WO2008012747A2

WO2008012747A2 - Process for the manufacture of fluorinated surfactants

Info

Publication number: WO2008012747A2
Application number: PCT/IB2007/052903
Authority: WO
Inventors: Manuela Cinzia Candido; Lino Conte; Alessandro Zaggia
Original assignee: Sicit Chemitech S.P.A.
Priority date: 2006-07-26
Filing date: 2007-07-20
Publication date: 2008-01-31
Also published as: WO2008012747A3; ITRM20060400A1

Abstract

The present invention relates to new fluorinated quaternary ammonium compounds of formula (1) and (5), to new fluorinated proteic hydrolisates, to processes for their preparation and to fire-fighting compositions that contain said compounds against fires originated from both apolar and polar hydrocarbon liquids.

Description

PROCESS FOR THE MANUFACTURE OF FLUORINATED SURFACTANTS

DESCRIPTION

The present ^■ invention relates to new fluorinated quaternary ammonium compounds, to new fluorinated proteic hydrolysates, to processes for their preparation and to fire-fighting compositions that contain said compounds against fires originated from both apolar and polar hydrocarbon liquids.

Background Art Fire-fighting foams known by the acronym AFFF (Aqueous- Film-Forming-Foams ), to which the foams of the present invention belong, have the property of extending in the form of an aqueous film on the surface of the combustible liquid, increasing the speed of the extinguishing process. This is made possible by the presence of fluorinated surfactants able to lower the surface tension of the solution to values of 15-20 mN irf¹. The film serves several functions. First of all, it isolates the combustible material from atmospheric oxygen, moreover it produces water vapour directly at the base of the flames. Lastly, it acts as a heat insulator, hindering the formation of combustible vapours . It is known that a liquid B can spread on a liquid A only if the spreading work W^ , pertaining to the interface A-

B, is positive. The term W^₈, also called spreading coefficient S, is defined in the equation (7) as follows:

where : Y_AV ~ surface tension of the liquid A (mN m^"1) γ_BV- surface tension of the liquid B (mN m^"1) γ_AB= interface tension between the liquids A and B (mN m^" ^x)

Said quantities can be determined directly through experimental measurements and it is, therefore, possible to predict the superficial behaviour of two non-mixable liquids when they are in contact. In particular, it is possible to determine whether or not a liquid A will spontaneously spread on the surface of another liquid B. The equation (7) highlights that the spreading of an aqueous solution of surfactants on a hydrocarbon occurs with inversely proportional ease to the surface tension of the aqueous solution and to the interface tension thereof with the hydrocarbon liquid. The interface tension depends exclusively on the molecular structure of the surfactant and of the hydrocarbon. The surface tension of the aqueous solution can be reduced by increasing surfactant concentration, however there is a limit imposed by the critical micellar concentration of the utilised surfactants. Among the surfactants, fluorinated surfactants are preferably used because they can assure very low values of interface tension (down to 1-2 mN m^"1) and reduced values of surface tension (down to 15-16 mN m^"1) . These properties make their use advantageous in contrasting fires fuelled by high-octane petrol, which has extremely low surface tensions (in the order of 22.4 mN m^"1) . Many AFFF fire-fighting foams have been developed for the suppression of fires developed from apolar hydrocarbon liquids such as petrol, kerosene, light oil fractions, heavy oil fractions, and crude oils of various origins. In literature, fluorinated surfactants of various nature are known, used in the formulation of fire-fighting foams. Fluorinated surfactants are normally added in fire-fighting concentrates based on proteic hydrolysates, with the goal of enhancing foam mobility, reduce extinguishing times, increase the spread coefficient, enabling the foam to be distributed spontaneously and rapidly on ample surfaces. However, when such foams are applied to fires of polar liquids as in the case of solvents such as alcohols, ketones, esters, ethers and amines, the cells of the foam (Benard structures) collapse due to a laminar destabilisation process that causes the drainage of inter-laminar water. Polar solvents considerably speed up this drainage process. To overcome this drawback, ,to fire-fighting foams for polar liquids are added hydro- soluble, or hydro-inflatable thixotropic polymers, e.g. polysaccharides, proteic hydrolisates and copolymers of acrylamide or methacrylamide or acrylic acid or methacrylic acid. Said compounds, through a mechanism of steric stabilisation of the colloidal unit, provide the foam with greater resistance, with respect to polar solvents . Moreover, they allow the formation of a protective gelatinous membrane once the foam comes in contact with the solvents.

Proteic hydrolysates, because of their surfactant properties, can be used in combination with polysaccharides.

Proteic hydrolisates are constituted by free aminoacids, by peptides and polypeptides. The elements that characterise proteic hydrolisates are: free aminoacid content, aminoacid composition, molecular weight distribution and average molecular weight.

The aminoacid composition of the free and total aminoacids of the proteic hydrolisates reflect the aminoacid composition of the starting material; free aminoacid content, molecular weight distribution and average molecular weight instead depend on the degree of advance of the hydrolysis. The values of the aforementioned analytical parameters are affected by the variability associated to the different degradability of the individual aminoacids and to the different hydrolysability of the peptidic bonds, characteristic for each hydrolysis reaction environment.

