CS232390B1 - Odpenovač - Google Patents

Abstract

The subject of the invention is a defoamer consisting of 60 to 99% hydrocarbons and/or oligomers of Cg to Cg alkenes and 1 to 40% oxygenated organic compounds with a molecular weight of 150 to 850, or polyolefins (atactic polypropylene) with a molecular weight of 1,000 to 32,000. The application possibilities are mainly in the pulp and paper industry and in the food industry.

Description

(54) Defoamer

The present invention is the anti-foam, consisting of 60 to 99% of hydrocarbons and / or oligomers of olefins Cg to C _g and 1-40% oxygen with organic compounds having a molecular weight of 150-850, optionally polyolefins (atactic polypropylene) of molecular weight 1000-32000 Application possibilities are mainly in the pulp and paper industry and in the food industry.

and

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The invention relates to a defoamer mainly based on readily available petrochemical as well as natural raw materials, which are technically easy to formulate and yet highly effective as antifoam foams produced by the action of surfactants, especially nonionic and anionic additives in aqueous and non-aqueous environments.

The theoretic foundations of foam formation and suppression are generally known. Basically, two types of suds suppressors are known: foam breakers and foam inhibitors. Among the first type, mention may be made of diethyl ether, alcohols and water vapor. Some weak post-active substances, which only foam in a dilute solution (amyl alcohol), act as foam breakers when applied to soap suds and foams from self-diluted solutions. Inhibitors of foaming are, for example, methylalcohol, does not foam itself and also inhibits foaming of dilute surfactant solution · The surface of the liquid is flooded with high concentration, the molecules diffuse rapidly and any increase in surface tension is canceled quickly ·

It is also known that silicone oil-based materials, which are water-insoluble and have a low surface tension of up to 20 mN.m *, are more efficient and versatile than solubilizers. Polyfluorocarbons are most commonly used to inhibit foaming. are used as oenomeric antifoams for lubricating oils as they have a superficial

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- 3 voltages very low (10 mN.m ” ¹ ) · Different types of defoamer are used for different applications. Thus, an antifoam combined with an emulsifier and a hydrocarbon (US Pat. No. 3,935,121) is often used in the oelolo-papermaking industry. The antifoam itself is of the amide type - ethylene-bis-stearamide, diethylene glycol monooleate, mineral oil and silicone oil. The antifoam-based antifoam antifoam is used with a behenic acid antifoam in a mixture with saponified ethylene-vinyl acetate copolymer, animal oils and polyethylene polyethylene.

893 9M) · Many aqueous systems that normally foam can be foamed * with a small amount of ethoxylated castor oil and its hydrogenate as well as propoxylated oils (U.S. Pat. No. 3,180,836) · For paper waste water are also known (U.S. Pat. No. 3 215 635) antifoams consisting of ethoxylated fatty acids, ethoxylated alkylphenols mixed with low molecular weight alcohols. Defoamers are also known (U.S. Pat. No. 3,697,438) for oleic acid polyglycol esters and mixed with alcohols up to C18, propylene glycol, isopropyl alcohol and mineral oil.

Similar types, combinations of esters, ethoxylates and propoxylates of fatty acids, amines and amides are used for various industries. Specifically, in some cases low toxicity is required (applications in the food industry). However, this requirement is generally applicable.

However, the foregoing and other antifoams and antifoam mixtures are complex systems of diverse substances and products, often raw and technically and economically.

However, these problems are solved substantially by the defoamer of the present invention.

SUMMARY OF THE INVENTION The present invention is based on a hydrocarbon and organic oxygen compound antifoam based on 60 to 99% by weight hydrocarbons and / or alkene oligomers having a molecular weight of 150 to 1000 and 1 to 40% oxygen-containing organic compounds of molecular weight 150 to 850 and / or polyolefins having a molecular weight of 1000 to 3200.

- 4,232,390

Advantages of antifoam according to the invention are raw material availability, high antifoaming efficiency and considerable versatility on foams produced by the action of various types of surfactants and other surfactants. Furthermore, high quality stability of antifoams, generally their health safety or only low toxicity, allowing wide application and, last but not least, a technically simple way of producing an antifoam or antifoam mixture.

