JPWO2006117997A1 - Physical stimulation response non-aqueous composition - Google Patents
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Abstract
溶媒が揮発せずに開放系で実用可能な新規の物理刺激応答非水系組成物を提供する。下記第１、第１及び第２、第１及び第３、又は第２及び第３の各モノマーの何れかを重合してなる高分子体とイオン液体を含み、架橋剤を用いずに重合した線形高分子を該イオン液体へ溶解した際、物理刺激に応じて該線形高分子が相分離状態と溶解状態とに可逆的に変化する。第１モノマー：（メタ）アクリル酸、ラクトン、グリコール、シロキサンの１種以上に、アリール基、Ｃ１以上の直鎖アルキル基、及びＣ３以上の分枝アルキル基の１種以上が結合。第２モノマー：（メタ）アクリル酸、（メタ）アクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの１種以上に、直鎖及び分枝アルキル基の１種以上が結合。第３モノマー：（メタ）アクリル酸、（メタ）アクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの１種以上に、水素、水酸基、複素環アミンの１種以上が結合、又はビニル基からなる骨格にアリール基が結合。A novel physical stimulus-responsive non-aqueous composition that can be used in an open system without volatilization of a solvent is provided. Polymerized without using a crosslinking agent, including a polymer obtained by polymerizing any of the following first, first and second, first and third, or second and third monomers, and an ionic liquid When the linear polymer is dissolved in the ionic liquid, the linear polymer reversibly changes between a phase-separated state and a dissolved state in accordance with a physical stimulus. First monomer: One or more of an aryl group, a linear alkyl group of C1 or more, and a branched alkyl group of C3 or more are bonded to one or more of (meth) acrylic acid, lactone, glycol, and siloxane. Second monomer: One or more of linear and branched alkyl groups are bonded to one or more of (meth) acrylic acid, (meth) acrylamide, lactone, glycol, vinyl group, and siloxane. Third monomer: One or more of (meth) acrylic acid, (meth) acrylamide, lactone, glycol, vinyl group, and siloxane are combined with one or more of hydrogen, hydroxyl group, and heterocyclic amine, or a skeleton composed of a vinyl group An aryl group is bonded to.
Description
本発明は、物理的刺激に応答するゲル等の組成物に関し、特に、新規の物理刺激応答非水系組成物に関する。 The present invention relates to a composition such as a gel that responds to a physical stimulus, and more particularly to a novel physical stimulus responsive non-aqueous composition.
従来から、高分子体ハイドロゲルが周囲の物理化学的刺激（温度、イオン強度、ｐＨ、電場、光、磁場等）に応答して体積変化することが知られている。そして、このようなハイドロゲルの体積変化を利用したアクチュエータ（例えば、特許文献１参照）、薬剤放出を制御してＤＤＳ(薬物送達システム)に用いるためのゲル（例えば、特許文献２参照）、培養体（例えば、特許文献３参照）等が応用技術として報告されている。
これらのハイドロゲルは、物理刺激に応じて、高分子体の網目構造の間に溶媒である水が出入りし、可逆的なゲルの体積変化を伴うものである。
しかしながら、上記したハイドロゲルの場合、溶媒である水が経時により蒸発するため、開放系でゲルを長期間使用することができず、実用性の点で問題があった。そこで、本発明者らは、高分子としてポリ（Ｎ−イソプロピルアクリルアミド）（PNIPAと称する）を用い、非水系溶媒として、不燃性、不揮発性を有する溶媒として注目されているイオン液体を用いた非水系ゲルを提案した（非特許文献１参照）。Conventionally, it is known that a polymer hydrogel undergoes a volume change in response to surrounding physicochemical stimuli (temperature, ionic strength, pH, electric field, light, magnetic field, etc.). And an actuator (for example, refer to patent document 1) using such a volume change of hydrogel, a gel (for example, refer to patent document 2) for controlling drug release and using it for DDS (drug delivery system), culture A body (see, for example, Patent Document 3) has been reported as an applied technology.
In these hydrogels, water, which is a solvent, enters and exits between the polymer network structures in response to physical stimulation, and is accompanied by a reversible gel volume change.
However, in the case of the above-described hydrogel, since the solvent water evaporates with time, the gel cannot be used for a long time in an open system, and there is a problem in terms of practicality. Accordingly, the present inventors use poly (N-isopropylacrylamide) (referred to as PNIPA) as a polymer, and use a non-aqueous solvent that uses an ionic liquid that is attracting attention as a nonflammable and non-volatile solvent. An aqueous gel was proposed (see Non-Patent Document 1).
しかしながら、上記したPNIPAの場合、物理刺激に対する応答性が緩慢であるという懸念がある。
従って、本発明の目的は、溶媒が揮発せずに開放系で実用可能な新規の物理刺激応答非水系ゲルを提供することにある。However, in the case of the above-described PNIPA, there is a concern that the response to physical stimulation is slow.
Accordingly, an object of the present invention is to provide a novel physical stimulus responsive non-aqueous gel that can be practically used in an open system without volatilization of the solvent.
本発明者らは、非水系溶媒として、不燃性、不揮発性を有する溶媒として注目されているイオン液体（イオン性液体）を用いることで上記課題を解決するに至った。イオン液体は、イオンのみから構成され、液体でありながら蒸気圧がなく（不揮発性）、耐熱性が高く、液体温度範囲が広いという特徴がある。
すなわち本発明の物理刺激応答非水系組成物は、第１モノマーを重合してなる高分子体とイオン液体とを含み、前記第１モノマーを架橋剤を用いずに重合した線形高分子を前記イオン液体へ溶解した場合に、物理刺激に応じて当該線形高分子が相分離状態と溶解状態とに可逆的に変化する物理刺激応答非水系組成物であって、前記第１モノマーは、アクリル酸、メタクリル酸、ラクトン、グリコール、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつアリール基、炭素数１以上の直鎖アルキル基、及び炭素数３以上の分枝アルキル基の群から選ばれる１種以上が前記骨格に結合している。The present inventors have solved the above-mentioned problems by using an ionic liquid (ionic liquid) that has attracted attention as a non-flammable and non-volatile solvent as a non-aqueous solvent. An ionic liquid is composed only of ions and has the characteristics that it is a liquid but has no vapor pressure (nonvolatile), has high heat resistance, and has a wide liquid temperature range.
That is, the physical stimulus responsive non-aqueous composition of the present invention includes a polymer obtained by polymerizing a first monomer and an ionic liquid, and a linear polymer obtained by polymerizing the first monomer without using a cross-linking agent. When dissolved in a liquid, a physical stimulus-responsive non-aqueous composition in which the linear polymer reversibly changes between a phase-separated state and a dissolved state in response to a physical stimulus, wherein the first monomer is acrylic acid, One or more selected from the group of methacrylic acid, lactone, glycol, and siloxane in the skeleton, and from the group of aryl groups, linear alkyl groups having 1 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms One or more selected are bonded to the skeleton.
又、本発明の物理刺激応答非水系組成物は、第１モノマーと第２モノマーとを共重合してなる高分子体とイオン液体とを含み、前記第１モノマーと第２モノマーとを架橋剤を用いずに重合した線形高分子を前記イオン液体へ溶解した場合に、物理刺激に応じて当該線形高分子が相分離状態と溶解状態とに可逆的に変化する物理刺激応答非水系組成物であって、前記第１モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつアリール基、炭素数１以上の直鎖アルキル基、及び炭素数３以上の分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、前記第２モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ直鎖アルキル基、及び分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、前記第２モノマーの直鎖アルキル基又は分枝アルキル基の炭素数は、前記第１モノマーの直鎖アルキル基又は分枝アルキル基の炭素数より小さく、前記第１モノマー及び第２モノマーを架橋剤を用いずに共重合した線形高分子が示す相分離温度は、前記第１モノマーのみを架橋剤を用いずに重合した線形高分子が示す相分離温度より高い。 The physical stimulus responsive non-aqueous composition of the present invention comprises a polymer obtained by copolymerizing a first monomer and a second monomer and an ionic liquid, and the first monomer and the second monomer are cross-linked with each other. When a linear polymer polymerized without using a polymer is dissolved in the ionic liquid, a physical stimulation response non-aqueous composition in which the linear polymer reversibly changes between a phase-separated state and a dissolved state in response to a physical stimulus. The first monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, and siloxane in the skeleton, and has an aryl group and a straight chain having 1 or more carbon atoms. One or more selected from the group of a chain alkyl group and a branched alkyl group having 3 or more carbon atoms is bonded to the skeleton, and the second monomer is acrylic acid, methacrylic acid, acrylamide, The skeleton has one or more selected from the group of tacrylamide, lactone, glycol, vinyl group, and siloxane, and at least one selected from the group of linear alkyl groups and branched alkyl groups is bonded to the skeleton. The carbon number of the linear alkyl group or branched alkyl group of the second monomer is smaller than the carbon number of the linear alkyl group or branched alkyl group of the first monomer, and the first monomer and the second monomer The phase separation temperature exhibited by the linear polymer copolymerized without using a crosslinking agent is higher than the phase separation temperature exhibited by the linear polymer obtained by polymerizing only the first monomer without using a crosslinking agent.