Some productive processes, used to obtain proteic hydrolisates obtained from by-products and/or waste and/or residues of the tanning cycle obtained before or after the tanning step, are described in Italian patent application 85511/A/82 and in the European patent application with publication number EP1021958A1. In recent years, the availability of enzymes at a relatively low cost and the continuous rise of energy costs made the possible introduction of enzymatic processes cost-effective. The availability of new technologies has enabled to introduce processes able to improve the quality of the finished product such as clarity, odour, salt content, etc. Also products of animal or vegetable origin and other byproducts and/or waste from the agro-industry, too, can be processed using in full or in part the productive processes employed to process by-products and/or waste and/or residues of the tanning of leather. Based on the acquired knowledge and experience, it is impossible to define a priori the particular chemical characteristics that a proteic hydrolisate must have in order to be particularly suited to foam-producing formulations. The choice of the proteic hydrolisates to be used is often conditioned by the cost/quality ratio. The most commonly used proteic hydrolisates in the production of foaming compounds are those obtained from scrap and/or waste of the work processes of the tanning industry (in particular hair, carniccio obtained from fleshing leather, shavings and trimmings obtained from shaving leather) and from meat processing waste, e.g. dried horns and hoofs. Proteic hydrolisates, being of vegetable and animal origin, derive from natural, renewable raw materials and hence they are characterised not only by considerable foam-making ability, but also by high bio-degradability and a remarkable eco- compatibility.

However, the addition of proteic hydrolisates to prior art fire-fighting compositions has not solved the problem completely, because the foams obtained are characterised by poor mobility on hydrocarbon surfaces. The addition of fluorinated surfactants is essential to obtain mobile foams able to spread spontaneously and rapidly on vast surfaces. Fluorinated surfactants assure very low values of interface tension (down to 1-2 mN πf¹) and reduced values of surface tension (down to 15-16 mN rrf¹) , indispensable to obtain compositions provided with positive spread coefficients. Numerous fluorinated surfactants are known which, added in percentages variable from 1% to 5% by weight to the protein concentrate, enable the formation of efficient fire- fighting foams.

The best results have been obtained with quaternary ammonium salts and amphoteric compounds obtained from fluoro-amines, fluoro-thiols and fluoro-alcohols .

It has now been surprisingly found that particular fluorinated compounds of quaternary ammonium and, or proteic hydrolisates modified with fluorinated epoxy compounds enable to produce fire-fighting foams effective both against fires developed from apolar and polar liquid hydrocarbons. Experimental tests conducted have demonstrated that also the aminoacids that constitute the proteic hydrolisates, the aminoacids isolated from proteic hydrolisates with various techniques and synthesis aminoacids, can be used to obtain molecules covered by this patent.

Therefore, the present invention relates to compounds of quaternary ammonium of the general formula

wherein R_F is a perfluoroalkyl radical that can have 1 to 20 carbon atoms;

Ri is an alkyl radical that can have 1 to 20 carbon atoms and that can be uninterrupted or interrupted by an ether group -0- and contain unsaturations;

R₂, R₃, R₄ are alkyl radicals that can be equal and, or different and have 1 to 20 carbon atoms and each terminated with a group selected among methyl, hydroxyl, vinyl, benzyl; X^" is an anion of inorganic acids, e.g. chloride, bromide, iodide, fluoride, sulphate or phosphate or of inorganic acids, e.g. benzenesulphonate, p- toluenesulphonate, ethanesulphonate, formate, acetate, propionate, benzoate. In the present invention, compounds with general formula (1) are preferred, in which R_F is a perfluoroalkylic radical containing 3 to 20, preferably 4 to 12 carbon atoms; R₁ is a methylene group; R₂ and R₄ are alkylic radicals, preferably equal, containing 2 to 4 carbon atoms and terminated with a methyl or oxydryl group;

R₃ is an alkylic radical with 1 - 20 carbon atoms terminated with an hydroxyl, vinyl or benzyl group and

X^" is a bromine ion. Compounds of general formula (1) are usable as surfactants .

The compounds of general formula (1) can advantageously be prepared . by reacting a fluorinated epoxy of formula (2) react with a secondary amine of formula (3) or an aminoacid of formula (3') and an alkylic halogenide of formula (4) according to the following scheme, which is also an object of the present invention:

Epoxy of formula

amine of formula

H R₂ N R₃ or aminoacid of formula

NH2 CR_xR_y- -COOH ( 3 ' )

in which R_x and R_y are H or radicals whose length and composition varies according to the aminoacid

and alkylic halogenide of formula

X R₄ in which the radicals have the meanings indicated with reference to formula (1) . The reaction between the various reactants can be conducted in the presence or absence of an inert solvent such as carbon tetrachloride, chloroform, dichloromethane, diethyl ether, diisopropyl ether or the like, at a temperature variable between O⁰C and 120⁰C, preferably between 40 and 80⁰C.

Examples of fluorinated epoxides of formula (2) are the following:

H₂ H

\ /

O

H₂ H₂ H₂ H

CQF^J C C C O C : CH₂

O

Examples of secondary amines of formula (3) are: dipropylamine, dibutylamine, diethanolamine, dibutanolamine .

Examples of alkylic halogenides of formula (4) can be: benzyl bromide, bromoethanol, allyl bromide, iodomethane. The compounds of formula (1) have fluorine content that is variable, on average, between 40 and 47% of surfactant weight. In percentages lower than 1% by weight, they are able to bring the value of the surface tension of the .solution below 17-18 mN irf¹.

A further object of the present invention are compounds of formula (5)

obtainable by reaction between a peptide or polypeptide of formula (6)

with fluorinated epoxy compounds of formula (2)

in which R_F is a perfluoroalkylic radical that can have 1 to 20 carbon atoms;

R_x and R_y are H or radicals whose length and composition varies according to the aminoacids and/or the peptidic and/or polypeptidic residues present in the compound of formula (6) .

