Isoprene rubber, additives

In view of the wide application of Py—GC in industry and research, the development of techniques and equipment for automatic analysis by this method is of great practical interest. An automatic Py—GC system was developed by Coulter and Thompson [69] for Curie-type cells with a filament for specific application in the tyre industry. A typical analysis involves the identification and determination of polymers in a tyre material sample. The material of a tyre is essentially a mixture of polymers, most often natural rubber (polyisoprene), synthetic polyisoprene, polybutadiene and butadiene-styrene copolymer. A tube is normally made of a material based on butyl rubber and a copolymer of isobutylene with small amounts of isoprene. In addition to the above ingredients, the material contains another ten to twelve, such as sulphur, zinc oxide, carbon black, mineral oil, pine pitch, resins, antioxidants, accelerators and stearic acid. In analysing very small samples of the tyre material, the chemist must usually answer the following question on the basis of which polymers is the tyre made and what is their ratio The problem is not made easier by the fact that cured rubber is not soluble in any solvent. 

Animation Carbonylation I Prins rcaciitin - ( butyl amine - Neopentanoic acid - Isoprene - Rubber accelerator, licrbicidcs, luhc-oil additives, pliarmaccuticals -> Resins - Paints - Elastomers... 

For isoprene rubber, the abstraction route predominates over radical addition. Two polymeric free radicals then unite to give a crosslink. 

In the case of BR or SBR, the efficiency can be much greater than 1.0, especially if all antioxidant materials are removed. A chain reaction is indicated here. It might be explained by steric considerations. In butadiene-based rubbers, double bonds are quite accessible. Radical addition to double bonds could give highly reactive radicals, which would be likely to add to other polymer double bonds. A chain of additions might be more likely in butadiene rubber than in the presence of hindering methyl groups in isoprene rubbers. 

The addition of hydrogen chloride to unsaturated elastomers has also received considerable attention. Extensive work has been done on the hydrochlorination of Hevea [poly(cis-l,4-l,4-isoprene)] and Balata [poly(rrans-l,4-isoprene)] rubbers since 1940 [36,37]. Both cis-1,4 and tram cis-1,4-polyisoprenes readily add hydrogen chloride following Markovnikov s rules with only a small amount of cyclization. 

For isoprene rubber, the abstraction route predominates over radical addition. Two polymeric free radicals then unite to give a cross-link. Cross-links could also form by a chain reaction that involves the addition of polymeric free radicals to double bonds. 

Ishida et reported melt blending of PLA with four types of common rubbers, ethylene-propylene copolymer (EPM), ethylene-acrylic rubber (EAM), acrylonitrile-butadiene rubber (NBR) and isoprene rubber (IR), to toughen PLA. All blends showed separated phase morphology where the elastomer phase was homogeneously distributed in the form of small droplets in the continuous PLA phase. Izod impact testing showed that toughening was achieved only when PLA was blended with NBR, which showed the smallest rubber particle size in the blends. In addition, the interfacial tension between both phases, PLA and NBR, was the lowest. 

Mass spectrometry techniques have been described for the analysis of rubber compounds. A GC/mass spectrometric procedure has been described [132] for the single injection separation and identification of allerogenic vulcanisation agents and antioxidants from isoprene rubber. Mass spectral fragmentation mechanisms were proposed for each of the additives studied. 

In solution, an additional factor is involved the interaction between polymer and solvent. This feature is detailed in Volume 2, Chapter VIIB. The related effect of polymer chain flexibility in solution has also been demonstrated in ultrasonic degradation by a lower degradation of natural (c/5-isoprene) rubber when compared with the trans conformer [30],... 

Rubber additive Pentene, isoprene Britain 1,204,730 1970 Shell... 

The structure of rubber corresponds to 1 4 addition of several thousand isoprene units to one another... 

Halogenated Butyl Rubber. The halogenation is carried out in hydrocarbon solution using elemental chlorine or bromine in a 1 1 molar ratio with enchained isoprene. The reactions ate fast chlorination is faster. Both chlorinated and brominated butyl mbbers can be produced in the same plant in blocked operation. However, there are some differences in equipment and reaction conditions. A longer reaction time is requited for hromination. Separate faciUties are needed to store and meter individual halogens to the reactor. Additional faciUties are requited because of the complexity of stabilising brominated butyl mbber. 

Butyl Rubber. In butyl mbber, isoprene is enchained by 1,4-addition ia the trans configuration (74). 

Natural rubber is composed of polymerized isoprene units. When rubber is under tension, ozone attacks the carbon-carbon double bond, breaking the bond. The broken bond leaves adjacent C = C bonds under additional stress, eventually breaking and placing shll more stress on surrounding C = C bonds. This "domino" effect can be discerned from the structural formulas in Fig. 9-4. The number of cracks and the depth of the cracks in rubber under tension are related to ambient concentrations of ozone. 

In addition there is the possibility that other olefins may generate polymers with low Tg s which show little or no crystallinity at room temperature and are therefore potentially elastomeric. One commercial example is butyl rubber (designated HR), a copolymer of isobutene with a small amount of isoprene. 

When polymerizing dienes for synthetic rubber production, coordination catalysts are used to direct the reaction to yield predominantly 1,4-addition polymers. Chapter 11 discusses addition polymerization. The following reviews some of the physical and chemical properties of butadiene and isoprene. 

Unlike polyethylene and other simple aikene polymers, natural rubber is a polymer of a diene, isoprene (2-methyl-l,3-butadiene). The polymerization takes place by addition of isoprene monomer units to the growing chain, leading to formation of a polymer that still contains double bonds spaced regularly at four-carbon intervals. As the following structure shows, these double bonds have Z stereochemistry ... 

Butadiene and isoprene have two double bonds, and they polymerize to polymers with one double bond per monomeric unit. Hence, these polymers have a high degree of unsaturation. Natural rubber is a linear cis-polyisoprene from 1,4-addition. The corresponding trans structure is that of gutta-percha. Synthetic polybutadienes and polyisoprenes and their copolymers usually contain numerous short-chain side branches, resulting from 1,2-additions during the polymerization. Polymers and copolymers of butadiene and isoprene as well as copolymers of butadiene with styrene (GR-S or Buna-S) and copolymers of butadiene with acrylonitrile (GR-N, Buna-N or Perbunan) have been found to cross-link under irradiation. 

Hydrocarbon resins comprise a range of low-molecular-weight products (M < 3000) used as adhesives, hot-melt coatings, tackifying agents, inks, and additives in rubber. These include products based on monomers derived from petroleum as well as plant sources. The petroleum-derived products include polymers produced from various alkenes, isoprene, piperylene, styrene, a-methylstyrene, vinyltuolene, and dicyclopentadiene. The plant-derived products include polyterpenes obtained by the polymerization of dipentene, limonene,... 

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