Vinylene carbonate

Last updated
Vinylene carbonate
Vinylene-carbonate-2D-skeletal.svg
Names
Preferred IUPAC name
2H-1,3-Dioxol-2-one
Other names
1,3-Dioxolene-2-one
Vinyl carbonate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.011.659 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 212-825-5
PubChem CID
UNII
  • InChI=1S/C3H2O3/c4-3-5-1-2-6-3/h1-2H
    Key: VAYTZRYEBVHVLE-UHFFFAOYSA-N
  • C1=COC(=O)O1
Properties
C3H2O3
Molar mass 86.05 g·mol −1
Appearancecolourless liquid [1]
Density 1.35
Melting point 22 °C (72 °F; 295 K)
Boiling point 178 °C (352 °F; 451 K) [2]
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H302, H311, H315, H317, H318, H373, H411
P260, P261, P264, P270, P272, P273, P280, P301+P312, P302+P352, P305+P351+P338, P310, P312, P314, P321, P322, P330, P332+P313, P333+P313, P361, P362, P363, P391, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Vinylene carbonate (VC) or 1,3-dioxol-2-one, is the simplest unsaturated cyclic carbonic acid ester. Vinylene carbonate can also be thought of as the cyclic carbonate of the hypothetical (Z)-ethene-1,2-diol. The activated double bond in this five-membered oxygen-containing heterocycle makes the molecule a reactive monomer for homopolymerization and copolymerization and a dienophile in Diels-Alder reactions. Below room temperature vinylene carbonate is a colorless stable solid.

Contents

Preparation

Since its first description in 1953, [3] ethylene carbonate has been commonly used as starting material for vinylene carbonate. In the first stage, monochlorethylene carbonate is produced in a UV-initiated photochlorination reaction with chlorine or sulfuryl chloride at 60-70 °C in bulk. In the second stage, monochlorethylenecarbonate undergoes dehydrochlorination with a base such as triethylamine. [4] [5] [6]

Vinylencarbonat-Synthese.svg

Instead of in the liquid phase, the dehydrochlorination may also be carried out in the gas phase on a zinc chloride impregnated catalyst in a fluidized bed reactor at 350-500 °C. [7] The seemingly simple reaction yields only 70 to 80% of impure end product due to a variety of side reactions. For example, in the chlorination of ethylene carbonate in substance or solution, 2-chloroacetaldehyde, polychlorinated ethylene carbonate and chlorinated ring-opening products are formed besides others. The separation of the by-products from the final product by distillation by thin-film evaporator, [4] fractional recrystallization [8] or zone melting [9] is very expensive. The content of by-products can be reduced by stirring with sodium borohydride [10] or urea [11] at elevated temperature. However, the purification is complicated by the pronounced thermolability of vinylene carbonate, as it decomposes at temperatures above 80 °C within minutes. [4] Highly pure vinylene carbonate can be obtained in yields of more than 70% by optimizing the chlorination conditions to suppress the formation of by-products [6] and a combination of several gentle purification processes. [12] The tendency of the liquid vinylene carbonate to polymerize is suppressed by addition of inhibitors such as butylhydroxytoluene (BHT).

Properties

Industrially produced vinylene carbonate is usually a yellow to brown liquid. By suitable process control and purification steps, a solid product with a melting point of 20-22 °C and a chlorine content below 10ppm can be obtained. Liquid vinylene carbonate turns rapidly yellow even in the absence of light and must be stabilized by the addition of radical scavengers. In solid form, the highly pure substance is long-term stable when stored below 10 °C. [13] Vinylene carbonate dissolves in a variety of solvents such as ethanol, tetrahydrofuran, ethylene carbonate, propylene carbonate, and other dipolar aprotic electrolyte solvents used for lithium ion rechargeable batteries such as dimethyl carbonate, diethyl carbonate and the like.

Use

The first publication on vinylene carbonate described its Diels-Alder reaction using the example of its addition reaction with 2,3-dimethylbutadiene to a bicyclic carbonate and subsequent hydrolysis to cis-4,5-dihydroxy-1,2-cyclohexene: [3]

Cis-4,5-Dihydroxy-1,2-cyclohexen-Synthese.svg

When cyclopentadiene is used as the diene, the vicinal norbornene diol bicyclo[2.2.1]hept-5-ene-2,3-diol is formed after hydrolysis. The Swern oxidation to the 1,2-ketone bicyclo[2.2.1]hept-5-ene-2,3-dione proceeds (in the variant with trifluoroacetic anhydride instead of oxalyl chloride) with a yield of 73%. [14]

