ITACONIC ACID
ITACONIC ACID
Itaconic acid, or methylidenesuccinic acid, is an organic compound. This dicarboxylic acid is a white solid that is soluble in water, ethanol, and acetone. Historically, itaconic acid was obtained by the distillation of citric acid, but currently it is produced by fermentation. The name itaconic acid was devised as an anagram of aconitic acid, another derivative of citric acid.
Preferred IUPAC name: 2-Methylidenebutanedioic acid
Itaconic acid is a dicarboxylic acid that is methacrylic acid in which one of the methyl hydrogens is substituted by a carboxylic acid group. It has a role as a fungal metabolite and a human metabolite. It is a dicarboxylic acid and an olefinic compound. It derives from a succinic acid. It is a conjugate acid of an itaconate(2-).
Itaconic acid, or methylidenesuccinic acid, is an organic compound. This dicarboxylic acid is a white solid that is soluble in water, ethanol, and acetone. Historically, itaconic acid was obtained by the distillation of citric acid, but currently it is produced by fermentation. The name itaconic acid was devised as an anagram of aconitic acid, another derivative of citric acid.
Itaconic acid or methylidenesuccinic acid is an organic compound, which is soluble in water. This dicarboxylic acid is a white solid, and it is obtained by the distillation of citric acid. But currently, the fermentation process is more popular among the processes. This chemical has usage in SRB latex, synthetic latex, chillant dispersant agent, and superabsorbent polymers. The market for Itaconic Acid is influenced by the rising demand for skincare products, the evolution of environment friendly chemicals required by end-use industries, and increasing demand for bio-based unsaturated polyester resin.
Itaconic acid is a white colourless crystalline carboxylic acid obtained by the fermentation of carbohydrates and used in the manufacture of synthetic resins. It occurs in some fermentations of sugars.
Itaconic acid and its polymers can be made into effective deodorant by adding a little natural substance, they can react with alkaline or acidic odor such as ammonium, amine, and hydrogen sulfide. They can also be utilized in paper and plastic thin film with deodoring function. Itaconic acid can copolymerize with styrene and butadiene to prepare SBR latex which is widely used in paper coatings, metal and concrete paint. It is used in paints to improve quality and used as fiber carpet sizing agent to make carpet more endurable. Itaconic acid can react with acrylic and methacrylic acid or their esters to prepare resins which can be widely used in emulsion coating, leather coating, coatings for car, refrigerator and other electrical appliances to improve adhesion, color and weather resistance. They are also used in eletroporetical coating with excellent adhesion, in dental binder with the help of metal oxides. With chloroalkyl dimethyl benzylammonium chloride added, they can be used to prepare water soluble coating for food packaging to reduce bacteria contamination. Esters of itaconic acid can be used in paint, ion-exchange resin, lubricant, binder, plasticizer, sealant and molding plastics.
APPLICATIONS
Acrylic Fibre, Binder, Coatings, Lubricants, Paper coatings, Plastizisers, Sealants, Metal, Concrete paint, Paints, Coatings, leather, Coatings, automotive, Coatings, emulsion, Electronics
Other names
2-Methylenesuccinic acid
Methylenesuccinic acid
1-Propene-2-3-dicarboxylic acid
CAS Number: 97-65-4
Production
Since the 1960s, it is produced industrially by the fermentation of carbohydrates such as glucose or molasses using fungi such as Aspergillus itaconicus or Aspergillus terreus.
For A. terreus the itaconate pathway is mostly elucidated.
The generally accepted route for itaconate is via glycolysis, tricarboxylic acid cycle, and a decarboxylation of cis-aconitate to itaconate via cis-aconitate-decarboxylase.[3]
The smut fungus Ustilago maydis uses an alternative route. Cis-aconitate is converted to the thermodynamically favoured trans-aconitate via aconitate-Δ-isomerase (Adi1).
trans-Aconitate is further decarboxylated to itaconate by trans-aconitate-decarboxylase (Tad1).
Itaconic acid is also produced in cells of macrophage lineage.
It was shown that itaconate is a covalent inhibitor of the enzyme isocitrate lyase in vitro.