又、本発明の物理刺激応答非水系組成物は、第１モノマーと第３モノマーとを共重合してなる高分子体とイオン液体とを含み、前記第１モノマーと第３モノマーとを架橋剤を用いずに重合した線形高分子を前記イオン液体へ溶解した場合に、物理刺激に応じて当該線形高分子が相分離状態と溶解状態とに可逆的に変化する物理刺激応答非水系組成物であって、前記第１モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつアリール基、炭素数１以上の直鎖アルキル基、及び炭素数３以上の分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、前記第３モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ水素、水酸基、複素環アミンの群から選ばれる１種以上が前記骨格に結合したものであるか、又はビニル基からなる骨格にアリール基が結合したものであり、前記第１モノマー及び第３モノマーを架橋剤を用いずに共重合した線形高分子が示す相分離温度は、前記第１モノマーのみを架橋剤を用いずに重合した線形高分子が示す相分離温度より低い。 The physical stimulus responsive non-aqueous composition of the present invention includes a polymer obtained by copolymerizing a first monomer and a third monomer and an ionic liquid, and the first monomer and the third monomer are cross-linked with each other. When a linear polymer polymerized without using a polymer is dissolved in the ionic liquid, a physical stimulation response non-aqueous composition in which the linear polymer reversibly changes between a phase-separated state and a dissolved state in response to a physical stimulus. The first monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, and siloxane in the skeleton, and has an aryl group and a straight chain having 1 or more carbon atoms. One or more selected from the group of a chain alkyl group and a branched alkyl group having 3 or more carbon atoms is bonded to the skeleton, and the third monomer is acrylic acid, methacrylic acid, acrylamide, The skeleton has one or more selected from the group of tacrylamide, lactone, glycol, vinyl group, and siloxane, and at least one selected from the group of hydrogen, hydroxyl group, and heterocyclic amine is bonded to the skeleton. Or a phase separation temperature indicated by a linear polymer obtained by copolymerizing the first monomer and the third monomer without using a cross-linking agent, wherein the first monomer and the third monomer are copolymerized without using a crosslinking agent. The temperature is lower than the phase separation temperature exhibited by a linear polymer polymerized only without using a crosslinking agent.
又、本発明の物理刺激応答非水系組成物は、第２モノマーと第３モノマーとを共重合してなる高分子体とイオン液体とを含み、前記第２モノマーと第３モノマーとを架橋剤を用いずに重合した線形高分子を前記イオン液体へ溶解した場合に、物理刺激に応じて当該線形高分子が相分離状態と溶解状態とに可逆的に変化する物理刺激応答非水系組成物であって、前記第２モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ直鎖アルキル基、及び分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、前記第３モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ水素、水酸基、複素環アミンの群から選ばれる１種以上が前記骨格に結合したものであるか、又はビニル基からなる骨格にアリール基が結合したものである。 The physical stimulus responsive non-aqueous composition of the present invention comprises a polymer obtained by copolymerizing a second monomer and a third monomer and an ionic liquid, and the second monomer and the third monomer are cross-linked with each other. When a linear polymer polymerized without using a polymer is dissolved in the ionic liquid, a physical stimulation response non-aqueous composition in which the linear polymer reversibly changes between a phase-separated state and a dissolved state in response to a physical stimulus. Wherein the second monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, vinyl group, and siloxane in the skeleton, and a linear alkyl group, and At least one selected from the group of branched alkyl groups is bonded to the skeleton, and the third monomer is acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, The skeleton has one or more selected from the group of coal, vinyl group, and siloxane, and one or more selected from the group of hydrogen, hydroxyl group, and heterocyclic amine is bonded to the skeleton, or vinyl. An aryl group is bonded to a skeleton composed of a group.
前記第１モノマーは、メタクリル酸ベンジル、オクタデシルメタクリレート、オクタデシルアクリレート、ε-カプロラクトンの群から選ばれる１種以上であることが好ましい。
前記イオン液体の極性パラメータＥＴ（30）が48.2〜52.4であることが好ましい。
前記高分子体は前記第１ないし第３モノマーを架橋重合してなり、前記物理刺激応答非水系組成物はゲル状であり、かつ物理刺激に応答して可逆的に体積変化することが好ましい。The first monomer is preferably at least one selected from the group consisting of benzyl methacrylate, octadecyl methacrylate, octadecyl acrylate, and ε-caprolactone.
The polar parameter E T (30) of the ionic liquid is preferably 48.2 to 52.4.
It is preferable that the polymer is formed by crosslinking polymerization of the first to third monomers, and the physical stimulus responsive non-aqueous composition is in a gel form and reversibly changes its volume in response to the physical stimulus.
本発明によれば、溶媒が揮発せずに開放系で実用可能な新規の物理刺激応答非水系組成物（ゲルを含む）を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, the novel physical stimulus responsive non-aqueous composition (a gel is included) which can be used by an open system without volatilization of a solvent can be obtained.
以下、本発明の実施形態について説明する。本発明に係る物理刺激応答非水系組成物は、以下の高分子体とイオン液体とを含む。又、本発明に係る組成物は、ゲル状のものと溶液のものとに分けられる。ゲル状のものは以下のモノマーを架橋重合した場合に得られ、溶液状のものはモノマーを架橋せずに重合した場合に得られる。 Hereinafter, embodiments of the present invention will be described. The physical stimulus responsive non-aqueous composition according to the present invention includes the following polymer and ionic liquid. The composition according to the present invention is divided into a gel-like composition and a solution composition. A gel is obtained when the following monomers are crosslinked and polymerized, and a solution is obtained when the monomers are polymerized without crosslinking.
１．ゲル状組成物
本発明に係る組成物がゲル状の場合について説明する。
<高分子体>
高分子体はモノマーを架橋重合してなり、架橋重合によって得られる網目構造の間に、溶媒であるイオン液体が出入りし、可逆的なゲルの体積変化を伴う。
モノマーと架橋剤の配合比率としては、例えば、モノマーの濃度を７００mmol（ミリモル）/L以上とし、架橋剤をそれに対して数％程度とすることができる。
モノマーの重合を行うため、重合開始剤を用いることができる。重合開始剤としては、例えば光開始剤を用いることができ、反応系に光照射することで重合を進行させることができる。なお、ゲル状の場合、高分子体の重合度は、通常無限大と定義される。1. Gel-like composition The case where the composition which concerns on this invention is a gel form is demonstrated.
<Polymer>
The polymer is formed by crosslinking polymerization of monomers, and an ionic liquid as a solvent enters and exits between the network structure obtained by the crosslinking polymerization, which is accompanied by a reversible gel volume change.
As a blending ratio of the monomer and the cross-linking agent, for example, the monomer concentration can be 700 mmol (mmol) / L or more, and the cross-linking agent can be about several percent of that.
In order to polymerize the monomer, a polymerization initiator can be used. As the polymerization initiator, for example, a photoinitiator can be used, and the polymerization can be advanced by irradiating the reaction system with light. In the case of gel, the degree of polymerization of the polymer is usually defined as infinite.
