ISSN:
0887-624X
Keywords:
copolymerization
;
photocross-linking reaction
;
photosensitivity
;
quantum efficiency
;
organotin copolymer
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Radical-initiated copolymerization of tri-n-butylstannyl methacrylate (TBSM) with allyl chloroacetate (ACA) was carried out in the presence of benzoyl peroxide as initiator in benzene at 70°C in nitrogen atmosphere. Monomer reactivity ratios of the TBSM (M1)-ACA (M2) monomer pair were determined by the Kelen-Tüdöş method: r1 = 1.25 ± 0.02 and r2 = 0.13 ± 0.005. From copolymerization kinetic data the values of effective energy of activation (Ea) and orders with respect to initiator (n) and to monomers (m), Ea = 79.0 kJ/mol, n = 0.51, and m = 1.2, were determined. Photochemical reactions of the copolymer were studied by using monochromatic UV-irradiation at 405 nm and FTIR spectroscopy. For the copolymer synthesized the quantum efficiency (φcrl = 0.62 mol/Einstein) and photosensitivity S = 25.5 cm2/J (in the presence of 1,9-dibromoanthracene as a sensitizer) were found. It was shown that the effects observed of the tin atom and Cl substituent via pentacoordinated complex ( - R3Sn…O=C - ) and σ(Cl - CH2)-π(C=O)-π(allyl) conjugation, respectively, are the main factors for reducing degradative chain transfer and for increasing the tendency of monomers to alternate as well as for the photocrosslinking of copolymer macromolecules. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2339-2345, 1998
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
