JP2000219715A - Siloxane segment-containing anionic block copolymer and method for obtaining the same - Google Patents
Siloxane segment-containing anionic block copolymer and method for obtaining the sameInfo
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- JP2000219715A JP2000219715A JP11164530A JP16453099A JP2000219715A JP 2000219715 A JP2000219715 A JP 2000219715A JP 11164530 A JP11164530 A JP 11164530A JP 16453099 A JP16453099 A JP 16453099A JP 2000219715 A JP2000219715 A JP 2000219715A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、残存モノマー及び
残存溶媒の極めて少ない粉末状ないし顆粒状のシロキサ
ンセグメント含有アニオン系ブロック共重合体に関す
る。The present invention relates to a powdery or granular siloxane segment-containing anionic block copolymer having very little residual monomer and residual solvent.
【０００２】[0002]
【従来の技術】近年、高分子化合物は機能性を求められ
ており、高分子アゾ重合開始剤を用いて合成されるブロ
ック共重合体は、高分子化合物に種々の機能を付与する
簡便な方法として注目を浴びている。中でも、シロキサ
ンセグメント含有のアゾ重合開始剤を用いて親水性のメ
タクリル酸と親油性のメタクリル酸エステルとを重合し
て成るシロキサンセグメント含有アニオン系ブロック共
重合体は、撥水性、防汚性、低摩擦抵抗、基材への密着
性等が優れていることもあり、塗料や化粧品等の基材ポ
リマー（特願平4-372675号、特願平9-157339号）として
広く利用されている。2. Description of the Related Art In recent years, polymer compounds have been required to have functional properties, and block copolymers synthesized using a polymer azo polymerization initiator are simple methods for imparting various functions to the polymer compounds. As attention has been drawn. Above all, a siloxane segment-containing anionic block copolymer obtained by polymerizing hydrophilic methacrylic acid and a lipophilic methacrylic acid ester using a siloxane segment-containing azo polymerization initiator has water repellency, antifouling property, and low water repellency. Due to its excellent friction resistance and adhesion to substrates, it is widely used as a base polymer for paints and cosmetics (Japanese Patent Application Nos. 4-372675 and 9-157339).
【０００３】従来、上記シロキサンセグメント含有アニ
オン系ブロック共重合体を製造する際、ｎ−ヘキサンや
アセトニトリルが沈殿剤として用いられてきたが、これ
らの沈殿剤は原料モノマーとの親和性が乏しいため、製
造されたポリマーから未反応の原料モノマーを完全に除
去することが困難であった。また、ポリマーを重合溶液
から沈殿させるためには多量の沈殿剤を要するので、こ
の沈殿剤をポリマーから完全に除去するのは困難であっ
た。即ち、シロキサンセグメント含有アニオン系ブロッ
ク共重合体は、濾過や脱液等が困難なため、モノマー、
沈殿剤及び溶媒等が残存したまま用いられてきた。しか
しながら、残存物を含有したままの該共重合体を取り扱
うのは困難であり、しかもその使用に際して、これら残
存物を原因とする種々の問題点を有している。Conventionally, n-hexane or acetonitrile has been used as a precipitant when producing the above-mentioned siloxane segment-containing anionic block copolymer. However, these precipitants have poor affinity with the raw material monomers. It was difficult to completely remove unreacted starting monomers from the produced polymer. Further, since a large amount of a precipitant is required to precipitate the polymer from the polymerization solution, it has been difficult to completely remove the precipitant from the polymer. That is, since the siloxane segment-containing anionic block copolymer is difficult to filter or remove liquid, the monomer,
A precipitant, a solvent, and the like have been used while remaining. However, it is difficult to handle the copolymer containing the residue, and there are various problems caused by the residue when the copolymer is used.
【０００４】例えば、モノマーや、沈殿剤であるｎ−ヘ
キサンやアセトニトリル等の不純物が多量に残存した、
シロキサンセグメント含有アニオン系ブロック共重合体
から成る塗料を用いた場合、塗膜中の不純物が経時的に
揮散し、塗膜自体の性能が低下するという問題点があ
る。また、不純物が多量に残存した上記共重合体を化粧
料用の基材として使用した場合、不純物は人体に炎症等
の悪影響を及ぼす虞があるだけでなく、化粧料本来の特
性を低下させるという問題点がある。For example, a large amount of impurities such as monomers and precipitants such as n-hexane and acetonitrile remain.
When a coating material comprising a siloxane segment-containing anionic block copolymer is used, there is a problem that impurities in the coating film volatilize over time, and the performance of the coating film itself deteriorates. In addition, when the copolymer containing a large amount of impurities is used as a base material for cosmetics, the impurities may not only have an adverse effect on the human body, such as inflammation, but also deteriorate the original properties of the cosmetics. There is a problem.
【０００５】そこで、残存モノマーの低減方法として、
重合液をアゾビスイソブチロニトリル等のアゾ系重合開
始剤や過酸化ベンゾイル等の過酸化物を添加して加熱す
る方法（特願平9-157339号）が考え出された。Therefore, as a method for reducing the residual monomer,
A method of heating a polymerization solution by adding an azo polymerization initiator such as azobisisobutyronitrile or a peroxide such as benzoyl peroxide (Japanese Patent Application No. 9-157339) has been proposed.
【０００６】しかしながら、これらの方法によって充分
に残存モノマーを低減するためには、添加物の量を多く
する必要があり、その結果添加物自体が、得られるブロ
ック共重合体の物性に悪影響を及ぼしたり、添加物の分
解物が共重合体中に残存して新たな問題を引き起こすと
いった問題点を有していた。However, in order to sufficiently reduce the residual monomer by these methods, it is necessary to increase the amount of the additive. As a result, the additive itself adversely affects the physical properties of the obtained block copolymer. And the decomposition product of the additive remains in the copolymer to cause a new problem.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記した如
き状況に鑑みなされたもので、残存モノマー及び残存溶
媒の割合が著しく低く、且つ粉末状ないし顆粒状である
シロキサンセグメント含有アニオン系ブロック共重合体
と該共重合体の取得方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned situation, and the present invention relates to an anionic block containing a siloxane segment containing a powdery or granular siloxane segment in which the ratio of residual monomer and residual solvent is extremely low. An object of the present invention is to provide a method for obtaining a polymer and the copolymer.
【０００８】[0008]
【課題を解決するための手段】本発明は、一般式［１］The present invention provides a compound represented by the general formula [1]:
【０００９】[0009]
【化７】 Embedded image
【００１０】（式中、Ｒ１及びＲ２は夫々独立して、水
素原子又は低級アルキル基を表し、Ｒ３ 及びＲ４は夫
々独立して水素原子、低級アルキル基又はアリール基を
表し、ｎは ０〜２００の整数を表す）（以下、［ＤＡ
Ｓ］と略記することがある）で示されるシロキサンセグ
メント、一般式［２］(Wherein R1 and R2 each independently represent a hydrogen atom or a lower alkyl group, R3 and R4 each independently represent a hydrogen atom, a lower alkyl group or an aryl group, and n is 0 to 200 Represents an integer of (hereinafter referred to as [DA
S], which may be abbreviated as S).
