JPH0339538B2 - - Google Patents
Info
- Publication number
- JPH0339538B2 JPH0339538B2 JP6192784A JP6192784A JPH0339538B2 JP H0339538 B2 JPH0339538 B2 JP H0339538B2 JP 6192784 A JP6192784 A JP 6192784A JP 6192784 A JP6192784 A JP 6192784A JP H0339538 B2 JPH0339538 B2 JP H0339538B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- molded article
- thermoreversible polymer
- shape
- aqueous solution
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- -1 poly(N-isopropylacrylamide) Polymers 0.000 description 36
- 230000007704 transition Effects 0.000 description 20
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005251 gamma ray Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001977 poly(N,N-diethylacrylamides) Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
本発明は熱可逆高分子架橋成形体の製造方法、
さらに詳しくいえば、架橋性を有する熱可逆高分
子成形体をその形状が保持されうるような温度に
調節された水中又は電解質水溶液中に浸漬した状
態で、該成形体に放射線照射を行うことにより、
熱可逆高分子架橋成形体を製造する方法に関する
ものである。
通常の水溶性高分子化合物は温度が高くなれば
なるほど水に対する溶解度が増加するが、ある種
の高分子化合物はその転移温度以下の低温域にお
いて水に溶解し、転移温度以上の高温域において
析出するという可逆的な溶解特性を示す。
このような高分子化合物は、一般に熱可逆高分
子化合物と呼ばれているものであり、その水溶液
の熱可逆特性に基づき、例えば遮光体、吸着剤、
被覆剤、捺染剤、水性接着剤など多方面への利用
が可能である。しかし、この熱可逆高分子化合物
を前記の用途に使用するに当つては、何らかの形
態を保つことが必要な場合が多く、例えば、架橋
成形体にすれば熱可逆特性を有する吸着剤、分離
膜、遮光体などとして新しい用途が可能になる。
ところで、架橋性を有する熱可逆高分子化合物
の水溶液に放射線を照射すると容易に架橋反応を
起こし、容器の形と相似形の架橋成形体が形成さ
れる。しかしながら、容器の形状以外の任意の形
状を有する架橋成形体を得ることは従来極めて困
難であつた。
本発明者らは、このような事情に鑑み、任意の
形状を有する熱可逆高分子架橋成形体を製造する
方法について鋭意研究を重ねた結果、熱可逆高分
子化合物の水溶液における転移温度は電解質を添
加することにより大きく変化することに着目し、
架橋性を有する熱可逆高分子成形体をその形状が
保持されうるような温度に調節された水中又は電
解質水溶液中に浸漬した状態で、該成形体に放射
線を照射することにより、その目的を達成しうる
ことを見出し、この知見に基づいて本発明を完成
するに至つた。
すなわち、本発明は、架橋性を有する熱可逆高
分子成形体をその形状が保持されうるような温度
又は濃度に調節された水中又は電解質水溶液中に
浸漬した状態で、該成形体に放射線照射を行うこ
とを特徴とする熱可逆高分子架橋成形体の製造方
法、及び架橋性を有する熱可逆高分子化合物水溶
液を形成された高分子成形体の形状が保持されう
るような温度に調節された水中又は電解質水溶液
中に送入して成形体を形成させ、次いでそのまま
の状態で該成形体に放射線照射を行うことを特徴
とする熱可逆高分子架橋成形体の製造方法を提供
するものである。
本発明方法において用いる架橋性を有する熱可
逆高分子化合物は、放射線照射により架橋反応を
起こすような、分子内に
The present invention provides a method for producing a thermoreversible polymer crosslinked molded article,
More specifically, by irradiating a crosslinkable thermoreversible polymer molded product with radiation while immersing it in water or an aqueous electrolyte solution whose temperature is adjusted to maintain its shape. ,
The present invention relates to a method for producing a thermoreversible polymer crosslinked molded article. The solubility of ordinary water-soluble polymer compounds in water increases as the temperature rises, but some types of polymer compounds dissolve in water at low temperatures below their transition temperature and precipitate at high temperatures above their transition temperature. It exhibits reversible dissolution properties. Such polymer compounds are generally called thermoreversible polymer compounds, and based on the thermoreversible properties of their aqueous solutions, they can be used as light shields, adsorbents, etc.
