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Synthesis of Hyperbranched Polymers via Metal‐Free ATRP in Solution and Microemulsion
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-02-24 , DOI: 10.1002/macp.202000008 Timothy Cuneo 1 , Xiaofeng Wang 1 , Yi Shi 1 , Haifeng Gao 1
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-02-24 , DOI: 10.1002/macp.202000008 Timothy Cuneo 1 , Xiaofeng Wang 1 , Yi Shi 1 , Haifeng Gao 1
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Atom transfer radical polymerization (ATRP), as one of the most successful controlled radical polymerization techniques, has been broadly used by polymer chemists and nonspecialists for synthesis of various functional materials, although the use of copper as traditional catalyst often results in undesired color or properties. The first homopolymerization of an initiable monomer, that is, inimer, is reported via metal‐free ATRP using 10‐phenylphenothiazine (Ph‐PTH) as photocatalyst in both solution and microemulsion media. Although polymerizations of inimers in both media can be carried out, only the microemulsion polymerization of methacrylate‐based inimer 1 effectively confines the random bimolecular reaction within each segregated latex and produces hyperbranched polymers with high molecular weight and low polydispersity. Several experimental parameters in the microemulsion polymerization of inimer 1 are subsequently studied, including the Ph‐PTH amount, the solids content of microemulsion, and the light source of irradiation. The results not only provide an effective method to tune the structure and molecular weights of hyperbranched polymers in confined‐space polymerization, but also expand the toolbox of using metal‐free ATRP method for synthesizing highly branched polymers in controlled manner.
中文翻译：
溶液和微乳液中无金属ATRP合成超支化聚合物
原子转移自由基聚合（ATRP）作为最成功的受控自由基聚合技术之一，已被聚合物化学家和非专业人员广泛用于合成各种功能材料，尽管使用铜作为传统催化剂通常会导致不良的颜色或性能。在溶液和微乳液介质中，使用10-苯基吩噻嗪（Ph-PTH）作为光催化剂，通过无金属ATRP报道了可引发单体的首次均聚反应，即imimer。尽管可以在两种介质中进行imimers的聚合反应，但是只有基于甲基丙烯酸酯的imimer 1的微乳液聚合才能有效地限制每个分离的胶乳中的无规双分子反应，并产生具有高分子量和低多分散性的超支化聚合物。随后研究了imimer 1的微乳液聚合中的几个实验参数，包括Ph-PTH量，微乳液的固体含量和照射光源。该结果不仅为调节密闭空间聚合中超支化聚合物的结构和分子量提供了一种有效的方法，而且扩展了使用无金属ATRP方法以受控方式合成高度支化聚合物的工具箱。
更新日期：2020-02-24
中文翻译：
溶液和微乳液中无金属ATRP合成超支化聚合物
原子转移自由基聚合（ATRP）作为最成功的受控自由基聚合技术之一，已被聚合物化学家和非专业人员广泛用于合成各种功能材料，尽管使用铜作为传统催化剂通常会导致不良的颜色或性能。在溶液和微乳液介质中，使用10-苯基吩噻嗪（Ph-PTH）作为光催化剂，通过无金属ATRP报道了可引发单体的首次均聚反应，即imimer。尽管可以在两种介质中进行imimers的聚合反应，但是只有基于甲基丙烯酸酯的imimer 1的微乳液聚合才能有效地限制每个分离的胶乳中的无规双分子反应，并产生具有高分子量和低多分散性的超支化聚合物。随后研究了imimer 1的微乳液聚合中的几个实验参数，包括Ph-PTH量，微乳液的固体含量和照射光源。该结果不仅为调节密闭空间聚合中超支化聚合物的结构和分子量提供了一种有效的方法，而且扩展了使用无金属ATRP方法以受控方式合成高度支化聚合物的工具箱。
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