JP3660941B2 - Degradable polymer compound - Google Patents

Description

〔式中、Ｘ及びＹは水素原子又は保護されていてもよい水酸基を表し、Ｘが水素原子のときＹは前記水酸基を示し、Ｙが水素原子のときＸは前記水酸基を示し、ｍは１〜４、ｎは５〜５０００を示す。〕
【０００６】
本発明の高分子化合物は、上記式（Ｉ）で示される共重合体構造のみからなる重合体であるポリスルホンであってもよく、また、上記式（Ｉ）で示される共重合体構造を含む重合体（IA）：
【化３】

（式中、Ａは共重合可能なモノマーを示し、ａ及びｂは任意の整数を示す。）
であってもよい。ａ及びｂは、使用するモノマーＡによって異なり、また、得られる重合体に要求される分解度に応じて選択される。
上記において、共重合可能なモノマーとしては、スチレン、ジビニルベンゼン、（メタ）アクリル酸、（メタ）アクリル酸エステル、酢酸ビニル等のビニル系モノマーが好ましい。
一般式（Ｉ）において、ｍは好ましくは１〜２、より好ましくは１であり、ｎは好ましくは５〜２０００、より好ましくは５〜１０００である。
【０００７】
以下に、本発明の高分子化合物（以下ポリスルホンという）の製法について説明する。
本発明のポリスルホンは、フェノール性水酸基を保護したスチレン誘導体を含むモノマーと、二酸化硫黄とのラジカル共重合により製造することができる。
重合開始剤は、通常この種の分野で使用されているものが使用できる。
フェノール性水酸基の保護は、常法にしたがって、トリメチルシリル（ＴＭＳ）基、ｔｅｒｔ−ブトキシカルボニル基、アセチル基などの保護基で行うことができる。共重合体（コポリマー）の組成（スチレン誘導体ユニットとスルホンユニットとの割合）は、温度、濃度、モノマーの仕込み組成などに依存する。モノマーは、フェノール性水酸基を保護したスチレン誘導体単独でも、あるいは、フェノール性水酸基を保護したスチレン誘導体以外のモノマーとの混合物でも良い。共重合反応後、得られたコポリマーのフェノール性水酸基の保護を外して（脱保護して）、フェノール性水酸基を有するポリスルホンとする。
水酸基の脱保護は、得られたコポリマーのアルカリ水溶液による分解性を得るために行われる。したがって、コポリマーからの水酸基の脱保護は、必要に応じて一部行うか又はまったく行わないで、その後の用途に用いることもできる。
保護基の異なるスチレン誘導体を選択して用いることによって、脱保護度の異なるポリスルホンを得ることができる。
【０００８】
脱保護したポリスルホンはアルカリ水溶液と接触させると、溶解と同時に分解する。水溶液として用いるアルカリは、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム、炭酸ナトリウム、炭酸水素ナトリウム、メタケイ酸ナトリウム、リン酸３ナトリウム、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシドなどが挙げられる。分解に必要なアルカリの量は、分解するポリスルホンの量に比例する。
【０００９】
本発明のポリスルホンがアルカリにより分解するのは、主鎖のスルホニル基と側鎖のフェノール性水酸基の働きによるものと推測される。すなわち、側鎖のフェノール性水酸基により、ポリスルホンはアルカリ水溶液に溶解する。溶解したポリスルホンにおいて、主鎖のスルホニル基に対してアンチ位にあるメチレンプロトンがアルカリにより引き抜かれ、プロトン引抜きによるカルバニオン生成と同時に、主鎖の炭素−硫黄結合が開裂してポリスルホンが分解する。
したがって、式（Ｉ）で示される重合体構造をポリマーの分子鎖中の任意の位置に介在させることによって、所望の位置で分解した低分子化合物を得ることができる。式（Ｉ）で示されるポリスルホン構造体は、モノマーからの重合のほか、グラフト重合、ブロック重合等の方法でポリマー中に組み込んでも良い。
【００１０】
上記ポリスルホンの分解において、４−ヒドロキシスチレンと二酸化硫黄との１：１交互共重合体であるポリスルホンをアルカリ水溶液中で分解すると、均一透明な溶液が得られ、この水溶液を酸で中和後エーテル抽出し、抽出後の水溶液を濃縮すると白色固体が得られる。さらに、白色固体生成物を２−メチル−２−プロパノールで抽出後、抽出溶媒を留去するとｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸を得ることができる。
このエテンスルフィン酸は文献未記載の新規化合物で、次式（II）：
【化４】

で示される水溶性に優れた化合物であり、写真薬品、めっき薬品等の種々の工業薬品、医薬及び農薬の製造原料又は中間体としての用途が見込まれる。
【００１１】
【実施例】
以下実施例をあげて本発明を具体的に説明するが、本発明はこれらの例に限定されるものではない。
【００１２】
実施例１ ４−ヒドロキシスチレンと二酸化硫黄との１：１交互共重合体の合成