It can be used in a wide range of applications such as coating agents, printing agents, and water-based adhesives. However, when using this thermoreversible polymer compound for the above-mentioned purposes, it is often necessary to maintain some form.For example, if it is made into a crosslinked molded product, it can be used as an adsorbent with thermoreversible properties, or as a separation membrane. , new uses such as light shields become possible. By the way, when an aqueous solution of a thermoreversible polymer compound having crosslinking properties is irradiated with radiation, a crosslinking reaction easily occurs, and a crosslinked molded article having a shape similar to that of the container is formed. However, it has conventionally been extremely difficult to obtain a crosslinked molded body having any shape other than the shape of a container. In view of these circumstances, the present inventors have conducted extensive research on a method for producing a thermoreversible polymer crosslinked molded article having an arbitrary shape, and have found that the transition temperature in an aqueous solution of a thermoreversible polymer compound is Focusing on the fact that it changes greatly by adding it,
This purpose is achieved by irradiating a crosslinkable thermoreversible polymer molded product with radiation while immersing it in water or an aqueous electrolyte solution whose temperature is adjusted to maintain its shape. Based on this knowledge, the present invention was completed. That is, the present invention involves irradiating a crosslinkable thermoreversible polymer molded product with radiation while immersing the molded product in water or an aqueous electrolyte solution whose temperature or concentration is adjusted to maintain its shape. A method for producing a thermoreversible polymer crosslinked molded article, characterized in that the thermoreversible polymer compound aqueous solution having crosslinking properties is added in water adjusted to a temperature such that the shape of the formed polymer molded article can be maintained. Alternatively, the present invention provides a method for producing a thermoreversible polymer crosslinked molded article, characterized in that the molded article is introduced into an electrolyte aqueous solution to form a molded article, and then the molded article is irradiated with radiation in that state. The thermoreversible polymer compound having crosslinking properties used in the method of the present invention has an intramolecular structure that causes a crosslinking reaction when irradiated with radiation.
【式】の
構造を有する熱可逆高分子化合物であり、このよ
うなものとしては、例えばポリビニルメチルエー
テル（転移温度37℃）、ポリ（Ｎ−イソプロピル
アクルアミド）（転移温度30〜31℃）、ポリ（Ｎ−
シクロプロピルアクリルアミド）（転移温度45
℃）、ポリ（Ｎ，Ｎ−ジエチルアクリルアミド）
（転移温度32℃）、ポリ（Ｎ−ｎ−プロピルアクリ
ルアミド）（転移温度21℃）、ポリアクリルピペリ
ジン（転移温度５℃）などが挙げられる。これら