As such, itaconate may possess antibacterial activities against bacteria expressing isocitrate lyase (such as Salmonella enterica and Mycobacterium tuberculosis).
However, cells of macrophage lineage have to “pay the price” for making itaconate, and they lose the ability to perform mitochondrial substrate-level phosphorylation.
Reactions
Upon heating, itaconic anhydride isomerizes to citraconic acid anhydride, which can be hydrolyzed to citraconic acid (2-methylmaleic acid).
Laboratory synthesis
Dry distillation of citric acid affords itaconic anhydride, which undergoes hydrolysis to itaconic acid.
Partial hydrogenation of itaconic acid over Raney nickel affords 2-methylsuccinic acid.
Itaconic acid is primarily used as a co-monomer in the production of acrylonitrile butadiene styrene and acrylate latexes with applications in the paper and architectural coating industry.
The global itaconic acid market is forecast to reach USD 121.9 Million by 2026, according to a new report by Reports and Data.
Itaconic acid includes a variety of products, such as Styrene Butadiene, Methyl Methacrylate, Polyitaconic Acid, Unsaturated Esters, 2-methyl-1, 4-BDO, and 3-methyl-THF, among others.
Itaconic acid is largely used for applications in synthetic latex, superabsorbent polymers, chilling dispersant agents, unsaturated polyester resins, methyl methacrylate, and detergent builders.
Itaconic acid is a white crystalline powder having a hygroscopic property and a specific odor.
Its melting point is 167–168 °C and the boiling point is 268 °C.
Water solubility is 83.1 g l−1, and a solution (80 mg l−1) of itaconic acid in pure water has a pH of 2.0.
The density of itaconic acid is 1.63 (20 °C). The pKa values of itaconic acid, its two dissociation steps, are 3.84 and 5.55 (25 °C).
The equilibrium constants are K1 = 1.4 × 10−4 and K2 = 3.6 × 10−6 (25 °C).
Itaconic acid is mainly used in the plastic and paint industry.
It is an unsaturated dicarbonic acid, and can readily be incorporated into polymers and used at a concentration of 1–5% (w/w) as a comonomer in polymers.
The polymerized methyl, ethyl, or vinyl esters of itaconic acid are used as plastics, adhesives elastomers, and coatings.
Styrene butadiene copolymers containing itaconic acid yield rubber-like resins of excellent strength and flexibility and water-proofing coatings with good electrical insulation.
Other fields for use are synthetic fibers, lattices, detergents, and cleaners.
On the other hand, several mono- and diesters of partially substituted itaconic acid possess anti-inflammatory or analgesic activities, and a special new market has opened for the use of itaconic acid pharmaceutical fields. A small quantity of itaconic acid is used as acidulant.
Itaconic acid is an example of a di-carbonic unsaturated acid.
These acids are used as building blocks for large numbers of compounds, such as resins, paints, plastics, and synthetic fibers (acrylic plastic, super absorbants, and antiscaling agents) [67].
Itaconic acid (2-methylenesuccinic acid, 1-propene-2–3-dicarboxylic acid) is an unsaturated, weak dicarboxylic acid (pKa =3.83 and 5.41), discovered in 1837 as a thermal decomposition product of citric acid.
The presence of the conjugated double bond of the methylene group allows polymerization both by addition and condensation. Esterification of the two carboxylic groups with different co-monomers is also possible (Kuenz et al., 2012). These diverse properties have led to a variety of applications in the pharmaceutical, architectural, paper, paint, and medical industries such as plastics, resins, paints, synthetic fibers, plasticizers, and detergents. Recently, itaconic acid applications have penetrated the dental, ophthalmic and drug delivery fields (Hajian and Yusoff, 2015). Itaconic acid polymers could even replace the petroleum-based polyacrylic acid, which has a multi-billion dollar market (Saha et al., 2019). Not surprisingly, the US Department of Energy assigned itaconic acid as one of the top 12 most promising building block chemicals for bio-based economy in 2004.
However, to fulfill its potential, the selling price of itaconic acid – currently at approximately $2.0 kg−1 – must drop considerably.
