JP3920224B2 - Method for producing ethylene oxide resin - Google Patents

Description

(ただし、R₁は、Ra(Raは、炭素数1〜16の、アルキル基、シクロアルキル基、アリール基、アラルキル基、（メタ）アクリロイル基およびアルケニル基の中のいずれかの基である)または-CH₂-O-Re-Ra基(Reは、-(CH₂-CH₂-O)p-の構造を有する(pは0から10までの整数))）
で示される置換オキシラン化合物とを含むコモノマー群を重合してなるものが好ましい。この重合は、各原料モノマーのオキシラン基の開環重合であることが好ましい。
【００１９】
上記構造式（１）におけるＲ₁基は、上記置換オキシラン化合物における置換基である。
原料モノマーとして用いる置換オキシラン化合物は、構造式（１）で示すことのできる置換オキシラン化合物１種のみであっても、２種以上を含むものであってもよい。
上記構造式（１）で示される置換オキシラン化合物としては、例えば、プロピレンオキシド、ブチレンオキシド、１，２−エポキシペンタン、１，２−エポキシへキサン、１，２−エポキシオクタン、シクロヘキセンオキシドおよびスチレンオキシド、または、メチルグリシジルエーテル、エチルグリシジルエーテルおよびエチレングリコールメチルグリシジルエーテルなどを挙げることができ、さらに、置換基Ｒ₁が架橋性の置換基である場合、つまり、置換基Ｒ₁がアリール基、アルケニル基、アクリロイル基およびメタクリロイル基などを有する場合として、エポキシブテン、３，４−エポキシ−１−ペンテン、１，２−エポキシ−５，９−シクロドデカジエン、３，４−エポキシ−１−ビニルシクロへキセン、１，２−エポキシ−５−シクロオクテン、アクリル酸グリシジル、メタクリル酸グリシジル、ソルビン酸グリシジルおよびグリシジル−４−ヘキサノエート、または、ビニルグリシジルエーテル、アリルグリシジルエーテル、４−ビニルシクロヘキシルグリシジルエーテル、α−テルペニルグリシジルエーテル、シクロヘキセニルメチルグリシジルエーテル、４−ビニルベンジルグリシジルエーテルおよび４−アリルベンジルグリシジルエーテルなども挙げることができる。上述したように、これらは単独で用いられても２種以上を併用されてもよい。
【００２０】
上記置換オキシラン化合物としては、上記架橋性の置換基を有する（置換基Ｒ₁が架橋性置換基である）置換オキシラン化合物を必須に用いることが、エチレンオキシド系樹脂（エチレンオキシド系共重合体）を架橋体にして用いるためには好ましい。
前記エチレンオキシド系樹脂の重量平均分子量（Ｍｗ）は、特に限定はされないが、２０，０００〜３００，０００であることが好ましく、より好ましくはより好ましくは３０，０００〜２００，０００、さらに好ましくは４０，０００〜１５０，０００である。上記重量平均分子量が２０，０００未満の場合は、成形物にタックが生じるおそれがあり、３００，０００を超える場合は、成形が困難となり、加工性およびハンドリング性が低下するおそれがある。
【００２１】
前記エチレンオキシド系樹脂の分子量分布（Ｍｗ／Ｍｎ）は、特に限定はされないが、３以下であることが好ましく、より好ましくは２以下である。上記分子量分布が３を超える場合は、成形体にした時にタックが生じ、ハンドリングが悪くなるおそれがある。
〔脱揮〕
本発明にかかる製造方法においては、エチレンオキシド系樹脂と溶媒とを含む重合後の重合反応液から溶媒成分を脱揮する（溶媒成分を揮発させる）ことにより、エチレンオキシド系樹脂を得るようにしているが、得られるエチレンオキシド系樹脂は、溶媒成分を全く含まないものには限定されるわけではなく、通常、脱揮により上記重合反応液の状態から所望の溶媒濃度となるまで減少させられ調整されたものであるとする。
【００２２】
脱揮の方法、脱揮する際に用いる装置および各種条件としては、通常の脱揮の際の方法、使用可能な装置および設定される条件等を採用すればよい。詳しくは以下に示す。
脱揮の方法としては、通常、プレ脱揮と本脱揮との二段階があり、脱揮の手順としては、プレ脱揮の後に本脱揮を行うことが好ましいが、特に限定されるわけではなく、プレ脱揮と本脱揮を区別せずに一段階の工程として行ってもよい。二段階に分けて行うことが好ましいのは、脱揮の効率アップ（コストダウン、処理時間の短縮、樹脂の品質など）が可能となるからであり、具体的には、▲１▼脱揮前の重合反応液に多く含まれる溶媒を効率良く脱揮処理が行える程度の溶媒量にまで急速に減らした後にゆっくりと脱揮処理を行うことができる、▲２▼前段を常圧脱揮とし後段を真空（減圧）脱揮とすることによって一段で処理する場合より機器サイズを小さくすることができる、▲３▼脱揮時にはある濃度域で急激に粘度上昇することがあり一段で処理する場合より駆動系を小さくできる、などの理由により理論的にも好適であるが、脱揮処理する重合反応液の種類（特に、重合反応液中の樹脂の種類）などよって、上記一段階の処理であっても、二段階の処理と同様に行える（二段階の処理と同様の効果が得られる）場合があるので、適宜選択すればよい。
【００２３】
脱揮する際に用いる装置（脱揮装置）としては、特に限定されるわけではないが、撹拌槽蒸発器、下流液柱蒸発器、薄膜蒸発器、表面更新型重合器、ニーダー、ロールミキサー、インテンシブミキサー（いわゆるバンバリーミキサー）、押出機などが好ましく挙げられ、これら装置のうち少なくとも１つの装置を用いて行うことが好ましい。また、用いる装置によって適宜使用条件を設定することができる。
撹拌槽蒸発器は、広範囲な粘度、広範囲な残留溶媒濃度に対応できる点で優れており、例えば、ヘリカル翼を搭載した撹拌槽、ダブルヘリカルリボン翼を搭載した撹拌槽、スーパーブレンド翼（内翼：マックスブレンド翼、外翼：螺旋状変形バッフル）を搭載した竪型同心二軸撹拌槽（例えば、製品名：スーパーブレンド、住友重機械工業（株）製）、ＶＣＲ逆円錐リボン翼式リアクター（三菱重工（株）製）などが好ましく挙げられる。これらは、バッチ式での処理および連続式での処理の両方に用いることができるが、バッチ式での処理に用いることが好ましい。また、装置の特性上、処理後の排出の際に多くの時間を必要とするので、大量の樹脂等を処理するというプロセスよりも、少量を正確に処理するプロセスに好ましく対応している。また、これらを用いた場合、蒸発プロセスは伝熱面更新により行われる。
【００２４】
上記各種撹拌槽蒸発器のなかでも、特に、竪型同心二軸撹拌槽については、以下▲１▼〜▲６▼のような優れた特徴を挙げることができる。▲１▼処理粘度領域が広範囲であり、１〜１０,０００ポイズの粘度領域で優れた混合性能を発揮することができる、▲２▼槽内の急激な粘度変化に追従して、内・外翼の混合機能が自然に変化・対応するため、良好な流動状態を保持することができる、▲３▼槽内壁面および槽内中心部での液流速（重合反応液の流速）を均一にすることができるため、高い温度均一性を保つことができ、樹脂の品質劣化を低減できる、▲４▼高粘度流体上での低粘度液の滑りおよび滞留が解消し、リフラックス還流液および重合後の各種添加剤等の分散性を向上させることができる、▲５▼高濃度スラリー処理時の槽壁およびバッフル部への付着・堆積を解消することができ、良好なスラリー分散性を示す、▲６▼外翼が槽壁面に近接して回転することによる安定した壁面流速により、内壁部の付着および槽内洗浄時間・回数を低減することができる。
【００２５】
下流液柱蒸発器としては、多管式熱交換器型（例えば、製品名：スルザーミキサー、住友重機械工業（株）製；製品名：スタテックミキサー、ノリタケ社製）、プレート熱交換器型（例えば、製品名：Ｈｉｖｉｓｃｏｕｓ Ｅｖａｐｏｒａｔｏｒ、三井造船（株）製）などが好ましく挙げられる。これらは、バッチ式での処理および連続式での処理の両方に用いることができ、どちらの処理も良好に行うことができる。また、装置の特性上、これらによる脱揮は、加熱を顕熱で行い、その後減圧下で顕熱を潜熱に転換して蒸発させるため、脱揮できる量は顕熱加熱量（潜熱として伝達し得る熱量）に依存することとなる。よって、顕熱加熱量に対応した処理量とするプロセスが好ましいが、多管式熱交換器型では、スティックミキサーによって伝熱を促進させることができるため、広範囲な処理量のプロセスにも対応できる。また、多管式熱交換器型の場合は、蒸発プロセスは界面積拡大により行われ、対応最大処理粘度は５０,０００ポイズであることが好ましく、プレート熱交換器型の場合は、蒸発プロセスは伝熱面積拡大により行われ、対応最大処理粘度は１０,０００ポイズであることが好ましい。
【００２６】
薄膜蒸発器は、ブレードにより遠心力が働き、均一な液膜が形成できる点で優れており、例えば、横型薄膜蒸発器（例えば、製品名：エバリアクター、関西化学機械製作（株）製）、固定ブレード式の竪型薄膜蒸発器（例えば、製品名：ＥＸＥＶＡ、神鋼パンテック（株）製）、可動ブレード式の竪型薄膜蒸発器（例えば、製品名：ワイプレン、神鋼パンテック（株）製）、槽型（鏡型）薄膜蒸発器（例えば、製品名：リカバリー、関西化学機械製作（株）製）などが好ましく挙げられる。これらについて、バッチ式での処理に関しては、横型および槽型のものは一般的ではないが可能であり、竪型のものは固定ブレード式、可動ブレード式に関わらず不可能である。また、連続式での処理に関してはすべて可能である。装置の特性上、これらはすべて、脱揮は、加熱を顕熱で行い、その後減圧下で顕熱を潜熱に転換して蒸発させるため、脱揮できる量は顕熱加熱量（潜熱として伝達し得る熱量）に依存することとなる。よって、顕熱加熱量に対応した処理量とするプロセスが好ましい。また、これらはすべて、蒸発プロセスは伝達面更新により行われる。
【００２７】
横型薄膜蒸発器は、竪型に比べ排出面で高粘度への対応が困難であるため、排出効果に優れたブレードを使用し、高粘度にも対応できるようになっており、対応最大処理粘度は５００ポイズであることが好ましい。竪型薄膜蒸発器は、自重で下降するため低粘度液よりも高粘度液のほうが適しているといえ、可動ブレード式の対応最大処理粘度は１,０００ポイズであることが好ましい。また、固定ブレード式では固定翼に掻き下げ効果を持たせることで高粘度に対応させており、対応最大処理粘度は１０,０００ポイズであることが好ましい。槽型薄膜蒸発器は、鏡を利用することにより低粘度液のショートパスを抑えることができ、対応最大処理粘度は１,０００ポイズであることが好ましい。
【００２８】
表面更新型重合器（横型薄膜重合器）は、気液表面の更新によって高い脱揮性能を示す点で優れており、例えば、単軸型表面更新型重合器、二軸型表面更新型重合器（例えば、製品名：バイボラック、住友重機械工業（株）製；製品名：日立メガネ翼重合機、（株）日立製作所製；製品名：日立格子翼重合機、（株）日立製作所製；製品名：ＳＣプロセッサ、栗本鉄工所社製）などが好ましく挙げられる。これらは、バッチ式での処理に関しては不可能であり、連続式での処理に関してはすべて可能である。装置の特性上、これらはすべて、脱揮の処理量は装置内の物質の移動速度に依存しており、蒸発プロセスは気液面更新により行われる。
【００２９】
ニーダー、ロールミキサー、インテンシブミキサー（いわゆるバンバリーミキサー）は、押出機と同様、高粘度融体などの混合に適し、付加機能として脱揮能力を備えるものである。これらは、バッチ式での処理も連続式での処理もすべて可能である。これらについては、その対応最大処理粘度は１０,０００ポイズであることが好ましい。
単軸型のものは、効率的な表面積の確保が可能なため高い脱揮性能を示し、その対応最大処理粘度は１０,０００ポイズであることが好ましい。また、二軸型のものは、容器内のデッドスペースの無さや高いピストンフロー性によりセルフクリーニング性および液の滞留抑制に優れており、その対応最大処理粘度は１０,０００ポイズであることが好ましい。
【００３０】
押出機は、高粘度融体などの混合に適し、付加機能として加熱、溶融、混練とともに脱揮能力を備えるものであり、例えば、単軸型押出機、二軸型押出機（例えば、製品名：ＳＵＰＥＲＴＥＸαＩＩ、日本製鋼所製；製品名：ＢＴ−３０−Ｓ２、プラスティック工学研究所製）、ＳＣＲセルフクリーニング式リアクター（三菱重工（株）製）などが好ましく挙げられる。これらは、バッチ式での処理は不可能であり、連続式での処理はすべて可能である。装置の特性上、これらは、上述のように、非常に粘度の高いものを対象に脱揮処理するプロセスに好適であり、蒸発プロセスは混練および蒸発等により行われる。
【００３１】
押出機においては、単軸型のもの、二軸型のもの共に、その対応最大処理粘度は１００,０００ポイズであることが好ましい。
上述したように、好ましい脱揮方法としてプレ脱揮の後に本脱揮する方法を挙げることができるが、上記各種脱揮装置のうち、プレ脱揮に好ましく用いることのできるものは、特に限定はされないが、ダブルヘリカルリボン翼を搭載した撹拌槽、スーパーブレンド翼を搭載した竪型同心二軸撹拌槽、プレート熱交換器型の下流液柱蒸発器および固定ブレード式の竪型薄膜蒸発器などが挙げられる。また、本脱揮に好ましく用いることのできるものは、特に限定はされないが、固定ブレード式の竪型薄膜蒸発器、二軸型表面更新型重合器、ニーダー、二軸型押出機などが挙げられる。
【００３２】
本発明の製造方法において、重合反応液の脱揮を行うに当たっては、前述した溶媒を用いた重合の工程等に供したいわゆる前段装置に、上記列挙した各種脱揮装置を直結させて脱揮を行ってもよいし、この前段装置から送液や移送を介した上で各種脱揮装置により脱揮を行ってもよい。後者については、例えば、上記前段装置から脱揮装置までの間が送液ラインで連結されているような形態や、上記前段装置から脱揮装置までの間にジャケットや撹拌機を備えた中間槽タンク（クッションタンク）を設けた形態等が挙げられる。
本発明の製造方法においては、脱揮により、脱揮後のエチレンオキシド系樹脂中の残存溶媒濃度を０．０１〜３０重量％となるようにすることを特徴とし、好ましくは０．０５〜２０重量％、より好ましくは０．１〜１０重量％である。上記残存溶媒濃度が０．０１重量％未満である場合は、脱揮条件を過剰に厳しくする必要があるため、エチレンオキシド系樹脂の熱劣化につながり、性能低下が生じることとなるおそれがあり、３０重量％を超える場合は、脱揮後のエチレンオキシド系樹脂にタックが生じ、ブロッキングなどが生じることとなるおそれがある。
【００３３】
本発明の製造方法においては、脱揮後のエチレンオキシド系樹脂中の含有水分量を、溶媒の脱揮の際に同時に調整することが好ましい。水分は、例えば、重合の際に用いた溶媒やモノマーなどに含まれる。本発明の製造方法においては、上記調整により上記含有水分量を２００ｐｐｍ以下にすることを特徴とする。上記含有水分量が２００ｐｐｍを超える場合は、樹脂の誘電率が必要以上に大きくなるため、例えば、得られたエチレンオキシド系樹脂をカラーフィルターの保護膜などに用いた場合は、樹脂が導電性となることにより上記保護膜としては致命的な機能低下を引き起こしてしまうおそれがあり、また、水分が金属イオン分などと反応して水酸化物等を生成してしまうため、例えば、エチレンオキシド系樹脂をポリマー電池の電解質層などに用いた場合は、金属−電解質層界面に絶縁層を形成してしまい、定電流下での電圧が上昇し続け、電池のサイクル特性も悪化することとなるおそれがある。
【００３４】
上記含有水分量の調整する手段としては、特に限定されるわけではないが、具体的には、脱揮温度を高くすること、および／または、脱揮の減圧度を大きくすることが好ましい（なお、減圧度を大きくすることは圧力を低くすることを意味し、減圧度を小さくすることは圧力を高くすることを意味する。）。脱揮温度を高くして含有水分量の調整をする場合、その温度は、特に限定はされないが、低すぎると、減圧度を過剰に大きくしなければならないため効率的ではなく、高すぎると、樹脂の熱劣化が生じることとなるおそれがあるため、これらを考慮し適宜設定するようにする。また、脱揮の減圧度を大きくして含有水分量の調整をする場合、その減圧度は、特に限定はされないが、大きすぎると、脱揮装置の密閉性を考慮すると困難であると考えられ、小さすぎると、脱揮温度をかなり上昇させないと含有水分量を２００ｐｐｍ以下にコントロールできないおそれがあるため、これらを考慮し適宜設定するようにする。