【００１１】[0011]
【化８】 Embedded image
【００１２】（式中、Ｒ５は水素原子又はメチル基を表
す）で示されるモノマー単位（以下、［ＵＣＡ］と略記
することがある）及び一般式［３］(Wherein R5 represents a hydrogen atom or a methyl group) (hereinafter sometimes abbreviated as [UCA]) and a general formula [3]
【００１３】[0013]
【化９】 Embedded image
【００１４】（式中、Ｒ６は低級アルキル基を表す）で
示されるモノマー単位（以下、［ＭＡＥ］と略記するこ
とがある）を構成成分とする共重合体であって、これら
３成分の組成比が図１に於ける点Ａ〜Ｆで囲まれる範囲
内に入るものであり、残存モノマーの量が１ｗ％以下で
且つ残存溶媒の量が１ｗ％以下である共重合体、の発明
である。(Wherein, R6 represents a lower alkyl group), which is a copolymer containing monomer units (hereinafter sometimes abbreviated as [MAE]) represented by the following formula: A copolymer having a ratio falling within a range surrounded by points A to F in FIG. 1 and having a residual monomer amount of 1 w% or less and a residual solvent amount of 1 w% or less. .
【００１５】また、本発明は、親水性有機溶媒中、一般
式［４］The present invention also relates to a compound represented by the general formula [4]:
【００１６】[0016]
【化１０】 Embedded image
【００１７】（式中、Ｒ７〜Ｒ１０は夫々独立して低級
アルキル基又はシアノ基を表し、ＡはＮ Ｈ又は酸素原
子を表し、Ｅは酸素原子を有していてもよい低級アルキ
レン基又は結合手を表し、ｍは０〜６の整数を表し、ｐ
は自然数を表す。Ｒ１〜Ｒ４及びｎは前記と同じ）で示
されるシロキサンセグメント含有マクロアゾ重合開始
剤、一般式［５］(Wherein, R7 to R10 each independently represent a lower alkyl group or a cyano group, A represents NH or an oxygen atom, and E represents a lower alkylene group which may have an oxygen atom or a bond. Represents a hand, m represents an integer of 0 to 6, p
Represents a natural number. R1 to R4 and n are the same as defined above), a siloxane segment-containing macroazo polymerization initiator represented by the following general formula [5]:
【００１８】[0018]
【化１１】 Embedded image
【００１９】（式中、Ｒ５は前記と同じ）で示される不
飽和カルボン酸（以下、ＵＣＡと略記することがある）
及び一般式［６］(Wherein R5 is the same as described above) (hereinafter sometimes abbreviated as UCA)
And the general formula [6]
【００２０】[0020]
【化１２】 Embedded image
【００２１】（式中、Ｒ６は前記と同じ）で示されるメ
タクリル酸エステル（以下、ＭＡＥと略記することがあ
る）を、得られる共重合体の主たる構成単位である一般
式［１］で示されるシロキサンセグメント、一般式
［２］で示されるモノマー単位及び一般式［３］で示さ
れるモノマー単位の組成比が図１に於ける点Ａ〜Ｆで囲
まれる範囲内に入るように夫々の使用量を選択設定して
重合反応させ、得られる溶液から、水を沈殿剤として用
いて晶析、単離することを特徴とする前記共重合体の取
得方法、の発明である。(Wherein R6 is as defined above), a methacrylic acid ester (hereinafter sometimes abbreviated as MAE) represented by the general formula [1] which is a main structural unit of the obtained copolymer. The siloxane segment, the monomer unit represented by the general formula [2], and the monomer unit represented by the general formula [3] have a composition ratio within a range surrounded by points A to F in FIG. The present invention also provides a method for obtaining the copolymer, characterized in that a polymerization reaction is carried out by selectively setting the amount, and crystallization and isolation are performed from the resulting solution using water as a precipitant.
【００２２】即ち、本発明者等は上記目的を達成すべく
鋭意研究を重ねた結果、残存モノマー及び残存溶媒の割
合が著しく低く、且つ粉末状ないし顆粒状であるシロキ
サンセグメント含有アニオン系ブロック共重合体及び該
共重合体の取得方法を見出し、本発明を完成するに到っ
た。That is, the present inventors have conducted intensive studies to achieve the above object, and as a result, the ratio of the residual monomer and the residual solvent is extremely low, and the anionic block copolymer containing a siloxane segment having a powdery or granular form is used. The present inventors have found a method of obtaining the copolymer and the copolymer, and have completed the present invention.
【００２３】一般式［１］に於いて、Ｒ１〜Ｒ４で示さ
れる低級アルキル基としては、直鎖状でも分枝状でもよ
く、通常炭素数１〜６のものが挙げられ、具体的には、
例えばメチル基，エチル基，ｎ-プロピル基，イソプロ
ピル基，ｎ-ブチル基，イソブチル基，ｔ-ブチル基，ｓ
-ブチル基，ｎ-ペンチル基，イソペンチル基，ネオペン
チル基，ｔ-ペンチル基，１-メチルペンチル基，ｎ-ヘ
キシル基，イソヘキシル 基，２-メチルペンチル基，３
-メチルペンチル基が挙げられる。In the general formula [1], the lower alkyl group represented by R1 to R4 may be linear or branched and usually has 1 to 6 carbon atoms. ,
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s
-Butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylpentyl group, n-hexyl group, isohexyl group, 2-methylpentyl group, 3
-Methylpentyl group.
【００２４】Ｒ３及びＲ４で示されるアリール基として
は、通常炭素数６〜１０のものが挙げられ、具体的に
は、例えばフェニル基，ｏ-トリル基，ｍ-トリル基，ｐ
-トリル 基，2,3-キシリル基，2,4-キシリル基，2,5-キ
シリル基，ナフチル基等が挙げられる。The aryl group represented by R3 and R4 is usually an aryl group having 6 to 10 carbon atoms. Specifically, for example, a phenyl group, an o-tolyl group, an m-tolyl group,
-Tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, naphthyl and the like.
【００２５】一般式［３］に於いて、Ｒ６で示される低
級アルキル基としては、直鎖状でも分枝状でもよく、通
常炭素数１〜６のものが挙げられ、具体的には、例えば
メチル基，エチル基，ｎ-プロピル基，イソプロピル
基，ｎ-ブチル基，イソブチル基，ｔ-ブチル基，ｓ-ブ
チル基，ｎ-ペンチル基，イソペンチル基，ネオペンチ
ル基，ｔ-ペンチル基，１-メチルペンチル基，ｎ-ヘキ
シル基，イソヘキシル基，２-メチルペンチル基，３-メ
チルペンチル基が挙げられる。In the general formula [3], the lower alkyl group represented by R6 may be linear or branched and usually has 1 to 6 carbon atoms. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, s-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, 1-pentyl Examples include a methylpentyl group, an n-hexyl group, an isohexyl group, a 2-methylpentyl group, and a 3-methylpentyl group.
【００２６】本発明の共重合体は、上記３つの構成成分
である［ＤＡＳ］、［ＵＣＡ］及び［ＭＡＥ］を図１に
於ける点Ａ（[DAS]:20%, [UCA]:30%,[MAE]:50%）、点Ｂ
（[DAS]:20%, [UCA]:60%, [MAE]:20%）、点Ｃ（[DAS]:3
0%, [UCA]:60%, [MAE]:10%）、点Ｄ（[DAS]:60%, [UC
A]:30%, [MAE]:10%）、点Ｅ（[DAS]:60%, [UCA]:10%,
[MAE]:30%）及び点Ｆ（[DAS]:60%, [UCA]:10%, [MAE]:5
0%）で囲まれる範囲内の組成比で含有するものである。In the copolymer of the present invention, [DAS], [UCA] and [MAE], which are the above three components, are combined with point A in FIG. 1 ([DAS]: 20%, [UCA]: 30). %, [MAE]: 50%), point B
([DAS]: 20%, [UCA]: 60%, [MAE]: 20%), point C ([DAS]: 3
0%, [UCA]: 60%, [MAE]: 10%), Point D ([DAS]: 60%, [UC
A]: 30%, [MAE]: 10%), Point E ([DAS]: 60%, [UCA]: 10%,
[MAE]: 30%) and point F ([DAS]: 60%, [UCA]: 10%, [MAE]: 5
0%).
