100-21-0 Usage
Chemical Properties
Different sources of media describe the Chemical Properties of 100-21-0 differently. You can refer to the following data:
1. Terephthalic acid is poorly soluble in water and alcohols, consequently up until around 1970 most crude terephthalic acid was converted to the dimethyl ester for purification. It sublimates when heated.
2. TPA is a white crystalline solid.
3. white powder
History
Terephthalic acid came to prominence through the work of Winfield and Dickson in Britain around 1940. Earlier work by Carothers and coworkers in the United States established the feasibility of producing high molecular weight linear polyesters by reacting diacids with diols, but they used aliphatic diacids and diols. These made polyesters which were unsuitable to be spun into fibers. Winfield and Dickson found that symmetrical aromatic diacids yield high-melting, crystalline, and fiberforming materials; poly(ethylene terephthalate) (PET) has since become the largest volume synthetic fiber.
Uses
Different sources of media describe the Uses of 100-21-0 differently. You can refer to the following data:
1. Terephthalic acid (TPA) is a high-tonnage chemical, widely used in the production of synthetic materials, notably polyester fibers (poly-(ethylene terephthalate)).
2. Terephthalic acid is a benzenepolycarboxylic acid with potential anti-hemorrhagic properties.
3. 1,4-benzenedicarboxylic acid is mainly used for the production of poly (ethylene terephthalate). Also production of plasticizer dioctyl phthalate (DOTP) and polyester plasticized agents. 1,4-benzenedicarboxylic acid and polyhydric alcohols have a condensation reaction withd iethylene glycol, triethylene glycol, glycerol, propylene glycol, butylene glycol, etc. preparation of the polyester plasticizer.
Definition
ChEBI: A benzenedicarboxylic acid carrying carboxy groups at positions 1 and 4. One of three possible isomers of benzenedicarboxylic acid, the others being phthalic and isophthalic acids.
Application
Virtually the entire world's supply of terephthalic acid and dimethyl terephthalate are consumed as precursors to polyethylene terephthalate (PET). World production in 1970 was around 1.75 million tones. By 2006, global purified terephthalic acid (PTA) demand had exceeded 30 million tonnes. There is a smaller, but nevertheless significant, demand for terephthalic acid in the production of poly butylene terephthalate and several other engineering polymers.
Production Methods
Different sources of media describe the Production Methods of 100-21-0 differently. You can refer to the following data:
1. Terephthalic acid is produced by oxidation of p-xylene by oxygen in air: This reaction proceeds through a p-toluic acid intermediate which is then oxidized to terephthalic acid. In p-toluic acid, deactivation of the methyl by the electron withdrawing carboxylic acid group makes the methyl one tenth as reactive as xylene itself, making the second oxidation significantly more difficult . The commercial process utilizes acetic acid as solvent and a catalyst composed of cobalt and manganese salts, with a bromide promoter.
2. Benzoic acid, phthalic acid and other benzene-carboxylic acids in the form of alkali-metal salts, comprise the chargestock. In a first step, the alkali-metal salts (usually potassium) are converted to terephthalates when heated to a temperature exceeding 350 °C (662 °F). The dried potassium salts (of benzoic acid or o- or isophthalic acid) are heated in anhydrous form to approximately 420 °C (788 °F) in an inert atmosphere (CO2) and in the presence of a catalyst (usually cadmium benzoate, phthalate, oxide, or carbonate). The corresponding zinc compounds also have been used as catalysts. In a following step, the reaction products are dissolved in H2O and the terephthalic acid precipitated out with dilute H2SO4. The yield of terephthalic acid ranges from 95 to 98%.
Preparation
The major commercial route to terephthalic acid which is suitable for the
direct preparation of poly(ethylene terephthalate) is from p-xylene:
p-Xylene is obtained largely from petroleum sources, being a product of the
fractionation of reformed naphthas. The oxidation is carried
out in the liquid phase. Typically, air is passed into a solution of p-xylene in
acetic acid at about 200℃ and 2 MPa (20 atmospheres) in the presence of a
catalyst system containing cobalt and manganese salts and a source of
bromide ions. The terephthalic acid produced contains only small amounts of
impurities (mainly p-carboxybenzaldehyde), which are readily removed. The
acid is dissolved in water at about 2500 e and 5 MPa (50 atmospheres) and
treated with hydrogen (which converts the aldehyde to p-toluic acid). The
solution is then cooled to 100℃ and pure terephthalic acid crystallizes.
