Polybutadiene mechanical properties

Dynamic Mechanical Properties. The dynamic mechanical properties of branched and linear polyethylene have been studied in detail and molecular interpretation for various transitions have already been given, although not necessarily agreed upon in terras of molecular origin.(52-56) Transitions for conventional LDPE (prepared by free radical methods) when measured at low frequencies, are located around +70°C, -20°C and -120°C and are assigned to o, 5, and y transitions respectively. (53) Recently Tanaka et al. have reported the dynamic mechanical properties for a sample of HB which was also prepared by anionic polymerization, but contrary to our system the hydrogenation of the polybutadiene was carried out by a coordinate type catalyst.(12) The transitions reported for such a polymer at 35 Hz are very similar to those of LDPE.(12)... 

Copolymers of styrene, especially with acrylonitrile, also attained increasing importance both in the unmodified form (30) and modified with rubber as ABS copolymers. The first products of this kind were blends of nitrile rubber and SAN (31). However, these only had mediocre mechanical properties because the interfacial compatibility was insufficient. The breakthrough came when nitrile rubber was replaced by a polybutadiene rubber which was grafted in emulsion with styrene and acrylonitrile... 

SBR is the most widely used synthetic elastomer. It is an amorphous random copolymer consisting of a mixture of l.2, cis and trans isomers. Cold SBR produced at —20 C consists of 17% 1,2. 6% cis and 77% trans isomers of polybutadiene. This commercial product has a Tt of -60 C, an index of refraction of 1.534S, and a coefficient of linear expansion of 66 X 10 s cm/ cm C. Because of the high percentage of the trans isomer, it is less flexible and has a higher heat buildup, when flexed, than Hevea rubber. Although carbon black-filled or amorphous silica-filled SBR has useful physical and mechanical properties, the SBR gum rubber is inferior to Hevea rubber. 

Poly butadienes. Hydroxyl-terminated polybutadienes are comparatively late comers and are still in the development stage. They combine the high specific impulse of the well-proved carboxy-terminated polybutadienes with the clean, stoichiometric urethane reaction yielding propellants with unsurpassed mechanical properties. 

Compatibility. Owing to the high reactivity of the isocyanate group, polyurethane propellants require a more sophisticated processing technique than the rather foolproof, carboxy-terminated polybutadiene aziri-dine and/or epoxy-cured propellant systems. Processing is even more complicated if bonding agents (see below) are present, which are used to bolster mechanical properties in practically any modern propellant. 

With only small differences in (Is)max the choice of the binder system is influenced by processability, physical properties, and propellant density. Thus, with the polyether binder an Is of 247 is reached with about 14% binder, but with the polyester the same Is is obtained with 11.5% binder, which is a definite disadvantage in terms of processability and mechanical properties. The higher Is with the polybutadiene binder is realized only at high solids loadings, but owing to its lower density, processability is still satisfactory. 

Effects of Curing Agent Type. Epoxide-Cured Propellant. Carboxyl-terminated polybutadiene is a linear, difunctional molecule that requires the use of a polyfunctional crosslinker to achieve a gel. The crosslinkers used in most epoxide-cured propellants are summarized in Table IV and consist of Epon X-801, ERLA-0510, or Epotuf. DER-332, a high-purity diepoxide that exhibits a minimum of side reactions in the presence of the ammonium perchlorate oxidizer, can be used to provide chain extension for further modification of the mechanical properties. A typical study to adjust and optimize the crosslinker level and compensate for side reactions and achieve the best balance of uniaxial tensile properties for a CTPB propellant is shown in Table V. These results are characteristic of epoxide-cured propellants at this solids level and show the effects of curing agent type and plasticizer level on the mechanical properties of propellants. 

Tristar polybutadienes prepared by the intermediacy of lithium acetal initiators were also converted to three dimensional networks in a liquid rubber formulation using a diisocyanate curing agent. Table IV shows normal stress-strain properties for liquid rubber networks at various star branch Hn s. It can be seen that as the branch Mn increases to 2920, there is a general increase in the quality of the network. Interestingly, the star polymer network with a star branch Mn of 2920 (Mc=5840) exhibits mechanical properties in the range of a conventional sulfur vulcani-zate with a Me of about 6000-8000. 

The commerical polybutadiene (a highly 1,4 polymer with about equal amounts of cis and trans content) produced by anionic polymerization of 1,3-butadiene (lithium or organolithium initiation in a hydrocarbon solvent) offers some advantages compared to those manufactured by other polymerization methods (e.g., it is free from metal impurities). In addition, molecular weight distributions and microstructure can easily be modifed by applying appropriate experimental conditions. In contrast with polyisoprene, where high cis content is necessary for suitable mechanical properties, these nonstereoselective but dominantly 1,4-polybutadienes are suitable for practical applications.184,482... 

In contrast to some theoretical predictions (23, 46, 52) aggregation or phase separation in block copolymers occurs at a slightly higher total concentration than in polymer mixtures. Covalent bonding of the two kinds of blocks thus slightly increases the mutual solubility. Polystyrene blocks with M = 2000 dissolve in polybutadiene (Af = 75000) up to concentrations of about 20% (33). Therefore, special mechanical properties are, in general, only to be expected in sequence copolymers above a certain block length (in most cases M8 > 103). 

Below a characteristic temperature, T0, of about 15° to 16°C, the shift factors appear to follow the WLF equation, Equation 2, with C = 7.1, C2 = 135.9°C, and Tr — 0°C. The coefficients were determined in the usual way (6). The temperature dependence of both the relaxation moduli and the creep compliances could be described with the same WLF equation within the experimental scatter. It appears that below T0 the triblock copolymer behaves essentially as a filled rubber, the polystyrene domains acting only as inert filler. However, the WLF equation which describes the temperature dependence of the mechanical properties in this region is not identical with that of pure 1,4-polybutadiene, for which Maekawa, Mancke, and Ferry (20) find cx — 4.20, c = 161.5°C,... 

The mechanical properties of a macrolattice of SBS has been investigated (65). The sample consists of a hexagonal array of polystyrene cylinders embedded in the polybutadiene matrix. The stress-strain curves... 

Dynamic Mechanical Properties. Figure 15 shows the temperature dispersion of isochronal complex, dynamic tensile modulus functions at a fixed frequency of 10 Hz for the SBS-PS specimen in unstretched and stretched (330% elongation) states. The two temperature dispersions around — 100° and 90°C in the unstretched state can be assigned to the primary glass-transitions of the polybutadiene and polystyrene domains. In the stretched state, however, these loss peaks are broadened and shifted to around — 80° and 80°C, respectively. In addition, new dispersion, as emphasized by a rapid decrease in E (c 0), appears at around 40°C. The shift of the primary dispersion of polybutadiene matrix toward higher temperature can be explained in terms of decrease of the free volume because of internal stress arisen within the matrix. On the other... 

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