d-Limonene (Lim) was used in various polymer formulations to achieve a more sustainable polymerization. Lim is a renewable and essentially non-toxic compound, derived from citrus fruit peels, that may replace some of the many toxic and fossil-based chemicals used in polymer synthesis.
Bulk free-radical polymerizations of n-butyl acrylate (BA) with Lim were performed to investigate Lim co-polymerization kinetics and estimate the monomer reactivity ratios, important parameters in the prediction of copolymer composition. Kinetic modeling of the BA/Lim copolymerization was performed with PREDICI simulation software. The model supports the presence of a significant degradative chain transfer reaction due to Lim. This reaction mechanism is due to the presence of allylic hydrogen in Lim. Nonetheless, relatively high molecular weight polymers were produced. It was concluded that Lim behaves more like a chain transfer agent than a co-monomer.
Terpolymerizations of BA, butyl methacrylate (BMA) with Lim were then performed. In order to predict the terpolymer composition, the monomer reactivity ratios for BA/BMA were estimated. By applying the three pairs of co-monomer reactivity ratios to the integrated Mayo-Lewis equation, terpolymer compositions were ably predicted up to high monomer conversion levels.
Lim was then used as a chain transfer agent to prepare core-shell latex-based pressure sensitive adhesives (PSA) comprising BA and styrene via seeded semi-batch emulsion polymerization. By varying the concentration of Lim and divinylbenzene crosslinker, the core polymer microstructure was modified to yield different molecular weights and degrees of crosslinking. The core latex was then used as a seed to prepare core-shell latexes. By changing the Lim concentration during the shell-stage polymerization, the molecular weight of shell polymer was also modified. The latexes were characterized for their microstructure and were cast as films for PSA performance evaluation. The PSA performance was shown to be highly related to the polymer microstructure. Tack and peel strength showed a decrease with increasing Lim concentration. Shear strength went through a maximum with a core Lim concentration increase from 0 to 5 phm.
| Identifer | oai:union.ndltd.org:uottawa.ca/oai:ruor.uottawa.ca:10393/35849 |
| Date | January 2017 |
| Creators | Ren, Shanshan |
| Contributors | Dubé, Marc |
| Publisher | Université d'Ottawa / University of Ottawa |
| Source Sets | Université d’Ottawa |
| Language | English |
| Detected Language | English |
| Type | Thesis |
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