JP3711851B2 - Production method of poly (p-tert-butoxystyrene) - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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Description
【０００１】
【発明の属する技術分野】
本発明は、ポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の製法に関する。
【０００２】
【従来の技術】
ポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）は、超ＬＳＩの製造に必要なレジスト材などとしてよく知られており、近年では分子量分布が狭い狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）、例えば重量平均分子量Ｍｗと数平均分子量Ｍｎから計算されるＭｗ／Ｍｎが１．３０程度以下、好ましくは１．２０程度以下のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）が要望されている。
【０００３】
かかるポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の製法としては、例えば特開平６−２９８８６９号公報において、反応溶媒と重合開始剤との混合物にｐ−ｔｅｒｔ−ブトキシスチレンの溶媒溶液を何ら前処理することなく加える方法が提案されている。
しかし、かかる製法ではＭｗ／Ｍｎが１．３０を超えるポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）が生成する場合があった。
【０００４】
一方、狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）を安定して製造し得る方法として、反応溶媒とｐ−ｔｅｒｔ−ブトキシスチレンとの混合物に、重合開始剤を加える方法が挙げられ（特開平８−２９９８３号公報）、短時間で重合開始剤を加えることにより狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）を得ることができるが、重合開始剤を短時間で加える結果、急激に反応が進行して発熱し、反応系の温度が上昇し易く、温度をコントロールし難くなるという工業上の問題があった。
【０００５】
【発明が解決しようとする課題】
そこで本発明者は、急激な発熱を防止しながら安定的に狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）を製造し得る方法を開発するべく鋭意検討した結果、反応溶媒とｐ−ｔｅｒｔ−ブトキシスチレンとの混合物に重合開始剤を加える方法では、用いるｐ−ｔｅｒｔ−ブトキシスチレンの水分含量が多くても、得られるポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量分布に影響しないのに対して、反応溶媒と重合開始剤との混合物にｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液を加える方法においては、ｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液に混入している水分が、得られるポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量分布に影響していることを見出すと共に、かかる方法においてｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液の水分含量を７０ｐｐｍ以下に調整することにより、狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）を安定的に製造し得ることを見出し、本発明に至った。
【０００６】
【課題を解決するための手段】
すなわち本発明は、反応溶媒と重合開始剤との混合物に、−５０℃〜−１０℃の温度範囲で、水分含量が７０ｐｐｍ以下に調整されたｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液を順次加え、上記温度範囲で保温することを特徴とするポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の製法を提供するものである。
【０００７】
【発明の実施の形態】
以下、本発明についてさらに詳細に説明する。
本発明の製法に用いられる反応溶媒としては、例えばベンゼン、トルエン、キシレンなどの芳香族炭化水素、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサンなどの脂肪族炭化水素などの炭化水素系溶媒、テトラヒドロフラン、１，４−ジオキサン、エチレングリコールジメチルエーテルなどのエーテル類、これら２種以上の混合物などが挙げられる。なかでも炭化水素系溶媒とエーテル類との混合溶媒が好ましく使用される。反応溶媒は、ｐ−ｔ−ブトキシスチレンに対して、通常１〜２０重量倍程度、好ましくは２〜１０重量倍程度使用される。
