화학공학소재연구정보센터
Macromolecules, Vol.36, No.17, 6346-6358, 2003
Nonuniformity of chain-length distributions in photopolymerized layers
For free-radical photopolymerization with a photobleaching initiator, constant chain propagation and termination rate constants k(p) and k(t), and termination occurring only by recombination, we account for Beer-Lambert attenuation and initiator consumption to predict how spatial variation of the final chain length distribution (CLD) depends on k(p), k(t), incident light intensity I-0, layer thickness L, photoinitiator absorption coefficient alpha(A) and initial concentration C-A,C-0, and quantum yield of photoinitiator consumption phi, for a typical value (10(-4)) of the initial ratio of initiator and monomer concentrations C-A,C-0/ C-M,C-0. We show how spatial variation of the final CLD depends on initial absorbance gamma = alpha(A)C(A,0)L and a parameter beta = k(p)[fC(A,0)/(phialpha(A)I(o)k(t))](1/2), where f primary radicals are produced per photoinitiator molecule consumed. For small gamma, the number-averaged mean chain length increases with depth at each beta and with beta at each depth. The chain length at which the CLD achieves its maximum value, along with a measure of polydispersity (half the CLD width at half-maximum, divided by the number-averaged mean), increase with depth at small beta and decrease with depth at large beta, with the CLD having its minimum nonuniformity at intermediate beta. Front-to-rear CLD variation increases as gamma increases. At small beta, nonuniformity is confined to a progressively smaller portion of the front of the layer as gamma increases, while for large beta, spatial variation is more evenly distributed. The results are discussed in terms of spatiotemporal variation of initiation and monomer conversion. Examples from the literature are used to illustrate the degree of CLD nonuniformity that can be expected in experiments.