Polybutadiene crystal structure

Suehiro, K. and Takayanagi, N. Structural studies of the high temperature form of trans-1,4-polybutadiene crystal. J. Macromol. Sci. Phys. B4, 39 (1970)... 

High -cis polybutadiene has relatively high heat resistance, which is advantageous in the processing of HIPS. On the other hand, this type of polybutadiene crystallizes at about 0 °C, owing to its stereoregular structure, with the consequence that the low-temperature toughness of polystyrene, produced in this way, is reduced. 

It was shown already above that cis-1,4-poly butadiene melts in one step with the expected entropy of fusion. In contrast, cis-l,4-poly(2-methylbutadiene) (natural rubber) has a more complicated fusion and crystallization behavior . The reported entropy of fusion of the common monoclinic (P2ja) crystal polymorph is only 14.4 J/(K mol), less than half of the expected value. The crystal structure has been reported statistically disordered, but only relative to packing of chains that are mirror images of each other along the crystallographic a-axis. Such geometric disorder cannot account for a 50% decrease in entropy of fusion. A full study of the thermod5mamic functions as available for the polybutadienes would be of value. 

Natta G, Corradini P (1960) The crystal structure of cis-1,4-polybutadiene. Nuovo Cimento, Suppl. 15 111 see also Angew. Chemie 68 615 (1956) and Nyburg SC (1954) Acta Cryst. 7 385... 

Rg. 13 (a) Projection of PHTP crystal structure along the channel axis, the polymer chains are omitted for clarity (b) Crystal structure of 1,4-frans-polybutadiene in the PHTP inclusion compound... 

Conformationally disordered crystals (condis crystals) were discovered in the 1980 s. They show positional and orientational order, but are partially or fully conformationally mobile. The condis crystals complete the comparison of mesophases in Figs. 2.103 and 2.107. Linear, flexible molecules can show chain mobility that leaves the position and orientation of the molecule unchanged, but introduces large-amplitude conformational motion about the chain axis. Again, the symmetry of the molecule is in this case increased. Condis crystals have often a hexagonal, columnar crystal structure. Typical examples of condis crystals are the high-temperature phase of polyethylene, polytetrafluoroethylene, frawj-1,4-polybutadiene, and the low-temperature phases of soaps, lipids and other liquid-crystal forming, flexible molecules. 

T.L. Boggs et al, AIAA J 8 (2), 370-72 (1970) CA 72, 113371 (1970) Scanning electron microscopy is used to study the surface structure of solid proplnts, prepd from AP (1) and polyurethane or caiboxylated polybutadiene. Polyurethane proplnts are self-extinguish-ing at high pressure due to the flow of molten binder over I crystals. I crystals formed a thin surface melt with gas liberation in the molten phase... 

The rate of crystallization of polybutadiene depends mainly on the cis content and therefore on the catalyst system. As far as commercial catalysts are concerned it increases in the order Li < Ti < Co < Ni. High-cis SE-BR, like U-BR, crystallizes more rapidly than all the other types (Table III). However, SE-BR with 93 % cis-1,4 content, and even one with only 90 % cis-1,4 content, crystallizes more rapidly than Ti-BR (93 % cis-1,4 content). In our opinion the reason for this anomaly is a structural disorder in molecules with different chain length. 

The polybutadienes prepared with these barium t-butoxide-hydroxide/BuLi catalysts are sufficiently stereoregular to undergo crystallization, as measured by DTA ( 8). Since these polymers have a low vinyl content (7%), they also have a low gl ass transition temperature. At a trans-1,4 content of 79%, the Tg is -91°C and multiple endothermic transitions occur at 4°, 20°, and 35°C. However, in copolymers of butadiene (equivalent trans content) and styrene (9 wt.7. styrene), the endothermic transitions are decreased to -4° and 25°C. Relative to the polybutadiene, the glass transition temperature for the copolymer is increased to -82°C. The strain induced crystallization behavior for a SBR of similar structure will be discussed after the introduction of the following new and advanced synthetic rubber. 

However, the excellent cold properties of the lithium polymer can be explained on the basis of microstructure in Table II. It seems reasonable to assume that of the three possible microstructures the 1,2 structure is the least desirable for low temperature flexibility followed by the frans-1,4 structure, with the cis-1,4 structure the most desirable. A comparison of the low temperature flexibility of balata (or gutta-percha) vs. Hevea rubber would indicate a preference for the cis-1,4 structure over the trans-1,4 structure, although these natural products are polyisoprenes rather than polybutadienes. In the case of the 1,2 structure, it is generally assumed that the prevalence of this structure in sodium-catalyzed polybutadiene, or butadiene copolymers, accounts for its poor cold properties however, the occurrence of a natural or synthetic product with an entirely 1,2 structure would help to confirm this more definitely. The relative predominance of any single structure is another important consideration in the performance of a rubber at low temperatures because a polymer with a large percentage of one structure would be more likely to crystallize at a low temperature. 

In Sect. 2.5 a similar two-step melting was discussed for the condis state of trans-1,4-polybutadiene. The c/ -isomer shows in Fig. 2.113 complete gain of the entropy of fusion at a single melting temperature, while the trans isomer loses about 2/3 of its entropy of transition at the disordering transition. The structure of the trans isomer is close to linear, so that conformational motion about its backbone bonds can support a condis crystal sttucture with little increase in volume of the unit cell. 

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