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EP0771865A1 - Cleaning composition based on 1,1,1,2,2,4,4-heptafluorobutane and alcohols - Google Patents

Cleaning composition based on 1,1,1,2,2,4,4-heptafluorobutane and alcohols Download PDF

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Publication number
EP0771865A1
EP0771865A1 EP96402131A EP96402131A EP0771865A1 EP 0771865 A1 EP0771865 A1 EP 0771865A1 EP 96402131 A EP96402131 A EP 96402131A EP 96402131 A EP96402131 A EP 96402131A EP 0771865 A1 EP0771865 A1 EP 0771865A1
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EP
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Prior art keywords
heptafluorobutane
composition according
weight
mcf
cleaning
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP96402131A
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German (de)
French (fr)
Inventor
Pascal Michaud
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Arkema France SA
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Elf Atochem SA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/24—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02803—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/5077—Mixtures of only oxygen-containing solvents
    • C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only

Definitions

  • the present invention relates to the field of fluorinated hydrocarbons and more particularly relates to new compositions which can be used for cleaning and degreasing solid surfaces.
  • 1,1,2-Trichloro-1,2,2-trifluoroethane (known in the art under the designation F113) has been widely used in the industry for cleaning and degreasing a wide variety of solid surfaces (metal parts, glasses , plastics, composites).
  • F113 1,1,2-Trichloro-1,2,2-trifluoroethane
  • F113 is most often combined with other organic solvents (for example methanol), preferably in the form of azeotropic or quasi-azeotropic mixtures which do not demix and which, when used at reflux, have substantially the same composition in the vapor phase than in the liquid phase.
  • organic solvents for example methanol
  • compositions based on F113 are now prohibited since F113 is one of the chlorofluorocarbons (CFCs) suspected of attacking or degrading stratospheric ozone.
  • CFCs chlorofluorocarbons
  • F113 can be replaced by 1,1-dichloro-1-fluoroethane (known under the designation F141b), but the use of this substitute is already regulated because, although weak, its destructive effect vis- ozone is not zero.
  • the present invention proposes to replace the compositions based on F113 or F141b by azeotropic or quasi-azeotropic compositions based on 1,1,1,2,2,4,4-heptafluorobutane.
  • This compound (CF 3 CF 2 CH 2 CHF 2 hereinafter designated by the term F347 mcf) is completely devoid of destructive effect with respect to ozone and has characteristics close to those of F113 and F141b.
  • compositions to be used according to the invention comprise by weight from 90 to 99.9% of F347 mcf and from 0.1 to 10% of a lower alcohol (methanol, ethanol, n-pro-panol, isopropanol).
  • a particularly preferred composition according to the invention is that which comprises by weight 90 to 99% of F347 mcf and 1 to 10% of methanol. In this area, there is an azeotrope with a boiling point of 30.6 ° C at normal atmospheric pressure (1.013 bar). This composition does not have a flash point under the standard determination conditions (ASTM D 3828) and therefore makes it possible to work in complete safety.
  • the cleaning compositions based on F347 mcf according to the invention can, if desired, be stabilized against hydrolysis and / or free radical attacks likely to occur.
  • a usual stabilizer such as, for example, a nitroalkane (nitromethane, nitroethane, nitropropane, ...), an acetal (dimethoxymethane) and 1,4-dioxolane, the proportion of stabilizer which can range from 0.01 to 5% relative to the total weight of the composition.
  • compositions according to the invention can be used in the same applications and according to the same techniques as the previous compositions based on F113 or F141b.
  • This azeotrope used for cleaning solder flux or degreasing mechanical parts, gives good results.
  • test circuits (standardized model IPC-25) are coated with rosin-based flux (R8F flux from the company ALPHAMETAL)) and annealed in an oven at 220 ° C for 30 seconds.
  • circuits are cleaned using a composition comprising 95% of 347 mcf and 5% of methanol in an ultrasonic machine for 3 minutes by immersion and 3 minutes in the vapor phase.
  • the cleaning is evaluated according to the standard procedure lPC 2.3.26 using a precision conductivity meter.
  • the value obtained, 0.63 ⁇ g / cm 2 eq.NaCl, is much lower than the ionic impurity threshold tolerated by the profession (2.5 ⁇ g / cm 2 eq.NaCl).
  • Example 1 By operating as in Example 1 with ethanol, it demonstrates the existence of an azeotrope F347 mcf / ethanol which boils at 32.4 ° C at 1.013 bar and contains by weight 98.45% of F347 mcf and 1.55% ethanol.
  • Example 1 By reproducing Example 1 with isopropanol, it is demonstrated the existence of an azeotrope F347 mcf / isopropanol containing, by weight, 99.85% of F347 mcf and 0.15% of isopropanol. Its boiling point under 1.013 bar is 32.8 ° C.
  • a one liter glass reactor is used, equipped with mechanical stirring, a dropping funnel (500 ml) and surmounted by a water condenser.
  • the reactor is maintained under a light nitrogen sweep (10 to 20 ml / min) and the outlet of the refrigerant is connected to a metal trap maintained at -80 ° C., making it possible to recover the olefin formed which leaves the reaction mixture under form of gas (Teb 10-11 ° C / 1 atm).
  • a washing bottle containing water is inserted, followed by a drying tube containing calcium chloride.
  • a tubular Inconel reactor is used (internal diameter: 28 mm, length: 420 mm) heated by an electrical tape and loaded with 48 g (100 ml) of a commercial Pd / carbon catalyst with 5% palladium.
  • the olefin synthesized in step 1 is hydrogenated in the gas phase on this catalyst previously activated by passing hydrogen (100 ml / min) at 80 ° C for one hour. Then hydrogen is introduced (100 ml / min measured at 20 ° C) and the olefin in gaseous form (40 ml / min measured at 20 ° C). The reactor temperature is maintained at 80 ° C. At the outlet of the reactor, the F347 mcf is condensed in a trap maintained at -80 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