Synthesis Reference(s)
Chemistry Letters, 15, p. 299, 1986Journal of the American Chemical Society, 82, p. 2876, 1960 DOI: 10.1021/ja01496a051The Journal of Organic Chemistry, 44, p. 4727, 1979 DOI: 10.1021/jo00393a063
General Description
White powder.
Air & Water Reactions
Insoluble in water.
Reactivity Profile
Terephthalic acid is a carboxylic acid. Terephthalic acid donates hydrogen ions if a base is present to accept them. This "neutralization" generates substantial amounts of heat and produces water plus a salt. Insoluble in water but even "insoluble" carboxylic acids may absorb enough water from the air and dissolve sufficiently in Terephthalic acid to corrode or dissolve iron, steel, and aluminum parts and containers. May react with cyanide salts to generate gaseous hydrogen cyanide. Will react with solutions of cyanides to cause the release of gaseous hydrogen cyanide. Flammable and/or toxic gases and heat are generated by reaction with diazo compounds, dithiocarbamates, isocyanates, mercaptans, nitrides, and sulfides. React with sulfites, nitrites, thiosulfates (to give H2S and SO3), dithionites (SO2), to generate flammable and/or toxic gases and heat. Reaction with carbonates and bicarbonates generates a harmless gas (carbon dioxide) but still heat. Can be oxidized by strong oxidizing agents and reduced by strong reducing agents. These reactions generate heat. May initiate polymerization reactions; may catalyze (increase the rate of) chemical reactions.
Fire Hazard
Flash point data for Terephthalic acid are not available. Terephthalic acid is probably combustible.
Flammability and Explosibility
Nonflammable
Safety Profile
Moderately toxic by intravenous and intraperitoneal routes. Mildly toxic by ingestion. An eye irritant, Can explode during preparation. When heated to decomposition it emits acrid smoke and irritating fumes.
Potential Exposure
TPA is used primarily in the production of polyethylene terephthalate polymer for the fabrication of polyester fibers and films. A high-volume production chemical in the United States.
Purification Methods
Purify the acid via the sodium salt which, after crystallisation from water, is re-converted to the acid by acidification with mineral acid. Filter off the solid, wash it with H2O and dry it in a vacuum. The S-benzylisothiuronium salt has m 204o (from aqueous EtOH). [Beilstein 9 IV 3301.]
Incompatibilities
Combustible; dust may form an explosive mixture with air. Compounds of the carboxyl group react with all bases, both inorganic and organic (i.e., amines) releasing substantial heat, water and a salt that may be harmful. Incompatible with arsenic compounds (releases hydrogen cyanide gas), diazo compounds, dithiocarbamates, isocyanates, mercaptans, nitrides, and sulfides (releasing heat, toxic and possibly flammable gases), thiosulfates and dithionites (releasing hydrogen sulfate and oxides of sulfur). Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides.
Waste Disposal
Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed.
Check Digit Verification of cas no
The CAS Registry Mumber 100-21-0 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,0 and 0 respectively; the second part has 2 digits, 2 and 1 respectively.
Calculate Digit Verification of CAS Registry Number 100-21:
(5*1)+(4*0)+(3*0)+(2*2)+(1*1)=10
10 % 10 = 0
So 100-21-0 is a valid CAS Registry Number.
