Radical Polymerization of methacrylates with an adamantane-like rigid core derived from naturally occurringmyo-inositol

Abstract

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

Radical polymerizations of two stereoisomeric trimethacrylates with rigid adamantane‐like cores from naturally occurring myo‐inositol

“…Using myo ‐inositol as a starting material for bioactive molecules, a variety of regioselective protection protocols for its hydroxyl groups have been established to enable precise syntheses of targeted myo ‐inositol‐derivatives . These protection protocols typically involve orthoesterification, which is commonly used for the protection of the three hydroxyl groups at the 1‐, 3‐, and 5‐positions to give corresponding triols such as 1 shown in Scheme . Interestingly, 1 has an adamantane‐like core structure, allowing the synthesis of polymers consisting of conformationally constrained repeating units.…”

“…Triol 1 was also used as a precursor for the synthesis of trimethacrylate T1 (Scheme ). The radical polymerization of T1 yielded the corresponding networked polymethacrylate, which was thermally more stable than polymers obtained from the radical polymerization of a trimethacrylate with a more flexible core derived from 1,3,5‐hydroxycyclohexane . In addition, to gain insight into the structure of the networked polymer obtained by the polymerization of T1 , triol 1 was modified to form dimethacrylate D1 , and its radical polymerization was investigated.…”

“…In addition, to gain insight into the structure of the networked polymer obtained by the polymerization of T1 , triol 1 was modified to form dimethacrylate D1 , and its radical polymerization was investigated. The two methacrylate moieties oriented axially with the core underwent cyclopolymerization to afford the corresponding polymer bearing a macrocyclic structure in the repeating unit . This provided a new example of efficient cyclopolymerization of divinyl monomers in addition to the bis‐styrenic monomer with a myo ‐inositol orthoester core .…”

Partially bio‐based tri‐ and hexaallyl monomers: Synthesis from naturally occurringmyo‐inositol and polyaddition with dithiols

“…This is because the use of renewable compounds means a reduction in the consumption of fossil‐based resources, and provides more green and sustainable approaches to polymer materials . The focus of our research interest has been on the utilization of myo ‐inositol as a starting material for designing monomers to prepare linear and networked polymers . myo ‐Inositol is a naturally occurring cyclic hexaol that can be obtained from its phosphate derivatives such as phosphatidyl inositol and phytic acid found abundantly in organs of plants and animals .…”

A highly rigid diamine monomer derived from naturally occurringmyo-inositol and its use for polyamide synthesis

“…Recently, we have focused our attention on the utilization of myo ‐inositol as a biobased building block for the synthesis of rigid monomers that can be used to prepare high‐performance polymers . myo ‐Inositol is a naturally occurring cyclic hexaol that is present in plant organs as its phosphate derivatives such as phosphatidyl inositol and phytic acid .…”