SE406194B - AMPHOLYTIC, FLUORALIFATIC, SURFACTIVE AGENT INTENDED FOR THE PREPARATION OF FIREFIGHTING FOAM - Google Patents

Description

The invention has unexpectedly different and advantageous properties in certain applications, in particular in the production of alkaline, aqueous, film-forming concentrates, which are used to minimize the loss of volatile hydrocarbon vapors, and in the production of foams for fire-fighting. The prior art materials include: + C Thus, when a compound I of the present invention of the formula + c6Fl3so2N (cH2) 3N (CH3) 3 CH2COO - in the form of a 6% solution is sprayed through a foam expansion nozzle in an amount of about 7.6 liters / min a foam height of 24.6 cm 3 is obtained, while a sulfonamide compound II according to the prior art of formula I + C 6 F 13 SO 2 NH (CH 2) 3 N (CH 3) 2 CH 2 COO is correspondingly sprayed as a 6% solution through a similar nozzle in an amount of about 7.6 liters / min a foam height of only 15.5 cm is obtained.The compound according to the invention thus gives a 160% thicker foam, which means a great advantage in firefighting.

It is an object of the present invention to create non-linear, ampholytic, fluoroaliphatic surfactants and in accordance with this and other objects a new class of surfactants has been invented, of which a special subgroup has the general formula 7200099-5 + //// W ~ NR3 R QN f \ YA 'where Rf is a, preferably fully fluorinated, saturated, monovalent, non-aromatic radical containing 1 to 20 carbon atoms, Q is -SO2- or -CO-, R3 is three identical or various groups, which may also be represented as R 1 R 2 R 3, each of which is independently unsubstituted alkyl of 1-18 carbon atoms, or alkyl of 1 to 18 carbon atoms, which is substituted by water solubilizing groups. Examples of water solubilizing groups are -OH, -N (alk) m_2Hm, -AH (where A is defined below), polyethyleneimine - (NHC2H4) nNH2 and polyoxyalkylene - (OCqH2á) nOH where alk means lower alkyl of 1-4 carbon atoms, m is an integer from 0 to m2, n is 2 to about 20 and q is 2-4. Each solubilizing group present in -NR 3, or -NRIRZR 3, is located on a carbon atom of the alkyl group and at least at a distance of one carbon atom from N, i.e. not closer than in the B position to N. RIRZR3 or R3 may, taken together with N, to which they are attached, be a cyclic nitrogen-containing ring, such as pyridyl, either unsubstituted or substituted by a solubilizing group as mentioned above, or piperidyl or morpholinyl and a lower alkyl group, such as CH 3 or C 2 H 5. When R 1, R 2 and R 3 are taken separately, it is preferred that at least two of them be small groups, such as methyl, ethyl or hydroxyethyl, and most preferably that at least two are methyl.

W and Y are divalent hydrocarbylene radicals, which are preferably free of non-aromatic unsaturation, for example alkylene, oxaalkylene, alkarylene or arylene having 2-12 carbon atoms and preferably 2-5 carbon atoms in the case of W and 1-12 carbon atoms in the case of Y ; A 'is -co ;, -soš.

In more detail, the fluorinated aliphatic radical Rf is a fluorinated, saturated, monovalent, non-aromatic aliphatic radical.

The chain may be straight, branched or cyclically large enough, and may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms, which are bound only to carbon atoms. A fully fluorinated group is preferred, but hydrogen or chlorine atoms may be present as substituents on the fluorinated aliphatic radical, provided that at most one atom of each kind is present in the radical for each of the two carbon atoms, and that the radical must contain at least one end-positioned perfluoromethyl group. "End position" in this context 7200099-5 refers to the position in the main chain of the radical which is located furthest from the quaternary ammonium group and the acid radical.

Preferably, the fluorinated aliphatic radical contains at most 20 carbon atoms, since such a large radical results in inefficient use of the fluorine content.

It will be appreciated, of course, that the formula shown represents only the zwitterionic form or the amphoionic form of the compounds of the invention, which form is generally present in neutral or alkaline solution. Under acidic conditions, the acid radical or group is wholly or partly protonated and the positive charge on the quaternary nitrogen atom is neutralized by a solution in anionic form, i.e. (anion) -, an anion from the acidifying material.

These forms are simply called acid salts of the zwitter or amphoionic ions. Under sufficiently basic conditions, basic salts are formed and the invention comprises zwitterions and acid salts as well as basic salts thereof.

In general, the internal linker structure of the molecule, by which means W / in the above formula, serves to link the / -QN \ Y \ the three end-placed groups, and this structure requires only that it does not contain any ionizable groups, such as basic or acidic groups, and preferably no non-aromatic, i.e. ethylenic or acetylenic, unsaturation. It will be appreciated that this internal linkage structure affects the solubility of the compounds of the invention.

