Novel Polymerization System of Acrylamides in the Presence of the Polymers having the Lower Critical Solution Temperature in Water

具有较低水中临界溶液温度的聚合物存在下的新型丙烯酰胺聚合体系

• 批准号: 14550841
• 负责人: YAMASHITA Natsuki
• 金额: $ 1.6万
• 依托单位: Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14550841/
• 关键词: Poly(N-isopropylacrylamide); Lower Critical Solution Temperature; Acrylamides; Aqueous Solution; Matrix Polymerization; Copolymerization; Radical Polymerization; Methyl methacrylate; ポリ(N-イソプロピルアクリルアミド

It has been found in this study that acrylamide(AAm) polymerizes in the presence of poly(N-isopropylacrylamide)(PNIPAAm) in water without any radical initiators. The mechanism of this polymerization is still not always clear at the presence, but the solution conditions of PNIPAAm in water at around its lower critical solution temperature(LCST=32℃) is one of the most important factors to induce the polymerization. In the presence of the resulting PNIPAAm, the coporlymerization of acrylamide(AAm) with methyl methacrylate(MMA) was also carried out, and found to give the corresponding copolymers which showed unimodal distributions in their molecular weights. The copolymer obtained under the condition of 50mol% of MMA in the monomer feed was found to show more than 60% of MMA content in the resulting copolymer. It is probably due to the monomer concentrating effect induced by the hydrophobic interaction between the PNIPAAm main chain and MMA monomers, and also by the hydrogen bondings between the amide groups on PNIPAAm and the carbonyl groups on MMA.The coporymerization of AAm with styrene(St) was also found to proceed in the presence of PNIPAAm in water. The copolymer obtained under the condition of 50mol% of St in the monomer feed was found to show more than 60% of St, but more than 70% of St in the monomer feed resulted in a remarkable decrease in the St content in the resulting copolymer. These results are reasonably explained by the fact that the monomer concentrationing processes of AAm and that of St proceed separately. Namely, the AAm monomers are concentrated in the PNIPAAm polyer matrix by the specific interaction between the amide groups on PNIPAAm and AAm, while the St monomers ony by the hydrophobic interaction between the PNIPAAm main chain and St monomers.

研究发现，丙烯酰胺（AAm）在聚（N-异丙基丙烯酰胺）（PNIPAAm）的存在下，在没有任何自由基引发剂的情况下，在水中聚合。PNIPAAm在水中的低临界溶解温度（LCST=32℃）是引发聚合的重要因素之一。在PNIPAAm的存在下，丙烯酰胺（AAm）与甲基丙烯酸甲酯（MMA）也进行了共聚反应，得到了分子量呈单峰分布的共聚物。在单体进料中MMA含量为50mol%的条件下得到的共聚物中MMA含量超过60%。这可能是由于PNIPAAm主链与MMA单体之间的疏水相互作用以及PNIPAAm上的酰胺基与MMA上的羰基之间的氢键作用所引起的单体浓缩效应。发现在单体进料中St为50mol%的条件下获得的共聚物显示出大于60%的St，但单体进料中St大于70%导致所得共聚物中St含量显著降低。这些结果合理地解释了AAm和St的单体浓缩过程分别进行的事实。即AAm单体通过PNIPAAm和AAm上的酰胺基团之间的特异性相互作用而集中在PNIPAAm聚合物基质中，而St单体仅通过PNIPAAm主链和St单体之间的疏水相互作用而集中在PNIPAAm聚合物基质中。

项目成果

Manabu Ishifune, Hajime Yamashita, Yoshiya Kera, Natsuki Yamashita, Keijiro Hirata, Hiroaki Murase, Shigenori Kashimura: "Electroreduction of Aromatics Using Magnesium Electrodes in Aprotic Solvents Containing Alcoholic Proton Donors"Electrochimica Acta.

Manabu Ishifune、Hajime Yamashita、Yoshiya Kera、Natsuki Yamashita、Keijiro Hirata、Hiroaki Murase、Shigenori Kashimura：“在含有酒精质子供体的非质子溶剂中使用镁电极进行芳香族化合物的电还原”《电化学学报》。

石船 学: "Electroreductive Synthesis and Caracterization of Polycarbosilanes Containing Oligosilane Units"J. Macromol. Sci., Part A-Pure and Appl. Chem. A41・4. 375-388 (2004)

Manabu Ishifune：“含有寡硅烷单元的聚碳硅烷的电还原合成和表征”J. Macromol.，A-Pure 和 Appl. 375-388 (2004)。

柏村 成史: "Magnesium and Ianthanide ions promoted electrochemical coupling of aliphatic esters and tetrahydrofuran for the synthesis of acetals"Electrochimica Acta. 48・1. 7-10 (2002)

Masashi Kashiwamura：“镁和镧系离子促进脂肪族酯和四氢呋喃的电化学偶联，用于合成缩醛”Electrochimica Acta 48・1（2002）。

石船 学: "Electroreduction of aromatics using magnesium electrodes in aprotic solvents containing alcoholic proton donors"Electrochimica Acta. 48・17. 2405-2409 (2003)

Manabu Ishifune：“在含有醇质子供体的非质子溶剂中使用镁电极进行芳族化合物的电还原”Electrochimica Acta 48・17（2003）。

Shigenori Kashimura, Hajime Yamashita, Yoshihiro Murai, Yoshiya Kera, Natsuki Yamashita, Hiroaki Murase, Manabu Ishifune: "Magnesium and Lanthanide Ions Promoted Electrochemical Coupling of Aliphatic Esters and Tetrahydrofuran for the Synthesis of Acetals

Shigenori Kashimura、Hajime Yamashita、Yoshihiro Murai、Yoshiya Kera、Natsuki Yamashita、Hiroaki Murase、Manabu Ishifune：“镁和镧系离子促进脂肪酯和四氢呋喃的电化学偶联，用于合成缩醛