上記高分子体は、重合するモノマーの種類に応じて以下の４つの種類がある。
（１）高分子体１
高分子体１は、アクリル酸、メタクリル酸、ラクトン、グリコール、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつアリール基、炭素数１以上の直鎖アルキル基、及び炭素数３以上の分枝アルキル基の群から選ばれる１種以上が前記骨格に結合しているモノマー（以下、「第１モノマー、又はモノマーＣ」という）を重合してなる。
第１モノマーは、モノマー中の主鎖（骨格）と側鎖（骨格に結合している部分）のイオン液体への親和性がそれぞれ異なるため、得られた高分子がイオン液体中で相転移を起こして物理的刺激に応答できるようになっている。
上記直鎖アルキル基は炭素数１０以上であることが好ましく、上記分枝アルキル基は炭素数１０以上であることが好ましい。The polymer has the following four types depending on the type of monomer to be polymerized.
(1) Polymer 1
The polymer body 1 has one or more selected from the group of acrylic acid, methacrylic acid, lactone, glycol, and siloxane in the skeleton, and has an aryl group, a linear alkyl group having 1 or more carbon atoms, and 3 carbon atoms. A monomer (hereinafter referred to as “first monomer or monomer C”) in which at least one selected from the group of branched alkyl groups is bonded to the skeleton is polymerized.
The first monomer has a different affinity for the ionic liquid of the main chain (skeleton) and side chain (part bonded to the skeleton) in the monomer, and the resulting polymer undergoes a phase transition in the ionic liquid. Wake up and respond to physical stimuli.
The linear alkyl group preferably has 10 or more carbon atoms, and the branched alkyl group preferably has 10 or more carbon atoms.
第１モノマーとしてメタクリル酸ベンジル、オクタデシルメタクリレート、オクタデシルアクリレート、ε-カプロラクトンの群から選ばれる１種以上を用いることが好ましい。特に、第１モノマーとして、化学式
メタクリル酸ベンジルを用いると、得られたゲルの透明性、屈折率が高くなり、光学材料として好ましい。It is preferable to use at least one selected from the group consisting of benzyl methacrylate, octadecyl methacrylate, octadecyl acrylate, and ε-caprolactone as the first monomer. In particular, as the first monomer, the chemical formula
When benzyl methacrylate is used, transparency and refractive index of the obtained gel are increased, which is preferable as an optical material.
（２）高分子体２
高分子体２は、上記第１モノマーと第２モノマー（又はモノマーＢという）とを共重合してなる。
第２モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ直鎖アルキル基、及び分枝アルキル基の群から選ばれる１種以上が前記骨格に結合しているものである。
第２モノマーとしては、例えば、メタクリル酸メチル、メタクリル酸ブチル、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸−２−エチルヘキシル、エチレングリコール、プロピレングリコール、ジメチルシロキサン、ビニルピロリドンが挙げられる。
高分子体２において、第２モノマーの直鎖アルキル基又は分枝アルキル基の炭素数は、前記第１モノマーの直鎖アルキル基又は分枝アルキル基の炭素数より小さい。例えば、第１モノマーの直鎖アルキル基の炭素数が５の場合、第２モノマーの直鎖アルキル基又は分枝アルキル基の炭素数を４以下とする。(2) Polymer 2
The polymer 2 is formed by copolymerizing the first monomer and the second monomer (or monomer B).
The second monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, vinyl group, and siloxane in the skeleton, and a linear alkyl group and a branched alkyl group One or more selected from the group consisting of these are bonded to the skeleton.
Examples of the second monomer include methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethylene glycol, propylene glycol, dimethylsiloxane, and vinylpyrrolidone.
In the polymer 2, the carbon number of the linear alkyl group or branched alkyl group of the second monomer is smaller than the carbon number of the linear alkyl group or branched alkyl group of the first monomer. For example, when the straight-chain alkyl group of the first monomer has 5 carbon atoms, the straight-chain alkyl group or branched alkyl group of the second monomer has 4 or less carbon atoms.
ここで、第１モノマー及び第２モノマーを架橋剤を用いずに共重合した線形高分子が示す相分離温度は、前記第１モノマーのみを架橋剤を用いずに重合した線形高分子が示す相分離温度より高い。第２モノマーとして第１モノマーより相分離温度温度が高いものを用いることで、これらを共重合した線形高分子の相分離温度を高くすることができ、本発明の物理刺激応答非水系組成物の用途に応じて相分離温度を調整できる。
好ましい第１モノマーとしてメタクリル酸ベンジルが挙げられ、第二モノマーとしてはメタクリル酸メチル(MMA)などの短鎖メタクリル酸エステル類が挙げられるが、溶媒に高い親和性を持つポリマーの構成成分であれば特に限定されない。Here, the phase separation temperature indicated by the linear polymer obtained by copolymerizing the first monomer and the second monomer without using the crosslinking agent is the phase indicated by the linear polymer obtained by polymerizing only the first monomer without using the crosslinking agent. Higher than the separation temperature. By using a monomer having a higher phase separation temperature than the first monomer as the second monomer, the phase separation temperature of the linear polymer copolymerized with these can be increased, and the physical stimulus responsive non-aqueous composition of the present invention can be used. The phase separation temperature can be adjusted according to the application.
A preferred first monomer is benzyl methacrylate, and a second monomer is a short-chain methacrylic acid ester such as methyl methacrylate (MMA). There is no particular limitation.
（３）高分子体３
高分子体３は、上記第１モノマーと第３モノマー（又はモノマーＡという）とを共重合してなる。
第３モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ水素、水酸基、複素環アミンの群から選ばれる１種以上が前記骨格に結合したものであるか、又はビニル基からなる骨格にアリール基が結合したものである。
第３モノマーとしては、例えば、ビニルアルコール、テトラフルオロエチレン、アクリルアミド、メタクリル酸、アクリル酸、４−ビニルピリジン、スチレンが挙げられる。(3) Polymer 3
The polymer 3 is formed by copolymerizing the first monomer and the third monomer (or monomer A).
The third monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, vinyl group, and siloxane in the skeleton, and from the group of hydrogen, hydroxyl group, and heterocyclic amine. One or more selected are bonded to the skeleton, or an aryl group is bonded to a skeleton made of a vinyl group.
Examples of the third monomer include vinyl alcohol, tetrafluoroethylene, acrylamide, methacrylic acid, acrylic acid, 4-vinylpyridine, and styrene.
ここで、第１モノマー及び第３モノマーを架橋剤を用いずに共重合した線形高分子が示す相分離温度は、前記第１モノマーのみを架橋剤を用いずに重合した線形高分子が示す相分離温度より低い。第３モノマーとして第１モノマーより相分離温度が低いものを用いることで、これらを共重合した線形高分子の相分離温度を低くすることができ、本発明の物理刺激応答非水系組成物の用途に応じて相分離温度を調整できる。
好ましい第１モノマーとしてメタクリル酸ベンジルが挙げられ、第三モノマーとしてはスチレン(St)などのアリール基を有するモノマーが挙げられる。第三モノマーとしては溶媒に低い親和性を持つポリマーの構成成分であれば特に限定されない。Here, the phase separation temperature indicated by the linear polymer obtained by copolymerizing the first monomer and the third monomer without using the crosslinking agent is the phase indicated by the linear polymer obtained by polymerizing only the first monomer without using the crosslinking agent. Below the separation temperature. By using the third monomer having a phase separation temperature lower than that of the first monomer, the phase separation temperature of the linear polymer copolymerized with these can be lowered, and the use of the physical stimulus responsive non-aqueous composition of the present invention The phase separation temperature can be adjusted according to the above.
A preferred first monomer is benzyl methacrylate, and a third monomer is a monomer having an aryl group such as styrene (St). The third monomer is not particularly limited as long as it is a constituent component of a polymer having a low affinity for the solvent.