Oligons, or low molecular weight polymers and copolymers of ethylene, propylene and olefins and dienes of C. Are also understood as hydrocarbons having a molecular weight of 250 to 100 ° according to the present invention. and C ~, Reach products formed by thermic cleavage of macromolecular substances. as well as hydrogenolysis of macromolecules and higher hydrocarbons, e.g. 1'ahkáho ťažkóho hydrocarbon to the fuel oil * Furthermore, can be used "and hydrogenated oligomers of alkenes and dienes mentioned-4 ^and θ'5 ·

ACP alkyl Šlik the organic compound priohádzajú account of the carboxylic acid ₂ and 0 _<(either pure or ACP. The mixture pričo® Black I ^ e comprise as the prípiosi-etůkyseldny, al * dehydokyspliny, alcohols and hydrocarbons. For the however, it is preferable to use stearic acid and palmitic acid, or technical stearin, as well as fats, but whether vegetable or animal but even more suitable are partially saponified or partially hydrolysed fats, as well as partially esterified polyols such as partially trimethylolpropane, partially esterified pentaarythritol and the like. Furthermore, the products of polyoxyalkylene and / or polyethoxylated aliphatic alcohols and / or acids, as well as propoxylation products and polypropoxyalkylated alcohols. or acid or steam hydrolyzed or phro-saponified fats, respectively. It can also be partially polycarbonated polyols.

Less suitable as oxygenated organic compounds, but those used are polyolefins of molecular weight 1QQ0 to 3200 ·

One of the most suitable is the low-density polyethylene as a by-product from the production of low density polyethylene. - Atactic polypropylene * Atactic propylene is more suitably free of isotactic polypropylene and possibly stereoblocks. However, atactic polypropylene without any pretreatment or refining is also applicable. Especially suitable is the combination and tactical poles—

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- 5 propylene or low molecular weight polyethylene with low viscosity hydrocarbons and oxygenated organic compounds ·

The antifoam according to the present invention can be refined, decolourised or perfumed. Further details of the antifoam composition or antifoam composition of the present invention, as well as the antifoam efficacy and other advantages are evident from the examples in which the composition of the substances is presented in a concentration by weight.

Example 1

97.5 kg of propylene oligomers are dispensed into a 0.2-liter container equipped with an anchor stirrer and a duplicator. Polypropylene oil (Propyloil K-300) having an average molecular weight of 449, density at 20 ° C = 840 kg.m · · ^, refractive index n ^ = 1.465, pour point -35 ° C and bromine number 53.5 S Br / 100 g of sample. Then, with stirring at 25 ° C, 2.5 kg of stearic acid is added. A liquid acid solution is obtained which has an anti-foaming performance of ´96 in the foaming test for nonionic surfactant (polyethoxylated primary aliphatic alcohols with up to 9 moles of ethylene oxide).

Further results of the antifoam performance of both K-300 polypropylene oil itself and stearic acid solutions therein are shown in Table 1.

Table 1

Type of defoamer Content of stearic acid in defoamer% At least efficiency on nonionic surfactant% Polypropylene oil K-300 0.00 18 Stearic acid solution in K-300 polypropylene oil 1.00 25 Stearic acid solution in polypropylene oil K-300 3.50 98 Stearic acid solution in polypropylene oil K-300 5.00 95

- 6 232 390

The foaming efficiency ’is determined by comparing the foaming power of the Standard S sample with that of the Standard Sample to which a defoamer is added. To do this, 100 a and p of a standard solution of sodium alkyl sulphate (as an anionic surfactant) or polyethoxylated primary alcohols C 1 g with up to 9 moles of ethylene oxide (as a non-ionic surfactant) at a concentration of 1 gL are carefully poured into · Standard solution is foamed by inverting the valoid 180 ° and back 50 times for 1 min at 20 ° C to 2 ° C. Measure the foam height and the height of the non-foaming solution after 1 min after foaming. P s is calculated from the relationship P s = ~ * 100, in which a = the height of the foam in cm and b = the height of the unfoamed solution in cm. The foaming efficiency účinnost is determined by the same procedure as the standard solution, but to 100 cm of the standard solution is added 1 drop of antifoam (0.02 g) and Po is determined (foaming power of the standard solution with antifoam). The foaming efficiency is calculated from the foaming graph (5µ) of the foaming efficiency, whereby the foaming efficiency is plotted on the x-axis (v from 100 to 0 and the foaming efficiency of the standard solution). the final result of crutches arithmetic mean of three measurements ·

