335-67-1

Usage

Uses

1. Used in Chemical Synthesis:
Pentadecafluorooctanoic acid is used as a fluorinated surfactant, primarily as its ammonium salt (APFO), as an aid in the chemical synthesis of fluoropolymers and fluoroelastomers. This application is the primary use of PFOA, and it can be found in various products such as nonstick cookware and utensils, stain-repellant fabric treatments, and waterproof treatments for garments.
2. Used in Electronics, Textiles, and Nonstick Cookware:
PFOA is utilized in the production of fluoropolymers that are used in electronics, textiles, and nonstick cookware. The ammonium salt of PFOA serves as an emulsifier or 'processing aid' in these industrial applications.
3. Used in Aqueous Film-Forming Foams for Firefighting:
PFOA is also used as a fluorosurfactant in aqueous film-forming foams, which are employed for fire fighting purposes.
4. Used as an Ion-Pairing Reagent in Chromatographic Methods:
Pentadecafluorooctanoic acid solution may be used as an ion-pairing reagent in the development of a chromatographic method for the separation and determination of underivatized proteinic amino acids using liquid chromatography with evaporative light scattering detection (LC-ELSD) and atmospheric pressure ionization-mass spectrometry (LC-API-MS).
Environmental and Regulatory Concerns:
Due to concerns about the potential environmental and toxicological impacts of long-chain perfluoroalkyl sulfonates and carboxylic acids, several actions have been taken to reduce the use and emissions of PFOA. These include the phaseout of production by major global manufacturers, stewardship agreements to reduce emissions and product content, restrictions on the use of PFOA in products, and the inclusion of related compounds in the Stockholm Convention on Persistent Organic Pollutants as restricted substances. Efforts are underway by the U.S. EPA and other regulatory bodies to reduce the use of PFOA and replace it with other substances.

Safety Profile

Poison by intraperitoneal route. Mutation data reported. Whenheated to decomposition it emits toxic vapors of Fí.

Environmental Fate

Perfluorooctanoic acid found in the environment may result from waste stream releases from manufacture of cosmetics, lubricants, paints, polishes, adhesives, fabric treatments, and fire-fighting compounds. It can partition to the vapor phase in the atmosphere, where it is degraded atmospherically with a half-life of 31 days. It is very resistant to hydrolysis, and immobile in soil. It will not likely evaporate from soil (depending on soil pH) or surface waters. It is not expected to be absorbed to sediments and suspended particles. Perfluorooctanoic acid is not expected to bioaccumulate in aquatic organisms (BCF =3.1–9.4) (NLM, 2013).

Purification Methods

Crystallise the acid from CCl4 and toluene, and distil it. It forms micelles in H2O and the solubility is 1% in H2O. The acid chloride has b 129-130o/744mm. The amide has m 138o. [Bernett & Zisman J Phys Chem 63 1911 1959, Bro & Sperati J Polym Sci 38 289 1959, Beilstein 2 IV 994.]

Toxicity evaluation

Studies with animals fed PFOA for a long period showed effects on the stomach, liver, and thyroid hormones. Animal studies also indicate that PFOA may cause cancer at relatively high levels. PFOA has also been shown to be a developmental toxicant, and to have effects on the immune system. PFOA affects primarily the liver and can cause developmental and reproductive toxic effects at relatively low dose levels in experimental animals. It increases the tumor incidence in rats, mainly in the liver. The carcinogenic effects in rats appear to be due to indirect/nongenotoxic modes of action. Epidemiological studies in PFOA-exposed workers do not indicate an increased cancer risk. There is relatively consistent evidence of modest positive associations between serum levels of PFOA and cholesterol, uric acid, and liver enzyme levels. The critical effects observed in rodents and monkeys are on the liver and include hypertrophy, changes in liver enzyme activity, and proliferation of peroxisomes. In rodents the anionic form of PFOA induces hepatocellular adenomas, Leydig cell adenomas, and pancreatic hyperplasia. The genotoxic activity of PFOA is a matter of current debate and controversy, with classifications as ‘devoid of significant genotoxicity’ as well as ‘weakly nonspecific genotoxic.’ PFOA does not appear directly genotoxic; animal data indicate that it can cause several types of tumors and neonatal death and may have toxic effects on the immune, liver, and endocrine systems.

