polysulfide

File:Na2S5Packing.tif

The alkali metal polysulfides arise by treatment of a solution of the sulfide with elemental sulfur, e.g. sodium sulfide to sodium polysulfide:

{{chem|S|2-| + n S → S|n+1|2−}}

In some cases, these anions have been obtained as organic salts, which are soluble in organic solvents.{{cite journal |last1=Dev|first1= S. |last2=Ramli|first2= E. |last3=Rauchfuss|first3= T. B. |last4=Wilson|first4= S. R. | title = Synthesis and Structure of [M(N-Methylimidazole)₆]S₈: Polysulfide Salts Prepared by the Reaction N-Methylimidazole + Metal Powder + Sulfur | journal = Inorg. Chem. | year = 1991 | volume = 30 | pages = 2514 | doi=10.1021/ic00011a011 | issue = 11}}

The energy released in the reaction of sodium and elemental sulfur is the basis of battery technology. The sodium–sulfur battery and the lithium–sulfur battery require high temperatures to maintain liquid polysulfide and {{chem2|Na+}}-conductive membranes that are unreactive toward sodium, sulfur, and sodium sulfide.

Polysulfides are ligands in coordination chemistry. Examples of transition metal polysulfido complexes include titanocene pentasulfide, {{chem2|[Ni(S4)2](2−)}}, and {{chem2|[Pt(S5)3](2−)}}.{{cite journal|last1=Draganjac|first1= M. E.|last2= Rauchfuss|first2= T. B.|title= Transition Metal Polysulfides: Coordination Compounds with Purely Inorganic Chelate Ligands|journal= Angew. Chem. Int. Ed. Engl.|date= 1985| volume= 24|issue= 9|page= 742 |doi=10.1002/anie.198507421}} Main group elements also form polysulfides.{{cite book|last1=Takeda|first1= N.|last2= Tokitoh|first2= N. |last3=Okazaki|first3= R. |date=2003 |title=Polysulfido Complexes of Main Group and Transition Metals |volume=231 |pages=153–202 |isbn= 3-540-40378-7 |doi=10.1007/b13184|series= Topics in Current Chemistry}}

Image:Lenthionine-2D-skeletal.png is an organic polysulfide found in shiitake mushrooms]]

In commerce, the term "polysulfide" usually refers to a class of polymers with alternating chains of several sulfur atoms and hydrocarbons. They have the formula {{chem2|R^{1}S_{n}R^{2}|}}. In this formula n indicates the number of sulfur atoms (or "rank"). Polysulfide polymers can be synthesized by condensation polymerization reactions between organic dihalides and alkali metal salts of polysulfide anions:

{{chem2|n Na2S5 + n ClCH2CH2Cl → [CH2CH2S5]_{n} + 2n NaCl}}

Dihalides used in this condensation polymerization are dichloroalkanes such as 1,2-dichloroethane, bis(2-chloroethoxy)methane ({{chem2 | ClCH2CH2OCH2OCH2CH2Cl}}), and 1,3-dichloropropane. The polymers are called thiokols. In some cases, polysulfide polymers can be formed by ring-opening polymerization reactions.

Polysulfide polymers are also prepared by the addition of polysulfanes to alkenes. An idealized equation is:

{{chem2|2 RCH\dCH2 + H2S_{n} → (RCH2CH2)2S_{n}|}}

In reality, homogeneous samples of {{chem2|H2S_{n}|}} are difficult to prepare.

Polysulfide polymers are insoluble in water, oils, and many other organic solvents. Because of their solvent resistance, these materials find use as sealants to fill the joints in pavement, automotive window glass, and aircraft structures.

Polymers containing one or two sulfur atoms separated by hydrocarbon sequences are usually not classified polysulfides, e.g. poly(p-phenylene) sulfide {{chem2|(C6H4S)_{n}|}}.

File:Vulcanization of POLYIsoprene V.2.png

Many commercial elastomers contain polysulfides as crosslinks. These crosslinks interconnect neighboring polymer chains, thereby conferring rigidity. The degree of rigidity is related to the number of crosslinks. Elastomers, therefore, have a characteristic ability to return to their original shape after being stretched or compressed. Because of this memory for their original cured shape, elastomers are commonly referred to as rubbers. The process of crosslinking the polymer chains in these polymers with sulfur is called vulcanization. The sulfur chains attach themselves to the allylic carbon atoms, which are adjacent to C=C linkages. Vulcanization is a step in the processing of several classes of rubbers, including polychloroprene (Neoprene), styrene-butadiene, and polyisoprene, which is chemically similar to natural rubber. Charles Goodyear's discovery of vulcanization, involving the heating of polyisoprene with sulfur, was revolutionary because it converted a sticky and almost useless material into an elastomer that could be fabricated into useful products.

In addition to water and ammonia, the clouds in the atmospheres of the gas giant planets contain ammonium sulfides. The reddish-brownish clouds are attributed to polysulfides, arising from the exposure of the ammonium sulfides to light.{{cite web|url=http://www.britannica.com/eb/article-54256/Jupiter |title=Jupiter: Cloud composition |website=Encyclopædia Britannica|date=6 June 2023 }}

Polysulfides, like sulfides, can induce stress corrosion cracking in carbon steel and stainless steel.

• {{annotated link|Disulfide}}
• {{annotated link|Trisulfide}}
• {{annotated link|Polyiodide}}
• {{annotated link|Catenation}}

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Category:Sulfur compounds

Category:Anions

Category:Inorganic polymers

Category:Corrosion

Category:Polysulfides