Thus, a relatively high hydrocarbon content in the linker group tends to increase the solubility in solvents such as petroleum oils and other organic media, and high molecular weight linker groups tend to decrease the solubility of the surfactant in aqueous solutions.

Although the molecular weight of the internal structure can be very high, provided that the molecule comprises about 10% or more carbon-bonded fluorine, the molecular weight is generally 1000 or less and preferably below about 600, except when low solubility in water is desired, such as in the formation of oil-repellent films on substrates by adsorption from aqueous solution, in which case the higher molecular weight compositions are desirable.

Although ampholytic surfactants are obtained when R 3, or R 1, R 2 and R 3 are unsubstituted alkyl groups, the use of groups substituted with polar solubilizing radicals is useful to increase the relative solubility of some of the surfactants. in aqueous solutions. Such polar solubilizing groups include anionic substituents, such as -AH, where A has the meaning given above; cationic substituents such as -NH 2, -N (CH 3) 3 Cl, - (C 2 H 4 NH) 4H; and neutral substituents such as -OH, - (C 2 H 4 O) 15 H. Other such are also equivalent.

The novel ampholytic, fluoroaliphatic surfactants of the invention are generally useful for lowering the surface tension of aqueous or non-aqueous media to increase wetting, spreading and penetration. They can be used to form oleophobic and generally stain-repellent coatings on paper, fabrics, textiles, leather, etc. They are also useful for creating oleophobic films, for example on glass or metal, to prevent fouling, deposition of fingerprints or the like. Their ability to produce aqueous solutions with low surface tension within a large pH range, ie in both strongly alkaline and strongly acidic as well as in substantially neutral aqueous solutions, is very valuable.

Representative compounds of the invention include: "_ + CBF11SO2N-C11HZ2N (m) (CSHSOHLQ I c2H, co; + c, F15coN-c3H5N (cH3) 2 (cH2cH2o) 1H ca fl esoš + caF1, so2N-c2H4N (cHH) 3H caaasoš + c, 4F29so2N-cH3H6N (C2H5) 2c3Haso3x cauasoš 7200099-5 + c4FBcoN> c3HsN (CH3) 2c2H4co2n 3H, so§ + c8F11so2N-cH2c5H4cH2N (CH3) 2c2H4NH2 CsfïsSÛš CAV + f sozn- c_3HaN (ma) (cnzcgns) about the FL. OH I C11Hà2SÛ§ + _ c3F5 (o-ïFcF2) 4ocFcoN-c11H22N (c4H $) 2 (cH2) 3so, cF3 cF3 c11H22co2H + ~ c3F7coNcH2c6H¿cH2n (cH3) 2 (cH2h2 '2; oc F so N> cH cu -N s 11 2 2 2 lNI-Iz cHa / canssoš cns H à + / * \\\ H c1F15co? -caacaz-N \\\ _ H Ca H4CO§ H CgF 17 CHg- CH - COO- N (CH: 1) a + - caFncnz-CH- (GHz-k OQO 'N (CHa) a' ~ + '7200099-5 7 c fl acoo' + cßF17so2N-CH2 cH2N (cH3) 3 c fl acoo '+. caE, 7so2N: @ H¿) 11-N (cHa) 2cH2cH2oH 4 mgmgmw '| _ + caFnsoa-N-caz G 112m cash., o exa- cH2-P \ - oR 0_ | + c @ _1- * 11S02N - (<: H2) 3N (CH3) 3 cF (cF3) 2 cnacøo '' + - _ (CF3) 2CF SO2- N- (CH2) sN (333): (CFaE cps cFa c fi ac fl gcoí 'CF3-cF2-cF2- o-åF-cF2-ocF-cF2-SO2-N- (C H2) @N (CH3) a (CH2) 2Soš cFacFa cFa [ocF (cm) C13]. ,, ocF (cFa) co + \ (GHz) 2N (C2H5) s +.

/ W CHa) a 05 n 41-1 sHe-ÛP0 (0_) 2 + 5F11 N (CHS) 3 c 7200099-5 8 In general, the ampholytic surfactants are prepared using methods known to those skilled in the art.

