Polybutadiene high-temperature crystalline

The polymeric hydrocarbon also acts as a binder of the particles, holding them together so as to formulate a propellant grain. Ammonium perchlorate (AP) is a typical crystalline oxidizer and hydroxy-terminated polybutadiene (HTPB) is a typical polymeric fuel. When AP and HTPB are decomposed thermally on the propellant surface, oxidizer and fuel gases are produced, which diffuse into each other and react to produce high-temperature combustion gases. 

Natta, Porri, Carbonaro and Lugli (25) have prepared copolymers of 1,3-butadiene with 1,3-pentadiene in the whole range of compositions. The properties of the copolymers, in which all butadiene and pentadiene comonomer units are in the trans-1,4 configuration, clearly show the isomorphous replacement between the two types of units. The melting point/composition data show that the copolymer melting temperatures are a regular function of composition and are always comprised between those of trans-1,4-polybutadiene modification II and trans-1,4-polypentadiene. Also the X-ray diffraction spectra of the copolymers show that the trans-1,4-pentadiene units are isomorphous with the trans-1,4-butadiene units crystallized in the crystalline modification of the latter stable at high temperatures (form II). 

Polybutadiene. Unlike cis- and trans-1,4-polybutadiene, high vinyl 1,2-polybutadiene has a chiral center which can exist in one of three different stere-ochemically related forms. The material can either be atactic, leading to an amorphous elastomer, or it can be isotactic or syndiotactic, both of which are crystalline. The elastomeric amorphous form has found utility in tire tread applications (271) and although certain molybdenum (272) coordination catalysts can produce this material, commercialization has focused on anionic alkali metal initiators modified with Lewis bases. Of the two crystalline forms, isotactic 1,2-polybutadiene with a melting temperature of 126° C is the most elusive isomer. A few chromium systems based on soluble salts and aluminum alkyls have been reported to give 45% of the isotactic polymer in a mixture of the atactic isomer (273,274). 

The commercial polydienes are elastomers. Q s-1,4 polybutadiene has a Tg of -100 °C and has a crystalline melting point of less than 0 °C. Q s-1,4 polyisoprene has a Tg of -70 °C and has a crystalline melting point of 35 C. Both polymers crystallize rather slowly. Trans-1,4 polybutadiene and polyisoprenes are crystalline thermoplastics at room temperature. They are not, however, used commercially because of their poor aging characteristics relative to polyolefins. This is associated with the double bonds in their backbones. Polybutadienes with high atactic 1,2-contents have been widely used in the tire industry. Their Tg is about -15 °C. Isotactic and syndiotactic 1,2-polybutadienes are high melting crystalline thermoplastics, but age poorly compared to polyolefins. The 1,2-polybutadienes have been used as packaging for additives in the rubber industry. 

Syndiotactic Polybutadiene. Syndiotactic polybutadiene is a unique material that combines the properties of plastic and mbber. It melts at high (150—220°C) temperatures, depending on the degree of crystallinity in the sample, and it can be molded into thin films that are flexible and have high elongation. The unique feature of this plastic-like material is that it can be blended with natural mbber. 1,4-Polybutadiene and the resulting blends exhibit a compatible formulation that combines the properties of plastic and mbber. 

Various types of polymers are used to formulate propellants and explosives. The nature of polymers is identified by their chemical bond structure. Two types of copolymers are used to formulate modern propellants and explosives (1) polyurethane copolymer and (2) polybutadiene copolymer. The chemical bond structures of polyether and polyester are used for polyurethane copolymers. Since the molecular concentration of oxygen is relatively high for polyurethane binder, this class of binder is used to achieve high combustion efficiency with low oxidizer concentration of crystalline materials. On the other hand, the heat of formation of polybutadiene copolymer is high and the molecular concentration of oxygen is low when compared with polyurethane copolymer. This class of binder is used to achieve a high combustion temperature when mixed with crystalline oxidizer particles. 

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