【００３５】
本発明の製造方法によれば、脱揮後のエチレンオキシド系樹脂には帯電防止剤を含ませないようにすることができる。理由としては、上述したように、本発明では、エチレンオキシド系樹脂を、重合後、加熱乾燥ではなく脱揮により得るため、加熱乾燥下の樹脂どうしの摩擦等で生じる樹脂の帯電を考慮する必要がないからである。得られるエチレンオキシド系樹脂に帯電防止剤が含まれる場合は、樹脂の誘電率を必要以上に高めてしまう、または、架橋度低下や吸湿性上昇を引き起こし樹脂の膨潤倍率を必要以上に増加させ強度を低下させてしまう、こととなる。よって、例えば、得られたエチレンオキシド系樹脂をカラーフィルターの保護膜などに用いた場合は、樹脂が導電性となることにより上記保護膜としては致命的な機能低下を引き起こしてしまう。また、該樹脂をフレキソ印刷版材などに用いた場合は、所望の形状や反発弾性が維持しにくいため画像再現性にも劣ったものとなる。さらに、該樹脂をポリマー電池のセパレーター、電極および電解質層などに用いた場合は、所望の形状が保てない。
【００３６】
前述した脱揮装置を用い、重合反応液から溶媒を加温下で脱揮する際は、その温度は、４０〜３００℃であることが好ましく、より好ましくは６０〜２５０℃、さらに好ましくは９０〜２００℃である。この温度範囲で脱揮を行うことによって、脱揮後に、上述した所望の残存溶媒濃度および含有水分量のエチレンオキシド系樹脂を得ることができる。上記温度が、４０℃未満の場合は、残存する溶媒が多くなるおそれがあり、３００℃を超える場合は、ポリエーテル自体が熱分解するおそれがある。ここで、上記温度とは、脱揮装置内のエチレンオキシド系樹脂の温度である。
【００３７】
同様に、上記脱揮装置を用いて溶媒を脱揮するにあたっては、圧力は、１３〜１００，０００Ｐａの範囲で行うことが好ましく、より好ましくは１３３〜７０，０００Ｐａ、さらに好ましくは１,３３３〜４０，０００Ｐａである。この圧力の範囲を満たすようにすることによって、脱揮後に、上述したような溶媒濃度および含有水分量のエチレンオキシド系樹脂を得ることができる。上記圧力が、１３Ｐａ未満の場合は、溶媒がフラッシュしてしまいフォーミングが起こるおそれがあり、１００，０００Ｐａを超える場合は、ポリエーテルが分解するぐらいまで温度をかけなければならないおそれがある。ここで、上記圧力とは、脱揮装置の槽内圧力である。
【００３８】
本発明の製造方法においては、脱揮後のエチレンオキシド系樹脂の粘度は、１００℃で５０〜１００，０００ポイズとなることが好ましく、より好ましくは１００℃で１００〜８０，０００ポイズ、さらに好ましくは１００℃で２２０〜６０，０００ポイズである。上記粘度が１００℃で５０ポイズ未満の場合は、残存する溶媒が多くなり、成形体としたときに発泡およびタックが生じるおそれがあり、１００，０００ポイズを超える場合は脱揮装置での脱揮が困難になるおそれがある。
〔エチレンオキシド系樹脂の用途〕
本発明の製造方法により得られるエチレンオキシド系樹脂は、例えば、接着剤、塗料、シーリング剤、エラストマー、床剤等のポリウレタン樹脂の他、硬質、軟質もしくは半硬質のポリウレタン樹脂、さらには、界面活性剤、サニタリー製品、脱墨剤、潤滑油、作動液、ポリマー電池に用いるセパレーター、電極および高分子電解質層や、カラーフィルター保護膜、レジストおよびフレキソ印刷版材等に用い得る感光性樹脂、などといった広範囲な用途に対する高分子材料として好ましく使用することができる。
【００３９】
【実施例】
以下に、実施例により、本発明をさらに具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、以下では、便宜上、「重量部」を単に「部」と、「時間」を単に「ｈ」と、「リットル」を単に「Ｌ」と記すことがある。
下記実施例および比較例での、各種測定の条件を以下に示す。
〔脱揮後の樹脂中の残存溶媒量の測定〕
高速液体クロマトグラフィー（カラム：ＯＤＳ−３（ＧＬサイエンス社製）、カラム温度：４０℃、流量：１．０ｍＬ／分、注入量：５μＬ、ＵＶ検出器：２１０ｎｍ、溶離液：「アセトニトリル／０．１ｗｔ％リン酸水溶液」の混合液（体積比：アセトニトリル／０．１ｗｔ％リン酸水溶液＝８５／１５））により、試料サンプル中の残存溶媒量（ｗｔ％）を測定する。試料サンプルとしては、測定対象とする脱揮後の樹脂を、固形分１．０ｗｔ％となるように上記溶離液で希釈したものを用いる。具体的な測定方法は、初めに所定の溶媒（例えば、トルエン）についての検量線サンプルを用いて検量線を作成しておき、その後、上記試料サンプルを測定し、検量線を用いて残存溶媒量を求める。
〔脱揮後の樹脂中の含有水分量の測定〕
グローブボックス中に、下記▲１▼〜▲４▼、すなわち、▲１▼脱揮後により得られたエチレンオキシド系樹脂を、乾燥雰囲気下、熱時で（脱揮温度に近い樹脂温度を保持した流動性ある状態で）サンプリングし自然冷却しておいたもの、▲２▼溶媒としてのトルエン（予めモレキュラーシーブス（ユニオン昭和社製、製品名：モレキュラーシーブ３Ａ１．６あるいはモレキュラーシーブ４Ａ１．６）にて含有水分量を極力減らしておいたもの）、▲３▼ガラス容器および▲４▼注射器を入れて、２時間以上乾燥する。
【００４０】
乾燥後、ガラス容器に、エチレンオキシド系樹脂２ｇとトルエン１８ｇとを投入し、マグネチックスターラーで十分に溶解させ樹脂溶液とした後、注射器で該樹脂溶液をすべて採取する。同時に、別の注射器でトルエンのみを１８ｇ採取する。
採取後のそれぞれの注射器をグローブボックスから外部へ持ち出し、ＡＱＵＡＣＯＵＮＴＥＲＱ−７（ＨＩＲＡＮＵＭＡ社製の含有水分量測定装置）を用いて、樹脂溶液とトルエンのみとにおける含有水分量をそれぞれ測定する。
この測定により求められる含有水分量（ｐｐｍ）の値から、樹脂溶液とトルエンのみとに含まれる水分の重量（ｍｇ）をそれぞれ算出し、その差からエチレンオキシド系樹脂に含まれる水分の重量（ｍｇ）を求める。そこで、この差である水分の重量（ｍｇ）を、初めに溶解させたエチレンオキシド系樹脂の重量（２ｇ）で割ることにより、エチレンオキシド系樹脂の含有水分量（ｐｐｍ）を算出する。
〔エチレンオキシド系樹脂の重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）の測定〕
ポリエチレンオキシドの標準分子量サンプルを用いて検量線を作成したＧＰＣ装置により測定した。反応後に得られた重合反応液（ポリマーを含む）を所定の溶媒に溶解後、測定した。
【００４１】
−実施例１−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ａ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ａ）を得た。なお、エチレンオキシド系樹脂（ａ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、メチルグリシジルエーテル由来の構造単位とを、順に、１８０重量部、１２重量部、８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１００，０００であった。
【００４２】
重合反応液（ａ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、４６ｋｇ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ａ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１７８℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ａ）とトルエンの重量％比（樹脂／トルエン）が９９．７９重量％／０．２１重量％であり、含有水分量が３５ｐｐｍであった。
【００４３】
−実施例２−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｂ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｂ）を得た。なお、エチレンオキシド系樹脂（ｂ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、メチルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、２５．２重量部、１６．８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが９０，０００であった。
【００４４】
重合反応液（ｂ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、３０ｋｇ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｂ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１７３℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｂ）とトルエンの重量％比（樹脂／トルエン）が９９．８３重量％／０．１７重量％であり、含有水分量が２８ｐｐｍであった。
【００４５】
−実施例３−
（二軸押出機）
溶液重合により、エチレンオキシド系樹脂（ｃ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｃ）を得た。なお、エチレンオキシド系樹脂（ｃ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、メチルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、２５．２重量部、１６．８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが９５，０００であった。
【００４６】
重合反応液（ｃ）をあらかじめ溶融させた後、原料タンクに仕込み、８０℃に加温しておく。同時に、３０φ二軸押出機（製品名：ＢＴ−３０−Ｓ２、プラスティック工学研究所製）のジャケットを、バックベントでは１８０℃に、供給ベントおよび第１ベントから第５ベントまででは全て１５０℃に加熱し、二軸を２００ｒｐｍで回転させておく。その後、原料タンクからギアポンプを用いて、重合反応液（ｃ）を１４．４ｋｇ／ｈの供給速度で、３０φ二軸押出機（製品名：ＢＴ−３０−Ｓ２、プラスティック工学研究所製）に供給し、供給と同時に、バックベントを１００Ｔｏｒｒ（１３，３３２Ｐａ）に、第１ベントを７０Ｔｏｒｒ（９，３３３Ｐａ）に、第２ベントから第４ベントまでを全て７０Ｔｏｒｒ（９，３３３Ｐａ）以下に減圧する（供給ベントおよび第５ベントは特に減圧しない）ことにより、重合反応液（ｃ）を脱揮により濃縮した。３０φ二軸押出機の出口の樹脂温度は２０８℃であった。
【００４７】
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｃ）とトルエンの重量％比（樹脂／トルエン）が９９．８３重量％／０．１７重量％であり、含有水分量が３０ｐｐｍであった。
−実施例４−
（二軸押出機）
溶液重合により、エチレンオキシド系樹脂（ｄ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｄ）を得た。なお、エチレンオキシド系樹脂（ｄ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、メチルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、２５．２重量部、１６．８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが８４，０００であった。
【００４８】
重合反応液（ｄ）をあらかじめ溶融させた後、原料タンクに仕込み、８０℃に加温しておく。同時に、３０φ二軸押出機（製品名：ＢＴ−３０−Ｓ２、プラスティック工学研究所製）のジャケットを、バックベント、供給ベント、第１ベントおよび第２ベントでは１２０℃に、第３ベントでは８０℃に、第４ベントおよび第５ベントでは１００℃に加熱し、二軸を８０ｒｐｍで回転させておく。その後、原料タンクからギアポンプを用いて、重合反応液（ｄ）を４．８ｋｇ／ｈの供給速度で、３０φ二軸押出機（製品名：ＢＴ−３０−Ｓ２、プラスティック工学研究所製）に供給し、供給と同時に、バックベントを１１０Ｔｏｒｒ（１４，６６５Ｐａ）に、第１ベントを７０Ｔｏｒｒ（９，３３３Ｐａ）に、第２ベント、第３ベントおよび第５ベントを全て７０Ｔｏｒｒ（９，３３３Ｐａ）以下に減圧する（供給ベントおよび第４ベントは特に減圧しない）ことにより、重合反応液（ｄ）を脱揮により濃縮した。３０φ二軸押出機の出口の樹脂温度は９５℃であった。
【００４９】
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｄ）とトルエンの重量％比（樹脂／トルエン）が９９．２５重量％／０．７５重量％であり、含有水分量が１２５ｐｐｍであった。
−実施例５−
（撹拌槽蒸発器）
溶液重合により、実施例４と同様の、エチレンオキシド系樹脂（ｄ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｄ）を得た。
【００５０】
重合反応液（ｄ）４５ｋｇを、スーパーブレンド翼（内翼：マックスブレンド翼、外翼：螺旋状変形バッフル）を搭載した竪型同心二軸撹拌槽（製品名：スーパーブレンド、住友重機械工業（株）製）に投入し、ジャケット温度を１６０℃に加熱した状態で、マックスブレンド翼を１６ｒｐｍ、螺旋状変形バッフルを１７ｒｐｍで正回転で撹拌させ、大気圧下で３時間トルエン脱揮し、更にその後、最大４１０Ｔｏｒｒ（５４，６６２Ｐａ）の減圧下で１．５時間トルエン脱揮することにより、重合反応液（ｄ）を濃縮した。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｄ）とトルエンの重量％比（樹脂／トルエン）が９２．４重量％／７．６重量％であり、含有水分量が２００ｐｐｍであった。
【００５１】
−実施例６−
（撹拌槽蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｅ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｅ）を得た。なお、エチレンオキシド系樹脂（ｅ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、メチルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、２５．２重量部、１６．８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１０３，０００であった。
【００５２】
重合反応液（ｅ）４５ｋｇを、スーパーブレンド翼（内翼：マックスブレンド翼、外翼：螺旋状変形バッフル）を搭載した竪型同心二軸撹拌槽（製品名：スーパーブレンド、住友重機械工業（株）製）に投入し、ジャケット温度を１６０℃に加熱した状態で、マックスブレンド翼を７５ｒｐｍ、螺旋状変形バッフルを３０ｒｐｍで正回転で撹拌させ、大気圧下で３．５時間トルエン脱揮し、更にその後、最大５０Ｔｏｒｒ（６，６６６Ｐａ）の減圧下で１．５時間トルエン脱揮することにより、重合反応液（ｅ）を濃縮した。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｅ）とトルエンの重量％比（樹脂／トルエン）が９９．６０重量％／０．４０重量％であり、含有水分量が８９ｐｐｍであった。
【００５３】
