Abstract
With the objective of synthesizing various insoluble polyelectrolytes and complexes, the chemical reactions of insoluble styrene copolymers (styrene–divinylbenzene or styrene–diallyl maleate) and of copolymers which become insoluble during the synthesis (styrene–butadiene) were studied. By substituting the chlorine atom in chloromethylated copolymers for ionic and complexogenic groups new polymer ion exchangers and complexes have been obtained. Chloromethylation of the copolymers was accomplished with the aid of paraformaldehyde and hydrogen chloride in the presence of zinc chloride in dichloroethane (copolymer I). The extent of conversion is determined by the structure and swelling capacity of the polymer and varies between 65 and 95%. The chlorine atom of copolymer I is completely replaced by an amino group under the action of triethanolamine (copolymer II). The polyelectrolytes formed possess the properties of quaternary ammonium bases with basicity 2.6–2.9 meq./g. The high swelling capacity of copolymer II has been utilized for investigating the possibility of polymerizing vinyl derivatives in the copolymer network. The polymerization of α‐methylvinylpyridine in copolymer II granules leads to a polymer‐in‐copolymer system containing up to 30% polymer and incapable of separation by extraction. The basicity of such a system attains a value of 5.1 meq./g. The replacement of chlorine in copolymer I by phosphine or sulfides gave new insoluble polymer of the phosphonium (copolymer III) or sulfonium (copolymer IV) type. A comparative study has been made of the properties of the ammonium, phosphonium, and sulfonium salts. From copolymer II insoluble complexes containing an aminotriacetic or aminodiacetic acid group
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or a β′, β″, β‴‐triaminotriethylamine group
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have been obtained. The instability constants of the Ni^++^, Cu^++^, Ca^++^, and Zn^++^ complexes with the insoluble polymeric complexes have been determined.