NEW AMMONIUM COMPOUNDS USEFUL AS SURFACTANTS

Abstract

The invention concerns new mono-ammonium compounds of formula (I) with surfactant properties and improved biodegradability. It concerns also new mixtures comprising such mono-ammonium compounds and di-ammonium compounds.

##STR00001##

Claims

1. An ionic mono-ammonium compound of formula (I) ##STR00031## wherein R, which may be the same or different at each occurrence, is a C.sub.5-C.sub.27 aliphatic group, Y is a divalent C.sub.1-C.sub.6 aliphatic group, and R, R and R, which may be the same or different, are hydrogen or a C.sub.1 to C.sub.4 alkyl group.

2. The compound according to claim 1 wherein R is chosen from C.sub.6-C.sub.17 alkyl and C.sub.6-C.sub.17 alkenyl groups.

3. The compound according to claim 2 wherein R is a C.sub.10-C.sub.17 group.

4. The compound according to claim 1 wherein Y is a methylene group.

5. The compound according to claim 1 wherein R, R and R are methyl.

6. An electroneutral compound of formula (II) ##STR00032## wherein R is as defined in claim 1 for the compound of formula (I), Y is as defined in claim 1 for the compound of formula (I), R, R and R are as defined in claim 1 for the compound of formula (I), and W is an anion or an anionic group bearing w negative charges.

7. The compound according to claim 6, wherein W is a halide anion and w is 1.

8. A monohydroxyl-monoester compound useful for the preparation of the compound of formula (I) of claim 1, said monohydroxyl-monoester compound being a compound of formula (III) ##STR00033## wherein R, which may be the same or different at each occurrence, is as defined in claim 1 for the compound of formula (I), Y, which may be the same or different at each occurrence, is as defined in claim 1 for the compound of formula (I), L is a leaving group and t is an integer which is at least 1.

9. The compound according to claim 8, wherein L is a nucleofuge group chosen from a halogen, a (hydrocarbyloxysulfonyl)oxy group of formula R.sup.aOSO.sub.2O wherein R.sup.a denotes a C.sub.1-C.sub.20 hydrocarbyl group and an oxysulfonyloxy group of formula .sup.OSO.sub.2O.

10. A mixture M.sub.Q comprising: at least one ionic mono-ammonium compound of formula (I) as claimed in claim 1, and at least one ionic di-ammonium compound of formula (VII) ##STR00034## wherein A is a tetravalent linker selected from the group consisting of A-1 to A-6 ##STR00035## m, m, m and m, which may be the same or different at each occurrence, are 0, 1, 2 or 3, k, k k, k and k, which may be the same or different, are 0, 1, 2 or 3, Q.sub.1 to Q.sub.4, which may be identical or different from each other, are selected from the group consisting of R and X, R, which may be the same or different at each occurrence, is as defined in claim 1 for the compound of formula (I), X, which may be the same or different at each occurrence, is represented by formula (VIII) ##STR00036## wherein two and only two of Q.sub.1 to Q.sub.4 are represented by X and two and only two of groups Q.sub.1 to Q.sub.4 are represented by R, Y is as defined in claim 1 for the compound of formula (I), R, R and R, which may be the same or different at each occurrence, are as defined in claim 1 for the compound of formula (I), and n and n, which may be the same or different at each occurrence, are 0 or 1 with the sum of n+n' being 1 or 2.

11. The mixture according to claim 10, wherein the ionic di-ammonium compound is of formula (VI) ##STR00037## wherein R, which may be the same or different at each occurrence, is as defined in claim 1 for the compound of formula (I), Y, which may be the same or different at each occurrence, is as defined in claim 1 for the compound of formula (I), and R, R and R, which may be the same or different at each occurrence, are as defined in claim 1 for the compound of formula (I).

12. The mixture according to claim 10, wherein the ratio w.sub.I, VII of the weight of the compound (I) over the combined weight of the compound (I) and the compound (VII) ranges from 10% to 90%.

13. A mixture M.sub.Q comprising: at least one electroneutral compound of formula (II) according to claim 6 and at least one electroneutral compound of formula (IX) ##STR00038## wherein A and Q.sub.1 to Q.sub.4, which may be identical or different from each other, are as defined for the ionic di-ammonium compound of formula (VII) comprised in the mixture M.sub.Q according to claim 10, and W is an anion or an anionic group bearing w negative charges.

14. The mixture according to claim 13, wherein the ratio wILIx of the weight of the compound (II) over the combined weight of the compound (II) and the compound (IX) ranges from 10% to 90%.

15. (canceled)

16. The M.sub.Q of claim 13 wherein ##STR00039## is the ionic di-ammonium compound of formula (VI) comprised in the mixture M.sub.Q according to claim 11, and W is an anion or an anionic group bearing w negative charges.

17. The mixture M.sub.Q of claim 13, wherein W is a halide anion and w is 1.

18. The mixture according to claim 10, wherein the ratio wIvu of the weight of the compound (I) over the combined weight of the compound (I) and the compound (VII) ranges from 50% to 90%.

19. The mixture according to claim 13, wherein the ratio worx of the weight of the compound (II) over the combined weight of the compound (II) and the compound (IX) ranges from 50% to 90%.

Description

WORKING EXAMPLES

Example 1 Synthesis of a Quaternary Mono-Ammonium Compound of Formula (I) Starting from C.SUB.16.-C.SUB.18 .(30:70) Fatty Acid Cut

[0163] Part 1.APiria Ketonization Toward Internal C.sub.31-C.sub.35 Ketones Cut

[0164] The reaction was conducted under an inert argon atmosphere in a 200 mL quartz reactor equipped with a mechanical stirring (A320-type stirring mobile manufactured by 3D-printing with Inox SS.sub.316 L), an insulated addition funnel, a distillation apparatus, a heating mattress and a temperature probe.

[0165] In the reactor were introduced: [0166] 12.5 g of MASCID acid 1865 (from Musim Mas Group) composed of 33.7 wt % of palmitic acid and 65.3 wt % of stearic acid (0.045 mole of fatty acids), and [0167] 0.935 g of MgO (0.023 mole).

[0168] In the insulated addition funnel were added 37.5 g of the same melted fatty acids mixture (0.135 mole).

[0169] The temperature of the reaction media was then raised to 250 C. Once the temperature reached 150 C., stirring was started (1200 rpm). After 2 h00 reaction time at 250 C., FTIR analysis showed complete conversion of the starting fatty acids into the intermediate magnesium carboxylate complex.

[0170] The temperature of the reaction mass was then raised further to 330 C. and the mixture was allowed to stir at this temperature during 1 h 30 in order to allow decomposition of the intermediate magnesium carboxylate complex to the desired ketone.

