Abstract
Crosslinked poly(methyl methacrylate) (PMMA) with high glass transition temperature (Tg) and thermal decomposition temperature was prepared by simple thermal crosslinking of PMMA-containing random copolymers bearing aryl trifluorovinyl ether (TFVE) moieties. A methacrylate monomer consisting of aryl TFVE moiety, 4-((1,2,2-trifluorovinyl)oxy)phenyl methacrylate (TFVOPMA), was first synthesized followed by radical copolymerization with methyl methacrylate (MMA) initiated by AIBN, providing the random copolymer containing aryl TFVE moieties, poly(4-((1,2,2-trifluorovinyl)oxy)phenyl methacrylate)-co-poly(methyl methacrylate) (PTFVOPMA-co-PMMA). Finally, crosslinked PMMA polymer with perfluorocyclobutyl (PFCB) aryl ether moieties as crosslinking units was obtained by [2π + 2π] cycloaddition reaction of aryl TFVE moieties in PTFVOPMA-co-PMMA copolymer. Thermal properties of both PTFVOPMA-co-PMMA and crosslinked PTFVOPMA-co-PMMA were examined by TGA and DSC. Compared to pure PMMA, Tg of PTFVOPMA-co-PMMA increased by 15.1 °C and no Tg was found in the DCS test of the crosslinked PTFVOPMA-co-PMMA. Thermal decomposition temperature (Td,5%) of crosslinked PMMA was 47 °C higher than that of pure PMMA. Furthermore, the water absorption of crosslinked PMMA film greatly reduced in comparison with that of pure PMMA.
Highlights
Poly(methyl methacrylate) (PMMA) is a kind of transparent polymeric material possessing diverse excellent properties such as superior light transmittance, light weight, chemical stability, weathering corrosion resistance, electrical insulation and good processability, which make poly(methyl methacrylate) (PMMA) widely applied in many elds including aerospace, building construction and optical instruments.[1,2,3,4] the glass transition temperature (Tg, 100 C) and heat-deformation temperature of PMMA are relatively low so as to limit its applications.[5,6] In order to improve Tg and the thermal stability of PMMA, investigators have explored various methods,[3,7,8,9,10,11,12,13,14,15] including the copolymerization of methyl methacrylate (MMA) with comonomers bearing rigid or bulky groups to overcome the miscibility puzzle, or the formation of a threedimensional network structure by the addition of crosslinking agent
Crosslinked poly(methyl methacrylate) (PMMA) with high glass transition temperature (Tg) and thermal decomposition temperature was prepared by simple thermal crosslinking of PMMA-containing random copolymers bearing aryl trifluorovinyl ether (TFVE) moieties
A methacrylate monomer consisting of aryl TFVE moiety, 4-((1,2,2-trifluorovinyl)oxy)phenyl methacrylate (TFVOPMA), was first synthesized followed by radical copolymerization with methyl methacrylate (MMA) initiated by AIBN, providing the random copolymer containing aryl TFVE moieties, poly(4-((1,2,2-trifluorovinyl)oxy)phenyl methacrylate)-copoly(methyl methacrylate) (PTFVOPMA-co-PMMA)
Summary
Poly(methyl methacrylate) (PMMA) is a kind of transparent polymeric material possessing diverse excellent properties such as superior light transmittance, light weight, chemical stability, weathering corrosion resistance, electrical insulation and good processability, which make PMMA widely applied in many elds including aerospace, building construction and optical instruments.[1,2,3,4] the glass transition temperature (Tg, 100 C) and heat-deformation temperature of PMMA are relatively low so as to limit its applications.[5,6] In order to improve Tg and the thermal stability of PMMA, investigators have explored various methods,[3,7,8,9,10,11,12,13,14,15] including the copolymerization of methyl methacrylate (MMA) with comonomers bearing rigid or bulky groups to overcome the miscibility puzzle, or the formation of a threedimensional network structure by the addition of crosslinking agent. Crosslinked poly(methyl methacrylate) (PMMA) with high glass transition temperature (Tg) and thermal decomposition temperature was prepared by simple thermal crosslinking of PMMA-containing random copolymers bearing aryl trifluorovinyl ether (TFVE) moieties.
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