CS264731B1 - Deodorant preparation - Google Patents

Abstract

The scouring agent consists of 92 to 99.5 wt. of propylene glycol to polypropylene glycol by mol. weight up to 2000 g.mol-! and 0.5 to 8, (1.5 to 5) wt. Ethanolamide of at least one saturated carboxylic acid Cyg to Cjq · In addition, it may contain 10 to 80 wt. mixtures of hydrocarbons and / or 20 to 80 wt. at least one aliphatic alcohol C4 to C14. The formulation is particularly suitable for foaming or preventing the formation of foams of liquid laundry detergents applied in oil and other engineering production as well as foaming in oil extraction.

Description

264731 2

BACKGROUND OF THE INVENTION The present invention relates to a defoaming composition, particularly suitable for defoaming, respectively. preventing the formation of foams of liquid alkaline aqueous degreasing solutions as well as hydrocarbon scouring agents applied either in the production of rolling bearings, metalworking and other engineering products, consisting of a defined content of individual components based on substantially organic compounds.

Many substances are known, generally polycomponent mixtures, which are effective as antifoam agents. Relatively wide application possibilities have defoamers consisting wholly or at least in part of organosilicon compounds. Among the technically available products are the oxyethylation of the acetic acid and oleic acid, the saline oxyethylation of tall acids and the products of ethoxylation of butbopropoxylation of 4 to 25 carbon atoms in the molecule, with 1 to 25 moles of alkylene oxide alone or more often with organosilicon compounds (U.S. Pat. , 3 235 501 and 3 235 502). Then they are at least partially esterified polyols, such as esterified glycerol, pentaerythritol and sorbitol (U.S. Pat. No. 3,235,498), Sallow defoamer based on unsaturated acids such as acrylic acid and methacrylic acid (U.S. Pat. No. 3,458,567).

A drawback of said antifoams is either the technically and economically demanding production of components or lower efficacy and often toxicity. In the case of organosilicon components, despite their remarkable effect on defoaming efficiency, they cannot be components, not only because of the technical complexity of the production, but also the effects on the pollution of the ultimate compounds of the antifoam system. In addition, mixtures of higher fatty acids as well as higher higher ethanolamides of higher hydrocarbons, in particular propylene oligomers (U.S. Pat. No. 232,390, 236,099 and 240,516), but for some foaming systems, such as laundry oil compositions, but alkali aqueous degreasing agents applied mainly in engineering are less efficient. Similarly, in the case of defoamers, suitable for selected applications mainly in the bio-chemical industry, based on propylene glycol to polypropylene glycol and higher hydrocarbon carboxylic acids (MS Authorized Certificate 259 271) which are inefficient to almost ineffective in defoaming said washing solutions. Advantages of the known defoamers are utilized by several deficiencies of the antifoaming agent according to the invention, particularly suitable for defoaming and / or preventing the formation of foamable detergents applied in bearing and other engineering production, consisting of 92 to 99.5% propylene glycol to polypropylene glycol of molar mass up to 1,200 gmol-1 and 0.5 to 8% wt. The advantage of the antifoam composition of the present invention, unlike other antifoam products, as well as aliphatic higher fatty alcohols, is the copolymerization of ethylene oxide with propylene oxide with a high antifoaming efficiency, especially for washing and degreasing agents applied in engineering. Then, the synergistic effect of the components, the raw material availability and their hygienic safety. Furthermore, its flexibility of composition, depending on the foaming environment, whether "oily" or aqueous solutions, as well as the temperature of the foaming environment. Reasonable temperature sensitivity, good shelf life and transportability.

At lower temperatures, it is desirable to increase the hydrocarbon concentration and to minimize the concentration of the carboxylic acid ethanolamide C1g to C20, since the viscosity, the extra-structural viscosity rises rapidly until the antifoam composition solidifies. At higher temperatures, the potential to increase the concentration of ethanolamides of the carboxylic acids, thereby increasing the antifoaming efficacy of the antifoam agent over a range of 5-8%. The hydrocarbons of the present invention include saturated or unsaturated, especially aliphatic and naphthenic hydrocarbons, optionally with aromatic admixtures. Most often, however, petroleum fractions and petroleum fractions, light and heavy gas oil fractions, especially refined oils. Then synthetic hydrocarbons, especially oligomers, co-oligomers, or low molecular weight polymers and copolymers of propylene, alkenes and dienes C4 and C, .alpha. Are the products resulting from the thermal cleavage of macromolecular substances, as well as hydrogenolysis of macromolecular substances and higher hydrocarbons, e.g. vacuum distillates of petroleum and the like. In addition, the hydrogenated oligomers of said alkenes and dienes to c.

