We report a reversible-deactivation radical copolymerization of styrene and methyl acrylate in the presence of tributylborane and different p-quinones. p-Quinones, such as 1,4-naphthoquinone, 2,3-dimethyl-1,4-benzoquinone, 2,5-ditert-1,4-butylbenzoquinone, and duroquinone, with addition of a catalytic amount of tributylborane, allow for the control over styrene/methyl acrylate copolymerization. The process proceeds in a controlled manner via a reversible homolytic dissociation of the active macromolecules with terminal aryloxyboron-groups. The rate of styrene/methyl acrylate copolymerization depends on the inhibition constants of quinones. The molecular weight and molecular weight distribution of copolymers are directly dependent on the inhibitory abilities of the quinones. 1,4-Naphthoquinone and 2,3-dimethyl-1,4-benzoquinone act as the most effective mediators of chain propagation. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) results showed that the macromolecules contained internal fragments of p-quinone. Also, of the terminal aryloxyboron-groups were detected in the mass spectra. On realization of the “living” mechanism of copolymerization, the structure of copolymers obtained at high conversions can be considered as similar to the gradient structure. Stereo-regularity of the copolymers differed from the conventional radical copolymerization. The glass-transition temperature (T_g) of the gradient copolymer differed from T_g of the random compositional heterogeneous copolymer. The effect of the macromolecular structure on the mechanical properties of the copolymers was studied.

中文翻译：

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用硼烷化学聚合。三丁基硼烷/对醌系统是苯乙烯和丙烯酸甲酯可逆失活​​自由基共聚合的新方法

我们报道了在三丁基硼烷和不同的对醌存在下，苯乙烯和丙烯酸甲酯的可逆失活自由基共聚。对苯醌，例如1,4-萘醌，2,3-二甲基-1,4-苯醌，2,5-二叔-1,4-丁基苯醌和二氢醌，并加入催化量的三丁基硼烷，苯乙烯/丙烯酸甲酯共​​聚的控制。该过程通过以下方式以受控方式进行活性大分子与末端芳氧基硼基团的可逆均质解离。苯乙烯/丙烯酸甲酯的共聚速率取决于醌的抑制常数。共聚物的分子量和分子量分布直接取决于醌的抑制能力。1,4-萘醌和2,3-二甲基-1,4-苯醌是最有效的链增长介质。基质辅助激光解吸电离飞行时间质谱（MALDI-TOF MS）结果表明，大分子包含p的内部片段-醌。另外，在质谱中检测到末端的芳氧基硼基。在实现共聚的“活性”机理时，可以认为以高转化率获得的共聚物的结构类似于梯度结构。共聚物的立体规则性不同于常规的自由基共聚。梯度共聚物的玻璃化转变温度（T _g）与无规组成的非均相共聚物的T _g不同。研究了高分子结构对共聚物力学性能的影响。