Vinylsulfonic acid

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Vinylsulfonic acid
Vinylsulfonic acid.svg
Names
Preferred IUPAC name
Ethenesulfonic acid
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.342 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • 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
  • C=CS(=O)(=O)O
Properties
C2H4O3S
Molar mass 108.11 g·mol−1
Appearancecolouless 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).

Vinylsulfonic acid is the organosulfur compound with the chemical formula CH2=CHSO3H. It is the simplest unsaturated sulfonic acid. [2] [3] The C=C double bond is a site of high reactivity. Polymerization 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.

Contents

Preparation

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

Vinylsulfonsaure aus Carbylsulfat.svg

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]

Vinylsulfonsaure via Isethionsaure.svg

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

ClCH2CH3 + SO2 + Cl2 → ClCH2CH2SO2Cl + HCl
ClCH2CH2SO2Cl → H2C=CHSO2Cl + HCl
CH2=CHSO2Cl + H2O → H2C=CHSO3H + HCl

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..

Related Research Articles

In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively charged sodium ions and negatively charged chloride ions.

Sulfonate

A sulfonate is a salt or ester of a sulfonic acid. It contains the functional group R-SO
3
, where R is an organic group. Sulfonates are the conjugate base of sulfonic acids. Sulfonates are generally stable in water, non-oxidizing, and colorless. Many useful compounds and even some biochemicals feature sulfonates.

Titanium tetrachloride Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula to the word.

Nafion Brand name for a chemical product

Nafion is a brand name for a sulfonated tetrafluoroethylene based fluoropolymer-copolymer discovered in the late 1960s by Walther Grot of DuPont. Nafion is a brand of the Chemours company. It is the first of a class of synthetic polymers with ionic properties that are called ionomers. Nafion's unique ionic properties are a result of incorporating perfluorovinyl ether groups terminated with sulfonate groups onto a tetrafluoroethylene (PTFE) backbone. Nafion has received a considerable amount of attention as a proton conductor for proton exchange membrane (PEM) fuel cells because of its excellent thermal and mechanical stability.

Ion-exchange resin Organic polymer matrix bearing ion-exchange functional groups

An ion-exchange resin or ion-exchange polymer is a resin or polymer that acts as a medium for ion exchange. It is an insoluble matrix normally in the form of small microbeads, usually white or yellowish, fabricated from an organic polymer substrate. The beads are typically porous, providing a large surface area on and inside them where the trapping of ions occurs along with the accompanying release of other ions, and thus the process is called ion exchange. There are multiple types of ion-exchange resin. Most commercial resins are made of polystyrene sulfonate.

In organometallic chemistry, acetylide refers to chemical compounds with the chemical formulas MC≡CH and MC≡CM, where M is a metal. The term is used loosely and can refer to substituted acetylides having the general structure RC−CM. Acetylides are reagents in organic synthesis. The calcium acetylide commonly called calcium carbide is a major compound of commerce.

Copper(II) chloride Chemical compound

Copper(II) chloride is the chemical compound with the chemical formula CuCl2. The anhydrous form is yellowish brown but slowly absorbs moisture to form a blue-green dihydrate.

Sulfonic acid Class of chemical compounds

A sulfonic acid (or sulphonic acid) refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound (with the organic substituent replaced by hydrogen) is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

Polystyrene sulfonate

Polystyrene sulfonates are a group of medications used to treat high blood potassium. Effects generally take hours to days. They are also used to remove potassium, calcium, and sodium from solutions in technical applications.

Aromatic sulfonation is an organic reaction in which a hydrogen atom on an arene is replaced by a sulfonic acid functional group in an electrophilic aromatic substitution. Aryl sulfonic acids are used as detergents, dye, and drugs.

The Reed reaction is a chemical reaction that utilizes light to oxidize hydrocarbons to alkylsulfonyl chlorides. This reaction is employed in modifying polyethylene to give chlorosulfonated polyethylene (CSPE), which noted for its toughness.

