AbstractNucleophilic displacement of chlorine from polyvinylchloride (PVC) suspended either in water or in solution can be achieved using a nucleophile such as a sodium thiolate (RS−, Na+). The nucleophilicity of the salt increases if an ether linkage exists in a β position to the thiol group RO(CH2)2S−, Na+. Addition of a solvent such as cyclohexanone (which is a good solvent for PVC) to the slurry increases substantially the degree of substitution. Elemental analysis shows that every chlorine displaced from the polymer is replaced by a thiolate group; thus almost no dehydrochlorination occurs. It is possible to obtain by this method a grafted polymer in which 33 of the chlorine atoms are replaced by the β‐ether thiolate group. The resulting polymer behaves like an internally plasticized PVC. The higher the degree of substitution of chlorine, the greater the flexibility of the grafted polymer is. Other compounds, such as lauryl thiolate and diethyl dithiocarbamate, also were used as nucleophiles, the latter one resulting in a brittle crosslinked polymer whenever sulfur was above 2. Grafting of polytetrahydrofuran from PVC also was achieved using tetrahydrofuran as solvent and silver‐perchlorate as catalyst. The resulting flexible grafted polymer is believed to consist of longer chains of polytetrahydrofuran grafted from few displaced chlorine atoms al
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