Natural rubber molecular weight

The chlorination of low molecular weight natural rubber from Guayule (Parthenium Argentatum Grey) has been accomplished. The structure of the chlorinated product is consistent with that of chlorinated Hevea rubber. The use of Azo-bis-isobutyronitrile was as a catalyst resulted in increased chlorine content with a concomitant reduction in molecular weight, thereby allowing the preparation of lower viscosity grades of chlorinated rubber. 

Natural rubber is obtained from the sap of the rubber tree, a sticky liquid called latex. Rubber is a polymeric hydrocarbon formed in the sap by the combination of about 2000 molecules of 2-methyl-l,3-butadiene, commonly called isoprene. The molecular weight of rubber is about 136,000. 

Natural rubber does not have as satisfactory a resistance to fuels and vegetable and animal oils as elastomeric thermoplastics and synthetic rubbers. Natural rubber has good resistance to acids and alkalis. It is soluble in aliphatic, aromatic, and chlorinated solvents, but natural rubber does not dissolve easily because of its high molecular weight. Synthetic rubbers have better aging properties. Synthetic rubbers will harden over time, whereas natural rubbers will soften over time. 

Natural Rubber. To obtain natural mbber (NR), the Hevea hrasiliensis tree is tapped for its sap. The off-white sap is collected and coagulated. This process produces a high molecular weight substance which is natural mbber. The principal producing countries are Malaysia, Indonesia, Thailand, India, China, and Sri Lanka (see Rubber, natural). 

Compatibility and Corrosion. Gas turbine fuels must be compatible with the elastomeric materials and metals used in fuel systems. Elastomers are used for O-rings, seals, and hoses as well as pump parts and tank coatings. Polymers tend to swell and to improve their sealing abiUty when in contact with aromatics, but degree of swell is a function of both elastomer-type and aromatic molecular weight. Rubbers can also be attacked by peroxides that form in fuels that are not properly inhibited (see Elastomers, synthetic Rubber, natural). 

There is much evidence that weak links are present in the chains of most polymer species. These weak points may be at a terminal position and arise from the specific mechanism of chain termination or may be non-terminal and arise from a momentary aberration in the modus operandi of the polymerisation reaction. Because of these weak points it is found that polyethylene, polytetrafluoroethylene and poly(vinyl chloride), to take just three well-known examples, have a much lower resistance to thermal degradation than low molecular weight analogues. For similar reasons polyacrylonitrile and natural rubber may degrade whilst being dissolved in suitable solvents. 

Natural rubber displays the phenomenon known as natural tack. When two clean surfaces of masticated rubber (rubber whose molecular weight has been reduced by mechanical shearing) are brought into contact the two surfaces become strongly attached to each other. This is a consequence of interpenetration of molecular ends followed by crystallisation. Amorphous rubbers such as SBR do not exhibit such tack and it is necessary to add tackifiers such as rosin derivatives and polyterpenes. Several other miscellaneous materials such as factice, pine tar, coumarone-indene resins (see Chapter 17) and bitumens (see Chapter 30) are also used as processing aids. 

A further deficiency of natural rubber, compared with the synthetics, is its very high molecular weight coupled with a variable microgel content. Whilst this is desirable in that it reduces the tendency of stacked bales of rubber to flatten out... 

Figure 11.16. Efficiency of mastication of rubber at different temperatures. Molecular weights (M) measured after 30-minute mastication of 200 g natural rubber in a size B laboratory Banbury...

By rolling on a two-roll mill the molecular weight of the polymer can be greatly reduced by mechanical scission, analogous to that involved in the mastication of natural rubber, and so mouldable materials may be obtained. However, bulk polymerisation is expensive and the additional milling and grinding processes necessary make this process uneconomic in addition to increasing the risk of contamination. 

A number of high molecular weight polyisoprenes occur in nature which differ from natural rubber in that they are essentially non-elastic. As with natural rubber they are obtained from the latex of certain plants but they differ in that they are either frani-l,4-polyisoprenes and/or are associated with large quantities of resinous matter. 

The author is unaware of any commerical polymers that are specifically designed to degrade oxidatively, although oxidation may be involved in association with hydrolytic and biological degradation. It may be of interest to note that before World War II products known as rubbones were produced by degrading natural rubber with cobalt linoleate in the presence of cellulosic materials to produce low molecular weight, fluid oxidised natural rubber (Section 30.4). 