の熱可逆高分子化合物の分子量については特に制
限はないが、風乾状態でひびわれなどが起こらな
い範囲のものが好ましく、一般には分子量5000以
上のもの又は極限粘度［η］0.05以上のものが好
適である。
前記の架橋性を有する熱可逆高分子化合物の水
溶液における移転温度は、電解質を添加すること
により大きく変化する。したがつて、電解質の種
類や濃度によつて移転温度を調節することが可能
である。例えば、ポリ（Ｎ−イソプロピルアクリ
ルアミド）においては、その水溶液にアニオンと
してCl-を含む各種のアルカリ金属塩（MCl）を
添加する場合、転移温度は電解質濃度に比例して
低下する。その低下度は第１図に示すようにLi+
＜Cs+＜K+≒Na+の順となる。また、該水溶液に
カチオンとしてNa+を含む各種のハロゲン塩
（NaX）を添加する場合、ハロゲンアニオンは同
様な効果を示し、その低下度は第２図に示すよう
にI-＜Br-＜Cl-＜F-の順である。
本発明の特徴は、このような知見に基づいて、
予め任意の形状に成形された架橋性を有する熱可
逆高分子成形体を、その形状が保持されうるよう
な温度に調節した水中又は電解質水溶液中に浸漬
し、該成形体の形状を保持した状態で放射線照射
により架橋反応させる点にある。さらに、架橋性
を有する熱可逆高分子化合物水溶液を、形成され
た高分子成形体の形状が保持されうるような温度
に調節された水中又は電解質水溶液中に射出、押
出、流下などにより送入して、糸状、棒状、板状
などの任意の形状を有する成形体を形成させ、次
いでそのままの状態で放射線照射により架橋反応
させる点にある。
本発明に用いる電解質の種類については特に制
限はなく、また電解質は１種のみを単独で用いて
もよいし、２種以上組み合わせて用いてもよい。
電解質水溶液の濃度については特に制限はない
が、好ましくは４モル／以下である。
本発明において架橋反応に用いる放射線として
は、例えばγ線、Χ線、電子線、α線などの電離
放射線が挙げられる。これらの放射線の強さは
102〜1011R／hrの範囲が好ましく、また、必要と
される全放射線量は103R以上である。
本発明における架橋反応の温度については、熱
可逆高分子成形体の形状が保持されうるような温
度であることが必要であり、通常０〜100℃の範
囲で選ばれる。また、反応の雰囲気については、
水の存在が必要である以外は特に制限はなく、空
気中、不活性ガス中、減圧下などいずれの雰囲気
においても架橋反応を行うことができる。
さらに、本発明においては、熱可逆高分子成形
体を電解質水溶液中に浸漬する場合、該成形体を
直接電解質水溶液中に浸漬するとひびわれなどが
生じやすいので、予め転移温度以上の水で該成形
体を処理したのち、電解質水溶液中に浸漬させる
ことが望ましい。
本発明方法によれば、任意の形状を有する熱可
逆高分子架橋成形体を容易に得ることができ、こ
のものは、例えば吸着剤、分離膜、遮光体などと
して利用が可能である。
次に実施例によつて本発明をさらに詳細に説明
する。
実施例 １
転移温度が５℃であるポリアクリルピペリジン
1.0ｇ（［η］＝0.19）をメタノール15mlに溶解し、
内径６cmのシャーレに流し、放置乾燥後、真空乾
燥器に入れ110℃に加熱し、メタノールを除去し、
ポリアクリルピペリジンフイルムを作成した。次
いでこのポリアクリルピペリジンフイルムの形態
を保つように調節された20℃の水10mlをシャーレ
に加え、その上部をポリエチレンフイルムで封を
し水が蒸発してなくならないように保ち、19〜20
℃、1.5×105R／hrの条件下で 60Coからのγ線照
射を536時間行つた。照射後、試料が照射前の形
態を保つて成形された姿で架橋していることを２
℃の水およびメタノールの溶解実験で確認した。
試料の１部（0.48ｇ）を２℃の水に20時間放置し
たところ、試料は、架橋していて水に膨潤し、そ
の重量は1.73ｇであり、その膨潤度は3.60であつ
た。
実施例 ２
転移温度が30℃であるポリ（Ｎ−イソプロピル
アクリルアミド）（［η］＝0.50）1.0ｇを20℃の水
10mlに溶解し、内径10cmのシャーレに流し、放置
し乾燥してポリ（Ｎ−イソプロピルアクリルアミ
ド）フイルムを作成した。次いでこのポリ（Ｎ−
イソプロピルアクリルアミド）フイルムに50℃の
水10mlを加え直ちにその水を捨てたのち、ポリ
（Ｎ−イソプロピルアクリルアミド）フイルムの
形態を保ちうるよう調節された20℃の10％食塩水
20ml［このときポリ（Ｎ−イソプロピルアクリル
アミド）の転移温度は9.2℃になる］を加え、そ
の上部をポリエチレンフイルムを用いて封をし、
水が蒸発してなくならない状態にし、19〜20℃、
1.5×105R／hrの条件下で 60Coからのγ線を740
時間照射した。照射後、試料が照射前の形態を保
つて成形された姿で架橋していることを水の溶解
実験で確認した。試料の１部0.05ｇを20℃の水に
浸漬し20時間放置したところ、試料は、架橋して
いて水に膨潤しその重量は0.53ｇであり、その膨
潤度は10.6であつた。
実施例 ３
転移温度が37℃であるポリビニルメチルエーテ
ル（3400cps、25℃）30％水溶液40mlを内径12cm
のシャーレに入れ、空気中で乾燥させポリビニル
メチルエーテルフイルムを作成した。次いでこの
ポリビニルメチルエーテルフイルムに50℃の水15
mlを加え直ちにその水を捨てたのち、ポリビニル
メチルエーテルフイルムの形体を保ちうるよう調
節された10％の食塩水20ml（このときポリビニル
メチルエーテルの転移温度は8.5℃になる）をシ
ャーレに加え、その上部をポリエチレンフイルム
を用いて封をし水が蒸発してなくならないような
状態にし19〜20℃、1.5×105R／hrの条件下で
60Coからのγ線を744時間照射した。照射後、試
料が照射前の形態を保つて成形された姿で架橋し
ていることを水の溶解実験で確認した。試料の１
部0.22ｇを20℃の水に浸漬し20時間放置したとこ
ろ、試料は、架橋していて水に膨潤し、その重量
は0.55ｇであり、その膨潤度は2.5であつた。
実施例 ４
転移温度が30℃であるポリ（Ｎ−イソプロピル
アクリルアミド）（［η］＝0.50）20％水溶液５ｇ
を形成された高分子成形体の形状が保持されうる
ように調節された20℃の10％食塩水溶液500ml中
に注射器を用いて送入し、成形体を形成させた。
次いで、その成形体を10％食塩水溶液に浸したま
ま、ポリエチレンシールし、水が蒸発してなくな
らないように保ち、19〜20℃、1.5×105R／hrの
