INVESTIGATION OF THE SYNTHSIS OF NOVEL NON-IONIC POLYMER SURFACTANT

作为一种新型的非离子型高分子表面活性剂，研究了含有亲水性聚（2-甲基-2-恶唑啉）（PMeOZO）和疏水性乙烯基聚合物链的接枝和嵌段共聚物的合成。采用乙烯基苄基封端的（m，p-混合物）PMeOZO大单体（VB-PMeOZO-n ; n（MeOZO的聚合度）=7-30）与疏水小单体（M），e.例如，在一个实施例中，甲基丙烯酸月桂酯（LMA）和苯乙烯，进料比（M/VB-PMeOZO-n）分别为0.5 -30，在乙腈和水中。在LMA/VB-PMeOZO-n=0.5-2.0下的聚合产生具有低表面张力（γ）的水溶性共聚物;在LMA/VB-PMeOZO-13=1.0下在乙腈中由LMA获得的共聚物表现出最低的γ值（32.2达因/cm），低于“吐温20”的γ值。接枝共聚物在1H NMR谱中表现出两亲性，并通过共混提高了PMMA膜表面的亲水性。以α，ω-PMeOZO二元醇（n= 8.3，38.6）为大分子偶氮引发剂，通过自由基聚合反应，合成了由亲水链（PMe-OZO）和疏水链组成的嵌段共聚物型高分子表面活性剂。在M/I=10 ~ 40的投料比下，聚合得到了Mn =1780-34390的共聚物。共聚物的亲水性随配比的减小而增大。在FPMA/I=10的条件下合成的共聚物具有水溶性，其水溶液的γ值远低于相应的大分子引发剂。

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.