InChI:InChI=1/C8H6O4/c1-9-5-13-18(24,15(9)22)7-11(8-21)6-12-14-17(3,4)20(14,26)16(23)10(2)19(12,13)25/h5-6,10,12-14,16,21,23-26H,7-8H2,1-4H3/t10-,12+,13-,14-,16-,18-,19-,20-/m1/s1
100-21-0Relevant articles and documents
Highly efficient conversion of aldehydes to carboxylic acid in the presence of platinum porphyrin sensitizers, air and sunlight
Hajimohammadi, Mahdi,Mofakham, Hamid,Safari, Nasser,Manesh, Anahita Mortazavi
, p. 93 - 100 (2012)
A variety of aromatic and aliphatic aldehydes were oxidized to the corresponding carboxylic acids in the presence of platinum porphyrin, sunlight and air in acetonitrile solvent under mild conditions. Nitrobenzaldehydes were found to be very efficient 1O2 scavengers that quench the formation of acids from any aldehyde in the presence of free-base porphyrin sensitizers. However, nitrobenzaldehydes were converted to the corresponding acids in the presence of platinum porphyrins. The platinum porphyrins are very good and efficient catalysts for a wide range of applications in the aerobic conversion of aldehydes to acids.
N-hydroxyphthalimide-catalyzed oxidative production of phthalic acids from xylenes using O2/HNO3 in an ionic liquid
Yavari, Issa,Karimi, Elham
, p. 3420 - 3427 (2009)
A simple and mild process for oxidation of xylenes to phthalic acids using N-hydroxyphthalimide/O2/HNO3 in an ionic liquid, wherein the ionic liquid can be successfully recovered and reused, is described.
Liquid-phase oxidation of p-xylene using N-hydroxyimides
Falcon,Campos-Martin,Al-Zahrani,Fierro
, p. 5 - 8 (2010)
In this communication, we describe p-xylene oxidation with molecular oxygen at 373 K and atmospheric pressure using N-hydroxyimide catalysts. p-Xylene conversion was rather high over the first 2 h of reaction and complete by the end of the experiment. The
Efficient oxidation of p-xylene to terephthalic acid by using N,N-dihydroxypyromellitimide in conjunction with Co-benzenetricarboxylate
Chen, Dawei,Jiang, Haoran,Xu, Luo,Yuan, Xia
, (2020)
The MOF Co-BTC (BTC = benzenetricarboxylate) has been synthesized by a hydrothermal method, and characterized by means of N2 physical adsorption, X-ray diffraction, scanning electron microscope, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The material has multiple crevices, as opposed to a pore structure, and shows high thermal stability, with Co in the divalent state. It has been used in conjunction with N,N-dihydroxypyromellitimide to catalyze the oxidation of p-xylene to terephthalic acid, the reaction conditions for which have been investigated and optimized. At 150 °C, with acetonitrile as solvent instead of acetic acid and in the absence of corrosive bromine, the conversion of p-xylene reached 100 % and the selectivity for terephthalic acid exceeded 97 %. Under the optimized conditions, Co-BTC exhibits stronger catalytic activity than cobalt(II) acetate, and maintains excellent stability during the reaction. The reaction mechanism has been deduced, and the roles of N,N-dihydroxypyromellitimide and Co-BTC as synergistic catalysts in the reaction have been clarified.
Novel oxidation of toluenes catalyzed by reusable vanadyl(IV) sulfate under mild conditions with molecular oxygen
Nakai, Takeo,Iwai, Toshiyuki,Mihara, Masatoshi,Ito, Takatoshi,Mizuno, Takumi
, p. 2225 - 2227 (2010)
Efficient oxidation system using reusable vanadyl(IV) sulfate catalyst was established. Toluenes were easily oxidized under molecular oxygen (0.1 MPa) at 100 °C catalyzed by vanadyl(IV) sulfate to afford the corresponding benzoic acids in excellent yields. The recovered catalyst could be reused without loss of activity.
A new and efficient aerobic oxidation of aldehydes to carboxylic acids with singlet oxygen in the presence of porphyrin sensitizers and visible light
Hajimohammadi, Mahdi,Safari, Nasser,Mofakham, Hamid,Shaabani, Ahmad
, p. 4061 - 4065 (2010)
A new aerobic route is introduced for the oxidation of a variety of aromatic and aliphatic aldehydes to the corresponding carboxylic acid derivatives using molecular oxygen in the presence of tetraphenylporphyrin (H2TPP), tetramesitylporphyrin (H2TMP), tetrakisdichlorophenylporphyrin (H2TDCPP), ZnTPP, and ZnTMP as sensitizers using visible light in an organic solvent. The method has a wide range of applications, does not involve cumbersome work-up, exhibits chemoselectivity, and proceeds under mild reaction conditions. The products are obtained with good conversions and in reasonable reaction times.
