JPH0350225A - Stimulus-responsive polymer - Google Patents
Stimulus-responsive polymerInfo
- Publication number
- JPH0350225A JPH0350225A JP18259889A JP18259889A JPH0350225A JP H0350225 A JPH0350225 A JP H0350225A JP 18259889 A JP18259889 A JP 18259889A JP 18259889 A JP18259889 A JP 18259889A JP H0350225 A JPH0350225 A JP H0350225A
- Authority
- JP
- Japan
- Prior art keywords
- stimulus
- responsive polymer
- polyether polyol
- water
- polymer
- 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 abstract description 31
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 14
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 6
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 230000004043 responsiveness Effects 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 etc.) Chemical compound 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FJGNTEKSQVNVTJ-UHFFFAOYSA-N 1-deoxy-D-lyxitol Natural products CC(O)C(O)C(O)CO FJGNTEKSQVNVTJ-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004660 morphological change Effects 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YAXKTBLXMTYWDQ-UHFFFAOYSA-N 1,2,3-butanetriol Chemical compound CC(O)C(O)CO YAXKTBLXMTYWDQ-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical group CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 241000546339 Trioxys Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- AALKGALVYCZETF-UHFFFAOYSA-N pentane-1,2,3-triol Chemical compound CCC(O)C(O)CO AALKGALVYCZETF-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
Landscapes
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、水の存在下において刺激を与えることにより
形態変化し得る刺激応答性ポリマーに関するものである
。更に、詳しく言えば、本発明は水の存在下に、温度変
化に伴って膨張と収縮とを可逆的に繰り返す事が可能な
ものであって、例えば、エネルギー変換用素材、エネル
ギー貯蓄用素材、アクチュエーター、センサー、吸脱水
剤、徐放剤、玩具などへの利用が可能な、メカノケミカ
ル材料として有用な刺激応答性ポリマーに関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a stimulus-responsive polymer that can undergo a shape change upon stimulation in the presence of water. More specifically, the present invention is capable of reversibly repeating expansion and contraction in response to temperature changes in the presence of water, such as energy conversion materials, energy storage materials, This invention relates to stimulus-responsive polymers useful as mechanochemical materials that can be used in actuators, sensors, water absorbing and dehydrating agents, sustained release agents, toys, etc.
従来、刺激により可逆的に膨張収縮を繰り返し得るポリ
マーとしては、ポリアクリルアミド、ポリメタクリル酸
などを用いたものが知られており、メカノケミカル材料
への使用が提案されている。この様なポリマーの刺激応
答性は、ポリマーへの液体の吸収と放出の繰り返しによ
り発現するものであり、ポリマーへの液体の拡散が刺激
応答性の律速となるのであるが、従来から知られている
ポリマーは刺激応答性が満足しうるものではなかった。Polyacrylamide, polymethacrylic acid, and the like have been known as polymers that can repeatedly expand and contract reversibly upon stimulation, and their use in mechanochemical materials has been proposed. The stimulus-responsiveness of polymers is developed through repeated absorption and release of liquid into the polymer, and the diffusion of liquid into the polymer is the rate-limiting factor for stimulus-responsiveness. The stimuli-responsiveness of these polymers was not satisfactory.
この様なポリマーを用いて刺激応答性の良いメカノケミ
カル材料を得るには、ポリマーを薄膜にしたり、繊維状
にしたりする必要があるが材料の強度や成形性の面で問
題を有している。In order to obtain a mechanochemical material with good stimulus response using such polymers, it is necessary to form the polymer into a thin film or fiber, but there are problems in terms of strength and moldability of the material. .
また、該材料は、乾燥時には柔軟性を失い、ゲル特有の
柔らかいという性質が生かされていないという欠点も有
している。Furthermore, this material also has the disadvantage that it loses its flexibility when dried, and the soft properties peculiar to gel are not utilized.
本発明の目的は、この様な事情のもとで成形性及び温度
応答性の面で優れ、しかも乾燥時にも柔軟性を保持でき
る刺激応答性ポリマーを提供することである。Under these circumstances, an object of the present invention is to provide a stimulus-responsive polymer that is excellent in moldability and temperature responsiveness and can maintain flexibility even when dried.
