EP1499658A1 - Öl- und alkoholabweisende perfluoralkylierte tenside, herstellungsverfahren dafür und verwendung davon als perfluoralkylierungsmittel - Google Patents

Öl- und alkoholabweisende perfluoralkylierte tenside, herstellungsverfahren dafür und verwendung davon als perfluoralkylierungsmittel

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Publication number
EP1499658A1
EP1499658A1 EP03740567A EP03740567A EP1499658A1 EP 1499658 A1 EP1499658 A1 EP 1499658A1 EP 03740567 A EP03740567 A EP 03740567A EP 03740567 A EP03740567 A EP 03740567A EP 1499658 A1 EP1499658 A1 EP 1499658A1
Authority
EP
European Patent Office
Prior art keywords
temperature
mole
added
perfluoroalkyl
chi
Prior art date
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.)
Withdrawn
Application number
EP03740567A
Other languages
English (en)
French (fr)
Inventor
Stéphane SZONYI
Istvan Szonyi
François SZONYI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Szonyi Franeois
SZONYI Istvan
SZONYI Stephane
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP1499658A1 publication Critical patent/EP1499658A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to new polyamines or perfluoroalkylated polyamides, alcolipophobic, free of sulfone or sulfonyl group (SO 2 ), capable of reacting with amines, polyamines, polypeptides derived from proteins and polysaccharides.
  • SO 2 sulfone or sulfonyl group
  • Patents EP 0390905 and EP 0386187 by the same authors respectively propose reactive polyamides and perfluoroalkylated polyamines, which can react with hydrolysed proteins and polysaccharides; thus their application in the field of fire-fighting foams gives excellent results. It should however be noted that these fluorotensides also contain one or more sulfonyl groups (SO 2 ).
  • the one-pot reaction process used respects the environment insofar as it produces no waste, by-product or solvent to be reprocessed. Any by-products produced are transformed during the process and condensed to the main product, so any excess raw material is "digested", without producing any waste.
  • patent EP-0955-327-172 recommends the use of high molecular weight polyamines as a raw material.
  • perfluoroalkyl iodides react with olefins, either in the presence of free radical initiators, of azo type or peroxide, according to well known methods (US 3 145 222), or by simultaneous action of these initiators of free radicals and of dithionite salt (WY Hung, J. Fluorine Chem. 58 (1992) 1-8), of bisulfite (WY Hung, J. Zhuang, Chin. J. Chem., 9 (1991) 373), or thiourea dioxide (WY Hung, J. Zhuang, Chin.
  • CH 2 CH-CH 2 -OH
  • CH 2 CH-CH 2 -O-Glycidyle
  • free radical initiators and bisulfite salts such as sodium metabisulfite or sodium dithionite.
  • the free radical initiators used, and which decompose between the two temperatures mentioned above, are peroxide type compounds such as benzoyl peroxide, ditertiobutyl peroxide, or azo type compounds such as 2,2'-azo -bis-isobutyronitrile, 2,2'-azo-bis- (2,4 dimétyhylvaléronitrile), l, l'-azo-bis- (cyclohexane carbonitrile), 2,2'-azo-bis- (2- methylpropanenitrile), etc.
  • polyamines which can be used are numerous, we will prefer dimethylaminopropylamine (H 2 NC 3 H 6 -N (CH 3 ) 2 ), dimethylaminoethylamine (H 2 NC 2 H 4 -
  • the intermediates obtained having an amino function distant from the fluorinated chain are polycondensed according to the invention by aminolytic action of the polyamine used in excess on an ester site introduced beforehand by means of an alkyl monochloracetate, to lead to the perfluoroalkylated polyamides or alkenylated according to the invention:
  • linkage -CH 2 CHI-CH 2 - between the perfluoroalkylated chain and the rest of the molecule is an ideal description, because, due to the basic nature of the reaction medium, a variable percentage of iodine contained in the molecule is eliminated during different stages of the reaction to lead to a mixture of 2-iodopropyl and allyl linkages between the perfluoroalkylated chain and the rest of the molecule.
  • Polycondensations can also be carried out with glycerol epichlorohydrin in the presence of an excess of amine, this in order to promote the presence of a single perfluorinated chain in the molecule, the solubilization being ensured by a treatment with sodium monochloracetate.
  • the perfluoroalkylated polyamines and the perfluoroalkyl thioureas are obtained according to the invention:
  • p -Glycidyl V