New azeotropic or quasi-azeotropic composition (I) contains 1,1,1,2,2,4,4-heptafluorobutane (II) and a 1-3C alcohol. (I) contains 90-99 weight % of (II) and 1-10 weight % of methanol or ethanol, or 90-99.9 weight % of (II) and 0.1-10 weight % of isopropanol. It also contains at least one stabiliser.

Description

La présente invention concerne le domaine des hydrocarbures fluorés et a plus particulièrement pour objet de nouvelles compositions utilisables pour nettoyer et dégraisser des surfaces solides.The present invention relates to the field of fluorinated hydrocarbons and more particularly relates to new compositions which can be used for cleaning and degreasing solid surfaces.

Le 1,1,2-trichloro-1,2,2-trifluoroéthane (connu dans le métier sous la désignation F113) a été largement utilisé dans l'industrie pour le nettoyage et le dégraissage de surfaces solides très diverses (pièces métalliques, verres, plastiques, composites). Outre son application en électronique au nettoyage des flux de soudure pour éliminer le flux décapant qui adhère aux circuits imprimés, on peut mentionner ses applications au dégraissage de pièces métalliques lourdes et au nettoyage de pièces mécaniques de haute qualité et de grande précision comme, par exemple, les gyroscopes et le matériel militaire, aérospatial ou médical. Dans ses diverses applications, le F113 est le plus souvent associé à d'autres solvants organiques (par exemple le méthanol), de préférence sous forme de mélanges azéotropiques ou quasi azéotropiques qui ne démixent pas et qui, employés au reflux, ont sensiblement la même composition dans la phase vapeur que dans la phase liquide.1,1,2-Trichloro-1,2,2-trifluoroethane (known in the art under the designation F113) has been widely used in the industry for cleaning and degreasing a wide variety of solid surfaces (metal parts, glasses , plastics, composites). In addition to its application in electronics to the cleaning of solder fluxes to eliminate the flux flux which adheres to printed circuits, one can mention its applications to the degreasing of heavy metal parts and to the cleaning of high quality and high precision mechanical parts such as, for example , gyroscopes and military, aerospace or medical equipment. In its various applications, F113 is most often combined with other organic solvents (for example methanol), preferably in the form of azeotropic or quasi-azeotropic mixtures which do not demix and which, when used at reflux, have substantially the same composition in the vapor phase than in the liquid phase.