−実施例７−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｆ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｆ）を得た。なお、エチレンオキシド系樹脂（ｆ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、アリルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、２５．２重量部、１６．８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが９７，０００であった。
【００５４】
重合反応液（ｆ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、３３Ｌ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｆ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１７５℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｆ）とトルエンの重量％比（樹脂／トルエン）が９９．８４重量％／０．１６重量％であり、含有水分量が２７ｐｐｍであった。
【００５５】
−実施例８−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｇ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｇ）を得た。なお、エチレンオキシド系樹脂（ｇ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、アリルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、２５．２重量部、４重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが９７，０００であった。
【００５６】
重合反応液（ｇ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、３３Ｌ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｇ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１７５℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｇ）とトルエンの重量％比（樹脂／トルエン）が９９．８３重量％／０．１７重量％であり、含有水分量が２９ｐｐｍであった。
【００５７】
−実施例９−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｈ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｈ）を得た。なお、エチレンオキシド系樹脂（ｈ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、アリルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、１５重量部、１６重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１１０，０００であった。
【００５８】
重合反応液（ｈ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、６０ｋｇ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｈ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を６００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１５０℃、圧力５００Ｔｏｒｒ（６６，６６１Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１３８℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｈ）とトルエンの重量％比（樹脂／トルエン）が９０．１０重量％／９．９０重量％であり、含有水分量が１９０ｐｐｍであった。
【００５９】
−実施例１０−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｉ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｉ）を得た。なお、エチレンオキシド系樹脂（ｉ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、アリルグリシジルエーテル由来の構造単位とを、順に、３７８重量部、４０重量部、１６重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１１０，０００であった。
【００６０】
重合反応液（ｉ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、６０ｋｇ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｉ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を６００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１５０℃、圧力５００Ｔｏｒｒ（６６，６６１Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１３８℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｉ）とトルエンの重量％比（樹脂／トルエン）が９０．１０重量％／９．９０重量％であり、含有水分量が１８０ｐｐｍであった。
【００６１】
−実施例１１−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｊ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｊ）を得た。なお、エチレンオキシド系樹脂（ｊ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位と、エポキシブテン由来の構造単位とを、順に、３７８重量部、２５．２重量部、１６．８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが２６，０００であった。
【００６２】
重合反応液（ｊ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、３０ｋｇ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｊ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１７３℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｊ）とトルエンの重量％比（樹脂／トルエン）が９９．８３重量％／０．１７重量％であり、含有水分量が２５ｐｐｍであった。
【００６３】
−実施例１２−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｋ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｋ）を得た。なお、エチレンオキシド系樹脂（ｋ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位とを、順に、２５７重量部、１６．８重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが８０，０００であった。
重合反応液（ｋ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、３０ｋｇ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｋ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１７３℃であった。
【００６４】
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｋ）とトルエンの重量％比（樹脂／トルエン）が９９．８３重量％／０．１７重量％であり、含有水分量が２６ｐｐｍであった。
−実施例１３−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｌ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｌ）を得た。なお、エチレンオキシド系樹脂（ｌ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位とを、順に、３７８重量部、２６重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１１０，０００であった。
【００６５】
重合反応液（ｌ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、４４Ｌ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｌ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器への供給時の樹脂温度は６９℃であり、薄膜蒸発器の出口の樹脂温度は１７５℃であった。
【００６６】
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｌ）とトルエンの重量％比（樹脂／トルエン）が９９．５３重量％／０．４７重量％であり、含有水分量が７８ｐｐｍであった。
−実施例１４−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｍ）とトルエンとの重量％比（樹脂／トルエン）が５０重量％／５０重量％である重合反応液（ｍ）を得た。なお、エチレンオキシド系樹脂（ｍ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位とを、順に、２００重量部、２５重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１０５，０００であった。
【００６７】
重合反応液（ｍ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、３９Ｌ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｍ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器の出口の樹脂温度は１７６℃であった。
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｍ）とトルエンの重量％比（樹脂／トルエン）が９９．７４重量％／０．２６重量％であり、含有水分量が４３ｐｐｍであった。
【００６８】
−実施例１５−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｎ）とトルエンとの重量％比（樹脂／トルエン）が３３重量％／６７重量％である重合反応液（ｎ）を得た。なお、エチレンオキシド系樹脂（ｎ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位とを、順に、３７８重量部、２９重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１７５，０００であった。
重合反応液（ｎ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、１１．４Ｌ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｎ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器への供給時の樹脂温度は７４℃であり、薄膜蒸発器の出口の樹脂温度は１８０℃であった。
【００６９】
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｎ）とトルエンの重量％比（樹脂／トルエン）が９９．７０重量％／０．３０重量％であり、含有水分量が５０ｐｐｍであった。
−実施例１６−
（薄膜蒸発器）
溶液重合により、エチレンオキシド系樹脂（ｏ）とトルエンとの重量％比（樹脂／トルエン）が３３重量％／６７重量％である重合反応液（ｏ）を得た。なお、エチレンオキシド系樹脂（ｏ）は、エチレンオキシド由来の構造単位と、ブチレンオキシド由来の構造単位とを、順に、２００重量部、２６重量部の割合で有する樹脂であり、重量平均分子量Ｍｗが１８０，０００であった。
【００７０】
重合反応液（ｏ）をあらかじめ５０〜１００℃で熱媒のスチームによって加温しておき、原料タンクに仕込んだ後、この原料タンクからギアポンプを用いて、２２．１Ｌ／ｈの供給速度で、薄膜蒸発器（製品名：ＥＸＥＶＡ、神鋼パンテック社製）に供給し、重合反応液（ｏ）を脱揮により濃縮した。薄膜蒸発器は、撹拌翼モーターの回転数を３００ｒｐｍ、排出スクリューの回転数を９０〜１００ｒｐｍ、ジャケット温度１８０℃、圧力５０Ｔｏｒｒ（６，６６６Ｐａ）に設定して用いた。薄膜蒸発器への供給時の樹脂温度は７４℃であり、薄膜蒸発器の出口の樹脂温度は１８２℃であった。
【００７１】
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｏ）とトルエンの重量％比（樹脂／トルエン）が９９．３９重量％／０．６１重量％であり、含有水分量が１０２ｐｐｍであった。
−実施例１７−
（二軸押出機）
溶液重合により、実施例１６と同様の、エチレンオキシド系樹脂（ｏ）とトルエンとの重量％比（樹脂／トルエン）が３３重量％／６７重量％である重合反応液（ｏ）を得た。
【００７２】
重合反応液（ｏ）をあらかじめ溶融させた後、原料タンクに仕込み、８０℃に加温しておく。同時に、３０φ二軸押出機（製品名：ＢＴ−３０−Ｓ２、プラスティック工学研究所製）のジャケットを、バックベント、供給ベントおよび第１ベントから第４ベントまででは全て１８０℃に、第５ベントでは１００℃に加熱し、二軸を１００ｒｐｍで回転させておく。その後、原料タンクからギアポンプを用いて、重合反応液（ｏ）を８．５ｋｇ／ｈの供給速度で、３０φ二軸押出機（製品名：ＢＴ−３０−Ｓ２、プラスティック工学研究所製）に供給し、供給と同時に、バックベントを１５０Ｔｏｒｒ（１９，９９８Ｐａ）に、第１ベントを８０Ｔｏｒｒ（１０，６６６Ｐａ）に、第２ベントから第４ベントまでを全て８０Ｔｏｒｒ（１０，６６６Ｐａ）以下に減圧する（供給ベントおよび第５ベントは特に減圧しない）ことにより、重合反応液（ｏ）を脱揮により濃縮した。
【００７３】
脱揮後に得られた樹脂は、エチレンオキシド系樹脂（ｏ）とトルエンの重量％比（樹脂／トルエン）が９９．２４重量％／０．７６重量％であり、含有水分量が１２７ｐｐｍであった。
【００７４】
【発明の効果】
