- Application of perfluoro(2-propoxypropyl vinyl ether) (PPVE-2) in the synthesis of perfluoro(propyl vinyl ether) (PPVE-1)
-
A novel preparative method for the conversion of n-C3F7OCF(CF3)CF2OCF = CF2 (PPVE-2) into n-C3F7OCF = CF2 (PPVE-1) is reported. It includes the catalytic oxidation of PPVE-2 with molecular oxygen to furnish a mixture of carbonyl fluorides which are subjected to alkaline hydrolysis resulting in a mixture of salts. Subsequent thermolysis of those salts give rise to an inseparable mixture of PPVE-1 and perfluoro-2-propoxypropanoyl fluoride. Treatment of this mixture with sodium carbonate allowed to obtain sodium perfluoro-2-propoxypropionate and to isolate PPVE-1. Thermolysis of this sodium salt produced an additional amount of PPVE-1, so that the total conversion of PPVE-2 into PPVE-1 is accomplished in good yields. The reaction conditions, the choice of reagent as well as the course of competitive reactions are discussed.
- Hintzer, Klaus,Hirschberg, Markus E.,Pajkert, Romana,R?schenthaler, Gerd-Volker,Smith, Sean M.,Tverdomed, Sergey N.
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-
- Hydrofluoroether compound and its preparation method and application (by machine translation)
-
The invention belongs to the field of hydrofluoroether, in particular to a hydrofluoroether compound and its preparation method and application. Hydrofluoroether compound expressed by following formula: F [CF (CF3 ) CF2 O]x - RH ; Wherein x=2 - 7; RH =CH3 , C2 H5 , N - C3 H7 Or i - C3 H7 . The present invention provides a hydrofluoroether compound, only fluorine-containing this the only halogen element, not having to damage the ozone layer material, is an environment-friendly non-combustible heat transfer agent, solvent and cleaning agent. (by machine translation)
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Paragraph 0066; 0068; 0069
(2019/04/26)
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- One stone two birds: Degradation of persistent organic pollutants to a valuable industrial chemical production of pentafluoropropionyl fluoride from HFPO oligomers catalyzed by cesium fluoride in tetraglyme
-
Hexafluoropropylene oxide (HFPO) oligomers are toxic, bioaccumulative, and persistent organic pollutants (POPs). Consuming the harmful chemicals to prevent them from releasing to nature is of serious significance as far as both natural environments and human health are concerned. In this study, investigation on degradation of HFPO oligomers to pentafluoropropionyl fluoride (PPF), a valuable industrial chemical, is reported. Different combinations of alkali metal fluoride in either diglyme or tetraglyme under both flask and batch autoclave conditions were examined. Under the optimal reaction conditions, HFPO oligomers (n?=?2–10) were completely degraded to PPF in over 90% yield. Reactions on 200?g scale were tested and no deduction of efficiency was observed, which indicates the potential for practical industrial application of this chemistry.
- Geng, Qian,Xiao, Xin,He, Guang-Rui,Yao, Su-Mei,Liang, Guang-Xin
-
supporting information
p. 1009 - 1012
(2016/08/01)
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- METHOD FOR PREPARING FLUORINE-CONTAINING VINYL ETHER
-
Provided is a method for preparing fluorine-containing vinyl ether. The method comprises: carrying out hydrolytic neutralization on a small molecular weight byproduct which is produced in the process of preparing perfluoropolyether or a perfluorinated surfactant by photooxidation of fluorine-containing olefin; and obtaining fluorine-containing vinyl ether by drying and cracking. The byproduct produced in the process of preparing perfluoropolyether or the perfluorinated surfactant is utilized, thereby solving the emission problem of industrial wastes, reducing environment pollution, and generating available fluorine-containing vinyl ether.
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Paragraph 0030-0031
(2014/10/29)
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- Catalytic synthesis of certain perfluorinated ketones and study of their structure by 19F NMR spectroscopy
-
An efficient catalyst of a perfluorinated ketone synthesis of a high selectivity in the absence of solvent was proposed. Products of reaction of perfluorinated fluorides of various structures with tetrafluoroethylene and hexafluoropropylene in the presence of efficient catalysts without solvent were examined. The structure of the resulting products and their isomeric composition were identified by 19F NMR spectrscopy. Pleiades Publishing, Ltd., 2013.
