Curing halogenated

Halobutyl Cures. Halogenated butyls cure faster in sulfur-accelerator systems than butyl bromobutyl is generally faster than chlorobutyl. Zinc oxide-based cure systems result in C—C bonds formed by alkylation through dehydrohalogenation of the halobutyl to form a zinc chloride catalyst (94,95). Cure rate is increased by stearic acid, but there is a competitive reaction of substitution at the halogen site. Because of this, stearic acid can reduce the overall state of cure (number of cross-links). Water is a strong retarder because it forms complexes with the reactive intermediates. Amine cure may be represented as follows ... 

Fig. 15. Primary thermograms for m-phenylenediamine-cured halogenated epoxides at various heating rates (26 ].

Figure 1.5 Ln versus 1/T for m-phenylenediamine-cured halogenated epoxide at the indicated values of W. Reproduced with permission from D.W. Levi, L. Reich and H.T. Lee, Polymer Engineering and Science, 1965, 5, 3, 135. 1965,...

Curatives, The function of curatives is to cross-link the polymer chains into a network the most common ones are the sulfur type for unsaturated rubber and peroxides for saturated polymers. Chemicals called accelerators may be added to control the cure rate in the sulfur system these materials generally are complex organic chemicals containing sulfur and nitrogen atoms. Stearic acid and zinc oxide usually are added to activate these accelerators. Metal oxides are used to cure halogenated polymers such as polychloroprene or chlorosulfonated polyethylene. 

Antwerp, Belgium, 22nd-23rd Nov. 1999, paper 16 NEW DEVELOPMENTS IN CURING HALOGEN-CONTAINING POLYMERS OhmRF... 

Unsaturated Polyesters. There are two approaches used to provide flame retardancy to unsaturated polyesters. These materials can be made flame resistant by incorporating halogen when made, or by adding some organic halogen compound when cured. In either case a synergist is needed. The second approach involves the addition of a hydrated filler. At least an equal amount of filler is used. 

The binder system of a plastic encapsulant consists of an epoxy resin, a hardener or curing agent, and an accelerating catalyst system. The conversion of epoxies from the Hquid (thermoplastic) state to tough, hard, thermoset soHds is accompHshed by the addition of chemically active compounds known as curing agents. Flame retardants (qv), usually in the form of halogens, are added to the epoxy resin backbone because epoxy resins are inherently flammable. 

Quinone dioximes, alkylphenol disulfides, and phenol—formaldehyde reaction products are used to cross-link halobutyl mbbers. In some cases, nonhalogenated butyl mbber can be cross-linked by these materials if there is some other source of halogen in the formulation. Alkylphenol disulfides are used in halobutyl innerliners for tires. Methylol phenol—formaldehyde resins are used for heat resistance in tire curing bladders. Bisphenols, accelerated by phosphonium salts, are used to cross-link fluorocarbon mbbers. 

Butyl and Halobutyl Rubber. Butyl mbber is made by the polymerization of isobutylene a small amount of isoprene is added to provide sites for curing. It is designated HR because of these monomers. Halogenation of butyl mbber with bromine or chlorine increases the reaction rate for vulcanization and laminates or blends of halobutyl are feasible for production of mbber goods. It is estimated that of the - 100 million kg of butyl (UR) and halobutyl (HIIR) mbber in North America, over 90% is used in tire apphcations. The halogenated polymer is used in the innerliner of tubeless tires. Butyl mbber is used to make innertubes and curing bladders. The two major suppHers of butyl and halobutyl polymers in North America are Exxon and Bayer (see ELASTOLffiRS,SYNTHETIC-BUTYLrubber). 

Meta.1 Oxides. Halogen-containing elastomers such as polychloropreae and chlorosulfonated polyethylene are cross-linked by their reaction with metal oxides, typically ziac oxide. The metal oxide reacts with halogen groups ia the polymer to produce an active iatermediate which then reacts further to produce carbon—carbon cross-links. Ziac chloride is Hberated as a by-product and it serves as an autocatalyst for this reaction. Magnesium oxide is typically used with ZnCl to control the cure rate and minimize premature cross-linking (scorch). 

