DYNAMICS OF ENTANGLED POLYMER-SOLUTIONS .1. ROUSE MODEL
DYNAMICS OF ENTANGLED POLYMER-SOLUTIONS .1. ROUSE MODEL
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DOI：
10.1021/ma60052a011
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发表时间：
1976-01-01
期刊：
影响因子：
5.5
通讯作者：
DEGENNES, PG
中科院分区：
文献类型：
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作者：
DEGENNES, PG
本文将Des Cloiseaux，Daoud et ah等人关于好溶剂中半稀聚合物溶液静态关联性质的最新进展推广到含时性质。在这第一篇论文中，我们忽略了单体之间的所有流体动力相互作用(Rouse模型)：这是不正确的，但在教学上是有用的。我们发现：(A)在纠缠点之间存在一个与链的运动有关的特征频率(与分子质量M无关，并随浓度c变化，如Rouse模型中的c2·75)；(B)在小于(但大于总链的某个弛豫速率1/Tr)的频率处，预期会出现类似于聚合物凝胶的行为；(C)在高于或小于相关长度的频率处，单个链的行为是预期的。我们重新考察了排除体积效应时的单链模式，并提出了一定的标度行为。讨论的一个副产品是对排除体积指数的Flory计算的成功的更好的理解。我们还用修正概念4和“管重组”模型试算了时间Tr，得到了Rouse模型的Tr~N3c。我们所有的结果都是定性的，缺乏精确的数值系数。
Recentadvances on the static correlation properties of semidilute polymer solutions in good solvents, due to Des Cloiseaux, Daoud et ah, etc, are extended here to time-dependent properties. In this first paper, we ne-glect all hydrodynamic interactions between monomers(Rouse model): this in incorrect, but pedagogically useful. We show that (a) there is a characteristic frequency associated with the motions of chains between entanglement points (is independent of the molecular mass M and varies with the concentration c like c2· 75 in the Rouse model);(b) at frequencies smaller than(but larger than a certain relaxation rate 1/Tr for the total chain) a behavior reminiscent of polymer gels is expected;(c) atfrequencies above, or at wavelengths smaller than the correlation length, individual chain behavior is expected. We reexamine the single-chain modes in thepresence of excluded volume effects, and propose a certain scaling behavior. A by-product of the discussion is an improved understanding of the success of the Flory calculation for excluded volume exponents. We also present a tentative calcula-tion of the time Tr, using the reptation concept4 plus a model of “tube reorganization” and obtain Tr~ N3c for the Rouse model. All our results are qualitative and lack precise numerical coefficients.