First-order Structure and Solution Properties of Monodisperse Graftcopolymers as Studied by Light Scattering

在这项研究中，我们合成了以下三种类型的接枝共聚物，并研究了它们的溶液性质：(1)具有部分氚臂的星形聚苯乙烯；(2)具有不同化学结构臂的星形聚苯乙烯；(3)在茎中部附近具有多个接枝链的嵌段接枝共聚物。(1)测量了CS2中内、外标星的小角中子散射。通过对数据的分析，我们得出了以下结论。(A)星形聚合物中臂链的内部比臂的外部膨胀约2倍。(B)真正的星形聚合物的结构函数与高斯星的结构函数相差很远，在靠近中心的短距离处具有很大的链段成对关联。(2)这是为对应于发光体的光散射测量而合成的。首先，我们制备了一种双嵌段共聚物，它由聚(2-乙烯基萘)和聚(4-乙烯基苯基二甲基乙烯基硅烷)组成，聚(2-乙烯基萘)是化学上不同的臂，聚(4-乙烯基苯基二甲基乙烯基硅烷)是中心聚合物。然后，将活性聚苯乙烯与中心聚合物偶联，形成星形臂。(3)茎聚合物为聚苯乙烯，接枝聚合物为聚乙二醇。该共聚物在选择性溶剂1-甲基环己醇中形成了大胶束。在30-45ﾟC范围内，临界胶束浓度强烈依赖于温度。表观分子质量、旋转半径、流体动力学半径和散射函数的实验结果表明，胶束的大小和形状可能不均匀，在胶束形成的初期为棒状，平衡时长大为中空球形或不规则形状。

In this study, the following three types of graftcoplymers were synthesized and their solution properties were investigated: (1) Star-shaped polystyrene having a portionally deuterated arm; (2) Star-shaped polystyrene having a chemically-different arm; (3) Block-graftcopolymer with many grafted chains near the middle part of the stem.(1) Small-angle neutron scattering from the inner- and outer- labeled stars in CS2 were measured. The data analysis has allowed us to make the following conclusions. (A) Inner part of an arm chain in the star-shaped polymer is more expanded by about 2 times than the outer part of the arm. (B) Structure function of real star-shaped polymers is far from that of the Gaussian star, having large segmental pairwise correlation at short distances near the center.(2) This was synthesized for light-scattering measurements corresponding to the issuer (1). First, we made a diblockcopolymer consisting of poly(2-vinlynaphthalene), which would be a chemically-different arm, and poly(4- vinylphenyldimethylvinylsilane), which would be the center polymer. Then, living polystyrenes were coupled with the center polymer to be the arms of star.(3) The stem polymer was polystyrene, while the grafted polymer was polyethylene glycol. The copolymer formed a large micelle in a selective solvent, 1-methylcyclohexanol. The critical micelle concentration depends strongly on the temperature in the range of 30 - 45ﾟC. Experimental results of apparent molecular weight, radius of gyration, hydrodynamic radius, and scattering function suggest that the micelle may be nonuniform in size and shape, being rather rod-shaped in the initial stage of micelle formation and grow up to be hollow spherical or disshaped at the equilibrium.