Diene rubbers free-radical polymerization

The elastomer produced in greatest amount is styrene-butadiene rubber (SBR) Annually just under 10 lb of SBR IS produced in the United States and al most all of it IS used in automobile tires As its name suggests SBR is prepared from styrene and 1 3 buta diene It is an example of a copolymer a polymer as sembled from two or more different monomers Free radical polymerization of a mixture of styrene and 1 3 butadiene gives SBR... 

Wallace Carothers will be the subject of one of our Polymer Milestones when we discuss nylon in Chapter 3. Among his many accomplishments in the late 1920s and early 1930s, Carothers and his coworkers made a major contribution to the discovery and eventual production of the synthetic rubber, polychloroprene. It was synthesized from the diene monomer, chloroprene, CH2=CCI-CH=CHr Chloroprene, which is a very reactive monomer—it spontaneously polymerizes in the absence of inhibitors— was a product of some classic studies on acetylene chemistry performed by Carothers and coworkers at that time. In common with butadiene and iso-prene, in free radical polymerization chloroprene is incorporated into the growing chain as a number of different structural isomers. Elastomeric materials having very different physical and mechanical properties can be made by simply varying the polym-... 

Free-radical polymerization of dienes. Rubber and rubber substitutes... 

Of all the dienes studied so far, the most important one is 1,3-butadiene, CH2=CH-CH=CH2. It is used in making synthetic rubber by free-radical polymerization. 

The data in Table 2.4 provide evidence that the slow rates and low molecular weights obtained in homogeneous free radical polymerization of these dienes are not due to a low rate constant for propagation but rather must be caused by a high rate constant for termination (as indicated in Table 2.1) (Matheson et al., 1949,1951 Morton and Gibbs, 1963). Hence, under the special conditions of emulsion polymerizations, where the termination rate is controlled by the rate of entry of radicals into particles, it becomes possible to attain both faster rates and higher molecular weights. It is this phenomenon which led to the rise of the emulsion polymerization system for the production of diene-based synthetic rubbers. 

Styrene can be relatively easily free radically polymerized. In addition, when a diene rubber is present, the styrene is grafted onto the rubber and the resulting graft polymer can then act as a kind of anchor between the two kinds of phase since, of course, it contains some of both components. Such... 

Rubber can also be made in the laboratory from polymerizing isoprene in the presence of suitable catalysts that favor formation of the c/s polymer. Rubber produced in this way is virtually indistinguishable from natural rubber. Other substituted dienes can also be polymerized in the laboratory to produce a wide variety of rubberlike, synthetic polymers. In the early 1930s, chemists at the Du Pont chemical company produced a commercially important polymer via the free-radical polymerization of chloroprene. The resulting polymer is sold under the trade name Neoprene. 

In emulsion polymerization, the monomer is dispersed in water containing a soap (usually about 5%) to form an emulsion such a dispersion is stable and its existence is not dependent on continued agitation. This technique is extensively used for the free radical polymerization of diene monomers in the preparation of synthetic rubbers. In this case a water-soluble initiator is used and the course of the polymerization is considerably different from that followed in the systems described previously. At the start of an emulsion polymerization three components are present ... 

The polymerization of 2-chloro-l,3-butadiene was one of the reactions considered by U.S. industry to replace rubber made from natural sources located in areas of the world that could be cut off in a crisis such as war. This diene structurally resembles isoprene, with a chlorine atom replacing the methyl group of isoprene. Free radical polymerization gives a mixture of cis and trans double bonds as well as a mixture of 1,2 and 1,4-addition products. Polymerization of 2-chloro-l, 3-butadiene using a Ziegler-Natta catalyst yields neoprene, a compound with trans double bonds. 

Conjugated dienes such as 1,3-butadiene very readily polymerize free radically. The important thing to remember here is that there are double bonds still present in the polymer. This is especially important in the case of elastomers (synthetic rubbers) because some cross-linking with disulfide bridges (vulcanization) can occur in the finished polymer at the allylic sites still present to provide elastic properties to the overall polymers. Vulcanization will be discussed in detail in Chapter 18, Section 3. The mechanism shown in Fig. 14.3 demonstrates only the 1,4-addition of butadiene for simplicity. 1,2-Addition also occurs, and the double bonds may be cis or trans in their stereochemistry. Only with the metal complex... 

Structure and Composition of Diene Copolymers. One finds that most of the reported copolymerization studies on butadiene or isoprene involve styrene as comonomer. In part this is due to the early interest in styrene-butadiene synthetic rubbers. The free radical produced copolymers (GRS, usually about 20—25% styrene units) contain about 20% of its butadiene fraction in the 1,2 form. The ratio of 1,2 to 1,4 units is little affected by polymerization variables such as temperature, conversion and styrene content (39). Butadiene and styrene copolymers contain 50 to 60% 1,2-diene units when prepared by sodium catalysts at 50° (39). This behaviour is once more significantly different when lithium is used in place of sodium as can be seen in Table 3. 

The ozone concentration in the troposphere during the daytime is typically about 1 pphm (parts per hundred million parts of air by volume) [20], Values up to 100 pphm were measured in some photochemical smog areas. The molecular mechanism of the ozone aging of diene based elastomers was studied in detail and is well understood [19,21], Products or intermediates different from those arising in autoxidation or photo-oxidation of polymers were identified ozonides (3), zwitterions (4), diperoxides (5), polyperoxides (6), polymeric ozonides (7) and terminal aldehydes (8). Reactivity of aminic antiozonants (AOZ) with these species accounts for the protection of rubbers against atmospheric 03. AOZ must also possess antioxidant properties, because the free radical processes are concerted with ozonation due to the permanent presence of oxygen. 

Because of their saturated structure, EPM rubbers cannot be vulcanized by using accelerated sulfur systems, and the less convenient vulcanization with free-radical generators (peroxide) is required. In contrast, EPDM rubbers are produced by polymerizing ethylene and propylene with a small amount (3-8%) of a diene monomer, which provides a cross-bnk site for accelerated vulcanization with sulfur. 

Many different polymers of conjugated dienes are prepared conunercially by a variety of processes, depending upon the need. They are formed by free-radical, ionic, and coordinated anionic polymerizations. In addition, various molecular weight homopolymers and copolymers, ranging from a few thousand for liquid polymers to high molecular weight ones for synthetic rubbers, are on the market. 

Amorphous copolymers of ethylene and propylene, EPM, also possess rubber-elastic properties. But they cannot be vulcanized with sulfur because of the absence of carbon-carbon double bonds, and so a special technique using peroxides as free radical sources for transfer reactions has had to be developed. However, polymerizing in a diene component such as, for example, cyclopentadiene or ethylidene norbornene, leads to the formation of what are known as EPDM rubbers with double bonds in the side chains. These can, on the one hand, be vulcanized in the classic way with sulfur, but, on the other hand, still have good aging properties. Consequently, EPDM rubbers are mainly used in automobile construction, the cable and construction industries, as well as for technical purposes. However, the EPDM rubbers have only slight self-adhesion, so that producing tires from cut sections is made more difficult. It is for this reason that EPDM rubbers are not used for tires. 

Classification of Polymers Free-Radical Chain-Growth Polymerization Cationic Chain-Growth Polymerization Anionic Chain-Growth Polymerization Stereoregular Polymers Ziegler-Natta Polymerization A WORD ABOUT... Polyacetylene and Conducting Polymers Diene Polymers Natural and Synthetic Rubber Copolymers... 

Whilst in general the production of thermoplastics and synthetic rubbers is dominated by free-radical type polymerizations this method is of limited use with the diene homopolymers. 

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