JPS63270674A - Novel vinyl compound - Google Patents
Novel vinyl compoundInfo
- Publication number
- JPS63270674A JPS63270674A JP10589387A JP10589387A JPS63270674A JP S63270674 A JPS63270674 A JP S63270674A JP 10589387 A JP10589387 A JP 10589387A JP 10589387 A JP10589387 A JP 10589387A JP S63270674 A JPS63270674 A JP S63270674A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- polymer
- solvent
- acrylamide
- alcohol
- 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
- -1 vinyl compound Chemical class 0.000 title claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 title claims description 15
- 239000000126 substance Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 34
- 239000002904 solvent Substances 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000001419 dependent effect Effects 0.000 abstract description 4
- ZCCPVTVGEQLONB-UHFFFAOYSA-N 1-(1,3-dioxolan-2-yl)-n-methylmethanamine Chemical compound CNCC1OCCO1 ZCCPVTVGEQLONB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 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
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JNNSPLJNNQEPEE-UHFFFAOYSA-N n-(1,3-dioxolan-2-yl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1OCCO1 JNNSPLJNNQEPEE-UHFFFAOYSA-N 0.000 description 1
- XMWVNAQQVRLLSY-UHFFFAOYSA-N n-(1,3-dioxolan-2-yl)-n-methylprop-2-enamide Chemical compound C=CC(=O)N(C)C1OCCO1 XMWVNAQQVRLLSY-UHFFFAOYSA-N 0.000 description 1
- COYVWKMZTCAFHO-UHFFFAOYSA-N n-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)N(C)C(=O)C=C COYVWKMZTCAFHO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001977 poly(N,N-diethylacrylamides) Polymers 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- 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、新規なビニル化合物に関するものである。更
に詳しく言えば、本発明は、遮光体、温度センサー、吸
着剤、更には玩具、インテリア、捺染剤、ディスプレイ
、分離膜、メカノケミカル材料に利用しうる水及びアル
コール溶剤依存性熱可逆型高分子化合物の原料モノマー
として好適なビニル化合物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 vinyl compound. More specifically, the present invention provides water and alcohol solvent dependent thermoreversible polymers that can be used in light shields, temperature sensors, adsorbents, toys, interiors, textile printing agents, displays, separation membranes, and mechanochemical materials. This invention relates to vinyl compounds suitable as raw material monomers for compounds.
従来の技術
水溶性高分子化合物の中には、水溶液状態においである
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
可逆型高分子化合物と呼ばれ、近年、温室、化学実験室
などの遮光体、温度センサー等として注目されるように
なってきた。Conventional technology Some water-soluble polymer compounds exhibit a special reversible dissolution behavior in which they precipitate and turn cloudy above a certain temperature (transition temperature or cloud point) in an aqueous solution state, and dissolve and become transparent below that temperature. This compound is called a hydrophilic to hydrophobic thermoreversible polymer compound, and has recently attracted attention as a light shielding material for greenhouses, chemical laboratories, etc., and as a temperature sensor.
このような親水性−疎水性熱可逆型高分子化合物として
は、これまで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、ポリビニルメチルエ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 hydrophilic-hydrophobic thermoreversible polymer compounds, partially saponified polyvinyl acetate, polyvinyl methyl ether, methylcellulose, polyethylene oxide, polyvinylmethylexazolidinone, and polyacrylamide derivatives have been known. There is.
