Siloxanes have been extensively used as additives to modulate surface properties such as surface tension, hydrophobicity/hydrophobicity, and adhesion, etc. Although, polydimethyl -siloxane and polydiphenylsiloxane are the most commonly used siloxanes, the properties are at extremes in terms of glass transition temperature and flexibility. It is proposed that the ability to control the properties in between the these extremes can be provided by cycloaliphatic substitutions at the siloxane backbone. It is expected that this substitution might work due to the intermediate backbone rigidity.
In order to achieve the above objectives, a synthetic route was developed to prepare cycloaliphatic (cyclopentane and cyclohexane) silane monomers followed by subsequent polymerization and functionalizations to obtain glycidyl epoxy, aliphatic amine and methacrylate telechelic siloxanes. The siloxanes were either thermally or UV- cured depending on end functionalizations. Chemical characterization of monomers, oligomers and polymers were performed using 1H, 13C, 29Si-NMR, FT-IR and GPC. The curing kinetics of photo-induced reactions were investigated through photo-differential scanning calorimetry (PDSC). The oxygen permeability, mechanical, coatings, and release properties of siloxanes were studied as a function of the backbone substitutions. The mechanical, coatings and released properties of cycloaliphatic siloxanes improved with respect to polydimethylsiloxanes. The thermal analysis of the cured films were carried out using differential scanning calorimetry (DSC). Viscoelastic properties of the cured siloxanes due to the variation of substitution at the siloxane backbone were measured using dynamic mechanical thermal analysis (DMTA). The cycloaliphatic substituted siloxanes showed an increased glass transition temperature and permeability but reduced crosslink density, conversion, and rate of curing with respect to polydimethylsiloxanes.
Hybrids of siloxanes were prepared with linseed oil based alkyds to study the effect of variation of alkyd oil lengths and cycloaliphatic substitutions on siloxane backbone. The oil length of an alkyd resin is defined as the number of grams of oil used to produce 100 grams of resin. Three linseed oil based alkyds representing long, medium, and short oil lengths were grafted with siloxanes substituted with methyl, cyclopentyl, and cyclohexyl groups. The reaction was monitored through FTIR and 1H-NMR. The hybrids were formulated with standard drier package and thermally cured for detailed film characterization. Improvement in crosslink density, flexibility, and reverse impact resistance were found as function of oil length. However, tensile modulus, elongation, glass transition temperature, drying time and fracture toughness decreased with increase in oil length. For hybrids, the cycloaliphatic substituents at the siloxane backbone showed enhanced mechanical and coating properties as compared to hybrids with polydimethylsiloxanes.
Random and block copolymer of polydimethylsiloxanes with polydicycloaliphatic- siloxanes were synthesized and compared with homopolymers of polydicycloaliphatic siloxanes. The chemical characterization of the copolymers and homopolymers were carried out through 1H, 13C, 29Si-NMR, and FT-IR. The glass transition temperatures (Tg) of the synthesized polymers were obtained through DSC and advanced rheometric expansion system (ARES). The Tg of random copolymers were found to be higher than the corresponding block copolymers. There was very small difference in Tg between cycloaliphaticsiloxanes homopolymers and corresponding random copolymers. From the above results, it can be inferred that the cycloaliphatic substitutions at the siloxane backbone can be used as a means to obtain properties intermediate to polydimethyl- and polydiphenyl siloxanes.