条件下で 60Coからのγ線照射を840時間行つた。
照射後、試料が照射前の形態を保つて成形され
た姿で架橋していることを、20℃の水の溶解実験
で確認した。試料の１部0.066ｇを20℃の水に20
時間放置したところ、試料は架橋していて水に膨
潤し、その重量は0.70であり、その膨潤度は10.6
であつた。
実施例 ５
転移温度が５℃であるポリ（アクリルヒペリジ
ン（［η］＝0.19）20％水溶液（０〜３℃）５ｇを
形成された高分子成形体の形状が保持されうるよ
うに調節された20℃の水100ml中に注射器を用い
て送入し成形体を形成させた。次いでその成形体
を水に浸したままポリエチレンシールし、水が蒸
発してなくならないように保ち、19〜20℃、1.5
×105R／hrの条件下で 60Coからのγ線照射を
536時間行つた。
照射後、試料が照射前の形態を保つて成形され
た姿で架橋していることを、20℃の水の溶解実験
で確認した。試料の１部0.10ｇを２℃の水に20時
間放置したところ、試料は架橋していて水に膨潤
し、その重量は0.65ｇであり、その膨潤度は6.5
であつた。
比較例
実施例２と同様にして作成したポリ（Ｎ−イソ
プロピルアクリルアミド）フイルムについて、水
及び食塩水不添加系で実施例２と同様の実験を行
つたところ、該フイルムは未架橋のままであり、
20℃の水に溶解した。It is a thermoreversible polymer compound having the structure of [Formula], such as polyvinyl methyl ether (transition temperature 37°C), poly(N-isopropylacrylamide) (transition temperature 30-31°C), Poly(N-
cyclopropylacrylamide) (transition temperature 45
℃), poly(N,N-diethylacrylamide)
(transition temperature: 32°C), poly(N-n-propylacrylamide) (transition temperature: 21°C), polyacrylpiperidine (transition temperature: 5°C), and the like. The molecular weight of these thermoreversible polymer compounds is not particularly limited, but it is preferably within a range that does not cause cracking when air-dried, and generally a molecular weight of 5000 or more or a limiting viscosity [η] of 0.05 or more is preferred. It is. The transition temperature in an aqueous solution of the thermoreversible polymer compound having crosslinking properties changes greatly by adding an electrolyte. Therefore, it is possible to adjust the transfer temperature depending on the type and concentration of electrolyte. For example, in poly(N-isopropylacrylamide), when various alkali metal salts (MCl) containing Cl - as an anion are added to its aqueous solution, the transition temperature decreases in proportion to the electrolyte concentration. As shown in Figure 1, the degree of decrease is Li +
The order is ＜Cs + ＜K + ≒Na + . Furthermore, when various halogen salts (NaX) containing Na + as cations are added to the aqueous solution, the halogen anions exhibit a similar effect, and the degree of decrease is I - < Br - < Cl as shown in Figure 2. The order is - <F - . The features of the present invention are based on such findings,
A state in which a crosslinkable thermoreversible polymer molded article previously formed into an arbitrary shape is immersed in water or an aqueous electrolyte solution whose temperature is adjusted to maintain its shape, and the shape of the molded article is retained. The point is that a cross-linking reaction is caused by radiation irradiation. Furthermore, an aqueous solution of a thermoreversible polymer compound having crosslinking properties is introduced by injection, extrusion, flowing, etc. into water or an aqueous electrolyte solution whose temperature is adjusted to such a temperature that