The hydrocarbons themselves have a very low defoaming efficiency, but show a distinctive synergistic effect in combination with propylene glycol to polypropylene glycol and at least a minimum amount of saturated carboxylic acid monoethanolamide to C2q.

Ethanolamides or monoethanolamides of carboxylic acids C16 to C20 can also be applied to the antifoam formulation of the present invention, which may also contain diethanolamide admixtures, but these are clearly less effective and, in addition, increase the viscosity of the antifoam even further and hence limit its application. options. Free diethanolamine triethanolamine, even free monoethanolamine, is also an undesirable ingredient. In contrast, the possible additives of aminoethyl esters of carboxylic acids C16 to C2Q have a positive effect.

Ethanolamides (ie, monoethanolamides, or 2-hydroxyethylamides of carboxylic acids) of saturated carboxylic acids up to θ2θ are more effective than unsaturated acids but also lower carboxylic acids as components. Additions of carboxylic acid ethanolamides in the above combinations with other components of the antifoam composition have a synergistic effect.

Suitable excipients are various powdered inorganic materials, especially those having a large surface area, such as silica, magnesium carbonate, calcium carbonate and the like. Furthermore, they are fungicides, bactericides, corrosion inhibitors, emulsifiers, optical brighteners, dyes and pigments. Further details of the formulation of the antifoams of the present invention, their efficacy, and other reservations are apparent from the examples. Example 1

The detersive efficacy of the individual formulations is determined by conducting the foaming of the standard sample with the foaming power of a standard sample with added defoamer. Thus, 100 cm 3 of aqueous sodium lauryl sulfate solution (anionic surfactant) at a concentration of 0.1% by weight. (1 gm-3) or polyethoxylated primary alcohols C 2 to C 4 4 with 9 moles of ethylene oxide (nonionic surfactant) of similar concentration and finally a similar solution of laurylammonium bromide (cationic surfactant) is carefully poured into 500 cm 4 graduated cylinders and sealed with ground-glass stopper. The standard solution is foamed by 180 ° over a cylinder and 50 times for 1 min at 23 ± 2 ° C. The foam height and the height of the unpulled solution are measured after 1 min of foaming.

Then the PS standard (%) foaming is calculated from the relation PS = a / b. 100, a = foam height cm; b = height of uncoated solution (cm -1); The de-oiling efficiency is determined by the same procedure as the standard solution, but 1 (0.02 g) or 2 drops (0.04 g) of odorants are added to 100 cm of the standard solution and the PQ (foaming mixture of standard solution and defoamer) is determined. Finally, the graph shows the foaming versus osti%] on the antifoaming efficiency, with the antifoaming efficiency [%] of 100 to 0 and the y-axis of the foaming solution being applied to the x-axis. [%] Of defoaming efficiency is subtracted from the diagonal intersection, taking the arithmetic mean of the three measurements as the final result. The antifoam formulation from the individual components is made at a temperature of 30 ± 5 ° C.

The components of the antifoam components are propylene glycol, dipropylene glycol, polypropylene glycol of average moles. weight 300 and polypropylene glycol with an average mol. Further, a kerosene fraction, paraffin-naphthenic oil, so-called white oil, propylene oligomers, so-called polypropylene oil K-1000 (Propyloil K 1000) with an average molar mass of 469 g.mol 3, 264731 4 with a density at 20 ° C = 847 kg.m-3; pour point = -25 ° C; there is an average of 1.5 to 1.6 double bonds per molecule. Then, pure 2-ethylhexanol as well as heavy fractions from the rectification of crude 2-ethylhexanol in the oxosynthesis process (2-EHTP) having the following composition: wt. OH = 12.9; bromine number = 4.7 g Br / 100 g; acid value = 0.9 mg KOH / g; deletion number = 22.1 mg KOH / g; 2-ethylhexanol = 36.3%; alcohols including diols c12 44.1 wt.% butyraldehyde diisobutyl acetal = 0.7 wt. and 7 additional oxygenated organic compounds in a concentration of 1 to 6% by weight; average molecular weight = 190; density at 20 ° C = 901.9 kg.m-3; n30 = 1.4530. Further, light (2-EHLP) from rectification of crude 2-ethylhexanol, fraction from 109 to 182.5 ° C / 101 kPa, density = 812.2 kg.m 3 and refractive index n * ® = 1.4088; % wt. OH = 19.4; CHO = 0.24 wt%; CHO bound = 0.25% by weight; bromine number = 1.3 g Br 2/100 g; H2O = 0.45%; acid value = 1.26 mg KOH / g; saponification number = 2.5 mg KOH / g; isobutanol content = 20.3%; n-butanol with an additional unknown component = 51.7 wt%; isoamyl alcohol = 4.1%; 3-heptanone = 4.1%; 2-ethylhexanol = 15.3%; 2-ethylhexanol = = 1.95%; further unidentified oxygenated organic compounds = 2.1 wt.

