Trimethacrylate and dimethacrylate with rigid adamantane-like cores were synthesized from myo-inositol orthoester, and their radical homopolymerization and copolymerization with methyl methacrylate (MMA) were investigated. The radical homopolymerization of trimethacrylate yielded a networked polymer with higher thermal stability than that of a networked polymer synthesized by radical homopolymerization of 1,3,5-cyclohexanetriol-derived trimethacrylate, demonstrating the effect of adamantane-like core rigidity on the increase in thermal stability. Further, dimethacrylate underwent cyclopolymerization, forming a macrocyclic structure in the repeating unit, as the two methacrylate groups were oriented axially from the rigid orthoester-core and thus located close to each other. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2411–2420
This paper deals with a triallyl monomer bearing a rigid adamantane-like core derived from myo-inositol, a naturally occurring cyclic hexaol. The core structure of the monomer can be readily constructed by orthoesterification of myo-inositol. The polyaddition of the triallyl monomer with dithiols based on the thermally induced radical thiol-ene reaction gives the corresponding networked polymers. These networked polymers exhibit much higher thermal stability than the comparative networked polymers obtained from a triallyl monomer bearing less rigid cyclohexyl core. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1193–1199
Two orthoester derivatives 1 and 2 that are easily accessible from naturally occurring myo-inositol were exploited as new triol- and diol-type monomers bearing a rigid adamantane-like structure to polyaddition with diisocyanates that gave the corresponding networked and linear polyurethanes. DSC analysis of the networked polyurethanes revealed their high glass transition temperatures ranging from 155 to 248 °C, suggesting the contribution of the rigidity of the adamantane-like structure introduced at the nodes of the networked polyurethanes 6. Besides, the polyaddition of 2 with diisocyanates gave the corresponding linear polyurethanes 4, of which glass transition temperatures were high, ranging from 105 to 177 °C, presumably by virtue of the rigidity of the adamantane-like structure introduced into the main chains. Tgs of the networked polyurethanes 6 were higher than those of the linear polyurethanes 4. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3498–3505
A bisketal of myo-inositol was used as a diol-type monomer for synthesis of polyurethanes. The monomer was obtained by treatment of myo-inositol with 1,1-dimethoxycyclohexane in the presence of p-toluenesulfonic acid as a catalyst. The ketalization resulted in the formation of a 5-6-5-fused ring system, which endowed the diol-type monomer with high rigidity. The diol readily reacted with diisocyanate to give the corresponding polyurethane, which exhibited excellent heat resistance due to the rigid 5-6-5 system in the main chain. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3956–3963
A glucose-functionalized diamine was prepared and used as a new monomer for polyurea synthesis. The diamine was prepared by N-glycosylation of 1,6-hexamethylenediamine with D-glucose. Upon adding diisocyanates to the diamine, isocyanate reacted selectively with the amino groups, not with the hydroxyl groups of the glucose-derived structure, to give the corresponding polyureas. The polyureas exhibited highly hydrophilic nature due to the presence of the glucose-derived side chain. A ternary system consisting of the glucose-functionalized diamine, piperazine, and diisocyanate gave the corresponding polyureas, where content of the glucose-derived moiety was tunable by feed ratio between the diamine and piperazine. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013
