Butyl rubber unsaturation

Cure Systems of Butyl Rubber and EPDM. Nonhalogenated butyl rubber is a copolymer of isobutjiene with a small percentage of isoprene which provides cross-linking sites. Because the level of unsaturation is low relative to natural mbber or SBR, cure system design generally requites higher levels of fast accelerators such as the dithiocarbamates. Examples of typical butyl mbber cure systems, thein attributes, and principal appHcations have been reviewed (26). Use of conventional and semi-EV techniques can be used in butyl mbber as shown in Table 7 (21). 

Butyl Rubber. Butyl mbber was the first low unsaturation elastomer, and was developed ia the United States before World War II by the Standard Oil Co. (now Exxon Chemical). It is a copolymer of isobutylene and isoprene, with just enough of the latter to provide cross-linking sites for sulfur vulcanization. Its molecular stmcture is depicted ia Table 1. 

Butyl rubber and other isobutylene polymers of technological importance iaclude various homopolymers and isobutylene copolymers containing unsaturation achieved by copolymerization with isoprene. Bromination or chlorination of the unsaturated site is practiced commercially, and other modifications are beiag iavestigated. 

Halogenated Butyl Rubber. Halogenation at the isoprene site ia butyl mbber proceeds by a halonium ion mechanism leading to a double-bond shift and formation of an exomethylene alkyl haUde. Both chlorinated and brominated mbber show the predominate stmcture (1) (>80%), by nmr, as described eadier (33,34). Halogenation of the unsaturation has no apparent effect on the isobutylene backbone chains. Cross-linked samples do not crystallize on extension due to the chain irregularities introduced by the halogenated isoprene units. 

The low unsaturation requires powerful curing systems whilst the hydrocarbon nature of the polymer causes bonding problems. To overcome these problems chlorinated and brominated butyl rubbers (CIIR and BUR) have been introduced and have found use in the tyre industry. 

Butyl rubber (BR) and polyisobutylene (PIB) are widely used in adhesives as primary elastomeric binders and as tackifiers and modifiers. The main difference between these polymers is that butyl is a copolymer of isobutylene with a minor amount of isoprene (which introduces unsaturation due to carbon-carbon double bonds), while polyisobutylene is a homopolymer. 

Polyisobutylene has a similar chemical backbone to butyl rubber, but does not contain double carbon-carbon bonds (only terminal unsaturation). Many of its characteristics are similar to butyl rubber (ageing and chemical resistance, low water absorption, low permeability). The polymers of the isobutylene family have very little tendency to crystallize. Their strength is reached by cross-linking instead of crystallization. The amorphous structure of these polymers is responsible for their flexibility, permanent tack and resistance to shock. Because the glass transition temperature is low (about —60°C), flexibility is maintained even at temperatures well below ambient temperature. 

Forms of BR and polyisobutylene. The properties of butyl rubber and polyisobutylene depend on their moleeular weight, degree of unsaturation, nature of the stabilizer incorporated during manufacture and, in some cases, chemical modification. It is common to produce halogenated forms of butyl rubber to increase polarity and to provide a reactive site for alternate cure mechanisms [6],... 

Chlorobutyl rubber is prepared by chlorination of butyl rubber (chlorine content is about 1 wt%). This is a substitution reaction produced at the allylic position, so little carbon-carbon double unsaturation is lost. Therefore, chlorobutyl rubber has enhanced reactivity of the carbon-carbon double bonds and supplies additional reactive sites for cross-linking. Furthermore, enhanced adhesion is obtained to polar substrates and it can be blended with other, more unsaturated elastomers. 

Most rubbers used in adhesives are not resistant to oxidation. Because the degree of unsaturation present in the polymer backbone of natural rubber, styrene-butadiene rubber, nitrile rubber and polychloroprene rubber, they can easily react with oxygen. Butyl rubber, however, possesses small degree of unsaturation and is quite resistant to oxidation. The effects of oxidation in rubber base adhesives after some years of service life can be assessed using FTIR spectroscopy. The ratio of the intensities of the absorption bands at 1740 cm" (carbonyl group) and at 2900 cm" (carbon-hydrogen bonds) significantly increases when the elastomer has been oxidized [50]. 

