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Concept
Polydimethylsiloxane
Summary
Polydimethylsiloxane (PDMS), also known as dimethylpolysiloxane or dimethicone, is a silicone polymer with a wide variety of uses, from cosmetics to industrial lubrication.
It is particularly known for its unusual rheological (or flow) properties. PDMS is optically clear and, in general, inert, non-toxic, and non-flammable. It is one of several types of silicone oil (polymerized siloxane). Its applications range from contact lenses and medical devices to elastomers; it is also present in shampoos (as it makes hair shiny and slippery), food (antifoaming agent), caulk, lubricants and heat-resistant tiles.
The chemical formula of PDMS is , where n is the number of repeating monomer units. Industrial synthesis can begin from dimethyldichlorosilane and water by the following net reaction:
The polymerization reaction evolves hydrochloric acid. For medical and domestic applications, a process was developed in which the chlorine atoms in the silane precursor were replaced with acetate groups. In this case, the polymerization produces acetic acid, which is less chemically aggressive than HCl. As a side-effect, the curing process is also much slower in this case. The acetate is used in consumer applications, such as silicone caulk and adhesives.
Hydrolysis of generates a polymer that is terminated with silanol groups (–). These reactive centers are typically "capped" by reaction with trimethylsilyl chloride:
Silane precursors with more acid-forming groups and fewer methyl groups, such as methyltrichlorosilane, can be used to introduce branches or cross-links in the polymer chain. Under ideal conditions, each molecule of such a compound becomes a branch point. This can be used to produce hard silicone resins. In a similar manner, precursors with three methyl groups can be used to limit molecular weight, since each such molecule has only one reactive site and so forms the end of a siloxane chain.
Well-defined PDMS with a low polydispersity index and high homogeneity is produced by controlled anionic ring-opening polymerization of hexamethylcyclotrisiloxane.
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