【０００８】
重合開始剤としては、有機アルカリ金属化合物、例えばｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｉ−ブチルリチウム、ｔ−ブチルリチウム、２−メチルブチルリチウム、リチウムナフタレンなどの有機リチウム化合物、ナトリウムナフタレン、ナトリウムアントラセン、α−メチルスチレンテトラマーナトリウム、ナトリウムビフェニルなどの有機ナトリウム化合物などが挙げられる。なかでもｎ−ブチルリチウム、ｓｅｃ−ブチルリチウムなどが好ましく使用される。
有機金属化合物の使用量は、目的とするポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量により変動するが、モノマーであるｐ−ｔｅｒｔ−ブトキシスチレン１ｇ当たり１０-5〜１０-3モル程度であることが好ましい。
【０００９】
本発明の製法は、かかる反応溶媒と重合開始剤との混合物にｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液を加える方法である。
【００１０】
ｐ−ｔｅｒｔ−ブトキシスチレンの溶媒溶液を加える場合、該溶液に使用される溶媒としては、例えばベンゼン、トルエン、キシレンなどの芳香族炭化水素、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサンなどの脂肪族炭化水素などの炭化水素系溶媒、テトラヒドロフラン、１，４−ジオキサン、エチレングリコールジメチルエーテルなどのエーテル類、これら２種以上の混合物などが挙げられ、その使用量はｐ−ｔｅｒｔ−ブトキシスチレンに対して通常０．０５〜１０重量倍程度、好ましくは０．１〜１重量倍程度である。かかる溶媒は、反応溶媒と同一であってもよいし、異なっていてもよい。
【００１１】
かかるｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液は、水分含量が７０ｐｐｍ以下に調整されている。水分含量が７０ｐｐｍを超えると狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）を得難くなるため、６０ｐｐｍ以下、さらには５０ｐｐｍ以下に調製することが好ましい。また水分含有量を５ｐｐｍ未満とするためには特殊な脱水剤が必要となり、複雑な乾燥工程を必要とするので、簡便に水分含量を調製し得る点で、５ｐｐｍ以上、さらには１０ｐｐｍ以上に調製することが好ましい。ｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液の水分含量は、例えばカールフィッシャー法などにより容易に測定できる。
【００１２】
ｐ−ｔｅｒｔ−ブトキシスチレンを単独で加える場合には、ｐ−ｔｅｒｔ−ブトキシスチレンの水分含量を本発明で規定する範囲に調整したのち、ｐ−ｔｅｒｔ−ブトキシスチレンを反応溶媒と重合開始剤との混合物に加えればよい。用いるｐ−ｔｅｒｔ−ブトキシスチレンには通常、保存されている間などに大気中から混入した水分が含まれているため、ｐ−ｔｅｒｔ−ブトキシスチレンの水分含量を本発明で規定する範囲に調整するには、通常は水分含量を本発明で規定する範囲に抑制すればよい。水分含量を抑制する方法としては、例えば減圧蒸留による方法、モレキュラーシーブやシリカゲルなどの乾燥剤を使用して乾燥する方法などが挙げられるが、乾燥剤を用いて乾燥する方法がより簡便である。
【００１３】
ｐ−ｔｅｒｔ−ブトキシスチレンの溶媒溶液を加える場合には、該溶液の水分含量を本発明で規定する範囲に調整したのち、ｐ−ｔｅｒｔ−ブトキシスチレンの溶媒溶液を反応溶媒と重合開始剤との混合物に加えればよい。ｐ−ｔｅｒｔ−ブトキシスチレンの溶媒溶液や該溶液の調製に用いられるｐ−ｔｅｒｔ−ブトキシスチレンおよび溶媒には、通常、保管されている間などに大気中から混入した水分が存在するため、ｐ−ｔｅｒｔ−ブトキシスチレンの溶媒溶液の水分含量を本発明で規定する範囲とするには、通常は該溶液の水分含有量を本発明で規定する範囲に抑制すればよい。溶液の水分含有量を抑制するには、例えばｐ−ｔｅｒｔ−ブトキシスチレンと溶媒とを混合した後にモレキュラーシーブ、シリカゲルなどの乾燥剤で乾燥してもよいし、上記したと同様の方法で乾燥したｐ−ｔｅｒｔ−ブトキシスチレンと予めモレキュラーシーブ、シリカゲルなどの乾燥剤で乾燥させた溶媒とを混合してもよい。
【００１４】
