Compounds, their preparation, and uses

Abstract

The current invention is directed towards compounds of the general formula (I), wherein the integers are defined as follows: R.sup.1 is —(CH.sub.2)nCH(CH.sub.3).sub.2, R.sup.2 is —(CH.sub.2).sub.n+2CH(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 4, n is a number in the range of from zero to 3. ##STR00001##

Claims

1. Mixture of compounds of general formula (I) ##STR00009## wherein: R.sup.1 is —(CH.sub.2).sub.nCH(CH.sub.3).sub.2, R.sup.2 is —(CH.sub.2).sub.n+2CH(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 4, n is a number in the range of from zero to 3.

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 1.9.

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

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 of compounds according to claim 1 and at least one of its isomers in which the sugar part is identical to G.sup.1 but the alkyl group is different.

7. Mixture, containing at least one mixture of compounds according to claim 1 and at least one non-ionic surfactant, selected from alkoxylated fatty alcohols and hydroxyl-group containing non-ionic surfactants.

8. Process for making a mixture of compounds according to claim 1, comprising the step of reacting an alcohol of the general formula (II) ##STR00010## with a monosaccharide, disaccharide or polysaccharide bearing a G.sup.1 group in the presence of a catalyst.

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

10. An aqueous formulation comprising from 0.05 to 50% by weight of said mixture of compounds of general formula (I) according to claim 1, and further comprising at least one by-product or starting material, stemming from the synthesis of said mixture of compounds.

11. Process for cleaning hard surfaces or fibers by contacting a hard surface or fiber or an arrangement of fibers with at least one aqueous formulation containing a mixture of compounds according to claim 1.

12. Process according to claim 11, characterized in that the cleaning comprises a degreasing.

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 I 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.

(5) 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.

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

(7) As alcohol (II.1), the following compound was used:

(8) ##STR00007##

(9) It was obtained by a Guerbet reaction of iso-amyl alcohol. It had an impurity of 10 mol-% of (II.1a)

(10) ##STR00008##

(11) It was thus a 9:1 mixture of isomers hereinafter also being referred to as “alcohol mixture (II.1)”.

(12) I.1 Synthesis of Inventive Compound (1.1)

(13) The 4 l glass reactor of the lab plant described above was charged with 703.6 g (2.4 moles) of glucose monohydrate and 1250 g of alcohol mixture (II.1). The resultant slurry was dried at 75° C. at a pressure of 30 mbar for a period of 30 minutes under stirring. Then, the pressure was adjusted to ambient pressure, and the slurry was heated to 90° C. An amount of 2.14 g of concentrated sulfuric acid (96% by weight), dissolved in 100 g of alcohol mixture (II.1), was added and heating was continued until a temperature of 106° 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.

(14) The reaction was then quenched by neutralizing the catalyst with 2.6 g of 50% by weight aqueous NaOH. The pH value, measured in a 10% solution in isopropanol/water (1:10), was at least 9.5. The reaction mixture was then transferred into a round flask, excess alcohol mixture (II.1) was distilled off at 140° C./1 mbar. During the removal of the excess alcohol mixture (II.1), the temperature was step-wise raised to 180° 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 compound I.1 had a degree of polymerization (number average) of 1.31 and a residual alcohol content of 0.04 g, and the paste so obtained had a water content of 40.8%. The pH value was 4.1, the colour number (Gardner) was 16.3.

(15) In order to improve the colour, 800 g of the above aqueous paste were transferred into a 4 l vessel and reacted with 38.5 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 7.5 to 8. Finally, the pH value was adjusted to 11.5 with 50% by weight aqueous NaOH. The colour number (Gardner) had dropped to 2.9, and the water content had raised to 45.9%. 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.

(16) I.2 Synthesis of Inventive Compound (I.2)

(17) The 4 l glass reactor described above was charged with 839.9 g (4.66 moles) of xylose and 1,511 g of alcohol mixture (II.1). The resultant slurry heated to 90° C. An amount of 2.55 g of concentrated sulfuric acid (96% by weight), dissolved in 100 g of alcohol mixture (II.1), was added and heating was continued until a temperature of 106° 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 255 minutes, no more water was formed, and the amount of water to be formed theoretically was in the cold traps.

