DE2829616A1 - FLUORINE SURFACE-ACTIVE AGENTS, THEIR MANUFACTURING AND USE IN FOAMABLE AQUATIC COMPOSITIONS THAT CAN BE USED IN FIRE FIGHTING - Google Patents

Description

2829616 Patent Attorney "July 5, 1978

DR. RICHARD KNEISSC Widsnmayerstr. 46

D-8000 MUNICH 22 Tel. 089/295125.

Folder 24 483 ICI Case MD 29646

IMPERIAL CHEMICAL INDUSTRIES LBiITED London / Great Britain

Fluorinated surfactants, their preparation and their use in foamable aqueous compositions, the Can be used in fire fighting

809886/0677

'-. ·. description

The invention relates to fluorine-containing surface-active agents and to a process for their preparation, in particular to fluorine-containing surface-active agents which contain a perfluorocarbon group and which are suitable for use as foaming agents in aqueous "Ksdier." F.euerbekär: pfungszusanr.c "setzvir.gen _i which with fresh water or odsr Eee -'.- water foamed v.'erder., Are suitable.

It is known that some fluorine-containing surfactants can be used as foaming agents in fire fighting compositions which are used with Water to be foamed, are suitable. For example, G3-PS 1 270 56-1 describes a foamable aqueous composition, which contains at least one surfactant derived from a branched tetrafluoroethylene oligomer of the

Formula ^C 2n ^F 4n-1 ~ ^0C 6 ^H 4 ^C0 ~ ^{R cder C} 2n ^F 4n-1 ~ ^0C 6 ^H 4 ^S0 2 " ^R S ·" ⁰¹ ® ¹ · ¹ ^ »where Pl stands for a hydrophilic group and η stands for 4, 5 or 6. "Furthermore, in GB-PS 1 349 509 a foamable composition for fire fighting is described, which a foaming agent, ¥ water, a flame-retardant compound with a content of bromine or iodine and a surface-active agent with a content of a terminal aliphatic perfluorocarbon chain with at least 3 Contains carbon atoms, the composition optionally containing a protein or a hydrolyzed protein. In addition, GE-PS 1 070 259 describes an aqueous foam which is suitable for fire extinguishing and which is made from an aqueous solution of a fluorine-containing surface-active agent which has a ferfluoroalkyl group Contains at least 3 carbon atoms, is produced as a foaming agent.

However, it must be stated that fire extinguishing compositions, which contain fluorine-containing surface-active agents derived from tetrafluoroethylene oligomers, although with foaming Tap water will produce a stable foam, but when it foams

809886/0677

ORIGINAL INSPECTED

- JSf .

using seawater to create a foam that does not expand and has no stability. There have now been new fluorine-containing surfactants Found means that when used as a foaming agent or as one of the foaming agents, a foam with a result in improved expansion and stability.

Thus, according to the invention, there are fluorine-containing surface active agents the formula:

proposed, where R ~ is a perfluorocarbon group of the formula ^C 2n ^F 4n-1 ~ ⁸ ^ ⁵ * ¹ ** where η is at least 4, m is an integer from 1 to 5, X is alkali metal, ammonium or substituted ammonium and R is hydrogen, alkyl, hydroxyalkyl or a group of the formula (CH ₂ ^ OSO - * ". X ⁺ .

The surfactant is a mono sulfate salt or a disulfate salt.

The new compounds are exceptionally surface-active in aqueous media. If they are present in only very low concentrations, such as 500 ppm, then they result in aqueous systems with a very low surface tension. For example, a 0.1% tap water solution of the surfactant in which R _{f is} C ₃ F ₁₅ -, η is 2 and X is triethanolamino, ie. the compound of the formula:

Therefore, a surface tension of only 23 dynes / cm at 25 ° C these surfactants are useful in applications where an aqueous system with low surface tension is desired is. One application in which the surfactants described above are particularly useful is in foamable aqueous compositions for fire fighting using

809886/0677

Frothed seawater. Accordingly, in a further aspect, the invention relates to a scoopable aqueous composition, the at least one fluorine-containing surfactant as described in the immediately preceding paragraph.

