Mixtures of compounds, their preparation, and uses

Abstract

The current invention is directed towards mixtures of compounds, comprising (A) in the range of from 93 to 97% by weight compound of general formula (I) (B) in the range of from 3 to 6.5% by weight compound of general formula (II) (C) in the range of from 0.2 to 0.5% by weight compound of general formula (III) wherein the integers are defined as follows: R.sup.1 is —(CH.sub.2).sub.nCH.sub.3, R.sup.2 is —(CH.sub.2).sub.n+2CH.sub.3, R.sup.3 is —(CH.sub.2).sub.n+1CH(CH.sub.3).sub.2, R.sup.4 is —(CH.sub.2).sub.n−1CH(CH.sub.3).sub.2 G.sup.1 selected from monosaccharides with 4 to 6 carbon atoms, x in the range of from 1.1 to 10, n is a number in the range of from 1 to 4. ##STR00001##

Claims

1. Mixture of compounds, comprising (A) in the range of from 93 to 97% by weight compound of general formula (I), ##STR00013## (B) in the range of from 3 to 6.5% by weight compound of general formula (II), ##STR00014## (C) and in the range of from 0.1 to 0.5% by weight compound of general formula (III) ##STR00015## wherein the integers are defined as follows: R.sup.1 is —(CH.sub.2).sub.nCH.sub.3, R.sup.2 is —(CH.sub.2).sub.n+2CH.sub.3, R.sup.3 is —(CH.sub.2).sub.n+1CH(CH.sub.3).sub.2, R.sup.4 is —(CH.sub.2).sub.n−1CH(CH.sub.3).sub.2 G.sup.1 is selected from monosaccharides with 4 to 6 carbon atoms, x in the range of from 1.1 to 10, n is a number in the range of from 1 to 4.

2. Mixture of compounds according to claim 1, characterized in that G.sup.1 is selected from glucose, arabinose and xylose.

3. Mixture of compounds according to claim 1, characterized in that x is in the range of from 1.15 to 2.

4. Mixture of compounds according to claim 1, characterized in that n is 1.

5. Mixture of compounds according to claim 1, characterized in that in molecules with x being 2 or more, the saccharide groups are linked in 1,4-position(s).

6. Mixture, containing at least one mixture according to claim 1 and at least one further isomer being different from each of compound according to general formulae (I), compound (II) and (III).

7. Process for making a mixture of compounds according to claim 1, comprising the step of reacting a mixture of alcohols of the general formulae (IV), (V) and (VI) ##STR00016## with a monosaccharide, disaccharide or polysaccharide containing a G.sup.1 group in the presence of a catalyst.

8. Process for cleaning hard surfaces comprising contacting said hard surface with a mixture of compounds according to claim 1.

9. Process according to claim 8, characterized in that the cleaning comprises a degreasing.

10. Aqueous formulation, containing in the range of from 0.05 to 50% by weight of at least one mixture of compounds according to claim 1.

11. Aqueous formulation according to claim 10, characterized that it further contains at least one by-product or starting material, stemming from the syntheses of compounds according to general formulae (I), (II) and (III).

12. Mixture of alcohols, comprising in the range of from 93 to 97% by weight alcohol of general formula (IV), ##STR00017## in the range of from 3 to 6.5% by weight alcohol of general formula (V) ##STR00018## and in the range of from 0.1 to 0.5% by weight alcohol of general formula (VI) ##STR00019## wherein the integers are defined as follows: R.sup.1 is —(CH.sub.2).sub.nCH.sub.3, R.sup.2 is —(CH.sub.2).sub.n+2CH.sub.3, R.sup.3 is —(CH.sub.2).sub.n+1CH(CH.sub.3).sub.2, R.sup.4 is —(CH.sub.2).sub.n−1 CH(CH.sub.3).sub.2 n is a number in the range of from 1 to 4.

Description

WORKING EXAMPLES

(1) General Remarks

(2) Percentages are % by weight (wt %) unless expressly noted otherwise.

(3) All measurements with respect to colour number were performed on a 10% by volume diluted paste or solution, respectively. For dilution, a 15% by volume aqueous solution of isopropanol was used.