本発明の製法において、ｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液は、通常、高真空下あるいはアルゴン、窒素などの不活性ガス雰囲気下に、反応溶媒と重合開始剤との混合物に順次加えられる。ｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液は−５０〜−１０℃程度の温度で、反応溶媒と重合開始剤との混合物に順次加えられ、通常１０分〜２０時間程度、好ましくは１５分〜５時間程度の時間をかけて、反応溶媒と重合開始剤との混合物に順次加えられる。加え終わった後には、同温度で５分〜５時間程度保温するのが好ましい。ｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液を反応溶媒と重合開始剤との混合物に加えることによりｐ−ｔｅｒｔ−ブトキシスチレンが重合して、目的とするポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）が生成する。
ｐ−ｔｅｒｔ−ブトキシスチレンの重合反応は、水、メタノールなどの重合反応停止剤を少量加えることにより、停止させることができる。
【００１５】
次いで、反応マスから溶媒を留去することにより、目的とする狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）を単離することができる。得られたポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）は、例えば溶媒留去した後、メタノールなどに注入する方法により、精製することもできる。
【００１６】
かくして得られたポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量分布は、ＧＰＣ分析によって求めたポリスチレン換算の数平均分子量（Ｍｎ）と重量平均分子量（Ｍｗ）とから算出される分子量分布（Ｍｗ／Ｍｎ）により確認し得る。
【００１７】
【実施例】
以下に本発明の実施例を示すが、本発明はこれら実施例によって限定されるものではない。
【００１８】
実施例１
窒素雰囲気下、モレキュラーシーブにより水分を十分に除去したヘキサン（水分含量は約１２ｐｐｍ）（５８７ｃｍ3）、ｓｅｃ−ブチルリチウム（５．９ｍｍｏｌ）を１０００ｃｍ3のフラスコに加え、−４０℃まで冷却し、そこにｐ−ｔｅｒｔ−ブトキシスチレン（８８ｇ）とエチレングリコールジメチルエーテル（６ｃｍ3）の混合溶液（モレキュラーシーブにより、カールフィッシャー法により測定した水分含量が１２ｐｐｍとなるまで乾燥させた）を１時間で滴下し、さらに−２０℃で１０分重合を行った後、メタノール（約３ｃｍ3）を加え反応を停止させた。次いで、得られた反応混合物の一部を採取し、溶媒留去したところ、白色固体生成物としてポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）が得られた。このポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量をＧＰＣ分析により測定したところ、数平均分子量Ｍｎは１４９００（ポリスチレン換算）であり、また分子量分布Ｍｗ／Ｍｎは１．１２であった。
【００１９】
実施例２
窒素雰囲気下、モレキュラーシーブにより水分を十分に除去したヘキサン（水分含量は約７ｐｐｍ）（５８７ｃｍ3）、ｓｅｃ−ブチルリチウム（５．９ｍｍｏｌ）を１０００ｃｍ3のフラスコに加え、−４０℃まで冷却し、そこにｐ−ｔｅｒｔ−ブトキシスチレン（８８ｇ）とエチレングリコールジメチルエーテル（６ｃｍ3）の混合溶液（モレキュラーシーブで水分含量が４３ｐｐｍとなるまで乾燥させた）を１時間で滴下し、さらに−２０℃で１０分重合を行った後、メタノール（約３ｃｍ3）を加え反応を停止させた。次いで、得られた反応混合物の一部を採取し、溶媒留去したところ、白色固体生成物としてポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）が得られた。このポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量をＧＰＣ分析により測定したところ、数平均分子量Ｍｎは１４３００（ポリスチレン換算）であり、また分子量分布Ｍｗ／Ｍｎは１．１８であった。
【００２０】
比較例１
窒素雰囲気下、モレキュラーシーブにより水分を十分に除去したヘキサン（７３０ｃｍ3）、ｓｅｃ−ブチルリチウム（５．６ｍｍｏｌ）を１０００ｃｍ3のフラスコに加え、−４０℃まで冷却し、そこにｐ−ｔｅｒｔ−ブトキシスチレン（９５ｇ）とエチレングリコールジメチルエーテル（６ｃｍ3）の混合溶液（水分含量は８３ｐｐｍ）を１時間で滴下し、さらに−２０℃で１０分重合を行った後、メタノール（約２ｃｍ3）を加え反応を停止させた。次いで、得られた反応混合物の一部を採取し、溶媒留去したところ、白色固体生成物としてポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）が得られた。このポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量をＧＰＣ分析により測定したところ、数平均分子量Ｍｎは１８４００（ポリスチレン換算）であり、また分子量分布Ｍｗ／Ｍｎは１．３３であった。
【００２１】
参考例１