The perfluorocarbon group R- has the formula C ₀ F / _o - »

χ 2n H-n — 2 *

where η is at least 4 and is preferably 4, 5 or 6. It is a branched perfluoroalkenyl group, which can be a residue of an oligomer of tetrafluoroethylene or kexafluoropropene. Gli ^ oinere of Tetrafiuoroäthylen are ethylenically unsaturated ₇ branched chain perfluoroolefins, as it is described in GB-PS 1 032 127, which also describes a process for their preparation. Improved processes for the preparation of such oligomers are described in British Patents 1,296,676 and 1,230,350. Oligomers of tetrafluoroethylene of the formula CF »-, where η is 4, 5 or 6, ie the tetrafluoroethylene, pentamer or hexamer of tetrafluoroethylene, have the formulas:

CF ₃
CF ₃ CF ₂ -C = C- CF ₂ CF ₃ . Tetramer

^CF 2 CF-.
I 3 CF
^Lt 3 CF ₃ cp ··· c ^ ·· I.
C = CF CF
r CF ₃ CF ₂ CF _?
C "- I.
CF ₃ ^CF 3
C. CF ₂ N «3
CF CF ₃ CF ₂ Π ^ CF ₂ CF ₃ CF ₃
CF 9 CF
j C ₄ F CF ₃ 809886/0677

Pan tamer

I · examer

'(ΙΪ)

Kexamer, which is obtained by the process described in the above GB-PSs, consists almost exclusively of the isoner (I) with only traces of the isoner (II). Eexafluoropropene oligomers are also branched, internally unsaturated perfluoroolefins of the empirical formula (C ^ F ^) ^, where η is 2 or 5 . These oligomers can be prepared, for example, by heating hexafluoropropene with an ionic catalyst such as a metal halide in a polar organic solvent such as diethyl form.

The fluorine-containing surface-active agents can be prepared by mixing the corresponding sulfonyl chloride compound of the formula Rf-OCgH ₄ SO ₂ Cl with a conoalkanolamine or a dialkanolamine of the formula NH (R) (ROH) or NK (R ¹ OH) ₂ , where R ' represents an alkyl group having 1 to 6 carbon atoms and R represents hydrogen or an alkyl group, wherein the alcohol

R - OC ^ Hz ₁ SO ₉ N (R) (R ¹ OH) or IU-OCsHf ₁ SO ₀ N (R ¹ OH) ₀

is obtained, and that the alcohol is then sulfated with chlorosulfonic acid or sulfur trioxide. Accordingly, the value of m in final surfactants depends on the alkyl group of the mono- or dialkanolamine used and can range from 1 to 6. For example, if diethanolamine JJH (CH ₂ CH ₂ OH) _{2 is used} as the reactant, then the ¥ ert of m in the surfactant is 2.

Accordingly, the invention further relates to a process for the preparation of fluorine-containing surface-active agents, which is carried out by adding an alcohol of the formula Rf-OCgH ₄ SO ₂ N (R) (CH ₂ ) _m OH or Rf-OCgK ₄ -SO ₂ Nf (CH _{2) m} 0H] ₂ wherein R _f, R and m are as defined hereinbefore, is reacted with chlorosulfonic acid or sulfur trioxide at a temperature below 60 ⁰ C.

809886/0677
ORIGINAL INSPECTED

-ν

The reaction of the alcohol with chlorosulfonic acid is exothermic, so the rate of addition of the acid, dia zwackmäßigerweise done by dropwise addition to the stirred reaction mixture is controlled so that the temperature of the reaction mixture to 60 ° C and preferably from 25 ⁰ C is not exceeded. Cooling measures can be taken to cool the reaction mixture during the addition of the acid and the subsequent reaction. The alcohol is preferably precooled, for example to 10 ^° C., before the acid is added. It is preferred that the temperature be consistently below. 20 ⁰ C is held. The reaction of the alcohol - • it sulfur dioxide can under conditions of moderate reflux Dder at low
be guided.

or at low temperatures, for example at about -O ⁰ C, from-

Usually the reaction is carried out in a solvent or diluent for the alcohol, which can be a viscous liquid, executed. Suitable solvents / diluents are aprotic "see organic solvents such as diglyme, triglya, tetrahydrofuran or dioxane. The alcohol is conveniently called. Solution in the solvent, for example as a 50 wt .- ^ ige solution, used.

