MOLECULAR CHARACTERISTICS AND CRYSTALLINE-STRUCTURE OF ETHYLENE-DIMETHYLAMINOETHYL-METHACRYLATE COPOLYMERS

1993 
The relationship between molecular and crystalline structural characteristics of the ethylene -dimethylaminoethylmethacrylate copolymers (EDAM) was investigated and related to melt flow index MI and average gross content of DAM comonomer, in comparison with low density polyethylene (LDPE) produced by the common high-pressure radical polymerization process. Although the average molecular weight and its distribution are influenced predominantly by the polymerization conditions, DAM-content seems not to depend significantly on molecular weight according to the GPC-FT/IR measurement. Comonomer sequence distributions were determined quantitatively with the C-13-NMR spectra entirely assigned by DEPT and H-1-C-13 COSY techniques. The result suggests the alternating copolymerization tendency and surprisingly coincides with the simulation out-puts based on the assumption of continuous complete mixing reactor model, using Mayo-Lewis equation and the same Q-e values as previously reported on different types of copolymers such as EVA and St.DAM (VA;vinylacetate, St;styrene). It was confirmed by WAXD and SAXS analyses that the crystallinity X(c) and the thickness of lamellar crystal l(c) decreased with increasing DAM-content, whereas the a-lattice and b-lattice dimensions enlarged. X(c) and l(c) can definitely be correlated to the heats of fusion and crystallization measured by DSC. The average size of spherulites measured with light scattering photometry tends to be enlarged with decreasing molecular weight (increasing MI) and DAM-content.
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