The reaction can be conducted in the presence or absence of an inert solvent chosen from the class formed by carbon tetrachloride, chloroform, dichloromethane, diethyl ether and, or diisopropyl ether at a temperature variable between 0⁰C and 12O⁰C, preferably between 40 and 80⁰C. ^• Compounds of general formula (5) are preferred in which R_F is a perfluoroalkylic radical containing 4 to 12 carbon atoms; R_x and R_y are H or radicals with variable length and composition according to the aminoacids and/or the peptidic and/or polypeptidic residues present in the compound of formula (6) .

Examples of fluorinated epoxides usable in the production of the compounds of formula (5) are those having the following formulas:

H₂ H₂ H₂ H

C₈P₁₇-C -C -C -O-C-CH₂

O The compounds of formula (5) are usable as surfactants and they are part of the class of fluorinated proteic hydrolisates .

The proteic hydrolisates of formula (6) has a percentage variable between 5% and 11% of organic nitrogen in the form of N-H and N-H₂ groups that can react with the fluorinated epoxide. The Degree of substitution of the aminic hydrogens with the epoxide molecule determines the water solubility of the compound obtained. The structure obtained is thus that of a macromolecule provided with a plurality of pending fluorocarbide chains able to modify the superficial properties, whilst the free N-H groups provide solubility. The preferred degree of saturation of the N-H groups with the epoxide can be between 5% and 25%, preferably between 15% and 20% for solubility reasons. The compounds of formula (6) can be obtained from by-products of animal origin and, or from waste and, or from residues coming from the tanning industry obtained before and after the tanning phase, by-products or products of vegetable origin, agro-industry waste, byproducts or products of vegetable origin, by-products or products of animal origin.

Further objects of the present invention are compositions containing one or more compounds of formula (1) and, or one or more compounds of formula (5) and, or mixtures thereof. These compositions are usable as fire-fighting compositions for fires of polar and apolar hydrocarbon liquids. In said compositions the compounds of formula (1) can be present in total quantities between 0.1 and 9% by weight and preferably from 0.5 to 5%. The compounds of general formula (5), fluoro-modified hydrolysed proteins, are used in total quantities between 0.01 and 5 % by weight and preferably from 0.1 to 3.0% by weight. The indicated weight percentages refer to the weight of the composition. The compositions can also contain both types of compounds, each in the indicated weight range. The compositions according to the present invention can also contain

(a) water (b) a proteic hydrolisate with a varying degree of hydrolysis

(c) a non fluorinated surfactant

(d) a solvent

(e) a polymer with thickening action (f) stabilisers, inorganic salts, anti-freeze agents, preservatives, buffer systems and anti- corrosion agents

The fire-fighting compositions can be prepared under the form of concentrates to be diluted before use. Non fluorinated proteic hydrolisates can be added in quantities variable from 10 to 70% and preferably from 30 to 60%, with reference to the total weight of the composition. In general, fire-fighting concentrates are formulated in such a way that they can be diluted at various concentrations to be used on different types of fire. In general, for fires caused by non polar hydrocarbon liquids, the concentrate is added to levels of 3% (3 parts of concentrate and 97 parts of water) . Fires involving polar liquids require concentrate quantity to be increased up to 6%. These products are commercially known as "3x6 concentrates" (3 by 6) . Today, formulations are available that can be diluted only at the concentration of 3% and can be used at this concentration in any application.

The compositions of the present invention can also comprise one or more non fluorinated surfactants, that contribute to assure a low value of surface tension. Such surfactants can be ionic, non ionic or amphoteric, e.g. as described in US Patents 5085786, 5359096. The non fluorinated surfactant can be used in quantities variable from 1 to 15% by weight and preferably from 2 to 11% by weight. It is also possible to add stabilisers and thickeners to improve the stability of the foam produced by aeration of the aqueous solution constituting the concentrate. Examples of polymers suitable as stabilisers and thickeners can be starches and modified starches, proteic hydrolisates, polyacrylic acids and salts and complexes thereof, polyethylenimines and salts and complexes thereof, polyvinyl resins, e.g. polyvinyl alcohols at various degrees of hydrolysis, polyacrylic resins, carboxyvinyl polymers and polyoxyethylene glycols. Polymeric stabilisers and thickeners can be added to the concentrate of the present invention in quantities variable between 0.1 and 15% of the weight of concentrate, and preferably between 1 and 7% of the weight of concentrate. Inorganic salts may also contribute to the production of the suitable foaming system, i.e. iron and zinc salts, which interact favourably in particular with the proteic hydrolisates providing persistence and consistency to the foam. Alternatively, for simpler operation, it is possible to use the proteic hydrolisates already in composition with inorganic metal salts.

The compositions of the concentrate of the present invention contain water and can also include water- soluble solvents to facilitate the solubilization of the surfactants and of the other components. The solvents themselves can act as stabilisers and as anti-freeze agents. They can also extend the shelf-life of the concentrate itself. Suitable solvents can be ethylene glycol, diethylene glycol, glycerol, monoethyl ether ethylene glycol, butyl ether diethylene glycol, dipropylene glycol monopropyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, methoxypropylene glycol and hexylene glycol. For optimal operability at the production level, alcohols can be added, e.g. isobutyl alcohol and butanol, which has a stabilising action on the foam. These solvents can be contained in the formulations of the present invention in quantities variable from 1 to 50% by weight, preferably from 5 to 30% by weight of concentrate. Other ingredients, known to experts, can additionally be contained in the compositions of the concentrate of the present invention. In particular, there can be preservatives, buffer solutions to regulate pH and corrosion inhibitors (e.g. toluoltriazole or sodium nitrite) . The foam-making power and the type of foam obtained for the different formulations is the result of the combination of different components that can have independent or synergetic effects. The surfactants of this patent are compatible with the additives that are added to manufacture products and foams for operational use. Proteic hydrolisates are susceptible to be functionalised chemically using the method described in this patent as if they were simple amines, obtaining a surfactant with improved properties because already active molecules are functionalised.

