CA2086219C - Process for the neutralization of perfluoropolyoxyalkylenes - Google Patents
Process for the neutralization of perfluoropolyoxyalkylenes Download PDFInfo
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- CA2086219C CA2086219C CA002086219A CA2086219A CA2086219C CA 2086219 C CA2086219 C CA 2086219C CA 002086219 A CA002086219 A CA 002086219A CA 2086219 A CA2086219 A CA 2086219A CA 2086219 C CA2086219 C CA 2086219C
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/323—Polymers modified by chemical after-treatment with inorganic compounds containing halogens
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Abstract
Perfluoropolyoxyalkylenes containing acid and/or ketonic groups are neutralized by reacting same in the liquid phase with elemental fluorine at temperatures of from -20° to +150°C in the presence of a supported catalyst consisting of fluorides of Ag, Pb, Co, Ni, Cu, Mn, V, Cr,or Fe.
In a preferred embodiment, a mixture of fluorides of the above mentioned metals and of fluorides, or fluoride precursors, of an alkali and/or alkaline-earth metal is used as catalyst, optionally supported on a suitable carrier.
In a preferred embodiment, a mixture of fluorides of the above mentioned metals and of fluorides, or fluoride precursors, of an alkali and/or alkaline-earth metal is used as catalyst, optionally supported on a suitable carrier.
Description
fn I
The present invention relates to a process for pre-paring fully fluorinated perfluoropolyoxyalkylenes by neutral-ization of the functional groups contained therein with fluor-ine.
The perfluoropolyoxyalkylenes are products known in the art.
They consist of repeating monomeric units having at least one of the following structures:
(-CFiCFO-O ; (-CFO--~ ( -CFzO~) . ( ~-CF~CFzO- ) ; ( -CFiCFZCF20- ) ;
CF; CF3 Depending on the type and combination of such mono-merit units in the macromolecule, the perfiuoropolyoxyalkyl-. R - n eves are commercially known under the names Fomblin'~, Fomblin Z, Fombli.n K, Galden, Demnum, Krytox.
They may be made by means of various technologies, which are described in several patents such as U.S. patents Nos. 4,523,039; 3,665,041 and European patent application No.
148,482.
Irrespective of the type of technology utilized for their preparation, in order to obtain chemically inert perfluoropolyoxyalkylenes it is necessary to carry out - z~s~2l~
a neutralization of the functional groups contained there-in, which consist for the most part of acid groups -COF and ketonic groups -COCF3.
For this purpose, several methods have been suggested.
One of them comprises treating the perfluoropolyoxyalkylenes with KOH at temperatures from 130° to 250°C. Such method involv-es the formation of hydrogenated groups such 'as -CF2H, -CFHCF3, which may be undesirable. Furthermore, the application of such method to low molecular weight perfluoropolyoxyalkylenes re-quires the use of rather high pressures, which is not practical.
Another method (British patent No. 1,226,566) con-sists sn reacting the perfluoropolyoxyalkylenes with fluorine at 50° - 250°C. However, this method requires operation at low temperatures when the perfluoropolyoxyalkylenes have a low molecular weight, what results in a low reaction rate. ., A third method (US-4,664,766) consists in reacting the perfluoropolyoxyalkylenes with fluorine in the presence of U.V.
radiations having a ~ ranging from 200 to 600 nm . However, it is well suited only for low molecular weight products.
U.S. patent No, 4,847,427 suggests the fluorination with elemental fluorine in the presence of alkali or alkaline earth-metal fluorides.
According to such process, the perfluoropolyoxyalkyene acid groups are firstly hydrolized to -COOH groups, then the fluorination is carried out at 50° - 300°C in the presence of the abovesaid fluorides, which are - 3 - z~s~z~~
used in near stoichiometric amounts.
This process exhibits the drawback of releasing large amounts of hydrofluoric acid both during the hydroiysis step and during the fluorination step.
Lastly, from U.S. patent No. 3,985,810 it is known to convert acid perfluoropolyoxyalkylenes of formula:
Rf(OIFCF2)xOiF-CO n -R R
(Rf = C,-C9 perfluoroalkyl; n = 1-2; R = F, CF3; x = 0-50) into neutral products, by fluorination of the alkyl fluoro--groups with elemental fluorine, at temperatures from 50° to 350°C, in the presence of catalysts composed of metals of Groups I 8 through VIII of the Periodic System, among which Ag.
In such case the fluorination reaction is too slow.
particularly at the lowest temper~':..~.., wherefore the process cannot be practised on an industrial scale. ' The Applicant has now found a process - which is the object of the present invention - not affected with the above-mentioned drawbacks, for thoroughly neutrali2ing perfluoropoly-oxyalkylenes of general formula:
(A) B-Rf-T, in which:
- T can be one of the following end groups:
-COF, -CFXCOF, -CF2COCF3, -CF2CFZCOF; (X = F, CF3) - B can be -C1, -OCF3, -OCZFS, -OC3F~, or a -OT group - Rf is a perfluoropolyoxyalkylene chain having one of _ zogs2~9 the following formulas:
(I) (-CF2CF0)m-(CF2CF20)n-(CFZO)p where Z = F, CF3; m, n, p are numbers which can be, not all simultaneously, also = 0 and exhibit in particular the following values:
(1) when n = 0, Z is = F, CF3, m and p are such that m/p is ~ 3 (2) when m = 0, Z is = F, n and p are such that w n/p ranges from 0.3 to 5 (3) when m, n, p are different from zero, the n/p ratio and the m/n+p ratio range from 1 to 10.
(II) (CF2CF2CF20)n the number average molecular weight of Rf in formulas (I) and (II) ranging from 300 to 20,000.
This process consists in reacting such perfluoro-polyoxyalkylenes in the liquid phase with element-al fluorine, at temperatures ranging from -2Q°C, to 150°C, preferably from 20°C to 100°C and more preferably from 20°C to 45°C, in the presence of a supported catalyst composed of Ag, Pb, Ni, Co, Cu, Mn, V, Fe, or Cr fluorides, either individually or in admixture with one another.
In particular, the process of the present invention permits operation, in comparison with the methods of the prior art, with simpler and more economic reactors than the ones in which it is operated with U.V. radiations. Furthermore, the invention allows for prevention of an evolvement of HF and elimination of the necessity to carry out hydrolysis reactions, as occurs in the process of U.S. patent 4,847,427, and, lastly, operation with extremely high reaction rates, even at low temperatures, so that i~c is possible to fluorinate also low molecular weight products.