ポリマー・プレプリント・ジャパン（Ｐｏｌｙｍ．Ｐｒｅｐｒ．，Ｊｐｎ．）１９８８年（第３７巻）３４３８頁に記載されている方法に準拠して行った。この低温ラジカル共重合反応の条件（−５０〜−８０℃）で、スチレン誘導体と二酸化硫黄との１：１交互共重合体が得られる。
【００１３】
二酸化硫黄はボンベよりドライアイス−メタノール（−８０℃）で冷却して液化し、五酸化二リンで乾燥した。フェノール性水酸基をトリメチルシリル基で保護したモノマーである４−トリメチルシリルオキシスチレン０．９１ｇを丸底フラスコに入れ、ドライアイス−メタノールで冷却した。乾燥した二酸化硫黄０．６５ｍＬを前記丸底フラスコに再蒸留し、４−トリメチルシリルオキシスチレンを溶解させた。重合開始剤としてｔｅｒｔ−ブチルヒドロペルオキシドの３．０Ｍ２，２，４−トリメチルペンタン溶液２０ｍｇを添加した後、−８０℃の低温槽に６８時間放置した。その後、反応容器（丸底フラスコ）を液体窒素（−１９６℃）で冷却して重合を停止させ、排気しながら室温に戻した。そのまま２時間排気を続けた後、生成物をジメチルスルホキシド（ＤＭＳＯ）に溶解し、１，４−ジオキサン中に投入して精製し、白色樹脂０．６７ｇを得た。
【００１４】
得られた白色樹脂のプロトン核磁気共鳴吸収スペクトルを図１に示した。図からわかるように、０ｐｐｍ付近の高磁場に出現するはずのトリメチルシリル基に基づく吸収は観測されず、代わりに９．７ｐｐｍに重水の添加によって消失するフェノール性水酸基のプロトン（ａ）の吸収が観測された。
また、図２に示す炭素１３核磁気共鳴吸収スペクトルでは、ポリマー鎖に対してオルト位（Ｃ−２及びＣ−６）及びパラ位（Ｃ−４）の芳香環炭素が、それぞれ１３１．２、１５８．３ｐｐｍに、いずれもシングレットで観測された。さらに、赤外線吸収スペクトルには、１１２４及び１３１１ｃｍ^-1にスルホニル基の伸縮振動に基づく強い吸収が存在した。
これらのスペクトルデータから、得られた白色樹脂は、トリメチルシリル基が空気中の水分により加水分解して脱離した、４−ヒドロキシスチレンと二酸化硫黄との１：１交互共重合体であるポリ（４−ヒドロキシスチレン スルホン）であると認められた。収率は７７％。このポリスルホンの分子量及び分子量分布はＧＰＣ（ゲル浸透クロマトグラフィー）測定により、それぞれＭｗ＝７６８００、Ｍｗ／Ｍｎ＝２．８４と決定された。
【００１５】
実施例２ ポリスルホンのアルカリ水溶液による分解
実施例１で得られたポリ（４−ヒドロキシスチレン スルホン）２５ｍｇを、濃度１．２〜１１．８ｗ／ｖ％（重量／容量％）の重水酸化ナトリウム重水溶液０．５６ｍＬと共に振盪すると、速やかに溶解して分解し、ｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸及び４−ヒドロキシスチレンが２：３のモル比で得られた。
図３に示すごとく、このポリスルホンの分解は定量的に進行し、どちらの生成物も、生成量はアルカリ濃度に依存しなかった。なお、図３の定量はプロトン核磁気共鳴吸収スペクトルの積分によって行い、縦軸のモル比は、原料に用いたポリ（４−ヒドロキシスチレン スルホン）のモノマー単位のモル数に対する生成物のモル数の比を表す。
【００１６】
以下に生成物の単離について記載する。
均一透明になった前記のポリ（４−ヒドロキシスチレン スルホン）のアルカリ水溶液を、重塩酸で中和後エーテルで抽出し、エーテル抽出液とアルカリ水溶液とに分離して、エーテル可溶の生成物と水溶性の生成物に分離した。エーテル可溶の生成物 ４−ヒドロキシスチレンは、エーテル抽出液を濃縮すると白色固体として得られた。収率５５％。得られた白色固体（４−ヒドロキシスチレン）のプロトン核磁気共鳴吸収スペクトルを図４に示す。
４−ヒドロキシスチレンは既に知られた化合物で、図４のスペクトルは公知の４−ヒドロキシスチレンのスペクトルと一致した。
【００１７】
次に、水溶性の生成物ｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸は、エーテル抽出後の重水溶液を乾涸させ、２−メチル−２−プロパノールで抽出後、抽出液を濃縮すると白色固体として得られた。収率３５％。ｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸は重水に容易に溶解し、図５のａに示すプロトン核磁気共鳴吸収スペクトルを与えた。
【００１８】
ｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸は、次亜塩素酸ナトリウム水溶液で酸化するとｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルホン酸に変化した。ｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルホン酸のプロトン核磁気共鳴吸収スペクトルを図５のｂに示した。
ｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルホン酸の赤外線吸収スペクトルでは、１０４１、１１７４、及び１２１１ｃｍ^-1にスルホン酸に基づく強い吸収が認められた。
スルフィン酸とスルホン酸は、２個のオレフィンプロトン（Ｇ２、Ｇ３）と４個の芳香環プロトン（Ｇ１）を有しており、図５のａ、ｂのスペクトルにおいて芳香環のプロトン（Ｇ１）はそれぞれ結合定数８．３Ｈｚのダブレットが充分離れて対になっていることからパラ置換ベンゼンに基づく吸収と認められ、スルフィン酸（スペクトルａ）ではオレフィンプロトン（Ｇ３）の結合定数１６．１Ｈｚからトランス（ｔｒａｎｓ）の立体配置を持つ１，２−ジ置換オレフィン化合物と認められた。スペクトルｂの２個の結合定数１５．６Ｈｚはスルホン酸の２個のオレフィンプロトン（Ｇ３）を示す。
【００１９】
実施例３
実施例１で得られたポリ（４−ヒドロキシスチレン スルホン）２５ｍｇ及び重水０．５６ｍＬの不均一溶液に、濃度２４ｗ／ｖ％の重水酸化ナトリウム重水溶液を１０μＬ添加した。その結果、重水酸化ナトリウムの添加量に対してモル比で０．６４のモノマー単位を有するポリスルホンが分解した。生成したｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸と４−ヒドロキシスチレンのモル比は０．７８：１であった。
【００２０】
実施例４
実施例３と同様に、実施例１で得られたポリ（４−ヒドロキシスチレン スルホン）２５ｍｇ及び重水０．５６ｍＬの不均一溶液に、濃度２６ｗ／ｖ％の重水酸化アンモニウム重水溶液を１０μＬ添加した。その結果、重水酸化アンモニウムの添加量に対してモル比で０．５１のモノマー単位を有するポリスルホンが分解した。生成したｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸と４−ヒドロキシスチレンのモル比は０．７７：１であった。
【００２１】
【発明の効果】
以上説明したように、本発明によれば、アルカリによる分解が可能なポリスルホンを得ることができる。本発明のポリスルホンは、主鎖にスルホニル基を有し、側鎖にフェノール性水酸基を有する化学構造を持つため、塩基の存在によって容易に分解する。この易分解性はフェノール性水酸基を有するスチレン誘導体と二酸化硫黄との共重合体構造によって得られるため、該重合体構造をポリマーの分子中に任意の箇所に任意の数で介在させることによって、所望の低分子量化合物で分解することができ、地球環境への負荷を軽減できる易分解性の高分子化合物を得ることができる。さらに、該ポリスルホンに、例えば、ｏ−ニトロベンジルカーバメートのような光塩基発生剤を共存させることによって、光照射によりポリスルホンを分解しパターンを形成する、フォトレジストへの応用が可能となる。なお、該ポリスルホンは、スルホニル基及びフェノール性水酸基の極性構造を有するため、接着性や溶解性等に優れている。
【００２２】
さらに、本発明によって、新規化合物であるｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸を得ることができる。この化合物は、フェノール性水酸基を有するスルフィン酸であり、水溶性に優れていることから、酸として使用できるほか、各種工業薬品、医薬、農薬等の合成材料として利用できる。より具体的には、写真薬品、めっき薬品等として有用である。
【図面の簡単な説明】
【図１】ポリ（４−ヒドロキシスチレン スルホン）のプロトン核磁気共鳴吸収スペクトルである。
【図２】ポリ（４−ヒドロキシスチレン スルホン）の炭素１３核磁気共鳴吸収スペクトルである。
【図３】分解生成物に及ぼすアルカリ水溶液の濃度依存性を示すグラフである。
【図４】４−ヒドロキシスチレンのプロトン核磁気共鳴吸収スペクトルである。
【図５】プロトン核磁気共鳴吸収スペクトルで、ａはｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルフィン酸、ｂはその次亜塩素酸ナトリウム水溶液による酸化物であるｔｒａｎｓ−２−（４−ヒドロキシフェニル）エテンスルホン酸のプロトン核磁気共鳴吸収スペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a degradable plastic that can be decomposed with an alkali and that can be reused, a decomposition method thereof, and a decomposition product.
[0002]
[Prior art]
