Non-extractable photoinitiators based on thiol-functionalized benzophenones and thioxanthones

Non-extractable photoinitiators could be advantageous for use in biological, electronic, and food packaging applications. Therefore, thioxanthone and benzophenone derivatives were synthesized from 1,6-hexane dithiol and chlorinated benzophenone or thioxanthone. The efficiency of thiol-functionalized photoinitiators in combination with amine co-initiators was compared to benzophenone and isopropylthioxanthone with amine co-initiators, and the cleavage of photoinitiator 2,2-dimethoxy-1,2-diphenylethan-1-one in acrylic resins. The reaction kinetics were analyzed using photo-differential scanning calorimetry and real-time FTIR. Coating physical properties were evaluated by pendulum and pencil hardness, steel-wool scratch and mandrel bend tests. The non-extractable photoinitiators had higher absorbance than their benzophenone or isopropylthioxanthone counterparts due to the sulfide substitution on the phenyl ring, and the free thiol groups reacted with the acrylate by either an amine catalyzed Michael addition or a free-radical chain process. The combination of thiol-functionalized photoinitiators with secondary amines provides an efficient photoinitiator system that is locked into the photopolymerized network and cannot be extracted with typical solvents.     

The preparation of non-extractable methylphenylpolysiloxane stationary phases for capillary column gas chromatography

Summary The synthesis of methylphenylpolysiloxane polymers and their use in the preparation of crosslinked, non-extractable stationary phases for fused-silica capillary columns are described. By preparing more viscous phenyl-containing polymers than are commercially available, stationary phase films of these polymers could be efficiently coated on fused-silica capillary columns and stabilized by a free radical crosslinking mechanism using peroxides. Four methylphenylpolysiloxane polymers containing different phenyl concentrations were prepared. These included three polymers containing 50% phenyl and one polymer containing 70% phenyl. Two of the 50% phenyl polymers had one phenyl and one methyl group attached to each silicon atom. One of these also had 1% vinyl incorporated. The third 50% phenyl polymer was synthesized in such a way that one half of the silicon atoms had two phenyl groups attached while the rest contained dimethyl groups. The 70% phenyl polymer also had 4% vinyl incorporated. Due to the intrinsic thermal stability of these phenyl phases and the enhanced film stability achieved by crosslinking, the 70% phenyl phase could be utilized up to 400 °C. Using the methods described in this paper, highly efficient and thermally stable fused silica capillary columns coated with crosslinked methylphenylpolysiloxane stationary phases can be successfully prepared.