The fluorides to be utilized as catalysts are used in a supported form. Suitable carriers are: A1F3 , alumina or at least partially fluorinated alumina, fluorinated polymers such as polytetrafluoroethylene. Particularly preferred is A1F3.
The preferred catalyst is Ag fluoride supported on A1F3.
Preferably, such fluorides are utilized in amounts ranging from 0.1 to 5% by weight calculated on perfluoropoly-oxyalkylene.
The mixtures of the abovesaid fluorides with the fluorides, or the fluoride precursors, of the alkali and/or alkaline earth metals, either as such or supported, have prov-ed to be particularly active as catalysts.
Thus, a further aspect of the present invention is a process for carrying out the neutralization of the above-cited perfluoropolyoxyalkylenes, by means of elemental fluor-2~8~219 ine, at temperatures from -20°C to 150°C preferably from 20°C to 100°C, and more preferably from 20°C to 45°C, in the presence of a catalyst comprising:
a) at least an Ag, Pb, Co, Cu, Ni, Mn, V, Fe, or Cr fluoride, and b) at least a fluoride, or a precursor of a fluoride, of and alkali or alkaline earth metal.
Examples of fluorides of group (b) are represented by KF, NaF, LiF, CsF, CaF2, MgF2 .
By precursors of the alkali or alkaline earth-metals are meant here the compounds of said metals that can be converted to fluorides by reaction with fluorine under the fluorination conditions of the perfluoropolyoxyalkylenes according to the present invention.
The alkali metal fluorides or alkaline-earth metal fluorides can be utilized as such, or carried on a carrier selected from those described above for fluorides (a). A preferred carrier is A1F3.
Preferably they are used in amounts ranging from 5 to 70%, and more preferably from 10 to 60% by weight calculated on the sum of their weight with fluoride (a).
The fluorination reaction according to the process of the invention is effected by placing the catalyst into the liquid perfluoropolyoxyalkylene to be neutralized, and by causing gaseous fluorine, optionally diluted with an inert gas such as e.g. nitrogen, to flow therethrough, maintaining the liquid phase at a temperature ranging from -20° to 150°C, preferably from 20° to 100°
and more preferably from 20°C to 45°C. The preferred reaction temperatures can be selected time by time in said ranges, depending on the nature and molecular weight of the perfluoropolyoxyalkylene.
The following examples are given to illustrate the present invention, without limiting, however, the scope thereof.
~~cAMPLE 1 - 7 -Operating according to the method described in U.S.
patent 4,755,330, a sample of 2 kg of perfluoropolyoxyalkylene (oil) having a viscosity of 1.76 cSt at 20°C was obtained.
The NMR analysis of this product revealed a structure B-(CF2CF(CF3)0)m-T having a number average molecular weight equal to 575; further it revealed the presence of end groups B, T = OCF3 (15%), OC2F5 (36%), OC3F7 (30.5%)~, OCF(CF3)COF
(5.5%) and (ketonic end groups) OCF2COCF3 (13%).
.. The potentiometric titration of the product indicat-ed an acidity equal to 0.38 meq/g of perfluoropolyoxyalkylene (oil).
200 g of this sample were placed into a glass re-actor having a 250 m1 volume and equipped with stirrer and cooler. 2 g of AgF were introduced into the reactor. The tem-perature was then brought to 80°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitro-gen in a F2/N2 volumetric ratio equal to 1/3 was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 173.2 g of product were obtained (yield = 86.~%). The NMR analysis and TR analysis of the product revealed the com-plete disappearance of the acyl fluoride end groups and of the ketones. The acidity degree was lower than 5~io~' meq/g of oil.
The iodometric titration indicated an active oxygen content (attributable to the presence of hypofluorites or peroxides) equal to zero.
' The conversion was of 3.5 g/h.
EXAMPLE 2 (COMPARATIVE) 200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250-ml reactor equipped with stirrer and cooler. The temperature was then brought to 130°C by means of a thermostatic bath and a mixture of element-al fluorine diluted with nitrogen in a volumetric ratio equal to 1/3 was made to flow at a rate of 4 1/h for total 80 hours.
After such stretch of time, the recovered mass did not exhibit any alterations. 199 g of product were obtained (yield = 99.5%). The acidimetric analysis, NMR analysis and IR analysis of the product revealed the presence of the initial acyl fluorides and of the initial ketoses.
200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250 ml reactor equipped with stirrer and cooler. 4 g of AgF were introduced into the reactor. It was brought to a temperature of 40°C by means of a thermostatic bath, and a mixture of elemental fluorine dil-uted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 76 hours.
After such stretch of time the mass was filtered and 168.9 g (yield = 84.4%) of product were obtained. The NMR
analysis and the IR analysis of the product revealed the com-9 - ~0~6219 plete disappearance of the ketonic end groups and of the acyl fluoride end groups. The acidimetric titration indicated an acidity lower than 5'10'° meq/g of oil. The iodometric titra-Lion indicated an active oxygen content (atributable to the presence of hypofluorites or peroxides) equal to zero.
The conversion was equal to 2.2 9/h~
_EXAMPLE 4 200 g of the perfluoropolyoxyalkylene described in - example 1 were introduced into a glass 250 ml reactor equip-ped with stirrer and cooler. 2 g of AgF and 2 g of KF were in-troduced into the reactor, The temperature was maintained at 20°C ~~ m~an~ of a thermostatic bath, and a mixture of element-al fluorine diluted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 180 g (yield = 90%) of product were obtained. The NMR and IR analyses of the product revealed the disappearance of the ketone and acyl fluoride end groups. The titration indicated an acidity lower than 5~10~ meq/g of oil. The NMR analysis and the iodometric analysis revealed that hypofluorite end groups were fully absent.
The conversion was of 3.6 9/h.
EXAMPLE 5 (COMPARATIVE) 200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250 ml reactor equipped 208~2i9 with stirrer and cooler. 6.4 g of KF were introduced into the reactor. The temperature was then brought to 40°C by means of a thermostatic bath, and a mixture of elemental fluorine dilut-ed with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 20 hours.
After such stretch of time the mass was filtered, and 195.3 g (yield = 97.6%) of product were obtained. The NMR
analysis and the IR analysis of the product revealed the com-plete disappearance of the ketone and COF end groups and the presence of hypofluorite end groups. The iodometric titration indicated an active oxygen content equal to 0.26%.
