CS264733B1 - Multi-purpose defoamer - Google Patents

Abstract

The defoamer consists of 90 to 99.8% of at least one of the following products: a product of polyaddition of alkylene oxides Cj to Cq to a monovalent to hexavalent aliphatic alcohol C4 to Clg or copolymers of alkylene oxides C? to C^ and 0.2 to 10% by weight of ethylene-bis-alkylamide (ethylene-bis-stearyl-amide, ethylene-bis-palmitylamide, etc.). In addition, it may contain aliphatic alcohols Cg to C14 and mixtures of hydrocarbons with a molecular weight of 130 to 1,000 g.mol-1, fine-grained to colloidal particles of mineral substances and other auxiliary substances (anticorrosive agents, fungicides, bactericides, aqueous substances, emulsifiers, pigments and dyes). It may be emulsified in water or dispersed in other media. It is mainly suitable for defoaming in the leather, pulp and chemical industries, as well as in oil extraction.

Description

The invention relates to a multipurpose defoamer based on organic oxygen, nitrogen and possibly hydrocarbon compounds and auxiliaries, formulated both on the basis of technically available products and intermediates, as well as intentionally produced and already in small concentrations in the defoamer synergistically acting components for high defoaming efficiency, not only for foams formed by the interaction of anionic, cationic, but also non-ionic surfactants.

Defoamers based on polycomponent mixtures are relatively widespread (US Pat. 2 923 687,

180 836, 3 697 438 and Czechoslovak patent 183 982), in which the important components are higher fatty acids, vegetable and mineral oils and products of polyaddition of alkylene oxides to higher fatty acids and alcohols, Fatty esters of polyglycols with oleic acid and in mixtures with alcohols Cj ₆ to C _lg . However, their disadvantage is lower defoaming efficiency and the need for a wide range of substances. Then defoamers based on oxygenated organic compounds containing carboxyl or hydroxyl groups in the molecule. Such are at least partially esterified glycerol, sorbitol and pentaerythritol (USA Pat. 3 235 498), Fatty defoamers based on stearic and methacrylic acid (USA Pat. 3 458 567).

Technically available products also include products of polyaddition of ethylene oxide with oleic acid, abietic acid, as well as with acids obtained from tall oil, while they are often combined with organosilicon compounds (USA Pat. 2 991 248, 3 235 501 and 3 235 502). However, their disadvantage is the relatively low defoaming efficiency and reactivity of some components with the components of the defoamed systems. Defoamers based on organosilicon compounds, such as polymethylsiloxane, polyethylsiloxanes and others, are important, but technically not easily available (Tichomirov V.K.! Foams, Chimija Moskva (1983)). Defoamers of this type also include those based on diethylene glycol monooleate, ethylene bis-stearamide, mineral and silicone oil (USA Pat. 3 935 121).

However, their disadvantages are ash content, relatively high viscosity and lower efficiency on foams formed by the interaction of non-ionic and ampholytic surfactants. On the other hand, a defoamer consisting of 50 to 99 wt. % hydrocarbons with 1 to 20 wt. % aliphatic acids (Czech author's certificate 232 390) or alkanolamides of carboxylic acids (Czech author's certificate 240 516) has a relatively good defoaming efficiency on foams formed mainly by non-ionic and anionic surfactants and especially in hydrophobic systems. However, they are quite viscous under usual application conditions and have lower efficiency on foams formed by the action of cationic surfactants, as well as in the elimination of foams in hydrophilic systems.

Thus, it is necessary to further expand the range of defoamers based on non-toxic components, technically easily available intermediates and effective for defoaming aqueous solutions as well as hydrophobic systems.

However, according to the present invention, the multi-purpose defoamer mainly based on organic, oxygen-containing and nitrogen-containing compounds and auxiliaries consists of 90 to 99.8% by weight of at least one of the polyaddition products of a C ₂ alkylene oxide to a monohydric to hexahydric aliphatic alcohol of C ₂ to C _1g and/or copolymers of C ₂ to C ₄ alkylene oxides and 0.2 to 10% by weight of an ethylene-bis-alkylamide of at least one C 1g to C ₂ θ carboxylic acid.

The advantage of the defoamer according to this invention is high defoaming efficiency on all types of foams, synergistic effect even in wide temperature ranges. Then inertness towards components of defoamed systems, towards metal materials. Finally, the possibility of emulsification even in water and raw material availability.