（４）高分子体４
高分子体４は、上記第２モノマーと第３モノマーとを共重合してなる。
この場合、温度に係わらず溶媒（イオン液体）に相溶するポリマーを構成する（イオン液体への親和性の高い）第２モノマーと、温度に係わらず溶媒(イオン液体)と相分離するポリマーを構成する（イオン液体への親和性の低い）第３モノマーとを共重合することにより、高分子中にイオン液体への親和性が異なる部分が生じ、これにより、高分子体１と同様、得られた高分子がイオン液体中で相転移を起こして物理的刺激に応答できるようになっている。
第３モノマー（モノマーＡ）はイオン液体と完全に相分離し、第２モノマー（モノマーＢ）はイオン液体と完全に相溶するため、これらのモノマーを共重合化することで、ゲルとしての適度の特性が得られる。(4) Polymer 4
The polymer body 4 is formed by copolymerizing the second monomer and the third monomer.
In this case, a second monomer (which has a high affinity for the ionic liquid) that is compatible with the solvent (ionic liquid) regardless of the temperature and a polymer that is phase-separated with the solvent (ionic liquid) regardless of the temperature. By copolymerizing the constituent third monomer (having a low affinity for the ionic liquid), a portion having a different affinity for the ionic liquid is generated in the polymer. The obtained polymer undergoes a phase transition in the ionic liquid and can respond to physical stimulation.
The third monomer (monomer A) is completely phase-separated from the ionic liquid, and the second monomer (monomer B) is completely compatible with the ionic liquid. The following characteristics can be obtained.
なお、本発明において、例えば高分子体１は、第１モノマーに規定される範囲のものであれば、複数のモノマーを重合したものも含む。他の高分子体も同様である。 In the present invention, for example, the polymer 1 includes a polymer obtained by polymerizing a plurality of monomers as long as it is within the range defined by the first monomer. The same applies to other polymer bodies.
<線形高分子>
本発明においては、上記モノマーを架橋剤を用いずに重合した線形高分子（モノマーの組合せは、上記高分子体１〜４にそれぞれ対応）を前記イオン液体へ溶解した場合に、物理刺激に応じて当該線形高分子が相分離状態と溶解状態とに可逆的に変化する特性を有する。
つまり、線形高分子がイオン液体と相分離した場合、上記高分子体のイオン液体への親和性が低下し、上記高分子体の網目構造からイオン液体が外部に排出されてゲルが収縮する。一方、線形高分子がイオン液体に溶解した場合、上記高分子体のイオン液体への親和性が向上し、上記高分子体の網目構造にイオン液体が取り込まれてゲルが膨潤する。従って、線形高分子が相分離状態と溶解状態とに可逆的に変化する場合、得られたゲルのイオン液体に対する親和性が物理刺激に応じて変化し、ゲルが可逆的に体積変化する。
線形高分子が相分離状態にあるか、溶解状態にあるかは、線形高分子をイオン液体へ溶解した液の光透過率を測定して判定することができ、線形高分子が相分離状態にあると液が白濁し、線形高分子が溶解状態にあると液が透明になる。<Linear polymer>
In the present invention, when a linear polymer obtained by polymerizing the above monomer without using a crosslinking agent (a combination of monomers corresponds to each of the above polymer 1 to 4) is dissolved in the ionic liquid, it responds to physical stimulation. Thus, the linear polymer has a characteristic of reversibly changing between a phase-separated state and a dissolved state.
That is, when the linear polymer is phase-separated from the ionic liquid, the affinity of the polymer to the ionic liquid is reduced, the ionic liquid is discharged from the network structure of the polymer, and the gel contracts. On the other hand, when the linear polymer is dissolved in the ionic liquid, the affinity of the polymer to the ionic liquid is improved, and the ionic liquid is taken into the network structure of the polymer to swell the gel. Therefore, when the linear polymer changes reversibly between a phase-separated state and a dissolved state, the affinity of the obtained gel for the ionic liquid changes according to physical stimulation, and the gel reversibly changes its volume.
Whether the linear polymer is in a phase-separated state or a dissolved state can be determined by measuring the light transmittance of a solution in which the linear polymer is dissolved in an ionic liquid. When there is, the liquid becomes cloudy, and when the linear polymer is in a dissolved state, the liquid becomes transparent.
<物理刺激>
本発明のゲルに与える物理刺激としては、温度、光、電磁波等が挙げられる。例えば、物理刺激を温度とした場合、温度上昇とともにゲルが収縮する場合と、ゲルが膨潤する場合とがある。上記したメタクリル酸ベンジルをモノマーに用いる場合、温度上昇とともにゲルが収縮する。又、上記したオクタデシルメタクリレート、オクタデシルアクリレート、ε-カプロラクトンの群から選ばれる１種以上を用いる場合、温度上昇とともにゲルが膨潤する。<Physical stimulation>
Examples of the physical stimulus applied to the gel of the present invention include temperature, light, and electromagnetic waves. For example, when the physical stimulus is temperature, there are cases where the gel contracts with increasing temperature and where the gel swells. When the above-mentioned benzyl methacrylate is used as a monomer, the gel shrinks with increasing temperature. Moreover, when using 1 or more types chosen from the group of the above-mentioned octadecyl methacrylate, octadecyl acrylate, and (epsilon) -caprolactone, a gel swells with a temperature rise.
<イオン液体>
イオン液体（イオン性液体）は、イオンのみから構成され、液体でありながら蒸気圧がなく（不揮発性）、耐熱性が高く、不燃性、不揮発性を有する。本発明において、イオン液体の融点は好ましくは１００℃以下、より好ましくは室温以下とする。<Ionic liquid>
An ionic liquid (ionic liquid) is composed only of ions, is a liquid, has no vapor pressure (nonvolatile), has high heat resistance, has nonflammability, and nonvolatility. In the present invention, the melting point of the ionic liquid is preferably 100 ° C. or lower, more preferably room temperature or lower.
イオン液体の極性パラメータＥＴ（30）が４８．２〜５２．４であることが好ましい。イオン液体はイオン伝導体であるため誘電損失が大きく、誘電率を見積もることが困難である。そこで、ソルバトクロミズムを利用した溶媒の極性パラメータＥＴ（30）をイオン液体の指標とすることが好ましい。
ここで、ＥＴ（30）が４８．２未満であるイオン液体や、ＥＴ（30）が５２．４を超えるイオン液体は入手し難いので、上記範囲とした。It is preferred polar parameter E T of the ionic liquid (30) is from 48.2 to 52.4. Since the ionic liquid is an ionic conductor, the dielectric loss is large and it is difficult to estimate the dielectric constant. Therefore, it is preferable that the polarity parameter E T (30) of the solvent using solvatochromism is used as an index of the ionic liquid.
Here, an ionic liquid having an E T (30) of less than 48.2 and an ionic liquid having an E T (30) of more than 52.4 are difficult to obtain, and thus are in the above range.
ＥＴ（30）は、化学式
ＥＴ（30）＝28591／λmax （１）
から計算することができる。ＥＴ（30）と、その溶媒のルイス酸性を定量化した値（アクセプターナンバー）との間に非常によい相関が見られるので、ＥＴ（30）はイオン液体のルイス酸性を表すと考えられる。E T (30) is the chemical formula
E T (30) = 28591 / λmax (1)
Can be calculated from Since there is a very good correlation between E T (30) and the quantified value (acceptor number) of the Lewis acidity of the solvent, E T (30) is considered to represent the Lewis acidity of the ionic liquid. It is done.
イオン液体としては、特に制限されないが、例えばカチオンとしてアンモニウム構造、イミダゾリウム構造、ピリジニウム構造、ピロリジニウム構造、スルフォニウム構造、ホスフォニウム構造等を用いることができ、アニオンとしてスルフォンイミド構造、ホスフェート構造（ヘキサフルオロホスフェート等）、ボレート構造（テトラフルオロボレート）、トリフルオロ酢酸、トリフルオロ硫酸、酢酸、ハロゲン系アニオン（Ｃｌ，Ｂｒ，Ｉ）、クロロアルミナート、チオシアネート等を用いることができる。具体的には、
化学式
なお、ＥＴ（30）の値から、EMITFSIのルイス酸性は非水系極性溶媒であるDMSOやDMFよりも高く、アルコール類と同程度であると考えられる。Although it does not restrict | limit especially as an ionic liquid, For example, an ammonium structure, an imidazolium structure, a pyridinium structure, a pyrrolidinium structure, a sulfonium structure, a phosphonium structure etc. can be used as a cation, and a sulfonimide structure, a phosphate structure (hexafluorophosphate) is used as an anion. Etc.), borate structure (tetrafluoroborate), trifluoroacetic acid, trifluorosulfuric acid, acetic acid, halogen-based anions (Cl, Br, I), chloroaluminate, thiocyanate, and the like. In particular,
Chemical formula
From the value of E T (30), the Lewis acidity of EMITFSI is higher than DMSO and DMF, which are non-aqueous polar solvents, and is considered to be comparable to alcohols.
