JPH066660B2 - Hydrophilic-hydrophobic thermoreversible material - Google Patents
Hydrophilic-hydrophobic thermoreversible materialInfo
- Publication number
- JPH066660B2 JPH066660B2 JP62314822A JP31482287A JPH066660B2 JP H066660 B2 JPH066660 B2 JP H066660B2 JP 62314822 A JP62314822 A JP 62314822A JP 31482287 A JP31482287 A JP 31482287A JP H066660 B2 JPH066660 B2 JP H066660B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- hydrophilic
- polymer
- present
- hydrophobic
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloylmorpholine
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は新規な親水性−疎水性熱可逆材料に関するもの
である。さらに詳しくいえば、本発明は、遮光体、温度
センサー、吸着剤、さらには玩具、インテリア、捺染
剤、ディスプレイ、分離膜、メカノケミカル素子材料な
どに応用しうる親水性−疎水性熱可逆材料に関するもの
である。TECHNICAL FIELD The present invention relates to a novel hydrophilic-hydrophobic thermoreversible material. More specifically, the present invention relates to a hydrophilic-hydrophobic thermoreversible material that can be applied to a light shield, a temperature sensor, an adsorbent, a toy, an interior, a printing agent, a display, a separation membrane, a mechanochemical element material, and the like. It is a thing.
従来の技術 水溶性高分子化合物の中には、水溶液状態においてある
温度（転移温度又は曇点）以上では析出白濁化し、その
温度以下では溶解透明化するという特殊な可逆的溶解挙
動を示すものがあり、このものは親水性−疎水性熱可逆
型重合体と呼ばれ、近年温室や化学実験室、ラジオアイ
ソープのトレーサー実験室などの遮光体、温度センサ
ー、あるいは水溶性有機物質用吸着剤などとして利用さ
れつつある。2. Description of the Related Art Some water-soluble polymer compounds show a special reversible dissolution behavior in which, in an aqueous solution state, when the temperature is higher than a certain temperature (transition temperature or cloud point), it becomes cloudy and precipitates, and below that temperature, it becomes transparent. This is called a hydrophilic-hydrophobic thermoreversible polymer, and in recent years it has been used as a light-shielding material in greenhouses, chemical laboratories, tracer laboratories of radioisops, temperature sensors, or adsorbents for water-soluble organic substances. Is being used as.
このような熱可逆型重合体としては、従来、ポリ酢酸ビ
ニル部分けん化物、ポリビニルメチルエーテル、メチル
セルロース、ポリエチレンオキシド、ポリビニルメチル
オキサゾリディノン及びポリアクリルアミド誘導体など
が知られている。As such a thermoreversible polymer, conventionally, a partially saponified product of polyvinyl acetate, polyvinyl methyl ether, methyl cellulose, polyethylene oxide, polyvinyl methyl oxazolidinone, polyacrylamide derivative and the like are known.
これらの熱可逆型重合体の中でポリアクリルアミド誘導
体は、水中で安定であり、かつ比較的安価に製造しうる
ので、前記用途に好適であるが、熱可逆性を有するもの
としては、これまでポリ（Ｎ−イソプロピルアクリルア
ミド）、ポリ（Ｎ，Ｎ−ジエチルアクリルアミド）、ポ
リ（Ｎ−アクリルピロリジン）などが知られているにす
ぎない。Among these thermoreversible polymers, the polyacrylamide derivative is stable in water and can be produced at a relatively low cost, and thus is suitable for the above-mentioned use, but as a thermoreversible polymer, Only poly (N-isopropylacrylamide), poly (N, N-diethylacrylamide), poly (N-acrylpyrrolidine), etc. are known.
このため、ポリアクリルアミド誘導体を例えば温度セン
サーや遮光体などに利用しようとしても、転移温度は物
質に固有で、任意に設定することができず、これまでの
限られた数の誘導体では利用範囲が制限されるのを免れ
ない。Therefore, even if a polyacrylamide derivative is used for a temperature sensor or a light-shielding body, the transition temperature is unique to the substance and cannot be arbitrarily set. I cannot avoid being restricted.