これらの親水性−疎水性熱可逆型高分子化合物の中でポ
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、特に育用であり、これまで
ポリ (N−エチル (メタ)アクリルアミド)、ポリ
(N−n−プロピル (メタ)アクリルアミド)、ポ
リ (N−イソプロピル (メタ)アクリルアミド)、
ポリ (N−シクロプロピル (メタ)アクリルアミド
)、ポリ (N、N−ジエチルアクリルアミド)、ポリ
(NSN−ジエチルアクリルアミド)、ポリ(N−メ
チル−N−n−プロピルアクリルアミド)、ポリ (N
−メチル−N−イソプロピルアクリルアミド)、ポリ
(N−アクリルピペリジン)、ポリ (N−テトラヒド
ロフルフリル (メタ)アクリルアミド)、ポリ (N
−メトキシプロピル (メタ)アクリルアミド)、ポリ
(N−エトキシプロピル (メタ)アクリルアミド)
、ポリ (N−イソプロポキシプロビル (メタ)アク
リルアミド)、ポリ (N−エトキシエチル (メタ)
アクリルアミド)、ポリ (N−(2゜2−ジメトキシ
エチル)−N−メチルアクリルアミド)等が知られてい
る。Among these hydrophilic-hydrophobic thermoreversible polymer compounds, polyacrylamide derivatives are particularly popular because they are stable in water and can be produced at relatively low cost. (meth)acrylamide), poly (N-n-propyl (meth)acrylamide), poly (N-isopropyl (meth)acrylamide),
Poly (N-cyclopropyl (meth)acrylamide), Poly (N, N-diethylacrylamide), Poly (NSN-diethylacrylamide), Poly (N-methyl-Nn-propylacrylamide), Poly (N
-methyl-N-isopropylacrylamide), poly
(N-acrylicpiperidine), poly (N-tetrahydrofurfuryl (meth)acrylamide), poly (N
-methoxypropyl (meth)acrylamide), poly(N-ethoxypropyl (meth)acrylamide)
, Poly (N-isopropoxypropyl (meth)acrylamide), Poly (N-ethoxyethyl (meth)
acrylamide), poly(N-(2°2-dimethoxyethyl)-N-methylacrylamide), etc. are known.
しかしながら、これらの熱可逆型高分子化合物は、いず
れも水溶液中では熱可逆的特性を示すが、その他の溶媒
例えばアルコールの溶液中においては、このような特性
を示さないため、利用範囲が制限されるのを免れなかっ
た。However, although all of these thermoreversible polymer compounds exhibit thermoreversible properties in aqueous solutions, they do not exhibit such properties in solutions of other solvents, such as alcohol, so their range of use is limited. I couldn't avoid it.
発明が解決しようとする問題点
本発明は、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、水以外の溶媒に溶解した場合でも、熱可逆特性を示
すポリアクリルアミド系の原料モノマーを提供すること
を目的としてなされたものである。Problems to be Solved by the Invention Under these circumstances, the present invention aims to expand the scope of use of hydrophilic-hydrophobic thermoreversible polyacrylamide derivatives, even when dissolved in a solvent other than water. This was done with the aim of providing a polyacrylamide-based raw material monomer that exhibits thermoreversible properties.
問題点を解決するための手段
本発明者らは、水以外の溶媒中においても熱可逆特性を
示す新規な高分子化合物を開発するために鋭意研究を重
ねた結果、
式
%式%
で表わされるビニル化合物をラジカル重合して得られる
式
%式%)
で表される繰り返し単位から成り、27℃における極限
粘度〔η)0.01〜6.0に相当する分子型を有する
高分子化合物は、水の外、アルコールに溶かした場合に
おいても、温度変化により不溶化する熱可逆特性を示す
ことを見出し、この知見に基づいて本発明を開発するに
至った。Means for Solving the Problems The present inventors have conducted intensive research to develop a new polymer compound that exhibits thermoreversible properties even in solvents other than water, and as a result, we have found that the formula % is expressed by the formula %. A polymer compound obtained by radical polymerization of a vinyl compound and consisting of repeating units represented by the formula % formula %) and having a molecular type corresponding to an intrinsic viscosity [η) of 0.01 to 6.0 at 27°C is: It was discovered that it exhibits thermoreversible properties of becoming insolubilized due to temperature changes even when dissolved in alcohol as well as water, and based on this knowledge, the present invention was developed.
