Silicone/Composition, structure, and properties

chemical compound

silicone, also called polysiloxane, any of a diverse class of fluids, resins, or elastomers based on polymerized siloxanes, substances whose molecules consist of chains made of alternating silicon and oxygen atoms. Their chemical inertness, resistance to water and oxidation, and stability at both high and low temperatures have led to a wide range of commercial applications, from lubricating greases to electrical-wire insulation and biomedical implants (such as breast implants).

Composition, structure, and properties

The silicones differ from most industrial polymers in that the chains of linked atoms that make up the backbones of their molecules do not contain carbon, the characteristic element of organic compounds. This lack of carbon in the polymer backbones makes polysiloxanes into unusual “inorganic” polymers—though in most members of the class two organic groups, usually vinyl (CH2), methyl (CH3), or phenyl (C6H5), are attached to each silicon atom. A general formula for silicones is (R2SiO)x, where R can be any one of a variety of organic groups.

The most common silicone compound, poly-dimethylsiloxane, can illustrate the central characteristics of the class. The starting material is metallic silicon, which is obtained from silica sand. Silicon is reacted with methyl chloride (CH3Cl) over a coppercatalyst, forming dimethyldichlorosilane ([CH3]2Si[Cl]2). By reacting this compound with water, the chlorine atoms are replaced by hydroxyl (OH) groups. The resultant unstable compound, silanol ([CH3]2Si[OH]2), polymerizes in a condensation reaction, the single-unit molecules linking together to form poly-dimethylsiloxane with concomitant loss of water. The dimethylsiloxane repeating unit of the polymer has the following structure:structure of the siloxane polymer, polydimethylsiloxane.

Siloxane molecules rotate freely around the Si-O bond, so, even with vinyl, methyl, or phenyl groups attached to the silicon atoms, the molecule is highly flexible. In addition, the Si-O bond is highly heat-resistant and is not readily attacked by oxygen or ozone. As a result, silicones are remarkably stable, and they have the lowest glass-transition temperature (the temperature below which the molecules are locked in a rigid, glassy state) and the highest permeability to gases of any polymer. On the other hand, the Si-O bond is susceptible to hydrolysis and attack by acids and bases, so silicone plastics and rubbers are relatively weak and readily swollen by hydrocarbon oils.