本発明のゲルは、温度等の物理刺激によって可逆的に体積変化を生じさせることができるので、例えば光学材料、表示素子、各種センサー、アクチュエータ、ＤＤＳ等に用いることができる。 Since the gel of the present invention can reversibly change its volume by physical stimulation such as temperature, it can be used for optical materials, display elements, various sensors, actuators, DDS, and the like.
<ゲルの製造>
本発明のゲルは、例えば、イオン液体中に上記モノマーを分散させた状態で、モノマーを架橋重合することにより、イオン液体を内部に取り込んだ高分子体を得ることができる。
特に、イオン液体の粘性率が水より数１０倍高い場合（例えば、EMITFSIを用いた場合）、ゲル網目の共同拡散係数が低下し、平衡到達時間が大幅に遅延する問題がある。そのため、微粒子ゲルを用いることが好ましい。<Manufacture of gel>
In the gel of the present invention, for example, a polymer having the ionic liquid incorporated therein can be obtained by crosslinking polymerization of the monomer in a state where the monomer is dispersed in the ionic liquid.
In particular, when the viscosity of the ionic liquid is several tens of times higher than that of water (for example, when EMITFSI is used), there is a problem that the co-diffusion coefficient of the gel network is lowered and the time to reach equilibrium is significantly delayed. Therefore, it is preferable to use a fine particle gel.
微粒子ゲルは、例えば、直径10μｍ程度の球状の細孔を有するマクロポーラスポリスチレンを鋳型とし、モノマー、イオン液体、架橋剤、及び必要に応じて重合開始剤を含有する溶液に上記鋳型を浸漬し、細孔内でモノマーを重合させることで製造することができる。その後、トルエンに鋳型を浸漬して鋳型を溶解し、球状の微粒子ゲルを得る。微粒子ゲルをエタノール及び純水で洗浄後、凍結乾燥し、イオン液体に微粒子ゲルを浸漬して減圧加熱することにより、ゲルを製造することができる。 The fine particle gel is, for example, a macroporous polystyrene having spherical pores with a diameter of about 10 μm as a template, and the template is immersed in a solution containing a monomer, an ionic liquid, a crosslinking agent, and, if necessary, a polymerization initiator, It can be produced by polymerizing monomers in the pores. Thereafter, the mold is immersed in toluene to dissolve the mold to obtain a spherical fine particle gel. The fine particle gel is washed with ethanol and pure water, freeze-dried, and the gel can be produced by immersing the fine particle gel in an ionic liquid and heating under reduced pressure.
上記した方法を用いてもよいが、懸濁重合によってゲルを製造することが好ましい。この方法は、強攪拌した水相に、モノマー、イオン液体、架橋剤、及び必要に応じて重合開始剤を含有する分散相を滴下し、高分子体の架橋重合を進行させ、微粒子ゲルを製造する。イオン液体を含むゲルは水より比重が大きいため、反応終了後の液からゲルを回収するのが容易である。通常、微粒子ゲルの粒径は数μｍ〜数１００μｍ程度である。微粒子ゲルは、表面積が大きく、物理刺激に対する応答が速いという利点がある。又、懸濁重合の場合、上記したマイクロポーラスポリスチレンによる鋳型が不要であり、生産性、コストの点でも好ましい。 Although the method described above may be used, it is preferable to produce a gel by suspension polymerization. In this method, a dispersed phase containing a monomer, an ionic liquid, a crosslinking agent and, if necessary, a polymerization initiator is added dropwise to a strongly stirred aqueous phase to proceed with the crosslinking polymerization of the polymer to produce a fine particle gel. To do. Since the gel containing the ionic liquid has a specific gravity greater than that of water, it is easy to recover the gel from the liquid after completion of the reaction. Usually, the particle size of the fine particle gel is about several μm to several 100 μm. The fine particle gel has the advantages of a large surface area and a quick response to physical stimulation. In the case of suspension polymerization, the above-described template using microporous polystyrene is unnecessary, which is preferable in terms of productivity and cost.
重合開始剤としては、例えば光開始剤を用いることができ、上記分散相を滴下後、反応系に光照射することで重合を進行させることができる。
得られた微粒子ゲルをイオン液体中に分散させ、減圧下で静置して高分子体の再膨潤と乾燥を行い、最終形態とすることができる。As the polymerization initiator, for example, a photoinitiator can be used, and the polymerization can be advanced by irradiating the reaction system with light after dropping the dispersed phase.
The obtained fine particle gel can be dispersed in an ionic liquid and allowed to stand under reduced pressure to re-swell and dry the polymer to obtain a final form.
２．溶液状組成物
次に、本発明に係る組成物が溶液の場合について説明する。溶液状組成物の場合、モノマーを架橋剤を用いずに重合すること以外は、上記したゲル状組成物の場合とまったく同様である。溶液状組成物に用いるモノマー、重合開始剤、イオン液体としては、上記ゲル状組成物に用いるものを例示できる。溶液状組成物の製造方法も、上記したゲルの製造において架橋剤を配合しないこと以外は、上記したゲル状組成物の場合とまったく同様である。
なお、溶液状組成物における高分子体は、上記線形高分子と同一物である。2. Next, the case where the composition according to the present invention is a solution will be described. In the case of a solution-like composition, it is exactly the same as the case of the gel-like composition described above, except that the monomer is polymerized without using a crosslinking agent. Examples of the monomer, polymerization initiator, and ionic liquid used in the solution composition include those used in the gel composition. The method for producing the solution-like composition is exactly the same as that for the gel-like composition described above, except that no crosslinking agent is blended in the production of the gel.
The polymer in the solution composition is the same as the linear polymer.
上記溶液状組成物に物理刺激を与えると、線形高分子が相分離状態と溶解状態との間で可逆的に変化する。線形高分子が相分離状態にあると液が白濁し、線形高分子が溶解状態にあると液が透明になる。物理刺激としては、温度、光、電磁波等が挙げられる。例えば、物理刺激を温度とした場合、温度上昇とともに溶液が白濁する場合と、溶液が透明になる場合とがある。 When a physical stimulus is applied to the solution-like composition, the linear polymer changes reversibly between a phase-separated state and a dissolved state. When the linear polymer is in a phase-separated state, the liquid becomes cloudy, and when the linear polymer is in a dissolved state, the liquid becomes transparent. Examples of physical stimuli include temperature, light, and electromagnetic waves. For example, when the physical stimulus is temperature, the solution may become cloudy as the temperature rises, and the solution may become transparent.
本発明の溶液状組成物は、温度等の物理刺激によって可逆的に液の透過率を変化させることができるので、例えば光学材料、表示素子、各種センサー、アクチュエータ、ＤＤＳ等に用いることができる。
例えば、上記溶液状組成物を透明な二枚の基板間に封入し、熱を帯びたペンで、基板上に刺激を与えると、加熱部分の溶液状組成物の透過率が周囲と変化し、文字が表示されるリライタブルペーパーを製造することができる。上記溶液状組成物は、水系組成物と異なり不揮発性であるので、二枚の基板間のシーリングが簡易的でも溶媒が揮発せず、性能劣化しないという利点がある。Since the solution-like composition of the present invention can reversibly change the liquid transmittance by physical stimulation such as temperature, it can be used for optical materials, display elements, various sensors, actuators, DDS, and the like.