Cependant, l'emploi de compositions à base de F113 est maintenant interdit car le F113 fait partie des chlorofluorocarbures (CFC) suspectés d'attaquer ou de dégrader l'ozone stratosphérique.However, the use of compositions based on F113 is now prohibited since F113 is one of the chlorofluorocarbons (CFCs) suspected of attacking or degrading stratospheric ozone.

Dans ces diverses applications, le F113 peut être remplacé par le 1,1-dichloro-1-fluoroéthane (connu sous la désignation F141b), mais l'utilisation de ce substitut est déjà réglementée car, bien que faible, son effet destructeur vis-à-vis de l'ozone n'est pas nul.In these various applications, F113 can be replaced by 1,1-dichloro-1-fluoroethane (known under the designation F141b), but the use of this substitute is already regulated because, although weak, its destructive effect vis- ozone is not zero.

Pour contribuer à résoudre ce problème, la présente invention propose de remplacer les compositions à base de F113 ou de F141b par des compositions azéotropiques ou quasi azéotropiques à base de 1,1,1,2,2,4,4-heptafluorobutane. Ce composé (CF3CF2CH2CHF2 ci-après désigné par le terme F347 mcf) est totalement dépourvu d'effet destructeur vis-à-vis de l'ozone et présente des caractéristiques voisines de celles du F113 et du F141b. Caractéristiques F113 F141b F347mcf Point d'ébullition (°C) 47,6 32 33 Tension superficielle à 25°C (mN.m-1) 19 19,1 14,2 Densité à 20°C 1,57 1,24 1,42 Point éclair (norme ASTM D 3828) néant néant néant O.D.P. (ozone-depletion potential) 1,07 0,11 0 To contribute to solving this problem, the present invention proposes to replace the compositions based on F113 or F141b by azeotropic or quasi-azeotropic compositions based on 1,1,1,2,2,4,4-heptafluorobutane. This compound (CF 3 CF 2 CH 2 CHF 2 hereinafter designated by the term F347 mcf) is completely devoid of destructive effect with respect to ozone and has characteristics close to those of F113 and F141b. Characteristics F113 F141b F347mcf Boiling point (° C) 47.6 32 33 Surface tension at 25 ° C (mN.m -1 ) 19 19.1 14.2 Density at 20 ° C 1.57 1.24 1.42 Flash point (ASTM D 3828 standard) nil nil nil ODP (ozone-depletion potential) 1.07 0.11 0

Les compositions à utiliser selon l'invention comprennent en poids de 90 à 99,9 % de F347 mcf et de 0,1 à 10 % d'un alcool inférieur (méthanol, éthanol, n-pro-panol, isopropanol).The compositions to be used according to the invention comprise by weight from 90 to 99.9% of F347 mcf and from 0.1 to 10% of a lower alcohol (methanol, ethanol, n-pro-panol, isopropanol).

Une composition particulièrement préférée selon l'invention est celle qui comprend en poids 90 à 99 % de F347 mcf et 1 à 10 % de méthanol. Dans ce domaine, il existe un azéotrope dont la température d'ébullition est de 30,6°C à la pression atmosphérique normale (1,013 bar). Cette composition ne présente pas de point éclair dans les conditions standard de détermination (norme ASTM D 3828) et permet donc de travailler en toute sécurité.A particularly preferred composition according to the invention is that which comprises by weight 90 to 99% of F347 mcf and 1 to 10% of methanol. In this area, there is an azeotrope with a boiling point of 30.6 ° C at normal atmospheric pressure (1.013 bar). This composition does not have a flash point under the standard determination conditions (ASTM D 3828) and therefore makes it possible to work in complete safety.