the shape of the formed polymer molded article can be maintained. The method is to form a molded article having an arbitrary shape such as a thread-like, rod-like, or plate-like shape, and then subject it to a crosslinking reaction by irradiation with radiation in that state. There is no particular restriction on the type of electrolyte used in the present invention, and one type of electrolyte may be used alone or two or more types may be used in combination.
The concentration of the electrolyte aqueous solution is not particularly limited, but is preferably 4 mol/less or less. Examples of the radiation used in the crosslinking reaction in the present invention include ionizing radiation such as γ rays, Χ rays, electron beams, and α rays. The strength of these radiations is
A range of 10 2 to 10 11 R/hr is preferred and the total radiation dose required is 10 3 R or more. The temperature of the crosslinking reaction in the present invention needs to be such that the shape of the thermoreversible polymer molded article can be maintained, and is usually selected in the range of 0 to 100°C. Regarding the reaction atmosphere,
There are no particular restrictions except that the presence of water is required, and the crosslinking reaction can be carried out in any atmosphere, such as in air, in an inert gas, or under reduced pressure. Furthermore, in the present invention, when a thermoreversible polymer molded body is immersed in an electrolyte aqueous solution, since cracks are likely to occur if the molded body is directly immersed in the electrolyte aqueous solution, the molded body is pre-soaked with water at a temperature higher than the transition temperature. After treatment, it is desirable to immerse it in an electrolyte aqueous solution. According to the method of the present invention, a thermoreversible polymer crosslinked molded article having an arbitrary shape can be easily obtained, and this article can be used as, for example, an adsorbent, a separation membrane, a light shielding body, and the like. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Polyacrylpiperidine with a transition temperature of 5°C
Dissolve 1.0g ([η] = 0.19) in 15ml of methanol,
Pour into a petri dish with an inner diameter of 6 cm, leave to dry, then place in a vacuum dryer and heat to 110°C to remove methanol.
A polyacrylic piperidine film was created. Next, add 10 ml of water at 20℃ adjusted to maintain the shape of this polyacrylic piperidine film to the petri dish, seal the top with polyethylene film to prevent the water from evaporating, and incubate for 19 to 20 minutes.
γ-ray irradiation from 60 Co was performed for 536 hours at a temperature of 1.5×10 5 R/hr. After irradiation, the sample maintains its pre-irradiation form and is cross-linked.
Confirmed by dissolution experiments in water and methanol at °C.