The composition of the universal defoamer according to the present invention is understood to mean only the content of organic components and powdered to colloidal inorganic materials. The defoamer can be emulsified or dispersed in water and other media and only then applied for defoaming.

The products of polyaddition to a monohydric aliphatic alcohol are understood to be individual alcohols

C, to C. _o , but more often they are mixtures of at least two aliphatic alcohols, or 4 lo with admixtures of practically inert substances under the above conditions, such as acetals and esters. In polyaddition, individual alkylene oxides are most often applied, and mixtures of alkylene oxides are more rarely applied. If two alkylene oxides are polyadditioned, then the polyaddition is most often carried out first with one alkylene oxide, e.g. ethylene oxide (oxirane) and then propylene oxide (methyloxirane), or then with another alkylene oxide or again with ethylene oxide, etc. The combination of polyaddition of several alkylene oxides is most often applied in polyaddition to polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, but also polypropylene glycol, polyethylene glycol, etc.

The hydrocarbons according to the present invention include saturated or unsaturated, mainly aliphatic and naphthenic hydrocarbons, optionally also with aromatic admixtures. Most often, however, petroleum fractions, and of these, in particular, kerosene fraction, light and heavy gas oil fractions, especially refined oils. Then synthetic hydrocarbons, in particular oligomers and co-oligomers, or low-molecular polymers and copolymers of ethylene, propylene, alkenes and dienes C ₄ and C ₈ , further products formed by thermal cleavage of macromolecular substances, as well as hydrogenolysis of macromolecular substances and higher hydrocarbons, e.g. vacuum distillates of petroleum, etc. In addition, hydrogenated oligomers of the above-mentioned alkenes and dienes C ₃ to C ₅ , can also be used.

Suitable components are aliphatic alcohols C ₃ to C ₁₄ , as well as secondary alcoholic fractions from the production of pure higher aliphatic alcohols, such as head fractions and distillation residue. This can be the head fraction and distillation residue from the rectification of crude 2-ethylhexanol, but the distillation residue (2-EHTP) is a more effective component. The presence of acetals, aldehydes and ketones is also not harmful.

Thus, the distillation residue from the rectification of crude 2-ethylhexanol most often contains 26 to 46 wt. 2-ethylhexanol, 35 to 50 wt. monohydric and dihydric alcohols C ₁₂ , as well as dihydric alcohols C _g , then acetals, aldehydes and other unidentified oxygenated organic compounds.

Furthermore, it is the front portion from the rectification of 2-ethylhexanol, containing a mixture of isobutanol with n-butanol in a total amount of usually 40 to 85% by weight, isoamyl alcohol 3 to 7%, 2-ethylhexanol 5 to 20%, further admixtures of ketones and other, unidentified oxygenated organic compounds.

Possible co-oligomers and copolymers of _C2 to _C4 alkylene oxides include statistical, sequential, grafted, but especially block co-oligomers and copolymers of propylene oxide and ethylene oxide, or of ethylene glycol to polyethylene glycol with propylene oxide or of propylene glycol to polypropylene glycol with ethylene oxide, etc.

Ethylene-bis-alkylamides of at least one carboxylic acid up to C _2g , mainly ethylene-bis-stearylamide CH ₃ (CH ₂ ) ₃ gCONHCH ₂ CH ₂ NHCO(CH ₂ ) _3g CH ₃ , ethylene-bis-palmitylamide, as well as unsaturated acids (oleic acid, linoleic acid and linolenic acid). Ethylene-bis-alkylamides formed from ethylenediamine (1,2-diaminoethane) and saturated carboxylic acids are more effective than from unsaturated acids, but they increase the viscosity of the universal defoamer much more.

Suitable excipients include emulsifiers, fungicides, bactericides, corrosion inhibitors, pigments, dyes, optical brighteners and fragrances.

Further details on the formulation of the defoamers according to the invention, their effectiveness, as well as further advantages are apparent from the examples.

Example

The defoaming efficiency of individual defoamer samples is determined by comparing the foaming of the standard sample with the foaming of the standard sample with the defoamer in question. Thus, 100 ml of an aqueous solution of standard sodium lauryl sulfate (anionic surfactant) with a concentration of 0.1% by weight (1 g.dm ^-3 ) or of polyethoxylated primary alcohols C ₁₂ to C ₁₄ with 9 moles of ethylene oxide (nonionic surfactant) with a similar concentration and finally a similar solution of lauryl ammonium bromide (cationic surfactant) are carefully poured into measuring cylinders with a volume of 500 cm and closed with a ground-glass stopper. The standard solution is foamed by inverting the cylinder by 180° and inverting fifty times for 1 min at a temperature of 23 ±2 °C. The height of the foam and the height of the unfoamed solution are measured after 1 min from the end of foaming.

