A one-pot strategy to improve end-capping efficacy in Stille poly-condensations†,Polymer Chemistry

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A one-pot strategy to improve end-capping efficacy in Stille poly-condensations†
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-01-19 00:00:00 , DOI: 10.1039/c7py01761h
Jared D. Harris _{1,

2,

3,

4} , Kenneth R. Carter _{1,

2,

3,

4}

Affiliation

Herein we examine the end-capping efficacy of several end-capping reagents (ECRs) in the Stille polymerization of 2,7-dibromo-9,9-bis(2-ethylhexyl)fluorene (Fl) and 2,5-bis(trimethylstannyl)-thieno[3,2-b]thiophene (TT). Polymerizations were carried out in a one-pot fashion where the molar ratio of TT relative to Fl was biased, ideally generating bis(trimethylstannyl) macromolecules. Various ECRs (bromobenzene, 4-bromotoluene, 4-(trifluoromethyl) bromobenzene, 4,4′-bromobiphenyl, 2-bromo-9,9-dimethylfluorene, iodobenzene, 4-iodotoluene, and 4,4′-iodobiphenyl) differing in reactivity were employed in the one-pot reaction. Polymers were characterized using GPC, ¹H NMR, and end-capping efficacy was evaluated with MALDI-ToF MS. The iodo derivatives were found to disrupt propagation, severely inhibiting molecular weight. The bromo ECRs varied in end-capping efficiency: bromofluorene ∼ bromobiphenyl > trifluoromethylbromobenzene ∼ bromobenzene > bromotoluene. Additionally, we demonstrate a strong efficiency dependence on initial monomer concentration and demonstrate this method's superiority over post-polymerization end-capping.

中文翻译：

一锅策略可提高Stille缩聚反应的封端效率†

本文中，我们研究了2,7-二溴-9,9-双（2-乙基己基）芴（F1）和2,5-双（三甲基锡烷基）的Stille聚合中几种封端剂（ECR）的封端效率）-噻吩并[3,2- b ]噻吩（TT）。以一锅方式进行聚合，其中TT相对于F1的摩尔比是有偏差的，理想地产生双（三甲基锡烷基）大分子。反应性不同的各种ECR（溴苯，4-溴甲苯，4-（三氟甲基）溴苯，4,4'-溴代联苯，2-溴-9,9-二甲基芴，碘代苯，4-碘甲苯和4,4'-碘代联苯）在一锅法反应中使用。使用GPC ¹表征聚合物1 H NMR和封端效率用MALDI-ToF MS评估。发现碘衍生物破坏了繁殖，严重抑制了分子量。溴ECR的封端效率各不相同：溴芴〜溴联苯>三氟甲基溴苯〜溴苯>溴甲苯。此外，我们证明了对初始单体浓度的强效依赖性，并证明了该方法优于聚合后的封端反应。

更新日期：2018-01-19

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