The influence of stearic acid, linoleic acid and their methylesters on crystallization of synthetic cis-1,4-polyisoprene was investigated at the isothermal crystallization temperature of −25°C by means of differential scanning calorimetry and dilatometry. The overall crystallization rate of cis-1,4-polyisoprene increased in step with increasing stearic acid content, while the glass transition temperature of cis-1,4-polyisoprene did not change with the additive level. The addition of 1 wt % stearic acid or methyl stearate showed an acceleration effect on the initial crystallization of the polymer, while 1 wt % linoleic acid or methyl linoleate suppressed the initial crystallization. Coexistence of stearic acid and linoleic acid or stearic acid and methyl linoleate in cis-1,4-polyisoprene gave rise to a dramatic increase in the overall crystallization rate of the polymer. The characteristic properties of natural rubber were revealed to be related to the specific ratio of miscible fatty acids to immiscible fatty acids in natural rubber.
Crystallization behavior of deproteinized natural rubber at −25°C was investigated by dilatometry in connection with the effect of long-chain fatty acid groups, esterified to the rubber chain, as well as free fatty acids and their esters. The overall crystallization rate decreased after removal of the acetone-extractable free fatty acids and their esters, while it increased significantly when the fatty acid groups esterified to natural rubber molecule were removed by transesterification with sodium methoxide. Both the acetone-extracted and transesterified rubbers showed a significant increase in the overall crystallization rate after the addition of 1 wt % stearic acid. The crystallization of acetone-extracted rubber was accelerated by the addition of 1 wt % methyl linoleate, a plasticizer of natural rubber, whereas it was suppressed in the case of transesterified rubber in which the esterified fatty acid groups were removed completely. The fatty acid groups esterified to natural rubber molecule gave rise to the accelerated crystallization of the rubber in conjunction with free fatty acids and their esters.
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