EXAt4PLE 6 200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250 ml reactor equip-ped with stirrer and cooler. 0.2 g of AgF supported on 1.8 g of A1F3 (commercially designated as MUC 4), having a surface area of 15 m2/9 were introduced into the reactor. The whole was then brought to a temperature of 80°C by means of a thermostat-is bath, and a mixture of elemental fluorine diluted with ni-trogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 20 hours.
After such stretch of time the mass was filtered and 176.9 g (yield = 88.4%) of product were obtained. The NMR
analysis and IR analysis of the product revealed the complete disappearance of the ketonic and acyl fluoride end groups. The - 2~8~~19 acidimetric titration indicated an acidity lower than 5~10~' ineq/g of oil. The NhiR analysis and the iodometric analysis in-dicated that hypofluorite end groups were fully absent.
The conversion was equal to 8.8 9/h.
EXAhIPLE 7 200 g of the perfluoropolyoxyalkylene utilized in ex-ample 1 were introduced into a glass reactor;.having a volume of 250 ml, equipped with stirrer and cooler. 0.2 g of AgF and 0.2 g of KF supported on 1.6 g of A1F3 having a surface area of 15 ..
m2/9 were introduced into the reactor. The whole was then brought to a temperature of 80°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was fed at a.rate of 4 liters/hour -----. ------ for a total time of 11 hours.
After such stretch of time, the mass was filtered and 186.9 g (yield = 93.4%) of product were obtained. The NMR
analysis and IR analysis of the product revealed the complete disappearance of the ketone and acyl fluoride end groups. The acidimetric titration indicated an acidity lower than 5~i0d meq/g of oil. The NMR analysis and the iodometric analysis re-vealed that hypofluorite end groups were fully absent.
The conversion was equal to 16.9 g/h.
A sample of a perfluoropolyoxyalkylene having struct-ure BO-(CF2CF20)n(CF20)p-T with n/p = 0.96 and T, B = CF2COF, - 12 - 2U862~9 CF3, -COF, -CF2C1, -CF2CF2C1 was prepared by photooxidation of tetrafluoroethylene at -38°C and subsequent thermal treat-ment of the resulting product in order to remove the peroxide oxygen contained therein, according to methods of the art.
The product exhibited a number average molecular weight equal to 7,500 and an acidity of 0.14 meq/g of per-fluoropolyoxyalkylene. -200 g of this sample were introduced into a glass re-actor having a 250 ml volume, equipped with stirrer and cooler.
2 g of AgF were introduced into the reactor. The whole was brought to a temperature of 80°C by means of a thermostatic bath. and a mixture of elemental fluorine diluted with nitrogen in a F2/N2 volumetric ratio = 1/3 was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 188.6 g (yield = 94.3Z) of product were obtained. The NMR
and IR analyses of the product revealed a full disappearance of the acyl fluoride end groups. The titration indicated an acidity lower than 5~1o~' meq/g of oil.
The NMR analysis and the iodometric analysis reveal-ed the full absence of hypofluorite end groups.
The conversion was equal to 3.8 g/h.
EXAf~IPLE 9 200 g of a perfluoropolyoxyalkylene having struct-ure BO-(CF2CF2CF20)n-T with B, T = -CF2CF2COF, -C2F5, -C3F~
were prepared according to the modalities described in European patent application No. 148,482, and by subsequent reduction of the molecular weight of the obtained product by means of treat-ment with A1F3 at 270°C, according to conventional techniques.
The perfluoropolyoxyalkylene exhibited a number average molecul-ar weight equal to 540 and an acidity of 3.37 meq/g of perfluo-ropolyoxyalkylene.
The sample was introduced into a glass reactor hav-ing a volume of 250 ml and equipped with stirrer and cooler.
2 g of AgF were put into the reactor. The whole was brought to a temperature of 80°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitrogen in a 1/3 volumetric ratio was made to flow at a rate of 4 1/h for total 56 hours.
After such stretch of time the mass was filtered and 181.2 g (yield = 90.6:) of product were obtained. The NMR and IR analyses of the product revealed the total disappearance of the acyl fluoride end groups. The titration indicated an acidi-ty lower than 510'° meq/g of oil.
The NMR analysis and the iodometric analysis revealed the full absence of hypofluorite end groups.
The conversion was of 3.2 9/h.
EXA~4PLE 10 By photooxidation at -40°C of a mixture of tetra-fluoroethylene and hexafluoropropene, a peroxide perfluoro-- 1~ - 2086219 polyoxyalkylene was obtained which, after thermal treatment, exhibited a viscosity of 258 cSt and a number average molecul-ar weight equal to 2,960.
The structure determined by means of NMR is represent-ed by the formula: BO-(CF2CF(CF3)0)m(CF2CF20)n(CF20)p-T, where m/n/p = 1.0/0.8/0.2 and B, T = CF(CF3)COF, CF2COF, COF, CF3, C2F5, C3F7, CF2COCF3. The product exhibited,. an acidity equal to 0.74 meq/g of oil.
200 g of this sample were placed into a glass reactor having a 250 ml volume, equipped with stirrer and cooler. 2 g of AgF were introduced into the reactor. The whole was brought to a temperature of 80°C by means of a thermostatic bath and a mixture of elemental fluorine diluted with nitrogen in a 1/3 volumetric ratio was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 194 g (yield = 97.0X) of product were obtained. The NMR and IR
analyses of the product revealed the complete disappearance of the ketone and acyl fluoride end groups. The titration indic-ated an acidity lower than 510'' meq/g of oil. The NMR analys-is and the iodometric analysis revealed the full absence of hypofluorite end groups.
The conversion was equal to 3.9 g/h.
EXAf~IPLE 11 200 g of the perfluoropoiyoxyalkylene described in ..
example 10 were introduced into a glass reactor having a 250 ml~ volume, equipped with stirrer and cooler. 2 g of AgF were introduced into the reactor along with 2 g of KF. The temper-ature was maintained at 40°C by means of a thermostatic bath and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was fed at a rate of 4 1/h for total 35 hours.
After such stretch of time the mass was filtered and 181.3 g (yield ~ 90.6%) of product were obtained. The NMR
analysis and the IR analysis of the product revealed the dis-appearance of the ketone and acyl fluoride end groups. The titration indicated an acidity lower than 510°° meq/g of oil.
The NMR analysis and the iodometric analysis reveal-ed the full absence of hypofluorite end groups.
The conversion was equal to 5.18 g/h.
200 g of the perfluoropolyoxyalkylene obtained ac-cording to example 1 were introduced into a glass reactor hav-ing a volume of 250 ml, equipped with stirrer and cooler.