発明が解決しようとする問題点 本発明の目的は、このような事情のもとで、親水性−疎
水性熱可逆型ポリアクリルアミド誘導体の利用範囲を拡
大すべく、さらに異なった転移温度を有する新規なポリ
アクリルアミド系の親水性−疎水性熱可逆材料を提供す
ることにある。Problems to be Solved by the Invention Under such circumstances, an object of the present invention is to provide a novel novel compound having a different transition temperature in order to expand the range of application of the hydrophilic-hydrophobic thermoreversible polyacrylamide derivative. Another object of the present invention is to provide a polyacrylamide-based hydrophilic-hydrophobic thermoreversible material.
問題点を解決するための手段 本発明者らは鋭意研究を重ねた結果、一般式 （式中のＲ1は水素原子又はメチル基である） で表されるビニル化合物をラジカル重合して得られる重
合体の水溶液から実質的に成る親水性−疎水性熱可逆材
料が、前記目的を達成しうることを見出し、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 As a result of intensive studies by the present inventors, the general formula (Wherein R 1 is a hydrogen atom or a methyl group), a hydrophilic-hydrophobic thermoreversible material consisting essentially of an aqueous solution of a polymer obtained by radical polymerization of a vinyl compound represented by They have found that they can be achieved, and have completed the present invention based on this finding.
すなわち、本発明は、一般式 （式中のＲ1は前記と同じ意味をもつ） で表される繰り返し単位から成り、30℃における極限粘
度〔η〕0.01〜6.0に相当する分子量を有する親水性−
疎水性熱可逆型重合体の水溶液から実質的になる親水性
−疎水性熱可逆材料を提供するものである。That is, the present invention has the general formula (R 1 in the formula has the same meaning as described above) and is hydrophilic with a molecular weight corresponding to intrinsic viscosity [η] 0.01 to 6.0 at 30 ° C.
The present invention provides a hydrophilic-hydrophobic thermoreversible material which consists essentially of an aqueous solution of a hydrophobic thermoreversible polymer.
本発明で用いる前記一般式(1)で表されるビニル化合物
は、例えば次式で示されるように、アクリル酸クロリド
又はメタクリル酸クロリドと３−メトキシプロピルアミ
ンとトリエチルアミンとをアセトン、ベンゼン、又はト
ルエン中において、好ましくは０〜10℃の温度で反応さ
せる方法によって製造することができる。The vinyl compound represented by the general formula (1) used in the present invention is, for example, as represented by the following formula, acrylic acid chloride or methacrylic acid chloride, 3-methoxypropylamine and triethylamine, acetone, benzene, or toluene. In the above, it can be produced by a method of reacting at a temperature of preferably 0 to 10 ° C.
（式中のＲ1は前記と同じ意味をもつ） 本発明で用いるビニル化合物としては、具体的には、Ｎ
−メトキシプロピルアクリルアミド（沸点98℃／2mmH
g）、Ｎ−メトキシプロピルメタクリルアミド（同105℃
／3mmHg）である。 (R 1 in the formula has the same meaning as described above) The vinyl compound used in the present invention is specifically N
-Methoxypropyl acrylamide (boiling point 98 ℃ / 2mmH
g), N-methoxypropyl methacrylamide (at 105 ° C)
/ 3mmHg).
本発明で用いる重合体は、これらのビニル化合物をラジ
カル重合させて製造する。重合方法としては、溶液重合
法及び塊状重合法があるが、通常溶液重合法が好ましく
用いられる。この重合法においては、溶媒中に該ビニル
化合物を溶かし１〜80重量％濃度の溶液として、放射線
を照射するか、ラジカル重合開始発剤の存在下に加熱、
あるいは光増感剤の存在下に光照射するなど、通常知ら
れている任意のラジカル重合法を用いることができる。
このような溶液重合法に用いられる溶媒については特に
制限はないが、例えば水、アルコール類、Ｎ，Ｎ−ジメ
チルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジ
メチルスルホキシド、アセトン、ジオキサン、テトラヒ
ドロフラン、ベンゼン、クロロホルム、四塩化炭素など
を挙げることができ、これらはそれぞれ単独で用いても
よいし、２種類以上組み合わせて用いてもよい。The polymer used in the present invention is produced by radically polymerizing these vinyl compounds. As the polymerization method, there are a solution polymerization method and a bulk polymerization method, and usually the solution polymerization method is preferably used. In this polymerization method, the vinyl compound is dissolved in a solvent to form a solution having a concentration of 1 to 80% by weight, and irradiation with radiation or heating in the presence of a radical polymerization initiator is performed.