Many of the plants in developed countries have therefore relocated to China, which now accounts for the overwhelming majority of global itaconic acid production, estimated at 42,000 tons per year (Geiser et al., 2016).
Little is known about the reasons why fungi produce itaconate.
Like the other organic acids, as outlined above, also itaconic acid might serve as acidifier of the environment and thus provide selective advantage for the acid-tolerant A. terreus over other micro-organisms. However, itaconic acid also has clear inhibitory properties: in macrophages of mammals, bacterial infection prompts the induction of a gene encoding a cis-aconitate decarboxylase, resulting in itaconic acid formation that inhibits bacterial metabolism as part of the immune response
Itaconic acid (methylenesuccinic acid, C5H6O4) (Figure 17) is a white colorless crystalline, hygroscopic powder soluble in water, ethanol, and acetone.
It is an unsaturated diprotic acid, which derives its unique chemical properties from the conjugation of one of its two carboxylic acid groups with its methylene group.
Itaconic acid is produced in batch fermentation in a process largely similar to that of citric acid.
The carbon source should be in an easily metabolizable form (glucose syroup, molasses, and crude starch hydrolysates) and diluted to approximately 10% wt.
Itaconic acid (or methylenesuccinic acid, CAS 97-65-4) is an unsaturated organic diacid.
That unsaturation makes itaconic acid a possible substitute for acrylic acid as a platform chemical, because it can be polymerized in a similar way—by addition
Itaconic acid or methylene succinic acid is a high-value platform chemical that finds application in polymer industry, wastewater treatment, and ion-exchange chromatography sector (Willke and Vorlop, 2001). It can be converted to 3-methyltetrahydrofuran that has superior emission and combustion properties when compared to gasoline. Industrial production of itaconic acid is carried out with A. terreus using glucose as the sole carbon source. Itaconic acid production by metabolically engineered Neurospora crassa using lignocellulosic biomass was evaluated by Zhao et al. (2018). Cis-aconitic acid decarboxylase gene was heterologously expressed in N. crassa to synthesize itaconic acid. The engineered strain was capable of producing itaconic acid (20.41 mg/L) directly from lignocellulosic biomass.
Itaconic acid production from biomass hydrolyzate using Aspergillus strains was reported by Jiménez-Quero et al. (2016). Acid and enzymatic hydrolyzates were evaluated for the production of itaconic acid. Maximum itaconic acid production (0.14%) was observed when submerged fermentation was carried out with corncob hydrolyzate by A. oryzae.
Itaconic acid or methylenesuccinic acid is a five-carbon unsaturated dicarboxylic acid with one carboxyl group conjugated to the methylene group.
Itaconic acid is a white crystalline powder having a hygroscopic property and a specific odor.
Its melting point is 167–168 °C and the boiling point is 268 °C.
Water solubility is 83.1 g l−1, and a solution (80 mg l−1) of itaconic acid in pure water has a pH of 2.0.
The density of itaconic acid is 1.63 (20 °C).
The pKa values of itaconic acid, its two dissociation steps, are 3.84 and 5.55 (25 °C).
The equilibrium constants are K1 = 1.4 × 10−4 and K2 = 3.6 × 10−6 (25 °C).
Itaconic acid is mainly used in the plastic and paint industry.
It is an unsaturated dicarbonic acid, and can readily be incorporated into polymers and used at a concentration of 1–5% (w/w) as a comonomer in polymers.
The polymerized methyl, ethyl, or vinyl esters of itaconic acid are used as plastics, adhesives elastomers, and coatings.
Styrene butadiene copolymers containing itaconic acid yield rubber-like resins of excellent strength and flexibility and water-proofing coatings with good electrical insulation.
Other fields for use are synthetic fibers, lattices, detergents, and cleaners.
On the other hand, several mono- and diesters of partially substituted itaconic acid possess anti-inflammatory or analgesic activities, and a special new market has opened for the use of itaconic acid pharmaceutical fields.
A small quantity of itaconic acid is used as acidulant.
Itaconic acid is an example of a di-carbonic unsaturated acid.