Then the foaming capacity of the Standard PŠ (%) is calculated from the relation PŠ = a/b . 100, a = foam height (cm)tb = height of unfoamed solution (cm). The defoaming efficiency is determined by the same procedure as for the standard solution, but 1 (0.02 g) or 2 drops (0.04 g) of defoamers are added to 100 cm ³ of the standard solution and P _Q (foaming capacity of the mixture of the standard solution and defoamer) is determined. The defoaming efficiency is finally calculated from the graph of the dependence of foaming capacity (%) on the defoaming efficiency, with the defoaming efficiency (%) from 100 to 0 plotted on the x-axis and the foaming efficiency (%) of the standard solution on the y-axis. The % defoaming efficiency is read at the intersection of the diagonal, with the arithmetic mean of three measurements taken as the final result. The defoamer formulation from the individual components is made at a temperature of 30 ±5 °C.

As components of defoamers, products of polyaddition of propylene oxide to aliphatic alcohols up to Ο^θ are tested, especially the product of polyaddition of 15 moles of propylene oxide to the distillation residue from the rectification of crude 2-ethylhexanol. This distillation residue (during its distillation, 86% is distilled as a fraction in the range of 184 to 285 °C/101 kPa), hereinafter abbreviated as 1-EHTP, has the following characteristics: % wt. OH = 12.9; bromine number = 4.7 g Br/100 g; acid number = = 0.9 mg KOH/g; saponification number =22.1 mg KOH/g; 2-ethylhexanol = 36.3% wt., alcohols, including C ₁₂ diols = 44.1 t wt.; butyraldehyde-diisobutyl acetate = 0.7% and 7 other oxygenated organic substances with a concentration of 1 to 6% by weight, average molecular weight = 190; density at 20 °C = 901.9 kg/m ³ ; n ²⁰ = 1.4530.

Then the product of polyaddition of 15 moles of polypropylene to 1 mole of Οθ and C^ ₂ alcohols in 2-EHTP, hereinafter referred to as EHTP-15.

Furthermore, the product of the copolyaddition of propylene oxide and ethylene oxide to trimethylolpropane is carried out in such a way that the alkali-catalyzed addition of ethylene oxide to trimethylolpropane begins at the earliest and only after almost all of the ethylene oxide has been consumed until practically all of the propylene oxide has reacted.

The polyether thus obtained has a hydroxyl number = 47.34 mg KOH/g; acid number = 0.153 mg -5 -4

KOH/g; sodium content 5.2.10 wt. % and potassium 1.6.10 wt. %, with molecular weight 2,700 ±400, hereinafter referred to as Polyether - 48. This polyether is also suitable as a component for the production of mainly soft polyurethane foams.

The hydrocarbon components examined are the petroleum fraction, hereinafter referred to as petroleum, then refined alkane-naphthenic oil, so-called white oil, and propylene oligomers, so-called polypropylene oil K-1000 with an average molecular weight of 469 g/mol; freezing point = -25 °C, with an average of 1.6 double vSzby per molecule. Then oligomers with a lower average molecular weight, referred to as polypropylene oil K-300.

Furthermore, there are aliphatic alcohols, even pure, but more often as mixtures. This is the already defined heavy fraction from the rectification of crude 2-ethylhexanol, referred to as 2-EHTP and then the light fraction (2-EHLP) from the rectification of crude 2-ethylhexanol; fraction with a boiling point of 109 to 182.5 °C/101 kPa, density d^° = 812.2 kg.m ^-3 and refractive index n ²⁰ = 1.4088; % wt. OH = 19.4; CHO = 0.24 % wt.; CHO bound = 0.25 i wt.; bromine number = 1.3 g Br ₂ /100 g; H ₂ O = 0.45 % wt.; acid number = 1.26 mg KOH/g; saponification number = 2.5 mg KOH/g; isobutanol content = = 20.3 % wt.; n-butanol with another unknown component = 51.7% by weight; isoamyl alcohol = 4.1% by weight; 3-heptanone = 4.1% by weight; 2-ethylhexanol = 15.3% by weight; 2-ethylhexanol = 1.95% by weight; other unidentified oxygenated organic compounds = 2.1% by weight. Then ethylene-bis-stearylamide (ethylene-bis-stearamide) CH^(CH ₂ ) ₃ gCONHCH ₂ CH ₂ NHCO(CH ₂ >^gCHg and ethylene-bis-palmitylamide.