(18) The reaction was then quenched by neutralizing the catalyst with 3.51 g of 50% by weight aqueous NaOH. The pH value, measured in a 10% solution in isopropanol/water (1:10), was at least 9.5. The reaction mixture was then transferred into a round flask, and at 140° C./1 mbar, excess alcohol mixture (II.1) was distilled off. During the removal of the excess alcohol mixture (II.1), the temperature was step-wise raised to 165° 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 compound 1.2 had a degree of polymerization (number average) of 1.32 and a residual alcohol content of 0.2 g, and the paste so obtained had a water content of 50.6%. The pH value was 7.8, the colour number (Gardner) was 10.1.

(19) In order to improve the colour, 1,793 g of the above paste were transferred into a 4 l vessel and reacted with 43.3 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 7.5 to 8. 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 50.6%. 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.

(20) II. Cleaning Properties of Compounds According to the Invention, and of Comparative Compounds

(21) As comparative compounds, the following compounds were used: C-C.1: mixture of linear C.sub.8-C.sub.14-alkyl glucosides, degree of polymerization (analogue to x): 1.5, molar quantities: n-C.sub.8-glucosides: 45 mole-%, n-C.sub.10-glucosides: 50 mole-%, n-C.sub.12-glucosides: 3 mole-%, n-C.sub.14-glucosides: 2 mole-% C-C.2: 2-ethylhexyl glucoside, degree of polymerization (analogue to x): 1.3 C-C.3: n-C.sub.8-alkyl glucoside, degree of polymerization (analogue to x): 1.3 C-C.4: n-C.sub.5H.sub.11—CH(n-C.sub.3H.sub.7)—CH.sub.2-glucoside (“n-2PH glucoside”), degree of polymerization (analogue to x): 1.3 C-C.5: n-C.sub.5H.sub.11—CH(n-C.sub.3H.sub.7)—CH.sub.2-xyloside (“n-2PH xyloside”), degree of polymerization (analogue to x): 1.3
Test Soil: 36 wt % white spirit (boiling range)80/110°; 17 wt % triglyceride (commercially available Myritol® 318; 40 wt % mineral oil (commercially available Nytex® 801), 7 wt % carbon black

(22) In order to prepare the test soil, a beaker was charged with the white spirit. The triglyceride and the mineral oil were added under stirring (500 rpm) until a clear solution had formed. The carbon black was then slowly added. The dispersion so obtained was then stirred for 30 minutes with an IKA Ultra-Turrax® T25 digital-basic. Thereafter, the dispersion was then stirred with a magnetic stirrer for 21 days at ambient temperature and then for 30 minutes with the Ultra-Turrax specified above. The dispersion so obtained was then stored in a closed glass bottle for additional 14 days under ambient conditions while being continuously stirred on a magnetic stirring device. The test soil so obtained was then ready for use.

(23) As test substrates, white PVC stripes (37.Math.423.Math.1.2 mm) were used, commercially available from Gerrits, PVC-Tanzteppich® 5410 Vario white.

(24) As test cleaners, the amounts of compound according to the invention or of comparative compound according to table 1 were dissolved in 50 ml of water. The pH value was adjusted to 7 with 0.1 M NaOH or 0.1 M acetic acid, if necessary. Then, the total mass of each of the test cleaners was adjusted to the total mass of 100 g (±0.2) g by addition of distilled water.

(25) The tests were Gardner tests performed in an automatic test robot. It contained a sponge (viscose, commercially available as Spontex® Z14700), cross section 9.4 cm. Per run, 5 test stripes were first soiled with 0.28 (±0.2) g of test soil by brush and then dried at ambient temperature for one hour. Then they were treated with the humid sponge, soaked with 20 ml of test cleaner, swaying ten times with a weight of 300 g and a swaying velocity 10 m/s, followed by rinsing twice with distilled water and drying at ambient temperature for 4 hours.

(26) For each test stripe, a new sponge was used. The soling and de-soiling was recorded with a digital camera.

(27) TABLE-US-00001 TABLE 1 Cleaning experiments with compound (I.1) and of comparative compounds solids content (only Soil Standard surfactant) removal deviation Name surfactant [g/100 ml] [%] [%] C-HSC.1 C-C.1 2 66.8 2.4 HSC.2 (I.1) 2 74.1 1.9 C-HSC.3 C-C.2 2 53.8 1.8 C-HSC.4 C-C.3 2 51.9 3.2 C-HSC.5 C-C.1 4 64.8 2.4 HSC.6 (I.1) 4 80.8 1.6 C-HSC.7 C-C.2 4 60.5 3.8 C-HSC.8 C-C.3 4 56.3 3.3

(28) The solids content refers to the test cleaner and is expressed in g solids/100 g. NaOH or acetic acid content are neglected.