Example 2

The procedure is similar to using K-300 polypropylene oil as in Example 1, except that the antifoam activity of the stearic acid solutions in the polypropylene oil is, unlike Example 1, determined to an anionic surfactant (sodium alkyl sulfates prepared by sulfating primary aliphatic alcohols G? followed by neutralization with sodium hydroxide or sodium carbonate) · Thus, a solution of stearic acid in K-300 polypropylene oil having a weight concentration of 1 has an antifoaming effect * at a concentration of 3.5% it has an antifoaming effect of $ 80 and at a concentration of 5%

- 7 Example 3 _2323go

The procedure is as in Example 1 _t with the only difference that, instead of polypropylene oil K-300 was used to prepare the antifoaming agent polypropylene oil having a higher average molecular weight (Propyloil C-1000), which amounts to 460, the density at 20 ° C, 847 kg.m &lt; -1 &gt; and a pour point of -23 [deg.] C. per molecule is 1.5 double bonds. This polypropylene oil K-1000 has an antifoaming effect on the non-ionic surfactant * $ 19. However, the stearic acid solution prepared at 50 ° C at a concentration of $ 2.5 has an antifoaming effect on the non-ionic surfactant.

100 jé.

Example 4

Further higher fatty acids and dicarboxylic acids are dissolved in the K-1000 polypropylene oil specified in Example 3. The anti-foaming effect of the palmitic acid solution in 5 $ polypropylene oil is 94. However, the 3.5% caprylic acid is only 10 non-ionic surfactant and dodecanedicarboxylic acid 66 Anti-foaming efficacy * of polypropylene palmitic acid solution against anionic surfactant 3 % is 535% and at a concentration of 5% the efficiency is 68%

Example 5

In K-1000 polypropylene oil, 5% and 10% respectively of tactical polypropylene are dissolved. A viscous mass is obtained with an antifoam efficiency of 86% nonionic surfactant. Dissolution of an additional 3.5% stearic acid in this blend of 10 $ atactic polypropylene yields an antifoaming efficiency of 87. However, at 5 and 10 $ a tactical polypropylene having an average molecular weight of 18,200 in K-300 polypropylene oil only and 65% ·

- 8 Example 6

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In polypropylene! K-1000 oil specified in Example 4, dissolve 5% of a mixture of monoglyoerides, diglyoerides, triglyoerides and higher fatty acids, having a monoglyoeride content of $ 29, an acid number of 6 and a melting point of 44 ° C (Smeller c). The anti-foaming effect of this solution is 100 flowers per nonionic surfactant. by dissolving 5% pork ointment in polypropylene! The oil-obtained solution has no (zero) antifoaming activity ´ · On the other hand, the anionic surfactant is polypropylene oil with 5 µ Emulsifier C having an antifoaming effect ´ 62% and with 5% pork ointment 41

Example 7

The procedure is similar to Example 1, but instead of polypropylene oil, light oil from atmospheric-vacuum oil distillation, gas oil and didodecylbenzene are used as stearic acid solvent. On the nonionic surfactant, the efficacy of the stearic acid solution with a concentration of 3.5% is 21%, in gas oil 51 and in didodeoylbenzene 46.