Preferably, a fluoroaliphatic sulfonyl or carbonyl halide, eg RfQCl 3 or ester, is first reacted with a diamine HZNWNRIRZ containing a single primary aliphatic amine group. In such diamines, both amino groups are attached to the linking chain through aliphatic carbon atoms, one of the amino groups being a primary amine and one a tertiary amine. Polyamines, in which all but one of the amino groups are tertiary amines, can be used, but the products tend to be inappropriately complex. The intermediate acylamino-tert-amine, RfQNHWNR R 1 can then be reacted with an alkylating agent, such as in a lactone or sultone, to create an acyl -RfQ1WWNR R 1 followed by YAH by quaternizing the tertiary amino group. Alternatively, excess alkylating agent can be used to substitute the amide nitrogen and quaternize the amino nitrogen simultaneously. As a further alternative, the amino nitrogen can first be quaternized and then the quaternized product can be reacted with the lactone or sultone. Other compounds are prepared, using as a step the desulfonylating coupling of an unsaturated compound and a fluoroaliphatic sulfonyl chloride.

If the quaternizing agent is divalent, additional conventional reactions can be used to modify the parent product. The new ampholytic, fluoroaliphatic surfactants of the invention are conveniently obtained, for example, from internal quaternary ammonium imides in _ + RfQN WN R3 where Rf, Q, W and R3 have the meaning given above, by condensation with a suitable derivative of the desired anion residue -YA. Thus, sodium chloroacetate, β-propiolactone, sodium omega-bromo-undecylenate, 1,3-propanesultone and sodium ethyl-2-chloroethylphosphonate are condensed with gentle heating, preferably in solution, with the desired internal imide, i.e. when Q is -SO 2 - a sulfonimide and when Q is fi a carbonimide. The imides are formed by basic treatment of the corresponding amides, in which the quaternary group is present with an associated anion. c8F17O2NH (cH2) 3i $ (cn3) 3c1 ", which is available in accordance with what is described in U.S. Pat. No. 2,759,019, is treated, for example, with sodium methoxide, as described in the following examples. 7200099-5 Example Gel 1 + To a solution of 127 g (0.2 mol) of c8r17so2Na (cn2) 3N (cH3; ¿c1 'in 200 g of isopropyl alcohol, 43.2 g (0.2 mol) of 25% methanolic NaOCH3 are added in a slow stream, the mixture is reacted at 60 ~ 70 ° C for 1.5 h and then cooled and filtered. + The precipitate, which amounts to 62.4 g, contains C8F17SO2N (CH2) 3N (CH3) 3 and sodium chloride.

Washing with water leaves a fine granular product, which melts at 260-267 ° C during decomposition.

Calculation for cl4H15N2o2Fl7s = c = 2s, 1, H = 2.5; N = 4.1, F = 54.0.

Found: C = 28.1; H = 2.6; N = 4.8; F = 53.8 Here, as elsewhere, analysis results and calculations are given in% by weight.

Example Gel 2 In a procedure similar to that of Example 1, C 6 F 13 SO 2 N (CH 2) 3 NICH 3) 3 is prepared from C 6 F 13 SO 2 NH (cH 2) 3 N (cH 3) 3 Cl 1 Calculated for C 12 H 15 N 2 O 2 F 13 S: C = 28.9; H = 3.0; N = 5.6.

Found: C = 28.3; H = 3.3; N = 5.7.

To a solution of 3.8 g of CICH2COOH in 80 g of isopropyl alcohol and 32 g of ethanol is added 8.6 g of 25% NaOCH3 in methanol and then 20 g of C6F13SO2N (CH2) 2N (CH3) 3, prepared as above. The mixture is heated at 74 ° C for 14.5 hours and cooled and then filtered.

The precipitate is washed with 80:20 isopropyl alcohol methanol. The filtrate and washings are combined and evaporated to dryness on a hot plate to give a residue of + c6Fl3so2N (cH2) 3N (CH3) 3 CH2COO Infrared spectroscopy showed a strong carbonyl band at 6.2 μm.

Calculated for C 14 H 17 N 2 O 4 F 13 S: C = 30.2; h = 3.1; N = 5.0.

Found: C = 28.3; H = 3.0; N = 5.0.

An aqueous foam composition concentrate for fire fighting, which concentrate is dilutable in the ratio of about 1:16 with water to a useful foam for fire fighting, has a surface tension at pH 9 of 18.8 dynes / cm. vzoqoes-s' w Exemgel 3 _ + C6Fl3SO2N (CH2) 3N (CH3) 3 according to example 2 is reacted with ß-propio: - lactone to give the carboxyethyl derivative according to the equation u ç6Fl3SO2š (CH2) 3§ (CH3) 3 + QÉÉ-CH2 -C = O --- + 0 + c6Fl3so2N (cH2) 3N (cH3) 3 cnzcnzcoo 'This compound also creates a good fire-fighting foam.

