Siloxane

A siloxane is a functional group in organosilicon chemistry with the Si−O−Si linkage. The parent siloxanes include the oligomeric and polymeric hydrides with the formulae H(OSiH₂)_''n''OH and (OSiH₂)_n. Siloxanes also include branched compounds, the defining feature of which is that each pair of silicon centres is separated by one oxygen (O^2-) atom. The siloxane functional group forms the backbone of silicones, the premier example of which is polydimethylsiloxane (PDMS). The functional group R₃SiO− (where the three Rs may be different) is called siloxy. Siloxanes are manmade and have many commercial and industrial applications because of the compounds’ hydrophobicity, low thermal conductivity, and high flexibility.

Structure

Siloxanes generally adopt structures expected for linked tetrahedral ("''sp''³-like") centers. The Si−O bond length is 1.64 Å (vs Si–C distance of 1.92 Å) and the Si-O-Si angle is rather open at 142.5°. By contrast, the C−O distance in a typical dialkyl ether is much shorter at 1.414(2) Å with a more acute C−O−C angle of 111°. It can be appreciated that the siloxanes would have low barriers for rotation about the Si−O bonds as a consequence of low steric hindrance. This geometric consideration is the basis of the useful properties of some siloxane-containing materials, such as their low glass transition temperatures.

Synthesis of siloxanes

140 px, Dimethyldichlorosilane (Si(CH₃)₂Cl₂) is a key precursor to cyclic (D₃, D₄, etc.) and linear siloxanes.Silicon: Organosilicon Chemistry. Encyclopedia of Inorganic Chemistry Online, 2nd ed.; Wiley: New Jersey, 2005. .
The main route to siloxane functional group is by hydrolysis of silicon chloride, silicon chlorides:
: 2 R₃Si−Cl + H₂O → R₃Si−O−SiR₃ + 2 HCl

The reaction proceeds via the initial formation of silanols (R₃Si−OH):
: R₃Si−Cl + H₂O → R₃Si−OH + HCl

The siloxane bond can then form via a silanol + silanol pathway or a silanol + chlorosilane pathway:
: 2 R₃Si−OH → R₃Si−O−SiR₃ + H₂O
: R₃Si−OH + R₃Si−Cl → R₃Si−O−SiR₃ + HCl

Hydrolysis of a silyldichloride can afford linear or cyclic products. Linear products are terminated with silanol groups:
: ''n'' R₂Si(OH)₂ → H(R₂SiO)_''n''OH + (''n'' − 1) H₂O
Cyclic products have no silanol termini:
: ''n'' R₂Si(OH)₂ → (R₂SiO)_''n'' + ''n'' H₂O

The linear products, polydimethylsiloxane (PDMS), are of great commercial value. Their production requires the production of dimethylsilicon dichloride.

Starting from trisilanols, cages are possible, such as the species with the formula (RSi)_''n''O_3''n''/2 with cubic (''n'' = 8) and hexagonal prismatic (''n'' = 12) structures. The cubic cages are cubane-type clusters, with silicon centers at the corners of a cube oxygen centres spanning each of the twelve edges.

Reactions

Oxidation of organosilicon compounds, including siloxanes, gives silicon dioxide. This conversion is illustrated by the combustion of hexamethylcyclotrisiloxane:
:((CH₃)₂SiO)₃ + 12 O₂ → 3 SiO₂ + 6 CO₂ + 9 H₂O

Strong base degrades siloxane group, often affording siloxide salts:
:((CH₃)₃Si)₂O + 2 NaOH → 2 (CH₃)₃SiONa + H₂O
This reaction proceeds by production of silanols. Similar reactions are used industrially to convert cyclic siloxanes to linear polymers.Röshe, L.; John, P.; Reitmeier, R. "Organic Silicon Compounds" Ullmann’s Encyclopedia of Industrial Chemistry. John Wiley and Sons: San Francisco, 2003. .

Uses

Polysiloxanes (silicones), upon combustion in an inert atmosphere, generally undergo pyrolysis to form silicon oxycarbide or silicon carbide (SiC). By exploiting this reaction, polysiloxanes have been used as preceramic polymers in various processes including additive manufacturing. Polyvinyl siloxane (vinyl polysiloxane) is used to make dental impressions and industrial impressions. The use of a poly-siloxane precursor in polymer derived ceramics allows the formation of ceramic bodies with complex shapes, although the significant shrinkage in pyrolysis needs to be taken into account.

Cyclomethicones

Cyclomethicones are a group of methyl siloxanes, a class of liquid silicones (cyclic polydimethylsiloxane polymers) that possess the characteristics of low viscosity and high volatility as well as being skin emollients and in certain circumstances useful cleaning solvents. Unlike dimethicones, which are ''linear'' siloxanes that do not evaporate, cyclomethicones are ''cyclic'': both groups consist of a backbone of CH₃)₂SiOsub>n. They are used in many cosmetic products including deodorants and antiperspirants which need to coat the skin but not remain tacky afterward. Dow is a major producer of cyclomethicones.

Cyclomethicones, like all siloxanes, degrade by hydrolysis, producing silanols. These silanols are produced at such low levels that they do not interfere with hydrolytic enzymes. Even though some cyclomethicones structurally resemble crown ethers, they bind metal ions only weakly.

Nomenclature

The word ''siloxane'' is derived from the words silicon, oxygen, and alkane. In some cases, siloxane materials are composed of several different types of siloxane groups; these are labeled according to the number of Si−O bonds:
: M-units: (CH₃)₃SiO_0.5,
: D-units: (CH₃)₂SiO,
: T-units: (CH₃)SiO_1.5.

Safety and environmental considerations

Because silicones are heavily used in biomedical and cosmetic applications, their toxicology has been intensively examined. "The inertness of silicones toward warmblooded animals has been demonstrated in a number of tests." With an LD₅₀ in rats of >50 g/kg, they are virtually nontoxic. Questions remain however about chronic toxicity or the consequences of bioaccumulation since siloxanes can be long-lived.

Findings about bioaccumulation have been largely based on laboratory studies. Field studies of bioaccumulation have not reached consensus. "Even if the concentrations of siloxanes we have found in fish are high compared to concentrations of classical contaminants like PCBs, several other studies in the Oslo Fjord in Norway, Lake Pepin in the US, and Lake Erie in Canada have shown concentrations of siloxanes decrease at higher range in the food chain. This finding raises questions about which factors influence the bioaccumulation potential of siloxanes."

Cyclomethicones are ubiquitous because they are widely used in biomedical and cosmetic applications. They can be found at high levels in American cities. They can be toxic to aquatic animals in concentrations often found in the environment. The cyclomethicones D₄ and D₅ are bioaccumulative in some aquatic organisms, according to one report.

In the European Union, D₄, D₅ and D₆ have been deemed hazardous as per the REACH regulation. They were characterized as substances of very high concern (SVHC) due to their PBT and vPvB properties. Canada regulates D₄ under a pollution prevention plan. A scientific review in Canada in 2011 concluded that "Siloxane D5 does not pose a danger to the environment."Report of the Board of Review for Decamethylcyclopentasiloxane (Siloxane D5) established under Section 333(1) of the Canadian Environmental Protection Act of 1999, October 20, 2011
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Literature

* Christoph Rücker, Klaus Kümmerer: ''Environmental Chemistry of Organosiloxanes.'' In: ''Chemical Reviews.'' 115(1), 2015, p. 466–524, .

References

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External links

EPA report: Siloxane D5 in Dry-cleaning

Journal Of Protective Coatings And Linings: Field Performance of Polysiloxanes

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