Siloxane#Cyclomethicones
{{Short description|Organic functional group (Si–O–Si)}}
In organosilicon chemistry, a siloxane is an organic compound containing a functional group of two silicon atoms bound to an oxygen atom: {{chem2|Si\sO\sSi}}. The parent siloxanes include the oligomeric and polymeric hydrides with the formulae {{chem2|H[OSiH2]_{n}OH}} and {{chem2|[OSiH2]_{n}|}}.[http://goldbook.iupac.org/S05671.html Siloxanes], IUPAC Gold Book. Siloxanes also include branched compounds, the defining feature of which is that each pair of silicon centres is separated by one oxygen atom. The siloxane functional group forms the backbone of silicones {{chem2|[\sR2Si\sO\sSiR2\s]_{n}|}}, the premier example of which is polydimethylsiloxane (PDMS). The functional group {{chem2|R3SiO\s}} (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 ("sp3-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°.H. Steinfink, B. Post and I. Fankuchen. "The crystal structure of octamethyl cyclotetrasiloxane". Acta Crystallogr. 1955, vol. 8, 420–424. {{doi|10.1107/S0365110X55001333}}. 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°.K. Vojinović, U. Losehand, N. W. Mitzel. "Dichlorosilane–dimethyl ether aggregation: a new motif in halosilane adduct formation". Dalton Trans., 2004, 2578–2581. {{doi|10.1039/B405684A}}. 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
image:Dichlorodimethylsilane.svg (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. {{doi|10.1002/0470862106.ia220}}.]]
The main route to siloxane functional group is by hydrolysis of 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)nOH + (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)nO3n/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.S. D. Kinrade, J. C. H. Donovan, A. S. Schach and C. T. G. Knight (2002), Two substituted cubic octameric silicate cages in aqueous solution. J. Chem. Soc., Dalton Trans., 1250–1252. {{doi|10.1039/b107758a}}.
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. {{doi|10.1002/14356007.a24_021}}.
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.{{citation needed|date=January 2022}}
Trisiloxanes may be used as diffusion pump fluid.{{citation needed|date=May 2025}}
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.{{cite book|author1=Barbara Kanegsberg|author2=Edward Kanegsberg|title=Handbook for Critical Cleaning: Cleaning Agents and Systems|url=https://books.google.com/books?id=CD6kqBW5U_wC&pg=PA19| year= 2011| publisher=CRC |isbn=978-1-4398-2827-4|page=19}} Unlike dimethicones, which are linear siloxanes that do not evaporate, cyclomethicones are cyclic: both groups consist of a backbone of [(CH3)2SiO]n. They are used in many cosmetic products including deodorants and antiperspirants which need to coat the skin but not remain tacky afterward.{{cite book|author=Amarjit Sahota|title=Sustainability: How the Cosmetics Industry is Greening Up|url=https://books.google.com/books?id=Svg8AgAAQBAJ&pg=PA208|date=25 November 2013|publisher=Wiley|isbn=978-1-118-67650-9|page=208}} Dow is a major producer of cyclomethicones.{{cite book|author=Meyer Rosen|title=Delivery System Handbook for Personal Care and Cosmetic Products: Technology, Applications and Formulations|url=https://books.google.com/books?id=wq2Oevdt16wC&pg=PA693|date=23 September 2005|publisher=William Andrew|isbn=978-0-8155-1682-8|page=693}}
Cyclomethicones, like all siloxanes, degrade by hydrolysis, producing silanols.S. Varaprath, K. L. Salyers, K. P. Plotzke and S. Nanavati "Identification of Metabolites of Octamethylcyclotetrasiloxane (D4) in Rat Urine" Drug Metab Dispos 1999, 27, 1267-1273. These silanols are produced at such low levels that they do not interfere with hydrolytic enzymes.{{cite journal|author=R. Pietschnig, S. Spirk|title=The Chemistry of Organo Silanetriols|journal=Coord. Chem. Rev.|year=2016|volume=323 |pages=87–106|doi=10.1016/j.ccr.2016.03.010 }} Even though some cyclomethicones structurally resemble crown ethers, they bind metal ions only weakly.{{cite journal|author=F. Dankert, C. von Hänisch|title=Siloxane Coordination Revisited: Si−O Bond Character, Reactivity and Magnificent Molecular Shapes|journal=Eur. J. Inorg. Chem.|year=2021|volume=2021 |issue=29 |pages=2907–2927|doi= 10.1002/ejic.202100275 |s2cid=239645449 }}
Nomenclature
File:Decamethylcyclopentasiloxane.svg, or D5, a cyclic siloxane]]
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)3SiO0.5,
: D-units: (CH3)2SiO,
: T-units: (CH3)SiO1.5.
