{"title":"利用 RAFT 工艺制备硅基热/光响应嵌段共聚物(由含有成对侧链偶氮中间体的单体制备)的合成、特性和热诱导自组装","authors":"Athmen Zenati , Kisan Koirala","doi":"10.1016/j.polymer.2024.127867","DOIUrl":null,"url":null,"abstract":"<div><div>Novel silicon-based liquid crystalline (LC) monomer (CASPA) and corresponding Poly(MMA)-b-Poly(CASPA) diblock copolymers (DBCs) containing symmetric azobenzene mesogens in the side chain were successfully synthesized by coupling reaction and reversible addition-fragmentation chain transfer (RAFT) polymerization, respectively. Block copolymerization by RAFT proceeded with well-controlled manner in anisole solution involving new CASPA monomer, Poly(MMA)-RAFT macroinitiator and AIBN initiator, yielding Poly(MMA)-b-Poly(CASPA) DBCs with excellent control over molecular weights (Mw/Mn ≤ 1.39) and compositions. Chemical structures and properties of CASPA and Poly(MMA)-b-Poly(CASPA) were extensively studied using <sup>1</sup>H NMR, FTIR, GPC, DSC, POM, AFM and GISAXS. The CASPA exhibited enantiotropic liquid crystallinity with nematic four-brush schlieren texture, while DBCs showed monotropic liquid crystallinity with batonnet textures of smectic A phase. All DBC films exhibited photochemical <em>trans</em>-cis isomerization and photoinduced phase transition from mesophase to isotropic phase under UV irradiation. Morphologies of DBC thin films under thermal annealing depended on volume ratio of building LC block relative to Poly(MMA) segment, DBC-2 containing approximately equal block volume fractions self-assembled into lamellar nanostructure with domain-spacing of 34 nm, whereas DBC-3 and DBC-4 possessing higher LC contents (65 wt% and 72 wt%) formed highly ordered hexagonal cylindrical nanostructures with domain-spacing ranging from 37 to 39 nm as evidence by AFM and GI-SAXS, conforming with the self-consistent field theory.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"316 ","pages":"Article 127867"},"PeriodicalIF":4.1000,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis, characteristics and thermally induced self-assembly of silicon-based thermo/photo-responsive block copolymers prepared from monomer bearing paired side-chain azo mesogens using RAFT process\",\"authors\":\"Athmen Zenati , Kisan Koirala\",\"doi\":\"10.1016/j.polymer.2024.127867\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Novel silicon-based liquid crystalline (LC) monomer (CASPA) and corresponding Poly(MMA)-b-Poly(CASPA) diblock copolymers (DBCs) containing symmetric azobenzene mesogens in the side chain were successfully synthesized by coupling reaction and reversible addition-fragmentation chain transfer (RAFT) polymerization, respectively. Block copolymerization by RAFT proceeded with well-controlled manner in anisole solution involving new CASPA monomer, Poly(MMA)-RAFT macroinitiator and AIBN initiator, yielding Poly(MMA)-b-Poly(CASPA) DBCs with excellent control over molecular weights (Mw/Mn ≤ 1.39) and compositions. Chemical structures and properties of CASPA and Poly(MMA)-b-Poly(CASPA) were extensively studied using <sup>1</sup>H NMR, FTIR, GPC, DSC, POM, AFM and GISAXS. The CASPA exhibited enantiotropic liquid crystallinity with nematic four-brush schlieren texture, while DBCs showed monotropic liquid crystallinity with batonnet textures of smectic A phase. All DBC films exhibited photochemical <em>trans</em>-cis isomerization and photoinduced phase transition from mesophase to isotropic phase under UV irradiation. Morphologies of DBC thin films under thermal annealing depended on volume ratio of building LC block relative to Poly(MMA) segment, DBC-2 containing approximately equal block volume fractions self-assembled into lamellar nanostructure with domain-spacing of 34 nm, whereas DBC-3 and DBC-4 possessing higher LC contents (65 wt% and 72 wt%) formed highly ordered hexagonal cylindrical nanostructures with domain-spacing ranging from 37 to 39 nm as evidence by AFM and GI-SAXS, conforming with the self-consistent field theory.</div></div>\",\"PeriodicalId\":405,\"journal\":{\"name\":\"Polymer\",\"volume\":\"316 \",\"pages\":\"Article 127867\"},\"PeriodicalIF\":4.1000,\"publicationDate\":\"2024-11-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0032386124012035\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0032386124012035","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Synthesis, characteristics and thermally induced self-assembly of silicon-based thermo/photo-responsive block copolymers prepared from monomer bearing paired side-chain azo mesogens using RAFT process
Novel silicon-based liquid crystalline (LC) monomer (CASPA) and corresponding Poly(MMA)-b-Poly(CASPA) diblock copolymers (DBCs) containing symmetric azobenzene mesogens in the side chain were successfully synthesized by coupling reaction and reversible addition-fragmentation chain transfer (RAFT) polymerization, respectively. Block copolymerization by RAFT proceeded with well-controlled manner in anisole solution involving new CASPA monomer, Poly(MMA)-RAFT macroinitiator and AIBN initiator, yielding Poly(MMA)-b-Poly(CASPA) DBCs with excellent control over molecular weights (Mw/Mn ≤ 1.39) and compositions. Chemical structures and properties of CASPA and Poly(MMA)-b-Poly(CASPA) were extensively studied using 1H NMR, FTIR, GPC, DSC, POM, AFM and GISAXS. The CASPA exhibited enantiotropic liquid crystallinity with nematic four-brush schlieren texture, while DBCs showed monotropic liquid crystallinity with batonnet textures of smectic A phase. All DBC films exhibited photochemical trans-cis isomerization and photoinduced phase transition from mesophase to isotropic phase under UV irradiation. Morphologies of DBC thin films under thermal annealing depended on volume ratio of building LC block relative to Poly(MMA) segment, DBC-2 containing approximately equal block volume fractions self-assembled into lamellar nanostructure with domain-spacing of 34 nm, whereas DBC-3 and DBC-4 possessing higher LC contents (65 wt% and 72 wt%) formed highly ordered hexagonal cylindrical nanostructures with domain-spacing ranging from 37 to 39 nm as evidence by AFM and GI-SAXS, conforming with the self-consistent field theory.
期刊介绍:
Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics.
The main scope is covered but not limited to the following core areas:
Polymer Materials
Nanocomposites and hybrid nanomaterials
Polymer blends, films, fibres, networks and porous materials
Physical Characterization
Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films
Polymer Engineering
Advanced multiscale processing methods
Polymer Synthesis, Modification and Self-assembly
Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization
Technological Applications
Polymers for energy generation and storage
Polymer membranes for separation technology
Polymers for opto- and microelectronics.