Synthesis and characterization of semi-IPNs and blends containing poly(styrene-b-vinylphenyldimethylsilanol)

Block copolymers of vinylphenyldimethylsilanol (VPDMS) and styrene were synthesized by living anionic polymerization of vinylphenyldimethylsilane and styrene with sec-butyllithium as initiator in THF at −78°C, followed by partial or complete oxygen insertion reaction via oxyfunctionalization with dimethyldioxirane. The resulting silanol group ($\equiv$Si-OH) at the 4-position of the styrene copolymer acts as a hydrogen bond donor, thus enhancing miscibility with polymers containing hydrogen bond accepting groups. The block copolymers containing varying amounts of silanol groups and their blends with poly(n-butylmethylacrylate) (PBMA), poly(vinylpyrrolidone) (PVPr), and poly(vinylpyridine) (P4VPy) were characterized by temperature modulated differential scanning calorimetry (MDSC), and Fourier Transform Infrared spectroscopy (FTIR). In blends with PBMA, the PVPDMS block is miscible with PBMA when it contains about 11–33 mo1% silanol groups and the polystyrene blocks retain their identity as separate domains. These observations suggest microphase separation as the dominant mechanism. However, at higher silanol contents, the Tg results indicate the presence of three different domains and are indicative of a micro-macro phase separation mechanism. The block copolymer containing 21% VPDMS units, PVPDMS-21, forms transparent films when blended with PVPr in all ratios; again, the PS blocks are unaffected and the Tg results conform to the predictions of a microphase separation mechanism. There is also a positive deviation of the Tg of the mixed phase from the calculated weight average value as a result of strong hydrogen bonding between the silanol and amide carbonyl groups. The interaction between pyridine and silanol groups results in a large shift in the −OH stretching frequency, ($D$v = 223cm−1), indicative of strong intermolecular hydrogen bonding interaction which is evidenced also by the presence of the pyridinium structure in the FTIR spectra. The strong interaction is responsible for microphase separation as the dominant mechanism in morphological development with a large synergistic Tg effect. Based on spectroscopic and Tg results, the relative strength of intermolecular hydrogen bonding in the blends can be ranked in the order P4VPy > PVPr > PBMA. The strength of the intermolecular hydrogen bonding between the homopolymer and the silanol containing block, in relation to the self association of silanol groups, governs the mechanisms of morphological development, i.e. microphase separation versus micro-macro phase separation.