Norbornendion.svg

Under UV irradiation, ketones react with vinylene carbonate to form bicyclic exo-oxetanes:

Exo-Oxetan 2.svg

With phosphorus(V)sulfide, vinylene carbonate reacts to the corresponding vinylenethionocarbonate (2-thiono-1,3-dioxol-4-ene), [15] which gives ketene in quantitative yield upon UV irradiation. The reaction is a good alternative to the decomposition of α-diazoketones. [16]

Keten aus Vinylencarbonat.svg

Vinylene carbonate is used widely as an electrolyte additive for lithium-ion batteries where it promotes the formation of an insoluble film between the electrolyte and the negative electrode: the SEI (solid-electrolyte-interface). [17] This polymer film allows ionic conduction, but prevents the reduction of the electrolyte at the negative (graphite) electrode and contributes significantly to the long-term stability of lithium-ion batteries. [18] [19] A 2013 publication suggests that the cyclic sultone 3-fluoro-1,3-propanesultone (FPS) is superior to vinylene carbonate in SEI formation. [20]

3-Fluor-1,3-propansulton.svg

Since 1,3-propane sultone (on which FPS is based) is classified as a particularly dangerous carcinogenic substance, a significant hazard potential must also be assumed for FPS.

Polymers

Already the first work on vinylene carbonate describes its bulk polymerization a colorless polymer, which hydrolyzes to a water-soluble product. [3] Subsequent publications suggest that the first authors produced only low molecular weight oligomers. [21] [22] The preparation of higher molecular weight polymers with useful properties depends critically on the purity of the vinylene carbonate monomer. [23] Vinylene carbonate can be homopolymerized in bulk, in solution, in suspension and in dispersion using radical initiators such as azobis(isobutyronitrile) (AIBN) or benzoyl peroxide. It can also be copolymerized with other vinyl monomers such as vinyl pyrrolidone or vinyl propionate. [24]

Polymerisation von Vinylencarbonat.svg

Polyvinylene carbonate is readily soluble in acetone and dimethylformamide. The solutions obtained, however, tend to decompose already at room temperature. [25] The patent literature describes the use of polyvinyl carbonate for strong fibers, clear, colorless and mechanically strong films, [21] [10] membranes for reverse osmosis [26] and as support during affinity chromatography. [27]

In addition to the instability in solutions, polyvinyl carbonate has the tendency towards hydrolysis in weakly alkaline medium. This forms polyhydroxymethylene (PHM) via cleavage of the cyclic carbon ring, with the repeating unit –(CHOH)–. Its behavior is much more similar to cellulose than to the structurally related polyvinyl alcohol with the repeating unit –(CH2–CHOH)–.

Hydrolyse von Polyvinylencarbonat zu Polyhydroxymethylen.svg

For example, polyhydroxymethylene films obtained by alkaline hydrolysis of polyvinylene carbonate films via sodium methoxide in methanol are crystalline and exhibit high tensile strengths. [10] Analogous to cellulose, polyhydroxymethylene can be dissolved in hot sodium hydroxide solution and converted by crosslinking into a highly swellable polymer which can take up to 10,000 times its weight in water. [28] Polyhydroxymethylene is soluble in anhydrous hydrazine [29] and can be converted into cellulose-like fibers by spinning in water. Similar to cellulose, polyhydroxymethylene reacts with carbon disulfide in the alkaline state to form a xanthate, from which water-insoluble polyhydroxymethylene is again obtained by precipitation in dilute sulfuric acid. [30]

Safety

Vinylene carbonate requires particular care when handling because of its problematic toxicological and ecotoxicological profile. [1]

Related Research Articles

<span class="mw-page-title-main">Alkene</span> Hydrocarbon compound containing one or more C=C bonds

In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or in the terminal position. Terminal alkenes are also known as α-olefins.

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

<span class="mw-page-title-main">Ethylene oxide</span> Cyclic compound (C2H4O)

Ethylene oxide is an organic compound with the formula C2H4O. It is a cyclic ether and the simplest epoxide: a three-membered ring consisting of one oxygen atom and two carbon atoms. Ethylene oxide is a colorless and flammable gas with a faintly sweet odor. Because it is a strained ring, ethylene oxide easily participates in a number of addition reactions that result in ring-opening. Ethylene oxide is isomeric with acetaldehyde and with vinyl alcohol. Ethylene oxide is industrially produced by oxidation of ethylene in the presence of a silver catalyst.

