Vinylsulfonic acid

Vinylsulfonic acid
Names
	IUPAC name ethenesulfonic acid
Identifiers
CAS Number	1184-84-5 ; 3039-83-6 (sodium salt) ;
3D model (JSmol)	Interactive image;
ChemSpider	56254;
ECHA InfoCard	100.013.342
PubChem CID	62474;
UNII	GJ6489R1WE ; F7K3L38Z7B (sodium salt) ;
CompTox Dashboard (EPA)	DTXSID2047018 ;
	InChI InChI=1S/C2H4O3S/c1-2-6(3,4)5/h2H,1H2,(H,3,4,5) Key: NLVXSWCKKBEXTG-UHFFFAOYSA-N; InChI=1/C2H4O3S/c1-2-6(3,4)5/h2H,1H2,(H,3,4,5) Key: NLVXSWCKKBEXTG-UHFFFAOYAA;
	SMILES C=CS(=O)(=O)O;
Properties
Chemical formula	C2H4O3S
Molar mass	108.11 g·mol−1
Appearance	colouless liquid
Boiling point	128 °C (1,29 hPa)[1] * 95 °C
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Vinylsulfonic acid is the organosulfur compound with the formula CH₂=CHSO₃H. It is the simplest unsaturated sulfonic acid.[2][3] The C=C double bond is a site of high reactivity. polymerize gives polyvinylsulfonic acid, especially when used as a comonomer with functionalized vinyl[4] and (meth)acrylic acid compounds.[5] It is a colorless, water-soluble liquid,[2] although commercial samples can appear yellow or even red.

Preparation

Vinylsulfonic acid is produced industrially by the alkaline hydrolysis of carbyl sulfate with subsequent acidification of the resulting vinyl sulfonate salt:[6]

The reaction is highly exothermic (reaction enthalpy: 1,675 kJ/kg) and requires exact maintenance of temperature and pH during the hydrolysis. When calcium hydroxide is used as the hydrolysis medium, a solution of calcium vinyl sulfonate is obtained. Acidification of this hydrolysis mixture with sulfuric acid gives vinylsulfonic acid, together with the poorly soluble calcium sulfate.

Vinylsulfonic acid also can be prepared by dehydration of isethionic acid with phosphorus pentoxide:[7]

Vinylsulfonic acid can also be prepared by sulfochlorination of chloroethane, dehydrohalogenation to vinylsulfonyl chloride and subsequent hydrolysis of the acid chloride.

{\begin{matrix}{}\\{\ce {ClCH2-CH3 + SO2 + Cl2 ->[][-{\ce {HCl}}] ClCH2-CH2-SO2Cl ->[][-{\ce {HCl}}] H2C=CH-SO2Cl ->[+{\ce {H2O}}][-{\ce {HCl}}] H2C=CH-SO3H}}\\{}\end{matrix}}

Use

The activated C=C double bond of vinylsulfonic acid reacts readily with nucleophiles in an addition reaction. 2-Aminoethanesulfonic acid is formed with ammonia and 2-methylaminoethanesulfonic acid with methylamine.[8]

Vinylsulfonic acid is the monomer in the preparation of highly acidic or anionic homopolymers and copolymers. These polymers are used in the electronic industry as photoresists, as ion-conductive polymer electrolyte membranes (PEM) for fuel cells. For example, transparent membranes with high ion exchange capacity and proton conductivity can be produced from polyvinylsulfonic acid.[9]

Research

Vinylsulfonic acid may also be grafted to polymeric supports (e.g. polystyrene) to give highly acidic ion exchangers, which used as catalysts for esterification and Friedel-Crafts acylations.[10] Where the sulfonic acid functionality is not essential, the much more usable alkaline aqueous solution of sodium vinylsulfonate is used, which is obtained directly in the alkaline hydrolysis of the carbyl sulfate and is commercially supplied as an aqueous solution..