Alternatively, any commonly known radical polymerization method such as light irradiation in the presence of a photosensitizer can be used.
The solvent used in such a solution polymerization method is not particularly limited, but for example, water, alcohols, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetone, dioxane, tetrahydrofuran, benzene, chloroform. , Carbon tetrachloride, etc., and these may be used alone or in combination of two or more kinds.
このようにして得られた本発明で用いる重合体は、低温
で水に溶け、高温で水に不溶となる高温疎水型の熱可逆
性を有している。本発明の親水性−疎水性熱可逆材料
は、上記重合体を水との組み合わせの形に調製する必要
がある。この際水溶液濃度は使用目的に応じて変わる
が、0.01重量％以上にする必要がある。通常0.05〜30重
量％の範囲にある。該重合体水溶液の転移温度は重合条
件によって異なるが、１重量％水溶液においては、ポリ
（Ｎ−メトキシプロピルアクリルアミド）で44〜48℃、
ポリ（Ｎ−メトキシプロピルメタクリルアミド）で58〜
65℃の範囲にある。転移温度は、水溶性物質例えば食塩
等の電解質、メチルアルコール等の水溶性有機物の添加
により変化する。The thus obtained polymer used in the present invention has a high temperature hydrophobic type thermoreversible property that it is soluble in water at a low temperature and insoluble in water at a high temperature. The hydrophilic-hydrophobic thermoreversible material of the present invention needs to be prepared by combining the above polymer with water. At this time, the concentration of the aqueous solution varies depending on the purpose of use, but needs to be 0.01% by weight or more. It is usually in the range of 0.05 to 30% by weight. The transition temperature of the aqueous polymer solution varies depending on the polymerization conditions, but in a 1% by weight aqueous solution, poly (N-methoxypropylacrylamide) is used at 44 to 48 ° C.
58 with poly (N-methoxypropyl methacrylamide)
It is in the range of 65 ℃. The transition temperature is changed by the addition of a water-soluble substance such as an electrolyte such as salt and a water-soluble organic substance such as methyl alcohol.
本発明で用いる重合体−ＣＯＮＨ−基、−Ｏ−ＣＨ
3基、−ＣＨ2−ＣＲ1−基を有するので、赤外線吸収ス
ペクトルなどによって同定することができる。またその
重合度については、メタノール溶液における30℃の温度
での極限粘度〔η〕が0.01〜6.0の範囲のものである。
さらに各種溶媒に対する溶解性については、冷水、メタ
ノール、エタノール、クロロホルム、アセトン、テトラ
ヒドロフラン、Ｎ，Ｎ−ジメチルホルムアミドなどには
可溶であるが、熱水、ｎ−ヘキサン、ｎ−ヘプタンなど
には不溶である。Polymer used in the present invention —CONH— group, —O—CH
Since it has 3 groups and —CH 2 —CR 1 — group, it can be identified by infrared absorption spectrum and the like. Regarding the degree of polymerization, the intrinsic viscosity [η] in a methanol solution at a temperature of 30 ° C. is in the range of 0.01 to 6.0.
Regarding the solubility in various solvents, it is soluble in cold water, methanol, ethanol, chloroform, acetone, tetrahydrofuran, N, N-dimethylformamide, etc., but insoluble in hot water, n-hexane, n-heptane, etc. Is.