When the reaction is complete, the mixture can be quenched in water suitably at room temperature to prepare an aqueous solution of the product. The pH of the aqueous r.ediums should be kept above 7.0 during the deterrent, im an "excessive degradation by hydrolysis of the surface-active I- ^ ttels, which would occur in an acidic I-Iadium, should be avoided. It is therefore desirable to add a base to the aqueous medium in order to ensure a pH greater than 7.0. Sine base is preferred introduced into the water in which the reaction product mixture is deterred. Suitable bases are alkali metal hydroxides and amines, such as triethanolamine,

809886/0677

* OF ^ GINAI; INSPECTION

If the temperature of the reaction mixture is ^{kept below 20 °} C. throughout and if it is ensured that the pH of an aqueous quenching medium is greater than 7.0, then the reaction can be carried out with a yield of 10% of the desired product.

The reaction requires 1 liter of chlorosulfonic acid for each hydroxyl group of alcohol. In practice, a slight excess of the acid will normally be used.

The alcohol used as the starting material can be prepared by reacting the corresponding sulfonyl chloride _{compound of the formula R f} —OC ^ H / —SQpCl with a monohedral dialkanolamine ,, 'as stated above. The reaction is normally carried out in a solvent or solvent mixture for the reaction participants. A convenient technique consists in adding a solution of the sulfonyl chloride compound, for example a 50% by weight solution in methylene chloride, to a stirred reading of the

Alkanolamine, for example to a 50% solution in acetone, is added. The reaction is exothermic. The exothere ^T, 7armetönung is controlled by the rate of addition of Sulfcrr / lchloridverbindung, so that a moderate reflux is maintained for example at a temperature of about 40 ⁰ C. Irach completion of the reaction the alcohol product with dilute hydrochloric acid and Nasser can be washed to To remove anine hydrochloride. The alcohol can be separated as a lower layer, dried vr.c. filtered and the solvent removed under reduced pressure.

Solvents involved in the reaction of the sulfonyl chloride compound with which alkanolamine can be used are e.g. chlorinated organic solvents such as 3. Kethylene chloride and 1,1,2-trichloro-1,2,2-trifluoroethane, and polar organic solvents such as acetone, methanol and isopropyl alcohol. Mixtures of Solvents can also be used, such as mixtures of ethylene chloride or 1,1,2-trichloro-1,2,2-trifluoroethane with Acetone and / or methanol.

809886/0677
ORIGINAL INSPECTED

The sulfonyl chloride compound for the preparation of the alcohol can be produced by reacting chlorosulfonic acid with an oligomeric phenyl ether of the formula R ^ -OCgH ₁ -.

For example, the Fnenyläther can slowly to the stirred chlorosulfonic acid are added at room temperature, the resulting product mixture is then quenched in Viasser or in einsn water / ice Gs-Tiocla, which is maintained at a temperature below 3O ⁰ C, ur: excessive K3 ^T to avoid drolysis of the product. The product is a white, waxy solid which, after extraction with 1-ethylene chloride, can be separated off, dried and filtered. The preparation of the sulfonyl chloride compounds from the oligomeric phenyl ethers is described in C-3 PS 1,366,691.