窒素雰囲気下、モレキュラーシーブにより水分を十分に除去したヘキサン（水分含量は約６ｐｐｍ）（７３０ｃｍ3）にｐ−ｔｅｒｔ−ブトキシスチレン（９５ｇ）とエチレングリコールジメチルエーテル（水分含量は８７ｐｐｍ）６ｃｍ3の混合溶液を１０００ｃｍ3のフラスコに加え、−４０℃まで冷却し、そこにｓｅｃ−ブチルリチウム（５．０ｍｍｏｌ）を一気に加えた。その後、さらに−２０〜−３０℃で１０分重合を行った後、メタノール（約２ｃｍ3）を加え反応を停止させた。次いで得られた反応混合物に含まれるポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）の分子量をＧＰＣ分析により測定したところ、数平均分子量Ｍｎは１８２００（ポリスチレン換算）であり、また分子量分布Ｍｗ／Ｍｎは１．０９であった。
【００２２】
【発明の効果】
本発明によれば、水分含量を７０ｐｐｍ以下の範囲に調整したｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液を、反応溶媒と重合開始剤との混合物に順次加えることにより、狭分散のポリ（ｐ−ｔｅｒｔ−ブトキシスチレン）を安定的に製造し得る。そのうえ、反応溶媒と重合開始剤との混合物にｐ−ｔｅｒｔ−ブトキシスチレンまたはその溶媒溶液を加えているので急激な反応熱の発生もなく温度のコントロールが容易であり、工業的に有利である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing poly (p-tert-butoxystyrene).
[0002]
[Prior art]
Poly (p-tert-butoxystyrene) is well known as a resist material necessary for the production of VLSI, and in recent years, a narrowly dispersed poly (p-tert-butoxystyrene) having a narrow molecular weight distribution, for example, a weight average There is a demand for poly (p-tert-butoxystyrene) having a Mw / Mn calculated from the molecular weight Mw and the number average molecular weight Mn of about 1.30 or less, preferably about 1.20 or less.
[0003]
As a method for producing such poly (p-tert-butoxystyrene), for example, in JP-A-6-298869, a mixture of a reaction solvent and a polymerization initiator is pretreated with a solvent solution of p-tert-butoxystyrene. A way to add it has been proposed.
However, such a production method sometimes produces poly (p-tert-butoxystyrene) having Mw / Mn exceeding 1.30.
[0004]
On the other hand, as a method for stably producing narrow-dispersed poly (p-tert-butoxystyrene), a method of adding a polymerization initiator to a mixture of a reaction solvent and p-tert-butoxystyrene can be mentioned (Japanese Patent Application Laid-Open No. Hei. No. 8-29983), a narrowly dispersed poly (p-tert-butoxystyrene) can be obtained by adding a polymerization initiator in a short time. However, as a result of adding the polymerization initiator in a short time, the reaction rapidly occurs. There was an industrial problem that the reaction system generated heat and the temperature of the reaction system was likely to rise, making it difficult to control the temperature.
