ISSN:
0022-3832
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The synthesis of metal-containing polymers is of considerable theoretical and practical interest (organotin rubbers, etc.). We investigated the polymerization and copolymerization capacities of various allyl and vinyl derivatives of tin and lead, of tin, lead and mercury methacrylates and of a number of metal-containing styrenes. The allyl derivatives of tin and lead and the vinyl derivatives of tin do not polymerize under conditions of radical polymerization and have an inhibiting effect on polymerization of vinyl monomers (styrene, methyl methacrylate). The inhibiting effect increases with the number of allyl and vinyl groups in the organometal molecule, the allyl compounds of tin being more effective than the corresponding vinyl derivatives. The inhibiting action on the polymerization of vinyl monomers of the compounds decreases in the order: tetraallyltin 〉 tetravinyltin 〉 allyltrimethyltin 〉 diallyldiphenyltin 〉 allyltriphenyltin 〉 vinyltriphenyltin 〉 vinyltrimethyltin. Another relation is found in the case of organometallic compounds where the vinyl group is bound to the metal atom through a polar group or benzene ring. The acrylates and methacrylates of aryl and alkyl derivatives of tin, lead and mercury easily polymerize and copolymerize with vinyl monomers. New compounds also are the metal-containing styrenes. We synthesized for the first time, under the conditions of a Leebrick-Ramsden reaction, mercury- and lead-containing styrenes. We investigated for the first time the polymerization and copolymerization as well as some properties of the following metallated styrenes: p-phenylmercurostyrene, p-styrenetriphenyllead, p-styrenetriphenyltin. The compounds polymerize easily and copolymerize with vinyl monomers under conditions of radical reaction. A study of the reaction kinetics showed that the metallated styrenes polymerize at greater rates than unsubstituted styrene. The thermal stability of the metal-containing styrenes decreases in the order: Sn 〉 Pb 〉 Hg. In studies on the polymerization of p-vinylphenylmercury disproportionation was found to take place, leading to the formation of the symmetric divinyl derivative of diphenylmercury (I) and of diphenylmercury (II). Specially synthesized p-vinylphenyl phenylmercury (I) was found to polymerize easily with the formation of an insoluble three-dimensional polymer, not melting up to 250° and decomposing above this temperature with the liberation of metallic mercury. The polymer of (I) evidently has the structure The investigation shows that there is a considerable difference in the polymerization capacity of unsaturated organometal compounds and in the properties of the polymers and copolymers formed, depending upon the nature of the bond between the vinyl group and the metal atom.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1961.1205215731
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