<span class="mw-page-title-main">Phthalic anhydride</span> Chemical compound

Phthalic anhydride is the organic compound with the formula C6H4(CO)2O. It is the anhydride of phthalic acid. Phthalic anhydride is a principal commercial form of phthalic acid. It was the first anhydride of a dicarboxylic acid to be used commercially. This white solid is an important industrial chemical, especially for the large-scale production of plasticizers for plastics. In 2000, the worldwide production volume was estimated to be about 3 million tonnes per year.

A diol is a chemical compound containing two hydroxyl groups. An aliphatic diol may also be called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified. They are used as protecting groups of carbonyl groups, making them essential in synthesis of organic chemistry.

<span class="mw-page-title-main">Polyvinyl alcohol</span> Chemical compound

Polyvinyl alcohol (PVOH, PVA, or PVAl) is a water-soluble synthetic polymer. It has the idealized formula [CH2CH(OH)]n. It is used in papermaking, textile warp sizing, as a thickener and emulsion stabilizer in polyvinyl acetate (PVAc) adhesive formulations, in a variety of coatings, and 3D printing. It is colourless (white) and odorless. It is commonly supplied as beads or as solutions in water. Without an externally added crosslinking agent, PVA solution can be gelled through repeated freezing-thawing, yielding highly strong, ultrapure, biocompatible hydrogels which have been used for a variety of applications such as vascular stents, cartilages, contact lenses, etc.

<span class="mw-page-title-main">Isosorbide</span> Chemical compound

Isosorbide is a bicyclic chemical compound from the group of diols and the oxygen-containing heterocycles, containing two fused furan rings. The starting material for isosorbide is D-sorbitol, which is obtained by catalytic hydrogenation of D-glucose, which is in turn produced by hydrolysis of starch. Isosorbide is discussed as a plant-based platform chemical from which biodegradable derivatives of various functionality can be obtained.

<span class="mw-page-title-main">Polyester</span> Category of polymers, in which the monomers are joined together by ester links

Polyester is a category of polymers that contain one or two ester linkages in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include naturally occurring chemicals, such as in plants and insects, as well as synthetics such as polybutyrate. Natural polyesters and a few synthetic ones are biodegradable, but most synthetic polyesters are not. Synthetic polyesters are used extensively in clothing.

Barrelene is a bicyclic organic compound with chemical formula C8H8 and systematic name bicyclo[2.2.2]octa-2,5,7-triene. First synthesized and described by Howard Zimmerman in 1960, the name derives from the resemblance to a barrel, with the staves being three ethylene units attached to two methine groups. It is the formal Diels–Alder adduct of benzene and acetylene. Due to its unusual molecular geometry, the compound is of considerable interest to theoretical chemists.

<span class="mw-page-title-main">Ethylene carbonate</span> Chemical compound

Ethylene carbonate (sometimes abbreviated EC) is the organic compound with the formula (CH2O)2CO. It is classified as the cyclic carbonate ester of ethylene glycol and carbonic acid. At room temperature (25 °C) ethylene carbonate is a transparent crystalline solid, practically odorless and colorless, and somewhat soluble in water. In the liquid state (m.p. 34-37 °C) it is a colorless odorless liquid.

Solution polymerization is a method of industrial polymerization. In this procedure, a monomer is dissolved in a non-reactive solvent that contains a catalyst or initiator.

<span class="mw-page-title-main">Sulfolene</span> Chemical compound

Sulfolene, or butadiene sulfone is a cyclic organic chemical with a sulfone functional group. It is a white, odorless, crystalline, indefinitely storable solid, which dissolves in water and many organic solvents. The compound is used as a source of butadiene.

<span class="mw-page-title-main">Housane</span> Chemical compound

Housane or bicyclo[2.1.0]pentane is a saturated cycloalkane with the formula C5H8. It is a colorless, volatile liquid at room temperature. It was named "housane" because of its shape, which resembles a simple drawing of a house. Structurally, the molecule consists of cyclopropane fused to cyclobutane. The synthesis of molecules containing multiple strained rings, such as housane, is a traditional endeavor in synthetic organic chemistry.

<span class="mw-page-title-main">Tetramethylurea</span> Chemical compound

Tetramethylurea is the organic compound with the formula (Me2N)2CO. It is a substituted urea. This colorless liquid is used as an aprotic-polar solvent, especially for aromatic compounds and is used e. g. for Grignard reagents.

<span class="mw-page-title-main">2-Ethyl-2-oxazoline</span> Chemical compound

2-Ethyl-2-oxazoline (EtOx) is an oxazoline which is used particularly as a monomer for the cationic ring-opening polymerization to poly(2-alkyloxazoline)s. This type of polymers are under investigation as readily water-soluble and biocompatible materials for biomedical applications.

