Telomerization of acrylic acid with mercaptans: Part 2. Kinetics of the synthesis of star-shaped macromolecules of acrylic acid
Telomerization of acrylic acid with mercaptans: Part 2. Kinetics of the synthesis of star-shaped macromolecules of acrylic acid
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DOI：
10.1002/pi.638
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发表时间：
2001-04-01
影响因子：
3.2
通讯作者：
Boutevin, B
中科院分区：
文献类型：
--
作者：
Loubat, C;Boutevin, B
本文首次研究了在有机溶剂（THF）中，65 ℃，2，2 ′-偶氮二异丁腈引发的丙烯酸与多官能转移剂的调聚反应。测定了三种硫醇的转移常数（C-T），乙二醇双巯基乙酸酯、正丙烷三（2-巯基乙酸酯）和季戊四醇四（3-巯基丙酸酯）分别为6.1、6.3和7.3。从这些结果可以看出，通过丙烯酸在THF中调聚不能合成轮廓清晰的星星聚（丙烯酸）。然而，在水/THF混合物中用四官能转移剂进行相同的研究。这项工作强调，溶剂的性质起着重要的作用，在确定的转移常数。因此，对于溶剂水/THF（80%，20%，v/v）的混合物，四官能转移剂的C-T值从THF中的7.3降低到1，这是调聚的“理想”情况（C（T）接近1）。利用该路线，可以通过调聚反应合成星形丙烯酸大分子。(C)2001年，化学工业协会。
The telomerization of acrylic acid with a polyfunctional transfer agent initiated by 2,2'-azobisisobutyronitrile, was first investigated in an organic medium (THF) at 65 degreesC. Transfer constants (C-T) for three mercaptans, ethylene glycol bisthioglycolate, trimethylolpropane tris(2-mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate) of about 6.1, 6.3 and 7.3, respectively, were determined. From these results, it followed that a well-defined star poly(acrylic acid) could not be synthesized via telomerization of acrylic acid in THF. Nevertheless, the same study was performed with the tetrafunctional transfer agent in water/THF mixtures. This work emphasized that the nature of the solvent plays an important role in determining the transfer constant. Thus, the value of C-T for the tetrafunctional transfer agent decreased from 7.3 in THF to 1, the 'ideal' case for telomerization (C(T)approximate to1), for the mixture of solvents water/THF (80%, 20%, v/v). With this route, it seems that acrylic acid star-shaped macromolecules could be synthesized via telomerization. (C) 2001 Society of Chemical Industry.