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surfactants, greases, lubricants, and heating baths. Resins are used as varnishes, paints, molding compounds, electrical insulation, adhesives, laminates, and release coatings. Elastomer applications include sealants, caulks, adhesives, gaskets, tubing, hoses, belts, electrical insulation such as automobile ignition cable, encapsulating and molding applications, fabric coatings, encapsulants, and a variety of medical applications (anti atulents, heart valves, encasing of pacemakers, prosthetic parts, contact lenses, coating of plasma bottles to avoid blood coagulation). Silicone elastomers differ markedly from other organic elastomers in the much greater effect of reinforcing llers in increasing strength properties. Polysiloxane uids and resins are obtained by hydrolysis of chlorosilanes such as dichlorodimethyl-, dichloromethylphenyl-, and dichlorodiphenylsilanes [Brydson, 1999; Hardman and Torkelson, 1989]. The chlorosilane is hydrolyzed with water to a mixture of chlorohydroxy and dihydroxysilanes (referred to as silanols), which react with each other by dehydration and dehydrochlorination. The product is an equilibrated mixture of approximately equal
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CH3 Cl Si CH3 Cl
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CH3 O Si CH3
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amounts of cyclic oligomers and linear polysiloxanes. The amount of cyclics can vary from 20 to 80% depending on reaction conditions. The major cyclic oligomer is the tetramer with progressively decreasing amounts of higher cyclics. After the initial equilibration, a disiloxane-terminating agent such as [(CH3)3Si]2O is added to stabilize the reaction mixture by termination of the linear species. The process may be carried out under either acidic or basic conditions depending on the desired product molecular weight. Basic conditions favor the production of higher molecular weight. Mixtures of cyclic oligomers and linear polymer may be employed directly as silicone uids, or the cyclic content may be decreased prior to use by devolitilization (heating under vacuum). The synthesis of silicone resins proceeds in a similar manner, except that the reaction mixture includes trichlorosilanes to bring about more extensive polymerization with crosslinking. Typically, the polymer product will be separated from an aqueous layer after the hydrolytic step, heated in the presence of a basic catalyst such as zinc octanoate to increase the polymer molecular weight and decrease the cyclic content, cooled, and stored. The nal end-use application of this product involves further heating with a basic catalyst to bring about more extensive crosslinking. Silicone elastomers are either room-temperature vulcanization (RTV) or heat-cured silicone rubbers depending on whether crosslinking is accomplished at ambient or elevated temperature. (The term vulcanization is a synonym for crosslinking. Curing is typically also used as a synonym for crosslinking but often refers to a combination of additional polymerization plus crosslinking.) RTV and heat-cured silicone rubbers typically involve polysiloxanes with degrees of polymerizations of 200 1500 and 2500 11,000, respectively. The highermolecular-weight polysiloxanes cannot be synthesized by the hydrolytic step polymerization process. This is accomplished by ring-opening polymerization using ionic initiators (Sec. 7-11a). One-component RTV rubbers consist of an airtight package containing silanolterminated polysiloxane, crosslinking agent (methyltriacetoxysilane, and catalyst (e.g., dibutyltin laurate). Moisture from the atmosphere converts the crosslinking agent to the
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corresponding silanol (acetic acid is a by-product), CH3SI(OH)3, which brings about further polymerization combined with crosslinking of the polysiloxane:
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CH3 SiR2 O Si O SiR2 O SiR2
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OH + CH3Si(OH)3
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Two-component RTV formulations involve separate packages for the polysiloxane and crosslinking agent. Hydrosilation curing involves the addition reaction between a polysiloxane containing vinyl groups (obtained by including methylvinyldichlorosilane in the original reaction mixture for synthesis of the polysiloxane) and a siloxane crosslinking agent that contains Si functional groups, such as 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (Eq. 2-189). H The reaction is catalyzed by chloroplatinic acid or other soluble Pt compound. Hydride functional siloxanes can also crosslink silanol-terminated polysiloxanes. The reaction is catalyzed by tin salts and involves H2 loss between Si and Si H groups. Heat curing of silicone H O rubbers usually involves free-radical initiators such as benzoyl peroxide (Sec. 9-2c). Hydrosilation at 50 100 C is also practiced.
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