発明の効果 本発明のポリアクリルアミド系親水性−疎水性熱可逆材
料は、低温で水に溶け、高温で水に不溶になるという高
温疎水型の熱可逆性を有するものであって、従来知られ
ている熱可逆型ポリアクリルアミド誘導体とは異なる転
移温度を有しており、温室や化学実験室、ラジオアイソ
ートプのトレーサー、実験室などの遮光体、温度センサ
ー、水溶性有機物質の吸着剤、さらには玩具、インテリ
ア、捺染剤、ディスプレイ、分離膜、メカノケミカル素
子材料などに応用することができる。EFFECT OF THE INVENTION The polyacrylamide hydrophilic-hydrophobic thermoreversible material of the present invention has a high-temperature hydrophobic thermoreversible property that it dissolves in water at low temperatures and becomes insoluble in water at high temperatures, and is conventionally known. It has a transition temperature different from that of thermoreversible polyacrylamide derivatives, and it is used in greenhouses, chemical laboratories, tracers of radio eye assortments, light shields in laboratories, temperature sensors, adsorbents for water-soluble organic substances, Further, it can be applied to toys, interiors, textile printing agents, displays, separation membranes, mechanochemical element materials and the like.
実施例 次に参考例及び実施例により本発明をさらに詳細に説明
する。EXAMPLES Next, the present invention will be described in more detail by reference examples and examples.
参考例 １の三角フラスコとトリエチルアミン50.9ｇ、３−メ
トキシプロピルアミン51.6ｇ及びアセトン450mlを入れ
氷で冷やして内容液を10℃未満の温度に保ち、かきまぜ
ながらこの中にアクリル酸クロリド41.5mlとアセトン50
mlの混合溶液を滴下漏斗から約３時間かけてゆっくり滴
下した。滴下完了後、反応液を１昼夜放置冷却したのち
ろ過し、ロータリエバポレータを用いてろ液からアセト
ンを除去して濃縮した。次いで減圧蒸溜して沸点98℃／
2mmHgの無色透明の留分を回収し、液状物質54.4ｇを得
た。The Erlenmeyer flask of Reference Example 1 and 50.9 g of triethylamine, 51.6 g of 3-methoxypropylamine and 450 ml of acetone were put and cooled with ice to keep the content liquid at a temperature of less than 10 ° C., while stirring, 41.5 ml of acrylic acid chloride and acetone were added. 50
The mixed solution of ml was slowly dropped from the dropping funnel over about 3 hours. After completion of dropping, the reaction solution was left standing and cooled for one day and then filtered, and acetone was removed from the filtrate using a rotary evaporator to concentrate the solution. Then distill under reduced pressure and boiling point is 98 ℃ /
A colorless transparent fraction of 2 mmHg was collected to obtain 54.4 g of a liquid substance.
このものはマススペクトル及びＩＲスペクトルからＮ−
メトキシプロピルアクリルアミドであることが確認され
た。同様にしてＮ−メトキシプロピルメタクリルアミド
を合成した。This is N- from mass spectrum and IR spectrum.
It was confirmed to be methoxypropyl acrylamide. Similarly, N-methoxypropyl methacrylamide was synthesized.
実施例 参考例で得た各種モノマーのラジカル重合体を製造し
た。Example A radical polymer of various monomers obtained in Reference Example was produced.
重合開始剤としてアゾビスイソブチロニトリルを用い、
重合開始剤濃度50mg／1mlのメタノール溶液20mgに所定
重量のモノマーを加え、これをアンプルに入れ、液体窒
素を用いて減圧脱気したのち封じ、温度60℃で51時間反
応させた。次いで反応液にアセトンを加えたのち、この
溶液をベンゼン−ｎ−ヘキサン混合溶媒中に投入してポ
リマーを沈澱させ、回収した。Using azobisisobutyronitrile as a polymerization initiator,
A predetermined weight of a monomer was added to 20 mg of a methanol solution having a polymerization initiator concentration of 50 mg / 1 ml, and this was placed in an ampoule, deaerated under reduced pressure using liquid nitrogen, sealed, and reacted at a temperature of 60 ° C. for 51 hours. Next, acetone was added to the reaction solution, and this solution was poured into a benzene-n-hexane mixed solvent to precipitate a polymer, which was then collected.