Thereafter, stearic acid ethanolamide (stearic acid 2-hydroxyethylamide), a C16 to C18 mixture of ethanol-amide and diethanolamide of unsaturated acids prepared with a predominance of oleic acid and linoleic acid.

The composition of the individual antifoams and their antifoaming efficacy on the foams formed by the interaction of anionic, cationic and nonionic surfactants is apparent from Table 1.

Table 1

Antifoam composition Foam relief efficacy with surfactant%

% Wt. nonionic anionic cationic 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops 1 2 3 4 5 6 7 8 Polypropylene Oil K 1000 50 2-Ethylhexanol 47,5 22 35 75 77 95 97 Stearic Ethanolamide 2,5 Polypropylene Oil K1000 50 2-EHTP 47.5 71 90 87 94 98 99 Stearic acid ethanolamide 2.5 Polypropylene glycol 900 50 2-EHTP 47.5 36 49 97 99 96 99 Stearic acid ethanolamide 2.5 Polypropylene glycol 900 500 2-Ethylhexanol 47.5 45 63 90 94 91 93

Stearic acid ethanolamide 2.5 5 264731 1 2 3 4 5 6 7 8 Polypropylene glycol 900 50 2-EHTP 45 Stearic acid ethanolamide 2.5 0 0 91 95 53 63 Stearic acid 2.5 Polypropylene glycol 1000 50 2-EHTP 47.5 39 45 71 74 91 96 Stearic ethanolamide 2,5 Dipropylene glycol 60 2-EHTP 37,5 94 97 73 76 87 90 Stearic acid ethanolamide 2,5 2-EHTP 100 58 65 81 89 81 84 2-EHTP 100 2 6 30 31 70 72 Polypropylene glycol 1000 97.5 44 48 83 85 56 58 Stearic Acid Ethanolamide 2.5 Dipropylene Glycol Ethanolamide / Dietanol Mix 97.5 39 40 60 72 2 7 Do not saturate amide. acids C16 to C18 2,5 Dipropylene glycol Ethanolamide acid 97,5 23 37 57 63 59 61 Stearic 2,5 Dipropylene glycol 59 2-EHTP 38,5 65 78 69 73 73 84 Stearic acid ethanolamide 2,5 Polypropylene oil K 1000Methanol amide 97,5 0 6 2 22 21 28 non-acids up to C ^ g 2,5 Kerosene 35 Polypropylene glycol 300 15 32 43 73 81 82 91 2-Ethylhexanol Ethanolamide 48,5 stearic i-.5 Polypropylene glycol 1000 30 2-Ethylhexanol 68, 5 43 56 70 74 86 95 Ethyl amide of palmitic acid 1,5 264731 6 Example 2

Efforts to test the efficacy of antifoam samples for washing liquid - Light Gas Oil (Petropal).

Air is bubbled through the 200 cm light petroleum gas (Petropal) in the washer for 2 min. After this time, the height of the foam is measured and the time of its disintegration is measured using a stopwatch. The results of the antifoaming efficacy obtained in dependence on the amount of antifoam agent are shown in Tab. 2.

Table 2

Defoaming agent composition Amount of defoamer applied (%) Foam height (cm) Foam disintegration time (s) Efficiency (%) Component Quantity (% by weight) 1 2 3 4 5 6 Petropal gas oil without defoaming agent 0,00 0,00 7,0 176 0 2-EHTP 100 0,58 7,3 170 3,6 Polypropylene oil K 1000 97,5 0,58 4,5 57 67,7 Stearic acid 2,5 Dipropylene glycol 60 2 -EHTP 37.5 0.58 4 25 85.8 Stearic Acid Ethanolamide 2.5 Dipropylene Glycol 60 2-EHTP 37.5 0.29 3.2 32 81.9 Stearic Acid Xoamide 2.5 - Polypropylene Glycol 1000 60 2- EHTP 37.0 0.29 4 24 91.3 Staer Monoethanolamide 2.5 SiO2 Powder 0.5 Polypropylene Glycol 930 50 2-EHTP 47.5 0.58 3.6 27 84.7 Stearic Ethanolamide 2.5