Finally, micro-grained to colloidal silicon dioxide and magnesium oxide. The composition of individual defoamer samples, as well as their defoaming efficiency on foams formed by the interaction of non-ionic, anionic and cationic surfactants, results from the results summarized in Table 1.

Table 1

Composition of defoamer Defoaming efficiency (%) on foam formed by co- Component (% Mass content) non-ionic effect of anionic surfactant cationic 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops 1 2 3 4 5 6 7 8 Polyether - 48 100 39 46 44 46 45 47 EHTP - 15 100 58 65 81 89 80 84 Polyether - 48 99.3 Ethylene bis stearylamide 0.7 81 88 89 97 98 100 Polyether - 48 98.0 Ethylene bis stearylamide 2.0 88 95 98 100 100 100 Polyether - 48 80 Isopropyl alcohol 19.0 75 81 100 100 99 100 Ethylene bis stearylamide 1.0 Polyether - 48 90.0 Ethylene bis stearylamide 8.0 86 92 100 100 99 100 MgO 2.0 Polyether - 48 50.0 Kerosene 48.5 84 86 100 100 99 100 Ethylene bis-stearamide 0.5 Si°2 1.0 EHTP - 15 Polypropylene oil 50.0 To 300 49.0 97 100 100 100 98 100 Ethylene bis-stearamide 1.0 EHTP - 15 60 Kerosene 38 86 93 100 100 99 100 Ethylene bis-stearamide 2.0 EHTP - 15 50 2-ethylhexanol 46.0 100 100 100 100 100 100 Ethylene bis-stearamide 4.0 EHTP - 15 50 Dipropylene glycol 47.5 66 72 92 ⁹⁶ 95 97 Ethylene bis-stearamide 2.5 Polyether - 15 50 Polypropylene glycol 45 100 100 100 100 100 100 Ethylene bis-stearamide 5 Polypropylene oil To 1000 90 Ethylene bis-stearamide 10 81 92 79 90 98 99 Polypropylene oil To 1000 97.5 Ethylene bis-stearamide 2.5 89 96 65 85 90 98

Continuation of table 1

1 2 3 4 5 6 7 8 Kerosene 97.2 23 53 67 76 69 77 Ethylene bis-stearamide 2.5 Polypropylene oil K 300 50 2-ethylhexanol 47 81 93 90 93 100 100 Ethylene bis-stearamide 3 EHTP - 15 50 Kerosene 47 97 100 96 100 100 100 Ethylene bis-stearamide 3 Polyethylene glycol with an average molecular weight of 300 97 39 45 0 11 97 99 Ethylene bis-stearamide 3 Kerosene 80.0 EHTP - 15 19.3 79 92 78 83 100 100 Ethylene bis stearyl amide 0.7 Kerosene 80 EHTP-15 19.3 80 92 79 84 100 100 Ethylene bis palmityl amide 0.7 Polyether 48 5 EHTP - 15 35 83 93 81 86 99 100 2-EHTP 50.3 Ethylene bis stearyl amide 0.7 Polyether 48 5 2-EHLP 94.2 80 91 82 87 96 100 Ethylene bis stearylamide 0.8

Example 2

Similar to example 1, the defoaming efficiency of aqueous solutions of nonionic, anionic and cationic surfactants, as well as of the copolymer of propylene oxide with ethylene oxide itself, prepared by polyaddition of ethylene oxide to polypropylene glycol with an average molecular weight of 1,800 g.mol, with 10 wt. % ethylene oxide, calculated on the starting polypropylene glycol, added to the polypropylene glycol from both ends of the chain, is investigated. Furthermore, this copolymer, hereinafter referred to as Copolymer 610 with additives of ethylene-bis-amide mixtures of saturated and unsaturated acids up to ^20. The results obtained are summarized in table 2.