Example 8

The procedure is similar to that of Example 1, except that instead of propylene oligomers (K-300 polypropylene oil), oligomers of C 4 -olefins, prepared according to US Patent No. 193,855, are used. A light yellowish liquid product of low molecular weight homopolymers and C 4 - copolymers. Alkenes and dienes have an average molecular weight of 507 and a bromine number of 82 g of Br / 100 g of product. It is prepared by homopolymersizing and copolymerizing essentially de-butadieneized pyrrole C C-fraction (composition in propylene with propane with 0.33 iz isobutane = 3 j O). -butane = 14.52} 1,3-butadiene = 0.13} 1-butene = 29.19} isobutane = 37.83} trans-2-butene = 10.0} ois-2-bute = 4.7 and isopentane = 0.3) at 26-1 ° C for 6 h with a catalytic effect of a $ 3 aluminum chloride / hydrogen chloride catalyst complex together with alkylbenzones. A solution of 3.5% stearic acid in low-molecular-weight 9,232 spherical homopolymers and copolymers of C 1-4 alkenes and dienes achieves an antifoaming effect on the nonionic surfactant ’94

Example 9

The procedure is similar to Example 1, but instead of polypropylene oil, a white oil (white oil 45) is used which is a mixture of refined petroleum dewaxed petroleum. liquid hydrocarbons, mostly in excess of 360 ° C. It forms a clear, colorless, non-fluorescent viscous liquid with a kinematic viscosity at 25 40 n · sh. A solution of 3,5 5 »stearic acid in this oil my antifoaming efficiency ´ on the nonionic surfactant 55,5 $ and on the anionic 91

Example 1.0

2.5% stearic acid and 3% polypropolated heavy fractions of rectal-sulfur-4-ethylhexanol are dissolved in polypropylene oil & -1000 with 15 moles (per 1 mol of distillation residue from non -ification of crude 2-ethylhexanol). efficiency '$ 91 »

Example 11

5% bovine fat (tallow) is dissolved in K-1000 polypropylene oil. The antifoaming efficiency of this antifoam is 82 After adding an additional $ 2.5 stearic acid to $ 94 ·

Brikla-d 12

The procedure is similar to that in Example 9, but 5% of a mixture of monoglycerides, diglycerides, triglycerides of higher fatty acids, containing monoglycerides 29 with an acid number of 6 and a melting point of 44 ° C (Emulsifier c) is dissolved in white oil. The anionic surfactant's antifoaming efficiency is 81.5% (one drop) & 90 in two drops.

- 10 Example 13 232 390

The procedure is similar to that of Example 1 except that the propylene oligomer is a mixture of n-alkanes up to (average molecular weight = 176) and the stearic acid content of it is 25. 100 per alkaline nonionic Standard also 100% and anion standard 82 $ ·

Example 14

The procedure is similar to that of Example 5 except that 5% and 10 low molecular weight polyethylene with an average molecular weight of 2,130 are used instead of tactical polypropylene, as a byproduct from the production of low density polyethylene in a high pressure process. With an additional 2.5% stearic acid, the efficacy on the nonionic surfactant 83 and 89 ¢ is antifoaming.

Claims (5)

-44 - SUBJECT OF THE INVENTION 232 390 1 · Hydrocarbon-based and organic oxygen-catalyzed odorants, characterized in that they comprise from 60 to 99% by weight of hydrocarbons and / or oligoierees of alkene molecular weight of 150 to 1000 and 1 to 40% oxygenated organic compounds having a molecular weight of 150 to 850a / or polyolefins having a molecular weight of 1000 to 3200. 2. Degreasing according to claim 1, characterized in that the hydrocarbon is petroleum fractions, preferably gas oil and white oil and / or synthetic hydrocarbon oils, preferably hydrogenated alkene oligomers and polymer cleavage products. 3) A method according to claim 1, wherein the oligomers of the alkenes are oligomers of at least one alkene C 8 to C 16, preferably oligomers of propylene and oligomers of C 1-4 -olefin and / or oligomers of a mixture of alkenes to C 1-4, preferably the olefin. the mixture of alkenes and diones of the hydrocarbon fractions Cj ^ and C ^éry. 4. Deoxidizing according to claim 1, characterized in that the oxygenated organic compounds form at least one carboxylic acid, preferably stearic acid and palmitic acid. 5. Deoxidizing according to claim 1 to 4, characterized in that the organic compounds form fats, preferably partially hydrolysed fats and / or partially esterified multi-alcohol alcohols with at least one higher fatty acid, preferably parenterally esterified glycerol.