(4) The lab plant for producing compounds according to the invention consisted of a jacketed 4 l glass reactor, a condenser with a Dean-Stark trap, a three stage agitator, a distillation receiver and a dropping funnel. The pressure was set with a vacuum system consisting of a vacuum pump, a pressure indicator, a pressure controller and two cold traps cooled with liquid nitrogen. To remove the excess alcohol by distillation, a 2 l round flask equipped with a stirrer, a PT 100, a Claisen distillation head, a cooler, a distillate receiver, a pressure measurement and a vacuum pump were used.

(5) I. Synthesis of Compounds According to the Invention

(6) As alcohol for the synthesis, the following inventive mixture of alcohols was sued:

(7) 95.47% by weight (IV.1),

(8) 4.13% by weight (V.1) and

(9) 0.18% by weight (VI.1)

(10) Experimental error: ±0.02%

(11) ##STR00012##

(12) It was obtained by a Guerbet reaction of a mixture of n-pentanol with iso-amyl alcohol.

(13) The inventive mixture was thus a mixture of isomers hereinafter also being referred to as “alcohol mixture (IV.1) to (VI.1)”.

(14) I.1 Synthesis of Inventive Mixture of Compounds (I.1), (II.1) and (III.1)

(15) The 4 l glass reactor of the lab plant described above was charged with 666.8 g (3.36 moles) of glucose monohydrate and 1812.6 g of alcohol mixture (IV.1) to (VI.1). The resultant slurry was dried at 75° C. at a pressure of 30 mbar for a period of 90 minutes under stirring. Then, the pressure was adjusted to ambient pressure, and the slurry was heated to 90° C. An amount of 5.7 g of sulfosuccinic acid (70% by weight), dissolved in 200 g of the above specified alcohol mixture (IV.1) to (VI.1), was added and heating was continued until a temperature of 110° C. was reached. The pressure was set to 30 mbar, and, under stirring, the water formed was distilled off at the Dean-Stark trap equipped with cold traps. After 5.5 hours, no more water was formed, and the amount of water to be formed theoretically was in the cold traps.

(16) The reaction was then quenched by neutralizing the catalyst with 2.43 g of 50% by weight aqueous NaOH. The pH value, measured in a 10% solution in isopropanol/water (1:10), was at least 10.2. The reaction mixture was then transferred into a round flask, excess alcohol mixture (IV.1) to (VI.1) was distilled off at 140° C./1 mbar. During the removal of the excess alcohol mixture (IV.1) to (VI.1), the temperature was step-wise raised to 180° C. within 2.75 hours. When no more alcohol would distil off, the liquid reaction mixture was stirred into water (room temperature) in order to adjust the solids content to 60% and cooled to ambient temperature, hereby forming an aqueous paste. The inventive mixture of compounds (I.1), (II.1) and (III.1) so obtained had an average degree of polymerization (number average) of 1.38 and a residual alcohol content of 0.04 g, and the paste so obtained had a water content of 38.4%. The pH value was 9.0, the colour number (Gardner) was 8.1.

(17) In order to improve the colour, 927 g of the above aqueous paste were transferred into a 4 l vessel and reacted with 73.5 g of 35% by weight aqueous H.sub.2O.sub.2 which was added in a way that the total peroxide content was in the range of from 300 to 1,500 ppm, determined with Merckoquant peroxide test sticks. The pH value was maintained in the range from 10.0 to 10.8 Finally, the pH value was adjusted to 11.5 with 50% by weight aqueous NaOH. The colour number (Gardner) had dropped to 3.0, and the water content had raised to 40.0%. All measurements with respect to pH value and peroxide content were performed on a 10% by volume diluted paste. For dilution, a 15% by volume aqueous solution of isopropanol was used.

(18) I.2 Synthesis of Inventive Mixture of Compounds (I.2), (II.2) and (III.2)

(19) The 4 l glass reactor described above was charged with 464.0 g (3.09 moles) of xylose and 1713.8 g of alcohol mixture (IV.1) to (VI.1). The resultant slurry heated to 50° C. An amount of 1.0 g of sulfosuccinic acid (70% by weight), dissolved in 150 g of the above specified alcohol mixture (IV.1) to (VI.1), was added and heating was continued until a temperature of 95° C. was reached. The pressure was set to 30 mbar, and, under stirring, the water formed was distilled off at the Dean-Stark trap equipped with cold traps. After 600 minutes, no more water was formed, and the amount of water to be formed theoretically was in the cold traps.