【００２７】本発明の共重合体は、例えば親水性有機溶
媒中、一般式［４］The copolymer of the present invention can be prepared, for example, in a hydrophilic organic solvent by the general formula [4]
【００２８】[0028]
【化１３】 Embedded image
【００２９】（式中、Ｒ７〜Ｒ１０は夫々独立して、低
級アルキル基又はシアノ基を表し、Ａは ＮＨ又は酸素
原子を表し、Ｅは酸素原子を有していてもよい低級アル
キレン基又は結合手を表し、ｍは０〜６の整数を表し、
ｐは自然数を表す。Ｒ１〜Ｒ４及びｎは前記と同じ）で
示されるシロキサンセグメント含有マクロアゾ重合開始
剤、一般式［５］(Wherein R7 to R10 each independently represent a lower alkyl group or a cyano group, A represents NH or an oxygen atom, and E represents a lower alkylene group or a bond optionally having an oxygen atom. Represents a hand, m represents an integer of 0 to 6,
p represents a natural number. R1 to R4 and n are the same as defined above), a siloxane segment-containing macroazo polymerization initiator represented by the following general formula [5]:
【００３０】[0030]
【化１４】 Embedded image
【００３１】（式中、Ｒ５は前記と同じ）で示される不
飽和カルボン酸及び一般式［６］Wherein R 5 is the same as defined above, and a general formula [6]
【００３２】[0032]
【化１５】 Embedded image
【００３３】（式中、Ｒ６は前記と同じ）で示されるメ
タクリル酸エステルを、得られる共重合体の主たる構成
単位である一般式［１］で示されるシロキサンセグメン
ト、一般式［２］で示されるモノマー単位及び一般式
［３］で示されるモノマー単位の組成比が図１に於ける
点Ａ〜Ｆで囲まれる範囲内に入るように夫々の使用量を
選択設定して重合反応させ、得られる溶液から、水を沈
殿剤として用いて晶析、単離することにより得られる。A methacrylic acid ester represented by the formula (1) wherein R6 is the same as defined above, is represented by the siloxane segment represented by the general formula [1], which is a main structural unit of the obtained copolymer, and the methacrylate represented by the general formula [2] The polymerization reaction is carried out by selecting and using the respective amounts so that the composition ratio of the monomer unit represented by formula (3) and the monomer unit represented by the general formula [3] fall within the range surrounded by points A to F in FIG. The obtained solution is obtained by crystallization and isolation using water as a precipitant.
【００３４】尚、重合反応を行う際に、上記各成分を同
時に反応系に存在させて一挙に共重合を行ってもよく、
又、先ず一般式［５］で示される不飽和カルボン酸と一
般式［４］で示されるシロキサンセグメント含有マクロ
アゾ重合開始剤を反応させ、次いで一般式［６］で示さ
れるメタクリル酸エステルを反応させてもよく、更にま
た、先ず、一般式［６］で示されるメタクリル酸エステ
ルと一般式［４］で示されるシロキサンセグメント含有
マクロアゾ重合開始剤を反応させ、次いで一般式［５］
で示される不飽和カルボン酸を反応させてもよい。In conducting the polymerization reaction, the above-mentioned components may be simultaneously present in the reaction system to carry out the copolymerization at once.
Further, first, an unsaturated carboxylic acid represented by the general formula [5] is reacted with a siloxane segment-containing macroazo polymerization initiator represented by the general formula [4], and then a methacrylic ester represented by the general formula [6] is reacted. Further, first, the methacrylic acid ester represented by the general formula [6] is reacted with the siloxane segment-containing macroazo polymerization initiator represented by the general formula [4], and then the general formula [5]
May be reacted.
【００３５】この共重合反応を行う際、必要に応じて連
鎖移動剤（例えばラウリルメルカプタン、オクチルメル
カプタン、ブチルメルカプタン、2-メルカプトエタノー
ル、チオグリコール酸ブチル等）を添加し、分子量の調
節を行ってもよい。In conducting the copolymerization reaction, a chain transfer agent (for example, lauryl mercaptan, octyl mercaptan, butyl mercaptan, 2-mercaptoethanol, butyl thioglycolate, etc.) is added as necessary to adjust the molecular weight. Is also good.
【００３６】一般式［４］で示されるシロキサンセグメ
ント含有マクロアゾ重合開始剤は、その構造式中の一般
式［７］The siloxane segment-containing macroazo polymerization initiator represented by the general formula [4] is represented by the general formula [7]
【００３７】[0037]
【化１６】 Embedded image
【００３８】（式中、Ｒ７〜Ｒ１０及びｍは前記と同
じ）で示される部分の一部が一般式［８］Wherein R7 to R10 and m are the same as those described above, and a part of the moiety represented by the general formula [8]
【００３９】[0039]
【化１７】 Embedded image
【００４０】（式中、Ｙは二価の炭化水素基を表わす）
で示される二塩基酸残基で置き換えられているものでも
よい。(Wherein, Y represents a divalent hydrocarbon group)
May be replaced by a dibasic acid residue represented by
【００４１】一般式［４］に於いて、Ｒ７〜Ｒ１０で表
される低級アルキル基としては、直鎖 状でも分枝状で
もよく、通常炭素数１〜６のものが挙げられ、具体的に
は、例えばメチル基，エチル基，ｎ-プロピル基，イソ
プロピル基，ｎ-ブチル基，イソブチル基，ｔ-ブチル
基，ｓ-ブチル基，ｎ-ペンチル基，イソペンチル基，ネ
オペ ンチル基，ｔ-ペンチル基，１-メチルペンチル
基，ｎ-ヘキシル基，イソヘキシ ル基，２-メチルペン
チル基，３-メチルペンチル基が挙げられる。In the general formula [4], the lower alkyl group represented by R7 to R10 may be linear or branched and usually has 1 to 6 carbon atoms. Are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, s-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl Groups, 1-methylpentyl group, n-hexyl group, isohexyl group, 2-methylpentyl group, and 3-methylpentyl group.
【００４２】Ｅで示される酸素原子を有していてもよい
低級アルキレン基の低級アルキレン基としては、直鎖状
でも分枝状でもよく、通常炭素数１〜６のものが挙げら
れ、具体的には、メチレン基，エチレン基，メチルメチ
レン基，トリメチレン基，プロピレン基，テトラメチレ
ン基，ブチレン基，ペンタメチレン基，ペンチレン基，
ヘキサメチレン基，ヘキシレン基等が挙げられる。酸素
原子を有している場合には前記低級アルキレン基の任意
の位置に通常１〜２個の酸素原子を有しているものが挙
げられ、具体的には、例えば-CH２-O-CH２-，-CH２CH２
-O-CH２-，-CH(CH３)-O-CH２-，-CH２-O-CH２-O-CH２
-，-CH２-O-CH(CH３)-，-CH２CH２CH２-O-CH２CH２-，-
CH２CH２-O-CH２CH２-O-CH２CH２-等が挙げられる。The lower alkylene group of the lower alkylene group optionally having an oxygen atom represented by E may be linear or branched, and usually has 1 to 6 carbon atoms. Include methylene, ethylene, methylmethylene, trimethylene, propylene, tetramethylene, butylene, pentamethylene, pentylene,
Examples include a hexamethylene group and a hexylene group. When the compound has an oxygen atom, those having usually 1 to 2 oxygen atoms at any position of the lower alkylene group can be mentioned. Specifically, for example, -CH2-O-CH2- , -CH2CH2
-O-CH2-, -CH (CH3) -O-CH2-, -CH2-O-CH2-O-CH2
-, -CH2-O-CH (CH3)-, -CH2CH2CH2-O-CH2CH2-,-
CH2CH2-O-CH2CH2-O-CH2CH2- and the like.