For example, when the solution-like composition is sealed between two transparent substrates and a stimulus is given on the substrate with a heated pen, the transmittance of the solution-like composition in the heated portion changes from the surroundings, Rewritable paper on which characters are displayed can be manufactured. Since the solution composition is non-volatile unlike the aqueous composition, there is an advantage that the solvent does not volatilize and the performance does not deteriorate even if the sealing between the two substrates is simple.
上記したゲル及び溶液状組成物を、所定の固体表面に固定化し、上記物理刺激に応答する基板を製造することもできる。固定化の方法としては、例えば、ガラス表面上の水酸基をシランカップリング剤（例えば、クロロジメチルビニルシラン）によりビニル基に変換し、このガラス基板上でイオン液体に溶解させたモノマーをラジカル重合する事によって化学的にゲルを表面に固定することができる。 The above-described gel and solution composition can be immobilized on a predetermined solid surface to produce a substrate that responds to the physical stimulus. As the immobilization method, for example, a hydroxyl group on the glass surface is converted into a vinyl group by a silane coupling agent (for example, chlorodimethylvinylsilane), and a monomer dissolved in an ionic liquid is radically polymerized on the glass substrate. Can chemically fix the gel to the surface.
以下に、実施例によって本発明を更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、特に断らない限り、％は質量％を示す。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In addition, unless otherwise indicated,% shows the mass%.
１．メタクリル酸ベンジル系ゲル及びメタクリル酸ベンジル系線形高分子
<イオン液体（EMITFSI）の調製>
Cl-メチルイミダゾールと臭化エチルとの４級化反応を生じさせ、１−エチル−３−メチルイミダゾリウム−Br（EMIBr）を得た。得られたEMIBrをLiTFSI（Li-トリフルオロメタンスルフォン）イミド（Li（CF3SO2）2N）とアニオン交換反応させ、EMITFSIを調製した。1. Benzyl methacrylate gel and benzyl methacrylate linear polymer
<Preparation of ionic liquid (EMITFSI)>
Cl - cause quaternization reaction of methylimidazole and ethyl bromide, 1-ethyl-3-methyl imidazolium -Br (EMIBr). The obtained EMIBr was subjected to an anion exchange reaction with LiTFSI (Li-trifluoromethanesulfone) imide (Li (CF 3 SO 2 ) 2 N) to prepare EMITFSI.
<ゲルの製造>
モノマー（メタクリル酸ベンジル）0.23ｇ、イオン液体（EMITFSI）1.25ｍＬ、架橋剤（ジメタクリル酸−エチレングリコール）11〜22ｍｇ、光開始剤（ジエトキシアセトフェノン）11ｍｇを混合して分散相とした。
イオン交換水50ｍＬに、分散安定剤（ノニオン系界面活性剤、花王社製の商品名エマルゲン）0.5ｇを分散させ、水相とした。
窒素雰囲気下、反応容器に入れた水相をマグネチックスターラで強攪拌しながら、分散相を滴下し、反応系に光を２０分間照射してモノマーを重合させた。
反応終了後、反応系を濾過し、濾過物を純粋で洗浄して微粒子ゲルを得た。得られた微粒子ゲルをEMITFSI中に分散させ、60℃で減圧下、24時間静置して高分子体の再膨潤と乾燥を行い、最終形態のゲルを得た。<Manufacture of gel>
Monomer (benzyl methacrylate) 0.23 g, ionic liquid (EMITFSI) 1.25 mL, crosslinking agent (dimethacrylic acid-ethylene glycol) 11-22 mg, and photoinitiator (diethoxyacetophenone) 11 mg were mixed to obtain a dispersed phase.
In 50 mL of ion-exchanged water, 0.5 g of a dispersion stabilizer (nonionic surfactant, trade name Emulgen manufactured by Kao Corporation) was dispersed to obtain an aqueous phase.
Under a nitrogen atmosphere, while the aqueous phase placed in the reaction vessel was vigorously stirred with a magnetic stirrer, the dispersed phase was dropped, and the reaction system was irradiated with light for 20 minutes to polymerize the monomer.
After completion of the reaction, the reaction system was filtered, and the filtrate was washed with pure to obtain a fine particle gel. The obtained fine particle gel was dispersed in EMITFSI, and left to stand at 60 ° C. under reduced pressure for 24 hours to re-swell and dry the polymer, thereby obtaining a final gel.
<線形高分子の製造>
エタノール溶媒中に、モノマー（メタクリル酸ベンジル）２mol/L、重合開始剤（AlBN）１mol%を溶解し、窒素バブルを２０分行った後、熱重合を２４時間行った。架橋剤は用いなかった。反応溶液を透析して線形高分子を精製した。
メタクリル酸ベンジルは以下の方法で重合した。まず、ベンゼン溶媒中にモノマー（メタクリル酸ベンジル、あるいはメタクリル酸ベンジルと、その共重合モノマー）の合計2mol/L、重合開始剤（2,2-ジエトキシアセトフェノン）1mol%を溶解し、窒素バブリングを20分行った後、光重合を30分行った。架橋剤は用いなかった。反応物に対し、ベンゼンを良溶媒、ヘキサンを貧溶媒とする再沈殿を行い、線形高分子を精製した。<Production of linear polymer>
In an ethanol solvent, 2 mol / L of a monomer (benzyl methacrylate) and 1 mol% of a polymerization initiator (AlBN) were dissolved, a nitrogen bubble was performed for 20 minutes, and then thermal polymerization was performed for 24 hours. No crosslinker was used. The reaction solution was dialyzed to purify the linear polymer.
Benzyl methacrylate was polymerized by the following method. First, a total of 2 mol / L of monomers (benzyl methacrylate or benzyl methacrylate and its copolymer monomers) and 1 mol% of a polymerization initiator (2,2-diethoxyacetophenone) are dissolved in a benzene solvent, and nitrogen bubbling is performed. After 20 minutes, photopolymerization was performed for 30 minutes. No crosslinker was used. The reaction product was re-precipitated using benzene as a good solvent and hexane as a poor solvent to purify the linear polymer.
<評価>
（１）線形高分子の溶解特性
上記した線形高分子をEMITFSI中に３％溶解させ、溶液の透過率を測定した。透過率の測定は、照射、及び透過光の検出に光ファイバーを用い、500ｎｍの波長光の透過率を分光光度計により測定した。
得られた結果を図１に示す。約105℃以下の温度では、溶液は透明（光透過率の値がほぼ１００％）であったが、約105℃以下を超えた近傍で溶液が白濁（光透過率の値がほぼ０％）した。これより、高温側で、線形高分子が相分離状態に変化することがわかった。なお、光透過率の変化率が最大となる温度を相溶・相分離温度（図１の例では約105℃）とした。
（２）ゲルの体積変化
上記したゲルをEMITFSI中に１ｍｏｌ／Ｌ含む溶液（微粒子ゲルが１ｗｔ％程度イオン液体中に分散したもの）を調製し、温度を変化させた時のゲルの膨潤度を求めた。膨潤度は、100℃におけるゲル状物質の体積Ｄ０を基準とした。ゲルの膨潤度は、450℃まで温度調節可能な顕微鏡用のホットステージ上に上記ゲル状物質を置き、各温度における微粒子ゲルの直径を倒立型顕微鏡にて測定した。
得られた結果を図２に示す。約80℃以下の温度ではゲルが膨潤し、約80℃でゲルが急激に収縮した。なお、高分子体の架橋密度を４％とした場合、約80℃近傍で、ゲルの体積は約２．５倍の変化を示した。なお、図２の架橋密度は、総モノマー濃度に対して、重合時に仕込んだ架橋剤物質のモル％を表す。<Evaluation>
(1) Dissolution characteristics of linear polymer 3% of the above-mentioned linear polymer was dissolved in EMITFSI, and the transmittance of the solution was measured. The transmittance was measured using an optical fiber for irradiation and detection of transmitted light, and the transmittance of light having a wavelength of 500 nm was measured with a spectrophotometer.
The obtained results are shown in FIG. At a temperature of about 105 ° C or lower, the solution was transparent (light transmittance value was almost 100%), but the solution became cloudy at a temperature exceeding about 105 ° C or lower (light transmittance value was almost 0%). did. From this, it was found that the linear polymer changes to a phase separation state on the high temperature side. Note that the temperature at which the rate of change in light transmittance is maximized was set to the compatibility / phase separation temperature (about 105 ° C. in the example of FIG. 1).
