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Modelling the Kinetics of Photoinitiated Polymerization of Di(meth)acrylates

✍ Scribed by Andrzejewska, Ewa; Lindén, Lars-Åke; Rabek, Jan F.


Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
371 KB
Volume
42
Category
Article
ISSN
0959-8103

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✦ Synopsis


The kinetics of photoinitiated polymerization of six analogous di(meth)acrylates and diacrylates was analysed according to the autocatalytic model (where is polymerization rate, p is conversion degree, R p \ kpm(1 [ p)n R p k is reaction rate constant and m and n are exponents), in order to Ðnd the inÑuence of the reaction temperature and atmosphere, as well as monomer structure, on the parameters k, m and n. The best Ðt between the model prediction and experimental data was for the polymerization of diacrylates in an inert gas atmosphere. The autocatalytic exponent, m, for polymerization in argon of both dimethacrylates and diacrylates was found to be close to unity, whereas the reaction order exponent, n, was twice as high for the former compared with the latter (in the range of c. 3È5 and c. 1É3È2, respectively). An increase in the polymerization temperature caused a drop in both exponents. This drop is much more rapid in the case of the exponent n. Changes in the m and n exponents with temperature, as well as the di †erence in n exponents for the polymerization of acrylates and methacrylates, may be related to changes and di †erences in the mobility of reactive species during the reaction. The inÑuence of atmospheric oxygen on the polymerization parameters is manifested by a very high increase in value of the exponent n. In the photochemically initiated process, an increase in the polymerization rate with temperature results mainly from a rapid decrease in the exponent n and, to a much lesser degree, from an increase in the reaction rate constant k. Key words : kinetics of photoinitiated polymerization, di(


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