doi:

DOI: 10.3724/SP.J.1105.2014.13217

Acta Polymerica Sinica (高分子学报) 2014/014:2 PP.248-254

Photo-induced Synthesis of PVC Macroinitiators and Preparation of Amphiphilic Graft Copolymers


Abstract:
To increase number of labile sites on PVC and thus facilitate grafting from PVC by aids of free radical polymerization (FRP) under mild conditions, self-initiated, or bi-isopropyl thioxanthone (BIITX) and isopropylthioxanthone (ITX) initiated FRP of vinyl chloride (VC) in THF at 0 ℃ or 20 ℃ was carried out under UV irradiation.Influences of monomer concentration,incident light intensity, reaction time and temperature on monomer conversion, polymer molecular weight and its distribution were investigated. Radical ITX· produced by dissociation of BIITX or by H abstraction of ITX from monomer could combine with a macroradical. This allowed ITX residues to be incorporated onto PVC via weak C—C bonds which could be cleaved easily to regenerate radicals under UV light or heat stimuli, and thus yielded new labile sites on PVC for initiation. UV-Vis,1H-NMR and FTIR spectra analyses demonstrated the presence of labile chlorines and ITX residues on the resultant PVC, and indicated that PVC resulted from self-initiated or ITX initiated FRP contained great labile sites. Using the PVC as a macroinitiator, grafting polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA) in THF at 50 ℃ was started, and PVC-based graft copolymer (PVC-g-PDMAEMA) was synthesized. Compared with the initial PVC used, the graft copolymer achieved an increased molecular weight and narrowed molecular weight distribution.1H-NMR and FTIR analyses further confirmed the formation of PVC-based graft copolymer, and revealed that more labile chlorines or ITX residues on PVC favored initiation of graft polymerization. SEM and TEM observations showed that the graft copolymers containing more than 15 mol% (analyzed by 1H-NMR) of PDMAEMA segments could assemble into stable core-shell micelles in water (pH 3).The grafted hydrophilic PDMAEMA stretched towards aqueous media,forming the shell, while hydrophobic PVC portion coiled up to the core. This phenomenon suggested an amphiphilicity of the graft copolymers. In contrast, the copolymer with less content (only 0.15%) of grafted PDMAEMA could not form micelles due to its insufficient amphiphilicity.

Key words:Photopolymerization, PVC, Macroinitiator, Graft copolymer, Amphiphilicity

ReleaseDate:2014-07-21 17:05:30



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