CS258732B1 - Hydrophilic defoamer - Google Patents

Abstract

The hydrophilic defoamer consists of 55 to 98 wt. % diethylene glycol to polyethylene glycols with an average molecular weight of up to 1,500 g.mol-1 and 2 to 45 wt. % at least one aliphatic carboxylic acid C4 to C24 and/or a by-product from the production of cyclohexanol and cyclohexanone by oxidation of cyclohexane and possibly auxiliary substances. The defoamer is particularly suitable for defoaming in the pulp and paper industry, in the cone industry and in other production processes in which foam is generated predominantly in aqueous environments.

Description

258732

BACKGROUND OF THE INVENTION The present invention relates to a hydrophilic antifoam agent based on oxygenated organic compounds, optionally with the addition of excipients, which is readily formulated with the use of predominantly petrochemical raw materials and intermediates. More recently, defoamers for base-oxygenated organic compounds are known, such as partially esterified polyols (U.S. Pat. No. 3,235,498), as well as defoamers based on acrylic acid and methacrylic acid (U.S. Pat. No. 3,458,567). The technically available products include the polyadditions of ethylene oxide with oleic acid, abietic acid and tall oil acids, and are rarely combined with organosilicon compounds (U.S. Pat. Nos. 2,991,248, 3,235,501 and 3,335,502). However, their deficiency is relatively low defoaming efficiency. Significant but costly are antifoams based on organosilicon compounds such as polymethylsiloxane, polyethylsiloxane and others [Tichomirov V.K .: Foams, "Chimia", Moscow (1983)].

The defoamers on base-polycomponent mixtures are relatively widespread (U.S. Pat. Nos. 923,687, 3,180,836, 3,697,438 and 183,982), in which higher fatty acids, vegetable and mineral oils and higher fatty acid polyaddienkylene oxide products are important ingredients. acids or alcohols, further esters of polyglycols with oleic acid and in admixture with alcohol C 1 to C 18, propylene glycol and isopropanol. Their drawback is the need for a wide range of fabrics, some of which are toxic, but the antifoaming efficacy of the antifoam is not high. A relatively high antifoaming efficiency of foam formed mainly by non-ionic and non-ionic surfactants, especially in hydrophobic systems, has an antifoaming agent of 50 to 99% by weight. hydrocarbon and 1 to 20 wt. aliphatic acids (MS Author's Certificate 232 390). However, it is known to have less efficacy on foams produced by the action of cationic surfactants as well as on the disposal of foams in hydrophilic systems. In addition, the raw material-based antifoam range can be further expanded with readily available intermediates.

According to the present invention, the hydrophilic antioxidant based on oxygenated organic compounds, optionally with the addition of excipients, consists of 55 to 98 wt. from diethylene glycol to polyethylene glycols having an average molar mass of up to 1500 g.mol -1 and 2 to 45% of at least one aliphatic C4 to C24 acid and / or byproduct isolated as distillation residue at least part of the process hydrolysis degree water the production of cyclohexanol and / or cyclohexanone by oxidation of cyclohexane, having an amount of 180 to 360 mg KOH / g, a bromine number of 2 to 40 g Br / 100 g and / or at least one fraction thereof. The advantage of the defoamer according to the invention is its hydrophilicity, it does not remain in the foams, resistance and good efficiency even at lower temperatures, and raw material availability, not least, of the formulated defoamer variants according to the invention. is non-toxic.

The present invention makes use of the surprising effect of combining diglycol to polyglycols with carboxylic acids, as well as a mixture of acids, esters, lactones, hydroxy- and ketones, with the antifoaming effect generally and immediately. not directly related to the quantitative representation of individual components. Ethylene glycol and polyethylene glycol alone, having an average molecular weight of about 300 g / mol, have only a slight foaming effect, but combinations with C4 to C24 carboxylic acids, whether saturated or unsaturated, have a relatively large effect on foams formed, i.e. nonionic, antenna or cationic with their surfactants.

While the antifoaming agent of the present invention may also contain ethylene glycol, it is not recommended because of its considerable toxicity. Although less toxic, but also less suitable is diethylene glycol. Most preferred are polyglycides having a molar mass above 100 g / mol. Polyglycols over 1500 g. mol-1 is tough again, it is difficult to manipulate, and their antifoam activity is lower. Of the acids, saturated carboxylic acids or mixtures saturated with unsaturated carboxylic acids are preferable. Most preferably, in terms of efficacy, the handling of defoamers is carboxylic acids C7 to C18. Below, they are less effective and cause the defoamer odor to increase significantly the defoamer viscosity, especially at temperatures below 20 ° C. Aliphatic carboxylic acids include aliphatic keto acids and hydroxy acids, which are also present in the side products of cyclohexane to cyclohexanol and cyclohexanone oxidation. Auxiliaries include petroleum butbosynthetic hydrocarbons, perfume additives, biocides, and coloring agents. Further details of the antifoam formulation as further advantages are apparent from the examples. Example 1

