Abstract
In the course of work on linear and ring polybutadienes with 62% 1,2 units, a number of discrepancies were noted with data on polybutadienes of various microstructure available in the literature. For example, GNο=870 kPa for our 62% 1,2-polybutadiene. This is larger than GNο=730 kPa for a 56% 1,2-polybutadiene and GNο=550 kPa for a 78% 1,2-polybutadiene sample. The cis : trans ratio of our 62% 1,2-polybutadiene, prepared with potassium counterion, is 1 : 4, On the other hand, the cis : trans ratio of 62% 1,2-polybutadiene prepared with a modified Li catalyst is estimated to be 1 : 2. It is conceivable that the different cis : trans ratio leads to different properties at constant 1,2 content. Nevertheless, the low levels of both the cis and the trans units are not expected to cause more than minor differences in the properties of the polybutadienes. Correct values for GNο of model polymers are important for the study of the influence of the chemical structure on the melt characteristics of a polymer. For this reason, it was thought useful to reinvestigate 1,2-polybutadiene itself in some detail. The synthesis of narrow molecular-weight distribution 1,2-polybutadiene by anionic polymerization techniques has been described recently. The dilute-solution properties of 1,2-polybutadiene has been investigated. The melt rheology of two 1,2-polybutadiene samples have been studied, but no systematic study of the molecular-weight dependence of the melt properties was made. 1,2-Polybutadiene has been used as a component in block copolymers with 1,4-polybutadiene. These studies have permitted an investigation of the phase behavior of two rubbery blocks at room temperature. Poly(l,4-butadiene-graft-l,2-butadiene)s with well-defined composition and architecture have also been prepared. Hydrosilylated 1,2-polybutadiene has found use as the coupling agent for multiarm star polymer, and this method can easily be extended to the preparation of poly( l,2-butadiene-graft-l,4-butadiene). Hydrogenated 1,2-polybutadienes are prepared as model polymers for poly(l-butene). The synthesis and characterization of a series of 1,2-polybutadienes are described here. Special attention is given to low-molecular-weight polymers. The linear viscoelastic properties of the melts are also described. In the discussion, the relation between the characteristic ratio, C∞, and the plateau modulus, GNο, of a number of model polymer systems is explored.
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