In another reaction, C6F13SO2N (CH2) 3N (CH3) 3 is reacted with 1,3-propanesultone ηz-CH2-CH2 O --- SO2 to give _ + c6F1332- (cH2) 3- N (cH3) 3 (cH2) 3-so; Example 5.

In a solution of 12.8 g (0.02 mol) of c7F15coNH (cn2) 3; (cH3) 3 '' in 50 ml of CH3OH, 4.3 g (0.02 mol) of 25% methanolic NaOCH3 are added in a slow stream. The solution is evaporated and the residual solid is slurried in 40 ml of water. The lower layer is separated and washed once with 30 ml of distilled H 2 O, separated and evaporated to dryness and taken up in 35:15 isopropyl alcohol: methanol and charged to an equivalent amount of ClCH 2 COO and heated to reflux for 15 hours.

Filtration of the cooled solution and evaporation of the filtrate gives cazco '+ c7F15coN (cH2) 3N (cH3) 3 which has a surface tension in 0.1% aqueous solution of 16 dynes.

Example gel 6 A solution of 48.4 g (0.1 mol) of C 6 F 13 SO 2 NHC 3 H 6 N (CH 3) 2 dissolved in 60 g of tert-butanol is heated to reflux and 13 g of ethylene oxide is bubbled into the solution with stirring. After the addition is complete, the butanol is evaporated at atmospheric pressure to give a residue of 55.8 g, which residue is essentially a mixture of about 7200099-5 11 equimolar amounts of: ZCH 2 OH - + C6Fl3SO2NC3H6N (CH3) 2CH and + c6Fl3so2Nc3H6N (2 c fl zc fl zo) ZH The preparation is repeated and 6 g of the product mixture are recrystallized from 20 g of hot isopropyl alcohol. The air-dried product melts at 210-214 ° C.

- + Calculated for C 6 F 13 SO 2 NC 3 H 6 N (CH 3) 2 CH 2 CH 2 OH: C = 29.55; H = 3.2; N = 5.3; F = 46.7; on = 3.2.

Found: C = 29.4; H = 3.2; N = 5/3; F = 4511; OH = 3,2- The above mixture, which is 38 g (0.07 mol), is dissolved in 40 g of CH 3 OC 2 H 4 OCH 3 in a 250 ml glass flask, 8.5 g (0.07 mol) of CH 2 CH 2 CH 2 SO 2 -O are added, and the mixture is heated at After evaporation of the solvent under reduced pressure on a steam bath, 45.8 g of residue are obtained, which consists of a mixture in approximately equimolar amounts of: C6F13SO2N (C3H6SO3) C3H6N (CH3) CCH2F2Z (CH3) C3H6SO3) C3H6N (CH3) 2 (CH2CH2O) 2H The infrared spectrum of the product is consistent with these structures.

This product produces an excellent, vapor-reducing, foam-forming composition. when replacing C 6 F 13 SO 2 N (CH 2 CO 2) C 3 H 6 N (CH 3) 3 in Example 10 below.

Example 7 To a 500 ml round bottom glass flask, equipped for stirring, heating and cooling as well as for adding liquid and collecting evolved gaseous products, is added: 100 g (0.206 mol) of C6Fl3SO2NHC3H6N (CH3) 2 3.7 g ( 0.206 mol) H 2 O 19.4 g (0.22 mol) ethylene carbonate CH 2 CH 2 O-CO ~ 0 150 g C 4 H 90 C 2 H 4 O 2 C 2 H 4 OH The mixture is heated at 140 ° C for 9 hours with stirring, during which time 8.5 g of CO 2 are collected (calculated 8.8 g ). The mixture is cooled to 78 ° C and 26.8 g (0.22 mol) of propane sultone are added. 72oo099-5 ~ k 0 12 There is an immediate exothermic reaction to about 9200. The contents are kept at about 90 ° C for 2 hours and then diluted with deionized water. The product is isolated and identified as: CGF13 SO2N (CH2CH2CH2SOš) C3H6§ (CH3) ZCHZCHZOH.

The product forms salts, such as a hydrochloride, in acidic solutions.

If the quaternary ammonium compound of Example 10 below is exchanged for this product, an excellent fire-fighting foam is obtained which is stable over a wide pH range.

Use of an equivalent amount of propiolactone in place of the above propane sultone gives C6F13SO2N (CH2CH2CO6) C3H6š (CH3) 2CH2CH2OH Sulfonamides, which contain a wide variety of fluoroaliphatic radicals, hydrocarbylene radicals and substituents on the corresponding substituent ampholytic surfactants. Replacement of the exemplified sulfonamidoamine starting material (in which Q is -SO 2 -) with the carbonamidoamines (in which Q is ~ CO-) results in corresponding amolytic surfactant carbonamido compounds.