〔課題を解決するための手段及び作用］本発明は一般式
（Ｉ）
Ｒ１〔＋０Ｃ８Ｈ４−地＝−→−ＯＲ、＋ 、−０旧、
（Ｉ）（式中、Ｒ１は炭素数１〜８で２〜８価の炭化水
素基であり、Ｒ８は炭素数３〜６のアルキレン基であり
、ａは２〜２００００の整数であり、ｍは０又は１〜２
００００の整数であり、ｎは２〜８の整数であり、＋
ＯＣ□Ｈ４＋単位と＋ＯＲ，十単位とはどのような配列
で結合していてもよい、）で示され、かつ水溶性のポリ
エーテルポリオール（Ａ）とポリイソシアネート化合物
（Ｂ）とを反応してなる刺激応答性ポリマーに関する。[Means and effects for solving the problems] The present invention is based on the general formula (I)
(I) (wherein R1 is a divalent to octavalent hydrocarbon group with 1 to 8 carbon atoms, R8 is an alkylene group with 3 to 6 carbon atoms, a is an integer of 2 to 20,000, m is 0 or 1-2
is an integer of 0000, n is an integer of 2 to 8, +
OC□H4+ units and +OR, 10 units may be bonded in any arrangement), and by reacting a water-soluble polyether polyol (A) and a polyisocyanate compound (B). The present invention relates to a stimulus-responsive polymer.
本発明におけるポリエーテルポリオール（Ａ）は前記一
般式（Ｉ）で表わされ、かつ水溶性のものである。ここ
で水溶性とは、水に溶解可能である事を意味し、通常水
に対する溶解度が５重量％以上である事が好ましい、水
への溶解度が５重量％未滴の場合は、得られるポリマー
の吸水倍率や吸収速度が低下し、刺激応答性を発現し難
くなる場合がある。The polyether polyol (A) in the present invention is represented by the above general formula (I) and is water-soluble. Here, water-soluble means that it can be dissolved in water, and it is usually preferable that the solubility in water is 5% by weight or more.If the solubility in water is less than 5% by weight, the obtained polymer Water absorption capacity and absorption rate may decrease, making it difficult to develop stimulus responsiveness.
式中のＲ１（多価アルコール残基）の好ましい例として
は、脂肪族二価アルコール（エチレングリコール、プロ
ピレングリコール、１．４−ブチレングリコール、ネオ
ペンチルグリコール等）、三価アルコール（グリセリン
、トリオキシイソブタン、１，２．３−ブタントリオー
ル、１，２．３−ペンタントリオール、トリメチロール
プロパン等）、四価アルコール（１，２，３，４−ペン
タンテトロール、２．３．４．５−ヘキサンテトロール
等）、三価アルコール（アトニット、キシリット等）、
六価アルコール（ソルビット、マンニット等）等２〜８
価のアルコールの残基が挙げられるが、２〜５価のアル
コールの残基がより好ましい０本発明に用いるポリエー
テルポリオール（Ａ）は、かかる２〜８価のアルコール
に、常法によりエチレンオキサイド又はエチレンオキサ
イドと炭素数３〜６個のアルキレンオキサイドとを所望
の分子量となるように付加せしめることにより得られる
ものであって、その際、数式（Ｉ）中のρ、ｍおよびｎ
は上記規定の範囲内にある事が必要で、Ａ、ｒａ及びｎ
のうちの一つでもこの範囲をはずれた場合は刺激応答性
を有するポリマーが得られなくなる。好ましくは、２が
１０〜２０００、ｍが１〜２０００、ｎが２〜５の範囲
である。Ｉ２と１との使用比率は、得られる刺激応答性
ポリマーに所望の性能に応じて広い範囲とすることがで
きるが、本発明の効果をより高度に発現させるために、
Ｑ ／ ｍの比率を９５１５〜２０／８０の比率とする
のが好ましい。Preferred examples of R1 (polyhydric alcohol residue) in the formula include aliphatic dihydric alcohols (ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentyl glycol, etc.), trihydric alcohols (glycerin, trioxy Isobutane, 1,2.3-butanetriol, 1,2.3-pentanetriol, trimethylolpropane, etc.), tetrahydric alcohols (1,2,3,4-pentanetetrol, 2.3.4.5- hexanetetrol, etc.), trihydric alcohols (atonit, xylit, etc.),
Hexahydric alcohol (sorbitol, mannitol, etc.) etc. 2-8
The polyether polyol (A) used in the present invention includes residues of divalent alcohols, but residues of divalent to pentavalent alcohols are more preferred. Alternatively, it is obtained by adding ethylene oxide and an alkylene oxide having 3 to 6 carbon atoms so as to have a desired molecular weight, and in this case, ρ, m and n in formula (I)
must be within the range specified above, A, ra and n
If even one of them is out of this range, a stimulus-responsive polymer cannot be obtained. Preferably, 2 is in the range of 10 to 2,000, m is in the range of 1 to 2,000, and n is in the range of 2 to 5. The usage ratio of I2 and 1 can be set in a wide range depending on the desired performance of the stimulus-responsive polymer obtained, but in order to express the effects of the present invention to a higher degree,
The ratio of Q/m is preferably 9515 to 20/80.