<span class="mw-page-title-main">Alkenylsuccinic anhydrides</span> Class of chemical compounds

Alkenyl succinic anhydrides (ASA) are derivatives of succinic anhydrides. One H of the succinic anhydride ring is replaced with an iso-alkenyl chain (C14 to C22). ASA's are colorless and usually viscous liquids. They are widely used, especially in surface sizing of paper, paperboard, and cardboard, as well as in the hydrophobicization of cellulose fibers. Products treated with it show reduced penetration of aqueous media, such as inks or drinks (like milk or fruit juices).

1,4-butane sultone is a six-membered δ-sultone and the cyclic ester of 4-hydroxybutanesulfonic acid. As a sulfo-alkylating agent, 1,4-butanesultone is used to introduce the sulfobutyl group (–(CH2)4–SO3−) into hydrophobic compounds possessing nucleophilic functional groups, for example hydroxy groups (as in the case of β-cyclodextrin) or amino groups (as in the case of polymethine dyes). In such, the sulfobutyl group is present as neutral sodium salt and considerably increases the water solubility of the derivatives.

Dimethylaminoethyl acrylate or DMAEA is an unsaturated carboxylic acid ester having a tertiary amino group. It is a colorless to yellowish, water-miscible liquid with a pungent, amine-like odor. DMAEA is an important acrylic monomer that gives basic properties to copolymers.

<span class="mw-page-title-main">Glycerol-1,2-carbonate</span> Organic chemical compound

Glycerol-1,2-carbonate is formally the cyclic ester of carbonic acid with glycerol and has aroused great interest as a possible product from the "waste materials" carbon dioxide CO2 and glycerol (especially from biodiesel production) with a wide range of applications.

<span class="mw-page-title-main">Diallyl carbonate</span> Acrylating agent

Diallyl carbonate (DAC) is a colorless liquid with a pungent odor. Its structure contains allyl groups and a functional carbonate group. The presence of double bonds in the allyl groups makes it reactive in various chemical processes. This compound plays a key role in the production of polymers, including polycarbonates and polyurethanes. Diallyl carbonate is soluble in ethanol, methanol, toluene, and chloroform. Diallyl carbonate reacts with amines, alcohols, and thiols.

