JPS60168706A - Temperature-sensitive copolymer - Google Patents
Temperature-sensitive copolymerInfo
- Publication number
- JPS60168706A JPS60168706A JP2429084A JP2429084A JPS60168706A JP S60168706 A JPS60168706 A JP S60168706A JP 2429084 A JP2429084 A JP 2429084A JP 2429084 A JP2429084 A JP 2429084A JP S60168706 A JPS60168706 A JP S60168706A
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- Japan
- Prior art keywords
- temperature
- polymer
- copolymer
- ethyl
- water
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Abstract
Description
【発明の詳細な説明】
本発明は感温性共重合体に関する。更に詳しくは特定さ
れた不飽和アミド化合物を含有してなる共重合体よりな
る感温性重合体に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to temperature-sensitive copolymers. More specifically, the present invention relates to a temperature-sensitive polymer comprising a copolymer containing the specified unsaturated amide compound.
従来、水溶液中で加温により水に不溶化する、即ち具体
的には濁りを生じて不透明になる感温性重合体としては
、ポリエチレンオキサイドまたはエチレンオキシドとプ
ロ、ピレンオキシドとの共重合体、メチルセルロース、
ポリメチルビニルセルロース等が知られている。しかし
ながら、これらの重合体を製造する場合においては、原
料単量体の取り扱いおよび重合等に特別の装置あるいは
技術が必要であるとか、更に過酷な条件下で反応が要求
される等種々の問題があった。Conventionally, temperature-sensitive polymers that become insolubilized in water by heating in an aqueous solution, that is, specifically, become cloudy and opaque, include polyethylene oxide or a copolymer of ethylene oxide and pro- or pyrene oxide, methyl cellulose,
Polymethylvinyl cellulose and the like are known. However, when producing these polymers, there are various problems such as the need for special equipment or technology for handling and polymerization of raw material monomers, and the need for reactions to be conducted under harsher conditions. there were.
近年、ある欅のアクリルアミドまたはメタクリルアミド
誘導体（以下（メタ）アクリルアミド誘導体と略記する
）の重合体、たとえばＮ−プロピルアクリルアミドの重
合体において、水溶液中で加温することにより白濁し不
溶化することがＪ。In recent years, it has been reported that certain polymers of acrylamide or methacrylamide derivatives (hereinafter abbreviated as (meth)acrylamide derivatives), such as N-propylacrylamide polymers, become cloudy and insolubilized when heated in an aqueous solution. .
ＭＡＣ囮５ＶＩ−ＯＬ、 ＳＣＬ −ｃＨｇｌ’ｔ 、
Ａ ２ 、巻、１４．４１−１４５５頁（１９’６８
年発行）に開示されており、また最近同様の技術がＪ、
ｐｅ←ルＳｃ；、、 、 Ｐｃｔ％”−シフ。６６巻
、２０９−２１９頁（１９７９年発行）、特開昭５８−
１７４４０８号、特開昭５８−１７９２５６号、特開昭
５８−２０６６５４号により、またジエチルアクリルア
ミドに関しては特開昭５８−２０６６５５号に開示され
ている。MAC decoy 5VI-OL, SCL-cHgl't,
A2, Vol., pp. 14.41-1455 (19'68
(published in 2013), and similar technology has recently been published in J.
pe←LeSc;,, , Pct%”-Schiff. Volume 66, pages 209-219 (published in 1979), JP-A-1983-
174408, JP 58-179256, JP 58-206654, and diethyl acrylamide is disclosed in JP 58-206655.
それらの（メタ）アクリルアミド誘導体は、一般に粉体
状であるか又は高沸点の液体であるので、取り扱いは簡
単であり、更にラジカル重合等の方法により容易に重合
できる等の利点がある。しかし乍ら、前記の開示技術に
よれば、（メタ）アクリルアミド誘導体の重合体を水溶
液中で加温することによ＋７水に不溶化し白濁する温度
（以下争点と略す）は約２０〜４０℃の範囲に偏在して
いるので、実用面での１つの問題点となっていた。These (meth)acrylamide derivatives are generally powder-like or high-boiling liquid, so they are easy to handle and have the advantage of being easily polymerized by methods such as radical polymerization. However, according to the disclosed technology, the temperature at which a (meth)acrylamide derivative polymer becomes insoluble in +7 water and becomes cloudy by heating it in an aqueous solution (hereinafter referred to as the point of contention) is approximately 20 to 40°C. Since it is unevenly distributed in the range of , it has become a practical problem.
上記の点に鑑み鋭意検討した結果、特定の不飽十ロアミ
ド化合物を用いることにより、比較的広い温度範囲で加
温により水に不溶化する温度（以下争点と略記する）を
制御できることを見い出し、本発明に到達した。As a result of intensive studies in view of the above points, we discovered that by using a specific unsaturated decaroamide compound, the temperature at which it becomes insolubilized in water by heating (hereinafter abbreviated as the issue at issue) can be controlled over a relatively wide temperature range. invention has been achieved.