Phenyl ether oligomers can easily be prepared by reacting an oligomer with phenol in the presence of an organic solvent and an amine such as triethylamine, for example by slowly adding the oligomer to a stirred solution of the phenol and amine in a solvent such as eg dimethylformamide, at about 75 ^° C. The product can be washed with dilute hydrochloric acid and water, separated off and dried. The reaction conditions for this reaction, in which IHoI phenol Ce Hol oligomers are used, are described in GBPS 1,366,691, for example. An alternative reaction for the preparation of the phenyl ether is described in GB-PS 1,371,054 and consists in reacting an oligomer with phenol in the presence of an alkali metal salt of an acid, the salt being one in which. the alkali metal has replaced a weakly acidic hydrogen atom of the acid, as is the case, for example, with sodium carbonate.

809886/0677

~ 44- -

Ali

^As already described above, the fluorine-containing surface-active agents according to the invention are suitable for a wide variety of applications, a particular application being in foamable aqueous compositions for fire-fighting. For this application, these aqueous compositions will typically contain from 0.01 to 5% by weight of the surfactant. The compositions can additionally contain any ingredients that are normally incorporated into fire extinguishing compositions, such as protein or hydrolyzed protein, additional surfactants, which can be hydrocarbon surfactants, or other fluorine-containing surfactants, ureas or thioureas, thixotropic agents and flame retardants Gowns that contain bromine or chlorine.

The surfactants do not emulsify oil in water and are therefore useful in oil recovery and coalescing of oil. Their aqueous compositions have a high fuel tolerance in the hot and cold state.

The invention is illustrated in more detail by the following examples. example 1

400 g of tetrafluoroäthylente tramer, CgF-ig, were slowly added to a stirred solution of 94 g of phenol and 101 g of triethylamine in 200 g of dimethylformamide in a reactor, the rate of addition of the tetramer being controlled such that the temperature of the reaction mixture was 45 until 50 ⁰ C remained. After the addition of the tetramer had ended, the stirred mixture was ^{kept at 45 to 50 °} C. for a further 2 h and then allowed to cool to room temperature (20 ^{° C.) without stirring.} The resulting lower layer was separated and washed successively with dilute hydrochloric acid and then with water until all of the unreacted phenol and triethylamine were removed. Approximately 430 g of a pale yellow liquid was obtained. This product was identified as a tetramer (phenyl ether) of the formula C ₃ F ₁₅ -OCgH ₅ .

809886/0677 |

- j? ^j -

474 g of tetramer phenyl ether were slowly added with stirring to a four-molar excess of 580 g of chlorosulfonic acid at room temperature, and the resulting mixture was stirred for a further 2 hours after the addition of the plienyl ether had ended. The mixture was then quenched by pouring into ice / Was3er, wherein the temperature of the resulting mixture was kept below 30 ⁰ C. A white waxy solid was obtained which was extracted into methylene chloride. Approximately 50 g of isopropyl alcohol were added to the extract, vcn. to break the methylene chloride / water emulsion, whereupon "the! ■ '• ethylenechlcr-dlc-solution off = reti-snr.t, dried and filtered". Their concentration was adjusted to 50 percent - adjusted%.. The product was identified as the sulfonyl chloride _{compound of the formula C 3} F ₁₅ -OCgH ^ SO ₂ Cl.

572 "g of the 50% by weight solution of the sulfonyl chloride compound in methylene chloride was slowly added to 210 g of a stirred 50% by weight solution of diethanolamine in acetone, the rate of addition being such that moderate reflux (approx 40 ^° C. After the addition of the sulfonyl chloride compound had ended, the mixture was stirred for a further 2 hours, and the resulting lower layer was separated off, washed successively with dilute hydrochloric acid and water until all of the unreacted diethanolamine had been removed, dried and filtered The product was identified as an alcohol of the formula C ₈ F ₁₅ -OCgH ^ SO ₂ N (CH ₂ CH ₂ OH) ₂ .

641 g of a 50 wt .-% solution of the alcohol in diglyme were cooled below 10 ⁰ C and stirred, after which 61 g of chlorosulfonic acid were added dropwise at such a rate that the temperature of the mixture remained below 20 ^0C. A cooling coil in the reactor helped to maintain the temperature of the mixture. After completion of the addition of the chlorosulfonic acid, the mixture was stirred for 15 min below 20 ⁰ C and then quenched in a reading of 100 g of triethanolamine in 1500 g water. The pH of the solution was kept above 7 by adding additional amounts of triethanolamine during the quenching. After quenching, the

809886/0677

ORIGINAL INSPECTED

resulting solution diluted with water, so that a 20 wt .-% A solution of the fluorine-containing surfactant resulted.

