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江苏大学材料科学与工程学院 镇江 212013
Published:20 February 2017,
Received:7 July 2016,
Revised:9 August 2016,
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Zhou Zhi-ping, Hao Tong-fan. Theoretical Model of Hyperbranched Polymerization with AB
Zhou Zhi-ping, Hao Tong-fan. Theoretical Model of Hyperbranched Polymerization with AB
超支化聚合物的可控制备与分子设计对其工业化应用是十分重要的,这有待于弄清超支化聚合物的形成机理.本文回顾了早期关于超支化聚合物的Flory-Stockmayer理论,重点介绍与AB
g
型单体相关的超支化聚合反应的动力学原理,这是我国科学家在这一领域的工作亮点,在国际上受到了广泛的关注.相比其它一些理论方法,聚合反应动力学理论原理清晰,可通过解动力学微分方程导出反应产物的平均支化度和聚合度分布函数的解析式,由此可以计算各种分子参数,为超支化聚合物的分子设计和可控制备提供了理论基础.
Molecular design and controllable preparation of hyperbranched polymers are of great significance for their industrialized application
which depends on the understanding for their formation mechanism. At the end of 1980's
Kim
et al
. successfully prepared hyperbranched polyphenylenes. Since then
the hyperbranched polymers have been a hot topic in polymer science and great progress has been made in both experiments and theory. The topological structure and molecular parameters can be estimated by the theory of hyperbranched polymers
which provided a great help to the molecular design and controllable preparation of hyperbranched polymers. Among the various theoretical models
kinetics of hyperbranched polymerization is the most perfect due to the clear principle and rigorous derivation
by which the analytical expressions of the molecular weight distribution functions and the various molecular parameters of the products can be derived. It is one of highlights of scientists working in China. The polymerization of AB
g
type monomer is one of the most important technologies to prepare the hyperbranched polymers. However
the molecular weight distribution is extremely wide for the products of the polycondensation with pure AB
g
type monomer. The presence of a little of multifunctional group can narrow the molecular weight distribution. Moreover
the polydispersity of hyperbranched polymers obtained can drastically decrease when the monomers are slowly added to the reaction system. Another deficiency of the hyperbranched polymers resulted from the polycondensation with pure AB
g
type monomer is the poor mechanical properties. One of the improved approaches is the copolymerization of AB and AB
g
monomers
in which some linear segments can be incorporated into the hyperbranched polymer obtained. Thus
the degree of branching and the mechanical properties of the polymer can be designed by suitable monomer feed ratio. Taking account of the substitution effect
various degree of branching of the products also can be understood. Yan
et al
. developed kinetic model for a large variety of hyperbranched polymerizations and successfully explained these phenomena mentioned above. In this work
the early Flory-Stockmayer theory for hyperbranched polymers is reviewed and
specially
the kinetic theory of hyperbranched polymerization with AB
g
type monomer is introduced.
超支化聚合物聚合反应动力学分子量分布函数支化度
Hyperbranched polymerPolymerization kineticsMolecular weight functionDegree of branching
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