【００４３】ｐは通常１〜500、好ましくは３〜200、よ
り好ましくは３〜50、更に好ましくは３〜10の自然数で
あり、得られる本発明の共重合体の使用目的に応じて適
宜選択される。P is a natural number of usually 1 to 500, preferably 3 to 200, more preferably 3 to 50, and still more preferably 3 to 10, and is appropriately selected according to the intended use of the obtained copolymer of the present invention. Is done.
【００４４】一般式［４］で示されるシロキサンセグメ
ント含有マクロアゾ重合開始剤の数平均分子量は、小さ
すぎると実質的にアゾ基を含有しない分子が多く存在す
ることになり、ブロックポリマーの生成効率が低下し、
また、大きすぎるとブロックポリマーの製造に時間を有
するだけでなく、それ自体の溶解性が低くなるので、通
常1500〜200,000、好ましくは10,000〜150,000である。If the number average molecular weight of the siloxane segment-containing macroazo polymerization initiator represented by the general formula [4] is too small, a large number of molecules substantially containing no azo group will be present, and the efficiency of forming the block polymer will be reduced. Drop,
On the other hand, if it is too large, not only does it take time to produce the block polymer, but also the solubility of the block polymer itself becomes low, so that it is usually from 1500 to 200,000, preferably from 10,000 to 150,000.
【００４５】一般式［５］で示される不飽和カルボン酸
の具体例としては、アクリル酸、メタクリル酸等が挙げ
られる。Specific examples of the unsaturated carboxylic acid represented by the general formula [5] include acrylic acid and methacrylic acid.
【００４６】一般式［６］で示されるメタクリル酸エス
テルの具体例としては、例えばメタクリル酸メチル、メ
タクリル酸エチル、メタクリル酸-ｎ-プロピル、メタク
リル酸イソプロピル、メタクリル酸-ｎ-ブチル、メタク
リル酸イソブチル、メタクリル酸-ｔ-ブチル、メタクリ
ル酸-ｎ-ペンチル、メタクリル酸イソペンチル、メタク
リル酸-ｔ-ペンチル、メタクリル酸ネオペンチル、メタ
クリル酸-ｎ-ヘキシル、メタクリル酸-ｔ-ヘキシル等が
挙げられる。Specific examples of the methacrylate represented by the general formula [6] include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, t-pentyl methacrylate, neopentyl methacrylate, n-hexyl methacrylate, t-hexyl methacrylate, and the like.
【００４７】一般式［８］に於いて、Ｙで示される二価
の炭化水素基としては、例えば炭素数１〜１０のアルキ
レン基及び二価の芳香族基等が挙げられる。アルキレン
基としては、例えばメチレン基、エチレン基、メチルメ
チレン基、トリメチレン基、ブロピレン基、テトラメチ
レン基、ブチレン基、ペンタメチレン基、ペンチレン
基、ヘキサメチレン基、ヘキシレン基、ヘプタメチレン
基、オクタメチレン基、ノナメチレン基、デカメチレン
基等が挙げられ、二価の芳香族基としては、例えばｏ-
フェニレン基、ｍ-フェニレン基、ｐ-フェニレン基、ジ
フェニレン基、-CH２-C６H４-等が挙げられる。In the general formula [8], examples of the divalent hydrocarbon group represented by Y include an alkylene group having 1 to 10 carbon atoms and a divalent aromatic group. Examples of the alkylene group include a methylene group, an ethylene group, a methylmethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, a pentamethylene group, a pentylene group, a hexamethylene group, a hexylene group, a heptamethylene group, and an octamethylene group. , Nonamethylene group, decamethylene group and the like. Examples of the divalent aromatic group include o-
Phenylene group, m-phenylene group, p-phenylene group, diphenylene group, -CH2-C6H4-, and the like.
【００４８】一般式［４］で示されるシロキサンセグメ
ント含有マクロアゾ重合開始剤の一般式［７］で示され
る部分の一部が、一般式［８］で示される基で置換され
ている場合、その置換量は一般式［４］で示されるアゾ
重合開始剤の重合活性が失われない程度である。When part of the portion represented by the general formula [7] of the siloxane segment-containing macroazo polymerization initiator represented by the general formula [4] is partially substituted by the group represented by the general formula [8], The substitution amount is such that the polymerization activity of the azo polymerization initiator represented by the general formula [4] is not lost.
【００４９】重合溶媒としては、例えばアセトン，メチ
ルエチルケトン等のケトン類、メタノール，エタノー
ル，ｎ-プロパノール，イソプロパノール等のアルコー
ル類、テトラヒドロフラン，1,4-ジオキサン等の環状エ
ーテル類、Ｎ-メチルピロリドン、Ｎ,Ｎ'-ジメチルアセ
トアミド、ジメチルスルホキシド等の親水性有機溶媒が
挙げられる。これらは単独で用いても２種類以上適宜組
み合わせて用いてもよい。また、反応に影響が出ない範
囲であれば、含水溶媒であってもよい。Examples of the polymerization solvent include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, n-propanol and isopropanol; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; N-methylpyrrolidone; , N'-dimethylacetamide, dimethylsulfoxide and the like. These may be used alone or in combination of two or more. In addition, a water-containing solvent may be used as long as the reaction is not affected.
【００５０】重合温度は、高すぎると反応の制御が困難
になり、低すぎると反応速度が遅くなり反応に時間を要
するため、通常３０〜１５０℃、好ましくは６０〜１２
０℃である。また、重合反応の進行に合わせて重合温度
を変化させ、反応の制御を行ってもよい。If the polymerization temperature is too high, it is difficult to control the reaction. If the polymerization temperature is too low, the reaction rate slows down and the reaction requires time, so that it is usually 30 to 150 ° C., preferably 60 to 12 ° C.
0 ° C. Further, the reaction may be controlled by changing the polymerization temperature in accordance with the progress of the polymerization reaction.
【００５１】重合時間は、通常３〜２４時間、好ましく
は５〜１５時間である。沈殿剤として用いる水の使用量
は、少なすぎると、得られる共重合体に含まれる残存重
合溶媒の量や未反応の不飽和カルボン酸、メタクリル酸
エステル等の残存モノマーの量が多くなるため、通常重
合溶媒の３倍容量以上、好ましくは３〜２０倍容量、よ
り好ましくは５〜１０倍容量である。The polymerization time is usually 3 to 24 hours, preferably 5 to 15 hours. If the amount of water used as a precipitant is too small, the amount of residual polymerization solvent and unreacted unsaturated carboxylic acid contained in the obtained copolymer and the amount of residual monomer such as methacrylic acid ester are increased. The volume is usually 3 times or more, preferably 3 to 20 times, more preferably 5 to 10 times the volume of the polymerization solvent.
【００５２】仕込み時に於ける一般式［４］で示される
シロキサンセグメント含有マクロアゾ重合開始剤、一般
式［５］で示される不飽和カルボン酸及び一般式［６］
で示されるメタクリル酸エステルの使用量の割合は、重
合条件等によって変わることがあるが、通常、得ようと
するポリマー中の各構成単位の組成比とおよそ同じ程度
である。The siloxane segment-containing macroazo polymerization initiator represented by the general formula [4], the unsaturated carboxylic acid represented by the general formula [5], and the general formula [6]
Although the ratio of the amount of the methacrylic acid ester represented by may vary depending on the polymerization conditions and the like, it is usually about the same as the composition ratio of each structural unit in the polymer to be obtained.