[0005]
[Problems to be solved by the invention]
Therefore, the present inventors have intensively studied to develop a method capable of stably producing narrow-dispersed poly (p-tert-butoxystyrene) while preventing rapid heat generation, and as a result, the reaction solvent and p-tert-butoxy are obtained. In the method of adding a polymerization initiator to a mixture with styrene, even if the water content of p-tert-butoxystyrene used is large, the molecular weight distribution of the resulting poly (p-tert-butoxystyrene) is not affected. In the method of adding p-tert-butoxystyrene or a solvent solution thereof to a mixture of a reaction solvent and a polymerization initiator, the water mixed in the p-tert-butoxystyrene or the solvent solution is obtained from the resulting poly (p- the molecular weight distribution of tert-butoxystyrene) and in such a process p-tert-butoxy By adjusting the water content of Shisuchiren or solvent solution below 70 ppm, it found that it is possible to manufacture stably a narrow dispersion of poly (p-tert-butoxystyrene), leading to the present invention.
[0006]
[Means for Solving the Problems]
That is, the present invention sequentially adds p-tert-butoxystyrene or a solvent solution thereof having a water content adjusted to 70 ppm or less to a mixture of a reaction solvent and a polymerization initiator in a temperature range of −50 ° C. to −10 ° C. The present invention provides a method for producing poly (p-tert-butoxystyrene), characterized by maintaining the temperature within the above temperature range.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
Examples of the reaction solvent used in the production method of the present invention include aromatic hydrocarbons such as benzene, toluene and xylene, hydrocarbon solvents such as aliphatic hydrocarbons such as hexane, heptane, cyclohexane and methylcyclohexane, tetrahydrofuran, 1, Examples include ethers such as 4-dioxane and ethylene glycol dimethyl ether, and mixtures of two or more of these. Of these, a mixed solvent of a hydrocarbon solvent and ethers is preferably used. The reaction solvent is usually used in an amount of about 1 to 20 times by weight, preferably about 2 to 10 times by weight with respect to pt-butoxystyrene.
[0008]
As the polymerization initiator, organic alkali metal compounds such as n-butyllithium, sec-butyllithium, i-butyllithium, t-butyllithium, 2-methylbutyllithium, lithiumnaphthalene and other organic lithium compounds, sodium naphthalene, sodium And organic sodium compounds such as anthracene, α-methylstyrene tetramer sodium and sodium biphenyl. Of these, n-butyllithium, sec-butyllithium and the like are preferably used.
The amount of the organometallic compound used varies depending on the molecular weight of the target poly (p-tert-butoxystyrene), but is about 10 −5 to 10 −3 mol per gram of monomer p-tert-butoxystyrene. Is preferred.
[0009]
The production method of the present invention is a method in which p-tert-butoxystyrene or a solvent solution thereof is added to a mixture of such a reaction solvent and a polymerization initiator.
[0010]
When a solvent solution of p-tert-butoxystyrene is added, examples of the solvent used in the solution include aromatic hydrocarbons such as benzene, toluene, and xylene, and aliphatic hydrocarbons such as hexane, heptane, cyclohexane, and methylcyclohexane. Hydrocarbon solvents such as tetrahydrofuran, ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, mixtures of two or more of these, etc., and the amount used is usually 0.1 with respect to p-tert-butoxystyrene. It is about 05-10 weight times, Preferably it is about 0.1-1 weight times. Such a solvent may be the same as or different from the reaction solvent.
[0011]
Such p-tert-butoxystyrene or a solvent solution thereof is adjusted to have a water content of 70 ppm or less. When the water content exceeds 70 ppm, it becomes difficult to obtain narrowly dispersed poly (p-tert-butoxystyrene). Therefore, it is preferably adjusted to 60 ppm or less, more preferably 50 ppm or less. The water content of Ri Do require special dehydrating agent to less than 5 ppm, because it requires complicated drying process, simply in that may be prepared water content, 5 ppm or more, further more 10ppm It is preferable to prepare it. The water content of p-tert-butoxystyrene or a solvent solution thereof can be easily measured by, for example, the Karl Fischer method.
