Shear rheological properties of acrylic copolymers and terpolymers suitable for potentially melt processable carbon fiber precursors

In an effort to generate melt processable polyacrylonitrile (PAN) precursor fibers suitable for conversion to carbon fibers, an acrylonitrile/methyl acrylate (AN/ MA) copolymer and two acrylonitrile/methyl acrylate/acryloyl benzophenone (AN/MA/ABP) terpolymers were synthesized at molar ratios of 85/15 and 85/14/1, respectively. The termonomer (ABP) was incorporated to accelerate crosslinking via UV irradiation, which serves to prevent relaxation of orientation and flow as the temperature of the fiber is raised during thermooxidative stabilization. Two molecular weights of the terpolymer and one molecular weight of the copolymer were studied to determine the effect of the termonomer, and the effect of molecular weight (MW), on the steady shear viscosity (eta) and magnitude of the complex viscosity ( eta*). A higher rate of increase of 71 as a function of time was observed for the high MW terpolymer relative to that of the copolymer over the temperature range used. Using a temperature sweep and monitoring levels of,eta*, a minimum was observed at lower temperatures for both terpolymers. These results suggest that copolymerization with ABP significantly increased the thermally induced kinetics of crosslinking. Comparison of the eta and eta* data for the low and high MW terpolymers suggested that molecular weight also significantly reduced the melt stability (increased the kinetics of crosslinking). A chemorhelogical correlation was then used to quantify the effects of the termonomer and of molecular weight on the kinetics of crosslinking of the AN terpolymers. (C) 2004 Wiley Periodicals, Inc.