【００５３】本発明の方法で得られる本発明のシロキサ
ンセグメント含有アニオン系ブロック共重合体に於ける
［ＤＡＳ］、［ＵＣＡ］及び［ＭＡＥ］の３つの構成成
分の組成比は図１で示される範囲である。FIG. 1 shows the composition ratios of the three components [DAS], [UCA] and [MAE] in the siloxane segment-containing anionic block copolymer of the present invention obtained by the method of the present invention. Range.
【００５４】本発明の共重合体は、形状が粉末状ないし
顆粒状である為、その取り扱いが容易であるというだけ
でなく、残存モノマーや残存溶媒の量が極めて微量であ
るので、該共重合体から得られる塗料や化粧料等の基材
等の性能が低下することはなく、またこれらが人体へ悪
影響を及ぼすことも殆どない。Since the copolymer of the present invention is in the form of powder or granules, not only is it easy to handle, but also the amount of residual monomers and residual solvent is extremely small, so The performance of base materials such as paints and cosmetics obtained from the coalescence does not decrease, and these hardly adversely affect the human body.
【００５５】以下、実施例及び参考例を挙げて本発明を
詳細に説明するが、本発明はこれらによって何等限定さ
れるものではない。Hereinafter, the present invention will be described in detail with reference to Examples and Reference Examples, but the present invention is not limited thereto.
【００５６】[0056]
【実施例】実施例１．式(１)で示されるシロキサンセグ
メント含有マクロアゾ重合開始剤[Embodiment 1] A siloxane segment-containing macroazo polymerization initiator represented by the formula (1)
【００５７】[0057]
【化１８】 Embedded image
【００５８】（但し、ｎ＝５６、ｐ＝８）（和光純薬工
業(株)製、商品名：ＶＰＳ−０５０１）４０ｇ、メタク
リル酸４０ｇ、メタクリル酸-ｔ-ブチル２０ｇ及びイソ
プロパノール２３０ｇを混合し、窒素雰囲気下、８０℃
で６時間重合した。重合終了後、反応液に純水を1000ml
注入し、ブロック共重合体を粉末状に晶析させた。該晶
析物を濾取し、減圧下８０℃で６時間乾燥させ、ブロッ
ク共重合体９６.６ｇ を得た。ＮＭＲ分析の結果、得ら
れた共重合体に於けるシロキサンセグメント、メタクリ
ル酸由来のモノマー単位及びメタクリル酸-ｔ-ブチル由
来のモノマー単位の組成比は、41.2：34.8：24.0であ
り、共重合体中には残存モノマー及び残存溶媒は検出さ
れなかった。これら原料の仕込量及び結果等を表１に示
す。表１(However, n = 56, p = 8) 40 g of a product (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VPS-0501), 40 g of methacrylic acid, 20 g of t-butyl methacrylate and 230 g of isopropanol were mixed. 80 ° C under nitrogen atmosphere
For 6 hours. After polymerization is completed, 1000 ml of pure water is added to the reaction solution.
The mixture was poured, and the block copolymer was crystallized into a powder. The crystallized product was collected by filtration and dried under reduced pressure at 80 ° C. for 6 hours to obtain 96.6 g of a block copolymer. As a result of NMR analysis, the composition ratio of the siloxane segment, the monomer unit derived from methacrylic acid, and the monomer unit derived from t-butyl methacrylate in the obtained copolymer was 41.2: 34.8: 24.0, and the copolymer was obtained. No residual monomer or residual solvent was detected in any of them. Table 1 shows the charged amounts of these raw materials and the results. Table 1
【００５９】実施例２〜１６．ＶＰＳ−０５０１の量、
並びに不飽和カルボン酸、メタクリル酸エステル、溶媒
及び沈殿剤の種類と量を、表１に示したようにした以外
は実施例１と同様にしてブロック共重合体を得た。得ら
れたブロック共重合体の形状、収量、そのＮＭＲ分析に
よる各構成成分の組成比並びに残存物の測定結果を表１
に併せて示す。尚、表中、ＡＡはアクリル酸、ＭＡＡは
メタクリル酸、ＭＭＡはメタクリル酸メチル、ＢＭＡは
メタクリル酸-t-ブチル、ＩＰＡはイソプロパノール、
ＭＥＫはメチルエチルケトン、ＥＡはエタノールを夫々
表し、他の略号は前記と同じ。 表１Embodiments 2 to 16 The amount of VPS-0501,
A block copolymer was obtained in the same manner as in Example 1 except that the types and amounts of the unsaturated carboxylic acid, methacrylic acid ester, solvent and precipitant were as shown in Table 1. Table 1 shows the shape and yield of the obtained block copolymer, the composition ratio of each component by NMR analysis, and the measurement results of the residue.
Are shown together. In the table, AA is acrylic acid, MAA is methacrylic acid, MMA is methyl methacrylate, BMA is t-butyl methacrylate, IPA is isopropanol,
MEK represents methyl ethyl ketone, EA represents ethanol, and other abbreviations are the same as described above. Table 1
【００６０】[0060]
【表１】 [Table 1]
【００６１】表１から明らかなように実施例１〜１６で
得られた本発明のシロキサンセグメント含有アニオン系
ブロック共重合体は、何れも残存モノマーの量が合計で
１ｗ％以下且つ残存溶媒量が１ｗ％以下であり、且つそ
の形状は粉末状ないし顆粒状であることが判る。As is clear from Table 1, the siloxane segment-containing anionic block copolymers of the present invention obtained in Examples 1 to 16 all had a total amount of residual monomers of 1% by weight or less and a residual solvent amount of 1% by weight or less. It is found that the content is 1 w% or less and the shape is powdery or granular.
【００６２】実施例１７ 式(１)で示されるシロキサンセグメント含有マクロアゾ
重合開始剤Example 17 A siloxane segment-containing macroazo polymerization initiator represented by the formula (1)
【００６３】[0063]
【化１９】 Embedded image
【００６４】（但し、ｎ＝１５０、ｐ＝８．９）（和光
純薬工業（株）製、商品名：ＶＰＳ−１００１）１２
ｇ、メタクリル酸２２ｇ、メタクリル酸−ｔ−ブチル６
ｇ及びイソプロパノール１６０ｇを混合し、窒素雰囲気
下、８０℃で６時間重合した。重合終了後、反応液に純
水を８００ｍｌ注入し、ブロック共重合体を粉末状に晶
析させた。該晶析物を濾取し、減圧下８０℃で６時間乾
燥させ、ブロック共重合体３３.３ｇを得た。(However, n = 150, p = 8.9) (trade name: VPS-1001 manufactured by Wako Pure Chemical Industries, Ltd.) 12
g, methacrylic acid 22 g, t-butyl methacrylate 6
g and 160 g of isopropanol were mixed and polymerized at 80 ° C. for 6 hours under a nitrogen atmosphere. After the completion of the polymerization, 800 ml of pure water was injected into the reaction solution, and the block copolymer was crystallized into a powder. The crystallized product was collected by filtration and dried under reduced pressure at 80 ° C. for 6 hours to obtain 33.3 g of a block copolymer.