Rubbers differ in their resistance to ozone. All the highly unsaturated rubbers (natural rubber, styrene-butadiene rubber, butyl rubber, nitrile rubber) are readily cracked while the deactivated double carbon-carbon bonds rubber (such as polychloroprene rubber) shows moderate ozone resistance. 

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). 

When the butyl rubber was compounded with up to 30 percent of polyisobutylene, which, lacking the unsaturated isoprene units, did not enter into the cross-linking reaction, the tensile strengths were, of course, considerably reduced. They were found nevertheless to be accurately represented by the same equation, (53), provided merely that Sa is taken as the fraction of the composite specimen consisting of network chains subject to orientation. Thus, in this case... 

Butyl rubber (a copolymer of isobutylene and 1-3 mole per cent isoprene) and its halogenated derivatives have unsaturation in the carbon-carbon backbone and consequently do not have as good aging properties as EPDM. There are also reports (9-12) that ozone-resistant butyl rubber with a high degree of unsaturation can be prepared by copolymerization of isobutylene with either cyclopentadiene or 9-pinene. 

Butyl rubber is not compatible with natural rubber, SBR, nitrile rubber or with any other elastomer having an appreciable degree of unsaturation modified butyls (chlorobutyl and bromobutyl) are compatible with such elastomers and used as liners in tubeless tyres to improve air retention. 

Chlorinated butyl rubber. Chlorination or bromination of butyl rubber overcomes the difficulty of vulcanising butyl rubber in mixtures with more highly unsaturated substances due to the preferential absorption of the sulphur by the more highly unsaturated component. Chlorohydrin Rubbers... 

Commercial grades of HR (butyl rubber) are prepared by copolymerising small amounts of isoprene with polyisobutylene. The isoprene content of the copolymer is normally quoted as the mole percent unsaturation , and it influences the rate of cure with sulphur, and the resistance of the copolymer to attack by oxygen, ozone and UV light. The polyisobutylene, being saturated, however, naturally confers on the polymer an increased level of resistance to these agencies when compared to natural rubber. Commercial butyl rubbers typically contain 0.5-3.0% mole unsaturation. 

Uses Production of isooctane, butyl rubber, polyisobutene resins, high octane aviation fuels, tert-butyl chloride, ferf-butyl methacrylates copolymer resins with acrylonitrile, butadiene, and other unsaturated hydrocarbons organic synthesis. 

Butyl rubber is a copolymer of 1 -butene, (CH3)2C = CH2, and small amounts (about 2%-3%) of isoprene or other unsaturated compounds. The unsaturation allows subsequent cross-linking of the material. 

Several polymers based on 1,3-dienes are used as elastomers. These include styrene-1,3-butadiene (SBR), styrene-1,3-butadiene terpolymer with an unsaturated carboxylic acid (carboxylated SBR), acrylonitrile-1,3-butadiene (NBR or nitrile rubber) (Secs. 6-8a, 6-8e), isobutylene-isoprene (butyl rubber) (Sec. 5-2i-l), and block copolymers of isoprene or... 

Here PNO2 partial pressure of nitrogen dioxide in pascals (1 Pa = 0.000145 psi), and the activation energy is 3870 kJ/mol. Other saturated polymers are less susceptible to attack by NO2 than most unsaturated polymers such as synthetic rubbers (polyiso-prene, polybutadiene, and butyl rubber). The presence of oxygen also tends to accelerate degradation by NO2. The reaction of sulfur dioxide with saturated polymers is complex, but appears to be activated by ultraviolet radiation. 

