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Rational synthesis of epoxy-functional spheres, worms and vesicles by RAFT aqueous emulsion polymerisation of glycidyl methacrylate
Polymer Chemistry ( IF 4.6 ) Pub Date : 2020-09-10 , DOI: 10.1039/d0py01097a
Fiona L. Hatton 1, 2, 3, 4, 5 , Matthew J. Derry 1, 2, 3, 4, 5 , Steven P. Armes 1, 2, 3, 4, 5
Affiliation  

The rational synthesis of epoxy-functional diblock copolymer nano-objects has been achieved via RAFT aqueous emulsion polymerisation of glycidyl methacrylate (GlyMA; aqueous solubility ∼22 g dm−3 at 50 °C) by utilising relatively mild conditions (pH 7, 50 °C) to preserve the epoxy groups. High monomer conversions were achieved within 1 h when using a poly(glycerol monomethacrylate) chain transfer agent with a mean degree of polymerisation (DP) of 28, with GPC analysis indicating relatively narrow molecular weight distributions (Mw/Mn < 1.40) when targeting PGlyMA DPs up to 80. A phase diagram was constructed to identify the synthesis conditions required to access pure spheres, worms or vesicles. Transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering (SAXS) studies indicated the formation of well-defined worms and vesicles when targeting relatively long PGlyMA blocks. These epoxy-functional nano-objects were derivatised via epoxy-thiol chemistry by reaction with L-cysteine in aqueous solution. Finally, an in situ SAXS study was conducted during the RAFT aqueous emulsion polymerisation of GlyMA at 50 °C to examine the nucleation and size evolution of PGMA48-PGlyMA100 diblock copolymer spheres using a bespoke stirrable reaction cell.

中文翻译:

通过RAFT甲基丙烯酸缩水甘油酯水乳液聚合合理合成环氧官能团,蠕虫和囊泡

通过使用相对温和的条件(pH 7、50 °),通过RAFT甲基丙烯酸缩水甘油酯的水乳液聚合(GlyMA;在50°C时的水溶解度约为22 g dm -3),已经实现了环氧官能二嵌段共聚物纳米物体的合理合成。C)保留环氧基。当使用平均聚合度(DP)为28的聚甘油单甲基丙烯酸甘油酯链转移剂时,在1小时内可实现高单体转化率,GPC分析表明分子量分布相对较窄(M w / M n<1.40)时,目标是PGlyMA DPs最高可达80。构建了一个相图,以鉴定进入纯球体,蠕虫或囊泡所需的合成条件。透射电子显微镜,动态光散射和小角度X射线散射(SAXS)研究表明,以相对较长的PGlyMA块为靶标时,会形成清晰的蠕虫和囊泡。这些环氧官能的纳米物体通过与水溶液中的L-半胱氨酸反应,通过环氧-硫醇化学衍生化。最后,在50°C的GlyMA的RAFT水乳液聚合过程中进行了原位SAXS研究,以检查PGMA 48 -PGlyMA 100的形核和尺寸演变 使用定制的可搅拌反应池制备二嵌段共聚物球。
更新日期:2020-10-13
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