即ち、本発明は、一般式
（但し、１（、は水素またはメチル基であり、鴇は水素
またはエチル−Ａ（であり、山はエチル基またはプロピ
ル基である。鳥が水素の時は鴇は水素で鳥はプロピル基
であるか、鵬及び鳥ともエチル基である。■（２がメチ
ル基の時は、ｉ４は水素でＲ３はプロピル基である。）
で示される不飽和アミド化合物の１種以上と他の共重合
しうる単量体との共重合体よりなり加温により水に不溶
化する感温性共重合体である。That is, the present invention is based on the general formula (where 1() is hydrogen or a methyl group, Toshi is hydrogen or ethyl-A (, and the mountain is an ethyl group or a propyl group. When the bird is hydrogen, Toshi is is hydrogen and Tori is a propyl group, or both Peng and Tori are ethyl groups. (When 2 is a methyl group, i4 is hydrogen and R3 is a propyl group.) It is a temperature-sensitive copolymer made of a copolymer of one or more copolymerizable monomers with other copolymerizable monomers and becomes insoluble in water by heating.
本発明で欧州される前記一般式で表わされる不飽和アミ
ド化合物としては、たとえば凡Ｎ−ジエチルアクリルア
ミド、Ｎ−ｎ−プロピルアクリルアミド、Ｎ−イソプロ
ピルアクリルアミド、Ｎ −ｎ−プロピルメタクリルア
ミド、Ｎ−イソプロピルメタクリルアミドである。Examples of the unsaturated amide compound represented by the above general formula used in the present invention include N-diethylacrylamide, N-n-propylacrylamide, N-isopropylacrylamide, N-n-propylmethacrylamide, and N-isopropylmethacrylamide. It is an amide.
一方、上記一般式で表わされる不飽和アミド化合物と共
重合しうる単量体としては親水性単量体、イオン性単量
体、親油性単量体の一種以上を適用できる。On the other hand, as the monomer copolymerizable with the unsaturated amide compound represented by the above general formula, one or more of hydrophilic monomers, ionic monomers, and lipophilic monomers can be used.
上記の親水性単量体、換言すれば単独重合体が水溶液中
において加温により水に不溶化しない親水性単量体とし
ては、１ことえばアクリルアミド、メタクリルアミド、
Ｎ−メチルアクリルアミド、Ｎ、 Ｎ−ジメチルアクリ
ルアミド、Ｎ、Ｎ−ジメチルメタクリルアミド、Ｎ−エ
チルアクリルアミド、ジアセトンアクリルアミド、ヒド
ロキシエチルメタクリレート、ヒドロキシエチルアクリ
レート、ヒドロキシエチルアクリレート、ヒドロキシプ
ロピルアクリレート、各種のメトキシポリエチレングリ
コールメタクリレート、各種のメトキシポリエチレング
リコールアクリレート、Ｎ−ビニル−２−ピロリドン等
をあげることができるし、まｆ： −酢酸ビニル、グリ
シジルメタクリレート等を共重合により導入して、それ
を加水分解して親水性を賦与することもできる。イオン
性単量体としては、たとえばアクリル酸、メタクリル酸
、ビニルスルホンし竣、アリルスルホン酸、メタリル区
々ホン酸、スチレンスルホイ酸、２−アクリルアミ）ビ
ー２’−フエニルプロパンスルホンｅ、２−７クリルア
ミドー２−メチルプロパンスルホン酸等の酸及びそれら
の塩、Ｎ、 Ｎ−ジメチルアミノエチルメタクリレート
、Ｎ、Ｎ−ジエチルアミノエチルメタクリレート、Ｎ、
Ｎ−ジメチルアミノエチルアクリレート、Ｎ、 Ｎ−ジ
メチルアミノプロピルメタクリルアミド、Ｎ、 Ｎ−ジ
メチルアミノプロピルアド゛
クリルアミド等のアミＸ及びそれらの塩等をあげること
かできる。また、各種アクリレート、メタクリレート、
アクリルアミド、メタクリルアミド、アクリロニ） Ｉ
Ｊル等を共重合により導入して、それな加水分解してイ
オン性を賦与することもできる。Examples of the above-mentioned hydrophilic monomers, in other words, hydrophilic monomers whose homopolymers do not become insolubilized in water by heating in an aqueous solution, include acrylamide, methacrylamide,
N-methylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-ethylacrylamide, diacetone acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, various methoxypolyethylene glycols Methacrylate, various methoxypolyethylene glycol acrylates, N-vinyl-2-pyrrolidone, etc. can be mentioned, and vinyl acetate, glycidyl methacrylate, etc. can be introduced by copolymerization, and then hydrolyzed to make it hydrophilic. can also be given. Ionic monomers include, for example, acrylic acid, methacrylic acid, vinyl sulfonic acid, allyl sulfonic acid, methallyl diphonic acid, styrene sulfonic acid, 2-acrylami)bi-2'-phenylpropanesulfonic acid, Acids and their salts such as 2-7 crylamide 2-methylpropanesulfonic acid, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N,
Examples include amide X and salts thereof such as N-dimethylaminoethyl acrylate, N,N-dimethylaminopropylmethacrylamide, and N,N-dimethylaminopropyladacrylamide. In addition, various acrylates, methacrylates,
acrylamide, methacrylamide, acryloni) I
It is also possible to introduce ionicity through copolymerization and hydrolyze it.
