Macromonomers, telechelics and more complex architectures of PMA by a combination of biphasic SET-LRP and biphasic esterification,Polymer Chemistry

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Macromonomers, telechelics and more complex architectures of PMA by a combination of biphasic SET-LRP and biphasic esterification
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-02-22 00:00:00 , DOI: 10.1039/c8py00150b
Adrian Moreno _{1,

2,

3,

4,

5} , Ryan L. Jezorek _{1,

2,

3,

4,

5} , Tong Liu _{1,

2,

3,

4,

5} , Marina Galià _{6,

7,

8,

9,

10} , Gerard Lligadas _{1,

2,

3,

4,

5} , Virgil Percec _{1,

2,

3,

4,

5}

Affiliation

The high bromine chain end functionality of polyacrylates synthesized by single electron transfer living radical polymerization (SET-LRP) mediated by TREN in a biphasic acetone–water mixture containing Cu(II)Br₂ can be exploited to introduce specific functional groups to the chain-ends of these polymers. Here, the α-bromoester end groups of poly(methyl acrylate) (PMA) synthesized in this biphasic SET-LRP system using non-activated Cu(0) wire as catalyst were reacted also under heterogeneous biphasic conditions with potassium acrylate to yield PMA macromonomers and telechelics with α- and α,ω-acrylate chain ends. The reagents used in both steps are air insensitive and inexpensive. 500 MHz ¹H NMR, GPC and MALDI-TOF analyses in combination with the thio-bromo “click” reaction were used to confirm the high efficiency of this two-step protocol. The reactive nature of these macromonomers by the preparation of a PMA-g-PMA more complex architecture was also demonstrated.

中文翻译：

通过双相SET-LRP和双相酯化的结合，可实现PMA的大分子单体，遥螯剂和更复杂的体系结构

可以利用TREN在含Cu（II）Br ₂的双相丙酮-水混合物中通过TREN介导的单电子转移活性自由基聚合（SET-LRP）合成的聚丙烯酸酯的高溴链端官能度，将特定的官能团引入到链中，这些聚合物的末端。在此，在非双相双相条件下，使用非活化Cu（0）线作为催化剂，在该双相SET-LRP系统中合成的聚（丙烯酸甲酯）（PMA）的α-溴酸酯端基也与丙烯酸钾反应生成PMA大分子单体和具有α-和α，ω-丙烯酸酯链端的远螯。这两个步骤中使用的试剂对空气不敏感且价格便宜。500 MHz ¹1 H NMR，GPC和MALDI-TOF分析与硫代溴“点击”反应结合使用，证实了此两步方案的高效性。通过制备更复杂的PMA- g- PMA，还证明了这些大分子单体的反应性。

更新日期：2018-02-22

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