本発明の刺激応答性ポリマーの製造に用いるポリイソシ
アネート化合物ＣＢ）は、分子中にイソシアネート基を
２個以上有するものであれば特に制限されず、例えばト
リレンジイソシアネート、ヘキサメチレンジイソシアネ
ート、ジフェニルメタンジイソシアネート、メチルシク
ロヘキサンジイソシアネート等が挙げられ、これらの一
種又は二種以上を使用することができる。The polyisocyanate compound CB) used in the production of the stimulus-responsive polymer of the present invention is not particularly limited as long as it has two or more isocyanate groups in the molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, methyl Examples include cyclohexane diisocyanate, and one or more of these can be used.
本発明の刺激応答性ポリマーは上記のポリエーテルポリ
オール（Ａ）とポリイソシアネート化合物（Ｂ）を直接
反応させて製造できるが、例えばこれらから末端ＮＧＯ
基の含有率が１〜１２重量％（生成するインシアネート
基含有プレポリマーに対して）のインシアネート基含有
プレポリマーをまず製造し、かかるイソシアネート基含
有プレポリマーを大気中で養生して硬化させるか、又は
活性水素化合物と混合して硬化させ製造することもでき
る。かかる活性水素化合物とは、１分子当り２〜６個の
活性水素基を有し、且つ活性水素基当りの平均分子量が
３０〜２００００であるポリオ−ル、ポリアミン又はそ
れらの混合物であって例えばエチレングリコール、グリ
セリン、エチレンジアミン、テトラエチレンペンタミン
等が挙げられる。The stimulus-responsive polymer of the present invention can be produced by directly reacting the above-mentioned polyether polyol (A) and polyisocyanate compound (B).
An incyanate group-containing prepolymer having a group content of 1 to 12% by weight (based on the inocyanate group-containing prepolymer to be produced) is first produced, and the isocyanate group-containing prepolymer is cured by curing in the atmosphere. Alternatively, it can also be produced by mixing it with an active hydrogen compound and curing it. Such active hydrogen compounds are polyols, polyamines, or mixtures thereof having 2 to 6 active hydrogen groups per molecule and an average molecular weight per active hydrogen group of 30 to 20,000, such as ethylene. Examples include glycol, glycerin, ethylenediamine, and tetraethylenepentamine.
イソシアネート基含有プレポリマーと活性水素化合物と
の反応に際しては、イソシアネート基と活性水素との反
応を促進させる目的で従来から常用の触媒、例えば、ト
リエチルアミン、トリエチレンジアミン、ジブチルチン
ジクロライド等を添加することができる。When reacting an isocyanate group-containing prepolymer with an active hydrogen compound, conventionally used catalysts such as triethylamine, triethylenediamine, dibutyltin dichloride, etc. may be added for the purpose of promoting the reaction between the isocyanate groups and the active hydrogen. can.
さらに本発明の刺激応答性ポリマーは、各種成形方法に
よって所望の形状に変形してもよい。Further, the stimulus-responsive polymer of the present invention may be deformed into a desired shape by various molding methods.
［発明の効果］
本発明の刺激応答性ポリマーは従来のものに比べ格段に
優れた成形性、及び温度応答性を有し、しかも乾燥時に
おいても柔軟であるという特徴を有するため各種メカノ
ケミカル材料、ロボット、アクチュエーターなどに有効
に利用できる。[Effects of the Invention] The stimulus-responsive polymer of the present invention has significantly superior moldability and temperature responsiveness compared to conventional polymers, and is also flexible even when dry, so it can be used in various mechanochemical materials. It can be effectively used in robots, actuators, etc.
以下、実施例により本発明の詳細な説明するが、本発明
の範囲がこれらの実施例にのみ制限されるものではない
。Hereinafter, the present invention will be explained in detail with reference to Examples, but the scope of the present invention is not limited only to these Examples.
