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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1969-1978 
    ISSN: 0887-624X
    Keywords: poly(methyl methacrylate) ; TMPD ; two-photon ionization ; main chain scission ; ESR ; GPC ; radical anion ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The main chain scission reaction of poly(methyl methacrylate) (PMMA) doped with N,N,N,′,N′-tetramethyl-p-phenylenediamine (TMPD) was examined by ESR spectroscopy and GPC measurement, and the scission mechanism was analyzed. The two-photon ionization of TMPD with excimer laser excitation at 77 K produced an ester radical anion of PMMA (PMMA·m̌), which becomes the main chain tertiary radical —CH2—C·(CH3)—CH2—after the detachment of the ester side group by annealing of the sample at room temperature. The main chain scission radical ·C(CH3)(COOCH3)—(PMMA·) which was produced by the β-scission from—CH2—·C(CH3)—CH2—showed the 13-line ESR spectrum instead of the ordinary 9-line, due to the fast quenching of the sample to 77 K. The change of the molecular weight distribution was measured by GPC after several irradiation-and-annealing operations. The simulation of the GPC curve confirmed that the scission re-action occurs at random in the PMMA chain in the solid and the main chain scission yield from the ester radical anion, [PMMA·]/[PMMA·m̌], is 0.30. © 1995 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0959-8103
    Keywords: poly(ethylene terephthalate) copolymer ; poly(ethylene glycol) ; poly(tetramethylene glycol) ; water absorption ; biodegradability ; in-vitro degradation ; lipase ; alkaline hydrolysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(ethylene terephthalate) copolymers were prepared by melt polycondensation of dimethyl terephthalate and excess ethylene glycol with 10-40mol% (in feed) of poly(ethylene glycol) (E) and poly(tetramethylene glycol) (B), with molecular weight (MW) of E and B 200-7500 and 1000, respectively. The reduced specific viscosity of copolymers increased with increasing MW and content of polyglycol comonomer. The temperature of melting (Tm), cold crystallization and glass transition (Tg) decreased with the copolymerization. Tm depression of copolymers suggested that the E series copolymers are the block type at higher content of the comonomer. Tg was decreased below room temperature by the copolymerization, which affected the crystallinity and the density of copolymer films. Water absorption increased with increasing content of comonomer, and the increase was much higher for E1000 series films than B1000 series films. The biodegradability was estimated by weight loss of copolymer films in buffer solution with and without a lipase at 37°C. The weight loss was enhanced a little by the presence of a lipase, and increased abruptly at higher comonomer content, which was correlated to the water absorption and the concentration of ester linkages between PET and PEG segments. The weight loss of B series films was much lower than that of E series films. The abrupt increase of the weight loss by alkaline hydrolysis is almost consistent with that by biodegradation.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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