Butyl rubber is produced by a process in which isobutylene is copolymerized with a small amount of isoprene using aluminum chloride catalyst at temperatures around — 150° F. (20). The isoprene is used to provide some unsaturation, yielding a product that can be vulcanized (43). Vulcanized Butyl rubber is characterized by high tensile strength and excellent flex resistance furthermore, as a result of its low residual unsaturation (only 1 to 2% of that of natural rubber) it has outstanding resistance to oxidative aging and low air permeability. These properties combine to make it an ideal material for automobile inner tubes (3), and Butyl rubber has continued to be preferred over natural rubber for this application, even when the latter has been available in adequate supply. 

It appears from the evolution of the adhesion index that a distinction has to be made between the interactions carbon blacks are able to have with unsaturated or with saturated (or near-to-saturated) elastomers. Thus, the adhesion index of butyl rubber is enhanced upon oxidation of the black, while the reverse is observed with polybutadiene 38). The improvement of the reinforcing ability of carbon black upon oxidation, in the former case, has been interpreted by Gessler 401 as due to chemical interactions of butyl rubber with active functional groups on the solid surface. Gessler, relating the reinforcing characteristics of the oxidized carbon black for butyl rubber to the presence of carboxyl groups on the surface of the filler, postulated a cationic... 

McNiell has developed a useful technique for the determination of unsaturation using chlorine-36. It is not suggested that the technique should replace existing methods but that it is highly suitable for micro analyses when only small samples are available or for estimation of very low unsaturation values where other methods are not sufficiently sensitive. The superiority of the method for the analysis of butyl rubbers has been demonstrated (61) and it has also been used to measure unsaturation of 0.1—0.01 mole-% of polyisobutene (62). 

Grades of butyl differ by the level of unsaturation, molar masses characterized by Mooney viscosity ML 1 + 8 (100 or 125° C), and the characteristics of the eventually added stabilizer (staining or nonstaining). Butyl rubber, which ranks third in total synthetic elastomers consumed, has unique properties and applications, due to its low gas permeability, to its high hysteresis, and to its low level of unsaturation, sufficient for vulcanization but still providing excellent resistance to oxygen and ozone. 

About 40 different grades of regular butyl rubbers are available [63], depending on molar mass (Afv 3-6-105, polydispersity MW M 3-5) and on unsaturation level. For 0.7 mol% of isoprene the molar mass of subchain in the cross-linked rubber is =8000, and =2500 for the highest level (2.2%), which is much more than in polydienes or natural rubber networks. They are shared in two main families characterized by their range of Mooney viscosity, typically ML(I + 8)(100°C) 41-57 and 60-80. 

This situation is substantially undian in the case of butyl rubber, where a few percent (0.6—3 mol %) of trans-l, 4-isoprene units, i. e. C-CH2 -CH=C—CH2 -CH2 —C, are present and each methjdene group is adjacent to at l t one methyl substituted carbon atom. In fact. Loan has shmvn that the unsaturations of butyl rubber react more easily with the fragn nts arising frcan the dicung l peroxide decomposition than the H atoms of isobutene methyl groups. The ratio of the two rate constants is... 

Halogenation of saturated hydrocarbon polymers can hardly be controlled and is frequently assodated with chain degradation phenomena In contrast, the presence of randomly distributed olefinic unsaturations, allows selective halogenation reactions by adopting appropriate conditions. For instance, butyl rubber can be chiorinated or brominated in allylic positions and chloro-butyl or bromo-butyl rubber results The latter polymers are very interesting since they exhibit fast curing rates when sulfur and ZnO are introduced in the formulations. 

As shown in Table 1, poly(isobutylene-co- -pinenes) containing up to 10 mole% -pinene are rubbery materials Tg< —53 ). In view of the structural similarity between our copolymer and butyl rubber, we decided to use conventional butyl rubber cure conditions (3) to prepare our vulcanizates (see Experimental). Figure 2 shows the curing rate of two copolymers containing 3 and 10 mole% fi-pi-nene units respectively, as determined by a Monsanto Rheometer at 160 C (320 F). As expected, the curing rate of the cr lymer containing 10 mole% unsaturation is several times hi r than that of the material with 3 mole% unsaturation level. 

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