Upstream product

• 623-66-5 octanoic acid anhydride 
• 335-58-0 perfluoroheptyl iodide 
• 124-38-9 carbon dioxide 
• 673-32-5 1-Phenylprop-1-yne 
• 507-63-1 1-iodoheptadecafluorooctane 
• 764-93-2 1-decyne 
• 629-05-0 n-octyne 
• 124-07-2 Octanoic acid 
• 590-67-0 1-Methylcyclohexanol 
• 96-41-3 Cyclopentanol 
• 100-49-2 cyclohexylmethyl alcohol 
• 108-93-0 cyclohexanol 
• 111-87-5 octanol 
• 111-27-3 hexan-1-ol 

Downstream Products

• 375-88-2 1-bromopentadecafluoroheptane 
• 307-30-2 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-1-octanol 
• 335-64-8 pentadecafluorooctanoyl chloride 
• 376-27-2 methyl perfluorooctanoate 
• 355-63-5 perfluoro-1-heptene 
• 335-66-0 perfluorooctanoyl fluoride 
• 754-85-8 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononan-2-one 
• 76427-70-8 2,3,3,3-Tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-heptafluoropropyloxy-propoxy)-N-hydroxy-propionamidine 
• 60308-67-0 2,3,3,3-Tetrafluoro-2-(1,1,2,3,3,3-hexafluoro-2-heptafluoropropyloxy-propoxy)-propionamide 
• 335-95-5 sodium perfluorooctanoate 
• 812-72-6 1H,1H-pentadecafluorooctyl allyl ether 
• 81559-39-9 α-Methylphenacyl perflurooctanoate 
• 335-93-3 silver(I) perfluoro-n-hexanesulfonate 
• 124-38-9 carbon dioxide 

Relevant academic research and scientific papers

A rationally designed perfluorinated host for the extraction of PFOA from water utilising non-covalent interactions

Perfluorooctanoic acid (PFOA) is a persistent organic pollutant and widespread in the environment. Three hosts have been synthesized based upon the formation of a fluorous cavity and hydrogen bonding receptors with the aim of extracting PFOA from water into organic solvents. The hosts based upon a calix[4]arene functionalized at the lower rim with amide groups and fluorous ponytails are effective for the quantitative removal of PFOA. Modification to a partial cone or a trisaminoamine framework reduces the conformational rigidity and lowers the extraction efficiency. A comprehensive NMR spectroscopic analysis both in solution and the solid state, along with other characterization techniques, has elucidated the stoichiometry of the host:guest species and the binding constants have been measured. A computational study has given further insight into the binding modes and corroborated the spectroscopic measurements.

Photocatalytic amidation and esterification with perfluoroalkyl iodide

The successful generation of perfluoroalkyl radicals (Rf˙) through photoredox catalysis has inspired us to investigate the preparation of various organofluorine species. In this work, visible light-induced photocatalytic reactions for the preparation of perfluoroalkyl amides and esters from the corresponding amines and alcohols using different types of triplet emitters as photocatalysts have been studied. The effects of the excited-state characteristics and redox potentials of the photocatalysts have been elucidated. Under optimized reaction conditions, these reactions can be performed successfully with different types of amines or alcohols and perfluoroalkyl iodides. Detailed mechanistic studies based on emission quenching experiments have been performed to study the photocatalytic cycles as well as the role of the different reagents. The proposed mechanism has also been examined by DFT calculations.

Preparation method of fluorine-containing carboxylic acid

The invention discloses a preparation method of fluorine-containing carboxylic acid. The method comprises the following steps: reacting fluorine-containing carboxylate used as a raw material with an acylating chlorination reagent to obtain a corresponding mixture of fluorine-containing acyl chloride and fluorine-containing anhydride, and hydrolyzing and drying the mixture of fluorine-containing acyl chloride and fluorine-containing anhydride to obtain high-purity fluorine-containing carboxylic acid. The method provided by the invention is suitable for post-treatment of fluorine-containing carboxylic acid prepared by a fluorine-containing olefin (monoolefine, diene, cycloolefin and the like) oxidation method, replaces the traditional strong acid acidification and ether continuous extractionprocess, and is simpler, more convenient and more applicable; and the method can also be used for recovering and purifying a fluorine-containing carboxylate emulsifier. The purity of the fluorine-containing carboxylic acid prepared by the method can reach 98% or above.

Synthetic method of medicine raw material namely 3-methyl perfluorooctanoic acid

The invention relates to a synthetic method of a medicine raw material namely 3-methyl perfluorooctanoic acid. The synthetic method comprises the following steps of putting raw materials of caprylyl chloride, hydrogen fluoride and a few n-butyl sulfuric acid into an electrolytic cell, performing electrifying (the voltage is 5-8V) at 20-25 DEG C, neutralizing an electrolytic product with an alkali, then sequentially performing acidification and methylation, and finally performing distillation so as to obtain the 3-methyl perfluorooctanoic acid. The synthetic method of the medicine raw material namely the 3-methyl perfluorooctanoic acid disclosed by the invention is simple, efficient, safe to operate and quite practical in specific production.