| class="wikitable" |
| Cyclic siloxanes (cyclomethicones)
!CAS !Linear siloxanes !CAS |
|---|
| |
|L2, MM: hexamethyldisiloxane |107-46-0 |
| D3: hexamethylcyclotrisiloxane
|541-05-9 |L3, MDM: octamethyltrisiloxane |107-51-7 |
| D4: octamethylcyclotetrasiloxane
|556-67-2 |L4, MD2M: decamethyltetrasiloxane |141-62-8 |
| D5: decamethylcyclopentasiloxane
|541-02-6 |L5, MD3M: dodecamethylpentasiloxane |141-63-9 |
| D6: dodecamethylcyclohexasiloxane
|540-97-6 |L6, MD4M: tetradecamethylhexasiloxane |107-52-8 |
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.{{Ullmann|first1=Hans-Heinrich |last1=Moretto |first2=Manfred |last2=Schulze |first3=Gebhard |last3=Wagner |title= Silicones |year= 2005 |doi=10.1002/14356007.a24_057 |isbn=3527306730 }} 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."[https://partner.sciencenorway.no/enviroment-forskningno-nilu/siloxanes-soft-shiny--and-dangerous/1421529 "Siloxanes: Soft, shiny -- and dangerous?" by Christine Solbakken, Science Nordic, August 28, 2015. Retrieved May 31, 2016]
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.{{cite news|last1=Karpus|first1=Jennifer|title=Exec: Silicone industry must focus on safety, environment|url=http://www.rubbernews.com/article/20140620/NEWS/306169977|access-date=8 April 2015|work=Rubber & Plastic News|date=20 June 2014}}{{cite news|last1=Bienkowski|first1=Brian|title=Chemicals from Personal Care Products Pervasive in Chicago Air|url=http://www.scientificamerican.com/article/chemicals-from-personal-care-products-pervasive-in-chicago-air/|access-date=8 April 2015|work=Scientific American|date=30 April 2013}} The cyclomethicones D4 and D5 are bioaccumulative in some aquatic organisms, according to one report.{{cite journal|last1=Wang|first1=De-Gao|last2=Norwood|first2=Warren|last3=Alaee|first3=Mehran|last4=Byer|first4=Jonatan D.|last5=Brimble|first5=Samantha|title=Review of recent advances in research on the toxicity, detection, occurrence and fate of cyclic volatile methyl siloxanes in the environment|journal=Chemosphere|date=October 2013|volume=93|issue=5|pages=711–725|doi=10.1016/j.chemosphere.2012.10.041|pmid=23211328|bibcode=2013Chmsp..93..711W}}
In the European Union, D4, D5, D6 and octamethyltrisiloxane have been deemed hazardous as per the REACH regulation. They were characterized as substances of very high concern (SVHC) in 2024 due to their PBT (persistent, bioaccumulative and toxic) and vPvB (very persistent and very bioaccumulative) properties and were subsequently added to the REACH Candidate List in 2025.{{cite web|url=https://echa.europa.eu/candidate-list-table|title=Candidate List of substances of very high concern for Authorisation|publisher=ECHA|access-date=2019-12-18}} 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."[https://www.canada.ca/en/environment-climate-change/services/canadian-environmental-protection-act-registry/historical/public-consultations/notices-objection/report-board-review-decamethylcyclopentasiloxane-siloxane-d5.html Report of the Board of Review for Decamethylcyclopentasiloxane (Siloxane D5)]
Literature
- Christoph Rücker, Klaus Kümmerer: Environmental Chemistry of Organosiloxanes. In: Chemical Reviews. 115(1), 2015, p. 466–524, {{doi|10.1021/cr500319v}}.
References
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