JP2015174921A - カチオン系重合開始剤、カチオン系重合開始剤の生成方法、ポリマーの生成方法およびセルロースブロック共重合体 - Google Patents
カチオン系重合開始剤、カチオン系重合開始剤の生成方法、ポリマーの生成方法およびセルロースブロック共重合体 Download PDFInfo
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Abstract
Description
(1) 下記一般式(1)で表わされる化合物および下記一般式(2)で表わされる化合物のうちの少なくとも1種を含むことを特徴とするカチオン系重合開始剤。
セルロースまたは該セルロースのグルコピラノース環上の側鎖が備える水酸基がアセチル化されたものを、無酸素雰囲気下において機械的に破壊することにより、前記一般式(1)で表わされる化合物および前記一般式(2)で表わされる化合物のうちの少なくとも1種を生成することを特徴とするカチオン系重合開始剤の生成方法。
前記一般式(1)で表わされる化合物および前記一般式(2)で表わされる化合物のうちの少なくとも1種と、カチオン重合性化合物とを、無酸素雰囲気下において混合した後、前記カチオン重合性化合物が液化あるいは気化する温度範囲に設定することを特徴とするポリマーの生成方法。
カチオン系重合開始剤(本発明のカチオン系重合開始剤)は、後述するカチオン系重合開始剤の生成方法において、セルロースに機械的処理を施すことにより生成される、下記一般式(1)で表される化合物および下記一般式(2)で表される化合物のうちの少なくとも1種であることを特徴とする、カチオンを有するセルロースに由来する化合物である。
[1]まず、セルロースを用意する。
このような、セルロースは、下記一般式(5)で表される。
かかる雰囲気下で、セルロースを破壊することで、破壊されたセルロースにおいて、イオンが生成し、その結果、前記一般式(1)および前記一般式(2)で表されるカチオン系重合開始剤が生成される。
上記のようなカチオン系重合開始剤を用いて、カチオン重合性化合物をカチオン重合させることで、ポリマーが生成されるが、以下、カチオン重合させるべきカチオン重合性化合物について説明する。
また、アルキルビニルエーテルは、CH2=CHORで表されるモノマーであり、Rは、直鎖状、分岐鎖状もしくは環式のアルキル基、または、アラルキル基からなり、例えば、メチルビニルエーテル、エチルビニルエーテル、n−プロピルビニルエーテル、n−ブチルビニルエーテル、イソ−プロピルビニルエーテル、イソ−ブチルビニルエーテル、t−ブチルビニルエーテル、シクロヘキシルビニルエーテル、ベンジルビニルエーテル等が挙げられる。
<ポリマーの生成方法>
ポリマーの生成は、無酸素雰囲気下において、前記一般式(1)および前記一般式(2)で表されるカチオン系重合開始剤のうちの少なくとも1種と、カチオン重合性化合物とを混合した後、カチオン重合性化合物が固体として存在できる温度未満、すなわちカチオン重合性化合物が気化あるいは液化する温度範囲に設定することにより行われる。
木質セルロースとして微結晶セルロース(MCC; 1g)を硝子製粉砕子(直径7mm)が入っている硝子製ボールミル容器に入れ、真空ラインに接続し、100℃、6時間の条件で真空(1Pa)乾燥し、真空に保持した。
まず、木質セルロースとして微結晶セルロース(MCC) 1gを硝子製粉砕子(直径7mm)が入っている硝子製ボールミル容器に入れ、真空ラインに接続し、100℃、6時間の条件で真空(1Pa)乾燥し、真空に保持した。
また、Filtrateの1H-NMRスペクトルは図3と同じであった。
実施例2と同じ手法でIBVE存在下MCCを真空中室温で24時間粉砕、その後、クロロホルムによるソックスレー抽出を行い、透明な濾液を得た。これを真空乾燥し、Filtrate試料とした。
Claims (8)
- 請求項1に記載のカチオン系重合開始剤の生成方法であって、
セルロースまたは該セルロースのグルコピラノース環上の側鎖が備える水酸基がアセチル化されたものを、無酸素雰囲気下において機械的に破壊することにより、前記一般式(1)で表わされる化合物および前記一般式(2)で表わされる化合物のうちの少なくとも1種を生成することを特徴とするカチオン系重合開始剤の生成方法。 - 前記無酸素雰囲気下における前記セルロースの機械的な破壊は、前記セルロースと粉砕子とを容器に加えた後、該容器の内部を前記無酸素雰囲気とし、その後、前記容器を加振することで、前記容器内の前記セルロースに対して機械的エネルギーを付加することにより行われる請求項2に記載のカチオン系重合開始剤の生成方法。
- 前記無酸素雰囲気は、酸素分圧が0.2kPa以下の雰囲気である請求項2または3に記載のカチオン系重合開始剤の生成方法。
- 前記無酸素雰囲気における温度は、30℃以下である請求項2ないし4のいずれか1項に記載のカチオン系重合開始剤の生成方法。
- 請求項1に記載のカチオン系重合開始剤を用いたポリマーの生成方法であって、
前記一般式(1)で表わされる化合物および前記一般式(2)で表わされる化合物のうちの少なくとも1種と、カチオン重合性化合物とを、無酸素雰囲気下において混合した後、前記カチオン重合性化合物が液化あるいは気化する温度範囲に設定することを特徴とするポリマーの生成方法。 - 前記カチオン重合性化合物は、アルキルビニルエーテルである請求項6に記載のポリマーの生成方法。
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