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Computational simulation of poly(vinyl chloride) reduction with tri‐ n ‐butyltin hydride. The use of revised rate constants
Author(s) -
Knudson S. K.,
Starnes W. H.
Publication year - 2001
Publication title -
journal of vinyl and additive technology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.295
H-Index - 35
eISSN - 1548-0585
pISSN - 1083-5601
DOI - 10.1002/vnl.10291
Subject(s) - triad (sociology) , vinyl chloride , reaction rate constant , hydride , reactivity (psychology) , reduction (mathematics) , polyvinyl chloride , kinetic energy , materials science , set (abstract data type) , thermodynamics , reaction rate , chemistry , polymer chemistry , computational chemistry , mathematics , kinetics , copolymer , physics , organic chemistry , catalysis , computer science , geometry , alternative medicine , psychoanalysis , pathology , hydrogen , polymer , psychology , quantum mechanics , medicine , programming language
The computer simulation of the reductive dechlorination of poly(vinyl chloride) (PVC) with Bu 3 SnH is reexamined by using a new set of rate constants that has been corrected (a) statistically for the presence of different numbers of chloro substituents and (b) for a triad reactivity factor used to determine the constants for rr ‐and mm ‐VVV triads from that for mr ‐VVV triads. The simulation method is verified by comparison with analytic kinetic results for the reduction of 2,4‐dichloropentane and 2,4,6‐trichloroheptane model compounds. The revised rate constants should and do lead to a smaller ratio of racemic to meso diads in PVC as reaction nears completion, compared to the ratio obtained from the original set of rate constants that had been proposed by previous workers. Experimental data are not sufficiently accurate to distinguish between the two sets of simulation results.