一方、親油性単量体、換言すれば単独重合体が水に不溶
性である親油性単量体としては、たとえばＮ、 Ｉ’Ｊ
−ジエチルメタクリルアミド、Ｎ、 Ｎ−ジー礼−プロ
ビルアクリルアミド、Ｎ−ルーブチルアクリルアミド、
Ｎ −ｎ−ブチルメタクリルアミド、Ｎ −ｔｅｒｔ
、−ブチルアクリルアミド、Ｎ −ｔｅｒ ｔ、 −ブ
チルメタクリルアミド、Ｎ−η〜ヘキシルアクリルアミ
ド、Ｎ−ルーへキシルメタクリルアミドＮ−ルーオクチ
ルアクリルアミド、Ｎ −７１−オクチルメタクリルア
ミド、Ｎ ＝ ｔｅｒｔ、−オクチルアクリルアミド、
Ｎ−η、−ドデシルアクリルアミド、Ｎ−ｎ−ドデシル
メタクリルアミド等のＮ−アルキル（メタ〕アクリルア
ミド誘導体、エチルアクリレート、メチルメタクリレー
ト、ブチルメタクリレート、ブチルアクリレート、ラウ
リルアクリＬ／−’）、２−エチルへキシルメタクリレ
ート、クリシジルメタク；ル〜ト等の（メタ）アクリレ
ート誘導体、アクリロニトリル、酢酸ビニル、塩化ビニ
ル、スチレン、α−メチルスチレン等ヲあげることがで
きる。On the other hand, lipophilic monomers, in other words, lipophilic monomers whose homopolymers are insoluble in water include, for example, N, I'J
-diethyl methacrylamide, N, N-propylacrylamide, N-rubutylacrylamide,
N-n-butyl methacrylamide, N-tert
, -butylacrylamide, N-tert, -butyl methacrylamide, N-η~hexyl acrylamide, N-hexyl methacrylamide N-octylacrylamide, N-71-octyl methacrylamide, N = tert, -octylacrylamide ,
N-alkyl (meth)acrylamide derivatives such as N-η, -dodecyl acrylamide, N-n-dodecyl methacrylamide, ethyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, lauryl acrylate L/-'), 2-ethyl Examples include (meth)acrylate derivatives such as xyl methacrylate and chrycidyl methacrylate, acrylonitrile, vinyl acetate, vinyl chloride, styrene, and α-methylstyrene.
上記の不飽和アミド化合物を重合して感温性重合体を製
造する具体的方法としては、たとえば（１）単重体を溶
剤で稀釈せずにそのまま重合して重合体ブロックを製造
する方法、（２〕溶剤中で重合して重合体を得る方法で
は、重合体溶液より溶剤を留去もしくは析出重合体を沢
別して重合体を得る場合と重合体溶液そのままで使用す
る場合、（３）懸濁重合により粒子状重合体として得る
方法、（４）乳化重合により重合体ラテックスとして得
る方法等が採用できる。その際重合様式としては通常の
Ｎ−置換（メタ）アクリルア・ミドと同様にラジカル重
合及びアニオン重合により行うことかできる。その中で
もラジカル重合の方が種々の形態での重合方法が容易に
採用できるので好適である。Specific methods for producing a temperature-sensitive polymer by polymerizing the above-mentioned unsaturated amide compound include (1) a method in which a monopolymer is directly polymerized without diluting it with a solvent to produce a polymer block; 2] In the method of obtaining a polymer by polymerization in a solvent, there are cases where the solvent is distilled off from the polymer solution or the precipitated polymer is separated to obtain the polymer, and cases where the polymer solution is used as it is (3) suspension. (4) A method of obtaining a particulate polymer by polymerization, a method of obtaining a polymer latex by emulsion polymerization, etc. In this case, the polymerization mode is radical polymerization and It can be carried out by anionic polymerization. Among these, radical polymerization is preferable because it can easily employ various polymerization methods.