[0171] Then, 12.5 g of the melted fatty acid mixture was progressively added into the reactor thanks to the addition funnel during 30 minutes and the mixture was stirred at 330 C. during an additional 1 h 00. FTIR analysis showed complete conversion of fatty acids and magnesium complex to the desired ketone.

[0172] Two additional cycles of 12.5 g fatty acid addition during 30 minutes followed by additional 1 h 00 stirring at 330 C. were then realized.

[0173] After the last cycle the mixture was allowed to stir at 330 C. during an additional 1 h 00 to ensure complete conversion of the intermediate magnesium complex to the desired ketone which was confirmed by FTIR analysis.

[0174] The temperature of the reaction mixture was then allowed to cool down at room temperature and the crude was solubilized in hot CHCl.sub.3. The suspension was filtered on a plug of silica (70 g) and the product was further eluted with additional amounts of CHCl.sub.3.

[0175] After solvent evaporation 41.83 g (0.086 mole) of product was obtained as a white wax corresponding to an isolated yield of 96%.

[0176] .sup.1H NMR (CDCl.sub.3, 400 MHZ) (ppm): 2.45-2.25 (t, J=7.6 Hz, 4H), 1.62-1.46 (m, 4 H), 1.45-1.05 (m, 54 H), 0.86 (t, J=6.8 Hz , 6H).

[0177] .sup.13C NMR (CDCl3, 101 MHZ) (ppm): 212.00, 43.05, 32.16, 29.93, 29.91, 29.88, 29.84, 29.72, 29.65, 29.59, 29.51, 24.13, 22.92, 14.34 (terminal CH.sub.3).

Part 1.BHydrogenation of Ketones Mixture Toward Internal C.sub.31-C.sub.35 Fatty Alcohols Mixture

[0178] In a 100 mL autoclave equipped with a mechanical stirrer (Rushton turbine) were added: [0179] 4.36 g of Ru/C (4.87% Ru) catalyst (5 wt % of dry catalyst with respect to the ketone, catalyst containing 54.9% H2.sub.2O) [0180] 39.3 g (87.2 mmol) of melted internal C.sub.31-C.sub.35 ketones cut.

[0181] The reaction was performed under 20 bar hydrogen pressure. 4 nitrogen purges are performed followed by 3 purges of hydrogen at 20 bars. The temperature of the reaction mixture was then set at 100 C. to melt the ketone substrate. The temperature was left at 100 C. during 10 min and stirring was slowly started at 200 rpm. When proper stirring was confirmed, the stirring rate was increased at 1200 rpm and the temperature was set at 150 C.

[0182] After 6 h reaction time at 150 C., heating was stopped and the mixture was allowed to cool down at 90 C. while stirring. Stirring was then stopped. The mixture was cooled down to room temperature and the autoclave was carefully depressurized.

[0183] NMR analysis in CDCl.sub.3 of the crude showed a ketone conversion level >99% and molar purity of 99% for the fatty alcohol. The compact solid containing the product and the catalyst was grounded to powder and then introduced into a 1 L flask. 500 mL of chloroform were added and the flask was then heated at 60 C. to dissolve completely the alcohol. The suspension was filtered at 60 C. over celite. The solid cake was rinsed with hot chloroform at 60 C. several times. The filtrate was evaporated to give white powder with a weight purity of about 99% for the desired internal C.sub.31-C.sub.35 fatty alcohols mixture corresponding to about 90% isolated yield.

Part 1.CDehydration of C.sub.31-C.sub.35 Fatty Alcohols Into Internal Olefins

[0184] All the reactions were conducted under an inert argon atmosphere.

[0185] In a 200 mL quartz reactor equipped with a heating mattress, a mechanical stirrer (A320-type stirring mobile manufactured by 3D-printing with Inox SS.sub.316 L), surmounted by a condenser connected to a 50 mL two-neck distillate collection flask and a temperature probe were added: [0186] 41.3 g of C.sub.31-C.sub.35 fatty alcohols (85 mmol, 1 eq.), and [0187] 4.13 g (40 mmol, 10 wt %) of Al2O.sub.3-.

[0188] The temperature of the reaction media was increased to 150 C. to melt the alcohol and stirring was started (about 500 rpm). Then, the temperature was set-up at 300 C. and the mixture was allowed to stir at 1000 rpm under argon. The reaction progress was monitored thanks to NMR analysis with a borosilicate glass tube.

[0189] After 2 hours reaction at 300 C., NMR analysis in CDCl.sub.3 showed complete conversion of the fatty alcohol and the presence of 1.5 mol % of ketone which had been formed as a by-product.

[0190] Stirring and heating were then stopped and the temperature was lowered to 80 C. The molten crude was transferred to a beaker. The reactor vessel and the stirring mobile were rinsed with chloroform (Al2O.sub.3 is insoluble).

[0191] The mixture was filtered and the solvent was evaporated under vacuum to afford 39 g of a clear yellow oil which solidified at room temperature to give a white solid in the form of wax (98 wt % purity) corresponding to 97% yield (NMR).

[0192] .sup.1H NMR (CDCl.sub.3, 400 MHZ) (ppm): 5.38-5.29 (m, 2H), 2.03-1.93 (m, 4H), 1.35-1.19 (m, 55H (average H number)), 0.86 (t, J=6.8 Hz , 6H).

[0193] .sup.13C NMR (CDCl3, 101 MHz) (ppm): 130.6, 130.13, 32.84, 32.16, 30.01, 29.93, 29.8, 29.6, 29.55, 29.4, 22.93, 14.35 (terminal CH.sub.3).

Part 1.DEpoxidation of Internal Olefins to Afford C.SUB.31-35 .Oxiranes

[0194] The reaction was conducted under an inert argon atmosphere.

[0195] In a 300 mL double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows) and baffles, a condenser and a temperature probe were added: [0196] 38.2 g of C.sub.31-35 internal olefins (98 wt % purity, 80 mmol) [0197] 6.9 mL (7.2 g, 120 mmol) of acetic acid, and [0198] 11.3 g (30 wt %) of Amberlite IR 120H resin.

[0199] The mixture was heated to 75 C. to melt the fatty alkene. The agitation was then started and 12.3 mL (13.7 g, 120 mmol) of H.sub.2O.sub.2 30% were slowly added into the mixture using an addition funnel while monitoring temperature of the reaction medium to prevent temperature increase of the reaction mass (exothermicity). This required about 20 min. During the addition, the agitation was increased to improve transfers due to the heterogeneous nature of the reaction media.

[0200] At the end of the addition, the temperature of the reaction medium was increased at 85 C. and after 6 h 10 of stirring at this temperature, NMR analysis showed that the conversion level was around 99% with 98% selectivity.

