Using Changes in Initiation and Chain Transfer Rates To Probe the Kinetics of Cross-Linking Photopolymerizations: Effects of Chain Length Dependent Termination

Autor:	Lale G Lovell, Christopher N. Bowman, Bilge Hacioǧlu, Jun Nie, Kathryn A. Berchtold
Rok vydání:	2001
Předmět:	Kinetic chain length Acrylate Polymers and Plastics Chemistry Organic Chemistry Kinetics Chain transfer Kinetic energy Inorganic Chemistry Chain length chemistry.chemical_compound Polymerization Polymer chemistry PEG ratio Materials Chemistry Biophysics
Zdroj:	Macromolecules. 34:5103-5111
ISSN:	1520-5835 0024-9297
DOI:	10.1021/ma0019095
Popis:	The importance of incorporating chain length dependent termination (CLDT) behavior into the interpretation of the kinetics of cross-linked systems has been examined. Kinetic chain length distributions were varied in a variety of di(meth)acrylate photopolymerizations via the manipulation of the initiation rate and the chain transfer rate. Shifting the kinetic chain lengths toward shorter chains has little visible effect on multiacrylate systems. In contrast, similar changes in the corresponding multimethacrylate polymerizations changed the kinetics significantly. Shorter kinetic chains led to the delayed onset of reaction−diffusion-controlled termination behavior, as well as an increase in the ratio of kt/kp[M] at all conversions prior to the onset of reaction−diffusion control. Additionally, the magnitude of the kinetic constant ratio in the reaction−diffusion-controlled regime was affected by the kinetics at low conversion in the polymerization of a rubbery system, PEG(600)DMA. This behavior was independ...
Databáze:	OpenAIRE
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