[0012]
When p-tert-butoxystyrene is added alone, the water content of p-tert-butoxystyrene is adjusted to the range specified in the present invention, and then p-tert-butoxystyrene is added to the reaction solvent and the polymerization initiator. What is necessary is just to add to a mixture. Since p-tert-butoxystyrene to be used usually contains moisture mixed in from the atmosphere during storage, the water content of p-tert-butoxystyrene is adjusted to the range specified in the present invention. In general, the water content may be controlled within the range specified in the present invention. Examples of the method for suppressing the water content include a method using distillation under reduced pressure and a method using a desiccant such as molecular sieve or silica gel, and a method using a desiccant is more convenient.
[0013]
When a solvent solution of p-tert-butoxystyrene is added, the water content of the solution is adjusted to the range specified in the present invention, and then the solvent solution of p-tert-butoxystyrene is mixed with the reaction solvent and the polymerization initiator. What is necessary is just to add to a mixture. Since the solvent solution of p-tert-butoxystyrene and the p-tert-butoxystyrene and the solvent used for the preparation of the solution usually contain moisture mixed in from the atmosphere during storage, In order to make the water content of the solvent solution of tert-butoxystyrene within the range specified by the present invention, the water content of the solution should be usually controlled within the range specified by the present invention. In order to suppress the water content of the solution, for example, p-tert-butoxystyrene and a solvent may be mixed and then dried with a desiccant such as molecular sieve or silica gel, or dried in the same manner as described above. You may mix p-tert-butoxystyrene and the solvent previously dried with desiccants, such as a molecular sieve and a silica gel.
[0014]
In the production method of the present invention, p-tert-butoxystyrene or a solvent solution thereof is usually added sequentially to a mixture of a reaction solvent and a polymerization initiator under a high vacuum or an inert gas atmosphere such as argon or nitrogen. p-tert-Butoxystyrene or a solvent solution thereof is sequentially added to a mixture of a reaction solvent and a polymerization initiator at a temperature of about −50 to −10 ° C., and is usually about 10 minutes to 20 hours, preferably 15 minutes to 5 minutes. It is added sequentially to the mixture of the reaction solvent and the polymerization initiator over a period of time. After the addition, it is preferable to keep the temperature at the same temperature for about 5 minutes to 5 hours. By adding p-tert-butoxystyrene or a solvent solution thereof to the mixture of the reaction solvent and the polymerization initiator, p-tert-butoxystyrene is polymerized to produce the desired poly (p-tert-butoxystyrene). .
The polymerization reaction of p-tert-butoxystyrene can be stopped by adding a small amount of a polymerization reaction stopper such as water or methanol.
[0015]
Subsequently, the target narrowly dispersed poly (p-tert-butoxystyrene) can be isolated by distilling off the solvent from the reaction mass. The obtained poly (p-tert-butoxystyrene) can be purified by, for example, a method in which the solvent is distilled off and then injected into methanol or the like.
[0016]
The molecular weight distribution of the poly (p-tert-butoxystyrene) thus obtained is a molecular weight distribution (Mw / Mn) calculated from the polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) determined by GPC analysis. ).
[0017]
【Example】
Examples of the present invention are shown below, but the present invention is not limited to these examples.
[0018]
Example 1
Under a nitrogen atmosphere, hexane (water content is about 12 ppm) (587 cm 3 ) and sec-butyl lithium (5.9 mmol) from which water has been sufficiently removed by molecular sieves is added to a 1000 cm 3 flask, cooled to −40 ° C., A mixed solution of p-tert-butoxystyrene (88 g) and ethylene glycol dimethyl ether (6 cm 3 ) was then added dropwise over 1 hour using a molecular sieve until the water content measured by the Karl Fischer method was 12 ppm. Further, polymerization was carried out at −20 ° C. for 10 minutes, and methanol (about 3 cm 3 ) was added to stop the reaction. Subsequently, when a part of the obtained reaction mixture was collected and the solvent was distilled off, poly (p-tert-butoxystyrene) was obtained as a white solid product. When the molecular weight of this poly (p-tert-butoxystyrene) was measured by GPC analysis, the number average molecular weight Mn was 14900 (polystyrene conversion), and the molecular weight distribution Mw / Mn was 1.12.
