Polyisoprene—polybutadiene blends properties

Polybutadiene, CAS 9003-17-2, is a common synthetic polymer with the formula (-CH2CH=CHCH2-)n- The cis form (CAS 40022-03-5) of the polymer can be obtained by coordination or anionic polymerization. It is used mainly in tires blended with natural rubber and synthetic copolymers. The trans form is less common. 1,4-Polyisoprene in cis form, CAS 9003-31-0, is commonly found in large quantities as natural rubber, but also can be obtained synthetically, for example, using the coordination or anionic polymerization of 2-methyl-1,3-butadiene. Stereoregular synthetic cis-polyisoprene has properties practically identical to natural rubber, but this material is not highly competitive in price with natural rubber, and its industrial production is lower than that of other unsaturated polyhydrocarbons. Synthetic frans-polyisoprene, CAS 104389-31-3, also is known. Pyrolysis and the thermal decomposition of these polymers has been studied frequently [1-18]. Some reports on thermal decomposition products of polybutadiene and polyisoprene reported in literature are summarized in Table 7.1.1 [19]. 

While earlier attempts to produce satisfactory synthetic rubber from iso-prene were unsuccessful, in 1955 American chemist Samuel Emmett Horne Jr. (b. 1924) prepared 98 percent czr-l,4-polyisoprene via the stereospecific polymerization of isoprene. Home s product differs from natural mbber only in that it contains a small amount of rfr-l,2-polyisoprene, but it is indistinguishable from natural mbber in physical properties. First produced in 1961, BR (for butadiene mbber), a mbberlike polymer that is almost ex-clnsively czr-1,4-polybutadiene, when blended with natural or SBR mbber, has been nsed for tire treads. 

These concepts for formation of miscible blend of elastomers with similar or near equivalence of solubility parameters require the components to be similar in properties. Thus a wide variation in the properties of the elastomer blends by changing the relative amounts of the two elastomers is not typical since it is unlikely that, for example, a nonpolar polyolefin elastomer and a polar elastomer like acrylate would be similar in solubility parameters. This relative invariance in the properties of the blend compared to the components is an inherent limitation on the basic, economic, and technological need for elastomer blends, which is to generate new properties by blends of existing materials. Similar or near equivalence of solubility parameters can be difficult to predict from chemical structure. For example, chemically distinct 1,4-polyisoprene and 1,2-polybutadiene are miscible, but isomeric 1,2-polybutadiene and 1,4-polybutadiene are immiscible. It is illustrative of this concept that an apolar hydrocarbon elastomer and a highly polar elastomer such as an acrylate cannot have, under any practical structural manifestation for either, a similar solubility parameter and thus be miscible. 

Before reviewing in detail the fundamental aspects of elastomer blends, it would be appropriate to first review the basic principles of polymer science. Polymers fall into three basic classes plastics, fibers, and elastomers. Elastomers are generally unsaturated (though can be saturated as in the case of ethylene-propylene copolymers or polyisobutylene) and operate above their glass transition temperature (Tg). The International Institute of Synthetic Rubber Producers has prepared a list of abbreviations for all elastomers [3], For example, BR denotes polybutadiene, IRis synthetic polyisoprene, and NBR is acrylonitrile-butadiene rubber (Table 4.1). There are also several definitions that merit discussion. The glass transition temperature (Tg) defines the temperature at which an elastomer undergoes a transition from a rubbery to a glassy state at the molecular level. This transition is due to a cessation of molecular motion as temperature drops. An increase in the Tg, also known as the second-order transition temperature, leads to an increase in compound hysteretic properties, and in tires to an improvement in tire traction... 

It is necessary for the dispersed rubbery substance to have a Tg value lower than the temperature at which the high-impact material is to be used. Many elastomers will satisfy this condition they are butyl rubber, polybutadiene, SBR, BAN, ethylene-propene elastomer, polychloroprene, EVA, polyisoprene, polyacrylates, PIB, and chlorinated polyethylene (CPE) elastomers. However, they are not all useful for specific blends such as PVC-based blends because they do not fulfill the other necessary properties. 

The products have superior mechanical properties compared with the random copolymers or blends of homopolymers of the same overall composition. The literature reports block copolymers of polybutadiene with cyclopentene [69a], cyclooctadiene [69b], cyclodo-decene [69c] and substituted norbornenes [69d], of polyisoprene, polychloroprene, polypentenamer, and butyl rubber with norbornene derivatives [69c] and styrene-butadiene copolymers with cyclopentene [69a] and norbornene derivatives [69c]. Graft copolymers of type (103) will arise when unsaturation occurs in branched arms of the polymer to be grafted (e.g., 1,2-polybutadiene with cycloolefins) ... 

With respect to the last two examples, Bukhina etal [74] investigated, via Tg measurements, the long-term low-temperature properties of polybutadiene rubbers with differing ds-1,4 imit contents, and then made a comparison of the behaviour of blends of these rubbers with cis-l,4-polyisoprene, and SBR, and Cook, Groves and Tinker [75] demonstrated that a linear relationship existed between cross-link density and 7 for NR, polybutadiene and SBR gum (i.e. imfilled and im-plasticised) vulcanisates. 

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