[0201] Heating was then stopped and 150 mL of chloroform were added when the temperature of the reaction mass was around 50 C. The mixture was transferred to a separating funnel and the organic phase was washed 3 times with 150 ml of water. The resin catalyst that stayed in the aqueous phase was removed during phase separation. The aqueous phase was extracted twice with 50 mL of chloroform. The organic phase was dried over MgSO.sub.4, filtered and evaporated to afford 39.2 g of a white solid with a purity of 98 wt % (epoxide+dialcohol by-product). The yield taking into account the purity was 99%.

[0202] .sup.1H NMR (CDCl.sub.3, 400 MHZ) (ppm): 2.91-2.85 (m, 1.5H), 2.65-2.6 (m, 0.5H), 1.53-1.36 (m, 4H), 1.35-1.19 (m, 55H (aver. H number)), 0.86 (t, J=6.8 Hz, 6H).

[0203] .sup.13C NMR (CDCl.sub.3, 101 MHZ) (ppm): 58.97, 57.28, 32.18, 31.96, 29.72, 29.6, 29.4, 27.86, 26.95, 26.63, 26.09, 22.72, 14.15 (terminal CH.sub.3).

Part 1.EEpoxide Ring Opening With Chloroacetic Acid to Afford Chloroacetate Monoester C.SUB.31-35

[0204] ##STR00024##

[0205] The reaction was conducted under an inert argon atmosphere. In a 500 ml three necked round bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and an insulated addition funnel, were added 44.2 g of chloroacetic acid (463 mmol, 5 eq.)

[0206] In the insulated addition funnel maintained at 80 C. were added 45 g of melted C.sub.31-35 fatty epoxide (purity: 99.97 wt % , 92.6 mmol, 1 eq.)

[0207] The 1st step of hydroxy-ester formation through oxirane opening was conducted at 65 C. to limit the formation of ketone and dehydration by-products. The melted fatty epoxide was progressively added drop-wise over 1 h 20 into the reaction media containing melted chloroacetic acid under stirring at 65 C. The progressive addition of epoxide was carried out in order to limit by-products formed by condensation between two epoxide molecules. At the end of epoxide addition, the mixture was stirred at 65 C. during 1 h 30.

[0208] The 2nd step of hydroxy-ester formation through oxirane opening was conducted by an additional stirring at 80 C. during 1 h 00.

[0209] NMR analysis (CDCl.sub.3) of the crude showed complete conversion of the starting epoxide and a 88:12 mol % monoester : bisester mixture composition.

Part 1.FOptional Further Reaction With Chloroacetic Acid to Afford the Partial Conversion of the Chloroacetate Monoester C.SUB.31.-35 Into the Corresponding Diester

[0210] ##STR00025##

[0211] The condenser was replaced by a curved distillation column and the temperature of the reaction medium, that is to say the previously obtained crude having a 88:12 mol % monoester:bisester mixture composition, was increased to 90 C. followed by a progressive pressure decrease down to 10 mbar in order to distillate chloroacetic acid excess and to remove water formed as by-product.

[0212] After 1 h 30 distillation at 90 C. (10 mbar), .sup.1H NMR analysis showed a monoester : bisester ratio of 74:26 mol % with remaining chloroacetic acid.

[0213] At this stage the distillation was stopped and the mixture was allowed to cool down to room temperature. The crude was then solubilized into 150 ml of toluene and transferred into a separating funnel. The organic phase was washed 3 times with 150 ml of an aqueous NaOH solution (0.1M) followed by 150 ml of brine. The organic phase was separated, dried over MgSO.sub.4, filtered and evaporated to give 53 g of a residual beige oil.

[0214] .sup.1H NMR (CDCl.sub.3) after solvent evaporation showed the approximate composition of the beige oil: 66 wt % (70 mol %) of chloroacetate hydroxy-ester, 26 wt % (25 mol %) of chloroacetate bisester, 5 wt % (3 mol %) of monoester dimer, 2 wt % (1 mol %) of bisester dimer, 0.2 wt % (0.3 mol %) of ketone and 0.2 wt % (1 mol %) of chloroacetic acid.

[0215] The final yield in the chloroacetate mono+bisester taking into account the purity of the mixture was 88%.

[0216] .sup.1H NMR (CDCl.sub.3, 400 MHz) (ppm): 5.11-5.02 (m, 2H, diester), 4.96-4.83 (m, 1H, monoester), 4.07 (s, 1H, monoester), 4.06 (s, 1H, monoester), 4.04 (s, 2H, diester), 4.03 (s, 2H, diester), 3.74-3.67 (m, 1H, isomer 1, monoester), 3.64-3.54 (m, 1H, isomer 2, monoester), 1.73-1.61 (m, 2H, monoester), 1.61-1.48 (m, 4H, diester), 1.48-1.36 (m, 2H, monoester), 1.36-1.12 (m, 55 H (average number)), 0.86 (t, J=6.8 Hz , 6H).

[0217] .sup.13C NMR (CDCl.sub.3, 101 MHZ) (ppm): 167.39, 167.27, 167.15, 167, 79.84, 78.97, 76.21, 75.83, 72.95, 72.41, 41.06, 41.01, 40.90, 40.80, 33.63, 32.18, 31.98, 30.57, 29.75, 29.72, 29.65, 29.59, 29.5, 29.42, 28.85, 28.61, 25.9 25.6, 24.48 25.33, 24.97, 22.74, 14.15 (terminal CH.sub.3).

Part 1.GQuaternization With NMe.SUB.3

[0218] ##STR00026##

[0219] The reaction was conducted under an inert argon atmosphere. In a double-jacketed 1 L reactor equipped with a mechanical stirrer, a condenser, a temperature probe, a trap containing 0.1N HCl solution followed by a second trap containing activated carbon pellets, were added: [0220] 52 g (92.4 wt % purity, 80 mmol, 1 eq.) of a mixture of about 72 wt. % (74 mol. %) chloroacetate hydroxy-ester and about 28 wt.% (26 mol. %) of chloroacetate bisester, as obtainable upon completion of part 1-F, and [0221] 171 ml (320 mmol, 4 eq.) of a trimethylamine/THF solution (13 wt % concentration).

[0222] The reaction mixture was then heated at 40 C. and stirred at 1000 rpm. Reaction progress was followed up thanks to .sup.1H NMR analysis. After 6 h 00 stirring at 40 C., NMR analysis (CD3OD) showed complete conversion of chloroacetate esters and selective formation of the corresponding glycine betaine esters with the following approximate composition: 70 mol % of glycine betaine hydroxy-ester and 25 mol % of glycine betaine bisester.

