Main Chain-Type Block Copolymers through Atom Transfer Radical Polymerization from Double-Decker-Shaped Polyhedral Oligomeric Silsesquioxane Hybrids
Main Chain-Type Block Copolymers through Atom Transfer Radical Polymerization from Double-Decker-Shaped Polyhedral Oligomeric Silsesquioxane Hybrids
复制标题
双层多面体低聚倍半硅氧烷杂化物通过原子转移自由基聚合得到主链型嵌段共聚物
DOI：
10.3390/polym12020465
复制
发表时间：
2020-02-01
期刊：
影响因子：
5
通讯作者：
Kuo, Shiao-Wei
中科院分区：
文献类型：
--
作者：
Chen, Wei-Cheng;Tsao, Yu-Hsuan;Kuo, Shiao-Wei
在本研究中，我们以倍半硅氧烷(POSS)纳米粒子为引发剂，通过原子转移自由基聚合(ATRP)合成了两种主要的具有氢键给体和受体链段的链状嵌段共聚物。以双官能化倍半硅氧烷为引发剂VBC-DDSQ-VBC为平台，合成了主链型聚苯乙烯均聚物(PS-DDSQ-PS)、两嵌段共聚物聚(苯乙烯-b-4-乙烯基吡啶)(P4VP-b-PS-DDSQ-PS-b-P4VP)和两嵌段共聚物聚(苯乙烯-b-叔丁氧基苯乙烯)(PtBuOS-b-PS-DDSQ-PS-b-PtBuOS)。PtBuOS-b-PS-DDSQ-PS-b-PtBuOS的叔丁氧基单元选择性水解制得氢键较强的两嵌段共聚物聚(苯乙烯-b-乙烯基苯酚)(PVPh-b-PS-DDSQ-PS-b-PVPh)。利用傅里叶变换红外光谱、核磁共振光谱、尺寸排斥层析、差示扫描量热法、激光解吸电离质谱仪和透射电子显微镜等手段，研究了这些主要链型嵌段共聚物的化学结构、热行为和自组装纳米结构。
In this study, we synthesized two main chain-type block copolymers featuring hydrogen bond donor and acceptor segments through atom transfer radical polymerization (ATRP) using a bifunctionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the initiator. Hydrosilylation of vinylbenzyl chloride at the two corners of a double-decker silsesquioxane (DDSQ) provided the bifunctionalized benzyl chloride initiator VBC-DDSQ-VBC, which we applied as a platform to prepare a main chain-type polystyrene homopolymer (PS-DDSQ-PS), the diblock copolymer poly(styrene-b-4-vinylpyridine) (P4VP-b-PS-DDSQ-PS-b-P4VP), and the diblock copolymer poly(styrene-b-tert-butoxystyrene) (PtBuOS-b-PS-DDSQ-PS-b-PtBuOS) through sequential ATRP. Selective hydrolysis of the tert-butoxyl units of PtBuOS-b-PS-DDSQ-PS-b-PtBuOS yielded the strongly hydrogen bonding diblock copolymer poly (styrene-b-vinylphenol) (PVPh-b-PS-DDSQ-PS-b-PVPh). We used Fourier transfer infrared spectroscopy, nuclear magnetic resonance spectroscopy, size exclusion chromatography, differential scanning calorimetry, mass-analyzed laser desorption ionization mass spectrometry, and transmission electron microscopy to investigate the chemical structures, thermal behavior, and self-assembled nanostructures formed by these main chain-type block copolymers based on DDSQ.