本発明のビニル化合物は、文献未載の新規化合物、すな
わち、N−メチル−N−(1,3−ジオキソラン−2−
イル)アクリルアミドであり、例えば反応式
%式%
に従い、アクリル酸クロリドと2−メチルアミノメチル
−1,3−ジオキソランとトリエチルアミンとを、0〜
10℃に保った溶媒中において反応させるか、あるいは
反応式
%式%
に従いアクリル酸クロリドと2−メチルアミツメデル−
1,3−ジオキソランとを、0〜10℃に保った溶媒中
において、反応させることによって得ることができる。The vinyl compound of the present invention is a novel compound that has not been described in any literature, namely, N-methyl-N-(1,3-dioxolane-2-
For example, according to the reaction formula %, acrylic acid chloride, 2-methylaminomethyl-1,3-dioxolane, and triethylamine are
Either react in a solvent kept at 10°C, or react with acrylic acid chloride and 2-methylamizmedel according to the reaction formula %.
It can be obtained by reacting 1,3-dioxolane with 1,3-dioxolane in a solvent maintained at 0 to 10°C.
これらの方法において用いる溶媒については、アクリル
酸クロリドに対して不活性であれば特に制限はなく、一
般にはベンゼン、アセトン、トルエン等が用いられる。The solvent used in these methods is not particularly limited as long as it is inert to acrylic acid chloride, and benzene, acetone, toluene, etc. are generally used.
反応温度については、高すぎると副反応が起るので、0
〜10℃の範囲において反応させることが好ましい。Regarding the reaction temperature, side reactions will occur if it is too high, so
It is preferable to carry out the reaction in the range of -10°C.
このようにして得られた反応混合物から、目的化合物を
単離するには、通常まずろ過などによって、トリエチル
アミン塩酸塩又は2−メチルアミノメチル−1,3−ジ
オキソラン塩酸塩を除去したのち、ロータリーエバポレ
ーターを用いてろ液から溶媒を留去し、ついで減圧蒸留
して精製する。To isolate the target compound from the reaction mixture thus obtained, usually first, triethylamine hydrochloride or 2-methylaminomethyl-1,3-dioxolane hydrochloride is removed by filtration, etc., and then a rotary evaporator is used. The solvent is distilled off from the filtrate using a filtrate, followed by distillation under reduced pressure for purification.
この際の留出物は、必要に応じさらに減圧蒸留を繰り返
して高純度のものにすることができる。The distillate at this time can be further subjected to repeated distillation under reduced pressure as necessary to make it highly pure.
このようにして得られたN−メチル−N−(1゜3−ジ
オキソラン−2−イル)アクリルアミドは(沸点117
°C/Imlmm1(無色の液体であり、水、メチルア
ルコール、エチルアルコール、アトセン、テトランヒド
ロフラン、クロロホルム、四塩化炭素、ベンゼン等の溶
媒に可溶で、n−ヘキサン、n−へブタンには不溶であ
る。The thus obtained N-methyl-N-(1°3-dioxolan-2-yl)acrylamide (boiling point 117
°C/Imlmm1 (It is a colorless liquid, soluble in solvents such as water, methyl alcohol, ethyl alcohol, atocene, tetrahydrofuran, chloroform, carbon tetrachloride, benzene, etc., and soluble in n-hexane, n-hebutane, etc.) Insoluble.
本発明のビニル化合物は、CH、−CH−基、−CON
<基、−CI−(t −0−基、−CH<基、CtI
s−基等を有するので、赤外線吸収スペクトルや質量ス
ペクトル分析などによって同定することができる。The vinyl compound of the present invention has CH, -CH- group, -CON
< group, -CI- (t -0- group, -CH< group, CtI
Since it has an s-group etc., it can be identified by infrared absorption spectrum, mass spectrum analysis, etc.