- Fenichev,Berenblit,Bispen,Lebedev,Moldavskii
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p. 1243 - 1251
(2014/02/14)
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- Development of technology of perfluoroethyl isopropyl ketone production
-
Synthesis of perfluoroethyl isopropyl ketone by an interaction of hexafluoropropene with perfluoropropionic acid fluoride or hexafluoropropene oxide was examined. Interchangeability of perfluoropropionic acid fluoride and hexafluoropropene oxide was demonstrated. The features of perfluoroethyl isopropyl ketone synthesis were studied in polar aprotic solvents on catalysts: alkali metal fluoride. A method for obtaining perfluoroethyl isopropyl ketone by direct catalytic reaction in a tubular reactor without use of solvents was suggested and investigated. The mechanism of interaction was considered. The main impurities resulting in obtaining perfluoroethyl isopropyl ketone were determined. The methods of cleaning perfluoroethyl isopropyl ketone were worked out.
- Fenichev,Babenko,Bispen,Moldavskii
-
p. 376 - 386
(2013/07/05)
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- PROCESS FOR PRODUCTION OF FLUORINATED SULFONYL FLUORIDES
-
It is an object of the present invention to solve difficulty in production and to provide a process to obtain fluorinated sulfonyl fluoride compound having various molecular structures efficiently at a low cost. That is, the present invention provides a process which comprises reacting (FSO2-)nRA(-E-RB)m (1F) with fluorine in a liquid phase to form (FSO2-)nRAF(-EF-RBF)m (2), and decomposing this compound to obtain (FSO2-)nRAF(-EF1)m (3), provided that RA is a (n+m)valent organic group having at least two carbon atoms, RAF is a group having RA fluorinated, or the like, each of RB and RBF is a fluorinated monovalent organic group, or the like, E is -COOCH2- or the like, EF is -COOCF2- or the like, EF1 is -COF or the like, n is an integer of at least 2, and m is an integer of at least 1.
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Page/Page column 27
(2010/11/08)
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- FLUORINATED ADAMANTANE DERIVATIVES
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The present invention provides novel compounds which are useful for the production of fluorinated adamantane derivatives excellent in etching resistance and useful as photolithographic material and so on. Namely, the present invention provides compounds represented by the following formulae (3) and (4):A(-G-Q-R)nAf(-Gf-Q-Rf)n provided that the symbols in the formula have the following meanings:A: a n-valent group having n hydrogen atoms of adamantane converted to connecting bonds, wherein hydrogen atoms not converted to connecting bonds, may be each substituted by an alkyl group,R: a fluorinated monovalent organic group,n: an integer of from 1 to 4,G: -CH2- or a single bond,Q: -COO- or -OCO-,Af: a n-valent group (A) having n hydrogen atoms bonded to carbon atoms of adamantane converted to connecting bonds, wherein hydrogen atoms not converted to connecting bonds, may be each substituted by an alkyl group, in which at least one of hydrogen atoms forming C-H bonds is substituted by a fluorine atom,Rf: a fluorinated monovalent organic group,Gf: -CF2- or a single bond.
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Page/Page column 19
(2008/06/13)
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- COMPOUND HAVING PERFLUORO(4-METHYLENE-1,3-DIOXOLANE) STRUCTURE AND NOVEL POLYMER
-
Disclosed are a compound having a perfluoro(4-methylene-1,3-dioxolane) structure which has not been known yet, and a novel polymer. Specifically disclosed are a compound represented by the formula (a) below which has a perfluoro(4-methylene-1,3-dioxolane) structure, a method for producing such a compound, a novel compound useful for producing such a compound, and a novel polymer containing a repeating unit represented by the formula (A) below. (In the formulae, RF1-RF4 independently represent a fluorine atom, a chlorine atom or a monovalent perfluorinated saturated organic group having 1-20 carbon atoms.)
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Page/Page column 20
(2010/02/15)
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- NOVEL FLUORINATED ADAMANTANE DERIVATIVE
-
A novel fluorinated adamantane derivative. It is a compound represented by the formula AF(-COF)n, wherein AF means a fluorinated adamantane residue which is an n-valent group formed by removing n hydrogen atom(s) from adamantane (provided that when n is 2 or larger, then the hydrogen atoms to be removed are bonded to different carbon atoms) and in which at least one of the remaining hydrogen atoms may be replaced with a fluorine atom and the still remaining hydrogen atom(s) may be replaced with a C1-6 alkyl or fluoroalkyl group; and n is an integer of 1-4, provided that when n is 1, then the AF has at least one hydrogen atom.
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Page/Page column 15
(2008/06/13)
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- ULTRAVIOLET-PERMEABLE FLUOROPOLYMERS AND PELLICLES MADE BY USING THE SAME
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A pellicle which is excellent in transmittance and durability against short wavelength light, and which can be used for photolithography by using e.g. a KrF excimer laser, is provided. A pellicle for exposure to a light having a wavelength of at most 200 nm, which comprises a frame and a pellicle membrane bonded to the frame by means of an adhesive, wherein the pellicle membrane and/or the adhesive comprises a polymer containing repeating units represented by the following formula (1): wherein Q represents a C1-3 polyfluoroalkylene group having a linear structure, or a group having at least one atom selected from hydrogen atoms and fluorine atoms in such a polyfluoroalkylene group substituted by a substituent comprising a polyfluoroalkyl group which may contain an ethereal oxygen atom, or the like, and X represents a hydrogen atom, a fluorine atom or a C1-3 polyfluoroalkyl group which may contain an ethereal oxygen atom.
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Page/Page column 15
(2008/06/13)
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- A new procedure for preparing perfluoroalkoxypropanoic acid fluorides
-
Condensation of perfluoro carboxylic acid fluorides with hexafluoropropene epoxide in the presence of N,N, N,N-tetraalkyldiaminomethanes was studied.
- Igumnov,Lekontseva,Shipigusev,Mukhametshin
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p. 435 - 437
(2008/02/01)
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- An entirely new methodology for synthesizing perfluorinated compounds: Synthesis of perfluoroalkanesulfonyl fluorides from non-fluorinated compounds
-
A new synthetic procedure for the preparation of perfluoroalkanesulfonyl fluorides utilizing liquid-phase direct fluorination with elemental fluorine has been developed. Direct fluorination of a partially fluorinated ester, which has alkanesulfonyl fluoride in the end, was synthesized from non-fluorinated counterparts and perfluorinated acid fluoride according to the PERFECT process, gave the desired perfluorinated product in moderate yield as well as by-products arising from CS bond cleavage. The results of the direct fluorination of some model substrates suggest that the CS bond cleavage occurred due to radical formation at the α-position rather than the β-position.
- Okazoe, Takashi,Murotani, Eisuke,Watanabe, Kunio,Itoh, Masahiro,Shirakawa, Daisuke,Kawahara, Kengo,Kaneko, Isamu,Tatematsu, Shin
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p. 1695 - 1701
(2007/10/03)
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- Process for producing a fluorine atom-containing sulfonyl fluoride compound
-
The present invention provides a process whereby fluorine atom-containing sulfonyl fluoride compound(s) useful as e.g. materials for ion-exchange membranes, can be produced efficiently and at low cost without structural limitations while solving the difficulties in production. Namely, the present invention provides a process which comprises reacting XSO2RA-E1 (1) with RB-E2 (2) to form XSO2RA-E—RB (3), then reacting (3) with fluorine in a liquid phase to form FSO2RAF-EF-RBF (4), and further, decomposing the compound to obtain FSO2RAF-EF1 (5), wherein RA is a bivalent organic group, E1 is a monovalent reactive group, RB is a monovalent organic group, E2 is a monovalent reactive group which is reactive with E1, E is a bivalent connecting group formed by the reaction of E1 with E2, RAF is a bivalent organic group formed by the fluorination of RA, etc., RBF is the same group as RB, etc., EF is a bivalent connecting group formed by the fluorination of E, etc., EF1 is a monovalent group formed by the decomposition of EF, and X is a halogen atom.
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Page/Page column 11
(2008/06/13)
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- PROCESSES FOR PRODUCING FLUORINATED ESTER, FLUORINATED ACYL FLUORIDE, AND FLUORINATED VINYL ETHER
-
A process for producing a fluorinated ester through a small number of steps, is presented. The process for producing a fluorinated ester, comprises a transesterification step in which RAF-COOCF2-RAF and RA-CH2OH are subjected to a transesterification reaction to obtain RAF-COOCH2-RA, and a fluorination step in which the obtained compound is fluorinated to obtain a reaction product containing RAF-COOCF2-RAF. Here, in the formulae, RA is a monovalent organic group, and RAF is the same group as RA or a monovalent organic group obtained by fluorination of RA.
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Page/Page column 14
(2008/06/13)
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- Method for producing a fluorinated ester compound
-
The present invention provides a method for producing industrially useful fluorine-containing compounds such as a fluorinated ester compound and an acid fluoride compound. Namely, the present invention resides in a method for producing a fluorinated ester compound, which comprises fluorinating an ester compound which is an ester of a compound having hydroxyl group(s) with a compound having acyl fluoride group(s) and which has a structure which can be fluorinated, in a liquid phase to produce a fluorinated ester compound, wherein the fluorination is carried out in the form of a liquid mixture of the ester compound and the compound having acyl fluoride group(s).
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Page/Page column 10
(2010/01/31)
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- Viscosity effects on the thermal decomposition of bis(perfluoro-2-N-propoxypropionyl) peroxide in dense carbon dioxide and fluorinated solvents
-
The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, kobs, increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The kobs values are comparatively larger in dense carbon dioxide and similar to the zero-viscosity rate constants extrapolated from the decomposition kinetics in the fluorinated solvents. The decomposition activation parameters demonstrate a compensation behavior of the activation enthalpy with the activation entropy upon change in solvent viscosity. Comparison of the change in activation parameter values upon change in solvent viscosity for BPPP with two additional initiators, acetyl peroxide (AP) and trifluoroacetyl peroxide (TFAP), further suggests that carbon dioxide exerts a very minimal influence on the decomposition mechanism of these initiators through solvent-cage effects.
- Clayton Bunyard,Kadla,Desimone
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p. 7199 - 7206
(2007/10/03)
-
- Synthesis of Versatile Poly- and Perfluorinated Compounds by Utilizing Direct Fluorination, 1 A New Route to Perfluoro(Propyl Vinyl Ether) Monomer: Synthesis of Perfluoro(2-propoxypropionyl) Fluoride from Non-Fluorinated Compounds
-
Perfluoro(2-propoxypropionyl) fluoride (1a), which is the precursor of the perfluorinated propyl vinyl ether (PPVE) monomer of an industrially important perfluoroalkoxy copolymer (PFA), was synthesized by utilizing direct fluorination of the non-fluorinated counterpart for the first time. The partially-fluorinated ester 7 synthesized from the desired perfluorinated acid fluoride 1a itself and the non-fluorinated alcohol 5, which has a carbon skeleton corresponding to the desired compound 1a, was perfluorinated by liquid-phase direct fluorination with elemental fluorine. Degradation of the resulting perfluorinated ester 8 gave 2 mols of the desired acid fluoride 1a. In a sense, this process can be called self-multiplication of a perfluorinated acid fluoride from a non-fluorinated alcohol.
- Okazoe, Takashi,Watanabe, Kunio,Itoh, Masahiro,Shirakawa, Daisuke,Murofushi, Hidenobu,Okamoto, Hidekazu,Tatematsu, Shin
-
p. 215 - 219
(2007/10/03)
-
- Polyfluorinated ethers: IV.* By-products in the synthesis of polyfluorinated alkyl vinyl ethers in a solvating solvent
-
By-products formed in the synthesis of perfluoro(propyl vinyl ether), perfluoro(2-propoxypropyl vinyl ether), and methyl perfluoro(4-vinyloxybutanoate) in a solvating solvent have been studied. 1998 MAHK "Hayka/Interperiodica".
- Yuminov
-
p. 1715 - 1720
(2007/10/03)
-
- Polyfluorinated Ethers: III. Synthesis of Perfluorinated 2-Chloroethyl Vinyl Ether
-
A promising method was developed for preparing perfluorinated 2-chloroethyl vinyl ether by fluorosulfonylation of 1-hydro-2-chlorotetrafluoroethane followed by the condensation of the substance obtained with hexafluoropropene oxide and thermolysis of the condensation product.
- Yuminov, V. S.
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p. 300 - 302
(2007/10/03)
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- Radical additions to fluoro-olefins. Photochemical mono-fluoroalkylation and sequential bis-fluoroalkylation of oxolane
-
Oxolane was fluoroalkylated by its photoadditions under atmospheric pressure. Monofluoro-alkylations were carried out with hexafluoropropene (1) and perfluorovinyl ethers C3F7O-[CF(CF3)CF2O]n-CF=CF2 (2-4, n=0-2) by direct photoexcitation of the oleflns to give high yields of addition products 9-12 (81-94%). The reactions were completely regioselective at the oxolane molecule and almost completely regioselective (93-99%) at the double bond of fluoro-olefins; no bis-fluoroalkylated oxolanes were detected. The completely selective introduction of a second fluoroalkyl into position 5 of the oxolane molecule was accomplished by acetone-sensitised photoaddition of 2-fluoroalkylated oxolanes 9, 10 to fluoro-olefins 1 and 2. Byproducts from reactions of the dimethylketyl radical which is formed in the initiation step were isolated and have given some evidence about the reaction mechanism that is discussed.
- Paleta, Oldrich,Cirkva, Vladimir,Kvicala, Jaroslav
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p. 125 - 134
(2007/10/03)
-
- Utilisation of ammonium and phosphonium perfluorocyclobutane ylides as fluoride anion source
-
Ammonium- and phosphoniumperfluorocyclobutane glides 1 and 2, prepared from perfluorocyclobutene and tertiary amines or phosphines can be used as a masked fluoride anion source. These properties have been demonstrated in several reactions. Ylides 1 and 2 cleave C-Si or O-Si bonds, cause dimerisation of fluoroolefins or react with acid chlorides or activated aromatic compounds under halogen exchange.
- Pasenok, Sergej V.,De Roos, Marijn E.,Appel, Wolfgang K.
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p. 9755 - 9758
(2007/10/03)
-
- SURFACE ACTIVE SUBSTANCES CONTAINING AN OLIGO(HEXAFLUOROPROPENE OXIDE) CHAIN AS A HYDROPHOBIC AND OLEOPHOBIC MOIETY
-
Oil soluble surface active substances, (HFPO)n-Ar, where Ar is an aryl group and (HFPO)n is an oligo(hexafluoropropene oxide) group, n = 2 - 5, were prepared and tested for their surface activities in toluene or m-xylene.Addition of a small amount of (HFPO)4-6-Ar (0.2 - 0.5 wtpercent) was found to decrease remarkably the surface tension of these solvents (down to 12 - 14 dyncm-1 at 20 deg C).Water soluble surfactans (HFPO)n-Ar'SO3Na, where Ar' is an arylene group, were also prepared by sulfonation of (HFPO)n-Ar.Some of these subtances (n = 4 - 6) decreased the surface tension of water down to 16 dyncm-1 at 20 deg C in the concentration of 10-4 - 10-5 molel-1.
- Ishikawa, Nobuo,Sasabe, Mikio
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p. 241 - 254
(2007/10/02)
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- REACTION OF CESIUM PERFLUOROALKOXIDES WITH HEXAFLUOROPROPYLENE OXIDE IN TETRAHYDROFURAN IN THE PRESENCE OF ADDITIONS OF APROTIC SOLVENTS
-
The effect of adition of aprotic solvents in tetrahydrofuran on the reactivity of cesium perfluoroalkoxides with hexafluoropropylene oxide was investigated.It was shown that the rate of the model chain transfer to the monomer increases with increase in the concentration of tetraglyme in proportion to the increase in the electric conductivity of the system.The reactivity of cesium perfluoroalkoxides is determined by the structure of the perfluorinated radical.A mechanism is proposed for the chain growth and transfer reaction.
- Gubanov, V. A.,Tyul'ga, G. M.,Solodkaya, I. G.,Sherman, M. A.
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p. 444 - 448
(2007/10/02)
-
- OPTICALLY ACTIVE PERFLUORO-2-PROPOXYPROPIONIC ACID: A NEW CHIRAL REAGENT FOR 19F NMR STUDY
-
Perfluoro-2-propoxypropionic acid, which was prepared by the anionic dimerization of hexafluoro-1,2-epoxypropane, was optically resolved via diastereomeric salt formation with chiral amines.The optically pure (+) and (-) perfluoro-2-propoxypropionic acids thus obtained were found to be a convenient chiral reagent for determining enantiomeric compositions of α-amino acids by means of 19F nmr analysis.
- Kawa, Hajimu,Yamaguchi, Fumihiko,Ishikawa, Nobuo
-
p. 475 - 486
(2007/10/02)
-
- Thermal Decomposition of Some Perfluoro- and Polyfluorodiacyl Peroxides
-
Seven polyfluoroacyl peroxides were synthesized, some of them by a new procedure involving the direct interaction of an acyl fluoride with hydrogen peroxide.In the temperature range of 20-40 deg C, all these peroxides undergo first-order decomposition in dilute 1,1,2-trichloro-1,2,2-trifluoroethane (Freon-113) solutions (F-RF.Differing from other perfluoro or polyfluoro radicals, the perfluoro-α-isopropoxyethyl radicals (10) undergo substantial β scission to form perfluoroisopropyl radicals (11) during their lifetime.The ΔHexc. values for the perfluoroacyl peroxides are about 24 kcal mol-1, or about 5 kcal lower than that of the nonfluorinated diacyl peroxides (ca. 29 kcal mol-1).Apparently, the higher relative rates for 3 and 7 are caused by different factors.The latter peroxide (7) decomposes with a more favorable ΔSexc. term, whereas the former (3) decomposes with lower values of both ΔHexc. and ΔSexc..Thus, weakening of the peroxide bond by H bonding of the peroxide oxygen atom with the acidic ω-hydrogen atom seems to be implicated in the decomposition of 3.With a half-life of 81 min at 20 deg C, 3 may become a useful low-temperature initiator for free-radical reactions and polymerization.
- Chengxue, Zhao,Renmo, Zhou,Heqi, Pan,Xiangshan, Jin,Yangling, Qu,et al.
-
p. 2009 - 2013
(2007/10/02)
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- OPTICALLY ACTIVE PERFLUORO-2-PROPOXYPROPIONIC ACID
-
The diastereomeric amides prepared from (+/-)-perfluoro-2-propoxypropionyl fluoride and (-)-1-phenylethylamine were separated chromatographically, and subsequent hydrolysis of each amide gave (+) and (-)-perfluoro-2-propoxypropionic acids, the first example of optically active and enantiomeric perfluorocarboxylic acids.
- Kawa, Hajimu,Ishikawa, Nobuo
-
p. 843 - 846
(2007/10/02)
-
- Process for preparing perfluoro-alkoxy-propionic acid fluorides
-
Perfluoro carbonyl compounds react with hexafluoro propene epoxide in the presence of dimethylamino-difluoro-phosphorane producing perfluorinated carboxylic acid fluorides with ether linkages. Among the carbonyl compounds which can be used are perfluorinated ketones, acid fluorides of the formula (rf being a perfluoro-alkyl radical having from 1 to 4 carbon atoms) and perfluoro-2-oxo-3,6-dimethyl-1,4-dioxane.
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