Elastomers ozone-resistant polymer

The most prevalent approach to achieve long-lasting and nonstaining ozone protection of rubber compounds is to use an inherently ozone-resistant, saturated backbone polymer in blends with a diene rubber. The ozone-resistant polymer must be used in sufficient concentration (minimum 25 phr) and must also be sufficiently dispersed to form domains that effectively block the continuous propagation of an ozone-initiated crack through the diene rubber phase within the compound. Elastomers such as ethylene-propylene-diene terpolymers, halogenated butyl mbbers, or brominated isobutylene-co-para-methylstyrene elastomers have been proposed in combination with NR and/or butadiene rubber. 

Ozonc-rcsjstant elastomers which have no unsaturation are an exceUent choice when their physical properties suit the appHcation, for example, polyacrylates, polysulfides, siHcones, polyesters, and chlorosulfonated polyethylene (38). Such polymers are also used where high ozone concentrations are encountered. Elastomers with pendant, but not backbone, unsaturation are likewise ozone-resistant. Elastomers of this type are the ethylene—propylene—diene (EPDM) mbbers, which possess a weathering resistance that is not dependent on environmentally sensitive stabilizers. Other elastomers, such as butyl mbber (HR) with low double-bond content, are fairly resistant to ozone. As unsaturation increases, ozone resistance decreases. Chloroprene mbber (CR) is also quite ozone-resistant. 

Two propylene oxide elastomers have been commercialized, PO—AGE and ECH—PO—AGE. These polymers show excellent low temperature flexibihty and low gas permeabihty. After compounding, PO—AGE copolymer is highly resiUent, and shows excellent flex life and flexibiUty at extremely low temperatures (ca —65°C). It is slightly better than natural mbber in these characteristics. Resistance to oil, fuels, and solvents is moderate to poor. Wear resistance is also poor. Unlike natural mbber, PO—AGE is ozone resistant and resistant to aging at high temperatures. The properties of compounded ECH—PO—AGE he somewhere between those of ECH—EO copolymer and PO—AGE copolymer (22). As the ECH content of the terpolymer increases, fuel resistance increases while low temperature flexibihty decreases. Heat resistance is similar to ECH—EO fuel resistance is similar to polychloroprene. The uncured mbber is soluble in aromatic solvents and ketones. 

The styrenic thermoplastic elastomers are the only type which are fully compounded in the manner of conventional elastomers. In this case, however, the addition of carbon black, or other fillers, does not give reinforcement. Additions of polystyrene, or high impact polystyrene, and oil are used to vary hardness and tear strength, and fillers can be used to cheapen the material. Other added polymers, e g., EVA, can be used to increase ozone resistance. These materials also require antioxidants for protection during processing and service life, and the poor UV stability restricts their use in outdoor applications. 

Vinyl Acetate—Ethylene Copolymers. In these random copolymers, the ratio of ethylene to vinyl acetate (EVA) is varied from 30—60%. As the vinyl acetate content increases, the oil and heat resistance increases. With higher ethylene content the physical strength, tensile, and tear increases. The polymers are cured with peroxide. The main properties of these elastomers include heat resistance, moderate oil and solvent resistance, low compression set, good weather resistance, high damping, excellent ozone resistance, and they can be easily colored (see Vinyl polymers, polyvinyl acetate)). 

It is claimed that styrene/butadiene diblock polymers bring about an improvement in the hardness, strength, and processability of polybutadiene elastomers (27), as well as an improvement in the ozone resistance of neoprene rubber (28). Styrene diblock polymers have also been made with isoprene, a-methyIstyrene, methyl methacrylate, vinylpyridine, and a-olefins. Block copolymers of ethylene, propylene, and other a-olefins with each other have been made as well. Heteroatom block copolymers based on styrene or other hydrocarbons and alkylene oxides, phenylene oxides, lactones, amides, imides, sulfides, or slloxanes have been prepared. 