Table 2

Defoamer composition Defoaming efficiency (%) on foam formed in conjunction with surfactant

Component Content of nonionic anionic cationic

(% by weight) 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops 1 2 3 4 5 6 7 8 Propylene oxide-ethylene oxide copolymer (Copolymer 610) 100 11 18 91 96 66 71 Copolymer 610 Ethylene-bis-stearyl- 99.8 76 90 93 97 ⁹⁹ 100

amide 0.2

Continuation of table 2

1 2 3 4 5 6 7 8 Copolymer 610 Ethylene-bis-stearylamide 99.0 1.0 86 92 100 100 99 100 Copolymer 610 99.0 Ethylene bis-amide mixtures of acids up to C ₂ q 1.0 83 90 99 100 98 100

Example 3

The procedure is similar to that in Examples 1 and 2, except that the product of polyaddition of butene oxide (1,2-epoxybutane) to 2-ethylhexanol with an average molecular weight of 340 g.mol (designated BH) and the copolyaddition of butene oxide to dipropylene glycol with an average molecular weight of 480 g.mol ^- (designated BP) is investigated as a component of a multipurpose defoamer. The results obtained are summarized in Table 3.

Table 3

Defoamer composition Defoaming efficiency (%) on foam formed by the interaction of surfactants

Component Content of nonionic anionic cationic

(also mass.) 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops BH 20 2-ethylhexanol 77.5 89 99 92 100 97 100 ethylene bis stearylamide 2.5 BP 10 EHTP - 15 70 86 97 91 99 96 100

2-EHTP 18 ethylene-bis-stearylamide 2.0

Claims (6)

7 264733 Continued tab. 2 1 2 3 4 5 6 7 8 Copolymer 610Ethylene-bis-stearyl-amide 99.0 1.0 86 92 100 100 99 100 Copolymer 610 99.0 Ethylene bis-amide acid mixtures up to C2q 1.0 83 90 99 100 EXAMPLE 3 The procedure is similar to that of Examples 1 and 2, except that the product of the polyaddition of butene oxide (1,2-epoxybutane) to 2-ethylhexanol with an average molecular weight of 340 gmol is investigated as a component of the multipurpose foamer (labeled BH) and copolyaddition of butene oxide on dipropylene glycol with an average molecular weight of 480 g.mol (labeled BP). The results are summarized in Table 3. Table 3 Antifoam Antifoam Effectiveness (%) on the foam produced by the surfactant component Component Non-ionic anionic cationic (i) weight 1 drop 2 drops 1 drop 2 drops 1 drop 2 drops BH 20 2- ethylhexanol 77,5 89 99 92 100 97 100 ethylene-bis-stearylamide 2,5 BP 10 EHTP - 15 70 86 97 91 99 96 100 2-EHTP 18 ethylene-bis-stearylamide 2.0 SUBJECT OF THE INVENTION A multipurpose defoamer mainly based on organic, acidic and nitrogenous compounds and auxiliaries, characterized in that 90 to 99.8 wt. it comprises at least one product of alkylene oxide to C4 polyaddition to monovalent to hexavalent aliphatic C2 to and / or alkylene oxide copolymers of C2 to C4 and 0.2 to 10% by weight. ethylene-bis-alkylamide of at least one carboxylic acid C1g to C2Q. 2. A multipurpose defoamer according to claim 1, wherein the alkylene oxide polyaddition product with aliphatic alcohols forms the polyaddition product predominantly a mixture of 2-ethylhexanol and dodecanol and diol C12 with 3 to 20 moles of propylene oxide, preferably a polyaddition product. molpropylene oxide with 1 mole of distillation residue from the rectification of crude 2-ethylhexanol. 3. A multipurpose defoamer according to claim 1, wherein the polyaddition product of the divalent to hexavalent aliphatic alcohol is prepared by a polyaddition. trimethylolpropane and / or glycerol with propylene oxide and / or ethylene oxide, preferably trimethylolpropane with propylene oxide or propylene oxide and ethylene oxide to an average molecular weight of 2,000 to 3,500. 4. A multipurpose defoamer according to claim 1, wherein the co-oligomers and copolymers of C2-C4 alkylene oxides form copolymers of ethylene oxide with propylene oxide and butene oxide, preferably block oligomers and copolymers of propylene oxide with ethylene oxide. 264733 8 5. A multipurpose defoamer according to any one of claims 1 to 4, characterized in that said Salmon contains 10 to 70 wt. at least one aliphatic alcohol to C14, preferably mainly and by-products of the hydration of C3 to C14 alkenes and hydroformylation of C3 to C14 alkenes followed by hydrogenation of aldehydes. 6. A multipurpose defoamer according to any one of claims 1 to 5, wherein said Salmon contains 10 to 65 wt. mixtures of hydrocarbons having a molecular weight of 130 to 1000 g / mol, preferably oligomers of alkenes to C1 and fractions of hydrocracking products of higher hydrocarbons. Severografia, n. P., MOST Price 2,40 Kcs