Example 8 To a 250 ml, 3-necked glass flask equipped with a stirrer, reflux condenser and a Barret trap is added 54.6 g (0.1 mol) of C6F13SO2 - C3H6É (CH3) ZCHZCHZOH (from Example 6) dispersed in 50 ml. diisopropyl ether. The mixture is heated at reflux while collecting water until water ceases to distill over. A solution of 7.5 g (1.05 mol) of propiolactone in 50 ml of CH 3 CN is then added to the flask and heating is continued on a steam bath for 2 hours.

The resulting clear solution is evaporated to dryness under reduced pressure at 100 ° C to give 62 g of product having the formula: _ + C6Fl3SO2N (CH2CH2CO2) C3H6N (CH3) ZCHZCHZOH .

Example 9 In a 3 liter glass flask, a solution of 484 g (1 mol) of C 6 F 13 SO 2 §C 3 H 6 N (CH 3) 2 and 128.5 g (1 mol) of propane sultone in 800 g of dry CH 3 CN is prepared. The mixture is stirred and heated at about 75 ° C for 6 hours and then cooled to room temperature. The solid which is separated off during heating and on cooling is collected, washed with cold CH 3 CN and vacuum dried. The product amounts to 495 g and consists of _ + c6Pl3so2N (cH2cH2cn2so3) c3H6N fl (cH3) 2 This N-sulfonatopropyl-fluoroaliphatic sulfonamido-tertiary amine salt creates a good fire-fighting foam when it replaces the quaternary ammonium compound in Example 10 below.

To a 250 ml round bottom glass flask was added 30.3 g (0.05 mol) of the above ampholytic amine salt and 5.3 g of Na2CO3 dissolved in 60 g of cH3oc2H4oc2H4ocH3 and the flask was heated to 47 ° C. To the solution was slowly added 7.71 g (0.05 mol) of diethyl sulfate, and heating and stirring were continued at 60-65 ° C for 5 hours. The flask was cooled to room temperature and the solid was filtered off. 38.1 g (theoretical 38.1 g) of product containing 22% by weight of unreacted starting salt were obtained.

The product consisted of c6Fl3so2N (c3H6so3) c3H6 $ (cH3) zczns By inserting known alkylating agents, such as Br (CH2) 10CHFIL BrCH2C6H4CO2H, I (CH2CH2O) 5CH2CH2OH, a variety of substituents are described, as described above. .

Exemgelzlü A suitable composition for a concentrate, which is diluted to form a fire-fighting foam, is prepared with the following percentage composition: + C6Fl3SO2ï (CH2) 3N (CH3) 3 (from Example 2) 4% cnzcoo 'C8Fl7SO2N (C2H5% CH2 C8H17C6H4O (C2H40) 3GB (Triton® X 305, solid) 5% C4H9 (OC2H4) 2H (Butyl Carbitol) 35% deionized water 64% Parts of this concentrate are made slightly alkaline (pH 8-9) with potassium hydroxide and diluted in the ratio 1 : 16 with fresh water and other parts with seawater. Each solution is found to form abundant stable foam. Corresponding results are also obtained from neutral and acidic solutions.

Claims (3)

Claim 1. Ampholytic, fluoroaliphatic, surfactant, characterized in that it has the formula + W-NR //, / “\ Y_A_ 3 RfQN where Rf is a, preferably fully fluorinated, saturated, mono valent, non-aromatic radical containing 1 to 20 carbon atoms, Q is -SO 2 - or -CO-, R 3 are three identical or different, unsubstituted alkyls having 1 to 18 carbon atoms or alkyls having 1- 18 carbon atoms substituted with polar, water-solubilizing groups, such as an anionic substituent or a cationic substituent or a neutral substituent or, in combination with the nitrogen atom to which it is attached, R 3 is a cyclic nitrogen-containing ring in combination with at most one lower alkyl group, W is a divalent hydrocarbylene radical, which contains 2. -12 carbon atoms, Y is a divalent hydrocarbylene radical containing 1 to 12 carbon atoms, A- is C00 or SO 3. - and the salts of said ampholytic, fluoroaliphatic surfactants. 2. A surfactant according to claim 1, characterized in that it is a compound of the formula CH 2 COO C F CON (CH 2) 3 § (CH 3) 3 and salts thereof. 7. surfactant according to claim 1, characterized in that it is a compound of the formula c6Fl3so2Nc3H6§ (cH3) zcnzcnzon C3H6SOš and salts thereof. PROMISED PUBLICATIONS: US 2,759,019 (260-556), 2,764,602 (260-404.5), 3,258,423 (252-3)