These acids are used as building blocks for large numbers of compounds, such as resins, paints, plastics, and synthetic fibers (acrylic plastic, super absorbants, and antiscaling agents)
Itaconic acid is an important building block in the chemical industry.
It is a white crystalline powder and readily biodegrades in soil.
Hence, it is an optimum substitute for petro-derived chemicals such as acrylic acid, maleic anhydride, or acetone cyanohydrin in various end-user industries.
The demand for itaconic acid is high in the manufacturing of superabsorbent polymers, mainly used in diapers, adult incontinence, and feminine hygiene products.
Itaconic acid is used as a cross-linking agent due to its ability to efficiently take part in addition polymerization.
It also finds large application in seed coating, root dipping, ornamental gardens, food packaging, and artificial snow.
Moreover, increasing demand for unsaturated polyester resins in pipes, artificial stones, electrical cabinets, and laminating resins is expected to increase the demand for itaconic acid.
High price of itaconic acid is the major factor hampering the growth of itaconic acid market.
Polyitaconic acid (a derivative of itaconic acid) has the potential to replace sodium tripolyphosphate in detergents.
However, strong establishment of other phosphate-free builders impedes the growth of itaconic acid in detergents application.
Other application segments include lubricant oil, adhesives, paints and coatings, pharmaceuticals, emulsifiers, herbicides, printing chemicals, and acrylic fiber.
The global market is estimated to be worth around US $126 million/kg (TMR, 2015).
The production in China has boomed, and as a result, the market price decreased to around US $2/kg or even lower (Boy and Lappe, 2012).
Itaconic acid is a biobased product mainly produced by fermentation using certain filamentous fungi (e.g. Ustilago, Helicobasidium, and Aspergillus).
A mixture of itaconic acid, citraconic acid, and citraconic anhydride is also obtained by reaction of succinic anhydride with formaldehyde at 200–500°C in the presence of alkali or alkaline earth hydroxides.
Other methods involve carbonylation of propargyl chloride with metal carbonyl catalysts and thermal decomposition of citric acid, which is also a biobased chemical.
Aspergillus terreus is the strain commonly used for the industrial production of itaconic acid.
A significant amount of research has been put into the reduction of the production costs:
the replacement of sugar, used as the carbon source, by cheaper alternative substrates such as cellulolytic biomass; optimizing the bioreactor type and configuration; deriving innovations by which the process becomes more energy saving; strain improvement by genetic and metabolic engineering, allowing the effective use of cheap alternative substrates, etc.
Recent patent activity has particularly focused on the improvement of the producing strain, mainly by using recombinant DNA techniques, and several patents have been submitted worldwide in the last 10 years.
There is a significant market opportunity for the development of biobased products from the C5 building block, itaconic acid.
The major challenges are primarily associated with reducing the overall cost of the fermentation.
Itaconic acid (or methylenesuccinic acid, CAS 97-65-4) is an unsaturated organic diacid.
That unsaturation makes itaconic acid a possible substitute for acrylic acid as a platform chemical, because it can be polymerized in a similar way—by addition.