[0223] The reactor was drained, rinsed with THF and the solvent was evaporated under vacuum to afford 58.8 g of a beige wax with the following weight composition: 65.2 wt % glycine betaine monohydroxy-ester, 27.6 wt % of glycine betaine bisester, 4.7 wt % of dimer monoester, 2.2 wt % of dimer bisester and 0.18 wt % of ketone.

[0224] The global yield in glycine betaine monohydroxy-ester plus glycine betaine bisester taking into account product purity was 98%. The glycine betaine monohydroxy-ester over (glycine betaine monohydroxy-ester plus glycine betaine bisester) weight ratio was 70%.

[0225] .sup.1H NMR (MeOD-d4, 400 MHZ) (ppm): 5.17-5.06 (m, 2H, diquat), 5.02-4.87 (m, 1H, monoquat), 5.26-4.17/4.84-4.76/4.6-4.51/4.47-3.32 (m, 2H:monoquat, 4H:diquat), 3.41 (s, 18H, isomer 1, diquat), 3.38 (s, 18H, isomer 2, diquat), 3.36 (s, 9H, monoquat), 3.72-3.64 (m, 1H, isomer 1, monoquat), 3.56-3.47 (m, 1H, isomer 2, monoquat), 1.75-1.53 (m, 2H, monoquat), 1.53-1.44 (m, 4H, diquat), 1.44-1.35 (m, 2H, monoquat), 1.35-1.12 (m, 55 H (average number)), 0.86 (t, J=6.8 Hz , 6H).

[0226] .sup.13C NMR (MeOD-d4, 101 MHZ) (ppm): 165.46, 165.17, 81.33, 80.77, 77.17, 76.46, 72.35, 72.18, 63.89, 63.81, 63.54, 63.08, 54.46, 54.37, 54.22, 33.70, 32.51, 32.06, 31.18, 30.27, 30.03, 29.94, 29.8, 29.04, 28.8, 26.6, 26.3, 26.1, 26, 25.8, 23.24, 14.45 (terminal CH.sub.3).

Part 1.HPurification of a Crude Richer in Chloroacetate Monoester C.SUB.31-35

[0227] A crude having a 88:12 mol % monoester:bisester mixture composition as obtainable upon completion of part 1-E is allowed to cool down to room temperature. The crude is then solubilized into toluene and transferred into a separating funnel. The organic phase is washed 3 times with an aqueous NaOH solution (0.1M) followed by brine. The organic phase is separated, dried over MgSO.sub.4, filtered and evaporated to give a purified material rich in chloroacetate monoester C.sub.31-35, having approximately a 88:12 mol % monoester:bisester mixture composition, and an overall monoester plus bisester content of about 95 wt. %.

Part 1.IQuaternization With NMe.sub.3 of a Crude Richer in Chloroacetate Monoester C.sub.31-35

[0228] A quaternization reaction of the purified material obtained upon completion of part 1.H is achieved using the same quaternization reaction and purification protocols as described under part 1.G.

[0229] At the end, a purified surfactant material QA.sub.2 having approximately a 90:10 wt. % glycine betaine monohydroxy-ester: glycine betaine bisester mixture composition, and an overall glycine betaine bisester plus glycine betaine monoester content of about 95 wt. %, is obtained.

Example 2Determination of Biodegradability

[0230] Biodegradability of test substances is measured according to the 301 F OECD protocol.

[0231] A measured volume of inoculated mineral medium, containing a known concentration of a test substance in order to reach about 50 to 100 mg ThOD/l (Theoretical Oxygen Demand) as the nominal sole source of organic carbon, is stirred in a closed flask (Oxitop respirometric flask) at a constant temperature (20+2 C.) for up to 28 days. Oxitop respirometric bottles are used in this test in order to access the biodegradability of the test sample: sealed culture BOD flasks were used at a temperature of 20+2 C. during 28 days.

[0232] Evolved carbon dioxide is absorbed by pellets of Natrium or Potassium hydroxide present in the head space of the bottle. The amount of oxygen taken up by the microbial population (=oxygen consumption expressed in mg/l) during biodegradation process (biological oxidation of the test substance) decreases the pressure of the head space (P measured by the pressure switch) and is mathematically converted in mg O.sub.2 consumed/litre. Inoculum corresponds to a municipal activated sludge washed in mineral medium (ZW media) in order to decrease the DOC (Dissolved Oxygen Carbon) content. Control solutions containing the reference substance sodium acetate and also toxicity control (test substance+reference substance) are used for validation purposes. Reference substance, sodium acetate, is tested in one bottle (at a nominal concentration of 129 mg/l corresponding to 100 mg ThOD/l) in order to check the viability of the inoculum. Toxicity control corresponds to the mixture of the substance reference and the test substance; it will check if the test substance is toxic towards the inoculum (if so, the test has to be redone at a lower test substance concentration, if feasible regarding the sensitivity of the method).

[0233] As the compounds and mixtures of compounds of the present invention are usually poorly soluble in water (and for those which are soluble in water, their metabolite after hydrolysis containing the alkyl chain has often very low solubility in water), we use a specific protocol named the emulsion protocol. This protocol enables us to increase the bioavailability of the poorly water-soluble substances in the aqueous phase where we have the inoculum.

[0234] Emulsion protocol consists of adding the test substance in the bottle through a stock solution made in an emulsion.

[0235] Emulsion is a 50/50 v/v mixture of a stock solution of the test substance dissolved in a non-biodegradable surfactant (Synperonic PE 105 at 1 g/l) and then mixed with a mineral silicone oil AR 20 (Sigma).

[0236] The first dissolution of the test substance in the non-biodegradable surfactant solution often requires magnetic stirrer agitation followed by ultrasonication.

[0237] Once the dissolution is made, we mix the aqueous solution with a mineral silicone oil at a 50/50 volume/volume ratio. This emulsion is maintained by magnetic stirrer agitation and is sampled for an addition in the corresponding bottle in order to reach the required test substance concentration.

[0238] Two emulsion controls are run in parallel during the test in order to remove their value from the emulsion bottle containing the test substance added through the emulsion stock solution.

[0239] Biodegradability tests are achieved on the 70/30 w/w and 90/10 w/w glycine betaine monohydroxy-ester/glycine betaine bisester mixtures QA.sub.1 and QA.sub.2 of example 1. After 28 days, biodegradability is at least about 60% (OECD 301F). Similarly to the glycine betaine bisester taken alone, as reported herein after in Table 4, the compounds QA.sub.1 and QA.sub.2 displays final biodegradability rates over 60% after 28 days.

