INVESTIGATION OF THE SYNTHSIS OF NOVEL NON-IONIC POLYMER SURFACTANT

新型非离子聚合物表面活性剂的合成研究

• 批准号: 07555295
• 负责人: SHIMANO Yasuo
• 金额: $ 2.3万
• 依托单位: HACHINOHE NATIONAL COLLEGE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555295/
• 关键词: macromonomer; non-ionic surfactant; polymer surfactant; graft copolymer; polyoxazoline; surface tension; methacrylate; block copolymer; メタクリル酸ラウリル; ポリ塩化ビニル

As novel non-ionic polymer surfactants, synthesis of various graft and block copolymers containing both hydrophilic poly (2-methyl-2-oxazoline) (PMeOZO) moiety, and hydrophobic vinyl polymer chain was investigated. Graft copolymers were synthesized by radical copolymerization of vinylbenzyl-terminated (m, p-mixture)PMeOZO macromonomers (VB-PMeOZO-n ; n (degree of polymerization of MeOZO)=7-30) with hydrophobic small monomers (M), e. g., lauryl methacrylate (LMA) and stirene under feed ratio (M/VB-PMeOZO-n) of o.5-30 in acetonitrile and water respectively. Polymerization under LMA/VB-PMeOZO-n=0.5-2.0 produced water-soluble copolymers having low surface tension (gamma) ; the copolymers obtained from LMA under LMA/VB-PMeOZO-13=1.0 in acetonitrile exhibited lowest gamma value of (32.2 dynes/cm), being lower rather than that of "Tween 20". The graft copolymers showed amphiphilic properties in ^1H NMR spectroscopy and increased hydrophilicity of surface of PMMA films by blending. By radical polymerization of hydrophobic monomers (M) such as LMA and tetrafluoropropyl methacrylate (EPMA) using macroazoinitiators (I) derived from alpha, omega-PMeOZO glycols (n=8.3,38.6), block copolymer-type polymer surfactants composed of hydrophilic chain (PMe-OZO) and hydrophobic polymer chain were synthesized. Copolymers of M_n=1780-34390 were formed by the polymerization under feed ratio of M/I=10-40. Hydrophilicity of the copolymers increased as decrease of the ratio. The copolymers synthesized from FPMA under FPMA/I=10 were water-soluble and gamma value of their aqueous solution was much lower than that of corresponding macroinitiators.

作为一种新型的非离子聚合物表面活性剂，合成了具有亲水性的聚(2-甲基-2-恶唑啉)(PMeOZO)和疏水性乙烯基聚合物链的接枝共聚物和嵌段共聚物。在原料比(M/VB-PMeOZO-n)为0.5~30的条件下，采用自由基共聚合方法，将乙烯基苄基(m，p-混合物)大单体(VB-PMeOZO-n；n(MeOZO的聚合度)=7~30)与疏水小单体(M)如甲基丙烯酸十二酯(LMA)和苯乙烯(St)在乙腈和水中进行自由基共聚合，合成了接枝共聚物。在LMA/VB-PMeOZO-n=0.5~2.0下聚合得到表面张力较低的水溶性共聚物，在乙腈中LMA/VB-PMeOZO-13=1.0下聚合得到的共聚物伽马值最低，为32.2dynes/cm，低于吐温20。核磁共振氢谱分析表明，接枝共聚物具有两亲性，共混提高了PMMA薄膜表面的亲水性。以α，omega-PMeOzo二醇(n=8.3，38.6)为引发剂，以疏水单体LMA和甲基丙烯酸四氟丙酯(EPMA)为引发剂，通过自由基聚合，合成了由亲水链(PME-OZO)和疏水聚合链组成的嵌段共聚型聚合物表面活性剂。在进料比M/I=10~40的条件下聚合，得到了M_n=1780~34390的共聚物。共聚物的亲水性随配比的降低而增大。在FPMA/I=10的条件下合成的共聚物是水溶性的，其水溶液的伽马值远低于相应的大分子引发剂。

项目成果

Y.Shimano,S.Kobayashi: "Reactive Oligomers,J.C.Salamone論"Polymerie Materials Encyclopedia"" CRC Press,Florida,USA, 12 (1996)

Y. Shimano、S. Kobayashi：关于反应性低聚物的“聚合物材料百科全书”，J.C. Salamone，CRC Press，佛罗里达州，美国，12 (1996)

Y.Shimanao and S.Kobayashi: Reactive Oligomers.J.C.Salamone ed. Polymeric Materials Encyclopedia, Vol. 9, CRC Press Inc., Florida, USA, (1996)

Y.Shimanao 和 S.Kobayashi：反应性低聚物。J.C.Salamone 编辑。

Y.Shimano,K.Sato等: "Synthesis of Novel Macromonomers and Telechelies of Poly(2‐alkyl‐2‐oxazoline)s." Journal of Polymer Science:Part A:Polymer Chemistry. 33. 2715-2723 (1995)

Y. Shimano、K. Sato 等人：“新型大分子单体和聚（2-烷基-2-恶唑啉）的 Telechelies 的合成”。《高分子科学杂志》：A 部分：高分子化学 33. 2715-2723（1995 年）。 ）

Y.Shimano,S.Kobayashi: "Reactive Oligomers,in Polymeric Materials Encyclopedia" CRC Press,Inc.,Florida,U.S.A.(出版中), (1996)

Y. Shimano、S. Kobayashi：“高分子材料百科全书中的反应性低聚物”CRC Press, Inc.，佛罗里达州，美国（正在印刷中），（1996 年）