When a portion (0.48 g) of the sample was left in water at 2°C for 20 hours, the sample was crosslinked and swelled in water, weighing 1.73 g and swelling degree 3.60. Example 2 1.0 g of poly(N-isopropylacrylamide) ([η] = 0.50) with a transition temperature of 30°C was added to water at 20°C.
The solution was dissolved in 10 ml, poured into a Petri dish with an inner diameter of 10 cm, and left to dry to produce a poly(N-isopropylacrylamide) film. Then this poly(N-
Add 10 ml of water at 50°C to the poly(N-isopropylacrylamide) film, immediately discard the water, and then add 10% saline at 20°C, adjusted to maintain the form of the poly(N-isopropylacrylamide) film.
Add 20 ml [at this time, the transition temperature of poly(N-isopropylacrylamide) is 9.2°C], seal the top with polyethylene film,
Make sure the water does not evaporate and heat at 19-20℃.
740 γ-rays from 60 Co under the condition of 1.5×10 5 R/hr
Irradiated for hours. After irradiation, water dissolution experiments confirmed that the sample maintained its pre-irradiation form and was crosslinked. When 0.05 g of a portion of the sample was immersed in water at 20° C. and left for 20 hours, the sample was crosslinked and swelled in water, weighing 0.53 g and having a degree of swelling of 10.6. Example 3 40 ml of a 30% aqueous solution of polyvinyl methyl ether (3400 cps, 25° C.) with a transition temperature of 37° C. was poured into a tube with an inner diameter of 12 cm.
The mixture was placed in a petri dish and dried in the air to produce a polyvinyl methyl ether film. Next, this polyvinyl methyl ether film was poured with water at 50℃ for 15 minutes.
ml and immediately discarded the water, then added 20 ml of 10% saline solution adjusted to maintain the shape of the polyvinyl methyl ether film (at this time, the transition temperature of polyvinyl methyl ether is 8.5°C) to the petri dish. The upper part was sealed with polyethylene film to prevent the water from evaporating, and the temperature was 19 to 20℃ and 1.5×10 5 R/hr.
γ-rays from 60 Co were irradiated for 744 hours. After irradiation, water dissolution experiments confirmed that the sample maintained its pre-irradiation form and was crosslinked. Sample 1
When 0.22 g of the sample was immersed in 20°C water and left for 20 hours, the sample was crosslinked and swelled in water, weighing 0.55 g and swelling degree 2.5. Example 4 5 g of a 20% aqueous solution of poly(N-isopropylacrylamide) ([η] = 0.50) with a transition temperature of 30°C
Using a syringe, the mixture was introduced into 500 ml of a 10% saline solution at 20° C., which was adjusted so that the shape of the polymer molded product could be maintained, to form a molded product.
Next, the molded body was sealed with polyethylene while immersed in a 10% saline solution to prevent the water from evaporating, and was heated from 60 Co at 19 to 20°C and 1.5 × 10 5 R/hr. γ-ray irradiation was performed for 840 hours. After irradiation, we confirmed through a water dissolution experiment at 20°C that the sample maintained its pre-irradiation form and was crosslinked. One part of the sample, 0.066 g, was added to water at 20℃ for 20 minutes.
When left for an hour, the sample was crosslinked and swelled in water, its weight was 0.70, and its degree of swelling was 10.6.
It was hot. Example 5 5 g of a 20% aqueous solution (0 to 3°C) of poly(acrylichyperidine ([η] = 0.19) having a transition temperature of 5°C was adjusted so that the shape of the formed polymer molded product could be maintained. Using a syringe, the molded body was introduced into 100 ml of water at 20°C to form a molded body.The molded body was then sealed with polyethylene while immersed in water to prevent the water from evaporating. °C, 1.5
γ-ray irradiation from 60 Co under ×10 5 R/hr conditions.
I went for 536 hours. After irradiation, we confirmed through a water dissolution experiment at 20°C that the sample maintained its pre-irradiation form and was crosslinked. When 0.10 g of a sample was left in water at 2°C for 20 hours, the sample was crosslinked and swelled in water, weighing 0.65 g and swelling degree 6.5.