本発明のN−メチル−N−(1,3−ジオキソラン−2
−イル)アクリルアミドをラジカル重合することにより
水及びアルコール溶媒依存性熱可逆型高分子化合物を製
造することができるが、この重合は通常、溶液重合法や
塊状重合法により、過酸化ベンゾイル、過酢酸のような
過酸化物やアゾビスイソブチロニトリルのようなアゾ化
合物を重合開始剤として用い、あるいは紫外線、放射線
、電子線、プラズマなどの活性線の照射によって行うこ
とができる。この際の重合開始剤の使用量としては、単
量体の重量に基づき、0.005〜5重量%、特に0.
001〜2重贋%の範囲が適当である。N-methyl-N-(1,3-dioxolane-2 of the present invention)
Water and alcohol solvent-dependent thermoreversible polymer compounds can be produced by radical polymerizing acrylamide, but this polymerization is usually carried out by solution polymerization or bulk polymerization using benzoyl peroxide, peracetic acid, etc. The polymerization can be carried out using a peroxide such as or an azo compound such as azobisisobutyronitrile as a polymerization initiator, or by irradiation with actinic rays such as ultraviolet rays, radiation, electron beams, and plasma. The amount of polymerization initiator used in this case is 0.005 to 5% by weight, particularly 0.005 to 5% by weight, based on the weight of the monomer.
A range of 0.001% to 2% double forgeries is appropriate.
特に好適なのは溶液重合法により、N−メチル−N−(
1,3−ジオキソラン−2−イル)アクリルアミドを有
機溶媒中に1〜80重量%の濃度で溶解し、重合させる
方法である。Particularly preferred is the solution polymerization method, in which N-methyl-N-(
This is a method in which 1,3-dioxolan-2-yl)acrylamide is dissolved in an organic solvent at a concentration of 1 to 80% by weight and polymerized.
このような溶液重合法に用いられる溶媒についてはN−
メチル−N−(1,3−ジオキソラン−2−イル)アク
リルアミドをとかすものであればよく特に制限はない。Regarding the solvent used in such solution polymerization method, N-
There are no particular limitations as long as it dissolves methyl-N-(1,3-dioxolan-2-yl)acrylamide.
例えば、水、アルコール類、アセトン、テトラヒドロフ
ラン、クロロホルム、四塩化炭素、ベンゼン、酢酸アル
キル類などを挙げることができ、これらは、単独で用い
てよいし、場合により2種以上組み合わせて用いてもよ
い。Examples include water, alcohols, acetone, tetrahydrofuran, chloroform, carbon tetrachloride, benzene, alkyl acetates, etc., and these may be used alone or in combination of two or more. .
また、本発明のビニル化合物をラジカル重合させて得ら
れる高分子化合物の重合度については、テトラヒドロフ
ラン溶液における温度27℃での極限粘度〔η〕が0.
01〜6.0の範囲のものが実用的である。さらに各種
溶媒に対する溶解性については、冷水、テトラヒドロフ
ラン、クロロホルム、ベンゼンなどには可溶、冷アルコ
ール、酢酸エチル、酢酸n−アミル、酢酸イソブチル、
アセトンなどには不溶である。Regarding the polymerization degree of the polymer compound obtained by radical polymerization of the vinyl compound of the present invention, the intrinsic viscosity [η] at a temperature of 27°C in a tetrahydrofuran solution is 0.
A value in the range of 01 to 6.0 is practical. Furthermore, regarding solubility in various solvents, it is soluble in cold water, tetrahydrofuran, chloroform, benzene, etc., cold alcohol, ethyl acetate, n-amyl acetate, isobutyl acetate, etc.
It is insoluble in acetone etc.