References

H.C. Haas, M.S. Simon: Reactivity ratios of some monomer pairs in J. Polymer Sci. 9 (1952) 309–314, doi:10.1002/pol.1952.120090403.
Kosswig, Kurt (2000). "Sulfonic Acids, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. doi:10.1002/14356007.a25_503. ISBN 3-527-30673-0.
H. Distler: Zur Chemie der Vinylsulfonsäure in Angew. Chem. 77 (1965) 291–311, doi:10.1002/ange.19650770704 (PDF).
EP 0643081, H. Hoffmann et al., "Polymers of vinylsulfonic acid", issued 1995-03-15, assigned to Hoechst AG
US 2011017954, H. Akikaze et al., "VINYL SULFONIC ACID, POLYMER THEREOF, AND PRODUCTION METHOD THEREOF", issued 2011-01-27
US 3872165, Roland Dahlinger, Walter Schenk, Dieter Stockburger, "Manufacture of vinyl sulfonates and vinylsulfonic acid from carbylsulfate", issued 1975-03-18, assigned to BASF
US 2597696, J.A. Anthes, J.R. Dudley, "Preparation of Ethylenesulfonic acid", issued 1952-05-20, assigned to American Cyanamid
H. Distler (1965-04-07). "Zur Chemie der Vinylsulfonsäure". Angewandte Chemie. 77 (7): 291–302. doi:10.1002/ange.19650770704.
Teruyuki Okayasu, Toshiyasu Hibino, Hiroyuki Nishide (17 May 2011), "Free Radical Polymerization Kinetics of Vinylsulfonic Acid and Highly Acidic Properties of its Polymer", Macromolecular Chemistry and Physics, 212 (10), pp. 1072–1079, doi:10.1002/macp.201000773CS1 maint: multiple names: authors list (link)
T. Okayasu, K. Saito, H. Nishide, M.T W. Hearn: Poly(vinylsulfonic acid)-grafted solid catalysts: new materials for acid-catalysed organic synthetic reactions. In: Green Chem. 12 (2010) 1981–1989, doi:10.1039/C0GC00241K.

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[1] H.C. Haas, M.S. Simon: Reactivity ratios of some monomer pairs in J. Polymer Sci. 9 (1952) 309–314, doi:10.1002/pol.1952.120090403.

[Ullmann-2] Kosswig, Kurt (2000). "Sulfonic Acids, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. doi:10.1002/14356007.a25_503. ISBN 3-527-30673-0.

[3] H. Distler: Zur Chemie der Vinylsulfonsäure in Angew. Chem. 77 (1965) 291–311, doi:10.1002/ange.19650770704 (PDF).

[4] EP 0643081, H. Hoffmann et al., "Polymers of vinylsulfonic acid", issued 1995-03-15, assigned to Hoechst AG

[5] US 2011017954, H. Akikaze et al., "VINYL SULFONIC ACID, POLYMER THEREOF, AND PRODUCTION METHOD THEREOF", issued 2011-01-27

[Schenk-6] US 3872165, Roland Dahlinger, Walter Schenk, Dieter Stockburger, "Manufacture of vinyl sulfonates and vinylsulfonic acid from carbylsulfate", issued 1975-03-18, assigned to BASF

[7] US 2597696, J.A. Anthes, J.R. Dudley, "Preparation of Ethylenesulfonic acid", issued 1952-05-20, assigned to American Cyanamid

[8] H. Distler (1965-04-07). "Zur Chemie der Vinylsulfonsäure". Angewandte Chemie. 77 (7): 291–302. doi:10.1002/ange.19650770704.

[9] Teruyuki Okayasu, Toshiyasu Hibino, Hiroyuki Nishide (17 May 2011), "Free Radical Polymerization Kinetics of Vinylsulfonic Acid and Highly Acidic Properties of its Polymer", Macromolecular Chemistry and Physics, 212 (10), pp. 1072–1079, doi:10.1002/macp.201000773CS1 maint: multiple names: authors list (link)

[10] T. Okayasu, K. Saito, H. Nishide, M.T W. Hearn: Poly(vinylsulfonic acid)-grafted solid catalysts: new materials for acid-catalysed organic synthetic reactions. In: Green Chem. 12 (2010) 1981–1989, doi:10.1039/C0GC00241K.