References

  1. 1 2 Sigma-Aldrich Co., product no. {{{id}}}.
  2. ↑ Haynes, W. M., ed. (2016). CRC Handbook of Chemistry and Physics (96th ed.). Boca Raton, Florida: CRC Press/Taylor & Francis. p. 3-228. ISBN   978-1482260960.
  3. 1 2 3 M. S. Newman, R. W. Addor (1953), "Vinylene Carbonate", Journal of the American Chemical Society , vol. 75, no. 5, pp. 1263–1264, doi:10.1021/ja01101a526
  4. 1 2 3 US 6395908,B. Seifert et al.,"Process for the preparation of vinylene carbonate, and the use thereof",issued 2002-05-28, assigned to Merck Patentgesellschaft
  5. ↑ EP 1881972,Reinhard Langer, Anke Beckmann, Paul Wagner, Heinrich Grzinia, Marielouise Schneider, Ulrich Notheis, Lars Rodefeld, Nikolaus Müller,"Process for producing vinylene carbonate",issued 2013-08-28, assigned to Saltigo GmbH
  6. 1 2 US 8022231,M. Lerm et al.,"Process for preparing monochloroethylene carbonate and subsequent conversion to vinylene carbonate",issued 2011-09-20, assigned to Evonik Degussa GmbH
  7. ↑ EP 1881973,R. Langer et al.,"PROCESS FOR PRODUCING VINYLENE CARBONATE",issued 2008-01-30
  8. ↑ GB 899205,Nesbitt BF&Goodman I,"The purification and polymerisation of vinylene carbonate",issued 1962-06-20, assigned to ICI Ltd
  9. ↑ Zief, Morris; Ruch, Hollister; Schramm, Charles H (1963). "Low temperature zone refining apparatus". Journal of Chemical Education (in German). 40 (7): 351. Bibcode:1963JChEd..40..351Z. doi:10.1021/ed040p351.
  10. 1 2 3 N. D. Field, J. R. Schaefgen (1962), "High molecular weight poly(vinylene carbonate) and derivatives", Journal of Polymer Science A: Polymer Chemistry (in German), vol. 58, no. 166, pp. 533–543, Bibcode:1962JPoSc..58..533F, doi:10.1002/pol.1962.1205816630
  11. ↑ PCT-Anmeldung WO 2006/119910, Verfahren zur Reinigung von Vinylencarbonat, invent1: R. Langer et al., assign1: Lanxess Deutschland GmbH, veröffentlicht am 16. November 2006.
  12. ↑ EP 1881971,Reinhard Langer, Paul Wagner, Heinrich Grzinia,"High-purity vinylene carbonate and a method of purifying vinylene carbonate",issued 2008-01-30, assigned to Saltigo GmbH
  13. ↑ WO 2006119908,R. Langer,"METHOD OF STORING AND TRANSPORTING VINYLENE CARBONATE",issued 2006-11-16, assigned to Lanxess Deutschland GmbH
  14. ↑ T. Kobayashi, S. Kobayashi (2000), "Swern Oxidation of Bicyclo[2.2.1]hept-5-ene-2,3-diol and Its Pyrazine-fused Derivatives: An Improved Synthesis of Bicyclo[2.2.1]hept-5-ene-2,3-dione and An Unexpected Ring-Opening Reaction", Molecules (in German), vol. 5, no. 9, pp. 1062–1067, doi: 10.3390/50901062
  15. ↑ Hans-Michael Fischler, Willy Hartmann (1972), "Notiz über die Darstellung von Vinylenthioncarbonat und einigen alkyl- sowie arylsubstituierten Derivaten", Chemische Berichte (in German), vol. 105, no. 8, pp. 2769–2771, doi:10.1002/cber.19721050838
  16. ↑ Handbook of Reagents for Organic Syntheses, Sulfur-Containing Reagents, ed. L.A. Paquette, Wiley-VCH, 2010, ISBN   978-0-470-74872-5, p. 535.
  17. ↑ Lee, Hsiang-Hwan; Wang, Yung-Yun; Wan, Chi-Chao; Yang, Mo-Hua; Deng-Tswen Shieh, Hung-Chun Wu (2005). "The function of vinylene carbonate as a thermal additive to electrolyte in lithium batteries". Journal of Applied Electrochemistry (in German). 35 (6): 615–623. doi:10.1007/s10800-005-2700-x. S2CID   97739869.
  18. ↑ M. Broussely et al., Main aging mechanisms in Li ion batteries, J. Power Sources, 146 (1), 90–96 (2005), doi:10.1016/j.jpowsour.2005.03.172.
  19. ↑ DE 102004018929,V. Hennige et al.,"Elektrolytzusammensetzung sowie deren Verwendung als Elektrolytmaterial für elektrochemische Energiespeichersysteme",issued 2005-11-17, assigned to assign1 Degussa AG
  20. ↑ H.M. Jung et al., Fluoropropane sultone as an SEI-forming additive that outperforms vinylene carbonate, J. Mater. Chem. A, 1, 11975–11981 (2013), doi:10.1039/C3TA12580G.
  21. 1 2 US 2993030,G.E. Ham, M. Zief,"Process for polymerizing vinylene carbonate",issued 1961-07-16, assigned to J.T. Baker Chemical Co.
  22. ↑ M. Krebs, C. Schneider, Vinylene carbonate – A study of its polymerization and copolymerization behavior, Adv. Chem., 142 (9), 92–98 (1975), doi:10.1021/ba-1975-0142.ch009.
  23. ↑ GB 899205,Brenda Frances Nesbitt, Isaac Goodman,"The purification and polymerisation of vinylene carbonate",issued 1962-06-20, assigned to Imperial Chemical Industries Ltd
  24. ↑ US 4098771,H. Huemer, K. Burg,"Process for the preparation of polymers of vinylene carbonate",issued 1978-07-04, assigned to Hoechst AG
  25. ↑ J. Huang et al., Investigations on vinylene carbonate I. Preparation and properties of poly-(vinylene carbonate), Chinese J. Polym. Sci., 8(3), 197–203 (1990).
  26. ↑ US 3332894,P.A. Cantor, R.E. Kesting,"Polyvinyl carbonate desalination membrane and a method of producing the same",issued 1967-07-25
  27. ↑ US 4788278,O. Mauz,"Polyvinylene carbonate and polyhydroxymethylene, processes for their preparation and their use",issued 1988-11-29, assigned to Hoechst AG
  28. ↑ US 4061692,A. Holst, M. Kostrzewa,"Process for the manufacture of swellable, absorptive polymers of polyhydroxy methylene",issued 1977-12-06
  29. ↑ US 4076680,M.K. Akkapeddi, H.K. Reimschuessel,"Poly(hydroxymethylene) solutions",issued 1978-02-28
  30. ↑ US 3331800,H. Schübel et al.,"Preparation of solutions of polyhydroxymethylene-containing polymers",issued 1967-07-18
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.