In order to evaluate the gelation behavior of macromonomeric azoinitiators (MIMs), the free radical polymerization of MIM and macrocrosslinkers (MCRs) have been compared. MIMs were synthesized by the reaction between 4,4'-dicyano-4,4'-azovaleryl chloride and poly(ethy1ene glyco1)s PEG-400, -1O00, -1
Critical properties for gelation in free-radical crosslinking copolymerization
✍ Scribed by Oğuz Okay; Hamid J. Naghash; Önder Pekcan
- Publisher
- John Wiley and Sons
- Year
- 1995
- Tongue
- English
- Weight
- 617 KB
- Volume
- 4
- Category
- Article
- ISSN
- 1022-1344
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✦ Synopsis
Abstract
A kinetic model was used to predict the molecular weight developments and the critical properties in free‐radical crosslinking copolymerization. The predictions of the model were compared to the experimental data reported previously. Agreement of the kinetic model with experiments is satisfactory for both low and high crosslinker contents. The model parameters indicate increasing extent of shielding of pendant vinyl groups as the reaction proceeds due to the increasing number of multiple crosslinkages. The calculation results indicate that the real critical exponents can only be observed in the region ε < 10^−2^–10^−3^ where experimental studies are very difficult. Outside of this region, the apparent critical exponent γ describing the divergence of the weight‐average molecular weight was found to deviate from the classical value due to the conversion dependent kinetics of free‐radical crosslinking copolymerization.
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