The obtainable foam-making compositions belong to the class of extinguishing agents designated with the acronym AFFF (Aqueous-Film-Forming-Foam) . The foam-making compositions of the present invention can be constituted by simple aqueous solutions of the discovered fluorinated cationic surfactants, of general formula (1) and (5), or they can be obtained from mixtures of the aforesaid surfactants, of proteic hydrolisates, of non fluorinated anionic surfactants, of thickening agents, preferably of polymeric nature, of one or more organic solvents, of water, of stabilisers, of inorganic salts, of anti-freeze agents, of preservatives, of buffer systems and of anti-corrosion agents. The proteic hydrolisates can be obtained from by-products of animal origin and, or from waste and, or from residues coming from the tanning industry obtained before and after the tanning phase, by-products or products of vegetable origin, agro-industry waste, by-products or products of vegetable origin, by-products or products of animal origin.

The concentrates formulated according to the compositions of the present invention are employed in fire-fighting operations in the usual manner. The concentrates are particularly suitable for application under the form of foam. In general, it is stored in the form of aqueous concentrate which requires only to be diluted to 6% both with fresh water and with salt water, to form the "premix". Subsequently, the "premix" aeration operation is performed to produce the foam to be applied directly on the flaming combustible substance.

Some formulations could advantageously be used in the construction industry for the preparation of cellular cement for which foam-making products are required that are capable of producing dense, compact and persistent foams with competitive yields with respect to the foam- making agents currently present on the market. The fluorinated compounds of this patent prepared starting from aminoacids and proteic hydrolisates, both the compounds with formula (1) and with formula (2), can be used as water-repellent substances that also have considerable affinity for leather. Therefore, they are suitable for use as protecting agents in the preparation of water-repellent leathers in the tanning industry. The better to understand the present invention, and to implement the same, some non limiting illustrative examples are described below.

EXAMPLES A. Synthesis of the compounds of formula (1) Example 1

1-bis (2-hydroxyethyl) aiαino-3-heptadecafluoropropan-2-ol In a flask, provided with mechanical agitation, thermometer, fall condenser and heating bath, are loaded 142.8 g (300.0 mmol) of 1, 2-epoxy-3-perfluorooctylpropane and 34.6 g (330.0 mmol) of diethanolamine. The mixture, heated to the temperature of 60-65⁰C, is allowed to react for 12 hours. At the end of the reaction, the excess diethanolamine is removed by distillation under vacuum. The recovered product is a waxy brown-coloured solid, characterised by- mass spectroscopy. The yield of the reaction exceeds 92%. Mass Analysis. m/z (rel. ab. %) : 580 ([M-H]⁺, 5%); 536 ([M-CH₂CH₂OH]⁺, 60%), 463 ( [M-CH₂N (CH₂CH₂OH) ₂]⁺, 5%), 118 ([M- CF₃ (CF₂) ₇CH₂CH (OH) ]⁺, 100%).

Example 2

N- (2-hydroxyethyl) -2\7_/-\7^"-dihydroxyethyl-3-heptadecafluoro-

2-hydroxypropan-1-ammonium bromide

25.0 g (43.3 mmol) of 1-bis (2-hydroxyethyl) amino-3- heptadecafluoropropan-2-ol obtained as described in Example 1, are dissolved in 100 ml of chloroform and loaded in a flask provided with fall condenser, thermometer and magnetic agitator. Then, 10.8 g (86.0 mmol) of bromoethanol are loaded. The mixture is maintained at the temperature of 65-70⁰C and allowed to react for 2 hours. The cooling of the mixture at room temperature causes the precipitation of the salt which is recovered by filtration. The stove-dried product (60⁰C for 16 hours) is a yellow solid with the following structure:

Elementary analysis

Calculated: 28.9% C; 1.98% N; 45.75% F Found: 29.47% C; 2.05% N; 44.41% F By way of example, the ¹H NMR analysis of the compound obtained is provided NMR Analysis. ¹H NMR ( CD₃OCD₃ ) : C₈Fi₇CH₂ complex multiplet 2 . 55 ppm, 2H

C₈Fi₇CH₂CHCH₂ multiplet

4.10 ppm, IH

NCH₂ complex multiplet 2.72 ppm, 8H OCH₂ complex multiplet 3.59 ppm, 6H

OH broadened band 3.90 ppm, 3H Example 3

N-benzyl~2V_/,I\/-dihydroxyethyl-3-heptadecafluoro~2- hydroxypropan-1-ammonium bromide

25.0 g (41.3 mmol) of 1-bis (2-hydroxyethyl) amino-3- heptadecafluoropropan-2-ol obtained as described in Example 1, are dissolved in 100 ml of chloroform and loaded in a flask provided with fall condenser, thermometer and magnetic agitator. Then, 14.7 g (86.0 mmol) of benzyl bromide are loaded. The mixture is brought to the temperature of 65-7O⁰C and allowed to react for 6 hours. Once the mixture is cooled at room temperature, a white solid precipitates, which is recovered by filtration. The stove-dried product (6O⁰C for 15 hours) is a white solid with the following structure :

Elementary analysis

Calculated: 35.10% C; 1.86% N; 42.95% F

Found: 34.15% C; 1.95% N; 44.10% F Example 4 l-dipropylamino-3-heptadecafluoropropan-2-olo In a flask, provided with mechanical agitation, thermometer, fall condenser and heating bath, are loaded 142.8 g (300.0 mmol) pf 1, 2-epoxy-3-perfluorooctylpropane and 33.3 g (330.0 mmol) of dipropylamine . The mixture, heated to the temperature of 50⁰C, is allowed to react for three hours .