Triflic acid Chemical compound

Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for esterification. It is a hygroscopic, colorless, slightly viscous liquid and is soluble in polar solvents.

Hexafluorosilicic acid Octahedric silicon compound

Hexafluorosilicic acid is an inorganic compound with the chemical formula H
2
SiF
6
. Although no evidence has been presented for the existence of this species in solution or as a solid, aqueous solutions of hexafluorosilicic acid are well-defined, consisting of salts derived from various protonated forms of water as the cation and hexafluorosilicate as the anion. These salts and their aqueous solutions are colorless.

Sulfonyl halide groups occur when a sulfonyl functional group is singly bonded to a halogen atom. They have the general formula RSO2X where X is a halogen. The stability of sulfonyl halides decreases in the order fluorides > chlorides > bromides > iodides, all four types being well known. The sulfonyl chlorides and fluorides are of dominant importance in this series.

Sulfation is the chemical reaction that entails the addition of SO3 group. In principle, many sulfations would involve reactions of sulfur trioxide (SO3). In practice, most sulfations are effected less directly. Regardless of the mechanism, the installation of a sulfate-like group on a substrate leads to substantial changes.

Methanesulfonyl chloride (mesyl chloride) is an organosulfur compound with the formula CH3SO2Cl. Using the organic pseudoelement symbol Ms for the methanesulfonyl (or mesyl) group CH3SO2, it is frequently abbreviated MsCl in reaction schemes or equations. It is a colourless liquid that dissolves in polar organic solvents but is reactive toward water, alcohols, and many amines. The simplest organic sulfonyl chloride, it is used to make methanesulfonates and to generate the elusive molecule sulfene (methylenedioxosulfur(VI)).

Hydrochloric acid Strong mineral acid

Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid. It is a component of the gastric acid in the digestive systems of most animal species, including humans. Hydrochloric acid is an important laboratory reagent and industrial chemical.

2-Acrylamido-2-methylpropane sulfonic acid Chemical compound

2-Acrylamido-2-methylpropane sulfonic acid (AMPS) was a Trademark name by The Lubrizol Corporation. It is a reactive, hydrophilic, sulfonic acid acrylic monomer used to alter the chemical properties of wide variety of anionic polymers. In the 1970s, the earliest patents using this monomer were filed for acrylic fiber manufacturing. Today, there are over several thousands patents and publications involving use of AMPS in many areas including water treatment, oil field, construction chemicals, hydrogels for medical applications, personal care products, emulsion coatings, adhesives, and rheology modifiers.

Benzenesulfonic acid Chemical compound

Benzenesulfonic acid (conjugate base benzenesulfonate) is an organosulfur compound with the formula C6H6O3S. It is the simplest aromatic sulfonic acid. It forms white deliquescent sheet crystals or a white waxy solid that is soluble in water and ethanol, slightly soluble in benzene and insoluble in nonpolar solvents like diethyl ether. It is often stored in the form of alkali metal salts. Its aqueous solution is strongly acidic.

Carbyl sulfate Chemical compound

Carbyl sulfate is an organosulfur compound. The white solid is the product of the reaction of sulfur trioxide and ethylene. It is used in preparation of some dyes and other organosulfur compounds. Carbyl sulfate is a colorless, crystalline, hygroscopic substance although commercial product can appear as a liquid. Because of its unpleasant properties carbyl sulfate is difficult to handle and is usually not isolated but further processed to give secondary products.

References

  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.
  2. 1 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
  6. USpatent 3872165,Roland Dahlinger, Walter Schenk, Dieter Stockburger,"Manufacture of vinyl sulfonates and vinylsulfonic acid from carbylsulfate",issued 1975-03-18, assigned to BASF
  7. USpatent 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. Bibcode:1965AngCh..77..291D. 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 , vol. 212, no. 10, pp. 1072–1079, doi:10.1002/macp.201000773 {{citation}}: CS1 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.