IE58051B1

IE58051B1 - Water-removing composition based on fluorochloro-hydrocarbon and surfactant

Info

Publication number: IE58051B1
Application number: IE155385A
Authority: IE
Inventors: Jean Pierre Remond
Original assignee: Atochem
Priority date: 1984-06-29
Filing date: 1985-06-24
Publication date: 1993-06-16
Also published as: TR22965A; PT80740B; EP0189436B1; AU4492685A; ES544677A0; DE3565552D1; WO1986000329A1; JPS61502947A; CN85105017A; EP0189436A1; ATE37897T1; GR851606B; KR860700131A; PT80740A; FR2566788A1; IE851553L; AU577395B2; ES8608029A1

Abstract

The composition based on fluorochlorohydrocarbon contains a surface active agent resulting from the reaction of a quaternary ammonium chlorhydrate with an alkyl phosphoric acid in the presence of a fluor-containing amine and a carboxylic acid. The separation rate of the aqueous and organic phase is improved.

Description

The present invention relates to a composition which can be used, in particular, for removing water present on a wet surface.

Water-removing compositions of various types have 5 been described. Such compositions generally contain a fluorochlorohydrocarbon, more specifically 1,1,2-trichloro1,2,2-trifluoroethane, and one or more surfactants, for example an alkyl phosphate neutralised by means of an amine, an amine salt, a diamide, where appropriate in the presence of a carboxylic acid or a cationic imidazoline surfactant, or alternatively a surfactant resulting from the reaction of quaternary ammonium chloride with an alkylphosphoric acid in the presence of a fluorinated amine (see European Patent 83/400293.3).

The present invention relates to an improvement in the compositions described in the said European Patent, the improvement being in respect of the rate of separation of the aqueous phase from the organic phase during the removal of the water.

More specifically, the invention relates to a water-removing composition which can be used for displacing Liquid water, the said composition containing a solvent consisting of at least 50% by weight of a chlorofluorohydrocarbon and a surfactant resulting from the reaction of a quaternary ammonium chloride of formula: (R>2^+^N CR’)2 εΐ(-) (I) with an alkyl phosphoric acid of formula : (R0)p CH0)2-p CII) in the presence of a fluorinated amine of formula: Rp XNR-, R2 (III), in which formulae Rp denotes a linear or branched perfluorinated chain CqF2q+1z in wbich q is an integer between 2 and 20, X is a bivalently bonded group, optionally partially halogenated, R is an alkyl group having 6 to 18 carbon atoms, R' is an alkyl group having 1 to 2 carbon atoms, R-j and R2^ which may be identical or different, denote a hydrogen atom, an alkyl radical or a hydroxyalkyl radical having from 1 to 8 carbon atoms, and R is an alkyl group having from 1 to 18 carbon atoms, the said composition being characterised in that it contains at least one carboxylic acid chosen from saturated linear, branched or cyclic aliphatic mono- or diacids having from 5 to 10 carbon atoms, and optionally substituted; unsaturated Linear or branched aliphatic mono- or diacids having from 5 to 30 carbon atoms and optionally substituted; and aromatic acids having from 7 to 9 carbon atoms, optionally mono- or polysubstituted with amino, nitro, hydroxy or methoxy groups.

The compositions according to the invention advantageously contain, by weight: - from 90 to 99.9855 of solvent - from 0.01 to 85ό of surfactant - from 0.01 to 2?ό of carboxylic acid, the total of the amounts of the three constituents being 100%.

In these compositions, the chlorofluorohydrocarbon is advantageously 1,1,2-trichloro-1,2,2-trifluoroethane and the complementary solvent is advantageously an aliphatic hydrocarbon such as hexane, an aliphatic cut such as white spirit or kerosene, a halogenated aliphatic hydrocarbon such as chloroform, methylene chloride, a dichloroethane or trichloroethane, 1,1 , 2,2-tetrachloroethane , 1,1,2,2-tetrachloro-1,2-difluoroethane, perchloroethylene, trichloroethylene, or an aromatic hydrocarbon such as xylene.

The various surfactants described in European Patent 85/400293.3 can be used. The products are preferably those which result from the reaction of a quaternary ammonium chloride of formula (I) in which R' denotes a methyl group and R denotes an alkyl group having from 12 to 18 carbon atoms, with a mixture of mono- and dialkylphosphoric acids of formula (II), in which the symbol R denotes an alkyl radical having from 4 to carbon atoms, this reaction being performed in the presence of a fluorinated amine of formula (III), in which the symbol q is from 4 to 10, R^ and R2 denote a hydrogen atom or a methyl, ethyl or hydroxy ethyl radical, and X denotes a saturated or unsaturated bivalent radical which is wholly hydrocarbon or is hydrocarbon substituted by a fluorine atom or a radical consisting of one or more of the above bivalent radicals and a -CONH- or -NH- group.