The antifoam or components of the known antifoams are tested on the one hand with ethylene glycol to polyethylene glycols, as well as ethylene glycol to polyethylene glycols with aliphatic carboxylic acids, and by-products from cyclohexane to cyclohexanol-cyclohexanone oxidation. isolated as a distillation residue free of some of the water from the hydrolysis column of the cyclohexanol and cyclohexanol production plant, hereinafter referred to as MEK, then the organic phase of the fraction having a boiling point of 20 to 150 ° C / 2.67 kPa from this residue, hereinafter referred to as "MEK fraction up to 150 ° C / 2.67 kPa" and a fraction above 150 ° C / 2.67 kPa, hereinafter referred to as "MEK fraction above 150 ° C / 2.67 kPa".

Analysis and MEK analysis results are: 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 20 CC (D420) = 1,104 kg. m ~ 3; dynamic viscosity at 20 ° C - 268.9 mPa. with; cobalt content (as compound = 0.01% by weight; ash = 0.05% by weight);

Differential distillation of MEK under reduced pressure yields 13.4% by weight. organic] fraction fraction 20 to 150 cC / 2.67 kPa (acid number = 225.6 mg KOH / g; saponification number = 320.9 mg KOH / g; OH = 6.44% w / w CHO = 0% H 3 O = 20.2 wt% acetic acid = 4.66 wt% propionic acid = 1.16 wt% butyric acid = 1.78 wt% capric acid = 10 , 45 ° / o) and the residual fraction, ie the fraction with tv above 150 ° C / 2.67 kPa, constitutes 1.24 wt. 77.2 wt. (acid number = 153.0 mg KOH / g; saponification number = 449.8 mg KOH / g; OH = 6.41% by weight; HaO = 1.14%; ash = 0; 22ppm).

The antifoam component may be an aliphatic carboxylic acid saturated or unsaturated acid up to C24.

The scavenging efficiency of the individual screed samples sc is determined by comparing the foam of a standard sample with that of a standard sample with a scavenger added.

Thus, 100 cm 3 of an aqueous solution of standard sodium lauryl sulphate (0.1% w / w). (1 gm-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 are carefully poured into the metering cylinder 500 cm3 and sealed with a ground-glass stopper. The standard solution is framed by a roll of < 0 180 ° and sleeps fifty times over 1 min at 20 ± 2 ° C. Foam tampering and unpopulated melt-cushioning are measured 1 min after the end of foaming. Thereafter, the foaming power of the Pš (%) standard is “,” and the feel of Ps = ——. 100 at which foam height (cm), b - height of unsealed solution (cm). The de-scavenging efficiency is determined by the same procedure as the standard solution, but 1 drop (0.02 g) and 1 drop (0.02 g) are added to the 100 cm 3 standard solution. 2 drops (0.04 g) of defoamer and fixed by Po (foaming of the mixture of standard solution and defoamer). Finally, the deprotection efficiency was calculated from the plot of dependence (%) on the antifoaming efficiency, with an antifoaming efficiency (%) of 100 to 0 and the y-axis foaming (%) of the standard solution applied to the x-axis. % Of the antifoaming efficiency is subtracted at the intersection of the angle bar, taking the a-ritmetic mean of the three measurements as the final result.

The composition of the individual antifoam samples and their antifoaming activity on nonionic (non-ionic) as well as anionic and possibly cationic surfactant is apparent from Table 1. 258732

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Claims (3)

EXAMPLE 2 The defoaming assay procedure is similar to Example 1. A deodorizer consisting of 50 wt. mixtures of aliphatic acids C 7 -C 15 and 50 wt. polyethylene polyolefin with an average mol. 300 g.mol-1 has an anionic surfactant 54 at 1 and 2 drops of this foaming agent, respectively. 60pere .; to non-ionic surfactant 73, respectively. 83% and cationic surfactant 81, respectively. 82%. OBJECT A hydrophilic defoamer based on oxygen-containing organic compounds, optionally with an adjuvant, characterized in that it comprises 55 to 98 wt. diethylene glycol to polyethylene glycols having an average molecular weight of up to 1500 g.mol-1 to 45 wt. at least one aliphatic carboxylic acid C4 to Ca4 and / or a byproduct isolated as a distillation residue free of at least a portion of the water from the hydrolysis step of the cyclohexanol and / or cyclohexanone by oxidation of cyclohexane with an acid number of 180 to 360 mg KOH / g, saponification number 200-550 mg KOH / inventive / g, bromine number 2 to 40 g Br / 100 g / g or at least one fraction from this residue. 2. A hydrophilic defoamer according to claim 1, wherein the aliphatic carboxylic acids form unsaturated and / or saturated carboxylic acids, including carboxylic acids in admixture with keto acids and hydroxy acids. 3. A hydrophilic defoamer according to claim 1, wherein the optional additives in the defoamer are hydrocarbons, biocides, and fragrances, in an amount of from about 10% to about 2% by weight.