Plastics as polymer compounds differ depending on the type, but they have physical strength, weather resistance, heat resistance, chemical resistance, etc., so they are used as industrial materials such as mechanical structural materials, electrical parts, and building materials. In addition to being used for packaging materials etc. after being molded into containers and films, it is also used in paints and is used in many industrial fields. However, many plastics are not easily decomposed by microorganisms in the soil or light and heat in the natural environment, and environmental pollution due to plastic products after use has become a problem. Although some are incinerated as a treatment method, there are problems of secondary contamination such as generation of soot and harmful gas generated by incineration. In addition, this method has a drawback that resources cannot be reused.
Therefore, a polymer compound that can efficiently lower the molecular weight is important from the viewpoint of reducing the burden on the global environment and effectively utilizing resources. Recently, a polymer compound intended to reuse a decomposition product from such a viewpoint has been developed (Japanese Patent Laid-Open No. 11-92503). However, many of these polymer compounds have chemical bonds such as esters and amides that hydrolyze with acids and alkalis, and do not decompose in a chain manner.
[0003]
[Problems to be solved by the invention]
The first object of the present invention is to provide a plastic (polymer compound) capable of separating low-molecular compounds that can be reused by chain decomposition unlike conventional hydrolysis, and a method for decomposing the plastic The second object is to provide a sulfinic acid excellent in water solubility obtained by the decomposition method.
[0004]
[Means for Solving the Problems]
The present invention relates to a polymer compound comprising a copolymer structure of a styrene derivative having a phenolic hydroxyl group and sulfur dioxide in the molecule. The high molecular compound of the present invention can be decomposed with an alkali, and can be formed into a desired pattern or a low molecular compound by decomposition.