Example3

The antifoaming efficacy of antifoams added to alkaline aqueous solutions - degreasing agents with a concentration of 3% by weight is tested. (trade name of alkaline degreaser -3 3

Radical) by pouring into the 500 cm graduated cylinder 150 cm of scouring liquid-degreaser or washing liquid with the addition of defoamer. The measuring cylinder is capped and rotated sixty times by 180 ° for 1 min. The cylinder is then placed on a flat surface and the foam height and the time required to break the foam are measured.

Composition of antifoam samples and their effectiveness to reduce the foaming power of alkaline aqueous solutions of 3% by weight. (Radical) are shown in Table 3. 7 264731

Table 3

Composition of antifoaming agent Komoonent amount Amount of antifoam applied (%) Height of foam (cm) Foam disintegration time (min) Efficiency of antifoam agent (%) <% by weight) - (without antifoaming agent) wash alkaline aqueous solution (Radikal) '0,00 3 217 0 2-EHTP 100 0.39 0 - 100 Polypropylene glycol 930 50 2-EHTP 47.5 0.19 0 - 100 Stearic acid ethanolamide 2.5 Dipropylene glycol 60 2-EHTP 37.5 0.19 0 - 100 Ethanolamide acid stearic 2.5 Dipropylene glycol 60 2-EHTP 37.5 0.19 0 - 100 Stearic acid ethanolamide 2.5 Polypropylene oil K 1000 97.5 Ethanolamide acid 0.19 1.5 70 67.8 stear 2.5 Polypropylene oil K 1000 97.5 0.19 2.5 69 68.3 Stearic acid 2.5 Polypropylene glycol 49.6 2-EHTP 47.5 Stearic acid ethanolamide 2.5 0.19 0 - 100 siO2 0.3 p-Sodium cumylphenol 0 , 1 Example 4

The efficacy of the individual antifoams is determined similarly to Example 1. The composition of the individual samples and the results obtained are shown in Table 4. Table 4 Antifoam Antifoam Effectiveness Foam Efficiency Compound% Component of the nonionic anionic cationic component % wt. 1 2 1 2 1 2 drop drop drop drop drop drop drop Dipropylene GlycolEtanolamide Acid 97,5 39 49 8 20 72 73 Stearic 2,5 Dipropylene Glycol 95 45 47 23 38 75 77 Stearic Ethanolamide 5 Dipropylene Glycol 55 2-Ethylhexanol 40 18 31 78 81 87 90

Stearic Acid Ethanolamide 5 In this table, as well as in Tables 1-3, the antifoams of the present invention are compared with known antifoams as well as the effectiveness of the individual components.

Claims (4)

SUBJECT OF THE INVENTION 1. Defoaming agent, particularly suitable for defoaming and/or preventing the formation of foam in liquid detergents applied in bearing and other mechanical engineering production, characterized in that it consists of 92 to 99.5% by weight of propylene glycol to polypropylene glycol with a molar mass of up to 1,200 g.mol ¹ and 0.5 to 8% by weight of monoethanolamide of at least one saturated C^g to C^q carboxylic acid. 2. Defoaming agent according to item 1, characterized in that it further contains 10 to 80% by weight of a mixture of hydrocarbons with an average molar mass of 130 to 1,100 g.mol ¹ , preferably a petroleum fraction and/or synthetic hydrocarbons, preferably oligomers of alkenes up to C1. 3. The defoaming preparation according to items 1 and 2, characterized in that it further contains 20 to 80% by weight of at least one aliphatic alcohol up to C^, preferably a heavy fraction from the rectification of crude 2-ethylhexanol in the oxo process, containing mainly a mixture of 2-ethylhexanol, monohydric to dihydric alcohols C^ ₂ ^and acetals and/or a light fraction from the rectification of 2-ethylhexanol, consisting mainly of a mixture of n-butanol, isobutanol, isoamyl alcohol and 2-ethylhexanol with other acidic organic impurities. 4. Defoaming agent according to points 1 to 3, characterized in that it contains auxiliary substances, preferably powdered water-insoluble inorganic materials, water, emulsifying additives, fungicides and bactericides.