本発明によれば、エチレンオキシド系樹脂を得るにあたり、帯電防止剤を含まないようにしつつ含有水分量も一定量以下にコントロールすることが容易で、かつ、該樹脂の熱的ダメージを防ぐと共にコストダウンを実現することもできる、新規なエチレンオキシド系樹脂の製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an ethylene oxide resin. Specifically, the present invention relates to a method for producing an ethylene oxide resin including a step of devolatilizing the resin reaction liquid obtained by a polymerization reaction.
[0002]
[Prior art]
Conventionally, ethylene oxide resins have been used for polyurethane resins such as adhesives, paints, sealing agents, elastomers, flooring, hard, soft or semi-rigid polyurethane resins, and surfactants, sanitary products, deinking agents. In recent years, in view of its versatility, it is considered to be used for various other new applications (for example, Non-Patent Document 1). reference.).
With respect to the method for producing the ethylene oxide resin, particularly the method for purifying and recovering the resin after the polymerization reaction, conventionally, (1) the polymerization reaction liquid after solution polymerization is poured into a large amount of poor solvent to precipitate the resin. In general, there are a method of filtering or centrifuging and drying to form a powder, and a method of drying a powder obtained by filtering or centrifuging a resin obtained by filtering or centrifuging the polymerization reaction liquid after precipitation polymerization, etc. Are known.
[0003]
However, in the methods (1) and (2), for the purpose of obtaining a high-purity resin, etc., the resin undergoes a process of drying by heating and pulverizing. There was a risk of explosion due to charging and heating. Therefore, in consideration of the prevention and safety, it is usually essential to add a sufficient amount of an antistatic agent.
The addition of this antistatic agent may increase the dielectric constant of the resulting resin more than necessary, reduce the degree of crosslinking and increase hygroscopicity, increase the resin swelling ratio more than necessary, and reduce the strength. Cause. Therefore, an ethylene oxide resin containing an antistatic agent is very difficult to use as a protective film for a color filter, for example, in terms of an increase in dielectric constant. It was very inappropriate to use it.
[0004]
In addition, the ethylene oxide resin is a resin having an ether bond in the main chain, and has a characteristic that the molecular structure (the ether bond portion) is weak against strong heating (high heat). There was a problem that would break down. In addition, in the above methods (1) and (2), in addition to heating and drying, a new additional element such as a poor solvent is necessary, or an increase in equipment costs due to a plurality of processes is not considered. In addition, cost increases were also a problem.
Further, ethylene oxide resins are often used in the form of a solution or paste at the time of use. In this case, once the powder is formed as in the above methods (1) and (2), a new solvent is added. Therefore, when it is made into a solution form or paste form, the treatment becomes very difficult, and there is a problem in terms of usability.
[0005]
On the other hand, in ethylene oxide-based resins, for example, when used for applications such as protective films for color filters and polymer electrolytes for polymer batteries, it is required to keep the resin moisture content below a certain level. In a general method, it is not easy to obtain the resin while satisfying various conditions for obtaining the desired resin and controlling the water content to be low.
If this moisture content cannot be controlled below a certain level, the dielectric constant of the resin will be larger than necessary.For example, when used as a protective film for a color filter, the protective film will become a conductor and cause functional deterioration. There was a problem that. Similarly, if the resin cannot be controlled, the moisture reacts with the metal ion component to generate hydroxide and the like. For example, when the resin is used for an electrolyte layer of a polymer battery, the metal-electrolyte layer Since an insulating layer is formed at the interface, there is a problem that the voltage under a constant current continues to rise and the cycle characteristics of the battery deteriorate.
[0006]
[Non-Patent Document 1]
Herman F. Mark, Norbert M. Bikales, Charles G. Overberger, edited by Georg Menges, “Encyclopedia of Polymer science and engineering”, volume 6, (USA), Wiley Interscience, 1986, p.225-322.
[0007]
[Problems to be solved by the invention]
Accordingly, the problem to be solved by the present invention is that, in obtaining an ethylene oxide resin, it is easy to control the water content to a certain level or less while containing no antistatic agent, and the thermal properties of the resin. An object of the present invention is to provide a novel method for producing an ethylene oxide-based resin that can prevent damage and realize cost reduction.
[0008]
[Means for Solving the Problems]
The present inventor has intensively studied to solve the above problems.
In that process, attention was paid to a processing method for purifying and recovering a resin by devolatilization, which has been known as one step in a general resin production method, and the effect obtained by this processing method was examined. Conventionally, in obtaining an ethylene oxide-based resin, there has been no knowledge of purifying and recovering it through devolatilization after synthesizing the resin by polymerization using a solvent, and it has not been actually performed. In view of various effects obtained by the devolatilization process, the present inventor thought that in order to solve the above problems, a process step by devolatilization should be included when obtaining an ethylene oxide resin. is there.
[0009]
In other words, according to the devolatilization treatment, there is no need to add an antistatic agent because there is no purification / recovery by heat drying, and there is no problem of increasing the cost mentioned above, and the water content of the resin is also devolatilized. I guessed that it could be easily adjusted during the process.
Therefore, in actual production of an ethylene oxide resin, when the polymerization reaction solution was obtained by polymerization using a solvent and subsequently combined with devolatilization of the reaction solution, the above problems could be solved at once. This has been confirmed, and the present invention has been completed.
[0010]
  That is, the method for producing an ethylene oxide resin according to the present invention is a method for obtaining an ethylene oxide resin by devolatilizing the solvent from a polymerization reaction solution containing a solvent,The content of the ethylene oxide resin in the polymerization reaction solution is 20 to 70% by weight, and the weight average molecular weight of the ethylene oxide resin is 20,000 to 300,000.The solvent concentration in the resin after devolatilization is0.1-10It is characterized in that the weight% and the water content are 200 ppm or less, and the resin does not contain an antistatic agent.