本発明のビニル化合物をラジカル重合させて得られる高
分子化合物は、低温域で水に溶け、高温−;
によっても異なるが、通常53〜65°Cの範囲である
。′□−また、この高分子化合物は、加温により脂肪族
1級アルコールに可溶化するアルコール溶媒依存性熱可
逆型高分子化合物でもある。例えばこの重合体の1重量
%アルコール溶液の転移温度は、重合条件によっても異
なるがメタノールでは0〜30℃、エタノールでは30
〜60℃、n−プロパツールでは30〜50℃、5eC
−ブチルアルコールでは35〜50℃、n−アミルアル
コールでは35〜50℃、イソプロピルアルコールでは
50〜65°Cであり、一般にアルコールの種類により
異なる。The polymer compound obtained by radical polymerization of the vinyl compound of the present invention is soluble in water at a low temperature, and the high temperature is usually in the range of 53 to 65°C, although it varies depending on the temperature. '□-This polymer compound is also an alcohol solvent-dependent thermoreversible polymer compound that is solubilized in aliphatic primary alcohol by heating. For example, the transition temperature of a 1% alcohol solution of this polymer varies depending on the polymerization conditions, but it is 0 to 30°C for methanol and 30°C for ethanol.
~60℃, 30-50℃ for n-propatool, 5eC
The temperature is 35 to 50°C for -butyl alcohol, 35 to 50°C for n-amyl alcohol, and 50 to 65°C for isopropyl alcohol, and generally varies depending on the type of alcohol.
発明の効果
本発明のビニル化合物は、文献未載の新規ビニル化合物
であって、その高分子化合物は、可逆的に低温域で水に
溶は高温域で水に不溶、高温域でアルコールに溶は低温
域でアルコールに不溶となる熱可逆性ポリアクリルアミ
ド誘導体で、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、例えば、
温室、化学実験室、ラジオアイソトープ実験室等の遮光
体、温度センサー、界面活性剤の吸着剤、更には玩具、
インテリア、捺染剤、ディスプレイ、分離膜、メカノケ
ミカル素子材料等に利用することができる。Effects of the Invention The vinyl compound of the present invention is a new vinyl compound that has not been published in any literature, and the polymer compound is reversibly soluble in water at low temperatures, insoluble in water at high temperatures, and soluble in alcohol at high temperatures. is a thermoreversible polyacrylamide derivative that is insoluble in alcohol at low temperatures, and has a different transition temperature from conventionally known thermoreversible polyacrylamide derivatives. For example,
Light shielding materials for greenhouses, chemical laboratories, radioisotope laboratories, etc., temperature sensors, surfactant adsorbents, and even toys,
It can be used for interior decoration, textile printing agents, displays, separation membranes, mechanochemical device materials, etc.
実 施 例 1aの三角フラスコにトリエチルアミン39.1g。Example Add 39.1 g of triethylamine to Erlenmeyer flask 1a.
2−メチルアミノメチル−1,3−ジオキソラン39.
1g及びトルエン450m1を入れ、水で冷やして内容
液を10℃未満の温度に保ちかきまぜながら、アクリル
酸クロリド27.6mlとトルエン50m1の混合液を
滴下漏斗を用い、約3時間かけて滴下した。滴下終了後
反応液を一昼夜冷蔵庫に保ち反応させた。2-Methylaminomethyl-1,3-dioxolane39.
1 g of toluene and 450 ml of toluene were added thereto, and while the contents were kept at a temperature below 10° C. by cooling with water and stirring, a mixed solution of 27.6 ml of acrylic acid chloride and 50 ml of toluene was added dropwise using a dropping funnel over about 3 hours. After completion of the dropwise addition, the reaction solution was kept in the refrigerator for one day and night to react.
ついで反応液をろ過し、ロータリーエバポレータを用い
てろ液からトルエンを除去し、さらに減圧蒸留を行い無
色透明の留分 (沸点117℃/ I mm T−(g
)42.6gを得た。Next, the reaction solution was filtered, toluene was removed from the filtrate using a rotary evaporator, and further vacuum distillation was performed to obtain a colorless and transparent fraction (boiling point 117°C/I mm T-(g
) 42.6g was obtained.
