated at 60'C''c for 1 hour under a nitrogen atmosphere. Zeta.
反応混合物を１００ｍＱのエーテル中に加え、沈澱した
共重合体をろ過、エーテルで洗浄後乾燥した。The reaction mixture was added to 100 mQ of ether, and the precipitated copolymer was filtered, washed with ether, and dried.
転化率５．３％、ポリマーの分子量は１８，０００．ポ
リマー中の無水マレイン酸単位の含有量は１．８モル％
であった。The conversion rate was 5.3%, and the molecular weight of the polymer was 18,000. The content of maleic anhydride units in the polymer is 1.8 mol%
Met.
前記共重合体１重量部を、ｐＨ３，５に調節した水溶液
９９３！量部に溶解し、昇温すると、４０．１℃におい
て相分離（白濁）した。またｐＨ２，６に調節した水溶
液を用いた場合には３３．３℃で相分離した。温度を３
５℃に固定してｐＨを変えていくと、第２図のｐｕと透
過率との関係を示すグラフに実線で示したようにｐＨ２
，９で急激な相転移が観察された。An aqueous solution of 1 part by weight of the above copolymer adjusted to pH 3.5 993! When dissolved in aliquots and heated, phase separation (white turbidity) occurred at 40.1°C. Further, when an aqueous solution adjusted to pH 2.6 was used, phase separation occurred at 33.3°C. temperature 3
When the pH is fixed at 5℃ and the pH is changed, the pH increases as shown by the solid line in the graph showing the relationship between pu and transmittance in Figure 2.
, 9, a rapid phase transition was observed.
実施例２
実施例１においてＮ−イソプロピルアクリルアミドの代
りにＮ、Ｎ−ジエチルアクリルアミド３．２８ｇを用い
た以外は、実施例１と同様に共重合反応を行った。転化
率４．１％、ポリマー中の無水マレイン酸単位の含量は
２．４モル％であった。この共重合体１重量部を含む水
溶液は、３７°ＣにおいてｐＨ２，９で急激な相転移を
示した。Example 2 A copolymerization reaction was carried out in the same manner as in Example 1 except that 3.28 g of N,N-diethylacrylamide was used instead of N-isopropylacrylamide. The conversion rate was 4.1%, and the content of maleic anhydride units in the polymer was 2.4 mol%. An aqueous solution containing 1 part by weight of this copolymer exhibited a rapid phase transition at pH 2.9 at 37°C.
実施例３
実施例１において無水マレイン酸の代りに４−ビニルピ
リジン７１ｍｇを用いた以外は、実施例１と同様に共重
合反応を行った。転化率１２％、ポリマーの分子量は３
３，０００、ポリマー中の４−ビニルピリジン残基の含
有量は２．０モル％であった。Example 3 A copolymerization reaction was carried out in the same manner as in Example 1, except that 71 mg of 4-vinylpyridine was used instead of maleic anhydride. Conversion rate 12%, polymer molecular weight 3
3,000, and the content of 4-vinylpyridine residues in the polymer was 2.0 mol%.
この共重合体１重量部を含む水溶液のｐＨを温度３５℃
に固定しつつ、変化させると、第２図のｐｎと透過率と
の関係を示すグラフに破線で示したように、ｐＨ４、３
で急激な相転移が観察された。The pH of an aqueous solution containing 1 part by weight of this copolymer was adjusted to 35°C.
As shown by the broken line in the graph showing the relationship between pn and transmittance in FIG.
A rapid phase transition was observed.
実施例４
４−アクロイルアミノベンゾ−１８−クラウン−６１０
０ｍｇとＮ−イソプロピルアクリルアミド５０にのｌＯ
ｍＱベンゼン溶液に２，２−アゾヒスイソブチロニトリ
ル１５ｍｇを加え、窒素雰囲気下に６０°Ｃで３時間か
きまぜた。反応混合物をｌＯＯ＋＋＋１２のエーテル中
に加え、沈澱した重合体をろ過、酢酸エチルで洗浄後乾
燥した。転化率４５％、共重合体中のクラウンエーテル
残基の含量は５．６モル％であった。Example 4 4-Acroylaminobenzo-18-crown-610
0 mg and N-isopropylacrylamide in 50 lO
15 mg of 2,2-azohisisobutyronitrile was added to the mQ benzene solution, and the mixture was stirred at 60°C for 3 hours under a nitrogen atmosphere. The reaction mixture was added to lOO+++12 of ether, and the precipitated polymer was filtered, washed with ethyl acetate, and dried. The conversion rate was 45%, and the content of crown ether residue in the copolymer was 5.6 mol%.