The preparation of the surfactant, preferably in the solvent medium of the composition according to the invention, is described in European Patent 83/400293.3.

Examples of acids which can be used include: valeric, caproic, oenanthic, caprylic, pimelic, suberic, azelaic and sebacic acids; oleic, linoleic, undecylenic and ricinoleic acids; cyclohexanemonocarboxylic or trans-1,2- or -1 , 4-cyc1ohexanedicarboxy1ic acids; benzoic, ortho- or para-hydroxybenzoic, 2-ami no-benzoic , 3-nitro15 salicylic, 5-nitrosalicylic, ortho-toluic and cinnamic acids The water-removing composition according to the invention can be prepared by simple mixing of its constituents. It can also be produced by adding the carboxylic acid to a composition containing the solvent and the surfactant, prepared separately or in the presence of all or part of the solvent. When the surfactant is prepared directly in the solvent, the composition can contain all or part of the fluorinated amine hydrochloride formed, and this product can be removed in different ways, for example by dissolution in water during drying, or by filtration, advantageously performed from a concentrated composition. The choice of extraction method of this hydrochloride is linked to its solubility in the medium as will be appreciated by those skilled in the art.

The compositions according to the invention make it possible to accomplish very effective drying, and more specifically to remove water from the surface of articles of various kinds. It is especially suitable for removing water from metal articles, objects made of glass or refractory materials, precious stones or plastic objects.

By means of these compositions, rapid removal or displacement of the water is observed; also there is a substantial increase in the rate of separation of the aqueous and organic phases formed during the removal of the water, which constitutes an advantage when the compositions are used in installations provided for this purpose. Thus, the water, rapidly separated from the drying composition, may be discharged into the drain by means of a suitable device (settler).

The Examples which follow further illustrate the present invention. In these examples, the abbreviations have the following significances: - + ) chloride: dimethyldi 1aurylammonium chloride ( + ) (-) L C Ί 2 h25^2 N C I The product used is commercially available, containing 75% of active material in isopropanol and 0.161 chlorine equivalent per 100 g. It is a mixture of homologues according to the following distribution (by weight):C8 3 % C16 10 %c10 6% C-^g saturated 2%C12 56% C -, g unsaturated 5%C1 4 18% - F 113 : 1,1,2-trichloro-1z2,2-trifIuoroetha P r epa ration and formulation Th e following mixture is prepared at room temperature: . chloride: 8.32 g (0.88 mole) . Buty I phosphoric acid: 2.69 g (1 mole) . Amine C^F-j 3H4S O2NH N (04^)27.82 g (1 mole) . F 113 : 150 g The initial solution becomes turbid quite quickly, and after the mixture has been left to stand for 24 hours, 4.2 g of a white crystallised solid, identified as the fluorinated amine hydrochloride, are collected after filtration.

The filtrate, which is completely clear, is diluted with F 113 (concentration 0.04% by weight).

This formulation, a control, is designated Formulation 1 .

Formulation 2 contains, by weight, 99.86% of F 113, 0.04% of filtrate of the Formulation 1 and 0.1% of ca p ry I i c acid. Formulation 3 contains, by weight, 99.86% of F 113, 0.04% o f the filtrate of the Formulation 1 and 0.1% o f benzoi c acid. • Exa mpI e 1: emulsification test 1.1. In a bottle, there are placed 50 g of the formulation to be tested and 18 g of distilled water. The bottle is shaken vigorously for 30 seconds. The emulsion formed is then allowed to stand, and the time, and the thickness of the interface between the organic lower phase and the aqueous upper phase, are measured.

The following observations are made: Thickness in mm of the interface Duration in Formulation Fo rmulation Formulation mi nut es No . 1 No. 2 No. 3 5 20 3 1 10 5 0 0 60 0 0 0 The bottles containing the above formulations are again shaken for 30 seconds.

Thickness in mm of the interface i Du ra t i on j Formulation formulation Formulation Min Hours No. 1 No. 2 No. 3 10 30 13 10 20 30 1 1 6 60 30 4 1 2 28 2 0 48 25 1 0 1.2. (Control). In a tank of approximate size 200 x 150 x 150 mm, a mixture consisting of 7 I of the Formulation No. 1 and 0.800 I of distilled water is circulated with continuous recycling by means of a pump and at a flow rate of approximately 300 l/h.

