Main Chain-Type Block Copolymers through Atom Transfer Radical Polymerization from Double-Decker-Shaped Polyhedral Oligomeric Silsesquioxane Hybrids

Wei-Cheng Chen; Yu-Hsuan Tsao; Chih-Feng Wang; Chih-Feng Huang; Lizong Dai; Tao Chen; Shiao-Wei Kuo

doi:10.3390/polym12020465

Main Chain-Type Block Copolymers through Atom Transfer Radical Polymerization from Double-Decker-Shaped Polyhedral Oligomeric Silsesquioxane Hybrids

Polymers (Basel). 2020 Feb 17;12(2):465. doi: 10.3390/polym12020465.

Authors

Wei-Cheng Chen¹, Yu-Hsuan Tsao¹, Chih-Feng Wang², Chih-Feng Huang³, Lizong Dai⁴, Tao Chen⁵, Shiao-Wei Kuo^{1

6}

Affiliations

¹ Department of Materials and Optoelectronic Science, Center of Crystal Research, National Sun Yat-Sen University, Kaohsiung 80424, Taiwan.
² Advanced Membrane Materials Research Center, Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei 10607, Taiwan.
³ Department of Chemical Engineering, National Chung Hsing University, 145 Xingda Road, Taichung 402-27, Taiwan.
⁴ Fujian Provincial Key Laboratory of Fire Retardant Materials, College of Materials, Xiamen University, Xiamen 361005, China.
⁵ Ningbo Institute of Material Technology and Engineering, Chinese Academy of Science, Zhongguan West Road 1219, Ningbo 315201, China.
⁶ Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan.

Abstract

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.

Keywords: POSS; block copolymer; hydrogen bonding; self-assembly.