Condensation cures

SiHcone mbber has a three-dimensional network stmcture caused by cross-linking of polydimethyl siloxane chains. Three reaction types are predominantiy employed for the formation of siHcone networks (155) peroxide-induced free-radical processes, hydrosdylation addition cure, and condensation cure. SiHcones have also been cross-linked using radiation to produce free radicals or to induce photoinitiated reactions. 

Condensation Cure. The condensation of sdanol groups to form sdoxanes is an extremely important industrial reaction and may be represented in its simplest form as follows ... 

Condensation cure can also be carried out ia emulsions (200—209). In this case, the cross-linker and polydimethylsiloxanediol are emulsified usiag anionic, cationic, or nonionic surfactants ia water, and a condensation catalyst such as dibutyltin dilaurate is added. The polymer can then undergo cross-linking, forming a continuous film when the water is evaporated. 

Model Networks. Constmction of model networks allows development of quantitative stmcture property relationships and provide the abiUty to test the accuracy of the theories of mbber elasticity (251—254). By definition, model networks have controlled molecular weight between cross-links, controlled cross-link functionahty, and controlled molecular weight distribution of cross-linked chains. Sihcones cross-linked by either condensation or addition reactions are ideally suited for these studies because all of the above parameters can be controlled. A typical condensation-cure model network consists of an a, CO-polydimethylsiloxanediol, tetraethoxysilane (or alkyltrimethoxysilane), and a tin-cure catalyst (255). A typical addition-cure model is composed of a, ffl-vinylpolydimethylsiloxane, tetrakis(dimethylsiloxy)silane, and a platinum-cure catalyst (256—258). 

Using both condensation-cured and addition-cured model systems, it has been shown that the modulus depends on the molecular weight of the polymer and that the modulus at mpture increases with increased junction functionahty (259). However, if a bimodal distribution of chain lengths is employed, an anomalously high modulus at high extensions is observed. Finite extensibihty of the short chains has been proposed as the origin of this upturn in the stress—strain curve. 

Most processors of fiber-reinforced composites choose a phenol formaldehyde (phenoHc) resin because these resins are inherently fire retardant, are highly heat resistant, and are very low in cost. When exposed to flames they give off very Htde smoke and that smoke is of low immediate toxicity. PhenoHc resins (qv) are often not chosen, however, because the resole types have limited shelf stabiHty, both resole and novolac types release volatiles during their condensation cure, formaldehyde [50-00-0] emissions are possible during both handling and cure, and the polymers formed are brittle compared with other thermosetting resins. 

Newer silicone adhesives having solids levels up to 97% are also commercially available [109]. Instead of using silanol condensation reactions, they rely on addition chemistry between vinyl functional silicone oligomers and silicon hydride terminated silicones. This addition reaction is typically facilitated with platinum derived catalysts. This hydrosilation process can be run at reduced oven temperatures, but the finished products typically do not yield the same balance of properties as seen for condensation cure materials. 

Although waterborne systems were developed in the 1960s, the form of this chemistry that dominates the industry utilizes end-functional, high molecular weight base polymers dissolved in organic solvents. Work on solventless condensation systems continues, but has not yet become commonplace [45,47]. Solvent-borne condensation cure systems are convenient for their ease of pro-... 

One-part moisture condensation cure. The one-part condensation cure system is a room-temperature vulcanizing (RTV) system that is based on a reactive PDMS polymer that undergoes hydrolysis on contact of air moisture, followed by condensation to yield a crosslinked elastomer. The most common systems [3,12,14,33] are based on the reactions shown in Scheme 5. 

Scheme 5. Common moisture RTV condensation cure systems for silicone adhesives and sealants. R is typically methyl (CH3-) or ethyl (CH3CH2-) group.

Scheme 7. Hydrolysis as the first step reaction in the atmospheric moisture condensation cure system.

Two-part room temperature condensation cure. Silicone can be formulated into two-part systems [3,12,14,33] that prevent the reactive groups from coming into contact before they are needed. The reactions in these systems are based on the condensation of a silanol group with an alkoxy silane group, catalyzed by organo-tin compounds (Scheme 9). 

There are many applications for silicone adhesives, sealants, or coatings where the condensation curing systems are not suitable. This is because they are relatively slow to cure, they require moisture to cure that can itself be in some cases uncontrollable, and they evolve by-products that cause shrinkage. Adhesives needed in automotive, electronics, microelectronics, micro electromechanical systems, avionic, and other hi-tech applications are usually confined to vei7 small volumes, which can make access to moisture difficult. Also, their proximity to very sensitive mechanical or electronic components requires a system that does not evolve reactive chemicals. 

Typical components of a silicone sealant based on condensation cure system... 

Condensation-cured model systems, of silicone networks, 22 569 Condensation energy, 23 826 Condensation-hydrolysis technology,... 

Room temperature vulcanizing (RTV) condensation cure process, 10 4-5 dispersions, 20 244... 

Since the Initial work of White (IQ), the Bell System and other major semiconductor users have extensively used silicones In the protection of numerous thin-film and thlck-fllm devices (24.25). The materials primarily have been condensation-cure silicones In xylene dispersion. The performance of encapsulated semiconductors used within the Bell System Is well documented (26). and studies continually In process support the use of silicones for the prevention of electronic component deterioration under conditions similar to the In-vlvo environment. 

More recently Wong (2U, has reported the results of tests designed to characterize parameters of electronic silicones by Ther-mogravlmetrlc, Fourier Transform-Infrared, and Gas Chromatography/ Mass Spectrometry. This work has concentrated upon condensation-cure materials used within the Bell System, rather than the end-blocked free radical (addition-cure) silicones. 

The 6th material Is a condensation-cure product which has been previously used for medical Implant protection (I). As verified by lap shear tests, (described below), the first 3 elastomers provide minimal adhesion In the absence of a surface primer. The last 3 are self-prlmlng materials. To permit visual examination, we tried to select clear materials. All of the elastomers are clear except for types 5 and 6. 

This particular DSC has the added feature of an endotherm that is indicated by a valley just prior to the exotherm. The data is for a condensation-curing phenolic, and the endotherm is caused by evaporation of reaction by-products. This evaporation is confirmed by the third trace in Figure 15.2. The TGA shows a rapid weight loss beginning at about the same time as the endotherm in the DSC. 

Gomowicz GA, Zhang H (2000) Thermoplastic silicone vulcanizates prepared by condensation cure. US Patent 6153691, USA... 

The advantage of the swelling method is that it is not limited by the crosslinking reactions of each phase so any interference from these will be limited. A good representative example is the synthesis developed by Hamurcu and Baysal [75]. They synthesized a bimodal PDMS (15 000 gmoD1)/ PDMS (75 000 g mol ) IPN with the same condensation curing system. First, the 75 000 g mol 1 PDMS network was formed from the corresponding a, tw-dihydroxypolydimethylsiloxane and tetraethylorthosilicate catalyzed by stannous 2-ethylhexanoate. It was then swollen in a 15 000 g mol 1 a,a>-dihydroxy-poly(dimethylsiloxane) monomer. The second monomer was then crosslinked via the same condensation cure. The sequential full IPN structure... 

Silicone Room Temperature Vulcanizing Gross-Linking. Condensation-cured polydimethylsiloxanes contain terminal silanol groups which condense with the silanols produced by ambient moisture hydrolysis of acyloxysilanes. Methyltriacetoxysilane, ethyltriacetoxysilane, and tetraacetoxysilane are the most commonly used cross-linking agents. 

---