実施例１
プロピレングリコール１モルにプロピレンオキサイド９
．１モルおよびエチレンオキサイド５４５モルをランダ
ムに付加せしめて、オキシエチレン基含有量８０％、分
子量３０００で末端に水酸基を２個有するポリエーテル
ポリオール（Ｉ）を得た。このポリエーテルポリオール
（Ｉ）の末端をトリレンジイソシアネート２モルでイソ
シアネート化してなるイソシアネート基含有プレポリマ
ー（プレポリマー（Ｉ））１０．６ｇにトリエタノール
アミン０．３１ｇを加え溶媒として酢酸エチルを用いて
よく攪拌した後、シャーレ中に０．２ｍｍの厚さになる
ように流し込み、これを室温で６時間放置することによ
り刺激応答性ポリマー（Ｉ）を得た。この刺激応答性ポ
リマー（Ｉ）は、１００℃２日間の乾燥の後も柔軟であ
り、この柔軟性故に作業性は非常に良好であった。この
刺激応答性ポリマー（Ｉ）を１０ｍｍ重 １０ｍ＋■＊
０．２ｍｍ重さ０．０５ｇの板状に切りイオン交換水に
漬は温度を変化させたところ急激にその形態を変化させ
重量及び体積変化の倍率は表１のようになった。また、
この形態変化は何度も繰り返して可逆的に行うことがで
きた。Example 1 9 parts propylene oxide to 1 mole of propylene glycol
．． 1 mol and 545 mol of ethylene oxide were randomly added to obtain a polyether polyol (I) having an oxyethylene group content of 80%, a molecular weight of 3000, and two hydroxyl groups at the terminals. To 10.6 g of an isocyanate group-containing prepolymer (prepolymer (I)) obtained by isocyanating the ends of this polyether polyol (I) with 2 moles of tolylene diisocyanate, 0.31 g of triethanolamine was added, and ethyl acetate was used as a solvent. After stirring thoroughly, the mixture was poured into a petri dish to a thickness of 0.2 mm, and the mixture was left at room temperature for 6 hours to obtain stimulus-responsive polymer (I). This stimulus-responsive polymer (I) remained flexible even after drying at 100° C. for 2 days, and because of this flexibility, workability was very good. 10mm weight of this stimulus-responsive polymer (I) 10m+■*
When cut into plates of 0.2 mm and weighing 0.05 g and immersed in ion-exchanged water, the shape rapidly changed when the temperature was changed, and the weight and volume change ratios were as shown in Table 1. Also,
This morphological change could be repeated many times and reversibly.
表 １
実施例２
グリセリン１モルにプロピレンオキサイド１０．５モル
およびエチレンオキサイド６３゜６モ
ルをランダムに付加せしめて、オキシエチレン基含有量
８０％、分子量３５００で末端に水酸基を３個有するポ
リエーテルポリオール（ｎ）を得た。このポリエーテル
ポリオール（ＩＩ）１２．０ｇと実施例１で得られたプ
レポリマー（Ｉ）１７９ｇを酢酸エチルを溶媒としてよ
く混ぜこれに触媒としてジブチルチンジクロライドの０
．１％酢酸エチル溶液を２９．８ｇ加え、シャーレ中に
１．０ｍｍの厚さになるように流し込み、これを室温で
６時間放置することにより刺激応答性ポリマー（■）を
得た。この刺激応答性ポリマー（ｎ）は、１００℃２日
間の乾燥の後も柔軟であった。Table 1 Example 2 10.5 moles of propylene oxide and 63.6 moles of ethylene oxide were randomly added to 1 mole of glycerin to produce a polyether polyol with an oxyethylene group content of 80%, a molecular weight of 3500, and three hydroxyl groups at the terminals. (n) was obtained. 12.0 g of this polyether polyol (II) and 179 g of the prepolymer (I) obtained in Example 1 were mixed thoroughly using ethyl acetate as a solvent, and dibutyltin dichloride was added as a catalyst.
．． 29.8 g of 1% ethyl acetate solution was added, poured into a Petri dish to a thickness of 1.0 mm, and left at room temperature for 6 hours to obtain a stimulus-responsive polymer (■). This stimuli-responsive polymer (n) remained flexible even after drying at 100°C for 2 days.
この刺激応答性ポリマー（ｎ）をｌＯｍ＋＋＋＊１０厘
■＊１ｍｍ重さ０．１ｇの板状に切りイオン交換水に漬
は温度を変化させたところ急激にその形態を変化させ重
量及び体積変化の倍率は表２のようになった。また、こ
の形態変化は何度も繰り返して可逆的に行うことができ
た。This stimuli-responsive polymer (n) was cut into plates of lOm + + + * 10 * 1 mm and weighing 0.1 g and soaked in ion-exchanged water. When the temperature was changed, the shape suddenly changed and the weight and volume changed. The magnification was as shown in Table 2. Furthermore, this morphological change could be repeated many times and reversibly.