この共重合体１重量部を含む水溶液を温度３２℃に固定
し、Ｋ＋イオン濃度を変化させると、第３図に示したよ
うな結果が得られた。When an aqueous solution containing 1 part by weight of this copolymer was fixed at a temperature of 32 DEG C. and the K+ ion concentration was varied, the results shown in FIG. 3 were obtained.
すなわち、該共重合体は２種の特定のに＋イオン濃度に
おいて相転移現象を示し、この２種の濃度範囲内におい
てのみ透明状態（膨潤状態）をとる。That is, the copolymer exhibits a phase transition phenomenon at two specific concentrations of + ions, and assumes a transparent state (swollen state) only within the range of these two concentrations.
この現象はに＋イオンに特異的であり、Ｎａ＋イオンや
Ｌｉ＋イオンを用いた場合には認められなかった。This phenomenon is specific to Ni+ ions, and was not observed when Na+ ions or Li+ ions were used.
第１図は本発明の可逆的相転移材料における相転移の１
例を示すグラフ、第２図はＮ−アルキルアクリルアミド
系共重合体水溶液のｐＨ応答性の異なった例を示すグラ
フであって、実線はＮ−イソプロピルアクリルアミドと
無水マレイン酸との共重合体の場合、破線はＮ−イソプ
ロピルアクリルアミドと４−ビニルピリジンとの共重合
体の場合である。第３図はＮ−イソプロピルアクリルア
ミドと４−アクロイルアミノベンゾ−１８−クラウン−
６との共重合体水溶液の光透過率とカリウムイオン濃度
との関係の１例を示すグラフである。
第１図
Ｔ。
ｂ
温度
第２図
特許出願人 旭化成工業株式会社Figure 1 shows one phase transition in the reversible phase change material of the present invention.
Graph showing examples. Figure 2 is a graph showing different examples of pH responsiveness of N-alkylacrylamide copolymer aqueous solutions, and the solid line is for a copolymer of N-isopropylacrylamide and maleic anhydride. , the broken line is for a copolymer of N-isopropylacrylamide and 4-vinylpyridine. Figure 3 shows N-isopropylacrylamide and 4-acroylaminobenzo-18-crown-
6 is a graph showing an example of the relationship between the light transmittance and the potassium ion concentration of an aqueous copolymer solution with No. 6. Figure 1T. b Temperature Diagram 2 Patent Applicant Asahi Kasei Corporation
Claims (1)
クリルアミド単位と機能性置換基をもつビニルモノマー
単位とから構成される分子量１００００〜２０００００
の共重合体と水との組成物から成る可逆的相転移材料。1 Molecular weight 10,000 to 200,000 composed of N-alkyl acrylamide or N-alkyl methacrylamide units and vinyl monomer units having functional substituents
A reversible phase change material consisting of a composition of a copolymer of and water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2109152A JP2859690B2 (en) | 1990-04-25 | 1990-04-25 | Reversible phase change material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2109152A JP2859690B2 (en) | 1990-04-25 | 1990-04-25 | Reversible phase change material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH047385A true JPH047385A (en) | 1992-01-10 |
| JP2859690B2 JP2859690B2 (en) | 1999-02-17 |
Family
ID=14502946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2109152A Expired - Lifetime JP2859690B2 (en) | 1990-04-25 | 1990-04-25 | Reversible phase change material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2859690B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06207162A (en) * | 1992-09-16 | 1994-07-26 | S T Chem Co Ltd | Evaporation inhibitor |
| US5534229A (en) * | 1992-09-16 | 1996-07-09 | Nomura & Shibatani | Volatilization suppressing agent |
-
1990
- 1990-04-25 JP JP2109152A patent/JP2859690B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06207162A (en) * | 1992-09-16 | 1994-07-26 | S T Chem Co Ltd | Evaporation inhibitor |
| US5534229A (en) * | 1992-09-16 | 1996-07-09 | Nomura & Shibatani | Volatilization suppressing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2859690B2 (en) | 1999-02-17 |
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