  • the polycondensations described above can also be carried out using simultaneously or in different stages of the process, in the order that is desired and in a variable stoichiometric ratio, an alkyl monohaloacetate and the epichlorohydrin of glycerol. It will be noted, in the case of the products according to the invention, resulting from the use of polyethylene polyamines, that the distribution of the -CH 2 COOM groups is random when their molarity is lower than that of the nitrogen atoms present in the molecule, since no means of selective protection of these atoms is used in the process.
  • the products obtained according to the invention are water-soluble and foam well. They considerably reduce the surface tension of the water and give an oleophobic character to fire-fighting foams when used as an additive. It should be noted that, in addition to this oleophobic nature, the surfactants according to the invention also confer a very pronounced alkophobic character on these foams when they are used therein as an additive. The fact that the same product can make fire fighting foam resistant to hydrocarbon fires and polar liquid fires is completely new. Usually two types of surfactant are used, each of which gives one of the two properties to the foam.
  • the new perfluoroalkylated or alkenylated compounds according to the invention are not only compatible with protein foams, but they also react on the polypeptides to make them alcolipophobic.
  • the products according to the invention can be used as perfluoroalkylant in the macromolecular technique. They can for example react with polyamines, polyetheramines, or polypeptides derived from proteins:
  • R F -CH 2 CHI-CH 2 -O-CH 2 -CH (OH) -CH 2 -N (CH 2 -CO 2 M) -C 3 H 6 -N + (CH 3 ) 2 - [CH 2 OCH 2 CH (OH) -CH 2 -N (CH 2 -CO 2 M) -C 3 H 6 -N + (CH 3 ) 2 -] 2 -CH 2 -CH (OH) -CH 2 Cl Wm R F -CH 2 CHI-CH 2 -O-CH 2 -CH (OH) -CH 2 -N (CH 2 -CO 2 M) -C 3 H 6 -N + (CH 3 ) 2 - [CH 2 - O-CH 2 -
  • the ATC foam concentrate in 5% aqueous solution gives a resistance of 30 seconds -
  • the ATC foam concentrate in 5% aqueous solution, plus 0.1% of the product according to Example No. 9, gives a resistance of 90 seconds - After artificial aging of the previous solution (65 ° C for 24 hours) the resistance value is 200 seconds.
  • One of the additional innovations of the invention resides in the fact that the compounds according to the invention can react on polyamines, polysaccharides (xanthan gums), and polypeptides derived from proteins to make them alcolipophobic in the field of foams. extinguishing.
  • the relative value of oleophobia is 90 seconds.
  • Example 1 46 pp ( ⁇ 0.02 mole) of product obtained in Example 1 are introduced into a reactor fitted with a reflux condenser and an agitator, and 10 pp of water, 10 pp of technical caustic potash dissolved in 18 pp of water, then 10 pp of water. The temperature of the mixture is maintained at 90 ° C for 6 hours. 8 pp of 30% formaldehyde are then added and the mixture is heated at 75 ° C. for 2 hours. The mixture is cooled to 25-30 ° C, then 10 pp of butyldiglycol are added. After standing, the density at 24 ° C is 1.172 and the pH 9.37.
  • the mixture is maintained at 95 ° C for 5 hours, then is cooled to 60 ° C to add 28.9 pp (0.0545 mole) of perfluoroalkyl iodide containing 43% C 6 F 13 I, 35% C 8 F 17 I, 15% C ⁇ 0 F 21 I, 7% C 12 F 25 I) 0.5 pp of 2,2'-azobis (2-methylbutyronitrile) and 6.0 pp of sodium dithionite (85%) dissolved in 19 pp of water.
  • the reaction is exothermic.
  • the temperature rises to 75-80 ° C, the temperature is maintained at 75 ° C for 3 hours.
  • the mixture is maintained at 95 ° C for 5 hours then is cooled to 60 ° C to add 28.9 pp (0.0545 mole) of perfluoroalkyl iodide containing 43% C 6 F 13 I, 35% C 8 F 17 I, 15% C 10 F 21 I, 7% C 12 F 25 I, 0.5 pp of 2,2'-azo-bis (2-methylbutyronitrile) and 5.0 pp of sodium metabisulfite dissolved in 10 pp d 'water.
  • the reaction is exothermic.
  • the temperature rises to 70-80 ° C.
  • the temperature is maintained at 75 ° C for 5 hours. 38 pp of water are then added.
  • a product according to the invention can be used in the field of perfluoroalkylation of polyoxyethylamines.
  • 20 g (0.02 mole) of polyoxyethylamine (p. 1000) are introduced into a reactor equipped with a condenser and an agitator; diluted with 20 ml of water.
  • 80 g ( ⁇ 0.02 mole) of product obtained in Example 6 are added and the mixture is heated and the pH is kept at 9 by adding a 30% solution of caustic potassium. The temperature is maintained at 60 ° C for 1 hour and then at 80 ° C for 5 hours. A slightly viscous solution is obtained whose pH is equal to 9. The value of alkophobia is 80 seconds.