Furthermore, this invention provides the sulfinic acid excellent in the water solubility obtained by this decomposition method.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The alkali-decomposable polymer compound of the present invention comprises a polymer having a copolymer structure of a styrene derivative having a phenolic hydroxyl group at the 2-position or 4-position and sulfur dioxide. More specifically, the following general formula ( It is characterized in that it contains a copolymer structure of a styrene derivative having a phenolic hydroxyl group represented by I) and sulfur dioxide in the molecule.
[Chemical formula 2]

[Wherein, X and Y represent a hydrogen atom or an optionally protected hydroxyl group; when X is a hydrogen atom, Y represents the hydroxyl group; when Y is a hydrogen atom, X represents the hydroxyl group; -4, n represents 5-5000. ]
[0006]
The polymer compound of the present invention may be polysulfone, which is a polymer composed only of the copolymer structure represented by the above formula (I), and includes a copolymer structure represented by the above formula (I). Polymer (IA):
[Chemical 3]

(In the formula, A represents a copolymerizable monomer, and a and b represent arbitrary integers.)
It may be. a and b vary depending on the monomer A used, and are selected according to the degree of decomposition required for the polymer obtained.
In the above, as the copolymerizable monomer, vinyl monomers such as styrene, divinylbenzene, (meth) acrylic acid, (meth) acrylic acid ester, and vinyl acetate are preferable.
In general formula (I), m is preferably 1-2, more preferably 1, and n is preferably 5-2000, more preferably 5-1000.
[0007]
Below, the manufacturing method of the high molecular compound (henceforth polysulfone) of this invention is demonstrated.
The polysulfone of the present invention can be produced by radical copolymerization of a monomer containing a styrene derivative with a phenolic hydroxyl group protected and sulfur dioxide.
As the polymerization initiator, those usually used in this kind of field can be used.
The phenolic hydroxyl group can be protected with a protecting group such as a trimethylsilyl (TMS) group, a tert-butoxycarbonyl group, or an acetyl group according to a conventional method. The composition of the copolymer (copolymer) (the ratio of the styrene derivative unit and the sulfone unit) depends on the temperature, concentration, monomer charge composition, and the like. The monomer may be a styrene derivative alone with a phenolic hydroxyl group protected or a mixture with a monomer other than a styrene derivative with a phenolic hydroxyl group protected. After the copolymerization reaction, protection of the phenolic hydroxyl group of the obtained copolymer is removed (deprotection) to obtain a polysulfone having a phenolic hydroxyl group.
The deprotection of the hydroxyl group is performed in order to obtain the decomposability of the obtained copolymer with an alkaline aqueous solution. Thus, hydroxyl group deprotection from the copolymer can be used in subsequent applications with partial or no deprotection as required.
By selecting and using styrene derivatives having different protecting groups, polysulfones having different degrees of deprotection can be obtained.
[0008]
When deprotected polysulfone is brought into contact with an alkaline aqueous solution, it decomposes simultaneously with dissolution. Examples of the alkali used as the aqueous solution include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium metasilicate, trisodium phosphate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. The amount of alkali required for decomposition is proportional to the amount of polysulfone that decomposes.
[0009]
The degradation of the polysulfone of the present invention by alkali is presumed to be due to the action of the sulfonyl group in the main chain and the phenolic hydroxyl group in the side chain. That is, the polysulfone is dissolved in the alkaline aqueous solution by the phenolic hydroxyl group in the side chain. In the dissolved polysulfone, methylene protons in the anti-position with respect to the sulfonyl group of the main chain are extracted by alkali, and simultaneously with the generation of carbanion by proton extraction, the carbon-sulfur bond of the main chain is cleaved and the polysulfone is decomposed.
Therefore, a low molecular compound decomposed at a desired position can be obtained by interposing the polymer structure represented by the formula (I) at an arbitrary position in the molecular chain of the polymer. The polysulfone structure represented by the formula (I) may be incorporated into a polymer by a method such as graft polymerization or block polymerization in addition to polymerization from a monomer.
