PRODUCTS

VINYLSULFONIC ACID

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

CAS 1184-84-5
EINECS 214-676-1

Synonyms:
VINYLSULFONIC ACID; ethenesulfonic acid; Ethylenesulfonic acid; 1184-84-5; VINYLSULPHONIC ACID; UNII-GJ6489R1WE; GJ6489R1WE; Ethylenesulphonic acid; Sodium ethylenesulfonate; 1rql; Ethylenesulfonicacid; NSC8957; EINECS 214-676-1; vinyl sulfonic acid; ethylene sulfonic acid; SCHEMBL16079; Vinylsulfonic Acid, >/=97%; CHEMBL1236690; DTXSID2047018; Sodium ethenesulfonate(25%Nasalt); ZINC4216798; MFCD09743544; AKOS006230508; DB04359; VSO; DB-008982; FT-0722512; 30336-EP2309584A1; 30336-EP2311464A1; 184V845; Q2527228; 1184-84-5 [RN]; V214-676-1 [EINECS]; Acide éthènesulfonique [French] [ACD/IUPAC Name]; Ethenesulfonic acid [ACD/Index Name] [ACD/IUPAC Name]; Ethensulfonsäure [German] [ACD/IUPAC Name]; ethylenesulfonic acid; GJ6489R1WE; Vinylsulfonic acid [Wiki]; 3039-83-6 (SODIUM SALT); EINECS 214-676-1; ESA; Ethanesulfonic acid [ACD/Index Name] [ACD/IUPAC Name]; ethenesulphonic acid; Ethylenesulfonicacid; ethylenesulphonic acid; MFCD09743544; Sodium ethenesulfonate(25%Nasalt); UNII:GJ6489R1WE; UNII-GJ6489R1WE; vinyl sulfonic acid; vinylsulfonicacid; VINYLSULPHONIC ACID; VSO

Vinylsulfonic Acid
Purity / Analysis Method   >97.0%(T)
Molecular Formula / Molecular Weight   C2H4O3S = 108.11
Physical State (20 deg.C)   Liquid
Storage Temperature   0-10°C
Condition to Avoid   Light Sensitive,Heat Sensitive
CAS RN   1184-84-5
Reaxys Registry Number   1743040
PubChem Substance ID   354333146
MDL Number
MFCD09743544

Vinylsulfonic acid
Molecular FormulaC2H4O3S
Average mass108.116 Da
Monoisotopic mass107.988113 Da

