Styrene-butadiene rubber copolymer characteristics

Mixtures, formulated blends, or copolymers usually provide distinctive pyrolysis fragments that enable qualitative and quantitative analysis of the components to be undertaken, e.g., natural rubber (isoprene, dipentene), butadiene rubber (butadiene, vinylcyclo-hexene), styrene-butadiene rubber (butadiene, vinyl-cyclohexene, styrene). Pyrolyses are performed at a temperature that maximizes the production of a characteristic fragment, perhaps following stepped pyrolysis for unknown samples, and components are quantified by comparison with a calibration graph from pure standards. Different yields of products from mixed homopolymers and from copolymers of similar constitution may be found owing to different thermal stabilities. Appropriate copolymers should thus be used as standards and mass balance should be assessed to allow for nonvolatile additives. The amount of polymer within a matrix (e.g., 0.5%... 

As indicated in Section 18.5.1, the styrene-butadiene block copolymers which are of commercial interest are those which have the characteristics of thermoplastic rubbers . These polymers have the structure S—B—S, where S represents a block of about 150 styrene units and B represents a block of about 1000 butadiene units. (This composition corresponds to a styrene content of approximately 35% and a molecular weight of 85 000.)... 

FIGURE 5.7 Phase separation in styrene-butadiene-styrene (SBS) triblock copolymer. The isolated spherical styrene domains form the hard phase, which act both as intermolecular tie points and filler. The continuous butadiene imparts the elastomeric characteristics to this polymer. MW = molecular weight. (From Grady, B.P. and Cooper, S.L., Science and Technology of Rubber, Mark, J.E., Erman, B., and Eirich, F.R. (eds.). Academic Press, San Diego, CA, 1994. With permission.)... 

As occurs in natural rubber, only the 1,4-cis isomer exhibits elastomeric characteristics. The most important synthetic diene rubbers are polychlor-oprene (neoprene) and rubbers derived from butadiene such as styrene-butadiene and acrylonitrile-butadiene copolymers. 

Naturally, the more complex the composition of the substances to be pyrolysed, the more characteristics are needed for identification. For example, in identifying isoprene rubbers (NK, SKN-3, SKIL, Natsyn, Coral, Cariflex IR), the characteristic pyrolysis products are isoprene and dipentene, whereas with butadiene rubbers (SKB, SKD, Budene, Diene NF, Buna CB, Asadene NF, Cariflex BR, Ameripol CB) they are butadiene and vinylcyclohexane. With copolymer rubbers, the number of characteristic products necessary for identification increases to three, viz., butadiene, vinylcyclohexene and styrene are used for butadiene -styrene rubbers (SKS-10, SKS-30, Buna S. Europrene-1500, Solprene) and butadiene, vinylcyclohexene and methylstyrene are used for butadiene-methylstyrene rubbers (SKMS-10, SKMS-30) [139, 140]. Fig. 3.12 [139, 140] shows as an example pyrograms of individual general-purpose rubbers and a four-component mixture of rubbers. The shaded peaks correspond to those components in the pyrolysis products which are used for identification. The ratio of the pyrolysis products changes depending on the composition of the copolymer and the structure of the polymer. 

Acrylonitrile-butadiene rubber, NBR, styrene-aciylonitrile rubber, SAN, ethylene-vinyl acetate copolymer, EVA, and acrylic copolymers are helpful modifications of polyvinylchloride that change its processing characteristics and elastomeric properties. Blending with these copolymers helps to reduce the requirement for low molecular weight plasticizers. Ethylene-vinyl acetate copolymer plays a role of high molecular weight plasticizer in production of vinyl hose. This reduces the amount of DOP used in flexible hose applications. Ethylene copolymer is used plasticize PVC that reduces gel. "" Phthalate plasticizers can be eliminated from water based adhesives because of utilization of vinyl acetate ethylene copolymer as a high molecular plasticizer/modifier. " ... 

Polybutadiene (BR rubber) and the random styrene/butadiene copolymer (SBR rubber) are the most widely used polymers. Their principal use is in tyres, which are typically blends of natural/synthetic rubber. BR rubber has good resilience, abrasion resistance and low heat build-up. SBR contains 10-25% styrene which is added chiefly to reduce cost but also to improve wearing and blending characteristics compared with BR alone. BR and SBR are polymerized by a free-radical mechanism as a water emulsion at 50-60 °C (hot rubber) or 0°C (cold rubber). Typical compositions are 70% trans-1,4, 15% cis-1,4 and 15% 1,2. Ziegler systems used in solution polymerization yield an SBR which has higher MW, narrower MWD and higher cis-1,4-content than the emulsion free-radical type. 

It has already been pointed out in Chapter 13, Section Al, that maxima in the loss compliance and the retardation spectrum are characteristic of network structures as predicted from the Rouse theory, suitably modified, in Fig. 10-7. Such maxima appear in moderately cross-linked polymers as well as in uncross-linked polymers of high molecular weight, and their shapes are remarkably similar. In Fig. 14-3, J" is compared for styrene-butadiene copolymer without cross-links and cross-linked to a value of Gg = 7.3 X 10 dynes/cm, characteristic of a well-vulcanized soft rubber e.g., curve VI of Figs. 2-1 to 2-8). The curves are both close in shape to that predicted by the Rouse-Mooney theory for a most probable distribution of network strands, i.e., curve D of Fig. 10-7, as already evident from Fig. 13-1. 

Blending methyl methacrylate-butadiene-styrene copolymer with poly(vinyl chloride) for instance was shown to decelerate the dehydrochlorination (leading to discoloration). The gel content, surface energy, and the spectroscopic characteristics of the blend was altered by the presence of the seccHid polymer [158]. In ethylene-propylene-diene rubber EPDM where the third monomer is ethylene-2-norbomene (NB), the photo-oxidation rate as measured by the accumulation of typical products such as hydroperoxides, varied linearly with the NB content [159]. The same held true for peroxide-crosslinked compounds of the same EPDM except that the linear relationship was found between the relative carbonyl absorbance on photoxidation and the amoiuit of peroxide used to crosslink the material... 

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