  Moreover, the manufacturing method of the ethylene oxide-type resin concerning this invention WHEREIN: The temperature at the time of the said devolatilization can be 40-300 degreeC, and a pressure can be 13-100,000 Pa, The said devolatilization isEquipped with high viscosity stirring bladeStirred tank evaporator,Fixed blade typeIt can be carried out using at least one device selected from the group consisting of a thin film evaporator, a surface renewal type polymerizer, an extruder and a kneader.These apparatuses are all known as apparatuses suitable for handling a resin having a high viscosity.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, although the manufacturing method (henceforth the manufacturing method of this invention) of the ethylene oxide resin concerning this invention is demonstrated in detail, the scope of the present invention is not restrained by these description, Other than the above examples, modifications can be made as appropriate without departing from the spirit of the present invention.
The production method of the present invention is a method for obtaining an ethylene oxide resin by devolatilizing the solvent from a polymerization reaction solution containing a solvent, and the residual solvent concentration in the ethylene oxide resin after the devolatilization is 0.01. ˜30% by weight, the water content is 200 ppm or less, and the ethylene oxide resin does not contain an antistatic agent.
[0012]
Hereinafter, the polymerization reaction solution used for the devolatilization treatment and the devolatilization treatment in carrying out the present invention will be described in detail, and the use of the ethylene oxide resin obtained by the present invention will also be described.
[Polymerization reaction solution]
The polymerization reaction liquid containing a solvent in the production method of the present invention is obtained after polymerization of an ethylene oxide resin (ethylene oxide copolymer) by a polymerization method using a solvent, and after polymerization containing the resin and the solvent. It refers to the reaction solution, and refers to the resin solution that is the subject of the devolatilization treatment (solvent component devolatilization treatment) that follows this polymerization.
[0013]
The content of the ethylene oxide resin component in the polymerization reaction solution is not particularly limited, but is preferably 20 to 70% by weight, more preferably 25 to 65% by weight, and further preferably 30 to 60% by weight. is there. When the content ratio of the resin component is less than 20% by weight, the productivity of the resin may be extremely reduced, and when it exceeds 70% by weight, the viscosity of the polymerization reaction solution may increase, which may make stirring difficult. There is.
Although the content rate of a solvent component in the said polymerization reaction liquid is not specifically limited, It is preferable that it is 30 to 80 weight%, More preferably, it is 35 to 75 weight%, More preferably, it is 40 to 70 weight%. When the content ratio of the solvent component is less than 30% by weight, the viscosity of the polymerization reaction solution increases, so that stirring becomes difficult, and liquid feeding / transfer to the devolatilizer and devolatilization treatment itself may be difficult. If it exceeds 80% by weight, the resin productivity may be extremely reduced.
[0014]
  In addition to the ethylene oxide resin component and the solvent component, the polymerization reaction liquid may contain other components. For example, a reaction initiator, an antioxidant, a solubilizer, and the like that are generally used in the polymerization reaction. Can be mentioned.
  Examples of the reaction initiator include alkaline catalysts such as sodium hydroxide, potassium hydroxide, potassium alcoholate, sodium alcoholate, potassium carbonate and sodium carbonate, and metals such as metal potassium and metal sodium, such as aluminum hydroxide. Magnesium calcined product (JP-A-8-268919 etc.), metal ion added magnesium oxide (JP-B-6-15038, JP-A-7-227540 etc.) and calcined hydrotalcite (JP-A-2-718)4Al-Mg based composite oxide catalysts such as No. 1 etc.) or catalysts obtained by surface modification thereof8-268919Etc.), barium oxide, barium hydroxide56-056232Etc.), layered compounds (JP-A-6-505986, etc.), strontium oxide, strontium hydroxide (JP-B 63-32055, etc.), calcium compounds (JP-A-2-134336, etc.) Preferable examples include cesium compounds (JP-A-7-70308, etc.), double metal cyanide complexes (JP-A-5-339361, etc.), acid catalysts such as Lewis acids and Friedel-Crafts catalysts. These reaction initiators may be included in the polymerization reaction solution alone or in combination of two or more, and are not particularly limited.
[0015]
The viscosity of the polymerization reaction solution is not particularly limited, but is preferably 1,000 to 60,000 centipoise at 95 ° C, more preferably 10,000 to 45,000 centipoise at 95 ° C, and still more preferably 95 15,000-35,000 centipoise at ° C. If the viscosity is less than 1,000 centipoise at 95 ° C., the productivity of the resin may be drastically reduced. If it exceeds 60,000 centipoise at 95 ° C., the viscosity will increase even during polymerization. It may be difficult to stir and the like.
The polymerization method using the solvent is not particularly limited, but for example, a solution polymerization method or a precipitation polymerization method can be preferably mentioned, and among them, the solution polymerization method is more preferable because of its excellent productivity, A solution polymerization method in which polymerization is carried out while feeding monomer components to a previously charged solvent is particularly preferred because of safety such as easy removal of reaction heat. The solvent component in the polymerization reaction solution usually refers to a solvent used in the polymerization method using the above solvent, but after this polymerization, other solvents not used for the polymerization were included in the polymerization reaction solution. In some cases, the other solvent may be considered to be included in the solvent component in the polymerization reaction solution.
[0016]
Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as heptane, octane, n-hexane, n-pentane, and 2,2,4-trimethylpentane. Solvents: Cyclohexane, methylcyclohexane and other alicyclic hydrocarbon solvents; diethyl ether, dibutyl ether, methyl butyl ether and other ether solvents; dimethoxyethane and other ethylene glycol dialkyl ethers solvents; THF (tetrahydrofuran) Organic solvents not containing active hydrogen such as hydroxyl groups, such as cyclic ether solvents such as dioxane, and the like are preferable, and toluene and xylene are particularly preferable. The solvent is preferably the organic solvent and does not contain water at all.
[0017]
The ethylene oxide-based resin (ethylene oxide-based copolymer) contained in the polymerization reaction liquid is particularly limited as long as it is a resin that mainly contains a component derived from an ethylene oxide monomer in its molecular structure and has an ether bond in the main chain. Although not specifically, for example, as a raw material monomer, ethylene oxide and the following structural formula (1):
[0018]
[Chemical 1]

(However, R₁Is Ra (Ra is any group among alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, (meth) acryloyl groups and alkenyl groups having 1 to 16 carbon atoms) or -CH₂-O-Re-Ra group (Re is-(CH₂-CH₂-O) p-structure (p is an integer from 0 to 10)))
Those obtained by polymerizing a comonomer group containing a substituted oxirane compound represented by the formula: This polymerization is preferably ring-opening polymerization of the oxirane group of each raw material monomer.
[0019]
R in the above structural formula (1)₁The group is a substituent in the above substituted oxirane compound.
The substituted oxirane compound used as the raw material monomer may be only one type of substituted oxirane compound that can be represented by the structural formula (1) or may contain two or more types.
Examples of the substituted oxirane compound represented by the structural formula (1) include propylene oxide, butylene oxide, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, cyclohexene oxide, and styrene oxide. Or methyl glycidyl ether, ethyl glycidyl ether, and ethylene glycol methyl glycidyl ether, and the substituent R₁Is a crosslinkable substituent, that is, the substituent R₁Having an aryl group, an alkenyl group, an acryloyl group, a methacryloyl group, etc., include epoxybutene, 3,4-epoxy-1-pentene, 1,2-epoxy-5,9-cyclododecadiene, 3,4-epoxy -1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate and glycidyl-4-hexanoate, or vinyl glycidyl ether, allyl glycidyl ether, 4-vinylcyclohexyl Mention may also be made of glycidyl ether, α-terpenyl glycidyl ether, cyclohexenyl methyl glycidyl ether, 4-vinylbenzyl glycidyl ether and 4-allylbenzyl glycidyl ether. As described above, these may be used alone or in combination of two or more.
[0020]
The substituted oxirane compound has a crosslinkable substituent (substituent R₁It is preferable to use a substituted oxirane compound (wherein is a crosslinkable substituent) in order to use an ethylene oxide resin (ethylene oxide copolymer) as a crosslinked product.
The weight average molecular weight (Mw) of the ethylene oxide resin is not particularly limited, but is preferably 20,000 to 300,000, more preferably 30,000 to 200,000, still more preferably 40. , 150,000 to 150,000. When the weight average molecular weight is less than 20,000, the molded product may be tacked. When the weight average molecular weight exceeds 300,000, molding becomes difficult, and workability and handling properties may be deteriorated.
[0021]
The molecular weight distribution (Mw / Mn) of the ethylene oxide resin is not particularly limited, but is preferably 3 or less, and more preferably 2 or less. When the molecular weight distribution exceeds 3, tackiness may occur when the molded body is formed, and handling may be deteriorated.
[Devolatilization]
In the production method according to the present invention, an ethylene oxide resin is obtained by devolatilizing a solvent component from a polymerization reaction solution after polymerization containing an ethylene oxide resin and a solvent (volatilizing the solvent component). The obtained ethylene oxide resin is not limited to those containing no solvent component, and is usually adjusted by reducing the concentration of the polymerization reaction solution from the above state to the desired solvent concentration by devolatilization. Suppose that
[0022]
As a devolatilization method, an apparatus used for devolatilization, and various conditions, a normal devolatilization method, usable apparatus, and set conditions may be employed. Details are shown below.
As a method of devolatilization, there are usually two stages of pre-devolatilization and main devolatilization, and as a devolatilization procedure, it is preferable to perform main devolatilization after pre-devolatilization, but it is not particularly limited. Instead, pre-devolatilization and main-devolatilization may be performed as a one-step process without distinction. It is preferable to carry out in two stages because it is possible to increase the efficiency of devolatilization (cost reduction, shortening of processing time, resin quality, etc.). Specifically, (1) before devolatilization The amount of solvent contained in the polymerization reaction solution can be reduced to the amount of solvent that can be efficiently devolatilized, and then the devolatilization can be carried out slowly. By using vacuum (reduced pressure) devolatilization, the equipment size can be made smaller than when processing in one step. (3) When devolatilization, the viscosity may rise sharply in a certain concentration range than when processing in one step. Although it is theoretically preferable for the reason that the drive system can be reduced, the one-stage treatment described above depends on the type of polymerization reaction liquid to be devolatilized (particularly the type of resin in the polymerization reaction liquid). But the same as the two-stage process That (same effect as two-stage process is obtained) since if there is, it may be selected.
[0023]
The device used for devolatilization (devolatilization device) is not particularly limited, but a stirred tank evaporator, a downstream liquid column evaporator, a thin film evaporator, a surface renewal type polymerizer, a kneader, a roll mixer, Intensive mixers (so-called Banbury mixers), extruders and the like are preferred, and it is preferable to carry out using at least one of these devices. In addition, the use conditions can be appropriately set depending on the apparatus to be used.
