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Title: Reactions effected by basic polymers and other studies of polymer reactivity
Author: González, Conceicão de Jesus Gómez
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1968
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Polystyrene has been chloromethylated and the resultant polymer converted by reaction with triethylamine into the polymeric quaternary ammonium chloride; this on basification gave a solution of poly(vinylbenzyltriethyl-ammonium hydroxide). Rate-constants for the hydrolysis of six straight-chain aliphatic esters with this polymeric alkali at 0° have been determined, also the corresponding rate-constants with sodium hydroxide. The values of u, the ratio of the former to the latter rate-constant for each ester, range from 0.73 to 1.05. The rates of hydrolysis with polymeric alkali thus do not differ greatly from those with sodium hydroxide. The actual differences are ascribed to the operation of two relatively minor factors: a salting-out effect in the vicinity of the polymeric hydroxide and a hydrophobic association of the alcoholic alkyl group of the ester with the hydrocarbon structures of the polycation. These effects are in opposition, the former decelerating and the latter accelerating reaction. These results are discussed in relation to considerable other work (carried out in these laboratories) and a coherent account is presented of the factors which influence reactions of various types effected with poly(vinylbenzyltriethylammonium hydroxide). A number of further reactions of poly(chloromethyl-styrene) have been investigated, particular attention having been given to the insertion of acetylacetone units in the polymer. Further work was devoted to attempts to incorporate this unit in a macromolecule by addition polymerization and by polycondensation. In the final section an evaluation of the utility of poly(vinylpyridine)s as basic reagents in organic chemistry is described. The copolymer of 2-vinylpyridine and styrene is effective in the dehydrobromination of 1-bromooctane to 1-octene. Very little isomerization accompanies the reaction, and it is thought that the reagent will prove of use in specific dehydrohalogenations.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available