Comme dans les compositions de nettoyage connues à base de F113 ou de F141b, les compositions de nettoyage à base de F347 mcf selon l'invention peuvent, si on le désire, être stabilisées contre l'hydrolyse et/ou les attaques radicalaires susceptibles de survenir dans les processus de nettoyage, en y ajoutant un stabilisant usuel tel que, par exemple, un nitroalcane (nitrométhane, nitroéthane, nitropro-pane,...), un acétal (diméthoxyméthane) et le 1,4-dioxolane, la proportion de stabilisant pouvant aller de 0,01 à 5 % par rapport au poids total de la composition.As in the known cleaning compositions based on F113 or F141b, the cleaning compositions based on F347 mcf according to the invention can, if desired, be stabilized against hydrolysis and / or free radical attacks likely to occur. in cleaning processes, by adding a usual stabilizer such as, for example, a nitroalkane (nitromethane, nitroethane, nitropropane, ...), an acetal (dimethoxymethane) and 1,4-dioxolane, the proportion of stabilizer which can range from 0.01 to 5% relative to the total weight of the composition.

Les compositions selon l'invention peuvent être utilisées dans les mêmes applications et selon les mêmes techniques que les compositions antérieures à base de F113 ou de F141b.The compositions according to the invention can be used in the same applications and according to the same techniques as the previous compositions based on F113 or F141b.

Les exemples suivants illustrent l'invention sans la limiter.The following examples illustrate the invention without limiting it.

EXEMPLE 1 : Azéotrope F347 mcf/méthanol EXAMPLE 1: Azeotrope F347 mcf / methanol a) Mise en évidence de l'azéotrope a) Demonstration of the azeotrope

Dans le bouilleur d'une colonne à distiller (30 plateaux), on introduit 100 g de F347 mcf et 100 g de méthanol. Le mélange est ensuite mis à reflux total pendant une heure pour amener le système à l'équilibre.100 g of F347 mcf and 100 g of methanol are introduced into the boiler of a distillation column (30 trays). The mixture is then put under total reflux for one hour to bring the system to equilibrium.

Au palier de température (30,6°C), on recueille une fraction d'environ 50 g que l'on analyse par chromatographie en phase gazeuse.At the temperature level (30.6 ° C), a fraction of about 50 g is collected which is analyzed by gas chromatography.

L'examen des résultats, consignés dans le tableau suivant, indique la présence d'un azéotrope F347 mcflméthanol.

Figure imgb0001
Examination of the results, recorded in the following table, indicates the presence of an azeotrope F347 mcflmethanol.
Figure imgb0001

b) Vérification de la composition azéotropiqueb) Verification of the azeotropic composition

Dans le bouilleur d'une colonne à distiller adiabatique (30 plateaux), on introduit 200 g d'un mélange comprenant 97,4 % en poids de F347 mcf et 2,6 % en poids de méthanol. Le mélange est ensuite porté à reflux pendant une heure pour amener le système à l'équilibre, puis on soutire une fraction d'environ 50 g et on procède à son analyse par chromatographie en phase gazeuse ainsi qu'à celle du pied de distillation. Les résultats consignés dans le tableau suivant montrent la présence d'un azéotrope.

Figure imgb0002
200 g of a mixture comprising 97.4% by weight of F347 mcf and 2.6% by weight of methanol are introduced into the boiler of an adiabatic distillation column (30 trays). The mixture is then brought to reflux for one hour to bring the system to equilibrium, then a fraction of about 50 g is drawn off and its analysis is carried out by gas chromatography as well as that of the distillation bottom. The results recorded in the following table show the presence of an azeotrope.
Figure imgb0002

Cet azéotrope, employé pour le nettoyage de flux de soudure ou en dégraissage de pièces mécaniques, donne de bons résultats.This azeotrope, used for cleaning solder flux or degreasing mechanical parts, gives good results.

EXEMPLE 2 : Composition stabilisée au nitrométhane EXAMPLE 2 Composition stabilized with nitromethane

Dans une cuve de nettoyage à ultrasons, on introduit 150 g d'un mélange contenant en poids 96,9 % de F347 mcf, 3 % de méthanol et 0,1 % de nitrométhane comme stabilisant. Après avoir mis le système à reflux pendant une heure, on prélève un aliquot de la phase vapeur. Son analyse, par chromatographie en phase gazeuse, montre la présence de nitrométhane, ce qui indique que le mélange est stabilisé dans la phase vapeur.