The stirred tank evaporator is excellent in that it can handle a wide range of viscosities and a wide range of residual solvent concentrations. For example, a stirred tank equipped with a helical blade, a stirred tank equipped with a double helical ribbon blade, a super blend blade (inner blade) : Concentric twin-shaft stirred tank (for example, product name: Super Blend, manufactured by Sumitomo Heavy Industries, Ltd.), VCR reverse cone ribbon wing reactor equipped with: Max blend wing, outer wing: spiral deformed baffle (Mitsubishi Heavy Industries, Ltd.) etc. are mentioned preferably. These can be used for both batch processing and continuous processing, but are preferably used for batch processing. In addition, because of the characteristics of the apparatus, it takes a lot of time to discharge after processing, and therefore it is preferable to deal with a process for accurately processing a small amount rather than a process for processing a large amount of resin or the like. Moreover, when these are used, an evaporation process is performed by heat-transfer surface update.
[0024]
Among the various stirring tank evaporators described above, in particular, the vertical type concentric biaxial stirring tank can have excellent characteristics such as (1) to (6) below. (1) The processing viscosity range is wide, and excellent mixing performance can be demonstrated in the viscosity range of 1 to 10,000 poise. (2) Following the sudden viscosity change in the tank, the inside and outside Since the mixing function of the blades naturally changes and responds, a good flow state can be maintained. (3) Uniform liquid flow rate (polymerization reaction solution flow rate) on the inner wall of the tank and in the center of the tank Therefore, high temperature uniformity can be maintained, deterioration of resin quality can be reduced, and (4) slipping and stagnation of low viscosity liquid on high viscosity fluid can be eliminated. The dispersibility of various additives can be improved. (5) Adhesion / deposition on the tank wall and baffle during high-concentration slurry treatment can be eliminated, and good dispersibility of the slurry is exhibited. 6 ▼ By rotating the outer wing close to the tank wall Due to the stable wall flow velocity, it is possible to reduce the adhesion of the inner wall portion and the cleaning time and number of times in the tank.
[0025]
As the downstream liquid column evaporator, a multi-tube heat exchanger type (for example, product name: Sulzer Mixer, manufactured by Sumitomo Heavy Industries, Ltd .; product name: Stattech Mixer, manufactured by Noritake Co., Ltd.), plate heat exchanger type (For example, product name: Hiviscous Evaporator, manufactured by Mitsui Engineering & Shipbuilding Co., Ltd.) is preferable. These can be used for both a batch process and a continuous process, and both processes can be performed well. In addition, due to the characteristics of the device, devolatilization by these is performed by heating with sensible heat, and then sensible heat is converted into latent heat and evaporated under reduced pressure. It depends on the amount of heat obtained. Therefore, a process with a treatment amount corresponding to the sensible heat heating amount is preferable, but in the multi-tube heat exchanger type, heat transfer can be promoted by a stick mixer, and thus a process with a wide range of treatment amounts can be handled. . In the case of the multi-tube heat exchanger type, the evaporation process is performed by expanding the interfacial area, and the corresponding maximum processing viscosity is preferably 50,000 poise. In the case of the plate heat exchanger type, the evaporation process is It is carried out by expanding the heat transfer area, and the corresponding maximum processing viscosity is preferably 10,000 poise.
[0026]
The thin film evaporator is superior in that a centrifugal force works by the blade and a uniform liquid film can be formed. For example, a horizontal thin film evaporator (for example, product name: Evariactor, manufactured by Kansai Chemical Machinery Co., Ltd.), Fixed blade type vertical thin film evaporator (for example, product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), movable blade type vertical thin film evaporator (for example, product name: wiperen, manufactured by Shinko Pantech Co., Ltd.) ), Tank type (mirror type) thin film evaporator (for example, product name: recovery, manufactured by Kansai Chemical Machinery Manufacturing Co., Ltd.) and the like. Regarding these, the batch-type treatment is not possible for the horizontal type and the tank type, but the vertical type is impossible regardless of the fixed blade type or the movable blade type. In addition, all of the continuous processing is possible. Due to the characteristics of the equipment, all these devolatilization is performed by heating with sensible heat, and then sensible heat is converted into latent heat and evaporated under reduced pressure. It depends on the amount of heat obtained. Therefore, the process which makes the processing amount corresponding to the amount of sensible heat heating is preferable. In addition, all these processes are performed by transmission surface update in the evaporation process.
[0027]
The horizontal thin-film evaporator is difficult to cope with high viscosity on the discharge surface compared to the vertical type, so it uses a blade with excellent discharge effect and can cope with high viscosity. Is preferably 500 poise. Since the vertical thin film evaporator descends by its own weight, it can be said that a high-viscosity liquid is more suitable than a low-viscosity liquid, and the corresponding maximum processing viscosity of the movable blade type is preferably 1,000 poise. Further, in the fixed blade type, the fixed blade has a scraping effect to cope with high viscosity, and the corresponding maximum processing viscosity is preferably 10,000 poise. The tank-type thin film evaporator can suppress a short pass of a low-viscosity liquid by using a mirror, and the corresponding maximum processing viscosity is preferably 1,000 poise.
[0028]
Surface renewal type polymerizers (horizontal thin film polymerizers) are superior in that they exhibit high devolatilization performance by renewing the gas-liquid surface. For example, uniaxial surface renewal polymerizers, biaxial surface renewal polymerizers (For example, product name: Vivolak, manufactured by Sumitomo Heavy Industries, Ltd .; product name: Hitachi Glasses Blade Polymerizer, manufactured by Hitachi, Ltd .; product name: Hitachi lattice blade polymerizer, manufactured by Hitachi, Ltd .; product (Name: SC processor, manufactured by Kurimoto Iron Works Co., Ltd.) is preferred. These are not possible for batch processing, and are all possible for continuous processing. Due to the characteristics of the apparatus, all of these have a devolatilization throughput depending on the moving speed of the substance in the apparatus, and the evaporation process is performed by gas-liquid level renewal.
[0029]
Kneaders, roll mixers, and intensive mixers (so-called Banbury mixers) are suitable for mixing high-viscosity melts and the like, and have a devolatilizing capability as an additional function, like an extruder. These can be processed either batchwise or continuously. For these, the corresponding maximum processing viscosity is preferably 10,000 poise.
The uniaxial type exhibits high devolatilization performance because an efficient surface area can be secured, and the corresponding maximum processing viscosity is preferably 10,000 poise. The biaxial type is excellent in self-cleaning and liquid retention due to the lack of dead space in the container and high piston flow, and the corresponding maximum processing viscosity is preferably 10,000 poise. .
[0030]
Extruders are suitable for mixing high-viscosity melts, etc., and have additional functions such as heating, melting, and kneading, and devolatilization capability. For example, single-screw extruders, twin-screw extruders (for example, product names) : SUPERTEXαII, manufactured by Nippon Steel Works; product name: BT-30-S2, manufactured by Plastic Engineering Laboratory), SCR self-cleaning reactor (manufactured by Mitsubishi Heavy Industries, Ltd.), and the like. These cannot be processed in a batch system, and all processes in a continuous system are possible. Due to the characteristics of the apparatus, as described above, these are suitable for the process of devolatilizing a very high-viscosity target, and the evaporation process is performed by kneading and evaporation.
[0031]
In the extruder, it is preferable that the corresponding maximum processing viscosity is 100,000 poise for both the single screw type and the twin screw type.
As described above, the preferred devolatilization method can include the method of devolatilization after pre-devolatilization, but among the various devolatilization devices, those that can be preferably used for pre-devolatilization are particularly limited. However, there are a stirring tank equipped with a double helical ribbon blade, a vertical concentric biaxial stirring tank equipped with a super blend blade, a plate heat exchanger type downstream liquid column evaporator and a fixed blade type vertical thin film evaporator. Can be mentioned. Further, what can be preferably used for the present devolatilization is not particularly limited, but examples include a fixed blade type vertical thin film evaporator, a biaxial surface renewal polymerization reactor, a kneader, and a biaxial extruder. .
[0032]
In the production method of the present invention, the devolatilization of the polymerization reaction solution is carried out by directly connecting the above-mentioned various devolatilizers to the so-called pre-stage apparatus used for the polymerization process using the solvent described above. Volatilization may be performed, or devolatilization may be performed by various devolatilization apparatuses after liquid feeding or transfer from the preceding apparatus. For the latter, for example, a form in which the space between the preceding device and the devolatilizer is connected by a liquid feed line, or an intermediate tank provided with a jacket and a stirrer between the preceding device and the devolatilizer The form etc. which provided the tank (cushion tank) are mentioned.
In the production method of the present invention, by devolatilization, the residual solvent concentration in the ethylene oxide resin after devolatilization is 0.01 to 30% by weight, preferably 0.05 to 20% by weight. %, More preferably 0.1 to 10% by weight. When the residual solvent concentration is less than 0.01% by weight, it is necessary to make the devolatilization conditions excessively strict, which may lead to thermal deterioration of the ethylene oxide resin, resulting in a decrease in performance. When it exceeds wt%, tackiness may occur in the ethylene oxide-based resin after devolatilization and blocking or the like may occur.
[0033]
In the production method of the present invention, it is preferable to adjust the water content in the ethylene oxide resin after devolatilization at the same time as the devolatilization of the solvent. The moisture is contained in, for example, the solvent or monomer used in the polymerization. The production method of the present invention is characterized in that the water content is made 200 ppm or less by the adjustment. When the water content exceeds 200 ppm, the dielectric constant of the resin becomes larger than necessary. For example, when the obtained ethylene oxide resin is used for a protective film of a color filter, the resin becomes conductive. As a result, the protective film may cause a fatal deterioration of the function, and the water reacts with metal ions to generate hydroxides. For example, an ethylene oxide resin is polymerized. When used for a battery electrolyte layer or the like, an insulating layer is formed at the metal-electrolyte layer interface, the voltage under a constant current may continue to rise, and the battery cycle characteristics may deteriorate.
[0034]
The means for adjusting the water content is not particularly limited, but specifically, it is preferable to increase the devolatilization temperature and / or increase the degree of vacuum of devolatilization (note that Increasing the degree of decompression means lowering the pressure, and decreasing the degree of decompression means increasing the pressure. When adjusting the water content by increasing the devolatilization temperature, the temperature is not particularly limited, but if it is too low, it is not efficient because the degree of vacuum must be excessively large, and if it is too high, Since there is a possibility that the resin will be thermally deteriorated, it is set appropriately in consideration of these. Further, when adjusting the water content by increasing the degree of vacuum of devolatilization, the degree of vacuum is not particularly limited, but if it is too large, it is considered difficult considering the sealing performance of the devolatilizer. If it is too small, there is a possibility that the moisture content cannot be controlled to 200 ppm or less unless the devolatilization temperature is increased considerably.
[0035]
According to the production method of the present invention, it is possible to prevent the ethylene oxide resin after devolatilization from containing an antistatic agent. The reason is that, as described above, in the present invention, since the ethylene oxide resin is obtained by devolatilization instead of heat drying after polymerization, it is necessary to consider the charging of the resin caused by friction between the resins under heat drying. Because there is no. If the resulting ethylene oxide resin contains an antistatic agent, the dielectric constant of the resin will be increased more than necessary, or the degree of crosslinking will be lowered and the hygroscopicity will be increased, increasing the resin's swelling ratio more than necessary and increasing the strength. It will be reduced. Therefore, for example, when the obtained ethylene oxide-based resin is used for a protective film of a color filter, the resin becomes conductive, causing a fatal functional deterioration as the protective film. In addition, when the resin is used for a flexographic printing plate or the like, the desired shape and rebound resilience are difficult to maintain, resulting in poor image reproducibility. Furthermore, when the resin is used for a separator, an electrode, an electrolyte layer and the like of a polymer battery, a desired shape cannot be maintained.
