CS258732B1 - Hydrophilic antifoaming agent - Google Patents

Abstract

The hydrophilic defoamer comprises 55 to 98 wt. diethylene glycol to polyethylene glycols with an average molar mass to 1500 g.mol-1 and 2 to 45 wt. at least of one aliphatic carboxylic acid C4 to C24 and / or by-product from the production of cyclohexanol and cyclohexanone by oxidation cyclohexane and possibly auxiliary substances. The desiccant is best suited to defoaming in favor of pulp and paper mill industry, cones and v other manufacturing processes in which Foam is predominantly formed in aqueous media.

Description

The invention relates to a hydrophilic defoamer based on oxygen-containing organic compounds, optionally with the addition of excipients, which is easy to formulate using predominantly petrochemical raw materials and intermediates.

More recently, oxygen-based organic compound defoamers are known, such as partially esterified polyols (U.S. Pat. No. 3,235,498), and acrylic and methacrylic acid defoamers (U.S. Pat. No. 3,458,567). Technically available also include polyaddition products of ethylene oxide with oleic acid, abietic acid, and tall oil, often combined with organosilicon compounds (U.S. Pat. Nos. 2,991,248, 3,235,501 and 3,235,502). However, their deficiency is relatively low antifoaming efficiency. Important but costly are antifoams based on organosilicon compounds such as polymethylsiloxane, polyethylsiloxane and others [Tichomirov, V.K .: Foams, "Khimija", Moscow (1983)].

Relatively widespread are antifoams based on poly-component mixtures (U.S. Pat. Nos. 2 923 687, 3 180 836, 3 697 438 and the Czech author's certificate 183 982), in which higher fatty acids, vegetable and mineral oils and products of polyaddition of alkylene oxides are important components. higher fatty acids or alcohols, further polyglycol esters of oleic acid and in admixture with alcohols 0,8 to C ₁₈ , propylene glycol and isopropyl alcohol. Their drawback is the need for a wide range of substances, some of which are toxic, but the defoaming efficiency of the final defoamers is not high. In contrast, a relatively high antifoaming efficiency for foams produced mainly by nonionic and anionic surfactants, and especially in hydrophobic systems, has an antifoam based on 50 to 99 wt%. % hydrocarbons and 1 to 20 wt. aliphatic acids (Czech author's certificate 232 390). However, it has been found to be less effective on foams produced by the action of cationic surfactants, as well as in the destruction of foams in hydrophilic systems. In addition, it is necessary to further expand the range of defoamers based on raw materials and techniques of readily available intermediates.

According to the invention, the hydrophilic defoamer based on oxygen-containing organic compounds, optionally with the addition of excipients, consists of 55 to 98 wt. of diethylene glycol and polyethylene glycols with an average molecular weight of 1500 gmol ^"1 and up to 45% of at least one aliphatic C ₄ to C ₂₄ and / or by-product isolated as a residue-free at least a portion of water step hydrolysis process of production of cyclohexanol and / or cyclohexanone by oxidation of cyclohexane, having an acid number of 180 to 360 mg KOH / g, a bromine number of 2 to 40 g Br / 100 g and / or at least one fraction of this residue.

Advantages of the antifoam according to the present invention are its hydrophilicity, no residue in the antifoam systems, resistance and good efficiency even at lower temperatures and raw material availability. Last but not least, most of the formulated antifoam variants of the present invention are nontoxic.

The invention takes advantage of the surprising effect of combining diglycol to polyglycols with carboxylic acids as well as a mixture of acids, esters, lactones, hydroxy and keto acids, the antifoam effect as a rule being immediately, respectively. it is not directly related to the quantitative representation of individual components. The actual glycol and polyethylene glycol of an average molar mass of 300 gmol ^_J have only slight defoaming effect, but the combination of carboxylic acids, C ₄ to C 24, and either saturated or unsaturated, have a relatively high antifoaming effect in the foam produced, either nonionic, anionic or cationic surfactants.

While the antifoam agent of the present invention may contain ethylene glycol in terms of antifoam activity, it is not recommended for reasons of considerable toxicity. Although less toxic, diethylene glycol is less suitable. Most preferred are polyglycols having a molecular weight above 100 g / mol ^-1 . Polyglycols over 1,500 g. mole ^-1 are again solid, difficult to handle and their antifoam activity is poinerne lower.

Of the acids, saturated carboxylic acids or mixtures of saturated τ with unsaturated carboxylic acids are more suitable. Most preferably, from the point of view of efficacy, but especially the handling of antifoams are C ₇ to C ₁₈ carboxylic acids. Below, they are less effective and cause antifoaming odor and higher considerably increase the antifoam viscosity, especially at temperatures below 20 ° C. Aliphatic carboxylic acids also include aliphatic keto acids and hydroxy acids, which are also present in the by-products of the oxidation of cyclohexane to cyclohexanol and cyclohexanone.

Excipients include petroleum or synthetic hydrocarbons, fragrance additives, biocides, or colorants.

Further data on defoamer formulation as well as other advantages are evident from the examples.