Itaconic acid
97-65-4
2-Methylenesuccinic acid
Methylenebutanedioic acid
METHYLENESUCCINIC ACID
itaconate
Propylenedicarboxylic acid
2-methylidenebutanedioic acid
Butanedioic acid, methylene-
2-Propene-1,2-dicarboxylic acid
Succinic acid, methylene-
2-methylenebutanedioic acid
Poly(itaconic acid)
Itaconic acid polymers
Itaconic acid polymer
butanedioic acid, 2-methylene-
MFCD00004260
Methylenesuccinic acid polymers
Poly(2-methylenesuccinic acid)
UNII-Q4516562YH
AI3-16901
HSDB 5308
NSC 3357
EINECS 202-599-6
2-Methylene-Succinic Acid
Butanedioic acid, methylene-, homopolymer
CHEMBL359159
CHEBI:30838
NSC3357
Succinic acid, methylene- (8CI)
Q4516562YH
Itaconic acid, 99+%
DSSTox_CID_6608
DSSTox_RID_78161
2-methylenebutanedioate
DSSTox_GSID_26608
25119-64-6
CAS-97-65-4
Methylenesuccinate
Methylenebutanedioate
Succinic acid, methylene-, polymers
2-Methylenesuccinate
Methylensuccinic Acid
Propylenedicarboxylate
Methylenesuccinic acid|
ACMC-1CFCS
Itaconic acid, >=99%
bmse000137
Probes1_000076
Probes2_000247
EC 202-599-6
2-Methylenesuccinic acid #
NCIStruc1_001783
NCIStruc2_000502
2-methylene-butanedioic acid
NCIOpen2_004822
SCHEMBL21523
KSC486Q9J
2-Propene-1,2-dicarboxylate
DTXSID2026608
CTK3I6894
Itaconic acid, analytical standard
ZINC895261
HY-Y0520
KS-00000W8Q
NSC-3357
Tox21_201299
Tox21_303071
ANW-40876
BBL011584
BDBM50036216
LMFA01170063
Propylenedicarboxylic acid 97-65-4
s3095
STL163322
AKOS000118895
2-Hydroxy-3-Naphthoyl-2-Naphthylamine
MCULE-5221256796
NE10303
Butanedioic acid,ethylidene-,(E)-(9ci)
NCGC00249019-01
NCGC00257141-01
NCGC00258851-01
144368-21-8
AS-11816
LS-45750
LS-180669
Succinic acid, methylene-, polymers (8CI)
Itaconic acid is an unsaturated dicarbonic acid which has a high potential as a biochemical building block, because it can be used as a monomer for the production of a plethora of products including resins, plastics, paints, and synthetic fibers
Itaconic acid is well known as a precursor for polymer synthesis and has been involved in industrial processes for decades. In a recent surprising discovery, itaconic acid was found to play a role as an immune-supportive metabolite in mammalian immune cells, where it is synthesized as an antimicrobial compound from the citric acid cycle intermediate cis-aconitic acid.
Itaconic acid (2-methylidenebutanedioic acid) can be produced by microorganisms and has commercial value as a precursor of polymers, chemicals and fuels
What is itaconic acid?
Itaconic acid, also known as 2-methylidenebutanedioic acid, is an unsaturated dicarbonic acid.
It is considered to be a value-added product from biomass by the US Department of Energy, as it can be utilized as a precursor of polymers and chemical intermediates.
These include synthetic fibers, resins, paint, acrylic plastics, acrylate latexes, super-absorbent materials, anti-scaling agents, styrene, 2-methyl-1,4-butanediol, and 3-methytetrahydrofuran. Itaconic acid has also shown some antimicrobial capabilities.
How is itaconic acid produced by microorganisms?
Some microorganisms have the capability of producing itaconic acid by fermentation.
These are mainly fungal species and include Ustilago zeae, Ustilago maydis, species of Candida and Rhodotorula.
The main producer is the fungal species Aspergillus terreus, which can produce as much as 86g/L.
While this may seem high, it is not as high as levels of citric acid which can be produced, which is as much as 200g/L.
Biosynthetic pathway
Itaconic acid is produced from a citric acid cycle intermediate, cis-aconitate, which is formed from citric acid.
As it is linked to the citric acid cycle, itaconic acid can be produced from sugars such as glucose.
Initially, glucose is broken down into pyruvate by glycolysis, which is further converted into acetyl-CoA with the release of CO2.
Acetyl-CoA then joins the citric acid cycle, where the first steps form cis-aconitate.
Alternatively, pyruvate can be converted to oxalate by the addition of CO2, which is further converted to malate, another molecule involved in the citric acid cycle.
Producing itaconic acid on an industrial scale
Once itaconic acid is produced, it needs to be separated from the fermentation culture, typically by filtration and crystallization, before it is decolorized and dried. Crystallization is where the bulk of itaconic acid is recovered, and the yield is typically around 80%.
Other processes can be used in place of crystallization, including precipitation, liquid-liquid extraction, membrane separation and adsorption.
1759501 [Beilstein]
202-599-6 [EINECS]
2-Methylenbernsteinsäure [German] [ACD/IUPAC Name]
2-Methylenbutandisäure [German]
2-Methylenesuccinic acid [ACD/IUPAC Name]
2-methylidenebutanedioic acid
97-65-4 [RN]
Acide 2-méthylènesuccinique [French] [ACD/IUPAC Name]
Butanedioic acid, 2-methylene- [ACD/Index Name]
Itaconic acid [Wiki]
Methylenesuccinic acid
MFCD00004260 [MDL number]
144368-21-8 [RN]
2-methylenebutanedioate
2-METHYLENEBUTANEDIOIC ACID
2-Methylene-succinic acid
2-propene-1,2-dicarboxylic acid
3-Carboxy-3-butenoic Acid
5363-69-9 [RN]
Butanedioic acid, methylene-
Butanedioic acid,ethylidene-,(E)-(9ci)
http:////www.amadischem.com/proen/522824/
https://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:30838
Itaconic acid;Methylenesuccinic acid
itaconicacid
ITN
Methylenebutanedioic acid
Methylensuccinic Acid
N-(6-methoxy-2-pyridyl)-2,2-dimethyl-propanamide
propylenedicarboxylic acid
succinic acid, methylene-
衣康酸 [Chinese]
衣康酸
Itaconate;
Itaconic acid;
Methylenesuccinic acid
Chemical Properties
white to light beige crystalline powder
Uses
Copolymerizations, resins, plasticizers, lube-oil additive, intermediate.
Uses
The major uses for itaconic acid are in copolymerizations, resins, plasticizers, and as lube oil additives.
Definition
itaconic acid: A product of the fermentationof the flamentous fungus Aspergillus niger. Itaconic acid is usedcommercially in the production ofadhesives and paints.
Itaconic Acid (IA) is gradually emerging as a new high-technology industry across the globe.
With rising concerns of diminishing fossil fuel resources, efforts are being made to produce chemicals from green feedstock rather than petrochemical raw materials.
IA, although widely sourced from petrochemical feedstock, has the ability of being produced from renewable resources and is therefore being viewed as an ideal bio-based platform chemical for the chemicals industry.
Currently, production of the organic compound is mainly restricted to a limited number countries such as China, US, Japan and Russia, resulting in global production being much lower than the actual demand.
The consumption of Itaconic Acid is widespread, spanning across various sectors including artificial jewelry, specialty lens, pesticides, plastic additive, dental agglutinant, boiler rust remover, plastics, synthetic rubber and chemical fibers among others.
Market opportunities for the acid in the form of new applications areas are expected in the near future, with efforts currently being focused on extending applicability to biomedical fields such as drug delivery, dentistry, and ophthalmology.
Synonyms:
butanedioic acid, 2-methylene-
itaconicacid
methylene butane dioic acid
methylene succinic acid
methylenebutanedioic acid
2- methylenebutanedioic acid
methylenesuccinic acid
2- methylenesuccinic acid
2- methylidenebutanedioic acid
2- propene-1,2-dicarboxylic acid
propylene dicarboxylic acid
succinic acid, methylene- (8CI)
Itaconic acid is a dicarboxylic acid that is methacrylic acid in which one of the methyl hydrogens is substituted by a carboxylic acid group.
It has a role as a fungal metabolite and a human metabolite.
It is a dicarboxylic acid and an olefinic compound.
It derives from a succinic acid.
It is a conjugate acid of an itaconate(2-).
Methylenebutanedioic acid
Methylenesuccinic acid
Propylenedicarboxylic acid
Succinic acid, methylene-
Succinic acid, methylene- (8CI)
2-Propene-1,2-dicarboxylic acid
Butanedioic acid, 2-methylene-
Butanedioic acid, methylene-
Itaconic acid
Itaconic acid
itaconic acid
2-Methylenebutanedioic acid
2-Methylenesuccinic acid
2-methylenesuccinic acid
2-Methylidenebutanedioic acid
2-methylidenebutanedioic acid
Butanedioic acid, 2-methylene-
Itaconic Acid
Itaconic acid
itaconic acid
Itaconic acid
itaconic acid
Itaconsäure
Trade names
2-Methylenebutanedioic acid
ITACONIC ACID
Butanedioic acid, 2-methylene-
BUTANEDIOIC ACID, METHYLENE-