[0036]
When the solvent is devolatilized from the polymerization reaction solution under heating using the devolatilizer described above, the temperature is preferably 40 to 300 ° C, more preferably 60 to 250 ° C, and still more preferably 90. ~ 200 ° C. By performing devolatilization within this temperature range, it is possible to obtain an ethylene oxide-based resin having the above-mentioned desired residual solvent concentration and water content after devolatilization. When the said temperature is less than 40 degreeC, there exists a possibility that the residual solvent may increase, and when it exceeds 300 degreeC, there exists a possibility that polyether itself may thermally decompose. Here, the said temperature is the temperature of the ethylene oxide resin in a devolatilizer.
[0037]
Similarly, when the solvent is devolatilized using the devolatilizer, the pressure is preferably in the range of 13 to 100,000 Pa, more preferably 133 to 70,000 Pa, and still more preferably 1,333 to 33. 40,000 Pa. By satisfying this pressure range, an ethylene oxide resin having a solvent concentration and a water content as described above can be obtained after devolatilization. If the pressure is less than 13 Pa, the solvent may flash and foaming may occur, and if it exceeds 100,000 Pa, the temperature may have to be applied to the extent that the polyether is decomposed. Here, the said pressure is the tank internal pressure of a devolatilizer.
[0038]
In the production method of the present invention, the viscosity of the ethylene oxide resin after devolatilization is preferably 50 to 100,000 poise at 100 ° C., more preferably 100 to 80,000 poise at 100 ° C., more preferably It is 220-60,000 poise at 100 ° C. When the viscosity is less than 50 poise at 100 ° C., the remaining solvent increases, and foaming and tackiness may occur when formed into a molded body. When it exceeds 100,000 poise, devolatilization with a devolatilizer May become difficult.
[Use of ethylene oxide resin]
The ethylene oxide resin obtained by the production method of the present invention includes, for example, polyurethane resins such as adhesives, paints, sealing agents, elastomers, flooring agents, hard, soft or semi-rigid polyurethane resins, and surfactants. , Sanitary products, deinking agents, lubricants, hydraulic fluids, separators for polymer batteries, electrodes and polymer electrolyte layers, color filter protective films, photosensitive resins that can be used for resists, flexographic printing plates, etc. It can be preferably used as a polymer material for various applications.
[0039]
【Example】
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. Hereinafter, for convenience, “part by weight” may be simply referred to as “part”, “time” may be simply referred to as “h”, and “liter” may be simply referred to as “L”.
Conditions for various measurements in the following examples and comparative examples are shown below.
[Measurement of amount of residual solvent in resin after devolatilization]
High-performance liquid chromatography (column: ODS-3 (manufactured by GL Science), column temperature: 40 ° C., flow rate: 1.0 mL / min, injection amount: 5 μL, UV detector: 210 nm, eluent: “acetonitrile / 0. The amount of residual solvent (wt%) in the sample sample is measured using a mixed solution of “1 wt% phosphoric acid aqueous solution” (volume ratio: acetonitrile / 0.1 wt% phosphoric acid aqueous solution = 85/15). As a sample sample, a devolatilized resin to be measured is diluted with the eluent so as to have a solid content of 1.0 wt%. A specific measurement method is to first prepare a calibration curve using a calibration curve sample for a predetermined solvent (for example, toluene), then measure the sample sample, and use the calibration curve to determine the amount of residual solvent. Ask for.
[Measurement of moisture content in resin after devolatilization]
In the glove box, the following (1) to (4), that is, (1) ethylene oxide resin obtained after devolatilization is heated in a dry atmosphere and heated (with the resin temperature kept close to the devolatilization temperature). (2) Contained in toluene (previously molecular sieves (product of Union Showa Co., product name: molecular sieve 3A1.6 or molecular sieve 4A1.6)) (3) Glass container and (4) Syringe are put in and dried for 2 hours or more.
[0040]
After drying, 2 g of ethylene oxide resin and 18 g of toluene are put into a glass container, dissolved sufficiently with a magnetic stirrer to obtain a resin solution, and then the resin solution is all collected with a syringe. At the same time, 18 g of toluene alone is collected with another syringe.
Each syringe after collection is taken out from the glove box, and the moisture content in the resin solution and toluene alone is measured using AQUACOUNTERQ-7 (a moisture content measuring device manufactured by HIRANUMA).
From the value of the moisture content (ppm) determined by this measurement, the weight (mg) of moisture contained in the resin solution and toluene alone is calculated, respectively, and the weight of moisture contained in the ethylene oxide resin (mg) from the difference. Ask for. Therefore, the water content (ppm) of the ethylene oxide resin is calculated by dividing the weight (mg) of the water, which is the difference, by the weight (2 g) of the ethylene oxide resin dissolved first.
[Measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of ethylene oxide resin]
The measurement was performed by a GPC apparatus in which a calibration curve was prepared using a standard molecular weight sample of polyethylene oxide. It measured after melt | dissolving the polymerization reaction liquid (a polymer is included) obtained after reaction in the predetermined | prescribed solvent.
[0041]
Example 1
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (a) having a weight% ratio (resin / toluene) of the ethylene oxide resin (a) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide-based resin (a) is a proportion of 180 parts by weight, 12 parts by weight, and 8 parts by weight in order of a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether. The weight average molecular weight Mw was 100,000.
[0042]
The polymerization reaction liquid (a) is preheated at 50 to 100 ° C. with steam of a heating medium, charged into a raw material tank, and then evaporated from the raw material tank at a supply rate of 46 kg / h using a gear pump. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction solution (a) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 178 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (a) and toluene of 99.79% by weight / 0.21% by weight and a water content of 35 ppm.
[0043]
-Example 2-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (b) having a weight% ratio (resin / toluene) of the ethylene oxide resin (b) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide-based resin (b) contains, in order, a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether, 378 parts by weight, 25.2 parts by weight, and 16.8. The resin having a weight part ratio and the weight average molecular weight Mw was 90,000.
[0044]
The polymerization reaction liquid (b) is preheated at 50 to 100 ° C. with steam of a heating medium, charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 30 kg / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction liquid (b) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 173 ° C.
The resin obtained after devolatilization had a ratio by weight of ethylene oxide resin (b) and toluene (resin / toluene) of 99.83 wt% / 0.17 wt%, and a water content of 28 ppm.
[0045]
-Example 3-
(Twin screw extruder)
By solution polymerization, a polymerization reaction liquid (c) in which the weight% ratio (resin / toluene) of the ethylene oxide resin (c) and toluene was 50% by weight / 50% by weight was obtained. The ethylene oxide-based resin (c) is composed of, in order, a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether, 378 parts by weight, 25.2 parts by weight, and 16.8. The resin had a weight part ratio, and the weight average molecular weight Mw was 95,000.
[0046]
After the polymerization reaction liquid (c) is melted in advance, it is charged into a raw material tank and heated to 80 ° C. At the same time, the jacket of the 30φ twin screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory) is 180 ° C for the back vent and 150 ° C for all of the supply vent and the first to fifth vents. Heat and rotate biaxial at 200 rpm. Thereafter, the polymerization reaction liquid (c) is supplied from a raw material tank to a 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory) at a supply speed of 14.4 kg / h using a gear pump. Simultaneously with the supply, the back vent is reduced to 100 Torr (13,332 Pa), the first vent is reduced to 70 Torr (9,333 Pa), and the second vent to the fourth vent are all reduced to 70 Torr (9,333 Pa) or less ( The polymerization reaction liquid (c) was concentrated by devolatilization by not depressurizing the supply vent and the fifth vent in particular. The resin temperature at the outlet of the 30φ twin screw extruder was 208 ° C.
[0047]
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (c) and toluene of 99.83 wt% / 0.17 wt%, and a water content of 30 ppm.
Example 4
(Twin screw extruder)
By solution polymerization, a polymerization reaction liquid (d) having a weight% ratio (resin / toluene) of the ethylene oxide resin (d) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide resin (d) contains, in order, a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether, 378 parts by weight, 25.2 parts by weight, and 16.8. The resin having a weight part ratio, and the weight average molecular weight Mw was 84,000.
[0048]
After the polymerization reaction liquid (d) is melted in advance, it is charged into a raw material tank and heated to 80 ° C. At the same time, the jacket of the 30φ twin screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory) is set to 120 ° C. for the back vent, the supply vent, the first vent and the second vent, and to 80 for the third vent. Heat to 100 ° C. in the fourth vent and the fifth vent, and rotate the two shafts at 80 rpm. Thereafter, the polymerization reaction liquid (d) is supplied from a raw material tank to a 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory) at a supply rate of 4.8 kg / h using a gear pump. Simultaneously with the supply, the back vent is set to 110 Torr (14,665 Pa), the first vent is set to 70 Torr (9,333 Pa), the second vent, the third vent, and the fifth vent are all set to 70 Torr (9,333 Pa) or less. By reducing the pressure (the supply vent and the fourth vent are not particularly depressurized), the polymerization reaction liquid (d) was concentrated by devolatilization. The resin temperature at the outlet of the 30φ twin-screw extruder was 95 ° C.
[0049]
The resin obtained after devolatilization had a weight percent ratio (resin / toluene) of the ethylene oxide resin (d) and toluene of 99.25 wt% / 0.75 wt%, and a water content of 125 ppm.
-Example 5
(Stirred tank evaporator)
The same polymerization reaction solution (d) as in Example 4 in which the weight percent ratio of resin (d) to toluene (resin / toluene) was 50% by weight / 50% by weight was obtained by solution polymerization.
[0050]
A vertical concentric twin-shaft tank (product name: Super Blend, Sumitomo Heavy Industries, Ltd.) equipped with 45 kg of the polymerization reaction liquid (d) and a super blend blade (inner blade: Max blend blade, outer blade: spiral deformed baffle) In the state where the jacket temperature is heated to 160 ° C., the Max blend blade is stirred at 16 rpm and the helical deformation baffle is rotated at 17 rpm in a forward rotation, and toluene is devolatilized at atmospheric pressure for 3 hours. Thereafter, the polymerization reaction liquid (d) was concentrated by devolatilizing toluene under reduced pressure of maximum 410 Torr (54,662 Pa) for 1.5 hours.
The resin obtained after devolatilization had a weight percent ratio (resin / toluene) of the ethylene oxide resin (d) and toluene of 92.4% / 7.6% by weight and a water content of 200 ppm.
[0051]
-Example 6
(Stirred tank evaporator)
By solution polymerization, a polymerization reaction liquid (e) having a weight% ratio (resin / toluene) of the ethylene oxide resin (e) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide resin (e) contains, in order, a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from methyl glycidyl ether, 378 parts by weight, 25.2 parts by weight, and 16.8. The resin had a weight part ratio, and the weight average molecular weight Mw was 103,000.