  • the temperature increases slightly (55-60 ° C). Then the temperature is stabilized at around 50 ° C. to add 16.7 pp (0.18 mole) of glycerol epichlorohydrin. The reaction is exothermic. When the addition of the glycerol epichlorohydrin is complete, the mixture is heated to 70 ° C for 15 minutes, then the mixture is heated to 80 ° C for 6 hours. When the mixture is cooled to 25-30 ° C, 3.5 pp of water and 15 pp of butyldiglycol can be added. After standing, the density at 25 ° C is 1.171 and the pH 5.43.
  • the temperature increases slightly (55-60 ° C). Then the temperature is stabilized at around 50 ° C. to add 16.7 pp (0.18 mole) of glycerol epichlorohydrin. The reaction is exothermic. When the addition of glycerol epichlorohydrin is complete, the mixture is heated at 70 ° C for 15 minutes. Then the mixture is heated at 80 ° C for 6 hours. When the mixture is cooled to 25-30 ° C, 12.6 pp of water and 15 pp of butyldiglycol can be added. After standing, the density at 25 ° C is 1.158 and the pH 5.48.
  • a foaming solution is prepared with 6 pp of the concentrate described above and 94 pp of water.
  • Acetone 1 minute (re-ignition: 10 minutes)
  • Heptane AFNOR standard: 2 minutes (re-ignition: 15 minutes)
  • the temperature is allowed to rise to 60 ° C. and 0.1 g of azoisobutyronitrile is added; the temperature is then brought to 75 ° C., and the medium stirred for 6 hours.
  • the temperature is allowed to return to 50 ° C., a solution of 21 g of sodium monochloracetate (0.18 mole) in 30 g of water is added, the temperature is brought to 50-60 ° C. for one hour, and add 5 g of potash.
  • 2.75 g of glycerol epichlorohydrin (0.03 mole) are added and the mixture is heated at 75 ° C. for 6 hours. After cooling the mixture, add a solution of 1.6 g of caustic potassium in 6 g of water to adjust the pH to about 7.5. Then 2 g of butyldiglycol are added.
  • the temperature is allowed to slowly rise to 50-70 ° C; when it no longer increases, it is heated to 90 ° C for 6 hours.
  • the temperature is allowed to return to 50 ° C., a solution of 7 g of sodium monochloracetate (0.06 mol) in 12 g of water is added, and the mixture is heated at 75 ° C for 6 hours.
  • a solution of 2.6 g of caustic potash in 12 g of water is added to adjust the pH to about 7.15.
  • the temperature is allowed to slowly rise to 50-70 ° C; when it no longer increases, it is heated to 90 ° C for 6 hours.
  • the temperature is allowed to return to 50 ° C., a solution of 14 g of sodium monochloracetate (0.12 mole) in 23 g of water is added, and the mixture is heated at 75 ° C for 6 hours.
  • a solution of 5.0 g of potassium hydroxide in 13 g of water is added to adjust the pH to about 7.45.
  • the temperature is allowed to slowly rise to 50-70 ° C; when it no longer increases, it is heated to 90 ° C for 6 hours.
  • the temperature is allowed to return to 50 ° C, a solution of 21 g of sodium monochloracetate (0.18 mole) in 30 g of water is added, and the mixture is heated at 60 ° C for 3 hours; 2.5 g of caustic potash are added and the mixture is heated to 75 ° C. for 3 hours.
  • a solution of 4.0 g of potassium hydroxide in 14 g of water is added to adjust the pH to about 7.11.
  • the temperature is brought back to 40 ° C., 5 g of water are added, then 0.17 g of 2,2'-azobis (2-methylbutyronitrile), 9.63 g of perfluoroalkyl iodide (0.018 mole) containing 43 % C 6 F l, 35% C 8 F 17 I, 15% C 10 F 21 I, 7% C 12 F 25 I and a solution of 2.05 g of 85% sodium dithionite in 6.70 g d 'water. The temperature rises to 70 ° C; heated to 80 ° C for 3 hours.
  • the mixture is then cooled to 40 ° C and 5 g of water are added, then a solution of 21 g of sodium monochloroacetate (0.18 mole) in 30 g of water, and the mixture is heated at 60 ° C for 1 hour; a solution of 3.70 g of caustic potash in 4 g of water is added, and the mixture is heated at 80 ° C. for 6 hours. After cooling the mixture, 3.2 g of caustic potash is added to adjust the pH to about 7.33.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP03740567A 2002-04-30 2003-04-04 Öl- und alkoholabweisende perfluoralkylierte tenside, herstellungsverfahren dafür und verwendung davon als perfluoralkylierungsmittel Withdrawn EP1499658A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0205449A FR2839071B1 (fr) 2002-04-30 2002-04-30 Nouveaux tensioactifs perfluoroalkyles alcolipophobes, leur obtention et leur utilisation comme agents perfluoroalkylants
FR0205449 2002-04-30
PCT/FR2003/001061 WO2003093348A1 (fr) 2002-04-30 2003-04-04 Agents tensioactifs perfluoroalkyles alcolipophobes, leur obtention et leur utilisation comme agents perfluoroalkylants

