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Structural and Conformational Changes in Solid-Phase Chlorinated Polyethylene S. Stoeva Department of Organic Chemistry, Professor Assen Zlatarov University, 8010 Bourgas, Bulgaria Received 2 December 2003; accepted 30 March 2004 DOI 10.1002/app.20854 Published online in Wiley InterScience (). ABSTRACT: The structural and conformational changes absorption at 610 cm1 to the absorption at 660 cm1 for the in solid-phase chlorinated polyethylene samples of different corresponding characteristic absorption bands, the substitu- average molecular masses were studied with infrared spec- tion of the hydrogen atoms for chlorine ones occurred pre- troscopy. Characteristic absorption bands for both chlori- dominantly in the trans-methylene groups, which were lo- nated polyethylene and chlorinated high-molecular-mass cated within the amorphous and intermediate phases of polyethylene, containing 1–56% Cl, were identified. The polyethylene with chlorine concentrations as high as 20%. chlorine content in the macromolecular chains, ranging from Consequently, the relative part of the gauche chlorinated 1 to 15%, was associated with the presence of single chlo- methylene groups increased. A trans-to-gauche conforma- romethylene groups and short syndiotactic structural se- tional change was thought to have taken place during the quences of poly(vinyl chloride) derived from them. Higher solid-phase chlorination of polyethylene under the influence degrees of chlorination, ranging from 20 to 56%, resulted in of the bulky chlorine atoms. These changes were facilitated an increase in the relative part of the heterotactic structures by the corresponding segmental mobility of the macromo- with 1,2-, 1,3-, and 1,2,3-modes of mutual location of the lecular chains. © 2004

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