Figure imgb0003
150 g of a mixture containing by weight 96.9% of F347 mcf, 3% of methanol and 0.1% of nitromethane as stabilizer are introduced into an ultrasonic cleaning tank. After putting the system at reflux for one hour, an aliquot of the vapor phase is removed. Its analysis, by gas chromatography, shows the presence of nitromethane, which indicates that the mixture is stabilized in the vapor phase.
Figure imgb0003

EXEMPLE 3: Nettoyage de flux de soudure EXAMPLE 3 : Cleaning of welding flux

Cinq circuits tests (modèle normalisé IPC-25) sont enduits de flux à base de colophane (flux R8F de la Société ALPHAMETAL)) et recuits dans une étuve à 220°C pendant 30 secondes.Five test circuits (standardized model IPC-25) are coated with rosin-based flux (R8F flux from the company ALPHAMETAL)) and annealed in an oven at 220 ° C for 30 seconds.

Ces circuits sont nettoyés à l'aide d'une composition comprenant 95 % de 347 mcf et 5 % de méthanol dans une machine à ultrasons pendant 3 minutes par immersion et 3 minutes en phase vapeur.These circuits are cleaned using a composition comprising 95% of 347 mcf and 5% of methanol in an ultrasonic machine for 3 minutes by immersion and 3 minutes in the vapor phase.

Le nettoyage est évalué selon la procédure normalisé lPC 2.3.26 à l'aide d'un conductimètre de précision. La valeur obtenue, 0,63 µg/cm2 éq.NaCl, est très inférieure au seuil d'impuretés ioniques toléré par la profession (2,5 µg/cm2 éq.NaCl).The cleaning is evaluated according to the standard procedure lPC 2.3.26 using a precision conductivity meter. The value obtained, 0.63 µg / cm 2 eq.NaCl, is much lower than the ionic impurity threshold tolerated by the profession (2.5 µg / cm 2 eq.NaCl).

EXEMPLE 4EXAMPLE 4

En opérant comme à l'exemple 1 avec l'éthanol, on met en évidence l'existence d'un azéotrope F347 mcf/éthanol qui bout à 32,4°C sous 1,013 bar et contient en poids 98,45 % de F347 mcf et 1,55 % d'éthanol.By operating as in Example 1 with ethanol, it demonstrates the existence of an azeotrope F347 mcf / ethanol which boils at 32.4 ° C at 1.013 bar and contains by weight 98.45% of F347 mcf and 1.55% ethanol.

EXEMPLE 5EXAMPLE 5

En reproduisant l'exemple 1 avec l'isopropanol, on met en évidence l'existence d'un azéotrope F347 mcf/isopropanol contenant, en poids, 99,85 % de F347 mcf et 0,15 % d'isopropanol. Son point d'ébullition sous 1,013 bar est de 32,8°C.By reproducing Example 1 with isopropanol, it is demonstrated the existence of an azeotrope F347 mcf / isopropanol containing, by weight, 99.85% of F347 mcf and 0.15% of isopropanol. Its boiling point under 1.013 bar is 32.8 ° C.

Le F347 mcf utilisé dans les exemples précédents, a été préparé à partir du iodure de 1,1,3,3,4,4,4-heptafluorobutyle (R.D. Chambers et al., Tetrahedron 1964, vol. 20, pp.497-506) par un procédé en deux étapes, la première consistant en une deshydroiodation du iodure pour former l'oléfine CF3CF2CH = CF2 et la seconde consistant en l'hydrogénation catalytique de ladite oléfine.The F347 mcf used in the previous examples was prepared from 1,1,3,3,4,4,4-heptafluorobutyl iodide (RD Chambers et al., Tetrahedron 1964, vol. 20, pp. 497- 506) by a two-step process, the first consisting in a dehydroiodination of iodide to form the olefin CF 3 CF 2 CH = CF 2 and the second consisting in the catalytic hydrogenation of said olefin.