(29) The standard deviation refers to the 5 PVC stripes tested per run with the same cleaner and the same soil.

(30) II.2 Wetting Power and Foaming Power

(31) The wetting power was tested in accordance with ISO 8022:1990, modified in accordance with EN1772:1995. The wetting power is expressed in seconds and means the time necessary for wetting a cotton swatch in a beaker filled with aqueous solution of the respective surfactant until it sinks to the bottom of the beaker. The shorter the time the higher is the wetting power. As laundry cleaners (“LCW”), aqueous solutions consisting of 1 g/l of respective surfactant (±0.02 g) in distilled water were applied.

(32) As substrates, TNV30 Cotton Swatches, diameter 30 mm (Immersion) according to DIN ISO 8022 (wfk-Testgewebe GmbH) were applied.

(33) The temperature was constant in a range of ±2° C.

(34) 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.

(35) The results are summarized in tables 2a and 2b.

(36) TABLE-US-00002 TABLE 2a Wetting power Wetting power Wetting power Name surfactant at 23° C. [s] at 70° C. [s] LCW.2 (I.1) 72 73 C-LCW.3 C-C.4 80 88 LCW.4 (I.2) 2 3 C-LCW.5 C-C.5 10 7 C-LCW.2 C-C.2 >300 >300

(37) It can be seen that the polyglucoside based on reaction products of alcohol mixture (II.1) is superior over polyglucoside based on 2-n-propylheptanol with respect to the wetting power, and that the polyxyloside based on reaction products of alcohol mixture (II.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.

(38) TABLE-US-00003 TABLE 2b Foaming power Name surfactant Foaming power at 40° C. [ml] C-LCF.1 C-C.1 660 LCF.2 (I.1) 140 C-LCF.3 C-C.4 620 LCF.4 (I.2) 90 C-LCF.5 C-C.5 100 C-LCF.2 C-C.2 110

(39) The experimental error in determining the foaming power is less than ±5%. It can be seen that the polyglucoside based on reaction products of alcohol mixture (II.1) is superior over polyglucoside based on 2-n-propylheptanol with respect to the foaming power, and that the polyxyloside based on reaction products of alcohol mixture (II.1) is superior the respective polyxyloside based on 2-n-propylheptanol.

(40) II.3 Foam Stability Tests

(41) 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 in Table 3 or 3a or 3b, respectively. The results are summarized in Table 3. For Table 3a, the experiments were repeated but water with 16° dH (German hardness) was used instead of distilled water. For Table 3b, the experiments were repeated but 1% by weight aqueous NaOH solution was used instead of distilled water.

(42) TABLE-US-00004 TABLE 3 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] (I.1) 20 375 8 250 C-C.4 20 957 9 865 (I.2) 20 932 10 800 C-C.5 20 901 3 826 (I.1) 40 814 4 16 C-C.4 40 1085 7 843 (I.2) 40 966 6 417 C-C.5 40 972 5 616 (I.1) 60 100 4 0 C-C.4 60 1083 10 390 (I.2) 60 993 9 32 C-C.5 60 1037 6 103

(43) TABLE-US-00005 TABLE 3a results of the foam stability tests in water 16° dH Maximum Reached Foam volume 10 Temperature foam after minutes after Surfactant [° C.] volume [ml] time [min] stirrer set-off [ml] (I.1) 20 237 8 51 C-C.4 20 604 10 184 (I.1) 40 125 6 3 C-C.4 40 887 10 4 (I.1) 60 89 5 0 C-C.4 60 455 10 0

(44) TABLE-US-00006 TABLE 3b Results of the foam stability tests in 1% by weight aqueous NaOH Temperature Maximum foam Reached after Surfactant [° C.] volume [ml] time [min] (I.1) 20 224 10 C-C.4 20 888 7 (I.1) 40 141 2 C-C.4 40 906 6 (I.1) 60 87 2 C-C.4 60 570 10

(45) In examples according to the invention, the foam volume was less or at least formed less fast, and the undesired foam was less stable than in the comparative examples with the respective polyglycoside part.