Characterization of Block and Random Ethylene Propylene Copolymers by Differential Thermal Analysis

DTA furnishes a reliable method for the analysis of physical mixtures and for multisegment and bisegment block copolymers of ethylene and propylene in cases where chain randomness is minor. If a secondary method of analysis which is independent of crystallinity is possible, e.g., use of C14-tagged samples, the DTA method can aid in elucidating the chain structure, including degree of copolymer randomness. Block copolymers and physical mixtures have been found to have thermograms with endothermal minima at approximately 138 and 163° C. The ratio of heights of the two minima has been found to be a function of the ethylene and propylene content for mixtures of homopolymers and for block copolymers without randomnness. Cooling thermograms of block copolymers have been demonstrated to have two exotherms in all cases where the block ethylene content exceeded 10 per cent; the propylene limit was not fixed. Mixed homopolymers do not exhibit two freezing exotherms. The total heat of fusion of the polymer has been found to be a usable measure of chain randomness and block nature. Conditions for observation of single and multiple transitions have been extended. The following conclusions can be drawn from Table I. Multisegment block copolymers are characterized by heats of fusion almost equal to or lower than corresponding physical mixtures. Bisegment block copolymers have heats of fusion equivalent to physical mixtures within experimental error. Cooling curves definitely indicate that samples 3–6 and 3–13 are block copolymers according to Ke's criterion of double exotherms. Sample 3–3 may be inferred to have a large amount of randomness between blocks from its low heat of fusion, which is comparable to that of polymers with known randomness. Samples 3–35 and 3–40 are both block copolymers by the double freezing point technique. The block copolymer identification and the high heat of fusion (almost as large as a comparable physical mixture) indicate long block length and only a few blocks. Very little randomness is present (compare data of Figure 2). Low heats of fusion consistent with short block segments in sequential arrangement are noted for samples 3–30 and 3–31. No confirmation of the block nature can be obtained from freezing point data due to low ethylene content. The displacement from curve in Figure 2 indicates noncrystalline segments in the chain. Multisegment block copolymers are identified from heat of fusion data and freezing point thermograms; note samples 3–32, 3–33, and 3–34. The location of the peak height ratios in Figure 2 indicates the presence of random copolymer with some crystallinity between blocks in all cases.