重合を開始する方法としては、重合開始剤ケ使用′１−
る方法、光や熱による方法、又は放射線、電子線、プラ
ズマ等の高エネルギー線を照射１−る方法等が採用でき
る。上記の中でも特に重合開始剤な使用する方法は、重
合操作を簡略化できるとともに重合の制御を容易にでき
るので好ましい。重合開始剤としては、ラジカル重合を
開始する能力を有するものであれば制ｊ辰はなく、たと
えば無・濾過１俊化物、有機過酸化物、それらの過酸化
物と還元剤との２組合せおよびアゾ化合物などがある。The method for starting polymerization is to use a polymerization initiator'1-
A method using light or heat, a method using high energy rays such as radiation, electron beam, plasma, etc. can be adopted. Among the above methods, the method using a polymerization initiator is particularly preferable because it simplifies the polymerization operation and makes it easy to control the polymerization. There are no restrictions on the polymerization initiator as long as it has the ability to initiate radical polymerization, such as non-filtered atomized products, organic peroxides, combinations of these peroxides and reducing agents, and These include azo compounds.
具体的には過硫酸アンモニウム、過硫酸カリ、過酸化水
素、ｔｅｒｔ、−ブチルパーオキシド、ベンゾイルパー
オキシド、クメンヒドロキシパーオキシド、ｔｅｒｔ、
−ブチルパーオキシ−２−エチルヘキサノエート、過安
息香酸ブチル等があ弘それらと組合せる還元剤としては
亜硫酸塩、亜硫酸水素塩、鉄、銅、コバルトなどの低次
のイオン価の塩、アニリン等の有機アミン更にはアルド
ース、ケトース等の還元糖をあげることができる。Specifically, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert, -butyl peroxide, benzoyl peroxide, cumene hydroxy peroxide, tert,
-Butylperoxy-2-ethylhexanoate, butyl perbenzoate, etc.Reducing agents that can be combined with these include sulfites, bisulfites, salts with low ionic valences such as iron, copper, and cobalt, Examples include organic amines such as aniline, and reducing sugars such as aldose and ketose.
アゾ化合物としては、アゾビスイソブチロニトリル、２
，２′−アゾビス−２−アミジノプロパン塩酸塩、２，
２′−アゾビス−２，４−ジメチルバレロニトリル、４
．４’−アゾビス−４−シアツバレイン酸などを使用す
ることができる。また、上記した重合開始剤の２種以上
を併用することも可能である。Examples of azo compounds include azobisisobutyronitrile, 2
,2'-azobis-2-amidinopropane hydrochloride, 2,
2'-azobis-2,4-dimethylvaleronitrile, 4
．． 4'-azobis-4-cyatubaleic acid and the like can be used. It is also possible to use two or more of the above polymerization initiators in combination.
この場合の重合開始剤Ｑ添加量は通常採用される量的範
囲で充分であり、たとえば単量体自９００１〜５重量％
、好ましくは０．０５〜２重量係の範囲である。In this case, the addition amount of the polymerization initiator Q is sufficient to be within the normally adopted quantitative range, for example, the monomer itself is 9001 to 5% by weight.
, preferably in the range of 0.05 to 2 weight coefficients.
このようにして得られる共重合体のうち、ブロック状の
もの、および溶剤を留去或いは析出共重合体を沢別して
得られる共重合体は粉砕により粉状にまたは融解して粒
状、フレーク状、繊維状若しくはフィルム状に成型し、
粒子状共重合体はそのままの形で、またラテックス状共
重合体は布および紙のような繊維状物質に含浸コーティ
ングしたり、フィルム化して更には上記共重合体を水溶
液に溶解した液状品の形で感温性共重合体として提供で
きる。Among the copolymers obtained in this way, block-shaped copolymers and copolymers obtained by distilling off the solvent or separating the precipitated copolymers can be crushed into powder or melted into granules, flakes, Molded into fibrous or film form,
The particulate copolymer can be used as it is, and the latex copolymer can be used as an impregnated coating on fibrous materials such as cloth and paper, or as a film, or as a liquid product by dissolving the copolymer in an aqueous solution. It can be provided as a temperature-sensitive copolymer in the form of a thermosensitive copolymer.
以上のようにして製造した感温性共重合体は、固体状の
場合にはそれを水溶液に溶解して、また水溶液に溶存し
ている場合にはそのまま形で使用へ
する。本発明の感温性共重合体は、水溶液中に溶存して
いる状態で加温により不溶化１−るものであり、その不
溶化する温度を争点として表わす。When the temperature-sensitive copolymer produced as described above is in a solid state, it is dissolved in an aqueous solution, or when it is dissolved in an aqueous solution, it is used as it is. The temperature-sensitive copolymer of the present invention becomes insolubilized by heating while dissolved in an aqueous solution, and the temperature at which it becomes insolubilized is the point of contention.
