Polybutadienes of Controlled Cis, Trans and Vinyl Structures

The physical properties of polybutadiene vulcanizates have been measured as a function of polymer microstructure. Although the over-all properties of any one polybutadiene are determined by the relative ratio of cis, trans and vinyl units in the polymer chain, marked changes in physical properties do not occur until a relatively pure configuration is approached or unless the raw polymer displays crystallinity. Thus, polybutadienes containing more than 85 per cent cis, trans or vinyl units are characteristically different from each other and the differences are accentuated as the isomeric forms approach 100 per cent of a given configuration. Polybutadiene of 95 per cent cis configuration displays very low heat generation and high resilience (equaling natural rubber in these properties) and excellent abrasion resistance. trans-Polybutadiene (90 per cent), a crystalline plastic in the raw state, becomes rubbery after vulcanization. Gum vulcanizates possess high tensile strength, and tread stocks display high modulus and tensile strength, high hardness and fair hysteresis properties. Vulcanizates of amorphous 94 per cent vinyl polybutadiene are characterized by fair tensile properties, low hysteresis, and poor low temperature properties. Crystalline syndiotactic polybutadiene, 70 per cent vinly, displays much higher gum and tread tensile strengths than its amorphous counterpart. Amorphous polybutadienes containing less than 70–80 per cent of any one configuration are generally similar in most properties, and resemble emulsion polybutadiene in many respects. The wide range of properties of the various polybutadienes makes them suitable for many applications. cis-Polybutadiene is an excellent tire rubber, which has given as much as 40 per cent greater abrasion resistance than natural rubber in passenger tire tests. Heavy duty 10:00 × 20 truck tires fabricated with a 1:1 blend of cis-polybutadiene and natural rubber in the treads have given slightly better abrasion ratings and lower running temperatures than control tires fabricated entirely from natural rubber. Amorphous 80 per cent cis-polybutadiene has been found to possess exceptionally good low temperature properties, far superior to present arctic-type unsaturated elastomers, trans-Polybutadienes by virtue of their high modulus, high tensile strength, and high hardness could be utilized in the preparation of hard rubber goods, floor tiles, and shoe soles. While none of these polybutadienes is yet available commercially, their unusual properties and potential applicability in many areas should lead to their manufacture in the future.