【００６５】ＮＭＲ分析の結果、得られた共重合体にお
けるシロキサンセグメント、メタクリル酸由来のモノマ
ー単位及びメタクリル酸−ｔ−ブチル由来のモノマー単
位の組成比は、３４.４／４６.６／１９.１であり、共
重合体中には残存モノマー及び残存溶媒は検出されなか
った。As a result of NMR analysis, the composition ratio of the siloxane segment, the monomer unit derived from methacrylic acid and the monomer unit derived from t-butyl methacrylate in the obtained copolymer was 34.4 / 46.6 / 19. 1, and no residual monomer or residual solvent was detected in the copolymer.
【００６６】比較例１．ｎ-ヘキサンを沈殿剤とした共
重合体の合成 ＶＰＳ−０５０１ ４０ｇ、メタクリル酸４０ｇ、メタ
クリル酸-ｔ-ブチル２０ｇ及びイソプロパノール２３０
ｇを混合し、窒素雰囲気下、８０℃で６時間重合した。
重合終了後、反応液にｎ-ヘキサン2500ｍｌを注入した
後、ゲル状の沈殿物を減圧下８０℃で６時間乾燥させ、
シロキサンセグメント含有ブロック共重合体９３.３ｇ
を得た。ＮＭＲ分析の結果、得られた共重合体に於ける
シロキサンセグメント、メタクリル酸由来のモノマー単
位及びメタクリル酸-ｔ-ブチル由来のモノマー単位の組
成比は、36.4：35.5：28.1であった。また、共重合体中
には残存モノマーであるメタクリル酸が１.１w％、残存
溶媒であるイソプロパノールが６.３w％及び残存沈殿剤
であるｎ-ヘキサンが０.３w％検出された。Comparative Example 1 Synthesis of copolymer using n-hexane as a precipitant 40 g of VPS-0501, 40 g of methacrylic acid, 20 g of t-butyl methacrylate and 230 g of isopropanol
g were mixed and polymerized at 80 ° C. for 6 hours under a nitrogen atmosphere.
After the polymerization was completed, 2500 ml of n-hexane was poured into the reaction solution, and the gel precipitate was dried at 80 ° C. under reduced pressure for 6 hours.
93.3 g of siloxane segment-containing block copolymer
I got As a result of NMR analysis, a composition ratio of a siloxane segment, a monomer unit derived from methacrylic acid and a monomer unit derived from t-butyl methacrylate in the obtained copolymer was 36.4: 35.5: 28.1. In the copolymer, 1.1% by weight of methacrylic acid as a residual monomer, 6.3% by weight of isopropanol as a residual solvent, and 0.3% by weight of n-hexane as a residual precipitant were detected.
【００６７】比較例１の結果から、沈殿剤としてｎ−ヘ
キサンを用いた場合、得られた共重合体に於ける［ＤＡ
Ｓ］、［ＵＣＡ］及び［ＭＡＥ］の組成比は本発明の共
重合体のそれと同じ範囲に入るものの、共重合体の形状
は粉末状ないし顆粒状とはならず、また、残存溶媒も多
量に含まれており、更には沈殿剤自体も得られた共重合
体中に残存してしまうことが判る。From the results of Comparative Example 1, it was found that when n-hexane was used as the precipitant, [DA
Although the composition ratio of [S], [UCA] and [MAE] falls within the same range as that of the copolymer of the present invention, the shape of the copolymer does not become powdery or granular, and the amount of residual solvent is large. It is also found that the precipitant itself remains in the obtained copolymer.
【００６８】比較例２． 成分組成比が異なる共重合体
の合成（沈殿剤として水を使用） （１）ＶＰＳ−０５０１ ８ｇ、メタクリル酸４２ｇ、
メタクリル酸-ｔ-ブチル５０ｇを用いた以外は実施例１
と同様に共重合反応を行った。重合反応終了後、反応液
に純水1000mlを注入し、得られた餅状の固塊を切断して
小塊とし、減圧下８０℃で６時間乾燥させ、シロキサン
セグメント含有ブロック共重合体８５.５ｇを得た。Ｎ
ＭＲ分析の結果、得られた共重合体に於けるシロキサン
セグメント、メタクリル酸由来のモノマー単位及びメタ
クリル酸-ｔ-ブチル由来のモノマー単位の組成比は、9.
4：37.4：53.3であった。また、共重合体中には残存モ
ノマーであるメタクリル酸が１.９w％、メタクリル酸-
ｔ-ブチルが７.５w％及び残存溶媒であるイソプロパノ
ールが２.５w％検出された。Comparative Example 2 Synthesis of copolymers having different component composition ratios (using water as a precipitant) (1) 8 g of VPS-0501, 42 g of methacrylic acid,
Example 1 except that 50 g of t-butyl methacrylate was used.
A copolymerization reaction was carried out in the same manner as in 1. After the completion of the polymerization reaction, 1000 ml of pure water was poured into the reaction solution, and the obtained rice cake-like solid mass was cut into small masses, which were dried at 80 ° C. under reduced pressure for 6 hours. 5 g were obtained. N
As a result of MR analysis, the composition ratio of the siloxane segment, the monomer unit derived from methacrylic acid, and the monomer unit derived from t-butyl methacrylate in the obtained copolymer was 9.
4: 37.4: 53.3. The copolymer contained 1.9% by weight of methacrylic acid as a residual monomer, and methacrylic acid-
7.5% by weight of t-butyl and 2.5% by weight of isopropanol as a residual solvent were detected.
【００６９】（２）ＶＰＳ−０５０１ １５ｇ、メタク
リル酸１５ｇ、メタクリル酸-ｔ-ブチル７０ｇを用いた
以外は実施例１と同様に共重合反応を行った。重合反応
終了後、反応液に純水1000mlを注入した後、得られた餅
状の沈殿物を減圧下８０℃で６時間乾燥させ、シロキサ
ンセグメント含有ブロック共重合体９１.１ｇを得た。
ＮＭＲ分析の結果、得られた共重合体に於けるシロキサ
ンセグメント、メタクリル酸由来のモノマー単位及びメ
タクリル酸-ｔ-ブチル由来のモノマー単位の組成比は、
16.6：11.2：72.2であった。また、共重合体中には残存
モノマーであるメタクリル酸が０.５w％、メタクリル酸
-ｔ-ブチルが５.８w％及び残存溶媒であるイソプロパノ
ールが１.０w％検出された。(2) A copolymerization reaction was carried out in the same manner as in Example 1 except that 15 g of VPS-0501, 15 g of methacrylic acid, and 70 g of t-butyl methacrylate were used. After completion of the polymerization reaction, 1000 ml of pure water was poured into the reaction solution, and the obtained rice cake-like precipitate was dried at 80 ° C. under reduced pressure for 6 hours to obtain 91.1 g of a siloxane segment-containing block copolymer.
As a result of NMR analysis, the composition ratio of the siloxane segment in the obtained copolymer, a monomer unit derived from methacrylic acid and a monomer unit derived from t-butyl methacrylate,
16.6: 11.2: 72.2. The copolymer contains 0.5% by weight of methacrylic acid as a residual monomer,
5.8% by weight of -t-butyl and 1.0% by weight of isopropanol as a residual solvent were detected.