(2) Gel volume change Prepare a solution containing 1 mol / L of the above gel in EMITFSI (fine particle gel dispersed in about 1 wt% in ionic liquid), and determine the degree of gel swelling when the temperature is changed. Asked. The degree of swelling was based on the volume D 0 of the gel material at 100 ° C. The degree of swelling of the gel was determined by placing the gel substance on a microscope hot stage capable of adjusting the temperature to 450 ° C., and measuring the diameter of the fine particle gel at each temperature with an inverted microscope.
The obtained results are shown in FIG. The gel swelled at a temperature of about 80 ° C. or lower, and the gel contracted rapidly at about 80 ° C. When the cross-linking density of the polymer was 4%, the gel volume changed about 2.5 times around about 80 ° C. The cross-linking density in FIG. 2 represents the mol% of the cross-linking agent material charged during the polymerization with respect to the total monomer concentration.
２．メタクリル酸ベンジル−他のモノマーからなる線形高分子
<線形高分子の製造>
（１）メタクリル酸ベンジル−スチレン系線形高分子
ベンゼン溶媒中に、メタクリル酸ベンジル３．４９ｇ（総モノマー濃度に対して99mol%）と、スチレン０．０２１ｇ(総モノマー濃度に対して1mol%)を添加し、これらの総モノマー濃度が2mol/Lになるようにした。窒素バブルを20分行った後、重合開始剤（2,2-ジエトキシアセトフェノン）をモノマーに対して1mol%溶解し、光重合を30分行った。架橋剤は用いなかった。ベンゼンを良溶媒、ヘキサンを貧溶媒とする再沈殿を行い、線形高分子（Ｓｔ１％）を精製した。
又、メタクリル酸ベンジルの配合量を３．３５ｇ（総モノマー濃度に対して95mol%）に変え、スチレンの配合量を０．１０４ｇ（総モノマー濃度に対して5mol%）に変え、同様に線形高分子（Ｓｔ５％）を精製した。
（２）メタクリル酸ベンジル−ＭＭＡ系線形高分子
スチレンの代わりにＭＭＡ（メタクリル酸メチル）を用いたこと以外は上記メタクリル酸ベンジル−スチレン系線形高分子の場合と同様にして、線形高分子（ＭＭＡ５％及び１０％）を精製した。
ＭＭＡ５％の高分子は、メタクリル酸ベンジル３．３５ｇ（総モノマー濃度に対して95mol%）と、メタクリル酸メチル０．１ｇ(総モノマー濃度に対して５mol%)を配合した。ＭＭＡ１０％の高分子は、メタクリル酸ベンジル３．２３ｇ（総モノマー濃度に対して９０mol%）と、メタクリル酸メチル０．２ｇ（総モノマー濃度に対して１０mol%）を配合した。2. Benzyl methacrylate-linear polymer composed of other monomers
<Production of linear polymer>
(1) Benzyl methacrylate-styrene linear polymer In a benzene solvent, 3.49 g of benzyl methacrylate (99 mol% with respect to the total monomer concentration) and 0.021 g of styrene (1 mol% with respect to the total monomer concentration). They were added so that the total monomer concentration was 2 mol / L. After performing nitrogen bubble for 20 minutes, 1 mol% of a polymerization initiator (2,2-diethoxyacetophenone) was dissolved in the monomer, and photopolymerization was performed for 30 minutes. No crosslinker was used. Reprecipitation using benzene as a good solvent and hexane as a poor solvent was performed to purify the linear polymer (St 1%).
In addition, the amount of benzyl methacrylate was changed to 3.35 g (95 mol% with respect to the total monomer concentration), and the amount of styrene was changed to 0.104 g (5 mol% with respect to the total monomer concentration). The molecule (St 5%) was purified.
(2) Benzyl methacrylate-MMA linear polymer In the same manner as in the above benzyl methacrylate-styrene linear polymer except that MMA (methyl methacrylate) was used instead of styrene, linear polymer (MMA5 % And 10%).
The polymer of MMA 5% was blended with 3.35 g of benzyl methacrylate (95 mol% with respect to the total monomer concentration) and 0.1 g of methyl methacrylate (5 mol% with respect to the total monomer concentration). The polymer of MMA 10% was blended with 3.23 g of benzyl methacrylate (90 mol% with respect to the total monomer concentration) and 0.2 g of methyl methacrylate (10 mol% with respect to the total monomer concentration).
<線形高分子の溶解特性>
上記した線形高分子の溶解特性を実施例１とまったく同様にして測定した。得られた結果を図３に示す。第２モノマーとしてスチレンを用いた場合をSt、メタクリル酸メチルを用いた場合をMMAで表す。図３の５本の線のうち、真ん中の線は図１の高分子（第２モノマーを含まない）に対応する。Stを配合した高分子の場合、線形高分子の相溶・相分離温度が、実施例１の場合に比べて低下した。一方、MMAを配合した高分子の場合、線形高分子の相溶・相分離温度が、実施例１の場合に比べて上昇した。
なお、線形高分子の相溶・相分離温度と、そのモノマーを架橋重合したゲルが収縮（膨潤）する温度は対応関係にあるため、St又はMMAとの共重合によって、ゲルの体積変化温度が調整可能と考えられる。なお、図３の「St 1%」は、「スチレン1mol%」を意味する。<Dissolution characteristics of linear polymer>
The dissolution characteristics of the linear polymer described above were measured in the same manner as in Example 1. The obtained results are shown in FIG. The case where styrene is used as the second monomer is represented by St, and the case where methyl methacrylate is used is represented by MMA. Among the five lines in FIG. 3, the middle line corresponds to the polymer in FIG. 1 (not including the second monomer). In the case of the polymer containing St, the solubility / phase separation temperature of the linear polymer was lower than that in Example 1. On the other hand, in the case of the polymer blended with MMA, the solubility / phase separation temperature of the linear polymer increased as compared with the case of Example 1.
Note that the compatibility / phase separation temperature of the linear polymer and the temperature at which the gel obtained by crosslinking polymerization of the monomer shrinks (swells) has a corresponding relationship, so that the volume change temperature of the gel is increased by copolymerization with St or MMA. It is considered adjustable. In addition, “St 1%” in FIG. 3 means “styrene 1 mol%”.
各種モノマーからなる線形高分子の溶解特性
<線形高分子の製造>
表１に示すモノマーが架橋剤を用いずに重合された線形高分子としては、市販されている線形高分子を用いた。Dissolution characteristics of linear polymers composed of various monomers
<Production of linear polymer>
As the linear polymer obtained by polymerizing the monomers shown in Table 1 without using a crosslinking agent, a commercially available linear polymer was used.
<評価>
上記した線形高分子をEMITFSI中に５％溶解させ、実施例１とまったく同様にして、溶液の光透過率を測定した。温度にかかわらず光透過率の値がほぼ１００％の場合、線形高分子がイオン液体に完全に相溶したとみなした。温度にかかわらず光透過率の値がほぼ０％の場合、線形高分子がイオン液体と完全に相分離したとみなした。
又、所定の温度Ｔ以下で光透過率の値がほぼ０％となり、この温度Ｔより高温側で光透過率の値がほぼ１００％の場合、線形高分子が温度Ｔ以下ではイオン液体と相分離し、温度Ｔ以上でイオン液体に相溶したとみなした。<Evaluation>
The above linear polymer was dissolved in EMITFSI at 5%, and the light transmittance of the solution was measured in the same manner as in Example 1. When the light transmittance value was almost 100% regardless of the temperature, it was considered that the linear polymer was completely compatible with the ionic liquid. When the light transmittance value was almost 0% regardless of the temperature, it was considered that the linear polymer was completely phase-separated from the ionic liquid.
Further, when the light transmittance is almost 0% below a predetermined temperature T, and the light transmittance is almost 100% above the temperature T, the linear polymer is in phase with the ionic liquid below the temperature T. Separated and considered to be compatible with the ionic liquid above temperature T.