ETAPE 1: Synthèse de l'oléfine CFSTEP 1: Synthesis of the CF olefin 3-3- CFCF 2-2- CH = CFCH = CF 22

On utilise un réacteur en verre de un litre, muni d'une agitation mécanique, d'une ampoule de coulée (500 ml) et surmonté d'un condenseur à eau. Le réacteur est maintenu sous un léger balayage d'azote (10 à 20 ml/min) et la sortie du réfrigérant est reliée à un piège métallique maintenu à -80°C, permettant de récupérer l'oléfine formée qui sort du mélange réactionnel sous forme de gaz (Teb 10-11°C/1 atm). Entre le piège métallique et le réfrigérant, on intercale un flacon laveur contenant de l'eau puis un tube desséchant contenant du chlorure de calcium.A one liter glass reactor is used, equipped with mechanical stirring, a dropping funnel (500 ml) and surmounted by a water condenser. The reactor is maintained under a light nitrogen sweep (10 to 20 ml / min) and the outlet of the refrigerant is connected to a metal trap maintained at -80 ° C., making it possible to recover the olefin formed which leaves the reaction mixture under form of gas (Teb 10-11 ° C / 1 atm). Between the metal trap and the refrigerant, a washing bottle containing water is inserted, followed by a drying tube containing calcium chloride.

Dans le réacteur on charge 502g du composé CF3-CF2-CH2-CF2l (soit 1,62 mole) et 200 ml d'eau. Le mélange est porté à 50°C sous une forte agitation, puis on coule en 30 à 60 minutes 180 g de triéthylamine (soit 1,78 mole). On laisse encore 30 minutes à 50°C après la fin de coulée de la triéthylamine.502 g of the compound CF 3 -CF 2 -CH 2 -CF 2 l (ie 1.62 mole) and 200 ml of water are loaded into the reactor. The mixture is brought to 50 ° C. with vigorous stirring, then poured in 30 to 60 minutes 180 g of triethylamine (or 1.78 mole). Another 30 minutes are left at 50 ° C. after the end of the triethylamine pouring.

On obtient alors dans le piège métallique 272 g d'oléfine CF3-CF2-CH=CF2 (1,49 mole). La pureté du produit obtenu est de 99 % (analyse CPV).272 g of olefin CF 3 -CF 2 -CH = CF 2 (1.49 mole) are then obtained in the metal trap. The purity of the product obtained is 99% (CPV analysis).

ETAPE 2 : Synthèse du F347 mcf STEP 2: Synthesis of F347 mcf

On utilise un réacteur tubulaire en Inconel (diamètre interne: 28 mm, longueur: 420 mm) chauffé par un ruban électrique et chargé avec 48 g (100 ml) d'un catalyseur commercial Pd/charbon à 5 % de palladium.A tubular Inconel reactor is used (internal diameter: 28 mm, length: 420 mm) heated by an electrical tape and loaded with 48 g (100 ml) of a commercial Pd / carbon catalyst with 5% palladium.

L'oléfine synthétisée à l'étape 1 est hydrogénée en phase gaz sur ce catalyseur préalablement activé par passage d'hydrogène (100 ml/min) à 80°C pendant une heure. On introduit ensuite l'hydrogène (100 ml/min mesuré à 20°C) et l'oléfine sous forme gazeuse (40 ml/min mesuré à 20°C). La température du réacteur est maintenue à 80°C. En sortie de réacteur, le F347 mcf est condensé dans un piège maintenu à -80°C.The olefin synthesized in step 1 is hydrogenated in the gas phase on this catalyst previously activated by passing hydrogen (100 ml / min) at 80 ° C for one hour. Then hydrogen is introduced (100 ml / min measured at 20 ° C) and the olefin in gaseous form (40 ml / min measured at 20 ° C). The reactor temperature is maintained at 80 ° C. At the outlet of the reactor, the F347 mcf is condensed in a trap maintained at -80 ° C.

