The photoinitiated thiol-ene cross-linking of a dimethacrylate polyether of
Bisphenol A and pentaerythritol tetrakis 2-mercaptopropionate was studied
in the presence of 2,2-dimethyl-2-hydroxy acetophenone (Darocur 1173). Two
complementary techniques were used: photocalorimetry and real-time infrared
spectroscopy. In the first part, the kinetic reaction was characterized by
a stoichiometric mixture in reactive functions. The influence of temperatu
re, photoinitiator concentration and ultraviolet (UV) light intensity was i
nvestigated. The results mainly show that the methacrylate homopolymerizati
on is faster than the thiol-ene addition so that the reaction is usually st
opped because of the complete consumption of the methacrylate double bonds.
A theoretical approach has allowed us to determine a transfer constant of
0.26. Moreover, an increase in the autoacceleration rare was observed in th
e presence of the thiol monomer. In the second part, the molar fraction of
methacrylate double bonds and thiol functions was changed to determine the
effect on the kinetic reaction and the glass transition temperature of the
final material. (C) 2001 Elsevier Science Ltd. All rights reserved.