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Preparation of new (co)polymers from an organo-based CO2 valorization
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Huang, Jin (2018) Preparation of new (co)polymers from an organo-based CO2 valorization. PhD thesis, University of Warwick.
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WRAP_Theses_Huang_2018.pdf - Submitted Version - Requires a PDF viewer. Download (4Mb) | Preview |
Official URL: http://webcat.warwick.ac.uk/record=b3423567~S15
Abstract
Phosphaszene based organocatalysis was applied to prepare oligocarbonate from CO2 and cyclohexane oxide under very mild conditions. Modification of experimental conditions such as temperature, reaction time and co-catalyst content, reveal that the oligoccarbonate is a result of the polymerization of in situ generated cyclic carbonate. By changing the catalysis ratio, the product of oligo- and cyclic carbonates in selectivity is adjustable.
Iodine-based binary catalytic system has been applied to prepare poly(trimethylene carbonate) (PTMC) from CO2 and oxetane in bulk. The results reveal that the nature of co-catalyst is prime important to the formations of products. A comparable high molar mass of PTMC was observed in presence of iodine and guanidine catalysis as characterized by size extrusion chromatography, while a unique selectivity of trimethylene carbonate (TMC) was found in the residue using iodine and phosphazene as catalysis. The mechanism of polymerization was proposed that PTMC was a result of the polymerization of in situ generated TMC.
The preparation of TMC from CO2 and oxetane using iodine and ionic liquid catalytic system was studied. To enhance the selectivity and yield of TMC, temperature, co-catalyst, and solvent were investigated. Interestingly, the production of TMC and PTMC is controlled by temperature as catalyzed by iodine and ionic liquid. Importantly, the required energy to produce PTMC is only slightly higher than the one calculated by Darensbourg when applying the very efficient chromium salen catalytic complexes which provide useful information for the mechanism study with theoretical calculation.
| Item Type: | Thesis (PhD) | ||||
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| Subjects: | Q Science > QD Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Polymerization, Polycarbonates -- Synthesis, Carbon dioxide, Waste gases | ||||
| Official Date: | 2018 | ||||
| Dates: |
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| Institution: | University of Warwick | ||||
| Theses Department: | Department of Chemistry | ||||
| Thesis Type: | PhD | ||||
| Publication Status: | Unpublished | ||||
| Supervisor(s)/Advisor: | Coulembier, Olivier ; Dove, Andrew P. | ||||
| Sponsors: | European Commission | ||||
| Format of File: | |||||
| Extent: | xvi, 149 leaves : illustrations, charts | ||||
| Language: | English |
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