MIXTURE, THEIR MANUFACTURE AND USE

Abstract

Mixtures comprising a mixture of compounds (A), said mixture comprising a mixture of compounds according to the general formula (I) wherein R.sup.1 is C.sub.1-C.sub.4-alkyl, linear or branched, or hydrogen, R .sup.2 is —CH.sub.2CH.sub.2R.sup.1, each G.sup.1 is glucose or xylose, wherein in the range of from 70 to 95% mole-% are glucose and from 5 to 30 mole-% are xylose, the average of x is in the range of from 1.1 to 4.

##STR00001##

Claims

1. Mixture of compounds (A), said mixture comprising a mixture of compounds according to the general formula (I) ##STR00008## wherein R.sup.1 is C.sub.1-C.sub.4-alkyl, linear or branched, or hydrogen, R.sup.2 is —CH.sub.2CH.sub.2R.sup.1, each G.sup.1 is glucose or xylose, wherein in the range of from 70 to 95% mole-% are glucose and from 5 to 30 mole-% are xylose, and the average of x is in the range of from 1.1 to 4.

2. Mixture according to claim 1 wherein R.sup.1 is ethyl or n-propyl.

3. Mixture according to claim 1 wherein the average of x is in the range of from 1.15 to 1.9.

4. Mixture according to claim 1 wherein in specific molecules with x being 2 or more, the G.sup.1 groups are selected from glucose being linked in 1,4-position(s).

5. Mixture according to claim 1 which further comprises at least one isomer of a compound according to general formula (I), said isomer bearing an alkyl group being isomeric to CH.sub.2CHR.sup.1CH.sub.2CHR.sup.1.

6. Process of making a mixture according to claim 1, said process comprising the step of reacting a mixture of glucose and xylose or the respective di- or polysaccharides with an alcohol according to formula (II)
R.sup.1CH.sub.2—CH.sub.2—CHR.sup.1—CH.sub.2—OH   (II) R.sup.1 being defined as above, in the presence of a catalyst.

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

8. Aqueous formulation according to claim 7, which further comprises at least one by-product or starting material, stemming from the synthesis of the mixture of compounds.

9. (canceled)

10. Process for cleaning hard surfaces or fibers, the process comprising 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.

11. Process according to claim 10, further comprising a degreasing the hard surface or the fiber.

Description

WORKING EXAMPLES

[0112] General Remarks

[0113] Percentages are % by weight (wt %) unless expressly noted otherwise.

[0114] The colour numbers (Hazen and Gardner) of (A.1), (A.2) and C-(A.4) were determined in 15% by volume aqueous isopropanol. The respective solutions of (A.3) and C-(A.5) were slightly turbid. Therefore, the colour numbers of (A.3) and C-(A.5) were determined by comparison with similar solutions. Measurements with respect to colour numbers were performed on a 10% by volume diluted paste or solution, respectively.

[0115] 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 partial and a total condenser, a distillation receiver and a dropping funnel. The partial condenser was not heated and served to separate alcohol (II) which was co-evaporated with water. 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.

[0116] I Synthesis of Mixtures According to the Present Invention

[0117] As alcohol (II.1), the following compound was used:

##STR00006##

[0118] It was obtained by a Guerbet reaction of n-pentanol. It contained impurities of (II.1a) and (II.1b), the sum of said impurities generally being 3.8 to 6 mol-%, specifically 5 mol-%, in each case referring to the total alcohol (II.1).

[0119] The alcohol was thus a mixture of isomers hereinafter also being referred to as “alcohol mixture (II.1)”. The isomers (II.1a) and (II.1b) displayed about the same reactivity towards glucose and xylose as did the alcohol (II.1).

##STR00007##

[0120] General Procedure:

[0121] The para-toluene sulfonic acid monohydrate (“p-TSA”) according to Table 1 was dissolved in 150 g of alcohol mixture (II.1).

[0122] The 4 l glass reactor of the lab plant described above was charged with glucose and, optionally, xylose according to Table 1, and alcohol mixture (II.1) according to Table 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 85° C. The paratoluene sulfonic acid monohydrate according to Table 1, dissolved in 150 g of alcohol mixture (II.1), was added through the dropping funnel, and heating was continued until the minimum reaction temperature according to Table 1 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 the reaction time specified in Table 1, no more water was formed, and the amount of water to be formed theoretically was in the cold traps.