[0240] Thus, the glycine betaine monohydroxy-ester and the glycine betaine bisester contained in the mixture of example 1 exhibit outstanding biodegradability. This beneficial effect is achieved without detrimentally affecting the surfactant properties of the compounds.

Example 3Evaluation of Adsorption Properties on Nanocellulose Crystals

[0241] Adsorption of cationic surfactant on negatively charged surface is an important property for various applications. This property is linked to the minimal concentration of cationic surfactant needed to produce aggregation of negatively charged cellulose nano crystal (CNC) in suspension in aqueous media. Comparison of the aggregate size can be monitored by dynamic light scattering (DLS).

[0242] Following the protocol described in literature (Ref.: E. K. Oikonomou, et al., J. Phys. Chem. B, 2017, 121 (10), pp 2299-2307), adsorption properties of ammonium compounds are investigated by monitoring the ratio X=[surfactant]/[CNC] or the mass fraction M=[surfactant]/([surfactant]+[CNC]), at fixed [surfactant]+[CNC]=0.01wt % in aqueous solution, required to induce the agglomeration of the cellulose nano crystal.

[0243] The range of CNC aggregation corresponds to the range of ratio X (or M) triggering an aggregation of CNC, i.e. the range where the aggregate size measured by DLS is higher than a pure aqueous solution of CNC or an aqueous solution of surfactant at 0.01wt %.

[0244] Ranges of X and M of aggregation of CNC are summarized in Table 1 for 70/30 w/w and 90/10 w/w glycine betaine monohydroxy-ester/glycine betaine bisester mixtures QA.sub.1 and QA.sub.2 of example 1. Fentacare TEP is used as a comparison. Fentacare TEP is a commercial surfactant representing the benchmark.

[0245] The lower range of aggregation X or M, the better the adsorption properties on negatively charged surface.

TABLE-US-00001 TABLE 1 Range of CNC Range of CNC aggregation (Ratio) aggregation X = [surfactant]/[CNC] (Mass fraction) Cationic surfactant X.sub.min X.sub.max M.sub.min M.sub.max Fentacare TEP 1-33 0.50-0.97 70/30 w/w glycine <<X.sub.min X.sub.max range of <<M.sub.min M.sub.max range betaine monohydroxy- Fentacare TEP of Fentacare TEP ester/glycine betaine bisester mixture QA.sub.1 of example 1 90/10 w/w glycine <<X.sub.min X.sub.max range of <<M.sub.min M.sub.max range betaine monohydroxy- Fentacare TEP of Fentacare TEP ester/glycine betaine bisester mixture QA.sub.2 of example 1

[0246] The data show that the surfactant properties of the mixture of compounds of formulae (I) and (VI) in accordance with the present invention is superior compared to the commercial surfactant Fentacare TEP.

[0247] So are also the surfactant properties of the compounds of formulae (I) and (VI) taken individually. The surfactant properties of the compounds of formulae (I) and (VI) and of mixtures thereof are further similar to the properties of the mixture of compounds of formulae (X) and (XI) as synthesized under Example 4Part B for which values are reported in Table 5.

Example 4Additional Mixtures of Monoquaternary Ammonium Compounds of Formula (I) With Diquatemary Ammonium Compounds

[0248] Part 4.ASynthesis of a diquaternary ammonium compound of formula (VI) starting from C.sub.31 16-hentriacontanone

a) Obtention of C.SUB.31 .Internal Olefin

[0249] C.sub.31 internal olefin was obtained from palmitic acid according to the protocol described in U.S. Pat. No. 10,035,746, example 4.

b) Epoxidation of Internal Olefin to Fatty Epoxide

[0250] ##STR00027##

[0251] The reaction was conducted under an inert argon atmosphere.

[0252] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel and a temperature probe were added 61.9 g of C.sub.31 alkene (0.142 mol), followed by 16.3 mL (17.1 g, 0.285 mol) of acetic acid and 13.6 g (22 wt %) of Amberlite IR 120H resin. The mixture was heated to 65 C.to melt the fatty alkene. The agitation was started and then 21.8 mL (24.2 g, 0.214 mol) of an aqueous solution of H.sub.2O.sub.2 (conc. 30%) was slowly added to the mixture using the addition funnel at a rate avoiding a significant temperature increase. This required about one hour. The temperature was then increased to 75 C. and the reaction mixture was allowed to stir overnight (after 15 min, NMR analysis showed that the conversion level was already around 60% with 99% selectivity). Then additional 10.2 mL (11.3 g, 0.1 mol) of an aqueous solution of H.sub.2O.sub.2 (30%) was added slowly and after 4 hours following the second addition of H.sub.2O.sub.2 NMR analysis showed that the conversion level was around 88% (98% selectivity). Another addition of 8.14 mL of acetic acid (8.55 g, 0.142 mol) followed by 11.6 mL of 30% H.sub.2O.sub.2 (12.91 g, 0.114 mol) was finally performed in order to increase the conversion level.

[0253] The mixture was allowed to stir a second night at 75 C.

[0254] Finally NMR analysis showed a conversion level of 93% (95% selectivity).

[0255] The mixture was allowed to cool down to room temperature and then 300 mL of chloroform were added. The mixture was transferred to a separating funnel and the organic phase was washed three times with 300 ml of water and then the aqueous phase was extracted twice with 100 mL of chloroform. The Amberlite solid catalyst stayed in the aqueous phase and was removed during the first separation with the aqueous phase. The organic phases were collected, dried over MgSO.sub.4, filtered and evaporated to give 65.3 g of a white solid with a purity of 91% w/w (epoxide+dialcohol).

[0256] The yield taking into account the purity was 92%.

[0257] .sup.1H NMR (CDCl.sub.3, 400 MHZ) (ppm): 2.91-2.85 (m, 2H, diastereoisomer 1), 2.65-2.6 (m, 2H, diastereoisomer 2), 1.53-1.00 (m, 54H), 0.86 (t, J=6.8 Hz, 6H).

[0258] .sup.13C NMR (CDCl.sub.3, 101 MHZ) (ppm): 58.97, 57.28, 32.18, 31.96, 29.72, 29.6, 29.4, 27.86, 26.95, 26.63, 26.09, 22.72, 14.15 (terminal CH.sub.3).

c) Hydrolysis of Fatty Epoxide to Afford Fatty Diol

[0259] ##STR00028##

[0260] The reaction was conducted under an inert argon atmosphere.

[0261] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser and a temperature probe were added 82.9 g of C.sub.31 epoxide (purity: 94.5 wt %, 0.174 mol) followed by 480 ml of methyl-THF.