【００７０】（３）ＶＰＳ−０５０１ ３０ｇ、メタク
リル酸２０ｇ、メタクリル酸-ｔ-ブチル５０ｇを用いた
以外は実施例１と同様に共重合反応を行った。重合反応
終了後、反応液に純水1500mlを注入した後、得られた餅
状の沈殿物を減圧下８０℃で６時間乾燥させ、シロキサ
ンセグメント含有ブロック共重合体１０４.１ｇを得
た。ＮＭＲ分析の結果、得られた共重合体に於けるシロ
キサンセグメント、メタクリル酸由来のモノマー単位及
びメタクリル酸-ｔ-ブチル由来のモノマー単位の組成比
は、37.5：8.3：54.2であった。また、共重合体中には
残存モノマーであるメタクリル酸が０.６w％、メタクリ
ル酸-ｔ-ブチルが３.１w％及び残存溶媒であるイソプロ
パノールが０.６w％検出された。(3) A copolymerization reaction was carried out in the same manner as in Example 1 except that 30 g of VPS-0501, 20 g of methacrylic acid, and 50 g of t-butyl methacrylate were used. After the completion of the polymerization reaction, 1500 ml of pure water was poured into the reaction solution, and the obtained cake-like precipitate was dried at 80 ° C. under reduced pressure for 6 hours to obtain 104.1 g of a siloxane segment-containing block copolymer. As a result of NMR analysis, a composition ratio of a siloxane segment, a monomer unit derived from methacrylic acid and a monomer unit derived from t-butyl methacrylate in the obtained copolymer was 37.5: 8.3: 54.2. In the copolymer, 0.6% by weight of methacrylic acid as a residual monomer, 3.1% by weight of t-butyl methacrylate, and 0.6% by weight of isopropanol as a residual solvent were detected.
【００７１】（４）ＶＰＳ−０５０１ ５ｇ、メタクリ
ル酸７０ｇ、メタクリル酸-ｔ-ブチル２５ｇを用いた以
外は実施例１と同様にして共重合反応を行った。重合反
応終了後、反応液に純水1250mlを注入した後、得られた
餅状の沈殿物を減圧下８０℃で６時間乾燥させ、シロキ
サンセグメント含有ブロック共重合体７７.６ｇを得
た。ＮＭＲ分析の結果、得られた共重合体に於けるシロ
キサンセグメント、メタクリル酸由来のモノマー単位及
びメタクリル酸-ｔ-ブチル由来のモノマー単位の組成比
は、6.6：61.3：32.1であった。また、共重合体中には
残存モノマーであるメタクリル酸が１.３w％、メタクリ
ル酸-ｔ-ブチルが１.１w％及び残存溶媒であるイソプロ
パノールが０.６w％検出された。(4) A copolymerization reaction was carried out in the same manner as in Example 1 except that 5 g of VPS-0501, 70 g of methacrylic acid, and 25 g of t-butyl methacrylate were used. After the completion of the polymerization reaction, 1250 ml of pure water was poured into the reaction solution, and the obtained rice cake-like precipitate was dried at 80 ° C. under reduced pressure for 6 hours to obtain 77.6 g of a siloxane segment-containing block copolymer. As a result of NMR analysis, a composition ratio of a siloxane segment, a monomer unit derived from methacrylic acid and a monomer unit derived from t-butyl methacrylate in the obtained copolymer was 6.6: 61.3: 32.1. In the copolymer, 1.3% by weight of methacrylic acid as a residual monomer, 1.1% by weight of t-butyl methacrylate, and 0.6% by weight of isopropanol as a residual solvent were detected.
【００７２】（５）ＶＰＳ−０５０１ ７０ｇ、メタク
リル酸２０ｇ、メタクリル酸-ｔ-ブチル１０ｇを用いた
以外は実施例１と同様にして共重合反応を行った。重合
反応終了後、反応液に純水1500mlを注入した後、得られ
た餅状の沈殿物を減圧下８０℃で６時間乾燥させ、シロ
キサンセグメント含有ブロック共重合体９５.３ｇを得
た。ＮＭＲ分析の結果、得られた共重合体に於けるシロ
キサンセグメント、メタクリル酸由来のモノマー単位及
びメタクリル酸-ｔ-ブチル由来のモノマー単位の組成比
は、72.0：15.2：12.8であった。また、共重合体中には
残存モノマーであるメタクリル酸が０.１w％、メタクリ
ル酸-ｔ-ブチルが０.４w％及び残存溶媒であるイソプロ
パノールが０.２w％検出された。(5) A copolymerization reaction was carried out in the same manner as in Example 1 except that 70 g of VPS-0501, 20 g of methacrylic acid, and 10 g of t-butyl methacrylate were used. After the completion of the polymerization reaction, 1500 ml of pure water was poured into the reaction solution, and the obtained rice cake-like precipitate was dried at 80 ° C. under reduced pressure for 6 hours to obtain 95.3 g of a siloxane segment-containing block copolymer. As a result of NMR analysis, a composition ratio of a siloxane segment, a monomer unit derived from methacrylic acid, and a monomer unit derived from t-butyl methacrylate in the obtained copolymer was 72.0: 15.2: 12.8. In the copolymer, 0.1% by weight of methacrylic acid as a residual monomer, 0.4% by weight of t-butyl methacrylate, and 0.2% by weight of isopropanol as a residual solvent were detected.
【００７３】比較例２の結果から、沈殿剤として水を用
いても、得られた共重合体に於ける［ＤＡＳ］、［ＵＣ
Ａ］及び［ＭＡＥ］の組成比が本発明の共重合体のそれ
と異なる範囲のものである場合は、残存モノマー及び残
存溶媒の量が多いものが多く、またこれらの量が比較的
少ないものでも共重合体の形状は残存モノマー及び残存
溶媒量が多いものと同様に餅状等となり、粉末状ないし
顆粒状とは到底ならないことが判る。From the results of Comparative Example 2, it was found that even when water was used as the precipitant, [DAS] and [UC
When the composition ratio of [A] and [MAE] is in a range different from that of the copolymer of the present invention, the amount of the residual monomer and the residual solvent is large in many cases, and the amount of these is relatively small. It can be seen that the shape of the copolymer becomes cake-like or the like similarly to the case where the amount of the residual monomer and the amount of the residual solvent is large, and it can be seen that the shape of the copolymer does not become powdery or granular.
【００７４】比較例３．成分組成比が異なる共重合体の
合成（沈殿剤としてｎ−ヘキサンを使用） ＶＰＳ−０５０１ ２３ｇ、メタクリル酸７０ｇ、メタ
クリル酸-ｔ-ブチル７ｇを用いた以外は実施例１と同様
にして共重合反応を行った。重合反応終了後、反応液に
イソプロパノール１７０ｇを加えて希釈した後、該反応
液の一部に純水を注入したが、得られた共重合体は膨潤
状態であり濾取不可能であった。残りの反応液にｎ-ヘ
キサンを注入し共重合体を晶析させた後、該晶析物を減
圧下８０℃で６時間乾燥させ、結晶状ブロック共重合体
を得た。ＮＭＲ分析の結果、得られた共重合体に於ける
シロキサンセグメント、メタクリル酸由来のモノマー単
位及びメタクリル酸-ｔ-ブチル由来のモノマー単位の組
成比は、19.3：68.3：12.4であった。また、共重合体中
には残存モノマーであるメタクリル酸が１.０w％、残存
溶媒であるイソプロパノールが７.５w％及び残存沈殿剤
であるｎ-ヘキサンが０.５w％検出された。Comparative Example 3 Synthesis of copolymers having different component composition ratios (using n-hexane as a precipitant) Copolymerization was carried out in the same manner as in Example 1 except that 23 g of VPS-0501, 70 g of methacrylic acid, and 7 g of t-butyl methacrylate were used. The reaction was performed. After completion of the polymerization reaction, 170 g of isopropanol was added to the reaction solution to dilute the solution, and pure water was injected into a part of the reaction solution. However, the obtained copolymer was in a swollen state and could not be collected by filtration. After n-hexane was injected into the remaining reaction solution to crystallize the copolymer, the crystallized product was dried at 80 ° C. under reduced pressure for 6 hours to obtain a crystalline block copolymer. As a result of NMR analysis, a composition ratio of a siloxane segment, a monomer unit derived from methacrylic acid, and a monomer unit derived from t-butyl methacrylate in the obtained copolymer was 19.3: 68.3: 12.4. In the copolymer, 1.0% by weight of methacrylic acid as a residual monomer, 7.5% by weight of isopropanol as a residual solvent, and 0.5% by weight of n-hexane as a residual precipitant were detected.