Stannic chloride is also used widely as a catalyst in Eriedel-Crafts acylation, alkylation and cycHzation reactions, esterifications, halogenations, and curing and other polymerization reactions. Minor uses are as a stabilizer for colors in soap (19), as a mordant in the dyeing of silks, in the manufacture of blueprint and other sensitized paper, and as an antistatic agent for synthetic fibers (see Dyes, application and evaluation Antistatic agents). 

Polyisobutylene and isobutylene—isoprene copolymers are considered to have no chronic hazard associated with exposure under normal industrial use. Some grades can be used in chewing-gum base, and are regulated by the PDA in 21 CPR 172.615. Vulcanized products prepared from butyl mbber or halogenated butyl mbber contain small amounts of toxic materials as a result of the particular vulcanization chemistry. Although many vulcanizates are inert, eg, zinc oxide cured chlorobutyl is used extensively in pharmaceutical stoppers, specific recommendations should be sought from suppHers. 

Properties and Applieations. Aryloxyphosphazene elastomers using phenoxy and J-ethylphenoxy substituents have found interest in a number of appHcations involving fire safety. This elastomer has a limiting oxygen index of 28 and contains essentially no halogens. It may be cured using either peroxide or sulfur. Peroxide cures do not require the allyhc cute monomer. Gum physical properties are as follows (17) ... 

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],... 

The results obtained by Kuila et al. and Acharya et al. [63,64] from the EVA elastomer blended with lamellar-like Mg-Al layered double hydroxide (LDH) nanoparticles demonstrate that MH nanocrystals possess higher flame-retardant efficiency and mechanical reinforcing effect by comparison with common micrometer grade MH particles. Kar and Bhowmick [65] have developed MgO nanoparticles and have investigated their effect as cure activator for halogenated mbber. The results as shown in Table 4.2 are promising. 

Chlorobutyl (CIIR) and bromobutyl (BIIR) are modified types containing 1.2% wt of chlorine or bromine, the isoprene unit being the site of halogenation. Introduction of the halogen gives greater cure flexibility, and enhanced cure compatibility in blends with other diene rubbers. It also confers increased adhesion to other rubbers and metals. 

Butyl, and the halogenated butyls, can be cured by sulphur, dioxime and resin cure systems. In addition, the halogenated types can be crosslinked with zinc oxide, and diamines. Peroxides cannot be used because they tend to depolymerise the polyisobutylene. 

Resin cures utilise phenol-formaldehyde resins with reactive methylene groups and a small added amount of either a chlorinated rubber, e.g., polychloroprene, or stannous chloride. If halogenated phenolic resins are used the additional source of a halogen may not be required. Resin cures give butyl compounds excellent heat stability and are used to good effect where this is required, e.g., in tyre curing bags which have to resist service at 150 °C in a steam atmosphere. 

Resin cures utilise the same resins that are used for butyl rubber, but more resin (ca. 10-12 phr) and a halogen donor (10 phr), typically bromobutyl, or polychloroprene, are required. Although heat stability is slightly improved by resin curing when compared to sulphur cures, the effect is not as marked as in the resin curing of butyl. 

DIBF has the absorbance spectrum shown in Figure 4. Coating mixtures containing this photoinitiator can be cured with an intense tungsten halogen lamp, such as a projector bulb. When DIBF is irradiated it forms an excited state which has a very low absorbance, i.e., it photobleaches (1). This allows light to penetrate deeply into the coating. 

Butyl rubber(s), 4 433-458 9 561 14 265. See also Halogenated butyl rubber annual capacity, 4 451t carbon monoxide compatibility with, 5 4t chemical reactions, 4 448 copolymers, 4 444-446 cure systems for, 21 802-803 economic aspects, 4 451, 452t elastomeric vulcanizates, 4 448-450 formulation for reclaiming, 21 475t health and safety factors, 4 452-453 isobutylene polymerization mechanism, 4 434-436... 

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