At the end of the reaction, the excess dipropylamine is removed by distillation. The recovered product is a viscous, orange-coloured liquid, characterised by mass spectroscopy. The yield of the reaction exceeds 95%. Mass Analysis. m/z (rel. ab. %) : 576 ([M-H]⁺, 10%); 548 ([M-CH2CH3]⁺, 50%), 463 ([M-CH₂N (CH₂CH₂CH₃) ₂]⁺, 1%), 114 ([M- CF₃(CFs)₇CH₂CH(OH) ]⁺, 100%).

Example 5

IV-benzyl~Z\JVI\7-dihydroxyethyl-3-heptadecafluoro-2- hydroxypropan-1-ammonium bromide

25.0 g (43.3 mmol) of l-dipropylamino-3- heptadecafluoroundecan-2-ol, obtained as described in Example 4, are dissolved in 80 ml of chloroform and loaded in a flask provided with fall condenser, thermometer and magnetic agitator. Then, 15.0 g (87.7 mmol) of benzyl bromide are loaded. The mixture is brought to the temperature of 70⁰C and allowed to react for 48 hours. Once the mixture is cooled at room temperature, 200 ml of diethyl ether are added, which cause the precipitation of a white solid, that is recovered by filtration and stove dried (6O⁰C for 15 hours) . The product obtained with quantitative yield has the following structure:

Elementary analysis .

Calculated : 38 . 5% C ; 1 . 87 % N ; 43 . 18 % F

Found : 37 . 37% C; 2 . 0% N; 42 . 8% F

Example 6

JV-allyl-N_/N-dipropyl-3-heptadecafluoro-2-hydroxypropan-l- ammonium bromide

25.0 g (43.3 mmol) of l-dipropylamino-3- heptadecafluoroundecan-2-ol, obtained as described in Example 4, are dissolved in 120 ml of chloroform and loaded in a flask provided with fall condenser, thermometer and magnetic agitator. Then, 10.5 g (87.0 mmol) of allyl bromide are loaded. The mixture is maintained at the temperature of 65⁰C and allowed to react for 50 hours. Once the mixture is cooled at room temperature, 200 ml of diisopropyl ether are added, which cause the precipitation of a brown solid, recovered by filtration and stove dried (60⁰C for 15 hours). The product obtained with quantitative yield has the following structure:

with quantitative yield.

Elementary analysis.

Calculated: 34.38% C; 2.00% N; 46.27% F Found: 34.93% C; 1.90% N; 45.30% F Example 7

N- (2-hydroxyethyl) -I\7Vi\f-dipropyl-3-heptadecafluoro-2- hydroxypropan-1-ammonium bromide

25.0 g (43.3 mmol) of l-dipropylamino-3- heptadecafluoroundecan-2-ol, obtained as described in Example 4, are dissolved in 120 ml of chloroform and loaded in a flask provided with fall condenser, thermometer and magnetic agitator. Then, 11.0 g (88.0 mmol) of bromoethanol are loaded. The mixture is maintained at the temperature of 5O⁰C and allowed to react for 56 hours. Once the mixture is cooled at room temperature, 200 ml of diethyl ether are added, which cause the precipitation of a viscous brown compound, recovered by filtration and stove dried (60⁰C for 16 hours) . The product obtained with quantitative yield has the following structure:

C₃H₇

H2 H ^2 + H2 H2 —

C₈Fi₇ C C C N C C OH Br

OH C₃H₇

Elementary analysis. Calculated: 32.48% C; 2.00% N; 46.01% F Found: 33.02% C; 1.94% N; 47.8% F

Table 1 contains the data of surface tension, interface tension and spread coefficient for aqueous solutions of the surfactants synthesised in the previous examples. Table 1.

Surfact Concentr. of Surface Interface Spread ant solution tension tension on coeffici (*⁾ (iαN nf¹) cyclohexane ent

(mN πf¹) S*

Ex. 2 0.25 17 .7 8. 61 0.79

Ex. 3 0.5 14 .4 6. 70 6

Ex. 5 0.56 21. 35 4 .1 1.65

Ex. 6 1 17. 10 6. 80 3.20

Ex. 7 1 18. 40 6. 58 2.12 * Calculated according to equation (7) using cyclohexane as reference hydrocarbon (Ycycio_hexan_e = 27.1 ITiN m^"1) .

B. Synthesis of the compounds of formula (5)

Example 8

Epoxidation of a proteic hydrolisate at 66.4% of dry substance deriving from shaving and trimmings 50.0 g of isopropanol, 100 gr of proteic hydrolisate at 66.4% in water, 34 g of 1, 2-epoxy-3-perfluorooctylpropane and 10 g of a 30% solution of sodium hydroxide are loaded in a flask provided with fall condenser, thermometer and magnetic agitator. The mixture is maintained at the temperature of 80-85⁰C and allowed to react, under vigorous agitation for 12 hours. The reaction mass is concentrated and the residue is placed in a stove at 100⁰C for 10 hours. 97 g of a yellow solid are recovered. A dark brown, pasty product is recovered. Elementary analysis.

Calculated: 39.8% C; 10.76% N; 23% F Found: 38.1% C; 11.4% N; 22.8% F

Surface tension. An aqueous solution at 0.65% by weight of the present surfactant has a 17.25 mN m^"1.

An aqueous solution at 0.3% by weight of the present surfactant has a 22.3 mN m^"1.