Example 1

Ethylene glycol to polyethylene glycols, mixtures of ethylene glycol to polyethylene glycols with aliphatic carboxylic acids as well as by-products from the oxidation of cyclohexane to cyclohexanol-cyclohexanone, isolated as a distillation residue from the water-distillation column, cyclohexanone, hereinafter referred to as MEK, then or258732 the ganic phase of the fraction boiling at 20 to 150 ° C / 2.67 kPa from this residue, hereinafter referred to as the "MEK fraction to 150 ° C / 2.67 kPa" and fraction above 150 ° C / 2.67 kPa, hereinafter referred to as the "MEK fraction above 150 ° C / 2.67 kPa".

The analysis and results of the MEK analysis are as follows: water - 6.9% by weight; acid number = = 256.3 mg KOH / g; saponification number = 412.8 mg KOH / g; OH = 4.7 wt%; bromine number = 23.1 g Br / 100 g; density at 20 ^° C (D4 ²⁰ ) = 1 104 kg.m ³ ; dynamic viscosity at 20 ° C - 268.9 mPa. with; cobalt content (in the form of compounds) = 0.01 wt.%; ash = 0.05 wt.

By differential distillation of MEK under reduced pressure, 13.4 wt. organic phase fraction 20-150 ^c C / 2.67 kPa (acid number = 225.6 mg KOH / g; saponification number = 320.9 mg KOH / g; OH = 6.44 per weight; CHO = 0% H ₃ O = 20.2 wt% acetic acid = 4.66 wt% propionic acid = 1.16 wt% butyric acid = 1.78 wt% Caproic acid = 10.45% o] and the remaining fraction, ie the fraction with tv above 150 ° C / 2,67 kPa, at losses of 1,24% by weight 77,2% by weight (acid number = 153,0 mg KOH / g; saponification number = 449.8 mg KOH / g; OH = 6.41 wt%; H _and O = 1.14 wt%; ash = 0.22 per weight).

The antifoam component may be aliphatic carboxylic acid saturated or unsaturated acids Οθ to C24.

The foaming efficiency of the individual samples of the antifoams sr is determined by comparing the foaming of the standard sample with the foaming of the standard sample with an added defoamer.

Thus, 100 cm ^{3 of} an aqueous solution of standard sodium lauryl sulphate (antenna surfactant at a concentration of 0.1% w / w (1 g. Dm ^-3 )) or polyethoxylated primary alcohols C12 to C {4 with 9 moles of ethylene oxide (nonionic surfactant) or laurylammonium -bromide (cationic surfactant) of similar concentration is carefully poured into a 500 cm ³ graduated cylinder and sealed with a ground-glass stopper The standard solution is spied on by rotating the cylinder by 180 ° and slept fifty times for 1 min at 20 + 2 ° C. foaming and the height of the non-foaming solution after 1 min from the end of foaming.Then the foaming standard of Ps (%) is determined by the relation Ps = 100 in which a ~ the height of the foam (cm); The foaming efficiency is determined by the same procedure as the standard solution, but to 100 cm ^{3 of the} standard solution add 1 drop (0.02 g) and 2 drops (0.04 g) of the antifoam, respectively, and determine Po ( yeastiness The foaming efficiency is finally calculated from a graph of foaming (%) versus foaming efficiency, with the foaming efficiency (%) from 100 to 0 and the foaming axis (%) of the standard solution being plotted on the x-axis. At the intersection point of the diagonal, the% of antifoam efficiency is subtracted, taking the arithmetic mean of three measurements as the final result.

The composition of the individual antifoam samples and their antifoam activity on the nonionic (nonionic) as well as the anionic and possibly also the cationic surfactant is evident from Table 1.

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Example 2

The procedure for determining the antifoam efficiency is similar to that of Example 1. A defoamer consisting of 50 wt. % of a mixture of aliphatic acids (C ₇ -C _{8 )} and 50 wt. polyethylene glycol of average mol. 300 g.mol ^-1 has 1 and 2 drops of this antifoam to anionic surfactant 54, respectively. 60 pere .; to a nonionic surfactant 73, respectively. 83%, and for cationic surfactant 81, respectively. 82%.

Claims (3)

Hydrophilic defoamer based on oxygen-containing organic compounds, optionally with the addition of auxiliaries, characterized in that it consists of 55 to 98% by weight of the composition. diethylene glycol to polyethylene glycols having an average molecular weight of up to 1,500 g.mol ^-1 and up to 45 wt. at least one C ₄ to C ₂₄ aliphatic carboxylic acid and / or by-product isolated as a distillation residue, free from at least part of the water from the hydrolysis step of the cyclohexanol and / or cyclohexanone production process by oxidation of cyclohexane, acid number 180 to 360 mg KOH / / g; saponification number 200 to 550 mg KOH (inventive / g), bromine number 2 to 40 g Br (100 g) and / or at least one fraction of this residue. 2. The hydrophilic antifoam according to claim 1, characterized in that the aliphatic carboxylic acids form unsaturated and / or saturated carboxylic acids, including carboxylic acids in admixture with both keto and hydroxy acids. 3. The hydrophilic defoamer under points 1 and 2, characterized in that the optional ingredients of the excipients form a hydrocarbon antifoams, biocides, and fragrance, in an amount of 1.10 ^{- 3%} and 2% by weight.