Specific ion effects in solutions of salts of poly(vinyl sulfonic acid) in aqueous univalent supporting electrolyte are described in regard to observations of phase separation, dialysis equilibrium, light scattering, viscosity, and sedimentation. The most complete data have been obtained on two systems, ammonium poly(vinyl sulfonate) in 0.5M NH4Cl and potassium poly(vinyl sulfonate) in 0.5M KCl. Although the distribution of small ions across a semipermeable membrane is not markedly different in the two cases, other thermodynamic properties, the occurrence of phase separation in the KCl solution and its absence with NH4Cl, together with a larger second virial coefficient in the latter case, indicate that NH4Cl is a much better solvent for the corresponding polymer than is KCl. The hydrodynamic measurements concur in showing that the polymer chain configuration is more expanded in the NH4Cl solution. The interrelations among thermodynamic and hydrodynamic properties developed and generally substantiated for solutions of unionized polymers are found to be valid, at least qualitatively, for both these systems. This study also illustrates how the thermodynamic formalism for a two‐component system is applicable to three components, two diffusible and one non‐diffusible, provided solutions are equilibrated by dialysis against the solvent mixture.In this study, the effect of water soluble homopolymer of vinylsulfonic acid on spontaneous crystallization of calcium oxalate (CaOx) was investigated.A vinyl sulfonic acid, having a double bond content of 95 wt. % or more, and a sodium (Na) content of 1 ppm or less, and a content of at least one metal selected from the group consisting of alkali earth metal and first row transition metal of 1 ppm or less. Alternatively,a vinyl sulfonic acid, having a double bond content of 95 wt. % or more, and a sodium (Na) content of 100 ppb or less, and a content of at least one metal selected from the group consisting of alkali earth metal and first row transition metal of 100 ppb or less. Further, a homopolymer or copolymer thereof, a production method thereof, or a thin-film distillation apparatus suited for the production thereof.The present invention mainly relates to a vinyl sulfonic acid, a polymer thereof, a production method thereof, an apparatus suitable for production thereof, and an electric/electronic material comprising the vinyl sulfonic acid or polymer thereof.Vinyl sulfonic acids are attracting a great deal of attention as a monomer for constituting a functional polymer and a conductive material.
However, commercially available vinyl sulfonic acids have a double bond content of 75 wt. % or less. Consequently, when the vinyl sulfonic acid was to be polymerized after impregnating in a porous substrate, polymerization did not proceed sufficiently and thus a product functioning as a proton conductive polymer could not be obtained.
Patent Document 1 describes a vinyl sulfonic acid with a purity of 98%. However, the metal content is several ppm.
Recently, vinyl sulfonic acids or polymers thereof are attracting attention as a component constituting functional polymers and conductive materials, and as a material for electronic devices and semiconductors.However, a vinyl sulfonic acid or polymer thereof having a sufficiently reduced metal content is as yet unknown.On the other hand, various methods are known for producing a vinyl sulfonic acid (see Non-Patent Document 2). For example, Patent Document 15 describes a method for producing a vinyl sulfonic acid by performing a sodium removal treatment on sodium vinyl sulfonate with hydrochloric acid.Further, Patent Document 16 describes a method for producing a vinyl sulfonic acid by dehydrating isethionic acid using diphosphate pentoxide or pyrophosphoric acid as a dehydrating agent.It is the main object of the present invention to provide a vinyl sulfonic acid having a high double bond content and a low metal content. Further, it is an object of the present invention to provide a homopolymer and a copolymer comprising this vinyl sulfonic acid as a constituent component, and a production method thereof. In addition, it is an object of the present invention to provide an electric/electronic material comprising this vinyl sulfonic acid or a polymer thereof. Still further, it is an object of the present invention to provide an apparatus or a method suitable for the production of the above vinyl sulfonic acid.On the other hand, various methods are known for producing a vinyl sulfonic acid (see Non-Patent Document 2). For example, Patent Document 15 describes a method for producing a vinyl sulfonic acid by performing a sodium removal treatment on sodium vinyl sulfonate with hydrochloric acid.Further, Patent Document 16 describes a method for producing a vinyl sulfonic acid by dehydrating isethionic acid using diphosphate pentoxide or pyrophosphoric acid as a dehydrating agent.It is the main object of the present invention to provide a vinyl sulfonic acid having a high double bond content and a low metal content. Further, it is an object of the present invention to provide a homopolymer and a copolymer comprising this vinyl sulfonic acid as a constituent component, and a production method thereof. In addition, it is an object of the present invention to provide an electric/electronic material comprising this vinyl sulfonic acid or a polymer thereof. Still further, it is an object of the present invention to provide an apparatus or a method suitable for the production of the above vinyl sulfonic acid.Mainly for the purpose of resolving the above-described problems, and as a result of extensive investigations, the present invention discovered that a vinyl sulfonic acid having excellent qualities could be obtained, and as a result of further extensive investigations, completed the present invention.Specifically, the present invention provides the following vinyl sulfonic acids, homopolymers, copolymers, production methods, apparatuses, and electric/electronic materials.The vinyl sulfonic acid according to the present invention has reduced impurity and metal contents, and can be preferably used as a material for an electric/electronic material. In other words, the vinyl sulfonic acid according to the present invention can be preferably used as a material in a production of an electric/electronic material.For example, a homopolymer formed by impregnating the vinyl sulfonic acid in a substrate and then carrying out homopolymerization, or a copolymer formed by impregnating the vinyl sulfonic acid in a substrate and then copolymerizing with another polymerizable monomer, can be used as a fuel cell polymer electrolyte.Further, the vinyl sulfonic acid, or a homopolymer formed by polymerizing just this vinyl sulfonic acid or a copolymer formed by copolymerizing the vinyl sulfonic acid with another polymerizable monomer, can be used as a material for a photoresist composition, a polymer binder or a separator for a battery. In addition, the product obtained by polymerization of the vinyl sulfonic acid can be used as an anionic polymer acid dispersant in a polishing slurry for semiconductor fabrication, or as a conductive polymer dopant used in an EL device, such as an organic light-emitting diode (OLED).A method for producing the vinyl sulfonic acid according to the present invention is not especially limited, as long as the vinyl sulfonic acid has the above-described characteristics. Vinyl sulfonic acids obtained by the following production methods are preferred.A method