After 5 min, it is observed that the mixture has a homogeneous appearance. A sample withdrawn after this time shows, after 3 min, 2 phases: a slightly turbid lower organic phase and a viscous upper phase which is, in fact, an emulsion of the organic phase and the aqueous phase.

The appearance of a c I ea r aqueous phase is not observed after 48 hours .

. (Invention). The procedure described above is carried out using the Formulation No. 3. A sample is withdrawn after the mixture has been circulated at a flow rate of approximately 300 l/h for 5 minutes. The 9 sample shows, after distinctly separate emulsion. minutes, an a qu eous phase o rga ni c w i t h ou t phase and a a t ra c e of Example 2: drying tests 5 Drying of nickel 45 A 45 rpm sta mper is alkaline detergent solution rpm record stampers. previously degreased in an in the presence of ultrasound. and then rinsed in running tap water. It is then immersed in one of the Formulations 1, 2 or 3, brought to boiling 10 for 3 minutes, and then rinsed in pure F 113.

Over 5 tests, it is observed that 100% drying of this stamper is obtained with each of the formulations used: the compositions according to the invention hence combine great drying efficiency with the improved rate of separation of the phases.

Claims

1.CLAIMS Ί. A water-removing composition which comprises a solvent, at least 50% by weight of which is a chlorofluorohydrocarbon, a surfactant resulting from the reaction of a quaternary ammonium chloride of formula: (R) 2 ^ + ^N (R') 2 Cl (_) (I) with an alkyl phosphoric acid of formula: (R0) (H0)„ PO„H (II) in the presence of a p 2-p 2 fluorinated amine of formula: R^ XNR^ (III) > in which formulae R^ denotes a linear or branched perfluorinated chain C F„ . , in which q is an integer from 2 to q 2q+1 73 20, X denotes a bivalent hydrocarbon group, optionally partially halogenated, R denotes an alkyl group having 6 to 18 carbon atoms, R' denotes an alkyl group having 1 or 2 carbon atoms, Rand R^, which may be identical or different, denote a hydrogen atom, an alkyl radical or a hydroxyalkyl radical having from 1 to 8 carbon atoms, and R denotes an alkyl group having from 1 to 18 carbon atoms, and at least one carboxylic acid which is an optionally substituted saturated linear, branched or cyclic aliphatic mono- or diacid having from 5 to 10 carbon atoms; an optionally substituted unsaturated linear or branched aliphatic mono- or diacid having from 5 to 50 carbon atoms or an aromatic acid having from 7 to 9 carbon atoms, optionally substituted by one or more amino, nitro, hydroxy or methoxy groups.

2. A composition according to claim 1, which contains (by weight) from 90 to 99.98% of solvent, from 0.01 to 8% of surfactant and from 0.01 to 2% of carboxylic acid, the total amount of the three constituents being 1005o.

3. A composition according to claim 1 or 2,in which the chlorofluorohydrocarbon is 1 ,1 , 2-trichloro-1,2,2trif luoroeth ane .

4. A composition according to any one of claims 1 to 3 in which R’ denotes a methyl group and R denotes an alkyl group having from 12 to 18 carbon atoms.

5. A composition according to any one of claims 1 to 4 in which R denotes an alkyl radical having from 4 to 14 carbon atoms.

6. A composition according to any one of claims 1 to 5 in which q is from 4 to 10, R^ and R^ denote a hydrogen atom or a methyl, ethyl or hydroxyethyl radical and X denotes a saturated or unsaturated bivalent wholly hydrocarbon or hydrocarbon partially substituted by fluorine radical or a radical containing one or more said bivalent radicals and a -50^-, -CONH- or -NH- group.

7. A composition according to any one of claims 1 to 6, in which the surfactant is one resulting from the reaction of a quaternary ammonium chloride of formula I in which R' denotes a methyl group and R denotes an alkyl group having from 12 to 18 carbon atoms, with a mixture of mono- and dia1ky1 phosphoric acids of formula (II), in which R denotes an alkyl radical having from 4 to 14 carbon atoms, this reaction being performed in the presence of a fluorinated amine of formula (III), in which q is from 4 to 10, R^ and R 2 denote a hydrogen atom or a methyl, ethyl or hydroxy ethyl radical, and X denotes a saturated or unsaturated bivalent wholly hydrocarbon or hydrocarbon partially substituted by fluorine radical, or a radical containing one or more of the above bivalent radicals and a -SC^-» -CONH- or -NH- group. 5

8. A composition according to claim 1 substantially as described in the Examples.

9. A method of removing water from the surface of an article, which comprises applying thereto a composition as claimed in any one of the preceding claims.