【００７５】比較例３の結果から、沈殿剤として水を用
いても、粉末状ないし顆粒状のブロック共重合体が得ら
れない重合液中の共重合体を、ｎ-ヘキサンを用いて晶
析させると、粉末状ないし顆粒状のブロック共重合体が
得られるが、該共重合体に於ける［ＤＡＳ］、［ＵＣ
Ａ］及び［ＭＡＥ］の組成比が本発明の共重合体のそれ
と異なる場合には、残存溶媒の量が極めて多く、また沈
殿剤自体もブロック共重合体中に残存してしまうことが
判る。From the results of Comparative Example 3, it was found that a copolymer in a polymerization solution in which a powdery or granular block copolymer was not obtained even when water was used as a precipitant was crystallized using n-hexane. When this is done, a powdery or granular block copolymer is obtained, and [DAS], [UC
When the composition ratio of [A] and [MAE] is different from that of the copolymer of the present invention, the amount of the residual solvent is extremely large, and the precipitant itself remains in the block copolymer.
【００７６】[0076]
【発明の効果】本発明は、残存モノマー及び残存溶媒の
量が著しく少なく、且つ形状が粉末状ないし顆粒状であ
るシロキサンセグメント含有アニオン系ブロック共重合
体を提供するものであり、本発明の共重合体は、その取
得に際しては作業性に優れ、また、例えばこれを塗料用
或いは化粧料用の基剤として使用する場合には品質の面
で非常に優れた効果を有するものである。According to the present invention, there is provided an anionic block copolymer containing a siloxane segment, wherein the amount of the residual monomer and the residual solvent is extremely small and the shape is a powdery or granular form. The polymer is excellent in workability when it is obtained, and has a very excellent effect in terms of quality, for example, when it is used as a base for paints or cosmetics.
【００７７】[0077]
【図１】 本発明の共重合体に於ける［ＤＡＳ］、［Ｕ
ＣＡ］及び［ＭＡＥ］の組成比を示す。1] [DAS], [U] in the copolymer of the present invention
CA] and [MAE] are shown.
Claims (4)
級アルキル基を表し、Ｒ３ 及びＲ４は夫々独立して水
素原子、低級アルキル基又はアリール基を表し、ｎは
０〜２００の整数を表す）で示されるシロキサンセグメ
ント、一般式［２］ 【化２】 （式中、Ｒ５は水素原子又はメチル基を表す）で示され
るモノマー単位及び一般式［３］ 【化３】 （式中、Ｒ６は低級アルキル基を表す）で示されるモノ
マー単位を構成成分として含んで成る共重合体であっ
て、これら３成分の組成比が図１に於ける点Ａ〜Ｆで囲
まれる範囲内に入るものであり、残存モノマーの量が１
ｗ％以下で且つ残存溶媒の量が１ｗ％以下である共重合
体。1. A compound of the general formula [1] (Wherein, R1 and R2 each independently represent a hydrogen atom or a lower alkyl group, R3 and R4 each independently represent a hydrogen atom, a lower alkyl group or an aryl group, and n is
A siloxane segment represented by the general formula [2]: (Wherein R5 represents a hydrogen atom or a methyl group) and a general formula [3] (Wherein, R6 represents a lower alkyl group) is a copolymer containing, as a component, a monomer unit represented by the formula: wherein the composition ratio of these three components is surrounded by points A to F in FIG. Within the range, and the amount of the residual monomer is 1
w% or less and the amount of residual solvent is 1 w% or less.
の共重合体。2. The copolymer according to claim 1, which is in the form of a powder or granules.
タクリル酸由来のモノマー単位であり、一般式［３］で
示されるモノマー単位がメタクリル酸-ｔ-ブチル由来の
モノマー単位である請求項１又は２に記載の共重合体。3. The monomer unit represented by the general formula [2] is a monomer unit derived from methacrylic acid, and the monomer unit represented by the general formula [3] is a monomer unit derived from t-butyl methacrylate. 3. The copolymer according to 1 or 2.
はシアノ基を表し、ＡはＮ Ｈ又は酸素原子を表し、Ｅ
は酸素原子を有していてもよい低級アルキレン基又は結
合手を表し、ｍは０〜６の整数を表し、ｐは自然数を表
す。また、Ｒ１〜Ｒ４及びｎは前記と同じ）で示される
シロキサンセグメント含有マクロアゾ重合開始剤、一般
式［５］ 【化５】 （式中、Ｒ５は前記と同じ）で示される不飽和カルボン
酸及び一般式［６］ 【化６】 （式中、Ｒ６は前記と同じ）で示されるメタクリル酸エ
ステルを、得られる共重合体の主たる構成単位である一
般式［１］で示されるシロキサンセグメント、一般式
［２］で示されるモノマー単位及び一般式［３］で示さ
れるモノマー単位の組成比が図１に於ける点Ａ〜Ｆで囲
まれる範囲内に入るように夫々の使用量を選択設定して
重合反応させ、得られる溶液から、水を沈殿剤として用
いて晶析、単離することを特徴とする請求項１に記載の
共重合体の取得方法。4. A compound represented by the general formula [4] in a hydrophilic organic solvent: (Wherein, R7 to R10 each independently represent a lower alkyl group or a cyano group; A represents NH or an oxygen atom;
Represents a lower alkylene group or a bond which may have an oxygen atom, m represents an integer of 0 to 6, and p represents a natural number. R1 to R4 and n are the same as those described above), and a siloxane segment-containing macroazo polymerization initiator represented by the following general formula [5]: Wherein R5 is the same as defined above, and an unsaturated carboxylic acid represented by the general formula [6]: (Wherein R6 is the same as described above), a siloxane segment represented by the general formula [1], which is a main constituent unit of the obtained copolymer, and a monomer unit represented by the general formula [2] The amount of each monomer is selected and set so that the composition ratio of the monomer unit represented by the general formula [3] falls within the range surrounded by points A to F in FIG. The method for obtaining a copolymer according to claim 1, wherein crystallization and isolation are performed using water as a precipitant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11164530A JP2000219715A (en) | 1998-11-26 | 1999-06-11 | Siloxane segment-containing anionic block copolymer and method for obtaining the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-352151 | 1998-11-26 | ||
| JP35215198 | 1998-11-26 | ||
| JP11164530A JP2000219715A (en) | 1998-11-26 | 1999-06-11 | Siloxane segment-containing anionic block copolymer and method for obtaining the same |
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| Publication Number | Publication Date |
|---|---|
| JP2000219715A true JP2000219715A (en) | 2000-08-08 |
Family
ID=26489594
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11164530A Pending JP2000219715A (en) | 1998-11-26 | 1999-06-11 | Siloxane segment-containing anionic block copolymer and method for obtaining the same |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422194C (en) * | 2006-06-19 | 2008-10-01 | 浙江大学 | Siloxane precursor linked with branch-shaped azo chromophore and its synthesis method |
-
1999
- 1999-06-11 JP JP11164530A patent/JP2000219715A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422194C (en) * | 2006-06-19 | 2008-10-01 | 浙江大学 | Siloxane precursor linked with branch-shaped azo chromophore and its synthesis method |
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