[0123] 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 containing mixture of compounds (A.1) and compounds (III.1), them together constituting inventive mixture (A.1). The properties of inventive mixtures and of comparative mixtures are summarized in Table 2.

[0124] In order to improve the colour, the above aqueous paste were transferred into a 4 l vessel and reacted with 35% by weight aqueous H.sub.2O.sub.2 according to Table 1 which was added in a way that the total peroxide content was in the range of from 1,200 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 11.2 to 11.4 with 50% by weight aqueous NaOH. For dilution, a 15% by volume aqueous solution of isopropanol was used.

TABLE-US-00001 TABLE 1 Experimental data for syntheses of inventive mixtures and comparative mixtures Example unit (A.1) (A.2) (A.3) C-(A.4) C-(A.5) Glucose g 472.6 407.5 374.5 519.6 341.9 monohydrate xylose g 47.7 92.6 113.5 — 155.2 alcohol mix- g 1447.7 1447.7 1554.9 1715.8 1669.0 ture (II.1) p-TSA g 2.14 2.57 2.68 1.13 3.1 50% NaOH g 1.56 1.3 1.71 1.71 2.23 after dist. Reaction ° C.  95-110  93-110  88-110 110  88-110 temperature Reaction h 7.5 7.0 7.0 11.0 6.5 time Bleaching ° C. 60-80 80 80 60-80 80 temperature

TABLE-US-00002 TABLE 2 Properties Glucose Xylose H.sub.2O [mol-%] [mol-%] x pH Gardner content [%] (A.1) 88.3 11.7 1.30 11.4 2.2 46.3 (A.2) 77.2 22.8 1.28 11.2 3.7 45.2 (A.3) 71.7 28.3 1.25 11.2 3.2 38.5 C-(A.4) 100 — 1.27 11.3 1.1 41.4 C-(A.5) 62.9 37.1 1.24 11.3 2.8 38.2 Abbreviations: Gardner: colour number according to Gardner In each the above examples, the residual alcohol was in the range of from 0.05 to 0.08 g per total respective aqueous paste.

[0125] II. Cleaning Properties of Mixtures According to the Invention, and of Comparative Mixtures

[0126] Test Soil:

[0127] 36 wt % white spirit (boiling range)80/110°);

[0128] 17 wt % triglyceride (commercially available Myritol® 318;

[0129] 40 wt % mineral oil (commercially available Nytex® 801),

[0130] 7 wt % carbon black

[0131] 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.

[0132] As test substrates, white PVC stripes (37.Math.423.Math.1.2 mm) were used, commercially available from Gerrits, PVC-Tanzteppich® 5410 Vario white.

[0133] As test cleaners, the amounts of mixture according to the invention or of comparative compound according to tables 1 and 2 were dissolved in 50 ml of water. The pH value was adjusted to 7 with 0.1 M NaOH or 0.1 M hydrochloric 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. Cleaning liquids (CL) were obtained.

[0134] The tests were Gardner tests performed in an automatic test robot. It contained a sponge (viscose, commercially available as Spontex® Z14700), cross section 9.Math.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.

[0135] For each test stripe, a new sponge was used. The soiling and de-soiling was recorded with a digital camera. The results are summarized in Table 3.

TABLE-US-00003 TABLE 3 Cleaning experiments with mixtures of compounds (A.1) to (A.3) and with comparative compounds solids content (only surfactant) Soil Standard Name surfactant [g/100 ml] removal [%] deviation [%] CL.1-1 (A.1) 0.5 75.78 4.70 CL.1-2 (A.1) 1.0 86.20 3.76 CL.1-3 (A.1) 2.0 85.19 4.50 CL.2-1 (A.2) 0.5 65.26 2.88 CL.2-2 (A.2) 1.0 81.13 3.30 CL.2-3 (A.2) 2.0 85.90 3.58 CL.3-2 (A.3) 1.0 80.40 4.92 CL.3-3 (A.3) 2.0 81.78 3.59 C-CL.4-1 C-(A.4) 0.5 63.95 6.29 C-CL.4-2 C-(A.4) 1.0 68.28 3.04 C-CL.5-1 C-(A.5) 0.5 65.42 3.68 C-CL.5-2 C-(A.5) 1.0 71.14 4.65 C-CL.5-3 C-(A.5) 2.0 70.41 4.13 The solids content refers to the test cleaner and is expressed in g solids/100 g. NaOH or hydrochloric acid content are neglected. The standard deviation refers to the 5 PVC stripes tested per run with the same cleaner and the same soil.