Example 9 Epoxidation of a proteic hydrolisate at 60.5% deriving from carniccϊo obtained from fleshing leather in the tanning industry

60.0 g of isopropanol, 143 g of proteic hydrolisate at 0.65%, 60 g 1, 2-epoxy-3-perfluorooctylpropane and 10 g of a 30% solution of sodium hydroxide are loaded in a flask provided with fall condenser, thermometer and magnetic agitator. The mixture is maintained at the temperature of 80-85⁰C and allowed to react, under vigorous agitation for 12 hours. The reaction mass is concentrated and the residue is placed in a stove at 100⁰C for 12 hours. 140 g of a yellow solid are obtained.

Elementary analysis. Calculated : 35 . 56% C ; 6 . 39% N ; 27 . 79% F Found : 36 . 3 % C ; 6 . 59% N ; 26 . 1 % F

Surface tension.

An aqueous solution at 0.64% by weight of the present surfactant has a surface tension of 22 mN πf¹.

An aqueous solution at 0.3% by weight of the present surfactant has a surface tension of 25.1 mN irf¹.

Example 10

Epoxidation of the glycine coming from protein hydrolysis with 1, 2-epoxy~3perfluorooctylpropane

20.0 g of glycine with 17.24% of α-aminic nitrogen are loaded in a flask provided with mechanical agitation, condenser and thermometer. Then, 17g of a 28% solution of ammonia are added and subsequently 175 g of isopropyl alcohol, 350 g of water and 234 g of l,2-epoxy-3- perfluorooctylpropane . The mixture is maintained at the temperature of 80-85⁰C, under vigorous agitation for 36 hours. The reaction is monitored following the disappearance of fluorinated epoxy by gas-chromatographic analysis. At the end of the reaction, the water and isopropanol are evaporated from the reaction mass, 210 g of light-brown solid are obtained. Elementary analysis.

Calculated: 26.43% C; 2.68% N; 61,8% F Found: 27.5% C; 1.64% N; 59.5% F

The product obtained is treated with acetone, obtaining 152 g of product insoluble in acetone; the acetone solution is evaporated obtaining 51 g of solid. Elementary analysis on the two samples provided the following values:

part insoluble in acetone: 27.7% C; 2.24% N; 59% F part soluble in acetone: 27.31% C; 0.96% N; 60% F

Surface tension.

The surface tension measurements were carried out on two products obtained by treatment with acetone, obtaining the following values :

part insoluble in acetone: a saturated aqueous solution at 0.12% by weight has a surface tension of 24.2 mN m^"1. part soluble in acetone: a saturated aqueous solution at 0.05% by weight has a surface tension of 37.1 mN irf¹.

Example 11

Epoxidation of the glycine coming from protein hydrolysis with 1, 2-epoxy-3perfluorohexylpropane

28.4 g of glycine with 17.24% of α-aminic nitrogen are loaded in a flask provided with mechanical agitation, condenser and thermometer. Then, 23 g of a 28% solution of ammonia are added and subsequently 120 g of isopropyl alcohol, 175 g of water and 230 g of l,2-epoxy-3- perfluorohexylpropane. The mixture is maintained at the temperature of 80-85⁰C, under vigorous agitation for 36 hours. The reaction is monitored following the disappearance of fluorinated epoxy by gas-chromatographic analysis. At the end of the reaction, the water and isopropanol are evaporated from the reaction mass and 210 g of light-brown pasty solid are obtained. Elementary analysis. Calculated: 27.80% C; 3.27% N; 57.16% F Found: 26.7 C; 2.63 N; 55.0% F

Surface tension.

A saturated aqueous solution of product at 0.1% by weight has a surface tension of 17.9 mN m^"1.

Example 12

Epoxidation of the proteic hydrolisate base fert with 1 , 2-epoxy-3-perfluorohexylpropane

130 g of proteic hydrolisate with 3.26% of α-aminic nitrogen are loaded in a flask provided with mechanical agitation, condenser and thermometer. Then, 80 g of isopropyl alcohol, 13 g of 30% NaOH aqueous solution and 200 g of 1, 2-epoxy-3-perfluorohexylpropane are added. The mixture is maintained at the temperature of 85-9O⁰C, under vigorous agitation for 36 hours. The reaction is monitored following the disappearance of fluorinated epoxy by gas-chromatographic analysis . At the end of the reaction, the water and isopropanol are evaporated from the reaction mass; 271 g of a brown semi-solid material are obtained. Elementary analysis. Calculated: 35.25 C; 5.31 N; 46.37 F Found: 33.53 C; 4.93 N; 42.0% F Surface tension.

A saturated aqueous solution of product at 0,06%% by weight has a surface tension of 19.75 mN in^"1.

Example 13

Epoxidation of the proteic hydrolisate base fert with 1- perfluorooctylpropane-2-propenglycydylether

70.6 g of proteic hydrolisate with 4.25% of α-aminic nitrogen are loaded in a flask provided with mechanical agitation, condenser and thermometer. Then, 110 g of isopropyl alcohol, 10 g of 30% NaOH aqueous solution and 200 g of 1-perfluorooctylpropane-2-propenglycydylether are added. The mixture is maintained at the temperature of 90-95⁰C, under vigorous agitation for 36 hours. The reaction is monitored following the disappearance of fluorinated epoxy by gas-chromatographic analysis. At the end of the reaction, the water and isopropanol are evaporated from the reaction mass, 226 g of a brown semisolid material are obtained. Elementary analysis. Calculated: 32.62 % C; 3.26 % N; 50% F Found: 32.6 C; 3.28 N; 45-37 % F

Surface tension.

A saturated aqueous solution of product at 0.56% by weight has a surface tension of 20.2 mN rrf¹.

C. Preparation of the Fire-fighting Compositions from the Compounds of Formula (1) and, or (5) Example 14 Composition 1

In a beaker provided with magnetic agitation, 28.7 g of demineralised water and 0.3 g of surfactant, synthesised 5. as described in Example 5, are added.

