Monomers for Adhesive Polymers, 7a : Solution and Bulk Polymerization of N-(2-hydroxyethylmethyl)acrylamide and Copolymerization with N,N′-Diethyl-1,3-bis(acrylamido)propane
✍ Scribed by Norbert Moszner; Juraj Pavlinec; Jörg Angermann
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- English
- Weight
- 307 KB
- Volume
- 208
- Category
- Article
- ISSN
- 1022-1352
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✦ Synopsis
Abstract
Homopolymerization and copolymerization of N‐(2‐hydroxyethylmethyl)acrylamide (1) with N,N′‐diethyl‐1,3‐bis(acrylamido)propane (2) have been studied in ethanol/water solvents or in bulk. The polymerization rate exponent depends on the polymerization temperature and increased from 0.99 at 50 °C to 1.21 at 75 °C. The initial polymerization rate dependence on temperature between 50 and 75 °C in Arrhenius coordinates was linear. However, the slope increased with an increase in monomer concentration. The overall activation energy E~a~ varied from 64 kJ · mol^−1^ at 0.5 mol · L^−1^ to 76 kJ · mol^−1^ at 2.0 mol · L^−1^ monomer concentration. In addition, the reaction order with respect to the initiator AIBN deviated from the standard free radical polymerization kinetics. The exponent 0.42 indicated a significant participation of primary radicals in termination reactions. The polymerization reaction order declined from ideality as well, and the E~a~ and polymerization enthalpy changed with the batch composition variation, which could be explained through monomer/monomer, monomer/solvent, or monomer/polymer complexation. The chain transfer to polymer was considered as an origin for the polymer network formation in monomer 1 homopolymerization if its concentration in the batch was 1 mol · L^−1^ or higher. The more intensive polymerization acceleration with the monomer dilution and the greater heat released reduction with decrease in the monomer 1 to 2 ratios were evidenced in copolymerization. Nevertheless, the deviations from conventional reaction kinetics were not as pronounced as with acrylic or methacrylic acid polymerizations.
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