Precise synthesis and surface structures of architectural per- and semifluorinated polymers with well-defined structures

• Published in: Progress in polymer science Vol. 32; no. 12; pp. 1393 - 1438
• Main Authors: Hirao, Akira, Sugiyama, Kenji, Yokoyama, Hideaki
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 01.12.2007; Elsevier Science
• Subjects: Applied sciences; Block copolymer; Chain-end-multifunctionalized polymer; Dendrimer-like hyperbranched polymer; Exact sciences and technology; Fluorinated polymer; Living/controlled polymerization; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Star-branched polymer; Fluorinated polymer; GTP; PS; Ph 2CHLi; P(F4H2-MA); T g; RAFT; scCO 2; Ph 3CK; MMA; NEXAFS; Si-HEMA; TOA; P(F7H1-MA); PHEMA; EO; P( t BMA); Chain-end-multifunctionalized polymer; P(F8H3-S); ATRP; Ph 3Cli; VF; F1H1-MA; Dendrimer-like hyperbranched polymer; SMP; DPE; P2VP; F7H1-MA; PDMS; P(F6H2-MA); LB’-n; BnBr; PSLi; LP-n; DPE(SMP) 2; AFM; DLS; Ph 3CCs; BuLi; PFPO; P(FmHn-MA); F wt; F4H2-MA; t BMA; Living/controlled polymerization; Ph 2CHK; BnOH; Star-branched polymer; F3H1-MA; PMA; PTFE; ADXPS; FmHn; F at; SAXS; NMP; PS(BnOH) n; PEE; PB; F8H2-MA; LB-n; PMMA; SSIMS; PI; P(F8H2-MA); PEO; Block copolymer; End group; Branched polymer; Fluorine containing polymer; Living polymer; Review; Preparation; Hydrophobic group; Star polymer; Dendritic structure
• ISSN: 0079-6700; 1873-1619
• DOI: 10.1016/j.progpolymsci.2007.08.001

This article reviews the synthesis by methodologies based on living/controlled polymerization, of well-defined perfluorinated and semifluorinated (FL) homopolymers, chain-end-functionalized polymers with FL group(s), block copolymers having FL segment(s), chain-end-multifunctionalized polymers with a definite number of FL groups, and star-branched and dendrimer-like hyperbranched polymers having FL segment(s). Most of the FL groups and FL segments comprise perfluoroalkyl and/or semifluoroalkyl side chains, represented as a CF 3(CF 2) m −1(CH 2) n moiety. In the FL polymers herein presented, except for FL homopolymers, such FL components are chemically linked to non-FL polymer chains and readily separated at the molecular level, followed by self-organization, to form a variety of nanoscale molecular assemblies at the surface of a film, in bulk, and in solution. The FL components possess many unique and interesting characteristics, such as remarkably low surface energies, low friction coefficients, strong incompatibility with conventional hydrocarbon-based polymers, high thermal stability, chemical inertness, and phenyl-free liquid crystalline formation. The surface, solution, and bulk properties of polymer structures including FL units reflect these characteristics of the self-organization of polymers with FL components is of particular interest. Moreover, non-FL polymer chains may enhance the solubility of FL polymers, and render molecular assemblies more changeable in shape, form, and size. Recent reports on these subjects are presented in this review.