重合体の種類により異なり一様には述べられないが、一
般には加東によりまず溶液全体が白色半透明になりその
後白濁してくる。その時半透明から白濁に至る温度範囲
は重合体の濃度及び種類により異なるが、概ね５〜６℃
未満である。この白濁液）ま一般にはエマルジミン水溶
液と同様の様相を呈して、白色不透明であり温度を争点
以上に保っておくと、相分離等を伴なわず安定に存在す
る。しかし、重合体の濃度及び種類によっては白濁後、
更に時間の経過とともに白濁物同士が会合し、球状また
はひも状析出物を形成したり、更には器壁等への月着が
起り相分離する場合がある。当然、濃度が高いほうが不
透明度が増すとともに、重合体の種類によっては相分離
しやす（なる。Although it cannot be stated uniformly as it varies depending on the type of polymer, in general, the entire solution first becomes white and translucent due to Kato, and then becomes cloudy. The temperature range from half-transparent to cloudy varies depending on the concentration and type of polymer, but is approximately 5 to 6 degrees Celsius.
less than This cloudy liquid generally exhibits the same appearance as an aqueous emuldimine solution, is white and opaque, and exists stably without phase separation if the temperature is kept above the critical temperature. However, depending on the concentration and type of polymer, after becoming cloudy,
Furthermore, with the passage of time, the white turbid substances may come together to form spherical or string-shaped precipitates, or may even be deposited on the walls of the vessel, leading to phase separation. Naturally, the higher the concentration, the higher the opacity, and depending on the type of polymer, phase separation may occur more easily.
一方、上記したように加温により白色不透明となった溶
液を冷却してゆくと、争点付近で透明になる。この過程
は何度でも繰り返して行うことができる。On the other hand, when a solution that has become white and opaque due to heating as described above is cooled, it becomes transparent near the point of contention. This process can be repeated any number of times.
次に、上記のような現象が起る重合体の水溶液中での濃
度は、重合体の＄類及びその分子量により変化し一概に
は述べられなし・が、概ね数百ｐｐη以上の濃度、好ま
しくは１．０００ ｐｐｍ以上の濃度である。当然のこ
ととして重合体の濃度が稀薄になると、加温した時の濁
度は小さくなり、半透明になるとともに争点は上昇する
。Next, the concentration of the polymer in the aqueous solution at which the above phenomenon occurs varies depending on the class of the polymer and its molecular weight and cannot be stated unconditionally, but it is generally several hundred ppη or more, preferably a concentration of several hundred ppη or more. is a concentration of 1.000 ppm or more. As a matter of course, as the concentration of the polymer becomes dilute, the turbidity when heated becomes smaller, the material becomes translucent, and the issue becomes more difficult.
一方、重合体濃度の上限は、含水状態であれば流動性を
失った状態でもよく、概ね７０％程度である。On the other hand, the upper limit of the polymer concentration is approximately 70%, which may be in a state where fluidity has been lost as long as it is in a water-containing state.
また、上記重合体を溶解している水溶液は、水を含む媒
体であればよく、水そのものが最も好ましい。水として
は水道水、工業用水、イオン交換水、蒸留水等を使用で
きる。水と混和して使用できる溶媒としては水と混り合
うものであれば何れでもよく、メタノール、エタノール
等のアルコール類、アセトン等のケトンｄｌ、エチレン
グリコール、プロピレングリコール等のグリコール類、
ジオキサン、テトラハイドロフラン等の環状エーテル類
、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチルア
セトアミド等のアミド系溶媒、アセトニトリル等のニド
ＩＪル類、テトラグライム等のグライム類、ジメチルス
ルホキシド等である。Further, the aqueous solution in which the above polymer is dissolved may be any medium containing water, and water itself is most preferable. As water, tap water, industrial water, ion exchange water, distilled water, etc. can be used. The solvent that can be used miscibly with water may be any solvent as long as it is miscible with water, such as alcohols such as methanol and ethanol, ketone dl such as acetone, glycols such as ethylene glycol and propylene glycol,
Cyclic ethers such as dioxane and tetrahydrofuran, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, nitrides such as acetonitrile, glymes such as tetraglyme, dimethyl sulfoxide, etc. .
上記の加温により不溶化する現象を観察する手段として
は、直接的には目視、濁度計、紫外または可視の吸光光
度計等により不溶化に伴う白濁を検出する方法がある。As a means for observing the above phenomenon of insolubilization due to heating, there are methods of directly detecting the cloudiness caused by insolubilization using a turbidity meter, an ultraviolet or visible absorption photometer, or the like.