得られたポリマーについては、メタノール溶液とし、ウ
ベローデ粘度計を用いて30℃で粘度測定し、極限粘度
〔η〕を求めた。また、転移温度を水溶液の温度変化に
伴う光透過率の変化及びDSC測定から求めた。すなわ
ち、１重量％濃度のポリマー水溶液を調製して、温度コ
ントローラ付分光計にセットし、昇温速度１℃／minで
昇温させながら、波長500nmでの光透過率を測定し、転
移温度はこの光透過率が初期透過率の１／２となる温度
（ＴL）から求めた。またポリマー７〜８mgを水50〜60m
g中に加え、昇温速度１℃／minでDSC測定を行い、吸熱
ピークの頂点の温度（Ｔd）からも転移温度を求めた。The obtained polymer was used as a methanol solution, and the viscosity was measured at 30 ° C. using an Ubbelohde viscometer to determine the intrinsic viscosity [η]. In addition, the transition temperature was determined from the change in light transmittance with the temperature change of the aqueous solution and the DSC measurement. That is, prepare a 1% by weight aqueous polymer solution, set it in a spectrometer with a temperature controller, measure the light transmittance at a wavelength of 500 nm while raising the temperature at a temperature raising rate of 1 ° C / min, and determine the transition temperature. It was determined from the temperature ( TL ) at which this light transmittance was 1/2 of the initial transmittance. Also, add 7-8 mg of polymer to 50-60 m of water.
In addition to g, DSC measurement was performed at a temperature rising rate of 1 ° C./min, and the transition temperature was also determined from the temperature (T d ) at the apex of the endothermic peak.
これらの結果を次表に示す。また、第１図及び第２図に
透過率−温度曲線を、第３図及び第４図にDSC曲線を示
す。The results are shown in the table below. Further, FIGS. 1 and 2 show transmittance-temperature curves, and FIGS. 3 and 4 show DSC curves.
これらの図において、(1)はポリ−（Ｎ−メトキシプロ
ピルアクリルアミド）、(2)はポリ（Ｎ−メトキシプロ
ピルメタクリルアミド）のデータであり、また、第１図
及び第２図において、実線は昇温時、点線は降温時のデ
ータである。 In these figures, (1) is the data of poly- (N-methoxypropyl acrylamide), (2) is the data of poly (N-methoxypropyl methacrylamide), and the solid line in FIGS. When the temperature is raised, the dotted line is the data when the temperature is lowered.
上表から分かるように、ポリ（Ｎ−メトキシプロピルア
クリルアミド）及びポリ（Ｎ−メトキシプロピルメタク
リルアミド）の水溶液は熱可逆性である。As can be seen from the table above, aqueous solutions of poly (N-methoxypropyl acrylamide) and poly (N-methoxypropyl methacrylamide) are thermoreversible.
第１図及び第２図は本発明で用いる重合体の１重量％水
溶液における透過率−温度曲線を示すグラフ、第３図及
び第４図は、本発明で用いる重合体の水溶液のDSC曲線
を示すグラフである。1 and 2 are graphs showing a transmittance-temperature curve of a polymer used in the present invention in a 1% by weight aqueous solution, and FIGS. 3 and 4 are DSC curves of an aqueous solution of the polymer used in the present invention. It is a graph shown.
フロントページの続き (56)参考文献 特開 昭57−179211（ＪＰ，Ａ) 特開 昭51−115543（ＪＰ，Ａ) 特開 昭49−93013（ＪＰ，Ａ) 特開 昭49−23826（ＪＰ，Ａ) 特公 昭49−1457（ＪＰ，Ｂ１) 特公 昭49−27407（ＪＰ，Ｂ１)Continuation of front page (56) Reference JP-A-57-179211 (JP, A) JP-A-51-115543 (JP, A) JP-A-49-93013 (JP, A) JP-A-49-23826 (JP , A) JP-B-49-1457 (JP, B1) JP-B-49-27407 (JP, B1)
Claims (1)
度〔η〕0.01〜6.0に相当する分子量を有する親水性−
疎水性熱可逆型重合体の水溶液から実質的になる親水性
−疎水性熱可逆材料。1. A general formula (R 1 in the formula is a hydrogen atom or a methyl group) and has a molecular weight equivalent to the intrinsic viscosity [η] 0.01 to 6.0 at 30 ° C.