2 g of AgF and 2 g of KF were introduced into the reaetor.
The temperature was maintained at 80°C by means of a thermos-tatic bath and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 25 hours.
After such stretch of time the mass was filtered and 183 g (yield = 91.5p) of product were obtained. The NMR analys-- >_6 - 2t~~6219 is and the IR analysis of the product evidenced the disappear-ante of the ketone and acyl fluoride end groups. The titration indicated an acidity lower than 5'10-0 meq/g of oil.
The NMR analysis and the iodometric analysis revealed the full absence of hypofluorite end groups.
The conversion was equal to 7.3 9/h.
Z00 g of the perfluoropolyoxyalkylene obtained accord-inf to the modalities of example 1 were introduced into a glass reactor having a 250 ml volume, equipped with stirrer and cool-er. 2 g of NiF2 and Z g of KF were placed into the reactor. The temperature was maintained at 20°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 60 hours.
After such stretch of time the mass was filtered and 175 g (yield = 87.5%) of product were obtained. The NMR analys-is and IR analysis of the product revealed that the ketonenic and aryl fluoride end groups had disappeared. The titration in-dicated an acidity lower than 510'' meq/g of oil.
The NMR analysis and the iodometric analysis reveal-ed the full absence of hypofluorite end groups.
The conversion was equal to 2.9 g/h.
The present invention relates to a process for pre-paring fully fluorinated perfluoropolyoxyalkylenes by neutral-ization of the functional groups contained therein with fluor-ine.
The perfluoropolyoxyalkylenes are products known in the art.
They consist of repeating monomeric units having at least one of the following structures:
(-CFiCFO-O ; (-CFO--~ ( -CFzO~) . ( ~-CF~CFzO- ) ; ( -CFiCFZCF20- ) ;
CF; CF3 Depending on the type and combination of such mono-merit units in the macromolecule, the perfiuoropolyoxyalkyl-. R - n eves are commercially known under the names Fomblin'~, Fomblin Z, Fombli.n K, Galden, Demnum, Krytox.
They may be made by means of various technologies, which are described in several patents such as U.S. patents Nos. 4,523,039; 3,665,041 and European patent application No.
148,482.
Irrespective of the type of technology utilized for their preparation, in order to obtain chemically inert perfluoropolyoxyalkylenes it is necessary to carry out - z~s~2l~
a neutralization of the functional groups contained there-in, which consist for the most part of acid groups -COF and ketonic groups -COCF3.
For this purpose, several methods have been suggested.
One of them comprises treating the perfluoropolyoxyalkylenes with KOH at temperatures from 130° to 250°C. Such method involv-es the formation of hydrogenated groups such 'as -CF2H, -CFHCF3, which may be undesirable. Furthermore, the application of such method to low molecular weight perfluoropolyoxyalkylenes re-quires the use of rather high pressures, which is not practical.
Another method (British patent No. 1,226,566) con-sists sn reacting the perfluoropolyoxyalkylenes with fluorine at 50° - 250°C. However, this method requires operation at low temperatures when the perfluoropolyoxyalkylenes have a low molecular weight, what results in a low reaction rate. ., A third method (US-4,664,766) consists in reacting the perfluoropolyoxyalkylenes with fluorine in the presence of U.V.
radiations having a ~ ranging from 200 to 600 nm . However, it is well suited only for low molecular weight products.
U.S. patent No, 4,847,427 suggests the fluorination with elemental fluorine in the presence of alkali or alkaline earth-metal fluorides.
According to such process, the perfluoropolyoxyalkyene acid groups are firstly hydrolized to -COOH groups, then the fluorination is carried out at 50° - 300°C in the presence of the abovesaid fluorides, which are - 3 - z~s~z~~
used in near stoichiometric amounts.
This process exhibits the drawback of releasing large amounts of hydrofluoric acid both during the hydroiysis step and during the fluorination step.
Lastly, from U.S. patent No. 3,985,810 it is known to convert acid perfluoropolyoxyalkylenes of formula:
Rf(OIFCF2)xOiF-CO n -R R
(Rf = C,-C9 perfluoroalkyl; n = 1-2; R = F, CF3; x = 0-50) into neutral products, by fluorination of the alkyl fluoro--groups with elemental fluorine, at temperatures from 50° to 350°C, in the presence of catalysts composed of metals of Groups I 8 through VIII of the Periodic System, among which Ag.
In such case the fluorination reaction is too slow.
particularly at the lowest temper~':..~.., wherefore the process cannot be practised on an industrial scale. ' The Applicant has now found a process - which is the object of the present invention - not affected with the above-mentioned drawbacks, for thoroughly neutrali2ing perfluoropoly-oxyalkylenes of general formula:
(A) B-Rf-T, in which:
- T can be one of the following end groups:
-COF, -CFXCOF, -CF2COCF3, -CF2CFZCOF; (X = F, CF3) - B can be -C1, -OCF3, -OCZFS, -OC3F~, or a -OT group - Rf is a perfluoropolyoxyalkylene chain having one of _ zogs2~9 the following formulas:
(I) (-CF2CF0)m-(CF2CF20)n-(CFZO)p where Z = F, CF3; m, n, p are numbers which can be, not all simultaneously, also = 0 and exhibit in particular the following values:
(1) when n = 0, Z is = F, CF3, m and p are such that m/p is ~ 3 (2) when m = 0, Z is = F, n and p are such that w n/p ranges from 0.3 to 5 (3) when m, n, p are different from zero, the n/p ratio and the m/n+p ratio range from 1 to 10.
(II) (CF2CF2CF20)n the number average molecular weight of Rf in formulas (I) and (II) ranging from 300 to 20,000.
This process consists in reacting such perfluoro-polyoxyalkylenes in the liquid phase with element-al fluorine, at temperatures ranging from -2Q°C, to 150°C, preferably from 20°C to 100°C and more preferably from 20°C to 45°C, in the presence of a supported catalyst composed of Ag, Pb, Ni, Co, Cu, Mn, V, Fe, or Cr fluorides, either individually or in admixture with one another.
In particular, the process of the present invention permits operation, in comparison with the methods of the prior art, with simpler and more economic reactors than the ones in which it is operated with U.V. radiations. Furthermore, the invention allows for prevention of an evolvement of HF and elimination of the necessity to carry out hydrolysis reactions, as occurs in the process of U.S. patent 4,847,427, and, lastly, operation with extremely high reaction rates, even at low temperatures, so that i~c is possible to fluorinate also low molecular weight products.
