Novel ester substituted poly(alkylene oxides) were prepared from ester substituted epoxide monomers, where the ester groups were separated from the epoxide groups by a series of 0 to 7 methylene spacer groups. The reactivity of these monomers using coordinate and cationic initiators was examined, with the objective of determining the proximity effect of the ester groups on the polymerizability of the monomers. Homopolymerizations of the ester substituted monomers using the Al(C(,2)H(,5))(,3)/H(,2)O/AcAc (1/0.5/1) coordinate initiator system demonstrated a strong proximity effect of the ester groups on the monomer reactivity. Those monomers with 0 to 3 spacer groups gave polymers in much lower yields with lower molecular weights than the monomers with 4 to 7 spacer groups. The polymers were semicrystalline, and became more rubbery as the number of spacer groups increased. Copolymerizations of the ester substituted monomers having 1, 2, and 5 spacer groups with several cyclic ethers, using the Al(C(,2)H(,5))(,3)/H(,2)O/AcAc (1/0.5/1) initiator system, also demonstrated a strong proximity effect. Copolymers of the ester substituted monomer with 1 spacer group were produced in very low yields, while copolymers of the ester substituted monomer with 2 spacer groups were produced in low to good yields. Copolymers of the ester substituted monomer with 5 spacer groups were produced in good to high yields. The level of incorporation of the ester substituted monomers into the copolymers was generally > 80%. Many of the copolymers were semicrystalline. Cationic homopolymerizations of the ester substituted monomers having 1, 2, and 5 spacer groups were carried out using BF(,3)(.)O(C(,2)H(,5))(,2) and Al(C(,2)H(,5))(,3)/H(,2)O (1/0.5) as initiators. The polymers from the BF(,3)(.)O(C(,2)H(,5))(,2) initiated polymerizations were low molecular weight, ranging from viscous liquids to paste-like solids. The monomers with 1 and 5 spacer groups gave high molecular weight polymers when the Al(C(,2)H(,5))(,3)/H(,2)O (1/0.5) initiator system was used, while the monomer with 2 spacer groups gave a low molecular weight material. Anionic homopolymerizations of the ester substituted monomers with 1, 2 and 5 spacer groups were attempted, but were unsuccessful. Propylene oxide could be polymerized, however.
| Identifer | oai:union.ndltd.org:UMASS/oai:scholarworks.umass.edu:dissertations-5801 |
| Date | 01 January 1982 |
| Creators | MUGGEE, JOHN MARK |
| Publisher | ScholarWorks@UMass Amherst |
| Source Sets | University of Massachusetts, Amherst |
| Language | English |
| Detected Language | English |
| Type | text |
| Source | Doctoral Dissertations Available from Proquest |
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