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See detailThermal crosslinking of poly(methyl methacrylate) by reaction of methyl ester and quaternary ammonium salt and application to (meth)acrylate-based TPEs
Tong, Jiang-Dong; Goethals, Eric; Jérôme, Robert ULg

in Journal of Polymer Science. Part A, Polymer Chemistry (1999), 37(23), 4402-4411

Copolymers of N-vinylbenzyl N-methyl pyrrolidinium chloride (VBMPC) and methyl methacrylate, PVBMPC-co-poly(methyl methacrylate) (PMMA), were synthesized by free-radical copolymerization and proved to be ... [more ▼]

Copolymers of N-vinylbenzyl N-methyl pyrrolidinium chloride (VBMPC) and methyl methacrylate, PVBMPC-co-poly(methyl methacrylate) (PMMA), were synthesized by free-radical copolymerization and proved to be prone to crosslinking as a result of the reaction of methyl ester groups with benzyl methyl pyrrolidinium chloride (BMPC) moieties at temperatures higher than 110 °C. When the VBMPC content was lower than 20 wt %, these copolymers were miscible with homo-PMMA. Blends of homo-PMMA and PVBMPC-co-PMMA fully could be cured above 150 °C, when the molecular weight of PMMA exceeded 10,000 and the VBMPC content of the copolymer was higher than 5 wt %. This reaction was carried out to crosslink selectively the PMMA microdomains of PMMA-b-poly(isooctyl acrylate) (PIOA)-b-PMMA (MIM) triblock copolymers to explain the mechanism for the mechanical failure of fully (meth)acrylic thermoplastic elastomers. Comparison of the ultimate tensile properties of MIM block copolymers, when the dispersed PMMA phases and PIOA matrix were crosslinked, led to the conclusion that the ductile failure of the hard PMMA microdomains rather than the elastic failure of the PIOA matrix was the reason for the mechanical failure of MIM triblocks. [less ▲]

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See detailGlobal compartmental analysis of the fluorescence decay surface of the halato telechelic polymer (N,N-dimethyl-N-[3-(1-pyrenyl)propyl]ammonio)-trifluoro-methanesulfonate-end-capped poly(tetrahydrofuran
Hermans, Bart; De Schryver, Frans C; Van Stam, Jan et al

in Macromolecules (1995), 28(9), 3380-3386

The kinetic behavior of the halato telechelic polymer (N,N-dimethyl-N-[3-(1-pyrenyl)propyl]-ammonio)trifluoromethanesulfonate-end-capped poly(tetrahydrofuran) (POLYPROBE) in tetrahydrofuran is ... [more ▼]

The kinetic behavior of the halato telechelic polymer (N,N-dimethyl-N-[3-(1-pyrenyl)propyl]-ammonio)trifluoromethanesulfonate-end-capped poly(tetrahydrofuran) (POLYPROBE) in tetrahydrofuran is investigated by global compartmental analysis of the fluorescence decay surface. At low POLYPROBE concentrations the emission decays monoexponentially. When an analogous end-capped halato telechelic polymer without the pyrene chromophore ((N,N,N-triethylammonio)trifluoromethanesulfonate-end-capped poly(tetrahydrofuran), POLYSALT) is added to solutions containing a low POLYPROBE concentration, the emission can be fitted by a biexponential decay function. From these observations it is concluded that the second excited-state species in the POLYPROBE-POLYSALT system is POLYPROBE involved in ion aggregation due to dipole-dipole or ion-dipole interaction. At higher POLYPROBE concentrations, without added POLYSALT, a triexponential decay function is needed to describe the emission. The third excited-state species is POLYPROBE excimer, which can be formed via two pathways: either intermolecularly when a locally excited POLYPROBE encounters a ground-state POLYPROBE or intramolecularly when an aggregate of two POLYPROBE molecules rearranges. From the global compartmental analysis in which the value of one of the rate constants is scanned, it is found that the bimolecular processes are slowed down by the presence of the polymer chain, while intramolecular rearrangements are not affected. [less ▲]

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