for producing the vinyl sulfonic acid, comprising a step of subjecting a vinyl sulfonate to a metal removal treatment, wherein the metal removal rate in the metal removal treatment represented by the following formula is 95% or more:Metal removal rate(%)={(acid value after metal removal treatment)/(acid value before metal removal treatment)}×100.A method for producing the vinyl sulfonic acid, comprising a step of subjecting a vinyl sulfonate to a metal removal treatment, wherein the metal removal treatment is carried out using a strongly-acidic ion-exchange resin.Production method 4: The production method according to the above-described production method 3, wherein the thin-film distillation apparatus is an apparatus in which all or a part of a contact with the vinyl sulfonic acid or a composition thereof are formed from a material having a high corrosion resistance.The production method according to the above-described production method 3, wherein the thin-film distillation apparatus is an apparatus in which all or a part of a contact with the vinyl sulfonic acid or a composition thereof are made from tantalum.From the above-described production methods, a vinyl sulfonic acid can be obtained which has a high double bond content and a low metal content. In other words, the vinyl sulfonic acid used in the present invention includes the vinyl sulfonic acids which can be obtained by any of production methods 1 to 6. A vinyl sulfonic acid obtained by the above-described production methods has little discoloration and hardly any change in color over time.The present invention provides a thin-film distillation apparatus which can be preferably used in the method for producing the vinyl sulfonic acid. In other words, the present invention provides a thin-film distillation apparatus for vinyl sulfonic acid production, or a thin-film distillation apparatus for vinyl sulfonic acid purification.In the thin-film distillation apparatus according to the present invention, all or a part of a contact with the vinyl sulfonic acid or a composition thereof is formed from a material having a high corrosion resistance.The term “a contact with the vinyl sulfonic acid or a composition thereof” (hereinafter also referred to as “vinyl sulfonic acid contact region”) means, for example, a region that is in contact with the vinyl sulfonic acid composition serving as the distillation raw material after it has undergone the metal removal treatment, the evaporated vinyl sulfonic acid vapor, or the condensed vinyl sulfonic acid formed from the vinyl sulfonic acid vapor. These regions are also referred to as “liquid contact region” and/or “gas contact region”.Examples of the members included in the vinyl sulfonic acid contact region include a liquid feed pipe, the inner walls of the distillation tower, a stirring member, a wiper member, a cooling member, a stirring seal member, a distillation raw material introduction port, a distillate line, a receiver, a residue discharge line and the like.If the vinyl sulfonic acid contact region is formed from the material having a high corrosion resistance, contamination of impurities from the material or the region can be suppressed. Conventionally, a material such as SUS was used as a metal for the vinyl sulfonic acid contact region, so that impurities from this material contaminated the vinyl sulfonic acid. However, according to the above-described configuration, the level of contamination of impurities due to the material is reduced.The copolymer according to the present invention is a copolymer which has the above-described vinyl sulfonic acid as a constituent component. More specifically, the copolymer according to the present invention comprises the above-described vinyl sulfonic acid as an essential monomer.The vinyl sulfonic acid copolymer according to the present invention can be obtained by copolymerizing the above-described vinyl sulfonic acid with one or two or more other monomers.These “other monomers” are polymerizable compounds different from the above-described vinyl sulfonic acid, which serve as one of the constituent components of the copolymer.These other monomers are not especially limited, as long as they are a substance that is copolymerizable with the above-described vinyl sulfonic acid. A vinyl monomer can be preferably used as the other monomer.A method for producing the vinyl sulfonic acid copolymer is not especially limited. However, generally, the method is carried out by radical polymerization, photopolymerization, or radiation polymerization.The radical polymerization is carried out by mixing the vinyl sulfonic acid or aqueous solution thereof and the other monomer or aqueous solution thereof, adding a small amount of an initiator to the resultant mixture, and heating. As the initiator, a peroxide, a persulfate, an azo compound or a redox initiator can be used.The photopolymerization is carried out by mixing the vinyl sulfonic acid or aqueous solution thereof and the other monomer or aqueous solution thereof, and irradiating light on the resultant mixture. For example, the irradiation can be carried out using solar rays, UV rays and the like. Further, a photopolymerizable crosslinking agent, a photopolymerization initiator, a photopolymerization promoter and the like may optionally be added. It is especially preferred to carry out the photopolymerization in the presence of N,N-dimethylformamide.The radiation polymerization is carried out by mixing the vinyl sulfonic acid or aqueous solution thereof and the other monomer or aqueous solution thereof, and irradiating radioactive rays on the resultant mixture.The vinyl sulfonic acid according to the present invention has a high double bond content and a low metal content. According to the present invention, a vinyl sulfonic acid can be obtained which has little discoloration, hardly any change in color over time, and high quality.Further, the vinyl sulfonic acid homopolymer and copolymer according to the present invention obtained using this vinyl sulfonic acid for a monomer have almost no impurities, a low metal content, and excellent quality.Due to having such excellent properties, the vinyl sulfonic acid, homopolymer, and copolymer according to the present invention have sufficient durability even in a harsh environment of a high temperature and strong oxidizing atmosphere. Therefore, the vinyl sulfonic acid, homopolymer, and copolymer according to the present invention can be preferably used for an electric/electronic material, such as for a fuel cell electrolyte membrane, a photoresist composition, and a conductive polymer, or as a raw material thereof.Further, the present invention provides a thin-film distillation apparatus suited to the production of a high-quality vinyl sulfonic acid. If purified using the apparatus according to the present invention, a vinyl sulfonic acid having a high double bond content and a low metal content can be obtained. In addition, according to the present invention, large-scale production of a high-quality vinyl sulfonic acid can be achieved by continuous operation of the thin-film distillation apparatus.Vinylsulfonic acid is the organosulfur compound with the formula CH2=CHSO3H. It is the simplest unsaturated sulfonic acid. The C=C double bond is a site of high reactivity. polymerize gives polyvinylsulfonic acid, especially when used as a comonomer with functionalized vinyl and (meth)acrylic acid compounds. It is a colorless, water-soluble liquid, although commercial samples can appear yellow or even red.