この物質の赤外線吸収スペクトルを第1図に、質量スペ
クトルを第2図に示す。The infrared absorption spectrum of this substance is shown in FIG. 1, and the mass spectrum is shown in FIG.
これらスペクトル分析の結果は、次の通りである。The results of these spectral analyzes are as follows.
質量スペクトル分析 :
m/e
M+1 =172M
=171−CH2
0− CI−12
CH,=CH−C0−=55
CI−f2=CI−(−=27
赤外線吸収スペクトル分析 ニ
ーN< = 3500 cm−’CH2=C
H= 1803 cm−’0−= 1120 cm
−’
>C=O= 1640 cm−’
>CH−= 2940.2880cm”以上の分析結
果から、N−メチル−N−(1゜3−ジオキソラン−2
−イル)アクリルアミドであることが確認された。Mass spectrum analysis: m/e M+1 = 172M
=171-CH2 0- CI-12 CH, =CH-C0-=55 CI-f2=CI-(-=27 Infrared absorption spectrum analysis Knee N< = 3500 cm-'CH2=C
H= 1803 cm-'0-= 1120 cm
-'>C=O=1640cm-'>CH-=2940.2880cm'' From the analysis results, N-methyl-N-(1゜3-dioxolane-2
-yl) acrylamide.
参考例 1〜6
実施例で得たビニルモノマーのラジカル重合体を製造し
た。Reference Examples 1 to 6 Radical polymers of the vinyl monomers obtained in Examples were produced.
重合溶媒20mρにN−メチル−N−(1,3−ジオキ
ソラン−2−イル)アクリルアミド2.2g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後
封管し、照射線量率3.9X10’R/hr、温度24
℃で1時間コバルト60からのγ線照射を行い反応させ
た。反応後、脱溶媒したのちn−ヘキサンを加え重合体
を分離、回収した。参考例1〜6の重合反応結果を第1
表に示す。Add 2.2 g of N-methyl-N-(1,3-dioxolan-2-yl)acrylamide to 20 mρ of the polymerization solvent, put it into an ampoule, degas it under reduced pressure using liquid nitrogen, and then seal the tube. Rate 3.9X10'R/hr, temperature 24
The reaction was carried out by irradiating gamma rays from cobalt 60 at ℃ for 1 hour. After the reaction, the solvent was removed, and then n-hexane was added to separate and collect the polymer. The polymerization reaction results of Reference Examples 1 to 6 are
Shown in the table.
第1表
MDA PMDA 30℃における参考例
溶 媒 使用量(g)収量(g) PMDAの
溶解性1 ベンゼン 2.23 2.
23 ベンゼンに溶解PMDA : MDA重合体
参考例2の重合体の赤外線吸収スペクトルを第3′ 図
に示す。ビニルモノマーの赤外線吸収スペクトルと重合
体のそれとの比較より、1603cM −’のビニル基
が消滅し高分子化合物の生成が確認された。Table 1 MDA PMDA Reference example at 30℃
Solvent Amount used (g) Yield (g) Solubility of PMDA 1 Benzene 2.23 2.
23 PMDA dissolved in benzene: MDA polymer The infrared absorption spectrum of the polymer of Reference Example 2 is shown in Figure 3'. By comparing the infrared absorption spectrum of the vinyl monomer with that of the polymer, it was confirmed that the vinyl group at 1603 cM −' disappeared and a polymer compound was formed.
得られた重合体については、テトラヒドロフラン溶液と
し、ウベローデ粘度計を用いて27℃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性から求め、水中における熱可逆性
を調べた。すなわち、1重量%濃度の重合体水溶液を調
整して、温度コントローラー付分光光度計を用い、昇温
速度1’C/分で昇温させながら、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0.5となる温度 (TL) から求めた。こ
れらの結果を第2表に示す。The obtained polymer was made into a tetrahydrofuran solution, and the viscosity was measured at 27° C. using an Ubbelohde viscometer to determine the intrinsic viscosity [η]. In addition, the transition temperature was determined from the light transmittance associated with the temperature change of the aqueous solution, and the thermoreversibility in water was investigated. That is, an aqueous polymer solution with a concentration of 1% by weight was prepared, and the light transmittance at a wavelength of 500 nm was measured using a spectrophotometer with a temperature controller while raising the temperature at a rate of 1'C/min. The temperature was determined from the temperature (TL) at which the light transmittance was 0.5 of the initial transmittance. These results are shown in Table 2.