[0262] The mixture was allowed to stir at room temperature and 73 mL of a 3 M aqueous solution of H.sub.2SO.sub.4 was then added. The reaction medium was then stirred at 80 C. during 90 minutes. NMR analysis showed that the reaction was completed. The biphasic mixture was allowed to cool down to room temperature and the organic phase was separated. The solvent was then removed under vacuum and the residue was suspended in 200 mL of diethyl ether. The suspension was filtered and the resulting solid was washed 3 times with 50 mL of diethyl ether. The white solid was finally washed 2 times with 50 ml of methanol and was dried under vacuum to remove traces of solvent.

[0263] At the end 75.53 g of product was obtained as a white powder with a purity of 95.7% w/w corresponding to a yield of 89%.

[0264] .sup.1H NMR (CDCl.sub.3, 400 MHz) (ppm): 3.61-3.55 (m, 2H, diastereoisomer 1), 3.43-3.25 (m, 2H, diastereoisomer 2), 1.88 (brd, J=2.4 Hz, OH, diastereoisomer 2), 1.72 (brd, J=3.2 Hz, OH, diastereoisomer 1), 1.53-1.10 (m, 54H), 0.86 (t, J=6.8 Hz , 6H).

[0265] .sup.13C NMR (CDCl.sub.3, 101 MHZ) (ppm): 74.71, 74.57, 33.66, 31.96, 31.23, 29.71, 29.39, 26.04, 25.68, 22.72, 14.15 (terminal CH.sub.3)

d) Esterification of Fatty Diol With Trimethylglycine to Afford Compound of Formula (VI)

[0266] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0267] Fresh commercial anhydrous CHCl.sub.3 (amylene stabilized) and anhydrous toluene were used as such.

[0268] Betaine hydrochloride (19.66 g, 128.4 mmoles) was washed ten times with 20 mL of anhydrous THF followed by drying under vacuum to remove traces of solvent prior to use.

[0269] In a 100 mL four-neck round-bottom flask equipped with a magnetic stirrer, a heater, a condenser, a temperature probe and a curved distillation column connected to two traps of NaOH were quickly added: [0270] 19.66 g of dried betaine hydrochloride (128.4 mmoles) and [0271] 28 mL of SOCl.sub.2 (45.86 g, 0.386 mol).

[0272] The heterogeneous mixture was stirred and the temperature was then slowly increased to 70 C. It was observed that when the temperature reached 68 C., gas was released (SO.sub.2 and HCl) and the mixture turned homogeneous yellow.

[0273] The mixture was then allowed to stir at 70 C. during two hours and hot anhydrous toluene (25 mL, 80 C.) was added into the vessel. The mixture was stirred and then decanted at 0 C. (white-yellow precipitate formation) and the upper phase of toluene was removed through a cannula. The operation of toluene washing was repeated seven times in order to remove all SOCl.sub.2 excess. NMR analysis showed complete conversion of glycine betaine hydrochloride but also formation of NMe.sub.3.Math.HCl adduct (NMe.sub.3.Math.HCl content in the solid: 12.3 mol %).

[0274] 20 mL of dry CHCl.sub.3 was then added to the solid betainyl chloride.

[0275] A solution of 26.19 g (56 mmol) of fatty diol in 90 mL of anhydrous CHCl.sub.3 was prepared at 55 C. and was added dropwise under stirring to the reaction vessel at room temperature (exothermicity and emission of HCl was observed). The mixture was then allowed to stir at 55 C. overnight. Over the course of the reaction, the mixture turned homogeneously orange. NMR analysis showed that the conversion level was around 100%.

[0276] The mixture was then allowed to cool down to room temperature and the solvent was evaporated under vacuum.

[0277] The residue was solubilized in methanol at 0 C. and the formed precipitate was filtered out. The obtained filtrate was then evaporated to give 39.7 g of crude product.

[0278] This product was then deposited on a sinter filter and washed with cyclohexane to remove some remaining organic impurities. The resulting washed solid was dried under vacuum to afford 22 g of crude material. A final purification with a mixture of CH.sub.2Cl.sub.2/cyclohexane 50:50 was carried out; the solid was solubilized again in this solvent mixture at 50 C. and was allowed to cool down to room temperature. The formed precipitate was filtered out and after evaporation of the filtrate 19 g of a beige wax QA.sub.3 was obtained with the following composition: [0279] 95 wt % of glycine betaine diester, corresponding to a compound of formula (VI) [0280] 1.5 wt % of methyl betainate [0281] 2 wt % of trimethylamine hydrochloride [0282] 1.5 wt % of glycine betaine hydrochloride.

[0283] The purified yield was 44%. No presence of glycine betaine monoester compound of formula (I) was identified in wax QA.sub.3.

[0284] .sup.1H NMR (MeOD-d4, 400 MHZ) (ppm): 5.3-5.2 (m, 2H), 4.68 (d, J=16.8 Hz, 2H), 4.50 (d, J=16.8 Hz, 2H), 4.53 (s, 1H), 4.48 (s, 1H), 3.37 (s, 18H), 1.75-1.55 (m, 4H), 1.39-1.10 (m, 50 H), 0.9 (t, J=6.8 Hz , 6H).

[0285] .sup.13C NMR (MeOD-d4, 101 MHZ) (ppm): 164.58, 75.76, 62.43, 53.10, 31.68, 30.05, 29.41, 29.38, 29.33, 29.28, 29.15, 29.09, 28.96, 24.71, 22.34, 13.05 (terminal CH.sub.3).

Part 4.BSynthesis of a Mixture of Diquaternary Ammonium Compounds of Formulae (X) and (XI) Starting From C.SUB.31.-16-Hentriacontanone

a) Knoevenagel Condensation to Afford Diester Intermediate:

[0286] ##STR00029##

[0287] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0288] Fresh commercial anhydrous CHCl.sub.3, anhydrous THF and anhydrous pyridine were used as such.

[0289] In a 1 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser, an addition funnel and a temperature probe were added 36.5 mL of TiCl.sub.4 (63.00 g, 0.332 mole), followed by 146.3 mL of CHCl.sub.3.

[0290] The mixture was stirred at 10 C. and anhydrous THF (358 mL) was slowly added through the addition funnel at a rate avoiding a temperature increase of the reaction medium above +5 C. During THE addition, a yellow precipitate appeared. Then 15.3 mL of dimethyl malonate (17.69 g, 0.134 mole) were added into the reaction mixture which was then allowed to stir at room temperature for 1 hour in order to allow malonate complexation to occur.

[0291] Then the mixture was allowed to cool down to 0 C. and a solution of 71.80 mL of anhydrous pyridine (70.50 g, 0.891 mole) in 23 mL of THF was slowly added into the reactor. During addition, the colour of the mixture turned red. The mixture was then allowed to stir at room temperature during 20 minutes to allow deprotonation to occur.