[0052]
A vertical concentric twin-shaft tank (product name: Super Blend, Sumitomo Heavy Industries, Ltd.) equipped with 45 kg of the polymerization reaction solution (e) and a super blend blade (inner blade: Max blend blade, outer blade: spiral deformed baffle) In the state where the jacket temperature is heated to 160 ° C., the Max blend blade is stirred at 75 rpm and the helical deformation baffle is rotated at 30 rpm in a forward rotation, and toluene is devolatilized at atmospheric pressure for 3.5 hours. Thereafter, the polymerization reaction solution (e) was concentrated by devolatilizing toluene under reduced pressure of 50 Torr (6,666 Pa) at the maximum for 1.5 hours.
The resin obtained after devolatilization had a weight percent ratio (resin / toluene) of the ethylene oxide resin (e) and toluene of 99.60 wt% / 0.40 wt%, and a water content of 89 ppm.
[0053]
-Example 7-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (f) having a weight% ratio (resin / toluene) of the ethylene oxide resin (f) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide-based resin (f) contains, in order, a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from allyl glycidyl ether, 378 parts by weight, 25.2 parts by weight, and 16.8. The resin had a weight part ratio, and the weight average molecular weight Mw was 97,000.
[0054]
The polymerization reaction liquid (f) is heated in advance by steam of a heat medium at 50 to 100 ° C., charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 33 L / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction solution (f) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 175 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (f) and toluene of 99.84% / 0.16% by weight and a water content of 27 ppm.
[0055]
-Example 8-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (g) having a weight% ratio (resin / toluene) of ethylene oxide resin (g) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide-based resin (g) contains, in order, a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from allyl glycidyl ether, 378 parts by weight, 25.2 parts by weight, and 4 parts by weight. The weight average molecular weight Mw was 97,000.
[0056]
The polymerization reaction solution (g) is heated in advance by steam of a heat medium at 50 to 100 ° C., charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 33 L / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction solution (g) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 175 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (g) and toluene of 99.83% / 0.17% by weight and a water content of 29 ppm.
[0057]
-Example 9-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (h) having a weight% ratio (resin / toluene) of the ethylene oxide resin (h) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide resin (h) is a ratio of 378 parts by weight, 15 parts by weight, and 16 parts by weight of a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from allyl glycidyl ether in this order. The weight average molecular weight Mw was 110,000.
[0058]
The polymerization reaction liquid (h) is preheated at 50 to 100 ° C. with steam of a heating medium, charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 60 kg / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction liquid (h) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 600 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 150 ° C., and the pressure of 500 Torr (66,661 Pa). The resin temperature at the outlet of the thin film evaporator was 138 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (h) and toluene of 90.10% by weight / 9.90% by weight and a water content of 190 ppm.
[0059]
-Example 10-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (i) in which the weight% ratio (resin / toluene) of the ethylene oxide resin (i) and toluene was 50% by weight / 50% by weight was obtained. The ethylene oxide resin (i) is a ratio of 378 parts by weight, 40 parts by weight, and 16 parts by weight of a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from allyl glycidyl ether in this order. The weight average molecular weight Mw was 110,000.
[0060]
The polymerization reaction liquid (i) is heated beforehand with steam of a heat medium at 50 to 100 ° C., charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 60 kg / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction liquid (i) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 600 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 150 ° C., and the pressure of 500 Torr (66,661 Pa). The resin temperature at the outlet of the thin film evaporator was 138 ° C.
The resin obtained after devolatilization had a weight percent ratio (resin / toluene) of the ethylene oxide resin (i) and toluene of 90.10 wt% / 9.90 wt%, and a water content of 180 ppm.
[0061]
-Example 11-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (j) in which the weight% ratio (resin / toluene) of the ethylene oxide resin (j) and toluene was 50% by weight / 50% by weight was obtained. The ethylene oxide resin (j) is composed of 398 parts by weight, 25.2 parts by weight, and 16.8 parts by weight of a structural unit derived from ethylene oxide, a structural unit derived from butylene oxide, and a structural unit derived from epoxybutene. The weight average molecular weight Mw was 26,000.
[0062]
The polymerization reaction solution (j) is heated in advance by steam of a heat medium at 50 to 100 ° C., charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 30 kg / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction liquid (j) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 173 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (j) and toluene of 99.83 wt% / 0.17 wt%, and a water content of 25 ppm.
[0063]
-Example 12-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (k) having a weight% ratio (resin / toluene) of the ethylene oxide resin (k) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide resin (k) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in order of 257 parts by weight and 16.8 parts by weight, and has a weight average molecular weight Mw of 80,000.
The polymerization reaction liquid (k) is preheated at 50 to 100 ° C. with steam of a heating medium, charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 30 kg / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction liquid (k) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 173 ° C.
[0064]
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (k) and toluene of 99.83 wt% / 0.17 wt% and a water content of 26 ppm.
-Example 13-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (l) having a weight% ratio (resin / toluene) of the ethylene oxide resin (l) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide-based resin (l) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in order of 378 parts by weight and 26 parts by weight, and has a weight average molecular weight Mw of 110, 000.
[0065]
The polymerization reaction liquid (l) is heated beforehand with steam of a heating medium at 50 to 100 ° C., charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 44 L / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction liquid (l) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the time of supply to the thin film evaporator was 69 ° C., and the resin temperature at the outlet of the thin film evaporator was 175 ° C.
[0066]
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (l) and toluene of 99.53% by weight / 0.47% by weight and a water content of 78 ppm.
-Example 14-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (m) having a weight% ratio (resin / toluene) of ethylene oxide resin (m) and toluene of 50% by weight / 50% by weight was obtained. The ethylene oxide resin (m) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in order of 200 parts by weight and 25 parts by weight, and has a weight average molecular weight Mw of 105, 000.
[0067]
The polymerization reaction liquid (m) is preheated at 50 to 100 ° C. with a heating medium steam, charged into a raw material tank, and then evaporated from the raw material tank using a gear pump at a supply rate of 39 L / h. Was supplied to a vessel (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.), and the polymerization reaction liquid (m) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the outlet of the thin film evaporator was 176 ° C.
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of ethylene oxide resin (m) and toluene of 99.74% / 0.26% by weight and a water content of 43 ppm.
[0068]
-Example 15-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (n) having a weight% ratio (resin / toluene) of ethylene oxide resin (n) and toluene of 33% by weight / 67% by weight was obtained. The ethylene oxide-based resin (n) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in order of 378 parts by weight and 29 parts by weight, and has a weight average molecular weight Mw of 175, 000.
The polymerization reaction liquid (n) is heated in advance with steam of a heat medium at 50 to 100 ° C., charged into a raw material tank, and then from the raw material tank using a gear pump at a supply rate of 11.4 L / h, A thin film evaporator (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.) was supplied, and the polymerization reaction liquid (n) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the time of supply to the thin film evaporator was 74 ° C., and the resin temperature at the outlet of the thin film evaporator was 180 ° C.
[0069]
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (n) and toluene of 99.70 wt% / 0.30 wt%, and a water content of 50 ppm.
-Example 16-
(Thin film evaporator)
By solution polymerization, a polymerization reaction liquid (o) having a weight% ratio (resin / toluene) of ethylene oxide resin (o) and toluene of 33% by weight / 67% by weight was obtained. The ethylene oxide resin (o) is a resin having a structural unit derived from ethylene oxide and a structural unit derived from butylene oxide in order of 200 parts by weight and 26 parts by weight, and has a weight average molecular weight Mw of 180, 000.
[0070]
The polymerization reaction liquid (o) is heated beforehand with steam of a heating medium at 50 to 100 ° C., charged into a raw material tank, and then from this raw material tank using a gear pump at a supply rate of 22.1 L / h, A thin film evaporator (product name: EXEVA, manufactured by Shinko Pantech Co., Ltd.) was supplied, and the polymerization reaction liquid (o) was concentrated by devolatilization. The thin film evaporator was used by setting the rotation speed of the stirring blade motor to 300 rpm, the rotation speed of the discharge screw to 90 to 100 rpm, the jacket temperature of 180 ° C., and the pressure of 50 Torr (6,666 Pa). The resin temperature at the time of supply to the thin film evaporator was 74 ° C., and the resin temperature at the outlet of the thin film evaporator was 182 ° C.
[0071]
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (o) and toluene of 99.39% by weight / 0.61% by weight and a water content of 102 ppm.
-Example 17-
(Twin screw extruder)
The same polymerization reaction solution (o) as in Example 16 in which the weight percent ratio (resin / toluene) of ethylene oxide resin (o) and toluene was 33% by weight / 67% by weight was obtained by solution polymerization.
[0072]
After the polymerization reaction liquid (o) is melted in advance, it is charged into a raw material tank and heated to 80 ° C. At the same time, the jacket of the 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory) is the back vent, the supply vent, and the first vent to the fourth vent all at 180 ° C, the fifth vent Then, it is heated to 100 ° C. and the two axes are rotated at 100 rpm. Thereafter, the polymerization reaction liquid (o) is supplied from the raw material tank to the 30φ twin-screw extruder (product name: BT-30-S2, manufactured by Plastic Engineering Laboratory) at a supply rate of 8.5 kg / h using a gear pump. Simultaneously with the supply, the back vent is reduced to 150 Torr (19,998 Pa), the first vent is reduced to 80 Torr (10,666 Pa), and the second vent to the fourth vent are all reduced to 80 Torr (10,666 Pa) or less ( The supply vent and the fifth vent were not particularly depressurized), whereby the polymerization reaction liquid (o) was concentrated by devolatilization.
[0073]
The resin obtained after devolatilization had a weight% ratio (resin / toluene) of the ethylene oxide resin (o) and toluene of 99.24% / 0.76% by weight and a water content of 127 ppm.
[0074]
【The invention's effect】
According to the present invention, in obtaining an ethylene oxide-based resin, it is easy to control the water content to a certain amount or less without containing an antistatic agent, and it is possible to prevent thermal damage of the resin and reduce the cost. It is also possible to provide a novel method for producing an ethylene oxide resin that can realize the above.

Claims (3)

A method for obtaining an ethylene oxide resin by devolatilizing the solvent from a polymerization reaction solution containing a solvent, wherein the content of the ethylene oxide resin in the polymerization reaction solution is 20 to 70% by weight, and the weight of the ethylene oxide resin. The average molecular weight is 20,000 to 300,000, the solvent concentration in the resin after devolatilization is 0.1 to 10 % by weight, the water content is 200 ppm or less, and the resin is antistatic. A method for producing an ethylene oxide resin, characterized by not containing an agent. The method for producing an ethylene oxide resin according to claim 1, wherein a temperature at the time of devolatilization is 40 to 300 ° C and a pressure is 13 to 100,000 Pa. The devolatilization is performed using at least one device selected from the group consisting of a stirring vessel evaporator equipped with a high-viscosity stirring blade , a fixed blade type thin film evaporator, a surface renewal polymerization reactor, an extruder, and a kneader. The manufacturing method of the ethylene oxide-type resin of Claim 1 or 2.