得られた結果を表１に示す。 The obtained results are shown in Table 1.
表１から明らかなように、モノマーＡの場合、イオン液体と完全に相分離し、モノマーＢの場合、イオン液体と完全に相溶した。又、モノマーＣの場合、線形高分子がある温度以下ではイオン液体と相分離し、その温度以上でイオン液体に相溶した。 As is clear from Table 1, the monomer A was completely phase-separated from the ionic liquid, and the monomer B was completely compatible with the ionic liquid. In the case of monomer C, the linear polymer was phase-separated from the ionic liquid at a certain temperature or lower, and was dissolved in the ionic liquid at the temperature or higher.
第２モノマー（メタクリル酸メチル(MMA)）と第３モノマー（スチレン(St)）からなる線形高分子
ベンゼン溶媒中に、StとMMAの総モノマー濃度が2 mol/Lになるように適当量溶解させた。StとMMAの共重合組成比は仕込みモノマー量を変化させることで変えた。このモノマー溶液に重合開始剤(アゾイソブチロニトリル)を、総モノマー濃度に対して1mol%になるように溶解させ、窒素バブルを20分間行なった後、60℃で12時間重合させた。架橋剤は用いなかった。重合後、トルエンを良溶媒、ヘキサンを貧溶媒とする再沈殿を三回行うことによって精製を行なった。Linear polymer consisting of second monomer (methyl methacrylate (MMA)) and third monomer (styrene (St)) Dissolved in appropriate amount in benzene solvent so that total monomer concentration of St and MMA is 2 mol / L I let you. The copolymer composition ratio of St and MMA was changed by changing the amount of charged monomers. In this monomer solution, a polymerization initiator (azoisobutyronitrile) was dissolved so as to be 1 mol% with respect to the total monomer concentration, and after bubbling with nitrogen for 20 minutes, polymerization was carried out at 60 ° C. for 12 hours. No crosslinker was used. After the polymerization, purification was performed by performing reprecipitation three times using toluene as a good solvent and hexane as a poor solvent.
上記した線形高分子の溶解特性を実施例１とまったく同様にして測定した。得られた結果を図４に示す。完全相分離するスチレンの割合が多くなると（図の白丸）、線形高分子の相分離温度も低くなった。 The dissolution characteristics of the linear polymer described above were measured in the same manner as in Example 1. The obtained results are shown in FIG. As the proportion of styrene that undergoes complete phase separation increased (white circle in the figure), the phase separation temperature of the linear polymer also decreased.
Claims (7)
前記第１モノマーは、アクリル酸、メタクリル酸、ラクトン、グリコール、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつアリール基、炭素数１以上の直鎖アルキル基、及び炭素数３以上の分枝アルキル基の群から選ばれる１種以上が前記骨格に結合している物理刺激応答非水系組成物。When a linear polymer obtained by polymerizing the first monomer and polymerizing the first monomer without using a cross-linking agent is dissolved in the ionic liquid, the polymer is formed according to a physical stimulus. A physical stimulus-responsive non-aqueous composition in which a linear polymer reversibly changes between a phase-separated state and a dissolved state,
The first monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, lactone, glycol, and siloxane in the skeleton, and has an aryl group, a linear alkyl group having 1 or more carbon atoms, and a carbon number of 3 A physical stimulus responsive non-aqueous composition in which one or more selected from the group of branched alkyl groups is bonded to the skeleton.
前記第１モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつアリール基、炭素数１以上の直鎖アルキル基、及び炭素数３以上の分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、
前記第２モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ直鎖アルキル基、及び分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、
前記第２モノマーの直鎖アルキル基又は分枝アルキル基の炭素数は、前記第１モノマーの直鎖アルキル基又は分枝アルキル基の炭素数より小さく、
前記第１モノマー及び第２モノマーを架橋剤を用いずに共重合した線形高分子が示す相分離温度は、前記第１モノマーのみを架橋剤を用いずに重合した線形高分子が示す相分離温度より高い、物理刺激応答非水系組成物。A linear polymer obtained by polymerizing the first monomer and the second monomer without using a cross-linking agent includes a polymer obtained by copolymerizing the first monomer and the second monomer and an ionic liquid. When dissolved, a physical stimulus responsive non-aqueous composition in which the linear polymer reversibly changes between a phase-separated state and a dissolved state in response to a physical stimulus,
The first monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, and siloxane in the skeleton, and has an aryl group and a linear alkyl group having 1 or more carbon atoms. And one or more selected from the group of branched alkyl groups having 3 or more carbon atoms are bonded to the skeleton,
The second monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, vinyl group, and siloxane in the skeleton, and a linear alkyl group and a branched alkyl group One or more selected from the group of groups are bonded to the skeleton,
The carbon number of the linear alkyl group or branched alkyl group of the second monomer is smaller than the carbon number of the linear alkyl group or branched alkyl group of the first monomer,
The phase separation temperature indicated by the linear polymer obtained by copolymerizing the first monomer and the second monomer without using a crosslinking agent is the phase separation temperature indicated by the linear polymer obtained by polymerizing only the first monomer without using a crosslinking agent. Higher, physical stimulus responsive non-aqueous composition.
前記第１モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつアリール基、炭素数１以上の直鎖アルキル基、及び炭素数３以上の分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、
前記第３モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ水素、水酸基、複素環アミンの群から選ばれる１種以上が前記骨格に結合したものであるか、又はビニル基からなる骨格にアリール基が結合したものであり、
前記第１モノマー及び第３モノマーを架橋剤を用いずに共重合した線形高分子が示す相分離温度は、前記第１モノマーのみを架橋剤を用いずに重合した線形高分子が示す相分離温度より低い、物理刺激応答非水系組成物。A linear polymer obtained by polymerizing the first monomer and the third monomer without using a cross-linking agent includes a polymer obtained by copolymerizing the first monomer and the third monomer and an ionic liquid. When dissolved, a physical stimulus responsive non-aqueous composition in which the linear polymer reversibly changes between a phase-separated state and a dissolved state in response to a physical stimulus,
The first monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, and siloxane in the skeleton, and has an aryl group and a linear alkyl group having 1 or more carbon atoms. And one or more selected from the group of branched alkyl groups having 3 or more carbon atoms are bonded to the skeleton,
The third monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, vinyl group, and siloxane in the skeleton, and a group of hydrogen, hydroxyl group, and heterocyclic amine One or more selected from is bonded to the skeleton, or an aryl group is bonded to a skeleton composed of a vinyl group,
The phase separation temperature indicated by the linear polymer obtained by copolymerizing the first monomer and the third monomer without using a crosslinking agent is the phase separation temperature indicated by the linear polymer obtained by polymerizing only the first monomer without using a crosslinking agent. A lower, physical stimulus responsive non-aqueous composition.
前記第２モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ直鎖アルキル基、及び分枝アルキル基の群から選ばれる１種以上が前記骨格に結合していて、
前記第３モノマーは、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ラクトン、グリコール、ビニル基、及びシロキサンの群から選ばれる１種以上を骨格に有し、かつ水素、水酸基、複素環アミンの群から選ばれる１種以上が前記骨格に結合したものであるか、又はビニル基からなる骨格にアリール基が結合したものである、物理刺激応答非水系組成物。A linear polymer obtained by polymerizing the second monomer and the third monomer without using a cross-linking agent includes a polymer obtained by copolymerizing the second monomer and the third monomer and an ionic liquid. When dissolved, a physical stimulus responsive non-aqueous composition in which the linear polymer reversibly changes between a phase-separated state and a dissolved state in response to a physical stimulus,
The second monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, vinyl group, and siloxane in the skeleton, and a linear alkyl group and a branched alkyl group One or more selected from the group of groups are bonded to the skeleton,
The third monomer has at least one selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, lactone, glycol, vinyl group, and siloxane in the skeleton, and a group of hydrogen, hydroxyl group, and heterocyclic amine A physical stimulus responsive non-aqueous composition in which one or more selected from the above are bonded to the skeleton, or an aryl group is bonded to a skeleton made of a vinyl group.
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