第2表
6 クロロホルム −−−−54,5参考例
3の重合体水溶液の透過率一温度曲線を第4図に示す。Table 2 6 Chloroform ---54,5 The transmittance-temperature curve of the aqueous polymer solution of Reference Example 3 is shown in FIG.
この中で実線は昇温時のデータである。Among these, the solid line is the data when the temperature was increased.
参考例3の重合体について、種々のアルコール中におけ
る熱可逆性を調べた。転移温度は、そのアルコール溶液
の温度変化に伴う光透過性から決定した。即ち、1重量
%濃度の重合体アルコール溶液を調整して温度コントロ
ーラー付分光光度計を用い、降温速度1’C/分で降温
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0.5となる温
度(TL )から求めた。これらの結果を第3表に示す
。The thermoreversibility of the polymer of Reference Example 3 in various alcohols was investigated. The transition temperature was determined from the light transmittance associated with the temperature change of the alcohol solution. That is, a polymer alcohol solution with a concentration of 1% by weight was prepared, and using a spectrophotometer with a temperature controller, the light transmittance at a wavelength of 500 nm was measured while lowering the temperature at a cooling rate of 1'C/min, and the transition temperature was determined. , the light transmittance was determined from the temperature (TL) at which the light transmittance was 0.5 of the initial transmittance. These results are shown in Table 3.
第3表
イソプロピルアルコール 65.0 高温可
溶 低温不溶化参考例3の重合体アルコール溶液の透過
率一温度曲線を第5図に示す。この中で実線は昇温時の
データである。Table 3 Isopropyl alcohol 65.0 High temperature soluble Low temperature insolubilization The transmittance versus temperature curve of the polymer alcohol solution of Reference Example 3 is shown in FIG. Among these, the solid line is the data when the temperature was increased.
参考例7〜IO
実施例で得たビニルモノマーのラジカル重合体を製造し
た。Reference Example 7 to IO A radical polymer of the vinyl monomer obtained in the 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、
その0.5g/100m(2a度の溶媒20m(l!に
所定重量のN−メチル−N−(1,3−ジオキソラン−
2−イル)アクリルアミドを加え、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管し、温度5
0°Cで2時間恒温槽に保ち反応させた。反応後、脱溶
媒したのちn−ヘキサンを加え重合体を分離、回収した
。参考例7〜10の重合反応結果を第4表に示す。Using azobisisobutyronitrile as a polymerization initiator,
A predetermined weight of N-methyl-N-(1,3-dioxolane-
2-yl) acrylamide was added, this was put into an ampoule, the tube was degassed under reduced pressure using liquid nitrogen, the tube was sealed, and the temperature was increased to 5.
The mixture was kept in a constant temperature bath at 0°C for 2 hours to react. After the reaction, the solvent was removed, and then n-hexane was added to separate and collect the polymer. Table 4 shows the polymerization reaction results of Reference Examples 7 to 10.
第4表
10 テトラヒドロフラン 2,22 2.21
テトラヒドロフラン溶解これら重合体の極限粘
度及び転移温度を参考例1〜6と同様にして求めた。そ
の結果を第5表に示第5表
1G テトラヒドロフラン 0.06
65.0また、参考例8の重合体について、種々
のアルコール中における転移温度を実施例3と同様にし
て測定した。その結果を第6表に示す。Table 4 10 Tetrahydrofuran 2,22 2.21
The intrinsic viscosity and transition temperature of these polymers dissolved in tetrahydrofuran were determined in the same manner as in Reference Examples 1-6. The results are shown in Table 5 Table 5 1G Tetrahydrofuran 0.06
65.0 Furthermore, the transition temperature of the polymer of Reference Example 8 in various alcohols was measured in the same manner as in Example 3. The results are shown in Table 6.