一方、間接的には重合体水溶液の溶液粘度を温度を変え
て測定する方法、光散乱法により分子の拡りを温度を変
えて測定する等の不溶化に伴う他の物性の変化を検出す
る方法によっても行える。On the other hand, indirect methods include methods of measuring the solution viscosity of an aqueous polymer solution by changing the temperature, and methods of detecting changes in other physical properties due to insolubilization, such as measuring the spread of molecules by changing the temperature using a light scattering method. It can also be done by
本発明で一般式に示した不飽和アミド化合物の重合体の
争点は通常２０〜３５℃の範囲であり、その不皓和アミ
ド化合物の１種以上と前記した単量体との共重合により
、争点を−ｉｏ”ｃより１１０℃まで、好ましくは０℃
より１００”Ｃまでの間で制菌できる。争点を制御する
具体的方法としては、まず争点を高温部に移動するとき
は、親水性単量体またはイオン性単量体との共重合を行
えばよい。In the present invention, the temperature range for the polymer of the unsaturated amide compound shown in the general formula is usually in the range of 20 to 35°C, and by copolymerizing one or more of the unsaturated amide compounds with the above-mentioned monomers, -io”c to 110℃, preferably 0℃
Bacteria can be inhibited at temperatures up to 100"C. As a concrete method for controlling the problem, first, when moving the problem to a high temperature area, copolymerization with a hydrophilic monomer or an ionic monomer is carried out. That's fine.
一方、争点を低温部に移動するときは、親油性単量体と
の共重合を行えばよい。その場合、同一組成においても
親水性単量体及び親油性単量体の極性等の違いにより、
争点は異ってくる。親水性の強い親水性単量体では、少
量の冷加で４点は上昇し、一方、親油性の強い親油性単
量体では少量の添加で争点は下降する。しかしこの一般
則より外れるケースも多々あるので、種々の組合せで確
認することが好ましい。On the other hand, when moving the issue to a low temperature region, copolymerization with a lipophilic monomer may be performed. In that case, even if the composition is the same, due to differences in the polarity of the hydrophilic monomer and lipophilic monomer,
The points of contention are different. For hydrophilic monomers with strong hydrophilicity, the score increases by 4 points with a small amount of cooling, while with lipophilic monomers with strong lipophilic properties, the score decreases with the addition of a small amount. However, since there are many cases that deviate from this general rule, it is preferable to check various combinations.
次に、上記の感温性共重合体を加温により水に不溶化す
る具体的方法としては、基本的には上記共重合体を水に
溶解し、それを争点以上の温度を有する加熱媒体に接触
させればよい。その接触により溶液は白濁し重合体は不
溶化する。より具体的には該重合体水溶液を、通常の容
器に入れる、板、シート、フィルム等の板状又は膜状体
の間にはさむ、管の中に入れる、二重管の間にはさむ、
ビーズの如き微小球体とする等の方法により固定し、そ
れを太陽光、紫外線、可視光線、赤外線、遠赤外線、レ
ーザー光線等に暴露する、熱水、スチーム等の加熱媒体
と接触させる、それらの媒体を水溶液中に吹込む等の方
法により加温することにより該重合体を不溶化すること
ができ、結果として水溶液は白濁して白色不透明となる
。Next, as a specific method for making the above temperature-sensitive copolymer insolubilized in water by heating, basically, the above copolymer is dissolved in water, and then it is heated to a heating medium having a temperature higher than the temperature at issue. All you have to do is make contact. Due to this contact, the solution becomes cloudy and the polymer becomes insolubilized. More specifically, the aqueous polymer solution may be placed in a normal container, sandwiched between plate-like or membrane-like bodies such as plates, sheets, or films, placed in a tube, or sandwiched between double tubes.
These media are fixed by a method such as forming microspheres such as beads, and are exposed to sunlight, ultraviolet rays, visible light, infrared rays, far infrared rays, laser beams, etc., or brought into contact with a heating medium such as hot water or steam. The polymer can be insolubilized by heating it by blowing it into an aqueous solution, and as a result, the aqueous solution becomes cloudy and becomes white and opaque.
本発明の感温性共重合体の具体的応用ｕ＋ｌとしては、
温室、ビニールハウム、住居用窓ガラス、太陽熱温水器
のふた等へのある温度より遮光性を示す遮光性材料、再
生可能な記録材料、再生可能な表示材料、感温スイッチ
、温度センサー、感温性セッケン、感温性接着剤、高分
子凝集剤の脱水性向上剤、石油６次回収用ポリマー原料
、吸着分離樹脂原木」、防曇剤、壁材、オイルセパレー
ター等の例が考えられる。Specific applications u+l of the temperature-sensitive copolymer of the present invention include:
Light-shielding materials that block light at a certain temperature for greenhouses, vinyl houses, residential window glass, solar water heater lids, etc., reproducible recording materials, reproducible display materials, temperature-sensitive switches, temperature sensors, temperature-sensing materials Possible examples include thermosensitive adhesives, dehydration improvers for polymer flocculants, polymer raw materials for sixth oil recovery, adsorption/separation resin logs, antifogging agents, wall materials, and oil separators.
