Exclusive Synthesis of Poly(3‐hexylthiophene) with an Ethynyl Group at Only One End for Effective Block Copolymerization,Macromolecular Rapid Communications

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Exclusive Synthesis of Poly(3‐hexylthiophene) with an Ethynyl Group at Only One End for Effective Block Copolymerization
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2017-11-20 , DOI: 10.1002/marc.201700586
Geng Zhang ₁ , Yoshihiro Ohta ₁ , Tsutomu Yokozawa ₁

Affiliation

Well‐controlled synthesis of ethynyl‐functionalized poly(3‐hexylthiophene) (P3HT) is crucial for preparation of block copolymers containing the P3HT segment by means of click coupling reaction. A well‐known chain end modification method, in which Kumada–Tamao catalyst‐transfer polymerization is quenched with ethynylmagnesium chloride, under various conditions is re‐examined, but in all cases not only P3HT with an ethynyl group at one end but also P3HT di‐ethynylated at both ends is obtained. Accordingly, Sonogashira coupling reaction of P3HT having H/Br ends with trimethylsilylacetylene is tried, followed by removal of the trimethylsilyl group, and it is found that this protocol affords exclusively P3HT with an ethynyl group at one end. This post end‐modification method is applied to the synthesis of an amphiphilic diblock copolymer of P3HT and poly(2‐ethyl‐2‐oxazoline) (PEtOx) by means of click reaction between ethynylated P3HT and PEtOx with an azide group at one end, and the product is confirmed to be free from contamination with triblock copolymer. Micellization of this block copolymer is confirmed in tetrahydrofuran (THF)/water and THF/methanol mixtures.

中文翻译：

独家合成仅一端带有乙炔基的聚（3-己基噻吩），以实现有效的嵌段共聚

乙炔基官能化的聚（3-己基噻吩）（P3HT）的受控合成对通过点击偶联反应制备包含P3HT链段的嵌段共聚物至关重要。重新检验了一种著名的链端修饰方法，其中在各种条件下用乙炔基氯化镁淬灭了Kumada–Tamao催化剂转移聚合，但在所有情况下，不仅在一端具有乙炔基的P3HT，而且在所有情况下获得两端乙炔基化。因此，尝试了具有H / Br末端的P3HT与三甲基甲硅烷基乙炔的Sonogashira偶联反应，随后除去三甲基甲硅烷基，并且发现该方案仅提供了在一端具有乙炔基的P3HT。这种末端修饰方法适用于P3HT和聚（2-乙基-2-恶唑啉）（PEtOx）的两亲性二嵌段共聚物的合成，其方法是通过乙氧基化P3HT和PEtOx在一端带有叠氮基的点击反应，并且证实该产物没有三嵌段共聚物的污染。在四氢呋喃（THF）/水和THF /甲醇的混合物中证实了该嵌段共聚物的胶束化。

更新日期：2017-11-20

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