The fluorides to be utilized as catalysts are used in a supported form. Suitable carriers are: A1F3 , alumina or at least partially fluorinated alumina, fluorinated polymers such as polytetrafluoroethylene. Particularly preferred is A1F3.
The preferred catalyst is Ag fluoride supported on A1F3.
Preferably, such fluorides are utilized in amounts ranging from 0.1 to 5% by weight calculated on perfluoropoly-oxyalkylene.
The mixtures of the abovesaid fluorides with the fluorides, or the fluoride precursors, of the alkali and/or alkaline earth metals, either as such or supported, have prov-ed to be particularly active as catalysts.
Thus, a further aspect of the present invention is a process for carrying out the neutralization of the above-cited perfluoropolyoxyalkylenes, by means of elemental fluor-2~8~219 ine, at temperatures from -20°C to 150°C preferably from 20°C to 100°C, and more preferably from 20°C to 45°C, in the presence of a catalyst comprising:
a) at least an Ag, Pb, Co, Cu, Ni, Mn, V, Fe, or Cr fluoride, and b) at least a fluoride, or a precursor of a fluoride, of and alkali or alkaline earth metal.
Examples of fluorides of group (b) are represented by KF, NaF, LiF, CsF, CaF2, MgF2 .
By precursors of the alkali or alkaline earth-metals are meant here the compounds of said metals that can be converted to fluorides by reaction with fluorine under the fluorination conditions of the perfluoropolyoxyalkylenes according to the present invention.
The alkali metal fluorides or alkaline-earth metal fluorides can be utilized as such, or carried on a carrier selected from those described above for fluorides (a). A preferred carrier is A1F3.
Preferably they are used in amounts ranging from 5 to 70%, and more preferably from 10 to 60% by weight calculated on the sum of their weight with fluoride (a).
The fluorination reaction according to the process of the invention is effected by placing the catalyst into the liquid perfluoropolyoxyalkylene to be neutralized, and by causing gaseous fluorine, optionally diluted with an inert gas such as e.g. nitrogen, to flow therethrough, maintaining the liquid phase at a temperature ranging from -20° to 150°C, preferably from 20° to 100°
and more preferably from 20°C to 45°C. The preferred reaction temperatures can be selected time by time in said ranges, depending on the nature and molecular weight of the perfluoropolyoxyalkylene.
The following examples are given to illustrate the present invention, without limiting, however, the scope thereof.
~~cAMPLE 1 - 7 -Operating according to the method described in U.S.
patent 4,755,330, a sample of 2 kg of perfluoropolyoxyalkylene (oil) having a viscosity of 1.76 cSt at 20°C was obtained.
The NMR analysis of this product revealed a structure B-(CF2CF(CF3)0)m-T having a number average molecular weight equal to 575; further it revealed the presence of end groups B, T = OCF3 (15%), OC2F5 (36%), OC3F7 (30.5%)~, OCF(CF3)COF
(5.5%) and (ketonic end groups) OCF2COCF3 (13%).
.. The potentiometric titration of the product indicat-ed an acidity equal to 0.38 meq/g of perfluoropolyoxyalkylene (oil).
200 g of this sample were placed into a glass re-actor having a 250 m1 volume and equipped with stirrer and cooler. 2 g of AgF were introduced into the reactor. The tem-perature was then brought to 80°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitro-gen in a F2/N2 volumetric ratio equal to 1/3 was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 173.2 g of product were obtained (yield = 86.~%). The NMR analysis and TR analysis of the product revealed the com-plete disappearance of the acyl fluoride end groups and of the ketones. The acidity degree was lower than 5~io~' meq/g of oil.
The iodometric titration indicated an active oxygen content (attributable to the presence of hypofluorites or peroxides) equal to zero.
' The conversion was of 3.5 g/h.
EXAMPLE 2 (COMPARATIVE) 200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250-ml reactor equipped with stirrer and cooler. The temperature was then brought to 130°C by means of a thermostatic bath and a mixture of element-al fluorine diluted with nitrogen in a volumetric ratio equal to 1/3 was made to flow at a rate of 4 1/h for total 80 hours.
After such stretch of time, the recovered mass did not exhibit any alterations. 199 g of product were obtained (yield = 99.5%). The acidimetric analysis, NMR analysis and IR analysis of the product revealed the presence of the initial acyl fluorides and of the initial ketoses.
200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250 ml reactor equipped with stirrer and cooler. 4 g of AgF were introduced into the reactor. It was brought to a temperature of 40°C by means of a thermostatic bath, and a mixture of elemental fluorine dil-uted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 76 hours.
After such stretch of time the mass was filtered and 168.9 g (yield = 84.4%) of product were obtained. The NMR
analysis and the IR analysis of the product revealed the com-9 - ~0~6219 plete disappearance of the ketonic end groups and of the acyl fluoride end groups. The acidimetric titration indicated an acidity lower than 5'10'° meq/g of oil. The iodometric titra-Lion indicated an active oxygen content (atributable to the presence of hypofluorites or peroxides) equal to zero.
The conversion was equal to 2.2 9/h~
_EXAMPLE 4 200 g of the perfluoropolyoxyalkylene described in - example 1 were introduced into a glass 250 ml reactor equip-ped with stirrer and cooler. 2 g of AgF and 2 g of KF were in-troduced into the reactor, The temperature was maintained at 20°C ~~ m~an~ of a thermostatic bath, and a mixture of element-al fluorine diluted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 180 g (yield = 90%) of product were obtained. The NMR and IR analyses of the product revealed the disappearance of the ketone and acyl fluoride end groups. The titration indicated an acidity lower than 5~10~ meq/g of oil. The NMR analysis and the iodometric analysis revealed that hypofluorite end groups were fully absent.
The conversion was of 3.6 9/h.
EXAMPLE 5 (COMPARATIVE) 200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250 ml reactor equipped 208~2i9 with stirrer and cooler. 6.4 g of KF were introduced into the reactor. The temperature was then brought to 40°C by means of a thermostatic bath, and a mixture of elemental fluorine dilut-ed with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 20 hours.
After such stretch of time the mass was filtered, and 195.3 g (yield = 97.6%) of product were obtained. The NMR
analysis and the IR analysis of the product revealed the com-plete disappearance of the ketone and COF end groups and the presence of hypofluorite end groups. The iodometric titration indicated an active oxygen content equal to 0.26%.