[0292] Finally, 50.00 g of C.sub.31 ketone (0.111 mole) was added into the reaction mixture which was allowed to stir at room temperature during one night and during one more day at 35 C. 250 ml of water were then carefully added into the reactor followed by 250 mL of diethyl ether. The organic phase was separated and washed 4 times with 250 ml of water and one time with 200 mL of a saturated aqueous NaCI solution in order to remove pyridinium salts. The aqueous phases were combined and re-extracted with 3 times 250 mL of diethyl ether. The final organic phase was dried over MgSO.sub.4, filtered and evaporated under vacuum to afford 70.08 g of crude orange oil. At this stage the crude contains residual amount of starting ketone as well as a main impurity corresponding to the condensation (aldolisation+crotonisation) of 2 equivalents of ketone.

[0293] The product could be easily purified by dissolving the oil in ethanol (the by-product and the starting ketone being not soluble in ethanol) followed by a filtration over celite.

[0294] The filtrate was evaporated, re-dissolved in CHCl.sub.3, filtered again and evaporated to afford 52.57 g of oil with 95% of purity (RMN).

[0295] The overall purified yield was 79%.

[0296] .sup.1H NMR (CDCl.sub.3, 400 MHZ) (ppm): 3.68 (s, 6H), 2.32-2.19 (m, 4H), 1.45-1.39 (m, 4H), 1.30-1.10 (m, 48 H), 0.81 (t, J=6.4 Hz , 6H).

[0297] .sup.13C NMR (CDCl.sub.3, 101 MHZ) (ppm): 166.30, 164.47, 123.65, 52.15, 34.61, 32.15, 30.16, 29.92, 29.91, 29.87, 29.76, 29.60, 28.65, 22.92, 14.34 (terminal CH.sub.3).

b) Transesterification With Dimethylaminoethanol to Afford Diamine Mixtures Intermediates:

[0298] ##STR00030##

[0299] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0300] Fresh commercial anhydrous toluene and dimethylaminoethanol were used as such.

[0301] In a 2 L double-jacketed reactor equipped with a mechanical stirrer (propeller with four inclined plows), a condenser with a distillation apparatus and a temperature probe were added 42.7 g of the internal ketone/dimethyl malonate adduct (75.6 mmol) followed by 50 ml of toluene. The mixture was stirred at room temperature and 30.4 mL of dimethylaminoethanol (26.9 g, 302.2 mmol, 4 eq.) was added to the reaction system followed by 50 mL of toluene. Then 0.9 g of the catalyst dibutyltin oxide (3.8 mmol, 5 mol %) was added to the reaction mixture followed by 200 ml of toluene.

[0302] Then the mixture was allowed to stir at 120 C. and the reaction progress was followed by NMR analysis. To run a proper analysis an aliquot of the reaction medium was sampled and diluted in diethyl ether, quenched with water, decanted and the organic phase was evaporated under vacuum to be analysed in CDCl.sub.3 NMR solvent. After 4 days of stirring at 120 C. NMR analysis showed that the conversion level was around 83% with 91% selectivity. In addition, by-product methanol was also present in the distillation flask. The reaction mixture was then allowed to cool down at room temperature and quenched with 500 mL of water. The medium was decanted and the aqueous phase was extracted with three times of 500 ml of diethyl ether. The organic phases were collected and washed three times with 500 ml of water and one time with 500 ml of a saturated aqueous NaCl solution in order to remove excess of dimethylaminoethanol. The organic phase was then dried over MgSO.sub.4, filtered and evaporated to give 47.9 g of a crude dark oil. At this stage the crude contained a residual amount of the starting malonate.

[0303] The product was then purified by flash chromatography on silica gel with a first eluent consisting on CHCl.sub.3/AcOEt mixture going through a gradient from 100% CHCl.sub.3 to 100% AcOEt.

[0304] In order to remove all the product from the column, the column was also flushed with isopropanol+NEt.sub.3 mixture (10% vol NEt.sub.3) allowing getting additional pure product.

[0305] The clean fractions were collected affording, after solvent evaporation, 27.8 g of a pure product corresponding to 54% isolated yield.

[0306] NMR analysis showed that the product was in the form of a mixture of two position isomers with the following ratio: 54 mol % of the isomerized product (cis and trans diastereoisomers) and 46 mol % of methylenated product.

[0307] .sup.1H NMR (CDCl.sub.3, 400 MHZ) (ppm): 5.45-5.13 (m, 1H: isomer 2 cis+trans), 4.42 (s, 1H, isomer 2 cis or trans), 4.24-4.06 (m, 4H, isomer 1+2), 3.99 (s, 1H, isomer 2 cis or trans), 2.58-2.40 (m, 4H, isomer 1+2), 2.32-2.24 (m, 4H, isomer 1), 2.20 (s, 12H, isomer 1), 2.19 (s, 12H, isomer 2), 2.09-1.89 (m, 4H, isomer 2 cis+trans), 1.45-0.99 (m, 51 H, isomer 1+2), 0.81 (t, J=6.8Hz, 6H).

[0308] .sup.13C NMR (CDCl.sub.3, 101 MHZ) (ppm): 168.60, 168.41, 165.49, 164.05, 132.07, 131.57, 131.12, 130.77, 123.73, 63.35, 62.76, 58.08, 57.49, 57.45, 53.45, 45.73, 34.45, 30.07, 30.03, 29.72, 29.68, 29.58, 29.53, 29.45, 29.38, 28.46, 28.43, 28.27, 28.09, 22.70, 14.13 (terminal CH.sub.3).

c) Methylation to Afford a Mixture of Compounds (X) and (XI)

[0309] All the reactions were conducted in carefully dried vessels and under an inert argon atmosphere.

[0310] Fresh commercial anhydrous THF and dimethylsulfate were used as such.

[0311] In a 1 L double-jacketed reactor equipped with a mechanical stirrer, a condenser, an addition funnel and a temperature probe were added 100 ml of dry THF and 6.9 mL of dimethylsulfate (9.14 g, 72 mmol, 2 eq.). A solution of 24.6 g of the esteramine (36 mmol, 1 eq.) in 154 mL of THF was preliminary prepared in the addition funnel and was progressively added into the reactor under stirring at room temperature in order to limit the temperature increase. The mixture was then stirred at room temperature under argon and the reaction progress was monitored by NMR analysis. After 2 hours the mixture was brought to 40 C. and 0.2 mL of dimethyl sulfate (2 mmol, 0.06 eq.) were added to allow stirring and to achieve complete conversion.

[0312] Reaction was completed after one hour of stirring at 40 C. and all the volatiles (THF and remaining DMS) were removed under vacuum in order to afford 33.15 g of a 95 mol % purity product as a beige wax QA.sub.4 with 94% yield.