(20) The reaction was then quenched by neutralizing the catalyst with 1.2 g of 50% by weight aqueous NaOH. The pH value, measured in a 10% solution in isopropanol/water (1:10), was at least 11.0. The reaction mixture was then transferred into a round flask, and at 140° C./1 mbar, excess alcohol mixture (IV.1) to (VI.1) was distilled off. During the removal of the excess alcohol mixture (IV.1) to (VI.1), the temperature was step-wise raised to 175° C. within 2 hours. When no more alcohol would distil off, the liquid reaction mixture was stirred into water (room temperature) in order to adjust the solids content to 60% and cooled to ambient temperature, hereby forming an aqueous paste. The inventive mixture of compounds (I.2), (II.2) and (III.2) had an average degree of polymerization (number average) of 1.2 and a residual alcohol content of 0.2 g, and the paste so obtained had a water content of 39.9%. The pH value was 6.4, the colour number (Gardner) was >10.

(21) In order to improve the colour, 1040 g of the above paste were transferred into a 4 l vessel and reacted with 36.0 g of 35% by weight aqueous H.sub.2O.sub.2 which was added over a time of 3 h into the reactor. The pH value was maintained in the range from 10.1 to 11.2. Finally, the pH value was adjusted to 11.5 with 50% by weight aqueous NaOH. The colour number (Gardner) had dropped to 2.5, and the water content had raised to 41.9%. All measurements with respect to pH value and peroxide content were performed on a 10% by volume diluted paste. For dilution, a 15% by volume aqueous solution of isopropanol was used.

(22) I.3 Synthesis of Comparative Compound (1.1)

(23) Pure alcohol (IV.1) was obtained from an alcohol mixture (IV.1) to (VI.1) by fractionate distillation at 50 mbar with a packed column. Alcohol mixtures of (IV.1) to (VI.1) can be characterized by gas chromatography, for example operated with a 30 m Optima-1 column, diameter: 0.32 mm, FD 0.5μ, heating protocol: oven at 50° C. for 2 minutes, then heating with a rate of 20° C./min until a temperature of 130° C. has been reached, maintaining at 130° C. for 5 min., then heating with a rate of 7.5° C./min until a temperature of 200° C. has been reached, then increase heating rate to 20°/min until 250° C. have been reached, maintain at 250° C. until a total time of 40 min.

(24) The synthesis of protocol I.1 was repeated but alcohol mixture (IV.1) to (VI.1) was replaced by 1,301 g of alcohol (IV.1). Comparative compound C-(I.1) was obtained.

(25) I.4 Synthesis of Comparative Compound (I.2)

(26) The synthesis of protocol 1.2 was repeated but alcohol mixture (IV.1) to (VI.1) was replaced by 1250 g of alcohol (IV.1). Comparative compound C-(I.2) was obtained.

(27) II. Application Tests

(28) In the application tests, inventive mixture of compounds (I.1), (II.1) and (III.1) will also be abbreviated as (M.1), and inventive mixture of compounds (I.2), (II.2) and (III.2) will also be abbreviated as (M.2).

(29) II.1 Foaming Power

(30) The foaming power was determined according to EN12728/DIN 53902 at 40° C. with water of 10° dH (German hardness). As laundry cleaners (“LCF”), aqueous solutions consisting of 2 g/l of respective surfactant (±0.02 g) in distilled water were applied. The temperature was kept constant in a range of ±2° C.

(31) The results are summarized in table 1.

(32) TABLE-US-00001 TABLE 1 Wetting power surfactant Wetting power at 40° C. [s] (M.1) 140 C-(I.1) 410 (M.2)  40 C-(M.2)  60

(33) It can be seen that the polyglucoside based on alcohol mixture (IV.1) to (VI.1) is superior over polyglucoside based on 2-n-propylheptanol with respect to the wetting power, and that the polyxyloside based on alcohol mixture (IV.1) to (VI.1) is superior the respective polyxyloside based on 2-n-propylheptanol. Polyxylosides, however, have a higher price than polyglucosides and are therefore not accepted in all applications.