EXAt4PLE 6 200 g of the perfluoropolyoxyalkylene described in example 1 were introduced into a glass 250 ml reactor equip-ped with stirrer and cooler. 0.2 g of AgF supported on 1.8 g of A1F3 (commercially designated as MUC 4), having a surface area of 15 m2/9 were introduced into the reactor. The whole was then brought to a temperature of 80°C by means of a thermostat-is bath, and a mixture of elemental fluorine diluted with ni-trogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 20 hours.
After such stretch of time the mass was filtered and 176.9 g (yield = 88.4%) of product were obtained. The NMR
analysis and IR analysis of the product revealed the complete disappearance of the ketonic and acyl fluoride end groups. The - 2~8~~19 acidimetric titration indicated an acidity lower than 5~10~' ineq/g of oil. The NhiR analysis and the iodometric analysis in-dicated that hypofluorite end groups were fully absent.
The conversion was equal to 8.8 9/h.
EXAhIPLE 7 200 g of the perfluoropolyoxyalkylene utilized in ex-ample 1 were introduced into a glass reactor;.having a volume of 250 ml, equipped with stirrer and cooler. 0.2 g of AgF and 0.2 g of KF supported on 1.6 g of A1F3 having a surface area of 15 ..
m2/9 were introduced into the reactor. The whole was then brought to a temperature of 80°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was fed at a.rate of 4 liters/hour -----. ------ for a total time of 11 hours.
After such stretch of time, the mass was filtered and 186.9 g (yield = 93.4%) of product were obtained. The NMR
analysis and IR analysis of the product revealed the complete disappearance of the ketone and acyl fluoride end groups. The acidimetric titration indicated an acidity lower than 5~i0d meq/g of oil. The NMR analysis and the iodometric analysis re-vealed that hypofluorite end groups were fully absent.
The conversion was equal to 16.9 g/h.
A sample of a perfluoropolyoxyalkylene having struct-ure BO-(CF2CF20)n(CF20)p-T with n/p = 0.96 and T, B = CF2COF, - 12 - 2U862~9 CF3, -COF, -CF2C1, -CF2CF2C1 was prepared by photooxidation of tetrafluoroethylene at -38°C and subsequent thermal treat-ment of the resulting product in order to remove the peroxide oxygen contained therein, according to methods of the art.
The product exhibited a number average molecular weight equal to 7,500 and an acidity of 0.14 meq/g of per-fluoropolyoxyalkylene. -200 g of this sample were introduced into a glass re-actor having a 250 ml volume, equipped with stirrer and cooler.
2 g of AgF were introduced into the reactor. The whole was brought to a temperature of 80°C by means of a thermostatic bath. and a mixture of elemental fluorine diluted with nitrogen in a F2/N2 volumetric ratio = 1/3 was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 188.6 g (yield = 94.3Z) of product were obtained. The NMR
and IR analyses of the product revealed a full disappearance of the acyl fluoride end groups. The titration indicated an acidity lower than 5~1o~' meq/g of oil.
The NMR analysis and the iodometric analysis reveal-ed the full absence of hypofluorite end groups.
The conversion was equal to 3.8 g/h.
EXAf~IPLE 9 200 g of a perfluoropolyoxyalkylene having struct-ure BO-(CF2CF2CF20)n-T with B, T = -CF2CF2COF, -C2F5, -C3F~
were prepared according to the modalities described in European patent application No. 148,482, and by subsequent reduction of the molecular weight of the obtained product by means of treat-ment with A1F3 at 270°C, according to conventional techniques.
The perfluoropolyoxyalkylene exhibited a number average molecul-ar weight equal to 540 and an acidity of 3.37 meq/g of perfluo-ropolyoxyalkylene.
The sample was introduced into a glass reactor hav-ing a volume of 250 ml and equipped with stirrer and cooler.
2 g of AgF were put into the reactor. The whole was brought to a temperature of 80°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitrogen in a 1/3 volumetric ratio was made to flow at a rate of 4 1/h for total 56 hours.
After such stretch of time the mass was filtered and 181.2 g (yield = 90.6:) of product were obtained. The NMR and IR analyses of the product revealed the total disappearance of the acyl fluoride end groups. The titration indicated an acidi-ty lower than 510'° meq/g of oil.
The NMR analysis and the iodometric analysis revealed the full absence of hypofluorite end groups.
The conversion was of 3.2 9/h.
EXA~4PLE 10 By photooxidation at -40°C of a mixture of tetra-fluoroethylene and hexafluoropropene, a peroxide perfluoro-- 1~ - 2086219 polyoxyalkylene was obtained which, after thermal treatment, exhibited a viscosity of 258 cSt and a number average molecul-ar weight equal to 2,960.
The structure determined by means of NMR is represent-ed by the formula: BO-(CF2CF(CF3)0)m(CF2CF20)n(CF20)p-T, where m/n/p = 1.0/0.8/0.2 and B, T = CF(CF3)COF, CF2COF, COF, CF3, C2F5, C3F7, CF2COCF3. The product exhibited,. an acidity equal to 0.74 meq/g of oil.
200 g of this sample were placed into a glass reactor having a 250 ml volume, equipped with stirrer and cooler. 2 g of AgF were introduced into the reactor. The whole was brought to a temperature of 80°C by means of a thermostatic bath and a mixture of elemental fluorine diluted with nitrogen in a 1/3 volumetric ratio was made to flow at a rate of 4 1/h for total 49 hours.
After such stretch of time the mass was filtered and 194 g (yield = 97.0X) of product were obtained. The NMR and IR
analyses of the product revealed the complete disappearance of the ketone and acyl fluoride end groups. The titration indic-ated an acidity lower than 510'' meq/g of oil. The NMR analys-is and the iodometric analysis revealed the full absence of hypofluorite end groups.
The conversion was equal to 3.9 g/h.
EXAf~IPLE 11 200 g of the perfluoropoiyoxyalkylene described in ..
example 10 were introduced into a glass reactor having a 250 ml~ volume, equipped with stirrer and cooler. 2 g of AgF were introduced into the reactor along with 2 g of KF. The temper-ature was maintained at 40°C by means of a thermostatic bath and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was fed at a rate of 4 1/h for total 35 hours.
After such stretch of time the mass was filtered and 181.3 g (yield ~ 90.6%) of product were obtained. The NMR
analysis and the IR analysis of the product revealed the dis-appearance of the ketone and acyl fluoride end groups. The titration indicated an acidity lower than 510°° meq/g of oil.
The NMR analysis and the iodometric analysis reveal-ed the full absence of hypofluorite end groups.