Class and Chu demonstrated that if a tackifier is chosen that is largely incompatible with the elastomer, a modulus increase due to the filler effect is observed and little change in Ta results, and once again a PSA would not be obtained. This was observed for mixtures of low molecular weight polystyrene resin and natural rubber. The same polystyrene resin did tackify SBR, a more polar elastomer that is compatible with the resin. Hydrogenating the polystyrene to the cycloaliphatic polyvinylcyclohexane changed the resin to one now compatible with the less polar natural rubber and no longer compatible with SBR. These authors also provide... 

Among the different pressure sensitive adhesives, acrylates are unique because they are one of the few materials that can be synthesized to be inherently tacky. Indeed, polyvinylethers, some amorphous polyolefins, and some ethylene-vinyl acetate copolymers are the only other polymers that share this unique property. Because of the access to a wide range of commercial monomers, their relatively low cost, and their ease of polymerization, acrylates have become the dominant single component pressure sensitive adhesive materials used in the industry. Other PSAs, such as those based on natural rubber or synthetic block copolymers with rubbery midblock require compounding of the elastomer with low molecular weight additives such as tackifiers, oils, and/or plasticizers. The absence of these low molecular weight additives can have some desirable advantages, such as ... 

The chemical nature and molecular weight of the rubber will greatly determine the properties of elastomeric adhesives. However, some common characteristics can be found in most of the rubber base adhesives. The elastomeric adhesives show the following specific features in assembly operations. 

Natural latex is polydisperse (size of individual particles may vary from 0.01 to 5 p.m). Flowever, synthetic latex has a relatively narrow particle size, and therefore the viscosity at a given rubber content is higher in synthetic rubber (polyisoprene) solutions. The average molecular weight is typically about I million g/mol, although it depends on the gel content. 

Plasticizers can be classified according to their chemical nature. The most important classes of plasticizers used in rubber adhesives are phthalates, polymeric plasticizers, and esters. The group phthalate plasticizers constitutes the biggest and most widely used plasticizers. The linear alkyl phthalates impart improved low-temperature performance and have reduced volatility. Most of the polymeric plasticizers are saturated polyesters obtained by reaction of a diol with a dicarboxylic acid. The most common diols are propanediol, 1,3- and 1,4-butanediol, and 1,6-hexanediol. Adipic, phthalic and sebacic acids are common carboxylic acids used in the manufacture of polymeric plasticizers. Some poly-hydroxybutyrates are used in rubber adhesive formulations. Both the molecular weight and the chemical nature determine the performance of the polymeric plasticizers. Increasing the molecular weight reduces the volatility of the plasticizer but reduces the plasticizing efficiency and low-temperature properties. Typical esters used as plasticizers are n-butyl acetate and cellulose acetobutyrate. 

In natural rubber, the cross-linking of these radicals is hindered because of the bulkiness of the methyl side group. Consequently, these radicals prefer to disproportionate and cleave. This reduces the molecular weight and natural rubber softens on ageing. 

All grades of regular butyl rubber are tacky, rubbery and contain less unsaturation than natural rubber or styrene-butadiene rubber. On the other hand, low molecular weight grades of polyisobutylene are permanently tacky and are clear white semi-liquids, so they can be used as permanent tackifiers for cements, PSAs, hot-melt adhesives and sealants. Low molecular weight polyisobutylenes also provide softness and flexibility, and act as an adhesion promoter for difficult to adhere surfaces (e.g. polyolefins). 

Standard-grade PSAs are usually made from styrene-butadiene rubber (SBR), natural rubber, or blends thereof in solution. In addition to rubbers, polyacrylates, polymethylacrylates, polyfvinyl ethers), polychloroprene, and polyisobutenes are often components of the system ([198], pp. 25-39). These are often modified with phenolic resins, or resins based on rosin esters, coumarones, or hydrocarbons. Phenolic resins improve temperature resistance, solvent resistance, and cohesive strength of PSA ([196], pp. 276-278). Antioxidants and tackifiers are also essential components. Sometimes the tackifier will be a lower molecular weight component of the high polymer system. The phenolic resins may be standard resoles, alkyl phenolics, or terpene-phenolic systems ([198], pp. 25-39 and 80-81). Pressure-sensitive dispersions are normally comprised of special acrylic ester copolymers with resin modifiers. The high polymer base used determines adhesive and cohesive properties of the PSA. 

Rubber used in practical applications is crosslinked through disulfide (-S-S-) bonds, and is known as vulcanized rubber. Can you name another important class of polymers which are crosslinked through disulfide bonds Examine vulcanized rubber. How many individual strands does it comprise Are these strands of natural rubber or of gutta-percha What is the percentage (by weight) of sulfur incorporated into the polymer (The molecular weight of the sample is 1701 amu.) Does this classify as a low-sulfur polymer (<3%), a high-sulfur polymer (>10%) or in between ... 

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