Hydrolysis of p-nitrophenyl perfluoroctanoate in mixed surfactant systems

The kinetics of the hydrolysis reaction of p-nitrophenyl perfluoroctanoate were studied in the presence of different amphiphilic systems: two hydrocarbon surfactants (sodium dodecyl sulfate, SDS, and polyoxyethylene(23)lauryl ether, Brij-35), a perfluorinated detergent (perfluorononanoic acid, PFNA) and in mixtures of SDS-PFNA and Brij-35-PFNA. The study was performed at different compositions of the mixtures (characterized by the molar fraction of PFNA, αPFNA), and for each αPFNA the concentration was varied over a wide range. The kinetic probe p-nitrophenyl perfluoroctanoate showed a very strong interaction with the surfactants. In the presence of the mixed surfactants, the behaviour of the probe changed dramatically with the composition of the mixtures, which indicates that this substrate is very sensitive to the effect of the micellar media, being a very good molecule to study these types of surfactant systems. The use of the studied ester allowed us to confirm the presence of two different aggregates in the mixture Brij-35-PFNA as was previously observed with other techniques. The presence of hydrocarbon-rich micelles at low αPFNA, as well as perfluorinated rich micelles at high αPFNA was also confirmed. The kinetic behaviour of p-nitrophenyl perfluoroctanoate in SDS-PFNA mixtures fully agreed with our previous description of the aggregates formed in this system. The presence of a practically pure PFNA micelle at high αPFNA could be also demonstrated from the kinetic results.

METHODS OF PREPARING FLUORINATED CARBOXYLIC ACIDS AND THEIR SALTS

A method for preparing fluorinated carboxylic acids and theirs salts is described comprising subjecting a fluorinated alcohol of the general formula (A): A-CH2-OH to at least one first and at least one second oxidizing agent to produce a highly fluorinated carboxylic acid or their salts of the general formula (B): A-COO M+, wherein M+ represents a cation and wherein A in formulas (A) and (B) is the same and A represents the residue: Rf-[0]p-CX"Y"-[0]m-CX'Y'-[0]n-CXY- wherein Rf represents a fluorinated alkyl residue which may or may not contain one or more catenary oxygen atoms, p, m and n are independently from each other either 1 or O, X, X', X", Y, Y' and Y" are independently from each other H, F, CF3, or C2F5 with the proviso that not all of X, X', X", Y, Y' and Y' ' are H; or A represents the residue: R-CFX- wherein X and R are independently selected from a hydrogen, a halogen, or an alkyl, alkenyl, cycloalkyl, or aryl residue, which may or may not contain one or more fluorine atoms and which may or may not contain one or more catenary oxygen atoms; wherein said at least one first oxidizing agent is a compound that can be converted, by action of the second oxidizing agent, into a reactive species capable of oxidizing the fluorinated alcohol.

Efficient mineralization of hydroperfluorocarboxylic acids with persulfate in hot water

The persulfate (S2O82-)-induced decomposition of hydroperfluorocarboxylic acids (H-PFCAs), that is, HCnF2nCOOH (n = 4, 6, and 8), in hot water was investigated, and the results were compared with the

METHOD FOR PRODUCING FLUORINE-CONTAINING CARBOXYLIC ACID OR FLUORINE-CONTAINING CARBOXYLATE

PROBLEM TO BE SOLVED: To provide a method for producing fluorine-containing carboxylic acid or fluorine-containing carboxylate. SOLUTION: The fluorine-containing carboxylic acid [when M in formula (II) is H] or the fluorine-containing carboxylate [when M in formula (II) is a metal], represented by general formula (II) Rf-COOM [wherein Rf is a 1-20C fluoroalkyl; and M is H or the metal], is produced by reacting a fluorine-containing alkene of general formula (I) Rf-CF=CH-R [wherein Rf is the same as represented in formula (II); and R is a (substituted) alkyl] with an oxidizer.

PROCESS FOR THE SYNTHESIS OF POLYFLUOROCARBOXYLIC ACIDS

The invention relates to a process for the preparation of the acids of formula: Rf(CX2CF2)m-1CX2COOH by reaction of the sulphinates of formula: Rf(CX2CF2)m SO2Na with a radical initiator, in which formulae m is an integer from 2 to 6, Rf is a linear or branched perfluoroalkyl group comprising from 1 to 6 carbon atoms, X= F or H. According to one advantageous form, Rf is a linear or branched perfluoroalkyl group comprising from 2 to 4 carbon atoms. According to another advantageous form, m is an integer from 3 to 5.

PROCESS FOR PREPARING FLUOROCARBOXYLIC ACIDS

A fluorocarboxylic acid preparation process continuously carries out acidification reaction treatment and washing treatment, and includes subjecting a fluorocarboxylate-containing aqueous solution to acidification reaction treatment in the presence of sulfuric acid so as to form a sulfate-containing fluorocarboxylic acid phase; and subjecting the fluorocarboxylic acid phase to washing treatment using an aqueous sulfuric acid solution.