The conversion was equal to 5.18 g/h.
200 g of the perfluoropolyoxyalkylene obtained ac-cording to example 1 were introduced into a glass reactor hav-ing a volume of 250 ml, equipped with stirrer and cooler.
2 g of AgF and 2 g of KF were introduced into the reaetor.
The temperature was maintained at 80°C by means of a thermos-tatic bath and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 25 hours.
After such stretch of time the mass was filtered and 183 g (yield = 91.5p) of product were obtained. The NMR analys-- >_6 - 2t~~6219 is and the IR analysis of the product evidenced the disappear-ante of the ketone and acyl fluoride end groups. The titration indicated an acidity lower than 5'10-0 meq/g of oil.
The NMR analysis and the iodometric analysis revealed the full absence of hypofluorite end groups.
The conversion was equal to 7.3 9/h.
Z00 g of the perfluoropolyoxyalkylene obtained accord-inf to the modalities of example 1 were introduced into a glass reactor having a 250 ml volume, equipped with stirrer and cool-er. 2 g of NiF2 and Z g of KF were placed into the reactor. The temperature was maintained at 20°C by means of a thermostatic bath, and a mixture of elemental fluorine diluted with nitrogen in a 1/3 ratio was made to flow at a rate of 4 1/h for total 60 hours.
After such stretch of time the mass was filtered and 175 g (yield = 87.5%) of product were obtained. The NMR analys-is and IR analysis of the product revealed that the ketonenic and aryl fluoride end groups had disappeared. The titration in-dicated an acidity lower than 510'' meq/g of oil.
The NMR analysis and the iodometric analysis reveal-ed the full absence of hypofluorite end groups.
The conversion was equal to 2.9 g/h.
Claims (10)
1. A process for neutralizing perfluoropolyoxyalkylenes of gen-eral formula:
(A) B-Rf-T, in which:
- T can be one of the following end groups:
-COF, -CFXCOF, -CF2COCF3, -CF2CF2COF; (X = F, CF3) - B can be -Cl, -OCF3, -OC2F5, -OC3F7, or a -OT group - Rf is a perfluoropolyoxyalkylene chain having one of the following formulas:
where Z = F, CF3; m, n, p are numbers which can be, not all simultaneously, also = 0 and exhibit the following values:
(1) when n = 0, X is = F, CF3, m and p are such that m/p is > 3 (2) when m = 0, Z is = F, n and p are such that n/p ranges from 0.3 to 5 (3) when m, n, p are different from zero, the n/p ratio and the m/n+p ratio range from 1 to 10.
(II) (CF2CF2CF2O)n which process consists in reacting such perfluo-ropolyoxyalkylenes in the liquid phase with elem-ental fluorine, at temperatures ranging from -20°C to 150°C, in the presence of a catalyst composed of Ag, Pb, Ni, Co, Cu, Mn, V, Fe, or Cr fluorides, either individually or in admixture wino one another, and supported on a carrier.
(A) B-Rf-T, in which:
- T can be one of the following end groups:
-COF, -CFXCOF, -CF2COCF3, -CF2CF2COF; (X = F, CF3) - B can be -Cl, -OCF3, -OC2F5, -OC3F7, or a -OT group - Rf is a perfluoropolyoxyalkylene chain having one of the following formulas:
where Z = F, CF3; m, n, p are numbers which can be, not all simultaneously, also = 0 and exhibit the following values:
(1) when n = 0, X is = F, CF3, m and p are such that m/p is > 3 (2) when m = 0, Z is = F, n and p are such that n/p ranges from 0.3 to 5 (3) when m, n, p are different from zero, the n/p ratio and the m/n+p ratio range from 1 to 10.
(II) (CF2CF2CF2O)n which process consists in reacting such perfluo-ropolyoxyalkylenes in the liquid phase with elem-ental fluorine, at temperatures ranging from -20°C to 150°C, in the presence of a catalyst composed of Ag, Pb, Ni, Co, Cu, Mn, V, Fe, or Cr fluorides, either individually or in admixture wino one another, and supported on a carrier.
2. The process of claim 1, wherein the carrier is selected from AlF, alumina, at least partially fluorinated alumina, polytetrafluoroethylene.
3. The process of claim 2, wherein the carrier is A1F3.
4. The process according to anyone of the preceding claims, wherein the reaction temperature is from 20° to 100°C.
5. The process of claim 4, wherein the reaction temperature is from 20° to 45°C.
6. A process for neutralizing perfluoropolyoxyalkylenes of general formula:
(A) B-Rf-T, in which:
- T can be one of the following end groups:
-COF, -CFXCOF, -CF2COCF3, -CF2CF2COF; (X = F, CF3) - B can be -Cl, -OCF3, -OC2F5, -OC3F7, or a -OT group - Rf is a perfluoropolyoxyalkylene chain having one of the following formulas:
where Z = F, CF3; m, n, p are numbers which can be, not all simultaneously, also - D and exhibit the following values:
(1) when n - 0, X is - F, CF3, m and p are such that m/p is > 3 (2) when m - 0, Z is - F, n and p are such that n/p ranges from 0.3 to 5 (3) when m, n, p are different from zero, the n/p ratio and the m/n+p ratio range from 1 to 10.
(II) (CF2CF2CF2O)n which process consists in reacting such perfluo-ropolyoxyalkylenes in the liquid phase with elem-ental fluorine, at temperature ranging from -20° to 150°C
in the presence of a catalyst comprising:
a) at least an Ag, Pb, Co, Cu, Ni, Mn, V, Fe, or Cr fluoride;
b) at least a fluoride, or a precursor of a fluoride, of an alkali or alkaline-earth metal.
(A) B-Rf-T, in which:
- T can be one of the following end groups:
-COF, -CFXCOF, -CF2COCF3, -CF2CF2COF; (X = F, CF3) - B can be -Cl, -OCF3, -OC2F5, -OC3F7, or a -OT group - Rf is a perfluoropolyoxyalkylene chain having one of the following formulas:
where Z = F, CF3; m, n, p are numbers which can be, not all simultaneously, also - D and exhibit the following values:
(1) when n - 0, X is - F, CF3, m and p are such that m/p is > 3 (2) when m - 0, Z is - F, n and p are such that n/p ranges from 0.3 to 5 (3) when m, n, p are different from zero, the n/p ratio and the m/n+p ratio range from 1 to 10.