The materials are left under agitation until the complete solubilization of the surfactant is achieved. Then, 4 g of DEGMEE are added. The materials are left under agitation for 5 minutes. 0 Subsequently, 9 g of 30% DBS are added and it is left under agitation for 15 minutes. Then, 8 g of a 50% aqueous solution of polyacrylamide are added. Once the complete homogenisation of the solution is achieved, 50 g of 67.7% hydrolysed protein are added and the whole is5 left under further agitation for 10 minutes.

Example 15 Composition 2

In a beaker provided with magnetic agitation, 28.5 g of0 demineralised water and 0.5 g of surfactant, synthesised as described in Example 6, are added.

The materials are left under agitation until the complete solubilization of the surfactant is achieved. Then, 4 g of DEGMEE are added. The materials are left under5 agitation for 5 minutes.

Subsequently, 9 g of 30% DBS are added and it is left under agitation for 15 minutes. Then, 8 g of a 50% aqueous solution of polyacrylamide are added. Once the complete homogenisation of the solution is achieved, 50 g0 of 67.7% proteic hydrolisate are added and the whole is left under further agitation for 10 minutes.

Example 16 Composition 3

In a beaker provided with magnetic agitation, 28.5 g of demineralised water and 0.5 g of surfactant, synthesised as described in Example 7, are added. The materials are left under agitation until the complete solubilization of the surfactant is achieved. Then, 4 g of DEGMEE are added. The materials are left under agitation for 5 minutes. Subsequently, 9 g of 30% DBS are added and it is left under agitation for 15 minutes. Then, 8 g of a 50% aqueous solution of polyacrylamide are added. Once the complete homogenisation of the solution is achieved, 50 g of 67.7% proteic hydrolisate are added and the whole is left under further agitation for 10 minutes.

Example 17

Composition 4

In a beaker provided with magnetic agitation, 28.7 g of demineralised water and 0.3 g of surfactant, synthesised as described in Example 8, are added.

The materials are left under agitation until the complete solubilization of the surfactant is achieved. Then, 4 g of DEGMEE are added. The materials are left under agitation for 5 minutes. Subsequently, 9 g of 30% DBS are added and it is left under agitation for 15 minutes. Then, 8 g of a 50% aqueous solution of polyacrylamide are added. Once the complete homogenisation of the solution is achieved, 50 g of 67.7% proteic hydrolisate are added and the whole is left under further agitation for 10 minutes.

Example 18 Composition 5 In a beaker provided with magnetic agitation, 28.7 g of demineralised water and 0.3 g of surfactant, synthesised as described in Example 9, are added.

The materials are left under agitation until the complete solubilization of the surfactant is achieved. Then, 4 g of DEGMEE are added. The materials are left under agitation for 5 minutes.

Subsequently, 9 g of 30% DBS are added and it is left under agitation for 15 minutes. Then, 8 g of a 50% aqueous solution of polyacrylamide are added. Once the complete homogenisation of the solution is achieved, 50 g of 67.7% proteic hydrolisate are added and the whole is left under further agitation for 10 minutes.

D . Evaluation of the characteristics of the compositions according to the invention

The aptitude of the compositions according to the invention to be used as fire-fighting foams was determined through the evaluation of the following parameters: expansion rate, decanting time and flowing time .

Expansion rate

In a glass beaker of 1000 cc of volume are loaded 94 g of water and 6 g of concentrate. The materials are mixed with a kitchen mixer at maximum speed for 2 minutes and 15 seconds. The volume occupied by the foam produced is then measured. The expansion coefficient is defined:

_ final foam volume

E = — — = initial _ solution __ volume

Decanting time In a glass beaker of 1000 cc of volume are loaded 94 g of water and 6 g of concentrate. The materials are mixed with a kitchen mixer at maximum speed for 2 minutes and 15 seconds. The foam produced is then transferred into an Imhoff cone with a volume of 2 litres. The time needed for 25 cc of solution to decant is then measured.

Flowing time In a glass beaker of 1000 cc of volume are loaded 94 g of water and 6 g of concentrate. The materials are mixed with a kitchen mixer at maximum speed for 2 minutes and 15 seconds. 2500 cc of foam thus obtained are poured into the upper compartment of a box provided with removable wall. The box is laid on a plane inclined by 14° relative to the horizon. At time 0, the movable wall is eliminated. The time needed for the front of the foam to cover a surface of 600 cm² located downstream of the movable wall is then recorded. The dimensions of the box are : foam-collecting compartment: length x width x height = 11 x 24 x 10 cm free spreading surface: length x width x height = 24 x 24 x 10 cm The characteristics of the foams obtained starting from the concentrates prepared in the Examples 10 through 14 are shown in Table 3.

Table 3

Concen.tr Soluti Expansion Decanting Flowing ate on rate time time cone. Ξ (sec) (sec)

(%)

Example

10 6 >10 470 25

Example

11 6 9.5 412 21

Example

12 6 9.5 388 20

Example

13 β >10 341 25

Example

14 6 >10 381 21

Claims

2903- 30 -CLAIMS

1. Quaternary ammonium compounds of general formula

in which R_F is a perfluoroalkyl radical that can have 1 to 20 carbon atoms;

Ri is an alkyl radical that can have 1 to 20 carbon atoms and that can be uninterrupted or interrupted by an ether group -0- and contain unsaturations; R2, R3, R4 are alkylic radicals that can be equal and, or different and have 1 to 20 carbon atoms and each terminated with a group selected among methyl, hydroxyl, vinyl, benzyl; X- is an anion of inorganic acids selected from the class formed by chloride, bromide, iodide, fluoride, sulphate or phosphate or of organic acids, selected from the class formed by benzenesulphonate, p-toluenesulphonate, ethanesulphonate, formate, acetate, propionate, benzoate.