[0313] NMR analysis showed the presence of 2 position isomers with 55:45 ratio between isomerized derivative (cis and trans diastereoisomers) and conjugated non-isomerized methylenated derivative.

[0314] .sup.1H NMR (MeOD, 400 MHZ) (ppm): 5.60-5.25 (m, 1H: isomer 2 cis+trans), 4.80 (s, 1H, isomer 2 cis or trans), 4.75-4.50 (m, 4H, isomer 1+2), 4.38 (s, 1H, isomer 2 cis or trans), 3.84-3.72 (m, 4H, isomer 1+2), 3.69 (s, 6H, isomer 1+2), 3.22 (s, 18H, isomer 2), 3.21 (s, 18H, isomer 1), 2.50-2.35 (m, 4H, isomer 1), 2.22-2.02 (m, 4H, isomer 2 cis+trans), 1.60-1.09 (m, 35 H, isomer 1+2), 0.90 (t, J=6.8 Hz , 6H).

[0315] .sup.13C NMR (MeOD, 101 MHz) (ppm): 169.22, 169.01, 168.96, 165.52, 134.16, 133.22, 132.94, 131.74, 65.90, 65.81, 60.23, 60.18, 59.73, 55.27, 54.66, 54.62, 35.66, 35.54, 33.24, 33.23, 31.76, 31.01, 30.94, 30.91, 30.87, 30.85, 30.77, 30.74, 30.71, 30.66, 30.65, 30.63, 30.60, 29.73, 29.62, 29.45, 29.27, 23.89, 14.61 (terminal CH.sub.3).

Part 4.CAdditional Mixtures of Monoquaternary Ammonium Compounds of Formula (I) With Diquaternary Ammonium Compounds

[0316] Eight additional surfactant materials are prepared by mixing various amounts of surfactant materials QA.sub.1, QA.sub.2, QA.sub.3 and QA.sub.4.

[0317] The weight percentages of monoquaternary ammonium compounds of formula (I) and of diquaternary ammonium compounds contained in surfactant materials QA.sub.1, QA.sub.2, QA.sub.3 and QA.sub.4 are compiled here below, the remaining wt. % corresponding to impurities:

TABLE-US-00002 TABLE 2 Approximate wt. % of Approximate Mono over Formula(e) of mono- wt. % of diquaternary diquaternary quaternary diquaternary ammonium Surfactant ammonium ammonium ammonium compounds material compounds compounds compounds ratio, in % QA.sub.1 Formula (VI) 65.2 27.6 70 QA.sub.2 Formula (VI) 85 10 90 QA.sub.3 Formula (VI) 0 95 0 QA.sub.4 Formulae (X) 0 94 0 and (XI)

[0318] The following mixtures QA.sub.5 to QA.sub.12 are prepared using convention mixing techniques by mixina QA.sub.1 to QA.sub.4 in appropriate proportions:

TABLE-US-00003 TABLE 3 Mono-over di- quaternary ammonium Additional compounds surfactant QA.sub.1 to QA.sub.4 ratio, materials mixtures in % QA.sub.5 QA.sub.1 + QA.sub.2 80 QA.sub.6 QA.sub.1 + QA.sub.3 50 QA.sub.7 QA.sub.1 + QA.sub.3 30 QA.sub.8 QA.sub.1 + QA.sub.3 10 QA.sub.9 QA.sub.2 + QA.sub.4 80 QA.sub.10 QA.sub.2 + QA.sub.4 60 QA.sub.11 QA.sub.2 + QA.sub.4 40 QA.sub.12 QA.sub.2 + QA.sub.4 20

[0319] Optionally, surfactant materials QA.sub.1 to QA.sub.12 are made available in the form of an aqueous or hydro-alcoholic solution.

Example 5Additional Biodegradability Tests

[0320] Biodegradability of surfactant materials QA.sub.3 and QA.sub.4 were measured according to the OECD standard 301.

[0321] The results of the biodegradability test are reported in Table 4.

TABLE-US-00004 TABLE 4 Surfactant material Biodegradability after 28 days QA.sub.3 92% (OECD 301F) QA.sub.4 17% (OECD 301D)

[0322] The results show outstanding biodegradability for the glycine betaine bisester compound (surfactant material QA.sub.3) and fair biodegradability for the mixture of diquaternary ammonium compounds of surfactant material QA.sub.4. All this is achieved without detrimentally affecting the surfactant properties of the compounds.

Example 6Additional Evaluations of Adsorption Properties on Nanocellulose Crystals

[0323] Adsorption properties of surfactant materials QA.sub.3 and QA.sub.4 were measured in accordance with the protocol described in example 3.

[0324] Ranges of X and M of aggregation of CNC are summarized in Table 5. The lower range of aggregation X or M, the better the adsorption properties on negatively charged surface.

TABLE-US-00005 TABLE 5 Range of CNC Range of CNC aggregation (Ratio) aggregation Surfactant X = [surfactant]/[CNC] (Mass fraction) material X.sub.min X.sub.max M.sub.min M.sub.max Fentacare TEP 1-33 0.50-0.97 Glycine betaine <<X.sub.min X.sub.max range <<M.sub.min M.sub.max range diester QA.sub.3 of of Fentacare TEP, of Fentacare TEP, example 4-Part A similar to QA.sub.4 similar to QA.sub.4 QA.sub.4 (mixture of 0.1-1.82 0.09-0.65 compounds of formulae (X) and (XI)) of example 4-Part B

[0325] Fentacare TEP was used as a comparison. Fentacare TEP is a commercial surfactant representing the benchmark.

[0326] The data show that the surfactant properties of surfactant materials QA.sub.3 and QA.sub.4, which serve for the preparation of the mixtures QA.sub.5 to QA.sub.12 (in accordance with the present invention), are superior compared to the commercial surfactant Fentacare TEP.

[0327] Overall, the compounds of formula (I) show a good combination of surfactant properties combined with a good biodegradabiltya combination which is in many cases not achieved by commercial surfactants. Since the compounds of formula (I) are also easily available starting from internal ketones which are easily accessible from fatty acids or fatty acid derivatives, they also provide economical benefits over prior art ammonium surfactants.

[0328] The same attractive combination of surfactant and biodegradabilty properties is achieved with mixtures comprising comprising the compounds of formula (I) and the compounds of formula (VII). An additional advantage of such mixtures is that, by varying the respective proportions of the compounds of formulae (I) and (VII), it is possible to adjust the viscosity of the aqueous or hydro-alcoholic formulations prepared from the mixtures within a broad range of values, allowing for the use of such mixtures in a broad range of applications requiring different levels of viscosity.