Pour 622 g d'oléfine engagée, on a obtenu 609 g de F347 mcf (rendement : 97 %) de pureté supérieure à 95 % (analyse CPV) et dont la structure a été confirmée par l'analyse RMN en solvant CDCl3. Le tableau suivant indique pour les multiplets observés les déplacements chimiques en ppm par rapport au TMS pour l'analyse RMN H1 et par rapport au TFA (référence externe) pour l'analyse RMN F19. Les spectres ont été obtenus sur un appareil AC 300 BRUCKER équipé d'une sonde QNP.

Figure imgb0004
For 622 g of olefin used, 609 g of F347 mcf (yield: 97%) of greater than 95% purity (CPV analysis) were obtained, the structure of which was confirmed by NMR analysis in CDCl 3 solvent. The following table indicates for the multiplets observed the chemical shifts in ppm with respect to the TMS for the H 1 NMR analysis and with respect to the TFA (external reference) for the F 19 NMR analysis. The spectra were obtained on an AC 300 BRUCKER device equipped with a QNP probe.
Figure imgb0004

Claims (9)

Composition azéotropique ou quasi azéotropique constituée de 1,1,1,2,2,4,4-heptafluorobutane et d'un alcool en C1 à C3.Azeotropic or almost azeotropic composition consisting of 1,1,1,2,2,4,4-heptafluorobutane and a C 1 to C 3 alcohol. Composition selon la revendication 1 contenant en poids 90 à 99 % de 1,1,1,2,2,4,4-heptafluorobutane et 1 à 10 % de méthanol.Composition according to Claim 1 containing by weight 90 to 99% of 1,1,1,2,2,4,4-heptafluorobutane and 1 to 10% of methanol. Composition selon la revendication 2 sous forme d'azéotrope bouillant à 30,6°C à la pression normale.Composition according to Claim 2 in the form of an azeotrope boiling at 30.6 ° C at normal pressure. Composition selon la revendication 1 contenant en poids 90 à 99 % de 1,1,1,2,2,4,4-heptafluorobutane et 1 à 10 % d'éthanol.Composition according to Claim 1, containing by weight 90 to 99% of 1,1,1,2,2,4,4-heptafluorobutane and 1 to 10% of ethanol. Composition selon la revendication 4 sous forme d'azéotrope bouillant à 32,4°C à la pression normale.Composition according to Claim 4 in the form of an azeotrope boiling at 32.4 ° C at normal pressure. Composition selon la revendication 1 contenant en poids 90 à 99,9 % de 1,1,1,2,2,4,4-heptafluorobutane et 0,1 à 10 % d'isopropanol.Composition according to Claim 1, containing by weight 90 to 99.9% of 1,1,1,2,2,4,4-heptafluorobutane and 0.1 to 10% of isopropanol. Composition selon la revendication 6 sous forme d'azéotrope bouillant à 32,8°C à la pression normale.Composition according to Claim 6 in the form of an azeotrope boiling at 32.8 ° C at normal pressure. Composition selon l'une des revendications 1 à 7 comprenant en outre au moins un stabilisant.Composition according to one of claims 1 to 7 further comprising at least one stabilizer. Application d'une composition selon l'une des revendications 1 à 8 au nettoyage des surfaces solides, en particulier au défluxage des circuits imprimés et au dégraissage des pièces mécaniques.Application of a composition according to one of claims 1 to 8 for cleaning solid surfaces, in particular for defluxing printed circuits and for degreasing mechanical parts.
EP96402131A 1995-10-31 1996-10-07 Cleaning composition based on 1,1,1,2,2,4,4-heptafluorobutane and alcohols Withdrawn EP0771865A1 (en)

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FR9512843A FR2740469B1 (en) 1995-10-31 1995-10-31 CLEANING COMPOSITIONS BASED ON 1,1,1,2,2,4,4, - HEPTAFLUOROBUTANE AND ALCOHOLS
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AU7048496A (en) 1997-05-08
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CA2189061A1 (en) 1997-05-01
TW364016B (en) 1999-07-11
CN1157319A (en) 1997-08-20
FR2740469B1 (en) 1997-12-05
JPH09188636A (en) 1997-07-22
US5747437A (en) 1998-05-05

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