Butyl rubber cross-linking

Fig. 7.1 Plot of melting point depression (AT) as a function of fraction of units cross-linked, p, for polymer networks formed from random chains. A molten polyethylene cross-linked by ionizing radiation o natural rubber cross-linked with sulfur natural mbber cross-linked with di-t-butyl peroxide. (Data from Refs. (13) and (14))...

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. 

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. 

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. 

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. 

Several partially cross-linked butyl rubbers are commercially available. The more tightly cross-linked grades are designed for butyl tapes. On the other hand, various depolymerized butyl rubbers and butyl/plasticizers blends are also available. 

Phenol-formaldehyde resins. These arc used to cure butyl rubber forming thermally stable carbon-carbon cross-links. 

Ozone cracking is a physicochemical phenomenon. Ozone attack on olefinic double bonds causes chain scission and the formation of decomposition products. The first step in the reaction is the formation of a relatively unstable primary ozonide, which cleaves to an aldehyde or ketone and a carbonyl. Subsequent recombination of the aldehyde and the carbonyl groups produces a second ozonide [58]. Cross-linking products may also be formed, especially with rubbers containing disubstituted carbon-carbon double bonds (e.g. butyl rubber, styrene-butadiene rubber), due to the attack of the carbonyl groups (produced by cleavage of primary ozonides) on the rubber carbon-carbon double bonds. 

Standard butyl rubber, which is a copolymer of isobutylene with about 2% of isoprene vulcanises in the same manner as natural rubber but, as it only contains a small proportion of polyisoprene, the cross-link percentage is much reduced. It is therefore not possible to make ebonite from a butyl rubber. The same vulcanisation chemistry, with some modifications, applies to ethylene-propylene terpolymers and brominated butyl rubber. 

Fig. 103.—Tension r at a =4 vs. the reciprocal of the primary molecular weight for three butyl rubber series differing in degree of cross-linking (or in Me). (Flory. )...

Fig. 105.—Tensile strengths of butyl rubber fractions each vulcanized to the same cross-linking density p, corresponding to Me = 37,000, plotted against the primary molecular weight M. ...

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... 

In an acetone extract from a neoprene/SBR hose compound, Lattimer et al. [92] distinguished dioctylph-thalate (m/z 390), di(r-octyl)diphenylamine (m/z 393), 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyl)-isocyanurate m/z 783), hydrocarbon oil and a paraffin wax (numerous molecular ions in the m/z range of 200-500) by means of FD-MS. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out (Chapter 2). The method of Dinsmore and Smith [257], or a modification thereof, is normally used. Mass spectrometry (and other analytical techniques) is then used to characterise the various rubber fractions. The mass-spectral identification of numerous antioxidants (hindered phenols and aromatic amines, e.g. phenyl-/ -naphthyl-amine, 6-dodecyl-2,2,4-trimethyl-l,2-dihydroquinoline, butylated bisphenol-A, HPPD, poly-TMDQ, di-(t-octyl)diphenylamine) in rubber extracts by means of direct probe EI-MS with programmed heating, has been reported [252]. The main problem reported consisted of the numerous ions arising from hydrocarbon oil in the recipe. In older work, mass spectrometry has been used to qualitatively identify volatile AOs in sheet samples of SBR and rubber-type vulcanisates after extraction of the polymer with acetone [51,246]. 

Ethylene-propylene and silicone rubbers are crosslinked by compounding with a peroxide such as dicumyl peroxide or di-t-butyl peroxide and then heating the mixture. Peroxide cross-linking involves the formation of polymer radicals via hydrogen abstraction by the peroxy radicals formed from the decomposition of the peroxide. Crosslinks are formed by coupling of the polymer radicals... 

Experiments have been made in which uncross-linkable polymer rubbers have been added to a similar rubber that is subsequently cross-linked (199). As an example, polyisobutylene was added to butyl rubber before it was cross-linked. The polyisobutylene molecules were not attached to the network structure, so they could be extracted by a solvent. As expected, the polyisobutylene greatly increased the creep compliance over that of the pure butyl rubber. 

Butyl rubber, polyisobutylene, is an example of cationic polymerization with an acid. Review Chapter 14, Section 2.3. A small amount of isoprene is added to enable cross-linking during vulcanization through the allylic sites. 

Butyl rubber (HR) is widely used for inner tubes and as a sealant. It is produced using the cationic polymerization with the copolymerization of isobutylene in the presence of a small amount (10%) of isoprene. Thus, the random copolymer chain contains a low concentration of widely spaced isolated double bonds, from the isoprene, that are later cross-linked when the butyl rubber is cured. A representation is shown in structure 5.20 where the number of units derived from isobutylene units greatly outnumbers the number of units derived from the isoprene monomer. The steric requirements of the isobutylene-derived units cause the chains to remain apart giving it a low stress to strain value and a low Tg. 