Publications (1)

Publication Number Publication Date
EP1499658A1 true EP1499658A1 (de) 2005-01-26

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP03740567A Withdrawn EP1499658A1 (de) 2002-04-30 2003-04-04 Öl- und alkoholabweisende perfluoralkylierte tenside, herstellungsverfahren dafür und verwendung davon als perfluoralkylierungsmittel

Country Status (4)

Country Link
EP (1) EP1499658A1 (de)
AU (1) AU2003265502A1 (de)
FR (1) FR2839071B1 (de)
WO (1) WO2003093348A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2866027B1 (fr) * 2004-02-05 2007-09-21 Stephane Szonyi Nouveaux tensioactifs lipohobes et/ou alcophobes, leur obtention et leur utilisation.
FR2866883B1 (fr) * 2004-02-27 2006-03-31 Stephane Szonyi Nouveaux agents tensioactifs perfluoroalkyles, hydrophobes et oleophobes derives d'amides substituees, leur preparation et leur utilisation
FR2893629B1 (fr) * 2005-11-23 2009-10-16 Stephane Szonyi Nouveaux polyamides perfluoroalkyles lipophobes et leur obtention et leur utilisation
US8026289B2 (en) 2008-10-21 2011-09-27 E.I. Du Pont De Nemours And Company Fluorinated polyoxyalkylene glycol diamide surfactants

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990003966A1 (fr) * 1988-10-10 1990-04-19 Istvan Szonyi Composes amidofluores, leur obtention et leur utilisation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2605628B1 (fr) * 1986-10-23 1989-03-31 Atochem Imines fluoroalkylees et leurs procedes de preparation
FR2637590B1 (fr) * 1988-08-24 1991-01-04 Szonyi Istvan Nouveaux composes fluores reactifs, hydrosolubles, leurs obtention et leurs utilisations
FR2637506B1 (fr) * 1988-10-10 1993-04-30 Szonyi Istvan Nouveaux liquides emulseurs pour la production de mousse extinctrice; leur production et leur utilisation
FR2701407B1 (fr) * 1993-02-11 1995-05-19 Istvan Szonyi Nouveaux tensioactifs fluorés alco-oléphobes, leurs intermédiaires, leurs obtentions et leurs applications.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990003966A1 (fr) * 1988-10-10 1990-04-19 Istvan Szonyi Composes amidofluores, leur obtention et leur utilisation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO03093348A1 *

Also Published As

Publication number Publication date
WO2003093348A1 (fr) 2003-11-13
FR2839071B1 (fr) 2004-06-25
FR2839071A1 (fr) 2003-10-31
AU2003265502A1 (en) 2003-11-17

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