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

本研究合成了以下三种接枝共聚物，并对其溶液性能进行了研究：(1)部分氘化臂的星形聚苯乙烯；(2)具有化学异臂的星形聚苯乙烯；(3)嵌段接枝共聚物，在茎的中部附近有许多接枝链。(1)测量了CS2内标星和外标星的小角中子散射。通过数据分析，我们可以得出以下结论。(A)星形聚合物臂链的内部比外部膨胀约2倍。(B)真实星形聚合物的结构函数与高斯星形聚合物的结构函数相差甚远，在靠近中心的短距离处具有较大的节段两两相关。(2)这是为对应发行者(1)的光散射测量而合成的。首先，我们制作了一种由聚（2-乙烯炔）和聚（4-乙烯基苯基二甲基乙烯基硅烷）组成的二嵌段共聚物，聚（2-乙烯炔）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)茎部聚合物为聚苯乙烯，接枝聚合物为聚乙二醇。该共聚物在选择性溶剂1-甲基环己醇中形成大胶束。临界胶束浓度在30 ~ 45℃范围内受温度影响较大。表观分子量、旋转半径、流体动力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，在胶束形成初期呈棒状，在平衡状态下逐渐变成空心球形或变形。

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.