[0010]
When the polysulfone, which is a 1: 1 alternating copolymer of 4-hydroxystyrene and sulfur dioxide, is decomposed in an alkaline aqueous solution in the decomposition of the polysulfone, a uniform transparent solution is obtained. Extraction and concentration of the aqueous solution after extraction yields a white solid. Furthermore, after extracting a white solid product with 2-methyl-2-propanol, trans-2- (4-hydroxyphenyl) ethenesulfinic acid can be obtained by evaporating the extraction solvent.
This ethene sulfinic acid is a novel compound not described in the literature, and has the following formula (II):
[Formula 4]

It is expected to be used as a production raw material or intermediate for various industrial chemicals such as photographic chemicals and plating chemicals, pharmaceuticals and agricultural chemicals.
[0011]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
[0012]
Example 1 Synthesis of 1: 1 Alternating Copolymer of 4-Hydroxystyrene and Sulfur Dioxide Polymer Preprint Japan (Polym. Prepr., Jpn.) 1988 (Vol. 37), page 3438 Performed according to the method. Under this low temperature radical copolymerization reaction condition (-50 to -80 ° C), a 1: 1 alternating copolymer of a styrene derivative and sulfur dioxide can be obtained.
[0013]
The sulfur dioxide was liquefied by cooling with a dry ice-methanol (−80 ° C.) from a cylinder and dried with diphosphorus pentoxide. 0.91 g of 4-trimethylsilyloxystyrene, which is a monomer having a phenolic hydroxyl group protected with a trimethylsilyl group, was placed in a round bottom flask and cooled with dry ice-methanol. 0.65 mL of dried sulfur dioxide was redistilled in the round bottom flask to dissolve 4-trimethylsilyloxystyrene. After adding 20 mg of a 3.0M 2,2,4-trimethylpentane solution of tert-butyl hydroperoxide as a polymerization initiator, the mixture was left in a low temperature bath at −80 ° C. for 68 hours. Thereafter, the reaction vessel (round bottom flask) was cooled with liquid nitrogen (−196 ° C.) to stop the polymerization, and returned to room temperature while evacuating. After continuing to evacuate for 2 hours, the product was dissolved in dimethyl sulfoxide (DMSO), poured into 1,4-dioxane and purified to obtain 0.67 g of a white resin.
[0014]
The proton nuclear magnetic resonance absorption spectrum of the obtained white resin is shown in FIG. As can be seen from the figure, no absorption based on the trimethylsilyl group, which should appear in a high magnetic field near 0 ppm, is observed, but instead the absorption of proton (a) of the phenolic hydroxyl group that disappears by adding heavy water to 9.7 ppm is observed. It was done.
Further, in the carbon 13 nuclear magnetic resonance absorption spectrum shown in FIG. 2, the aromatic ring carbons at the ortho position (C-2 and C-6) and the para position (C-4) with respect to the polymer chain are respectively 131.2, All were observed with a singlet at 158.3 ppm. Furthermore, in the infrared absorption spectrum, strong absorption based on the stretching vibration of the sulfonyl group was present at 1124 and 1311 cm ⁻¹ .
From these spectral data, the obtained white resin is a poly (4) which is a 1: 1 alternating copolymer of 4-hydroxystyrene and sulfur dioxide in which trimethylsilyl groups are hydrolyzed and eliminated by moisture in the air. -Hydroxystyrene sulfone). Yield 77%. The molecular weight and molecular weight distribution of this polysulfone were determined to be Mw = 76800 and Mw / Mn = 2.84, respectively, by GPC (gel permeation chromatography) measurement.
[0015]
Example 2 Decomposition of Polysulfone with Alkaline Aqueous Solution 25 mg of the poly (4-hydroxystyrene sulfone) obtained in Example 1 was dissolved in a sodium hydrogen hydroxide heavy aqueous solution having a concentration of 1.2 to 11.8 w / v% (weight / volume%). When shaken with 0.56 mL, it quickly dissolved and decomposed, and trans-2- (4-hydroxyphenyl) ethenesulfinic acid and 4-hydroxystyrene were obtained in a molar ratio of 2: 3.