2. Compounds as claimed in claim 1, wherein R_F is a perfluoroalkyl radical containing 3 to 20 carbon atoms,

Ri is a methylene group

R₂ and R₄ are alkyl radicals, preferably equal, containing 2 to 4 carbon atoms and terminated with a methyl or hydroxyl group;

R₃ is an alkyl radical with 1 - 20 carbon atoms terminated with an hydroxyl, vinyl or benzyl group;

X^" is a bromine ion.

3. Compounds as claimed in claims 1 or 2, wherein R_F is a perfluoroalkylic radical containing 4 to 12 carbon atoms.

4. Compounds as claimed in at least one of the claims 1 through 3., for use as surfactants and, or as water- repellent substances in leather tanning.

5. Process for the preparation of the compounds of general formula (1) , wherein a fluorinated epoxy of formula (2)

is reacted with a secondary amine of formula (3)

or with an aminoacid of formula

NH2 CR_xR_y-COOH (3') wherein RX and Ry are H or radicals whose length and composάtion vary according to the aminoacid and with an alkyl halogenide of formula (4)

X R₄ wherein the radicals have the meanings indicated in claim 1.

6. Process as claimed in claim 5, wherein the reaction is conducted in the presence or absence of an inert solvent chosen from the class formed by carbon tetrachloride, chloroform, dichloromethane, diethyl ether, diisopropyl ether at a temperature ranging from O⁰C to 12O⁰C, preferably between 40⁰C and 8O⁰C.

7. Process as claimed in claims 5 or 6, wherein the following compounds are used as fluorinated epoxides of formula (2)

8. Process as claimed in at least one of the claims 5 through 7, wherein amines chosen from the class formed by dipropylamine, dibutylamine, diethanolamine and, or dibutanolamine are used as secondary amines of formula (3) .

9. Process as claimed in at least one of the claims 5 through 8, wherein halogenides chosen from the class formed by benzyl bromide, bromoethanol, allyl bromide and, or iodomethane are used as alkyl halogenides of formula (4 ) .

10. Compounds of formula (5)

obtainable by reaction between a peptide or polypeptide of formula (β)

with fluorinated epoxy compounds of formula (2)

wherein R_F is a perfluoroalkylic radical that can have 1 to 20 carbon atoms;

R_x and R_y are H or radicals whose length and composition vary according to the aminoacids and/or the peptide and/or polypeptide residues present in the compound of formula ( 6) , said reaction being carried out in the presence or absence of an inert solvent chosen from the class formed by carbon tetrachloride, chloroform, dichloromethane, diethyl ether and, or diisopropyl ether at a temperature ranging from 0⁰C to 12O⁰C, preferably between 40 and 8O⁰C.

11. Compounds as claimed in claim 10, wherein R_F is a perfluoroalkyl radical containing 4 to 12 carbon atoms, R_x and R_y are H or radicals with variable length and composition according to the aminoacids and/or the peptide and/or polypeptide residues present in the compound of formula (6) .

12. Compounds as claimed in claims 10 or 11, wherein said fluorinated epoxides are chosen among the following compounds

H₂ H₂ H₂ H C₈F₁₇ — Cc — - Cc — - CC O C CH₅

O

13. Compounds as claimed in at least one of the claims 10 through 12, for use as surfactants and, or as water- repellents in leather tanning.

14. Compounds as claimed in at least one of the claims 10 through 13, wherein said compounds of formula (6) come from by-products of animal origin and, or from waste and, or from residues originating from the tanning industry obtained before and after the tanning phase, by-products or products of vegetable origin, agro-industry waste, byproducts or. products of vegetable origin, by-products or products of animal origin.

15. Compositions containing one or more than one compounds of formula (1) or one or more than one compounds of formula (5) or mixtures thereof.

16. Compositions as claimed in claim 15, wherein said compounds of formula (1) are present in quantities of 0.1 - 9 % by weight, preferably 0.5 - 5 % by weight with reference to the total weight of the composition.

17. Compositions as claimed in claim 15, wherein said compounds of formula (5) are present in quantities of 0.01 - 5 % by weight, preferably 0.1 - 3 % by weight with reference to the total weight of the composition.

18. Compositions as claimed in claim 15, wherein said compounds of formula (1) are present in quantities of 0.1 - 9 % by weight, preferably 0.5 - 5 % by weight, and said compounds with formula (5) in quantities of 0.01 - 5 % by weight, preferably 0.1 - 3 % by weight, with reference to the total weight of the composition.

19. Compositions as claimed in claims 15 through 18, further containing one or more than one of the following components: water, proteic hydrolisates at various degrees of hydrolysis, non fluorinated surfactants, solvents, thickening agents, preferably of polymeric nature, stabilisers, inorganic salts, anti-freeze agents, preservatives, buffer systems and anti-corrosion agents.

20. Compositions as claimed in claim 19, wherein said proteic hydrolisates come from by-products of animal origin and, ^"or from waste and, or from residues originating from the tanning industry obtained before and after the tanning phase, by-products or products of vegetable origin, agro-industry wastes, by-products or products of vegetable origin, by-products or products of animal origin.

21. Compositions as claimed in claims 15 through 20, which can be used as fire-fighting compositions against fires caused by polar and apolar hydrocarbon liquids .

22. Compositions as claimed in claim 21, formulated as concentrates to be diluted before use.

23. Compositions as claimed in claims 15 through 20, which can be used for the production of cellular cement in the construction industry.