(34) II.2 Foam Stability Tests

(35) The experiments for determination of the foam stability were carried out in a Sita Foam Tester R-2000. As test solutions, aqueous solutions of 1 g/l of the respective polyglycoside in distilled water were used. An amount of 300 ml of the respective test solution was pumped into a glass vessel and heated to the respective temperature. Then it was stirred for 1 minute at 1,500 rpm. Then the volume of the foam was determined. Stirring and measuring was repeated 9 times. The stirrer was then set off, and the decay of the foam was determined. Measurements 10 minutes after set-off are listed in Table 2 or 2a or 2b or 2c, respectively. The results are summarized in Table 3. For Table 2a, the experiments were repeated but water with 16° dH (German hardness) was used instead of distilled water. For Table 2b, the experiments were repeated but a 1% by weight aqueous NaOH solution was used instead of distilled water. For Table 2c, the experiments were repeated but a 1% by weight aqueous methylsulfonic acid solution was used instead of distilled water.

(36) TABLE-US-00002 TABLE 2 Results of the foam stability tests in distilled water Maximum Reached Foam volume 10 Temperature foam after minutes after Surfactant [° C.] volume [ml] time [min] stirrer set-off [ml] (M.1) 20 897 10 543 C-(I.1) 20 911 3 874 (M.2) 20 426 10 327 C-(I.2) 20 927 4 871 (M.1) 40 939 6 591 C-(I.1) 40 989 5 936 (M.2) 40 471 10 155 C-(I.2) 40 1014 5 693 (M.1) 60 1041 8 27 C-(I.1) 60 1099 6 640 (M.2) 60 587 10 11 C-(I.2) 60 1077 6 147

(37) TABLE-US-00003 TABLE 2a Results of the foam stability tests in water of 16°dH Maximum Reached Foam volume 10 Temperature foam after minutes after Surfactant [° C.] volume [ml] time [min] stirrer set-off [ml] (M.1) 20 268 8 21 C-(I.1) 20 921 10 878 (M.2) 20 45 7 20 C-(I.2) 20 228 10 184 (M.1) 40 858 10 0 C-(I.1) 40 976 6 851 (M.2) 40 72 1 0 C-(I.2) 40 262 10 8 (M.1) 60 680 10 0 C-(I.1) 60 990 6 129 (M.2) 60 108 2 0 C-(I.2) 60 363 10 0

(38) TABLE-US-00004 TABLE 2b Results of the foam stability tests in 1 wt % aqueous NaOH Maximum Reached Foam volume 10 Temperature foam after minutes after Surfactant [° C.] volume [ml] time [min] stirrer set-off [ml] (M.1) 20 433 10 0 C-(I.1) 20 730 10 163 (M.1) 40 711 10 0 C-(I.1) 40 869 10 61 (M.1) 60 589 10 0 C-(I.1) 60 668 10 6

(39) TABLE-US-00005 TABLE 2c Results of the foam stability tests in 1 wt % aqueous methylsulfonic acid Maximum Reached Foam volume 10 Temperature foam after minutes after Surfactant [° C.] volume [ml] time [min] stirrer set-off [ml] C-(I.1) 20 354 10 298 (M.2) 20 13 9 0 C-(I.2) 20 39 4 0 C-(I.1) 40 1045 10 17 (M.2) 40 13 4 0 C-(I.2) 40 60 10 0 C-(I.1) 60 899 10 0 (M.2) 60 0 0 0 C-(I.2) 60 111 8 0
II.3 Emulsifying Behaviour
General Method:

(40) In a 400-ml-beaker, 50 g of a 2% by weight of aqueous solution (in distilled water) of the respective surfactant were mixed with 50 g of olive oil at 23° C. The mixture was stirred with 1200 (±3) rpm for exactly 2 minutes with the help of a power mixer, the mixer being positioned in the phase boundary oil-water. The emulsion so produced was then transferred to a cylinder to be observed. The emulsion stability was determined visually by measuring the volume of the water phase after one (1) and four (4) hours. The less “oil-free” water phase the more stable the emulsion. Results are summarized in Table 3.

(41) TABLE-US-00006 TABLE 3 Emulsifying behaviour surfactant Water phase after 1 h [ml] Water phase after 4 h [ml] (M.1) 4 14 C-(I.1) 8 23

(42) With (M.2) vs. C-(I.2), a similar trend can be observed.