As shown in FIG. 3, the decomposition of the polysulfone proceeded quantitatively, and the amount of production of both products did not depend on the alkali concentration. The quantification in FIG. 3 is performed by integrating the proton nuclear magnetic resonance absorption spectrum, and the molar ratio of the vertical axis is the number of moles of product relative to the number of moles of monomer units of poly (4-hydroxystyrene sulfone) used as a raw material. Represents the ratio.
[0016]
The product isolation is described below.
The alkali aqueous solution of the poly (4-hydroxystyrene sulfone) that became uniform and transparent was neutralized with deuterated hydrochloric acid, extracted with ether, separated into an ether extract and an aqueous alkali solution, and an ether-soluble product and Separated into water soluble product. Ether-soluble product 4-hydroxystyrene was obtained as a white solid upon concentration of the ether extract. Yield 55%. FIG. 4 shows a proton nuclear magnetic resonance absorption spectrum of the obtained white solid (4-hydroxystyrene).
4-Hydroxystyrene is a known compound, and the spectrum of FIG. 4 coincided with the spectrum of known 4-hydroxystyrene.
[0017]
Next, the water-soluble product trans-2- (4-hydroxyphenyl) ethenesulfinic acid is obtained by drying the heavy aqueous solution after ether extraction, extracting with 2-methyl-2-propanol, and then concentrating the extract. Obtained as a solid. Yield 35%. trans-2- (4-Hydroxyphenyl) ethenesulfinic acid readily dissolved in heavy water and gave a proton nuclear magnetic resonance absorption spectrum shown in FIG.
[0018]
When trans-2- (4-hydroxyphenyl) ethenesulfinic acid was oxidized with an aqueous sodium hypochlorite solution, it was converted to trans-2- (4-hydroxyphenyl) ethenesulfonic acid. The proton nuclear magnetic resonance absorption spectrum of trans-2- (4-hydroxyphenyl) ethenesulfonic acid is shown in FIG.
In the infrared absorption spectrum of trans-2- (4-hydroxyphenyl) ethenesulfonic acid, strong absorption based on sulfonic acid was observed at 1041, 1174, and 1211 cm ⁻¹ .
Sulfinic acid and sulfonic acid have two olefinic protons (G2 and G3) and four aromatic ring protons (G1). In the spectra of FIGS. 5a and 5b, the aromatic ring proton (G1) is Since the doublets having a coupling constant of 8.3 Hz are paired sufficiently apart from each other, absorption based on para-substituted benzene is recognized, and in the sulfinic acid (spectrum a), the coupling constant of the olefin proton (G3) is changed from 16.1 Hz to trans ( trans)), a 1,2-disubstituted olefin compound having a configuration of (trans). Two binding constants of 15.6 Hz in spectrum b represent the two olefinic protons (G3) of the sulfonic acid.
[0019]
Example 3
To a heterogeneous solution of 25 mg of poly (4-hydroxystyrene sulfone) obtained in Example 1 and 0.56 mL of heavy water, 10 μL of a sodium bicarbonate aqueous solution having a concentration of 24 w / v% was added. As a result, polysulfone having a monomer unit of 0.64 in terms of molar ratio with respect to the added amount of sodium bicarbonate was decomposed. The molar ratio of produced trans-2- (4-hydroxyphenyl) ethenesulfinic acid and 4-hydroxystyrene was 0.78: 1.
[0020]
Example 4
In the same manner as in Example 3, 10 μL of 26 wt / v% aqueous ammonium bicarbonate was added to the heterogeneous solution of 25 mg of poly (4-hydroxystyrene sulfone) obtained in Example 1 and 0.56 mL of heavy water. As a result, polysulfone having a monomer unit of 0.51 in terms of molar ratio with respect to the amount of ammonium bicarbonate was decomposed. The molar ratio of produced trans-2- (4-hydroxyphenyl) ethenesulfinic acid and 4-hydroxystyrene was 0.77: 1.