Blends of butadiene-acrylonitrile copolymer rubber (nitrile rubber or NBR) and PVC are among the oldest known examples of commercial elastomer/ thermoplastic blends. The shortage of natural rubber during World War II stimulated research in the USA on the compounding and modification of synthetic polymers to produce rubber-like materials. An outcome of this research was the commercial introduction of NBR/PVC blends by B.F. Goodrich in 1947 under the trade name of Geon Polyblends [Pittenger and Cohan, 1947]. The blend showed improved ozone resistance and melt processability compared to the nitrile rubber (Table 15.12). 

Ethylene-propylene rubber is particularly resistant to sun, weather, and ozone attack. Excellent weather resistance is obtained whether the material is formulated in color, white, or black. The elastomer remains free of surface crazing and retains a high percentage of its properties after years of exposure. Ozone resistance is inherent in the polymer, and for all practical purposes, it can be considered immune to ozone attack. It is not necessary to add any special compounding ingredients to produce this resistance. 

Elastomers are classically blended to improve the physical and mechanical properties of the final material. For example, Dubey et aiP incorporated suitable amounts of EPDM in the SBR matrix because it was expected to impart significant heat and ozone resistance to the SBR matrix. The irradiation-induced vulcanization of SBR/EPDM blends was proved to combine desired properties and high mechanical strength. For example, the formation of a cross-linked network led to a decrease in elongation at break. Cross-linking restricts the movement of the polymer chain against the applied force. Moreover, to decrease the radiation dose (and hence, the cost of radiation), multifunctional acrylates (MFAs) and allylic reactive molecules were used. 

Synonyms BIIR Brominated butyl rubber Brominated isobutylene/isoprene copolymer Bromobutyl rubber 1,3-Butadiene, 2-methyl-, polymer with 2-methyl-1-propene, brominated Butyl rubber, brominated Isobutylene, isoprene polymer, brominated Definition Elastomer vulcanized by sulfur systems vulcanizate offers low gas permeability, good weather/ozone resist., better chem./heat resist, than butyl rubber... 

Classification Polymer synthetic elastomer Definition Unsaturated polymer of chloroprene Empirical (C4HsCI)x Formula [CH2CH=CCICH2]x Properties As solid, latex, or flexible foam m.w. 100,000-300,000 dens. 1.23-1.35 brittle pt. -35 C softens. 80 C ref. index 1.5512 (20 C) high tens, str. resilient resistant to oils, oxygen, ozone, elec, current, abrasion... 

Brominated copolymer of isobutylene and para-methylstyrene (DIMS) is the latest new class of synthetic rubber that has been developed for the rubber industry. The sole producer of this new class of elastomer is ExxonMobil, which commercialized it successfully under the trade name Exxpro in the first decade of this new century. The advantage of this new polymer class vs. bromobutyl rubber is that this new elastomer possesses a completely saturated backbone and possesses more reactive benzylic bromine functionality than the bromine sites on the conventional bromobutyl backbone. This means that DIMS reportedly gives superior performance in service vs. BUR. This superiority is shown as better high-temperature resistance, better aging stability than either BUR or EPDM, better weathering resistance, and better ozone resistance. Also, BIMS provides the potential of imparting superior air permeability resistance. 

These are superior to oleoresinous caulks in weather resistance, ozone resistance, and impermeability to gases and vapors. Although not truly elastomeric, they can be used safely in joints with movement of up to 10-15%. They are solvent solutions of uncured butyl elastomers with 17-20% polymer and solids content... 

The ozone resistance of polyepichlorohydrin compounds is very good because of the saturated backbone of the polymer. This may be further enhanced by the inclusion of AGE, which further protects the backbone of the elastomer by providing some unsaturation in the side chain, which scavenges the ozone. This influence is shown in Table 7.7. 

The process yields a random, completely soluble polymer that shows no evidence of crystallinity of the polyethylene type down to —60°C. The polymer backbone is fully saturated, making it highly resistant to ozone attack even in the absence of antiozonant additives. The fluid resistance and low temperature properties of ethylene—acryUc elastomers are largely a function of the methyl acrylate to ethylene ratio. At higher methyl acrylate levels, the increased polarity augments resistance to hydrocarbon oils. However, the decreased chain mobiUty associated with this change results in less fiexibihty at low temperatures. 

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