One-Pot Enzyme Cascade for Controlled Synthesis of Furancarboxylic Acids from 5-Hydroxymethylfurfural by H2O2 Internal Recycling
Jia, Hao-Yu,Zong, Min-Hua,Zheng, Gao-Wei,Li, Ning
, p. 4764 - 4768 (2019)
Furancarboxylic acids are promising biobased building blocks in pharmaceutical and polymer industries. In this work, dual-enzyme cascade systems composed of galactose oxidase (GOase) and alcohol dehydrogenases (ADHs) are constructed for controlled synthesis of 5-formyl-2-furancarboxylic acid (FFCA) and 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF), based on the catalytic promiscuity of ADHs. The byproduct H2O2, which is produced in GOase-catalyzed oxidation of HMF to 2,5-diformylfuran (DFF), is used for horseradish peroxidase (HRP)-mediated regeneration of the oxidized nicotinamide cofactors for subsequent oxidation of DFF promoted by an ADH, thus implementing H2O2 internal recycling. The desired products FFCA and FDCA are obtained with yields of more than 95 %.
Synthesis, characterization and catalytic activity of manganese(II)-cobalt(II) complexes anchored SBA-16 for liquid phase oxidation of p-xylene
Nui, Pham Xuan,Dung, Nguyen Nho,Van Thi, Tran Thi
, p. 1486 - 1492 (2016)
In this study, the results of synthesis and modified mesoporous surface of SBA-16 by using Schiff-base complexes [Co(II)-Mn(II)-Sal-APTES] were presented. Manganese(II) and cobalt(II)-Schiff bases complexes were synthesized by reaction between salicylalde
Selectively Upgrading Lignin Derivatives to Carboxylates through Electrochemical Oxidative C(OH)?C Bond Cleavage by a Mn-Doped Cobalt Oxyhydroxide Catalyst
Zhou, Hua,Li, Zhenhua,Xu, Si-Min,Lu, Lilin,Xu, Ming,Ji, Kaiyue,Ge, Ruixiang,Yan, Yifan,Ma, Lina,Kong, Xianggui,Zheng, Lirong,Duan, Haohong
, p. 8976 - 8982 (2021)
Oxidative cleavage of C(OH)?C bonds to afford carboxylates is of significant importance for the petrochemical industry and biomass valorization. Here we report an efficient electrochemical strategy for the selective upgrading of lignin derivatives to carboxylates by a manganese-doped cobalt oxyhydroxide (MnCoOOH) catalyst. A wide range of lignin-derived substrates with C(OH)-C or C(O)-C units undergo efficient cleavage to corresponding carboxylates in excellent yields (80–99 %) and operational stability (200 h). Detailed investigations reveal a tandem oxidation mechanism that base from the electrolyte converts secondary alcohols and their derived ketones to reactive nucleophiles, which are oxidized by electrophilic oxygen species on MnCoOOH from water. As proof of concept, this approach was applied to upgrade lignin derivatives with C(OH)-C or C(O)-C motifs, achieving convergent transformation of lignin-derived mixtures to benzoate and KA oil to adipate with 91.5 % and 64.2 % yields, respectively.
Synthesis of Dicarboxylic Acids from Aqueous Solutions of Diols with Hydrogen Evolution Catalyzed by an Iridium Complex
Fujita, Ken-ichi,Toyooka, Genki
, (2020)
A catalytic system for the synthesis of dicarboxylic acids from aqueous solutions of diols accompanied by the evolution of hydrogen was developed. An iridium complex bearing a functional bipyridonate ligand with N,N-dimethylamino substituents exhibited a high catalytic performance for this type of dehydrogenative reaction. For example, adipic acid was synthesized from an aqueous solution of 1,6-hexanediol in 97 % yield accompanied by the evolution of four equivalents of hydrogen by the present catalytic system. It should be noted that the simultaneous production of industrially important dicarboxylic acids and hydrogen, which is useful as an energy carrier, was achieved. In addition, the selective dehydrogenative oxidation of vicinal diols to give α-hydroxycarboxylic acids was also accomplished.
