Rubbers (polyisoprene and polybutadiene)


There are many different kinds of rubber, but they all fall into two broad types: natural rubber (latex—grown from plants) and synthetic rubber (made artificially in a chemical plant or laboratory). Commercially, the most important synthetic rubbers are styrene butadiene (SBR), polyacrylics, and polyvinyl acetate (PVA); other kinds include polyvinyl chloride (PVC), polychloroprene (better known as neoprene), and various types of polyurethane. Although natural rubber and synthetic rubbers are similar in some ways, they’re made by entirely different processes and chemically quite different.


Polyisoprene, polymer of isoprene (C5H8) that is the primary chemical constituent of natural rubber, of the naturally occurring resins balata and gutta-percha, and of the synthetic equivalents of these materials. Depending on its molecular structure, polyisoprene can be a resilient, elastic polymer (elastomer), as in the case of natural rubber and isoprene rubber, or a tough, leathery resin, as in the case of natural and synthetic balata or gutta-percha.

The chemical structure of isoprene can be represented as CH2=C(CH3)—CH=CH2. Polyisoprene—built up from the linking of multiple isoprene molecules—can assume any one of four spatial configurations, or isomers, each of which imparts a unique set of properties to the polymers. As the repeating units of polyisoprene, the four isomers have the following structures:

Of these four isomers, the most important are the cis-1,4 polymer and the trans-1,4 polymer.

Cis-1,4 Polyisoprene

Natural rubber consists almost exclusively of the cis-1,4 polymer, which is produced in the milky latex of certain plants—most notably the rubber tree (Hevea brasiliensis). The uniqueness of natural rubber lies in its physical properties of extensibility and toughness, summarized by its ability to be stretched repeatedly to seven or eight times its original length. In the absence of tensile (stretching) stress, the polymer chains assume an amorphous, or disordered, arrangement. On being stretched, however, the molecules readily align into an ordered crystalline arrangement. Crystallinity lends greater strength to the material, so natural rubber is considered to be “self-reinforcing.” In its natural state, however, natural rubber is greatly affected by temperature: it crystallizes on cooling, taking only several hours to do so at −25 °C (−13 °F), and it becomes tacky and inelastic above 50 °C (120 °F). In addition, it is swollen and weakened by hydrocarbon oils, and it reacts with oxygen and ozone in the atmosphere, leading to rupture of the polymer molecules at the carbon-carbon double bonds and softening and cracking of the material over time. These disadvantages are overcome to a great extent by cross-linking the polymer chains through the process known as vulcanization.

Isoprene rubber (IR) is manufactured by the polymerization of synthetic isoprene, which is obtained from the thermal cracking of the naphtha fraction of petroleum. Polymerization is conducted in solution, using both anionic and Ziegler-Natta catalysts. The product is at most 98 percent cis-1,4 polyisoprene, and its structure is not as regular as natural rubber in other respects. As a result, it does not crystallize as readily as the natural material, and it is not as strong or as tacky in the raw (unvulcanized) state. In all other respects, though, isoprene rubber is a complete substitute for natural rubber. For both materials, the principal usage is in tires, although these elastomers are also preferred for rubber springs and mountings, owing to their good fatigue resistance and high resilience. Footwear is an important application, and natural rubber is still used in adhesives (such as rubber cement).

Trans-1,4 Polyisoprene

Trans-1,4 polyisoprene is the dominant isomer in gutta-percha and balata, two materials that, like natural rubber, are derived from the milky exudate of certain trees. Unlike the cis-1,4 polymer, however, the trans-1,4 polymer is highly crystalline, so balata and gutta-percha are tough, hard, and leathery materials—properties that led in the 19th century to their use as sheathings for underwater cables and golf balls. The trans-1,4 polymer can also be synthesized with Ziegler-Natta catalysts, yielding a synthetic balata of similar properties that also is employed in golf-ball covers as well as in orthopedic devices such as splints and braces.

Polybutadiene (Butadiene rubber)

Butadiene rubber, synthetic rubber widely employed in tire treads for trucks and automobiles. It consists of polybutadiene, an elastomer (elastic polymer) built up by chemically linking multiple molecules of butadiene to form giant molecules, or polymers. The polymer is noted for its high resistance to abrasion, low heat buildup, and resistance to cracking.

Much of the butadiene rubber produced is blended with natural rubber (polyisoprene) or with styrene-butadiene rubber to give it improved resilience and lower rolling resistance. More than half of all usage is in tires; other applications are footwear, wire and cable insulation, and conveyor belts. Polybutadiene is also processed with styrene monomer in order to produce a high-impact polystyrene and with styrene and acrylonitrile monomer in order to produce a high-performance plastic known as acrylonitrile-butadiene-styrene copolymer.

Applications of Polybutadiene

Polybutadiene is the second largest volume synthetic rubber produced, next to styrene-butadiene rubber (SBR). Consumption was about 1,953,000 metric tons worldwide in 1999.


Polybutadiene in Tyres

The major use of polybutadiene is in tyres with over 70% of the polymer produced going into treads and sidewalls. Cured BR imparts excellent abrasion resistance (good tread wear), and low rolling resistance (good fuel economy) due to its low glass transition temperature (Tg). The low Tg, typically <–90C, is a result of the low “vinyl” content of polybutadiene, which will be discussed below. However, low Tg also leads to poor wet traction properties, so polybutadiene is usually blended with other elastomers like natural rubber or styrene-butadiene rubber for tread compounds.

Polybutadiene as an Impact Modifier in Other Polymers

Polybutadiene also has a major application as an impact modifier for polystyrene and acrylonitrile-butadiene-styrene resin (ABS) with about 25% of the total volume going into these applications. Typically about 7% polybutadiene is added to the polymerisation process to make these rubber-toughened resins.


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