[0019]
Example 2
Under a nitrogen atmosphere, hexane (water content is about 7 ppm) (587 cm 3 ) and sec-butyl lithium (5.9 mmol) from which water has been sufficiently removed by molecular sieves is added to a 1000 cm 3 flask, cooled to −40 ° C., there was added dropwise a mixed solution of p-tert-butoxystyrene (88 g) and ethylene glycol dimethyl ether (6 cm 3) (water content in the molecular sieve is dried until 43 ppm) in 1 hour, 10 at further -20 ° C. After the partial polymerization, methanol (about 3 cm 3 ) was added to stop the reaction. Subsequently, when a part of the obtained reaction mixture was collected and the solvent was distilled off, poly (p-tert-butoxystyrene) was obtained as a white solid product. When the molecular weight of this poly (p-tert-butoxystyrene) was measured by GPC analysis, the number average molecular weight Mn was 14300 (polystyrene conversion), and the molecular weight distribution Mw / Mn was 1.18.
[0020]
Comparative Example 1
In a nitrogen atmosphere, hexane (730 cm 3 ) and sec-butyllithium (5.6 mmol) from which water has been sufficiently removed by molecular sieves are added to a 1000 cm 3 flask, cooled to −40 ° C., and p-tert-butoxy is added thereto. A mixed solution of styrene (95 g) and ethylene glycol dimethyl ether (6 cm 3 ) (water content is 83 ppm) was added dropwise over 1 hour, polymerized at −20 ° C. for 10 minutes, and then methanol (about 2 cm 3 ) was added for reaction. Was stopped. Subsequently, when a part of the obtained reaction mixture was collected and the solvent was distilled off, poly (p-tert-butoxystyrene) was obtained as a white solid product. When the molecular weight of this poly (p-tert-butoxystyrene) was measured by GPC analysis, the number average molecular weight Mn was 18400 (polystyrene conversion), and the molecular weight distribution Mw / Mn was 1.33.
[0021]
Reference example 1
A mixed solution of 6 cm 3 of p-tert-butoxystyrene (95 g) and ethylene glycol dimethyl ether (water content of 87 ppm) in hexane (water content of about 6 ppm) (730 cm 3 ) from which water has been sufficiently removed by molecular sieve in a nitrogen atmosphere Was added to a 1000 cm 3 flask, cooled to −40 ° C., and sec-butyllithium (5.0 mmol) was added all at once. Thereafter, polymerization was further performed at −20 to −30 ° C. for 10 minutes, and methanol (about 2 cm 3 ) was added to stop the reaction. Next, when the molecular weight of poly (p-tert-butoxystyrene) contained in the obtained reaction mixture was measured by GPC analysis, the number average molecular weight Mn was 18200 (polystyrene conversion), and the molecular weight distribution Mw / Mn was 1. 09.
[0022]
【The invention's effect】
According to the present invention, p-tert-butoxystyrene having a moisture content adjusted to a range of 70 ppm or less or a solvent solution thereof is sequentially added to a mixture of a reaction solvent and a polymerization initiator to thereby form a poly (p- tert-butoxystyrene) can be stably produced. In addition, since p-tert-butoxystyrene or a solvent solution thereof is added to the mixture of the reaction solvent and the polymerization initiator, the temperature can be easily controlled without generating rapid heat of reaction, which is industrially advantageous.
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| JP11-251559 | 1999-09-06 | ||
| JP2000266641A JP3711851B2 (en) | 1999-09-06 | 2000-09-04 | Production method of poly (p-tert-butoxystyrene) |
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