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. 

Polymers with solubility parameters differing from those of the solvent by at least 2.0 H, will not dissolve in the solvent at room temperature. Thus although unvulcanized natural rubber (NR), unvulcanized styrene-butadiene elastomer (SBR), unvulcanized butyl rubber, and EPDM dissolve in gasoline or benzene, the vulcanized (cross-linked) polymers are swollen but will not dissolve due to the presence of the crosslinks. 

The prevulcanization of natural rubber in latex form has also been a subject of much investigation. The cross-linking mechanism is not yet fully understood, but the water apparently plays a major role in it. Irradiation results in the cross-linking of the rubber molecules and in coarsening of the latex particles. A process of cross-linking of natural rubber latex has been developed to the point that it can be used for an industrial-scale application. The irradiation is performed in aqueous media by electron beam without a prorad (sensitizer) at a dose of 200 kGy (20 Mrad) or in the presence of n-butyl acrylate at considerably lower doses, typically 15 kGy. The cross-linked film exhibits physical properties comparable to those obtained from sulfur cured (vulcanized) film. As an alternative, the addition of a variety of chloroal-kanes makes it possible to achieve a maximum tensile strength with radiation doses of less than 5 Mrad (50 kGy). ... 

A process of cross-linking of natural rubber latex has been developed to where it should be soon ready for an industrial-scale process.149 The irradiation is performed in aqueous media by electron beam without a prorad ( sensitizer ) at a dose of 200 kGy (20 Mrad) or, in the presence of n-butyl acrylate at considerably lower doses, typically 15 kGy. The cross-linked film exhibits physical properties comparable to those obtained from sulfur-cured (vulcanized) film. 

In 1944, Flory (3) noted that the moduli of cross-linked butyl rubbers generally differ somewhat from values calculated from the crosslink density according to the kinetic theory of rubber elasticity. In many cases, the modulus also depends on the primary (uncross-linked) molecular weight distribution of the polymer. He attributed both observations to three kinds of network defects chain ends, loops, and chain entanglements. The latter are latent in the system prior to cross-linking and become permanent features of the network when cross-links are added. 

This depends on the cross link density. With a tighter cure, permanent sets are low. Some high saturation polymers such as butyl rubbers have characteristically high permanent set. 

The saturated rubbers such as butyl or EPDM cannot be cross linked by sulphur and accelerators. Organic peroxides are necessary for the vulcanization of these rubbers. When the peroxides decompose, free radicals are formed on the polymer chains and these chains can then combine to form cross links of the type where only carbon-carbon bonds are formed, unlike in sulphur vulcanization. These carbon-carbon bonds are quite stable ones. Such bonds are also formed by vulcanization using gamma or x-ray radiation of compounded rubbers. Some rubbers can be vulcanized by the use of certain bisfunctional compounds which form bridge type cross... 

Polymerization of 2-methylpropene in the presence of small amounts of 2-methyl-1,3-butadiene (isoprene) gives a copolymer with enough double bonds to permit cross-linking of the polymer chains through vulcanization. The product is a hard-wearing, chemically resistant rubber called butyl rubber. It is highly impermeable to air and is used widely for inner tubes for tires. 

Other thermoplastic elastomer combinations, in which the elastomer phase may or may not be cross-linked, include blends of polypropylene with nitrile (30,31), butyl (33), and natural (34) rubbers, blends of PVC with nitrile mbber (35,36), and blends of halogenated polyolefins with ethylene interpolymers (29). Collectively, thermoplastic elastomers of this type are referred to herein as hard polymer/elastomer combinations. Some of the more important examples of the various types are shown in Table 3. 

For peroxide cross-linking, organic peroxides, such as dicumyl, di-t-butyl, and benzoyl peroxides, are used in amounts 1 to 3 phr (parts per hundred parts of rubber). Typical cure cycles are 5 to 10 min at temperatures 115 to 170°C (239 to 338°F), depending on the type of peroxide used. Each peroxide has a specific use. A postcure is recommended to complete the cross-linking reaction and to remove the residues from the decomposition of peroxide. This improves the long-term heat aging properties.62... 

Sealants are often based on butyl rubber, polyisopropylene, polyurethane, or silicone rubber. Reactive sealants may be vulcanized at room temperature (RTV) or at high temperature (HTV). Silicone sealants are chemically-hardening, single-component systems in which cross-linking of the substrate is initiated by moisture from the air. This separates the reaction products. After rapid formation of a skin on the surface, cross-linking continues inside the mixture until it is fully hardened. 

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