Modeling Degradative Chain Transfer in d-Limonene/n-Butyl Methacrylate Free-Radical Copolymerization
Renewable monomers containing allylic C-H bonds in their structure are prone to degradative chain transfer in free-radical polymerization, which will dramatically decrease the polymerization rate. In order to understand this mechanism, a kinetic model incorporating a degradative chain transfer mechanism for the free-radical copolymerization of d-limonene (LIM) and n-butyl methacrylate (BMA) was developed using PREDICI. Model predictions offered insight on how degradative chain transfer reactions affect conversion, copolymer composition and molecular weight in the polymerization. Experimental data from copolymerizations at monomer feed compositions (LIM/BMA, mol/mol) of 10/90, 20/80 and 30/70 were compared to the model's predictions. Moreover, it was discovered that degradative chain transfer results in elevated concentrations of growing polymer chains ending in allylic limonene radicals, which inevitably influences termination reactions and molecular weight development.
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Document Type: Research Article
Publication date: 2015-10-01
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- The Journal of Renewable Materials (JRM) publishes high quality peer reviewed original research on macromolecules and additives obtained from renewable/biobased resources. Utilizing a multidisciplinary approach, JRM introduces cutting-edge research on biobased monomers, polymers, additives (both organic and inorganic), their blends and composites. It showcases both fundamental aspects and new applications for renewable materials. The fundamental theories and topics pertain to chemistry of biobased monomers, macromoners and polymers, their structure-property relationship, processing using sustainable methods, characterization (spectroscopic, morphological, thermal, mechanical, and rheological), bio and environmental degradation, and life cycle analysis. Demonstration of use of renewable materials and composites in applications including adhesives, bio and environmentally degradable structures, biomedicine, construction, electrical & electronics, mechanical, mendable and self-healing systems, optics, packaging, recycling, shape-memory, and stimulus responsive systems will be presented.
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