(II) (CF2CF2CF2O)n which process consists in reacting such perfluo-ropolyoxyalkylenes in the liquid phase with elem-ental fluorine, at temperature ranging from -20° to 150°C
in the presence of a catalyst comprising:
a) at least an Ag, Pb, Co, Cu, Ni, Mn, V, Fe, or Cr fluoride;
b) at least a fluoride, or a precursor of a fluoride, of an alkali or alkaline-earth metal.
7. The process of claim 6, wherein the catalyst is supported on a carrier selected from:
AlF3, alumina, at least partially fluorinated alumina, polytetrafluoroethylene.
AlF3, alumina, at least partially fluorinated alumina, polytetrafluoroethylene.
8. The process of claim 7, wherein the carrier is AlF3.
9. The process according to anyone of claims from 5 to 8, wherein the reaction temperature is from 20° to 100°C.
10. The process of claim 9, wherein the reaction temperature is from 20° to 45°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI91A003464 | 1991-12-23 | ||
| ITMI913464A IT1252657B (en) | 1991-12-23 | 1991-12-23 | PROCEDURE FOR THE NEUTRALIZATION OF PERFLUOROPOLYXIALKYLENE |
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| Publication Number | Publication Date |
|---|---|
| CA2086219A1 CA2086219A1 (en) | 1993-06-24 |
| CA2086219C true CA2086219C (en) | 2004-02-03 |
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|---|---|---|---|
| CA002086219A Expired - Fee Related CA2086219C (en) | 1991-12-23 | 1992-12-23 | Process for the neutralization of perfluoropolyoxyalkylenes |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5319147A (en) |
| EP (1) | EP0548743B1 (en) |
| JP (1) | JP3333253B2 (en) |
| KR (1) | KR100220655B1 (en) |
| CA (1) | CA2086219C (en) |
| DE (1) | DE69231913T2 (en) |
| IT (1) | IT1252657B (en) |
| TW (1) | TW240235B (en) |
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| BE1007822A5 (en) * | 1993-12-10 | 1995-10-31 | Solvay | SUPPORT FOR CATALYST hydrogenate ION SYSTEM INCLUDING THE CATALYST SUPPORT AND METHOD OF hydrodechlorination chlorofluorocarbons. |
| US5559069A (en) * | 1994-05-26 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Catalysts for halogenated hydrocarbon processing, their precursors and their preparation and use |
| US5847242A (en) * | 1995-05-19 | 1998-12-08 | E. I. Du Pont De Nemours And Company | Catalysts for halogenated hydrocarbon processing, their precursors and their preparation and use |
| US6386468B1 (en) * | 1999-11-29 | 2002-05-14 | Ceramoptec Industries, Inc. | Mechano-chemical flourination: improved method of fullerene fluorination |
| KR101041601B1 (en) * | 2007-10-25 | 2011-06-15 | 한국화학연구원 | The neutralization method of perfluoropolyether |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805503A (en) * | 1956-03-15 | 1958-12-10 | Dow Chemical Co | Improved fluorination catalyst and process |
| GB1000485A (en) * | 1962-02-07 | 1965-08-04 | Sicedison Spa | Improvements in or relating to the fluorination of halo-olefines |
| GB1226566A (en) * | 1967-04-04 | 1971-03-31 | ||
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
| DE2451493C2 (en) * | 1974-10-30 | 1982-06-24 | Hoechst Ag, 6000 Frankfurt | Process for the production of perfluorinated ethers |
| US4523039A (en) * | 1980-04-11 | 1985-06-11 | The University Of Texas | Method for forming perfluorocarbon ethers |
| DE3486428T2 (en) * | 1983-12-26 | 1996-10-10 | Daikin Ind Ltd | Halogen containing polyether |
| AU579374B2 (en) * | 1984-05-23 | 1988-11-24 | Ausimont S.R.L. | Process for preparing perfluoropolyethers with neutral and functional end-groups, having a regulated molecular weight |
| US4664766A (en) * | 1985-02-13 | 1987-05-12 | Montedison S.P.A. | Photochemical process for neutralizing perfluoropolyethers |
| IT1201498B (en) * | 1985-11-20 | 1989-02-02 | Ausimont Spa | FUNCTIONALIZED PERFLUOROPOLITERS AND PROCEDURE FOR THEIR PREPARATION |
| US4847427A (en) * | 1988-04-13 | 1989-07-11 | E. I. Du Pont De Nemours And Company | Process for preparing fluorocarbon polyethers |
| DE3902803A1 (en) * | 1989-01-31 | 1990-08-02 | Hoechst Ag | METHOD FOR CLEANING AND STABILIZING PERFLUORINE POLYETHERS |
| IT1238075B (en) * | 1990-01-31 | 1993-07-03 | Ausimont Spa | PROCESS FOR THE PREPARATION OF FLUOROPOLYETERS AND PERFLUOROLETERS AT NEUTRAL OR FUNCTIONAL TERMINALS OF CONTROLLED MOLECULAR WEIGHT |
-
1991
- 1991-12-23 IT ITMI913464A patent/IT1252657B/en active IP Right Grant
-
1992
- 1992-12-15 EP EP92121297A patent/EP0548743B1/en not_active Expired - Lifetime
- 1992-12-15 DE DE69231913T patent/DE69231913T2/en not_active Expired - Fee Related
- 1992-12-22 US US07/994,663 patent/US5319147A/en not_active Expired - Lifetime
- 1992-12-22 TW TW081110266A patent/TW240235B/zh active
- 1992-12-22 KR KR1019920025120A patent/KR100220655B1/en not_active IP Right Cessation
- 1992-12-23 CA CA002086219A patent/CA2086219C/en not_active Expired - Fee Related
- 1992-12-24 JP JP35754692A patent/JP3333253B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0548743A3 (en) | 1993-08-18 |
| IT1252657B (en) | 1995-06-20 |
| KR930012858A (en) | 1993-07-21 |
| TW240235B (en) | 1995-02-11 |
| CA2086219A1 (en) | 1993-06-24 |
| DE69231913T2 (en) | 2002-04-04 |
| JPH06122640A (en) | 1994-05-06 |
| ITMI913464A1 (en) | 1993-06-23 |
| DE69231913D1 (en) | 2001-08-09 |
| EP0548743A2 (en) | 1993-06-30 |
| ITMI913464A0 (en) | 1991-12-23 |
| JP3333253B2 (en) | 2002-10-15 |
| EP0548743B1 (en) | 2001-07-04 |
| US5319147A (en) | 1994-06-07 |
| KR100220655B1 (en) | 1999-09-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 20051223 |