The product was identified by titration as

.CH ₂ CH ₂ OSO ₃ ^ NH (CH ₂ CH ₂ OH) ₃

- OC _fi H.SO ~ N

b 4 Δ ^ c ^ Q ^ oso ^^ pHtCH ₂ CE ₂ CH) ₃

identified.

Aqueous solutions of the surfactants at concentrations of 1 and 0.1 wt .- o wurder prepared and their surface tensions were measured at 25 ⁰ C. The 1 / i solution had a surface tension of 24.4 dynes / cm and the 0.1 o solution had a surface tension of 23 dynes / cm.

Example 2

The procedure described in Example 1 was repeated except that 500 g of tetrafluoroethylene pentamer of the formula C ^ qF ^ q instead of the tetramer for the preparation of the pentamer phenyl ether of the formula CjQF ^ gOCgHc were used.

As in Example 1, 574 g of the pentanerphenyl ether were unset with a large molar excess of 580 g of chlorosulfonic acid, and the 672 g of the resulting 50% by weight solution of the sulfonyl chloride of the formula C ^ F ^ gOCVH-SOpCl in I-ethylene chloride ^ mrden with 210 g of diethanolamine reacted according to the procedure of Example 1, the diol of the formula C ₁₀ F ₁₉ OCgH ^ SO ₂ N (CEpCK ₂ OH) _{2 being} obtained. 741 g of the diol were again reacted as in Example 1 with 61 g of chlorosulfonic acid. The product was identified as C ₁ QF _1g -0C ₆ H ₄ S0 ₂ -N [CH ₂ CH ₂ OSO ₃ ^- N ⁺ K (CH ₂ CH ₂ OK) _5] identified. ₂

809886/0677

- IS

Example 3

The procedure described in Example 1 was repeated _P atisser that 150 g of N-Hethyläthanola.min of the formula NH (CH ₃ ) (CH ₂ CH ₂ OH) instead of diethanolamine for the preparation of the alcohol of the formula

OH ₃
CgF ₁ C-OC ₆ HrSO ₂ -N-CH ₂ CH ₂ OH were used.

in g of the 50% by weight solution of this alcohol in diglyme when reacted with 61 g of chlorosulfonic acid, an end product which was identified as follows:

C ₃ F ₁ CC ₆ H ₄ SO ₂ -N-CH ₂ CH ₂ OSO ₃ ". N ⁺ H (CH ₂ CH ₂ OH) _3. Example 4

The procedure described in Example 2 was repeated, except that 150 g of N-methylethanolamine used instead of diethanolamine and with 627 g of chlorosulfonic acid to produce the alcohol of

Formula C ₁₀ F ₁ QC ₆ H-SO ₂ -N-CH ₂ CH ₂ OH.

711 g of the 50 wt .- ^ igen solution of this alcohol were with 61 g Chlorosulfonic acid implemented.

The end product, which was only slightly soluble in water, was identified as follows:

CH,
₁ Q-OC ₆ H ₄ SO ₂ -N-CH ₂ CH ₂ OSO ₃ ".N ⁺ H (CH ₂ CH ₂ OH)

Example 5

This example illustrates the effect of incorporating the invention surfactants in foamable compositions upon the expansion of a foam.

809886/0677

Foamable compositions were made according to the following approach:

Ingredient weight percentage in %

Gelatin 0.45

surfactant (I) 0.03

Monolan P100 0.7

Enpicol TCR 0.03

Isopropyl alcohol 1.00

I Jams to ff 2.0

surface-active gown (II) see below

artificial lake water to 100

The surfactant (I) was a derivative of monophenyl ether of tetrafluoroetrylene tetramer.

Monolan P 100 is a commercially available ethylene oxide / propylene oxide copolymer.

