Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone)
Poly(2-vinyl-4,4-dimethylazlactone), pVDMA, is emerging as a versatile reactive platform in polymer chemistry. Herein, postpolymerization modification of pVDMA leading to thermoresponsive homo- and copolymers is investigated. VDMA was polymerized by reversible addition–fragmentation chain transfer (...
| Main Authors: | , , , |
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| Format: | Journal Article |
| Published: |
2013
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| Online Access: | http://hdl.handle.net/20.500.11937/39560 |
| _version_ | 1848755623397687296 |
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| author | Zhu, Y. Quek, J. Lowe, Andrew Roth, P. |
| author_facet | Zhu, Y. Quek, J. Lowe, Andrew Roth, P. |
| author_sort | Zhu, Y. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | Poly(2-vinyl-4,4-dimethylazlactone), pVDMA, is emerging as a versatile reactive platform in polymer chemistry. Herein, postpolymerization modification of pVDMA leading to thermoresponsive homo- and copolymers is investigated. VDMA was polymerized by reversible addition–fragmentation chain transfer (RAFT) polymerization. The resulting reactive scaffolds with molecular weights ranging from 3.0 to 12.5 kg/mol were converted with a selection of alcohols and amines of varying polarity into functional poly(2-acrylamido isobutyrate)s and poly(2-acrylamido isobutyramide)s with molecular weights ranging from Mn = 4.2–65.1 kg/mol and low polydispersity indices Mw/Mn < 1.37. Spectra obtained by 1H NMR and infrared spectroscopic measurements conformed to the expected structures. While alcohols and amines producing water-soluble or water insoluble VDMA-derived homopolymers were identified, seven homopolymers were found to show a lower critical solution temperature in aqueous solution; those formed by reacting pVDMA with N-ethylamine, N-isopropylamine, N,N-dimethylamine, N,N-diethylamine, N,N-diethylaminoethylamine, Jeffamine M-600, and tetrahydrofurfurylamine (THF amine). Cloud points increased with decreasing molecular weight. With a cloud point of 31 °C, the phase separation of poly(tetrahydrofurfuryl 2-acrylamido isobutyramide) (pTAI) occurred close to body temperature, was highly reproducible, and, above a concentration of 0.5 wt %, was largely concentration independent. The transition temperature of pTAI-based copolymers could easily be tuned by reacting pVDMA with a mixture of THF amine and varying amounts of pentylamine or di(ethylene glycol) methyl ether amine. |
| first_indexed | 2025-11-14T08:59:15Z |
| format | Journal Article |
| id | curtin-20.500.11937-39560 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T08:59:15Z |
| publishDate | 2013 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-395602017-09-13T14:24:11Z Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) Zhu, Y. Quek, J. Lowe, Andrew Roth, P. Poly(2-vinyl-4,4-dimethylazlactone), pVDMA, is emerging as a versatile reactive platform in polymer chemistry. Herein, postpolymerization modification of pVDMA leading to thermoresponsive homo- and copolymers is investigated. VDMA was polymerized by reversible addition–fragmentation chain transfer (RAFT) polymerization. The resulting reactive scaffolds with molecular weights ranging from 3.0 to 12.5 kg/mol were converted with a selection of alcohols and amines of varying polarity into functional poly(2-acrylamido isobutyrate)s and poly(2-acrylamido isobutyramide)s with molecular weights ranging from Mn = 4.2–65.1 kg/mol and low polydispersity indices Mw/Mn < 1.37. Spectra obtained by 1H NMR and infrared spectroscopic measurements conformed to the expected structures. While alcohols and amines producing water-soluble or water insoluble VDMA-derived homopolymers were identified, seven homopolymers were found to show a lower critical solution temperature in aqueous solution; those formed by reacting pVDMA with N-ethylamine, N-isopropylamine, N,N-dimethylamine, N,N-diethylamine, N,N-diethylaminoethylamine, Jeffamine M-600, and tetrahydrofurfurylamine (THF amine). Cloud points increased with decreasing molecular weight. With a cloud point of 31 °C, the phase separation of poly(tetrahydrofurfuryl 2-acrylamido isobutyramide) (pTAI) occurred close to body temperature, was highly reproducible, and, above a concentration of 0.5 wt %, was largely concentration independent. The transition temperature of pTAI-based copolymers could easily be tuned by reacting pVDMA with a mixture of THF amine and varying amounts of pentylamine or di(ethylene glycol) methyl ether amine. 2013 Journal Article http://hdl.handle.net/20.500.11937/39560 10.1021/ma401096r restricted |
| spellingShingle | Zhu, Y. Quek, J. Lowe, Andrew Roth, P. Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) |
| title | Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) |
| title_full | Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) |
| title_fullStr | Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) |
| title_full_unstemmed | Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) |
| title_short | Thermoresponsive (Co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) |
| title_sort | thermoresponsive (co)polymers through postpolymerization modification of poly(2-vinyl-4,4-dimethylazlactone) |
| url | http://hdl.handle.net/20.500.11937/39560 |