It was hot. Comparative Example When a poly(N-isopropylacrylamide) film prepared in the same manner as in Example 2 was subjected to an experiment similar to that in Example 2 without the addition of water or saline, the film remained uncrosslinked. ,
Dissolved in water at 20°C.
第１図はポリ（Ｎ−イソプロピルアクリルアミ
ド）の１％水溶液における転移温度に対するMCl
（ただし、ＭはNa、Ｋ、Cs及びLiである）の効
果を示すグラフであり、第２図はポリ（Ｎ−イソ
プロピルアクリルアミド）の１％水溶液における
転移温度に対するNaX（ただし、ＸはＦ、Cl、Br
及びＩであある）の効果を示すグラフである。
Figure 1 shows MCl versus transition temperature in a 1% aqueous solution of poly(N-isopropylacrylamide).
(wherein, M is Na, K, Cs, and Li). Figure 2 is a graph showing the effect of NaX (wherein, X is F, Cl, Br
and I) is a graph showing the effect of
Claims (1)
状が保持されうるような温度に調節された水中に
浸漬した状態で、該成形体に放射線照射を行うこ
とを特徴とする熱可逆高分子架橋成形体の製造方
法。 ２ 架橋性を有する熱可逆高分子成形体をその形
状が保持されうるように調節された電解質水溶液
中に浸漬した状態で、該成形体に放射線照射を行
うことを特徴とする熱可逆高分子架橋成形体の製
造方法。 ３ 架橋性を有する熱可逆高分子化合物水溶液を
形成された高分子成形体の形状が保持されうるよ
うな温度に調節された水中に送入して成形体を形
成させ、次いでそのままの状態で該成形体に放射
線照射を行うことを特徴とする熱可逆高分子架橋
成形体の製造方法。 ４ 架橋性を有する熱可逆高分子化合物水溶液を
形成された高分子成形体の形状が保持されうるよ
うに調節された電解質水溶液中に送入して成形体
を形成させ、次いでそのままの状態で該成形体に
放射線照射を行うことを特徴とする熱可逆高分子
架橋成形体の製造方法。[Claims] 1. A thermoreversible polymer molded product having crosslinking properties is immersed in water whose temperature is adjusted to maintain its shape, and the molded product is irradiated with radiation. A method for producing a thermoreversible polymer crosslinked molded article. 2. Thermoreversible polymer crosslinking characterized by irradiating a thermoreversible polymer molded article with crosslinking properties with radiation while the molded article is immersed in an electrolyte aqueous solution adjusted so that its shape can be maintained. Method for manufacturing a molded object. 3. A thermoreversible polymer compound aqueous solution having crosslinking properties is introduced into water whose temperature is adjusted to maintain the shape of the formed polymer molded product to form a molded product, and then the molded product is left in that state. A method for producing a thermoreversible polymer crosslinked molded article, the method comprising irradiating the molded article with radiation. 4. A thermoreversible polymer compound aqueous solution having crosslinking properties is introduced into an electrolyte aqueous solution adjusted so that the shape of the formed polymer molded article can be maintained to form a molded article, and then the molded article is left in that state. A method for producing a thermoreversible polymer crosslinked molded article, the method comprising irradiating the molded article with radiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6192784A JPS60203639A (en) | 1984-03-29 | 1984-03-29 | Production of crosslinked molded article of thermoreversible polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6192784A JPS60203639A (en) | 1984-03-29 | 1984-03-29 | Production of crosslinked molded article of thermoreversible polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60203639A JPS60203639A (en) | 1985-10-15 |
| JPH0339538B2 true JPH0339538B2 (en) | 1991-06-14 |
Family
ID=13185279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6192784A Granted JPS60203639A (en) | 1984-03-29 | 1984-03-29 | Production of crosslinked molded article of thermoreversible polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60203639A (en) |
-
1984
- 1984-03-29 JP JP6192784A patent/JPS60203639A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60203639A (en) | 1985-10-15 |
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