Micelle formation in the dilute solution mixtures of block-copolymers
Micelle formation in the dilute solution mixtures of block-copolymers
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DOI：
10.1021/ma980482n
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发表时间：
1998-11-03
期刊：
影响因子：
5.5
通讯作者：
Khokhlov, AR
中科院分区：
文献类型：
--
作者：
Borovinskii, AL;Khokhlov, AR
我们发展了两种嵌段共聚物(A-B和C-B)的稀溶液混合物中胶束形成的理论，这些嵌段共聚物具有很长的可溶B-嵌段和化学上相同的不溶嵌段A和C。在这种情况下，形成了具有A、C或AIC核和B冠层的球形胶束。根据前人对混合胶束核心自由能的计算结果和胶束形成理论，将这一过程描述为一系列具有一定化学常数的缔合-解离反应，确定了形成纯胶束和胶束的条件。结果表明，嵌段较长的嵌段共聚物通常最先形成聚集体(胶束)。在比CMC小得多的浓度下，这些胶束被较短的链富集。在相图上有一个较宽的区域，嵌段共聚聚合物在胶束中的聚集分布函数为双峰分布，对应于由较短的嵌段共聚聚合物组成的混合胶束和纯胶束的平衡共存。这与T.Nose等人最近的实验结果很好地一致。
We have developed a theory for the micelle formation in dilute solution mixtures of two block-copolymers (A-B and C-B) with very long soluble B-blocks and chemically identical insoluble blocks A and C differing in lengths. In this case spherical micelles with A, C, or AIC-core and B-corona are formed. The conditions for the formation of pure micelles and comicelles are determined by using the results of the calculation of the free energy of the core of the mixed micelles made previously by us and the theory of the micelle formation describing this process as a set of association-dissociation reactions with certain chemical constants. It is shown that the block-copolymers with longer blocks are normally the first to make aggregates (micelles). These micelles are enriched with shorter chains at the concentrations much smaller than cmc for these chains. There is a wide region on the phase diagram where the distribution function for the aggregation of block-copolymers in the micelles is bimodal, corresponding to the equilibrium coexistence of mixed micelles and pure micelles made of shorter block-copolymers. This is in good agreement with recent experimental findings by T. Nose et al.