Strain‐induced crystallization of cis‐1,4‐polybutadiene containing dispersed 1,2‐polybutadiene crystalline particles

Abstract

Some grades of cis-1,4-polybutadiene contain dispersed crystalline particles made up of a block copolymer having amorphous cis-1,4- and crystalline 1,2 blocks. The particles are known to enhance the strain-induced crystallization of cis-1,4 matrix rubber. The deformational behavior was examined by dynamic shear measurements at small deformation and tensile stress–strain measurements at large deformation. In the shear measurements (linear behavior), the temperature dependence of the shift factor in the time-temperature superposition has been evaluated. The higher temperature dependence was observed for the lower crystalline particle content and higher degree of branching of the matrix rubber. The presence of the crystalline particles resulted in the viscosity enhancement like that expected from the dispersed particles. In the tensile measurements (non-linear behavior), the rubbers showed strain softening. The higher degree of strain softening was observed for the higher amount of the crystalline particles and lower degree of branching. The strain softening is a result of the crystalline particles facilitating the elongation. Because these particles posses the branches which are cis-1,4 chains of the block copolymer, the branches are lubricating the system during the stretching. The length of the branches must be short enough so as to produce no significant entanglement constraint. This observation is in accord with the previous one that a relatively long branch gives strain hardening, whereas a relatively short branch gives strain softening. The strain softening was found to enhance the strain-induced crystallization. This conclusion is opposite to what one might expect from the entanglement constraints by the long branches, forcing the orientation of the chains, and thus enhancing the strain-induced crystallization. © 1996 John Wiley & Sons, Inc.