[0021]
【The invention's effect】
As described above, according to the present invention, polysulfone that can be decomposed by alkali can be obtained. Since the polysulfone of the present invention has a chemical structure having a sulfonyl group in the main chain and a phenolic hydroxyl group in the side chain, it is easily decomposed by the presence of a base. This easy degradability is obtained by a copolymer structure of a styrene derivative having a phenolic hydroxyl group and sulfur dioxide. Therefore, by interposing the polymer structure in an arbitrary number in an arbitrary position in the polymer molecule, the desired structure can be obtained. It is possible to obtain an easily decomposable polymer compound that can be decomposed with a low molecular weight compound and can reduce the burden on the global environment. Further, by allowing a photobase generator such as o-nitrobenzyl carbamate to coexist with the polysulfone, it is possible to apply to a photoresist in which the polysulfone is decomposed by light irradiation to form a pattern. In addition, since this polysulfone has the polar structure of a sulfonyl group and a phenolic hydroxyl group, it is excellent in adhesiveness, solubility, etc.
[0022]
Furthermore, according to the present invention, a novel compound trans-2- (4-hydroxyphenyl) ethenesulfinic acid can be obtained. This compound is a sulfinic acid having a phenolic hydroxyl group and is excellent in water solubility, so that it can be used as an acid, and can also be used as a synthetic material for various industrial chemicals, pharmaceuticals, agricultural chemicals and the like. More specifically, it is useful as a photographic chemical, a plating chemical or the like.
[Brief description of the drawings]
FIG. 1 is a proton nuclear magnetic resonance absorption spectrum of poly (4-hydroxystyrene sulfone).
FIG. 2 is a carbon-13 nuclear magnetic resonance absorption spectrum of poly (4-hydroxystyrene sulfone).
FIG. 3 is a graph showing the concentration dependence of an aqueous alkali solution on the decomposition product.
FIG. 4 is a proton nuclear magnetic resonance absorption spectrum of 4-hydroxystyrene.
FIG. 5 is a proton nuclear magnetic resonance absorption spectrum, in which a is trans-2- (4-hydroxyphenyl) ethenesulfinic acid, and b is trans-2- (4-hydroxy) which is an oxide of sodium hypochlorite aqueous solution. It is a proton nuclear magnetic resonance absorption spectrum of (phenyl) ethenesulfonic acid.

Claims (6)

The method for decomposing a polymer compound characterized by decomposing you containing a copolymer structure of styrene derivatives and sulfur dioxide having a phenolic hydroxyl group in the molecule high molecular compound with an alkali. The polymer compound has the following formula (I):

[Wherein, X and Y represent a hydrogen atom or an optionally protected hydroxyl group; when X is a hydrogen atom, Y represents the hydroxyl group; when Y is a hydrogen atom, X represents the hydroxyl group; -4, n represents 5-5000. ]
The method for decomposing a polymer compound according to claim 1, which is a compound containing in its molecule a copolymer structure of a styrene derivative having a phenolic hydroxyl group represented by formula ( II) and sulfur dioxide . The method for decomposing a polymer compound according to claim 1 or 2, wherein the polymer compound is a polysulfone having a copolymer structure of a styrene derivative having a phenolic hydroxyl group represented by the formula (I) and sulfur dioxide. The polymer compound is a 1: 1 alternating copolymer of a styrene derivative and a sulfur dioxide having a phenolic hydroxyl group in which X is a hydrogen atom, Y is a hydroxyl group, m is 1, and n is 5 to 5000 in the formula (I) The method for decomposing a polymer compound according to claim 2 or 3, which is a polysulfone having a structure . Formula (Ia):

[In formula, Y represents the hydroxyl group which may be protected, and n shows 5-5000. ]
An alkali-decomposable polymer compound comprising polysulfone, which is a 1: 1 alternating copolymer of a styrene derivative having a phenolic hydroxyl group and sulfur dioxide represented by : The following formula obtained by decomposing the polymer compound according to claim 5 with an alkali:

Trans-2- (4-hydroxyphenyl) ethenesulfinic acid represented by

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