本発明の感温性共重合体は、加温により不溶化づ−る温
度すなわち争点を前記した単量体との重合により、任意
の温度に設定できるという効果を有１″る。The temperature-sensitive copolymer of the present invention has the advantage that it can be set at any desired temperature by polymerization with the above-mentioned monomer, that is, the temperature at which it becomes insolubilized by heating.
以下に本発明を実施例により更に詳細に説明する。The present invention will be explained in more detail below using examples.
実確夕１１１
１００ｍｌの４ツロ丸底フラスコにチッソガス流通下で
撹拌しながら、蒸留水４７．５．９’、 Ｎ、Ｎ−ジエ
チルアクリルアミド１８８ｇ、アクリルアミド０．６５
７１を添加した。その後過硫酸アンモニウム０、２５
、ｊ９及、び亜硫酸水素ナトリウム０．１１．９を添加
し、１５〜３０℃で４時間重合した。111 In a 100 ml 4-bottle round bottom flask, while stirring under nitrogen gas flow, add 47.5.9' of distilled water, 188 g of N,N-diethylacrylamide, and 0.65 g of acrylamide.
71 was added. Then ammonium persulfate 0,25
, j9 and 0.11.9 of sodium bisulfite were added, and polymerization was carried out at 15 to 30°C for 4 hours.
上記重合体水溶液を内径１５羽の試験管に入れ、そこに
標準温度計を差し込み、恒温水中温度肝で攪拌しながら
徐々に加温した。４８℃で白濁がはしまり、４９ ”Ｃ
で温度計の水銀球が見えなくなる程に白濁した。この水
溶液を更に加温しても、水溶液は安定な白濁状態を保持
した。一方、水溶液を冷却してゆ（と白濁温度以下で透
明となった。The above polymer aqueous solution was placed in a test tube with an inner diameter of 15, a standard thermometer was inserted therein, and the mixture was gradually heated while stirring under constant temperature water. The cloudiness stopped at 48℃, and the temperature reached 49”C.
The mercury bulb on the thermometer became cloudy to the point where it was no longer visible. Even when this aqueous solution was further heated, it maintained a stable cloudy state. On the other hand, when the aqueous solution was cooled, it became transparent below the cloudy temperature.
比較例１〜４
表−１記載の単量体を使用し、過硫酸アンモニウム及び
亜硫酸水素す） ＩＪウムの添加量を実施例１記載の２
倍量とした以外は実施例１と全く同様にして重合を行っ
た。そのようにして得た重合体水溶液を使用し、実施例
１と全く同様にして白濁開始温度及び白濁温度を測定し
、得られた結果を表−１に示した。Comparative Examples 1 to 4 The monomers listed in Table 1 were used, and the amount of ammonium persulfate and hydrogen sulfite added was the same as that of Example 1.
Polymerization was carried out in exactly the same manner as in Example 1, except that the amount was doubled. Using the aqueous polymer solution thus obtained, the cloudiness onset temperature and cloudiness temperature were measured in exactly the same manner as in Example 1, and the obtained results are shown in Table 1.
ただし、白濁開始温度とは加温により白濁しはじめる温
度であり、白濁温度とは白濁により温度計の水銀球が見
えなくなった温度である。However, the cloudiness starting temperature is the temperature at which the temperature starts to become cloudy due to heating, and the cloudiness temperature is the temperature at which the mercury bulb of the thermometer becomes invisible due to the cloudiness.
なお、いずれの場合にも冷却にまり白ｇＡ液は無色透明
になった。In all cases, the white gA liquid became colorless and transparent upon cooling.
表−１
実施例２〜１６
表−２の単量体の１組合せを使用した以外は、実施例１
と全（同様にして重合を行った。そのようにして得た重
合体水溶液を使用し、実施例１と全く同様にして白濁開
始温度及び白濁温度を測定し得られた結果を表−２に示
した。Table 1 Examples 2 to 16 Example 1 except that one combination of monomers in Table 2 was used.
Polymerization was carried out in the same manner as above.Using the aqueous polymer solution thus obtained, the cloudiness onset temperature and cloudiness temperature were measured in exactly the same manner as in Example 1.The results are shown in Table 2. Indicated.