Enpicol TCR is a commercially available lauryl sulfate triethanolamine salt with an added amide stabilizer.

The artificial sea water was an aqueous solution of 2.7% sodium chloride and 1.0. ⁰ O magnesium sulfate. The surfactant (II) was as follows:

809886/0677

Foam Surfactant Concentration

No. {% weight /

Volume)

CH ₂ CH ₂ OH

f ³

[CH ₂ CH ₂ OH) ₃ 0.076

C ₈ F ₁₅ OC ₆ H ₄ SO ^ N-CH ₂ CH ₂ OSO ₃ ⁱ³ .IsFk (CH ₂ CH ₂ OH) ₃ 0.078

C _fl F, _q 0C _fi H. SO ₉ N [CH ₉ CK ₉ OSOf ⁵ * .N ³ H (CH ₀ CH ₀ OH) J 2 0.1

^ .Ά ( CH ₂ CH ₂ OH) ₃ ] 2 0.2

C ₁₀ F ₁₉ OC ₆ H ₄ SO ₂ NIJZH ₂ Ch ₂ OSO ₃ ³ ^ H (CH ₂ CH ₂ OH) ₃ I 2 0.2

The compositions were separated by a branched Standard production pipe (delivery 5 l / ain composition) foamed. The expansion of the resulting foams was recorded.

Foam No. foam expansion

1 6.52

2 6.90

3 7.47

4 x 7.65

5 6.77

6 6.43

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Claims (11)

Pat β η tan s ρ r ü ehe 1. / Fluorinated surface-active agents of the formula where Rf is a perfluorocarbon group of the formula ^c ? n ^F 4n-1 ', where η is at least 4, η is an integer from 1 to 6, X is alkali metal, ammonium or substituted ammonium and R is hydrogen, alkyl, hydroxyalkyl or a group of the formula (CIl ₂ ) _m OSO? ~. X ⁺ stands. 2. Surface-active agent according to claim 1, characterized in that the perfluorocarbon group is the remainder of a tetrafluoroethylene oligomer. 3. Process for the preparation of a fluorine-containing surface-active Means according to claim 1 or 2, characterized in that that one has an alcohol of the formula: Rf-OC ₆ H ₄ SO ₂ -N (R) (CH ₂ ) _m OH or Rf-OC ₆ H ₄ SO ₂ -N [(CK ₂ ) _m OH] ₂ with chlorosulfonic acid or sulfur trioxide at a temperature below 60 ⁰ C. 4. The method according to claim 3, characterized t that the reaction takes place in a solvent or diluent for which alcohol is running. 5. The method according to claim 3 or 4, characterized in that after the reaction has ended, the reaction mixture in water to form an aqueous solution of the Reaction product is quenched. 809886/0677 6. The method according to claim 5, characterized in that that the pH of the aqueous medium is kept above 7.0 throughout the quenching. 7. The method according to any one of claims 35 Ms 6 _T, characterized in that the alcohol by reaction
the corresponding sulfonyl chloride compound of the formula R ^ .- OCgHA. SOpCl nit a 1-Ionoalkanolar.ir: or a dialkanolamine, wherein each alkyl group contains 1 to β carbon atoms, will be produced. S. The method according to claim 7, characterized in that that the reaction between the sulfenyl chloride compound and the alkanolamine is in a solvent for the reactants is performed. 9. Use of a fluorine-containing surface-active agent according to one of claims 1 or 2 in foamable aqueous compositions. 10. Use of a fluorine-containing surface-active agent according to one of claims 1 or 2 together with a protein or
a hydrolyzed protein in an aqueous composition for fire fighting. 11. Use of a fluorine-containing surfactant according to one of claims 1 or 2 together with one or more of the following components: (a) a polymeric water-soluble compound with oxyalkylene repeating units, (b) a surface-active hydrocarbon, (c) an anti-gelling agent and 809886/0677 (d) "an additional fluorine-containing surfactant mil tel in a foamable aqueous composition for fire fighting. 809886/0677