A hydrophilic-hydrophobic thermoreversible material consisting essentially of an aqueous solution of a hydrophobic thermoreversible polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62314822A JPH066660B2 (en) | 1987-12-11 | 1987-12-11 | Hydrophilic-hydrophobic thermoreversible material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62314822A JPH066660B2 (en) | 1987-12-11 | 1987-12-11 | Hydrophilic-hydrophobic thermoreversible material |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6773585A Division JPS61225203A (en) | 1985-03-29 | 1985-03-29 | Thermally reversible hydrophilic and hydrophobic polymer and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63241007A JPS63241007A (en) | 1988-10-06 |
| JPH066660B2 true JPH066660B2 (en) | 1994-01-26 |
Family
ID=18058017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62314822A Expired - Lifetime JPH066660B2 (en) | 1987-12-11 | 1987-12-11 | Hydrophilic-hydrophobic thermoreversible material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH066660B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4123049A1 (en) * | 1991-07-12 | 1993-01-14 | Basf Ag | CROSSLINKED COPOLYMERISATE WITH CROSSLINKABLE GROUPS BASED ON ACRYLIC ACID OR METHACRYLIC ACID, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| EP0692506A3 (en) | 1994-07-14 | 1996-04-10 | Miyoshi Yushi Kk | Thermo-sensitive polyether polyurethane, production method thereof and thermo-sensitive composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS491457A (en) * | 1972-04-25 | 1974-01-08 | ||
| JPS4923826A (en) * | 1972-06-06 | 1974-03-02 | ||
| JPS4927407A (en) * | 1972-07-08 | 1974-03-11 | ||
| JPS4993013A (en) * | 1973-01-08 | 1974-09-04 | ||
| JPS51115543A (en) * | 1975-04-03 | 1976-10-12 | Nitto Electric Ind Co Ltd | Pressure-sinsitive adhesive composition |
| US4395524A (en) * | 1981-04-10 | 1983-07-26 | Rohm And Haas Company | Acrylamide copolymer thickener for aqueous systems |
-
1987
- 1987-12-11 JP JP62314822A patent/JPH066660B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63241007A (en) | 1988-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6355527B2 (en) | ||
| JPS6332804B2 (en) | ||
| JPH066660B2 (en) | Hydrophilic-hydrophobic thermoreversible material | |
| JPS6330331B2 (en) | ||
| JPS6330330B2 (en) | ||
| JPS6291509A (en) | Thermoreversibly hydrophilic and hydrophobic polymer and its production | |
| JPH0372218B2 (en) | ||
| JP3558354B2 (en) | Thermoreversible polymer compound and method for producing the same | |
| JPH0618970B2 (en) | Hydrophilic-hydrophobic thermoreversible material | |
| JPS63243112A (en) | Water and alcohol solvent dependent heat reversible high polymer compound and production thereof | |
| JPH066610B2 (en) | Hydrophilic-hydrophobic thermoreversible polymer material and method for producing the same | |
| JPH0613578B2 (en) | Hydrophilic-hydrophobic thermoreversible polymer compound and method for producing the same | |
| JPH0583085B2 (en) | ||
| JPS61225157A (en) | Novel vinyl compound | |
| JPH0613579B2 (en) | Hydrophilic-hydrophobic thermoreversible polymer compound and method for producing the same | |
| JPS63295613A (en) | Thermally reversible hydrophilic/hydrophobic polymeric compound and manufacture thereof | |
| JPH0518817B2 (en) | ||
| JPH0521102B2 (en) | ||
| JPH01249815A (en) | Hydrophilic-hydrophobic thermoreversible polymer and production thereof | |
| JPH0434985B2 (en) | ||
| JPH03275682A (en) | New vinyl compound | |
| JPH0518819B2 (en) | ||
| JPH0747569B2 (en) | Novel vinyl compound | |
| JPH0518818B2 (en) | ||
| JPH06145245A (en) | Heat-sensitive polymer compound undergoing phase transfer in alcohol solvent and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |