Alkyne-Functional Polymers through Sonogashira Coupling to Poly(4-bromostyrene)
Alkyne-Functional Polymers through Sonogashira Coupling to Poly(4-bromostyrene)
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DOI：
10.1021/ma0625915
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发表时间：
2007-02
期刊：
影响因子：
5.5
通讯作者：
Laura B. Sessions;Benjamin R Cohen;R. B. Grubbs
中科院分区：
文献类型：
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作者：
Laura B. Sessions;Benjamin R Cohen;R. B. Grubbs
通过钯催化的端炔偶联对聚4-溴苯乙烯（PBrS）进行后聚合改性，合成了含炔官能团的聚合物和嵌段共聚物。几种偶联方法，最显着的双（苄腈）二氯化钯/三叔丁基膦催化剂系统在室温下，进行了研究，在定义明确的聚合物和共聚物的4-溴苯乙烯制备的氮氧介导的聚合（NMP）与克里思。用PBrS的低分子量均聚物（8 - 15 kg/mol）获得了高的到炔官能重复单元的转化率，得到聚[（4-苯基乙炔基）苯乙烯]-共-聚（4-溴苯乙烯）和聚[（4-己炔基）苯乙烯]-共-聚（4-溴苯乙烯）的富含炔的无规共聚物。在较高分子量聚合物（70 kg/mol）或多嵌段共聚物上进行的偶联反应也得到高的聚[（4-苯基乙炔基）苯乙烯]转化率，而与1-己炔的偶联反应遭受副反应。偶联产物的~ 1H NMR分析表明，偶联产物的结构与分子结构有关。
Alkyne-functional polymers and block copolymers were synthesized by postpolymerization modification of poly(4-bromostyrene) (PBrS) via palladium-catalyzed coupling with terminal alkynes. Several coupling methods, most notably bis(benzonitrile)palladium dichloride/tris-tert-butylphosphine catalyst systems at room temperature, were examined on well-defined polymers and copolymers of 4-bromostyrene prepared by nitroxide-mediated polymerization (NMP) with TEMPO. High conversions to alkyne-functional repeat units were obtained with low molecular weight homopolymers of PBrS (8−15 kg/mol) to afford alkyne-rich random copolymers of poly[(4-phenylethynyl)styrene]-co-poly(4-bromostyrene) and poly[(4-hexynyl)styrene]-co-poly(4-bromostyrene). Coupling reactions run on higher molecular weight polymers (70 kg/mol) or multiblock copolymers also gave high conversions to poly[(4-phenylethynyl)styrene], while coupling reactions with 1-hexyne suffered from side reactions. 1H NMR analysis of the coupled products suggests tha...