表
２
比較例１
プロピレングリコール１モルにプロピレンオキサイド５
９モルを付加せしめて、分子量３５００で末端に水酸基
を２個有するポリエーテルポリオール（ＩＩりを得た。Table 2 Comparative Example 1 5 propylene oxide to 1 mole of propylene glycol
9 moles were added to obtain a polyether polyol (II) having a molecular weight of 3,500 and having two hydroxyl groups at the terminals.
得られたポリエーテルポリオール（ＩＩＩ）の末端をト
リレンジイソシアネート２モルでイソシアネート化して
なるウレタンプレポリマー１０．６ｇにトリエタノール
アミン０． ３１ｇを加え、触媒として酢酸エチルを用
いてよ（撹拌した後、シャーレ中に０．２ｍｍの厚さに
なるように流し込み、これを室温で６時間放置すること
により比較用ポリマー（Ｉ）を得た。この比較用ポリマ
ー（Ｉ）を１０ｍｍ重 １０ａｍ＊０．２ｍｍ重さ０．
０４ｇの板状に切りイオン交換水に漬は温度を変化させ
たが形態変化、重量変化は全く見られなかった。尚、こ
こで得られたポリエーテルポリオール（ＩＩＩ）は水に
不溶性であった。To 10.6 g of a urethane prepolymer obtained by isocyanating the ends of the obtained polyether polyol (III) with 2 moles of tolylene diisocyanate, 0.0 g of triethanolamine was added. Add 31 g and use ethyl acetate as a catalyst (after stirring, pour into a petri dish to a thickness of 0.2 mm, and leave it at room temperature for 6 hours to obtain comparative polymer (I). This comparative polymer (I) was 10mm x 10am*0.2mm x 0.
It was cut into 0.4 g plates and soaked in ion-exchanged water at varying temperatures, but no changes in shape or weight were observed. Note that the polyether polyol (III) obtained here was insoluble in water.
Claims (1)
であり、Ｒ＿２は炭素数３〜６のアルキレン基であり、
ｌは２〜２００００の整数であり、ｍは０又は１〜２０
０００の整数であり、ｎは２〜８の整数であり、▲数式
、化学式、表等があります▼単位と▲数式、化学式、表
等があります▼単 位とはどのような配列で結合していてもよい。）で示さ
れ、かつ水溶性のポリエーテルポリオール（Ａ）とポリ
イソシアネート化合物（Ｂ）とを反応してなる刺激応答
性ポリマー。[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 is a divalent to octavalent hydrocarbon group with 1 to 8 carbon atoms, and R_2 is an alkylene group having 3 to 6 carbon atoms,
l is an integer from 2 to 20,000, and m is 0 or 1 to 20
000 is an integer, n is an integer from 2 to 8, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Units ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In what arrangement are the units combined? Good too. ) and is obtained by reacting a water-soluble polyether polyol (A) with a polyisocyanate compound (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18259889A JPH0350225A (en) | 1989-07-17 | 1989-07-17 | Stimulus-responsive polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18259889A JPH0350225A (en) | 1989-07-17 | 1989-07-17 | Stimulus-responsive polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0350225A true JPH0350225A (en) | 1991-03-04 |
Family
ID=16121088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18259889A Pending JPH0350225A (en) | 1989-07-17 | 1989-07-17 | Stimulus-responsive polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0350225A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393858A (en) * | 1990-06-26 | 1995-02-28 | Commonwealth Scientific And Industrial Research Organisation | Polyurethane or polyurethane-urea elastomeric compositions |
| EP0773150A2 (en) | 1995-11-09 | 1997-05-14 | Kawasaki Jukogyo Kabushiki Kaisha | Method of releasing a stuck air valve and sticking release apparatus |
-
1989
- 1989-07-17 JP JP18259889A patent/JPH0350225A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5393858A (en) * | 1990-06-26 | 1995-02-28 | Commonwealth Scientific And Industrial Research Organisation | Polyurethane or polyurethane-urea elastomeric compositions |
| EP0773150A2 (en) | 1995-11-09 | 1997-05-14 | Kawasaki Jukogyo Kabushiki Kaisha | Method of releasing a stuck air valve and sticking release apparatus |
| US5771000A (en) * | 1995-11-09 | 1998-06-23 | Kawasaki Jukogyo Kabushiki Kaisha | Method of releasing a stuck air value and sticking release apparatus |
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