第6表
イソプロピルアルコール 65.5 高温
可溶 低温不溶化Table 6 Isopropyl alcohol 65.5 High temperature soluble Low temperature insolubilization
第1図は、実施例のビニルモノマーの赤外線吸収スペク
トルを、第2図は、実施例のビニルモノマーの質全スペ
クトルを、第3図は参考例2の重合体の赤外線吸収スペ
クトルを示す。第4図は、本発明の方法による参考例3
の重合体の1重量%水溶液におlする透過率−yM度曲
線を示す。第5図は本発明の方法による参考例3の重合
体の1重量%アルコール溶液におけろ透過率一温度曲線
を示士。
特許出願人 工業技術院長 飯
塚幸三指定代理人 工業技術院長H(ff高分子材料研
究所長 須;田昌男1 、”;′1::
第 1 図
4CO:l ゐ刀 蕉 b刀 加℃ 工 ツ
刀 ■刀 2刀 迫力 8I) α9波 数
(CM−“)
第 2 図
(−/e)
第 3 図
波 数 (OM−1)
第 4 図
第 5 図
温度(°C)FIG. 1 shows the infrared absorption spectrum of the vinyl monomer of Example, FIG. 2 shows the total spectrum of the vinyl monomer of Example, and FIG. 3 shows the infrared absorption spectrum of the polymer of Reference Example 2. FIG. 4 shows Reference Example 3 according to the method of the present invention.
The transmittance-yM degree curve of the polymer in a 1% by weight aqueous solution is shown. FIG. 5 shows the permeability versus temperature curve of the polymer of Reference Example 3 in a 1% by weight alcohol solution according to the method of the present invention. Patent applicant: Director of the Agency of Industrial Science and Technology Kozo Iizuka Designated agent: Director of the Agency of Industrial Science and Technology ■Sword 2 swords powerful 8I) α9 wave number
(CM-“) Fig. 2 (-/e) Fig. 3 Wave number (OM-1) Fig. 4 Fig. 5 Temperature (°C)
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10589387A JPS63270674A (en) | 1987-04-28 | 1987-04-28 | Novel vinyl compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10589387A JPS63270674A (en) | 1987-04-28 | 1987-04-28 | Novel vinyl compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63270674A true JPS63270674A (en) | 1988-11-08 |
JPH0372218B2 JPH0372218B2 (en) | 1991-11-18 |
Family
ID=14419586
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10589387A Granted JPS63270674A (en) | 1987-04-28 | 1987-04-28 | Novel vinyl compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63270674A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03275682A (en) * | 1990-03-22 | 1991-12-06 | Agency Of Ind Science & Technol | New vinyl compound |
JPH0482886A (en) * | 1990-07-24 | 1992-03-16 | Agency Of Ind Science & Technol | New vinyl compound |
JPH06145166A (en) * | 1992-11-06 | 1994-05-24 | Agency Of Ind Science & Technol | New vinyl compound |
-
1987
- 1987-04-28 JP JP10589387A patent/JPS63270674A/en active Granted
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03275682A (en) * | 1990-03-22 | 1991-12-06 | Agency Of Ind Science & Technol | New vinyl compound |
JPH0482886A (en) * | 1990-07-24 | 1992-03-16 | Agency Of Ind Science & Technol | New vinyl compound |
JPH06145166A (en) * | 1992-11-06 | 1994-05-24 | Agency Of Ind Science & Technol | New vinyl compound |
Also Published As
Publication number | Publication date |
---|---|
JPH0372218B2 (en) | 1991-11-18 |
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