Claims (1)
はエチル基であり、鳥はエチル基またはプロピル基であ
る。山が水素の時は鴇は水素で１（３はプロピル基であ
るか、１（２及び塊ともエチル基である。■（、！がメ
チル基の時は、■ｔ２は水素でＲ５はプロピル基である
。） で示される不飽和アミド化合物の１種以上と他の共重合
し５る単量体との共重合体よりなり、加温により水に不
溶化する感温性共重合体。(1) General formula (However, 几 is hydrogen or a methyl group, R7 is hydrogen or an ethyl group, and a bird is an ethyl group or a propyl group. When the mountain is hydrogen, the bird is hydrogen and 1 (3 is propyl) A type of unsaturated amide compound represented by 1 (both 2 and the mass are ethyl groups. (When , ! is a methyl group, ■ t2 is hydrogen and R5 is a propyl group.) A thermosensitive copolymer consisting of a copolymer of the above and other copolymerizable monomers, which becomes insoluble in water by heating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2429084A JPS60168706A (en) | 1984-02-14 | 1984-02-14 | Temperature-sensitive copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2429084A JPS60168706A (en) | 1984-02-14 | 1984-02-14 | Temperature-sensitive copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60168706A true JPS60168706A (en) | 1985-09-02 |
Family
ID=12134040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2429084A Pending JPS60168706A (en) | 1984-02-14 | 1984-02-14 | Temperature-sensitive copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60168706A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963632A (en) * | 1988-12-29 | 1990-10-16 | Exxon Research And Engineering Company | Mixed micellar process for preparing hydrophobically associating polymers |
| US4981935A (en) * | 1988-12-29 | 1991-01-01 | Exxon Research And Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| US4997878A (en) * | 1988-12-29 | 1991-03-05 | Exxon Research And Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| US5003000A (en) * | 1988-12-29 | 1991-03-26 | Exxon Research & Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| US5116923A (en) * | 1988-12-29 | 1992-05-26 | Exxon Research And Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| JPWO2013027668A1 (en) * | 2011-08-19 | 2015-03-19 | 国立大学法人九州大学 | Ion concentration gradient generation system, apparatus, method, and temperature-responsive electrolyte material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51127015A (en) * | 1975-04-25 | 1976-11-05 | Kohjin Co Ltd | Polymerization inhibition of n,n'- disubstituted acryl amides accompan ifd with less discoloration |
| JPS5391941A (en) * | 1976-03-24 | 1978-08-12 | Kohjin Co Ltd | Emulsion adhesive |
| JPS58179256A (en) * | 1982-03-31 | 1983-10-20 | Agency Of Ind Science & Technol | Thermally reversible material between hydrophilic and hydrophobic |
| JPS58206655A (en) * | 1982-05-27 | 1983-12-01 | Agency Of Ind Science & Technol | Material having thermally reversible hydrophilic- hydrophobic properties |
-
1984
- 1984-02-14 JP JP2429084A patent/JPS60168706A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51127015A (en) * | 1975-04-25 | 1976-11-05 | Kohjin Co Ltd | Polymerization inhibition of n,n'- disubstituted acryl amides accompan ifd with less discoloration |
| JPS5391941A (en) * | 1976-03-24 | 1978-08-12 | Kohjin Co Ltd | Emulsion adhesive |
| JPS58179256A (en) * | 1982-03-31 | 1983-10-20 | Agency Of Ind Science & Technol | Thermally reversible material between hydrophilic and hydrophobic |
| JPS58206655A (en) * | 1982-05-27 | 1983-12-01 | Agency Of Ind Science & Technol | Material having thermally reversible hydrophilic- hydrophobic properties |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963632A (en) * | 1988-12-29 | 1990-10-16 | Exxon Research And Engineering Company | Mixed micellar process for preparing hydrophobically associating polymers |
| US4981935A (en) * | 1988-12-29 | 1991-01-01 | Exxon Research And Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| US4997878A (en) * | 1988-12-29 | 1991-03-05 | Exxon Research And Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| US5003000A (en) * | 1988-12-29 | 1991-03-26 | Exxon Research & Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| US5116923A (en) * | 1988-12-29 | 1992-05-26 | Exxon Research And Engineering Company | Hydrophobically associating polymers containing dimethyl acrylamide functionality |
| JPWO2013027668A1 (en) * | 2011-08-19 | 2015-03-19 | 国立大学法人九州大学 | Ion concentration gradient generation system, apparatus, method, and temperature-responsive electrolyte material |
| US10137409B2 (en) | 2011-08-19 | 2018-11-27 | Kyushu University, National University Corporation | System, device and method for generating ion concentration gradient, and temperature-responsive electrolyte material |
| US10300432B2 (en) | 2011-08-19 | 2019-05-28 | Kyushu University, National University Corporation | System, device, and method for producing ion concentration gradient, and temperature-responsive electrolyte material |
| US10695714B2 (en) | 2011-08-19 | 2020-06-30 | Kyushu University, National University Corporation | System, device, and method for producing ion concentration gradient, and temperature-responsive electrolyte material |
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