CS225024B1 - The production of tensides - Google Patents

Description

The present invention relates to a process for the preparation of surfactants from the by-products of petrochemical production of organic oxy compounds containing active hydrogen in the form of hydroxyl groups.

It is known [Rosen M. J .: Surfactants and Interfacial Phenomena. John Wiley and Sons

New York-Chichester-Brisbane-Toronto (1978); Abramzon AA, Gaevoj GM: Poverchnostnoaktivnyje veSčestva, 299-309. Khimija, Leningrad (1979)] that nonionic surfactants are prepared by oxyethylation of higher fatty alcohols (polyethylene glycol alkyl ethers), further higher fatty acids, and oxyethylation of fatty amines. Thus, monoalkyl esters of polyethylene glycol based on primary fatty alcohols ⁽ ' _n ^ 2n + 1 ^^ 2 ^ 4 ° ^ m ^H ' ⁿ '8 to 10, m = 6 are direct emulsion emulsifiers, gentleman stabilizer, hair removal agent, raw material for production of other types surfactant, antistatic agents in the textile industry, wetting agents and detergent additives, polyglycols are a minor ingredient, and the rate constants for the addition or polyaddition of ethylene oxide to different alcohols are known [Schick JM: Nonionic Surfactants, M. Dekker, M. Dekker. , New York (1967); Blazej A. et al .: Surfactants, Alfa and SNTL, Bratislava-Prague (1977)], as well as addition and polyaddition catalysts, particularly alkali metal hydroxides, alcoholates, alkali metal carbonates, amines their activity increasingly with basicity (V. Brit. pat. 713 081 and 763 828), strontium carbonate and the like, also Lewis acids (AlCl4, BF4, SnCl4, FeCl4, SbCl4 and the like), as well as organometallic catalysts ·

Alkylpolyethylene glycols can be converted to alkylpolyethylene glycol phosphates, e.g. by treating phosphorus pentoxide or phosphorus oxychloride or alkylpolyethylene glycol sulfates by treating sulfur trioxide, chlorosulfonic acid or sulfuric acid, the two types being neutralized, most often by alkali metal hydroxides, ammonia, triethanolamine and the like.

Mixtures of propylene glycol monobutyl ethers of C CHgOCC ^HgOÍÍH are also well known, wherein m 75 * ± 5 as antifoams in antibiotic biosynthase, Sally block copolymers of ethylene oxide and propylene oxide, the starting materials for the synthesis of single hydrophobic and one hydrophobic group with one hydrophobic group and one hydrophobic group. alcohols. However, in addition to the obvious advantages of producing all known surfactants based on alcohols up to ,Ο, ethylene oxide and propylene oxide, there are limited sources of mainly higher fatty alcohols, as well as the need to use alcohols of the highest purity possible. Thus, the advantages of the known processes utilize and, moreover, enable the raw material base of the hydrophobic surfactant components to be extended by the production method of the present invention.

According to the present invention, a process for the preparation of surfactants by polyaddition of alkylene oxide and / or copolyaddition of alkylene oxides or a mixture of alkylene oxides of 2 to 4 carbon atoms into organic oxy compounds containing active hydrogen in the form of hydroxyl groups at a temperature of 10 to 220 ° C, usually in the presence of a catalyst or a mixture of catalysts optionally by further treatment of the polyaddition products, such that the olefin oxide or a mixture of olefin oxides having 2 to 4 carbon atoms is polyaddied and / or copolyaded to by-products from the production of 2-ethylhexanol containing at least two different alcohols, preferably monovalent and / or divalent an alcohol having n, 2n and 3n carbon atoms, wherein n = 4, in the presence of other oxygenated organic substances, such as esters, acetals, acids.

An advantage of the surfactant production method of the present invention is the expansion of the surfactant raw material base by using by-products from the production of 2-ethylhexanol, while not technically further processed for the production of nonionic surfactants. There is no need for them before use for addition or addition. polyaddition with alkylene oxides, refine the presence of admixtures such as esters, aldehydes and acetals etc. Another advantage is the possibility of higher flexibility of production of individual types of surfactants and their good biodegradability.

The polyaddition of an olefin oxide or mixture of olefins can be carried out with an individual olefin oxide, either the entire polyaddition with only one olefin oxide or, first with one and then the other (e.g., first with ethylene oxide and then with propylene oxide), alternately, once or once, then together with a mixture of olefin oxides. In addition, the polyaddition of the olefinic oxide mixture can be carried out first and the polyaddition can be terminated with only one olefinic oxide.

Possible by-products from the production of 2-ethylhexanol are, in particular, heavy fractions or distillation residues from distillation or distillation. the rectification of 2-ethylhexanol, as well as the lightweight fractions resulting from the rectification of 2-ethylhexanol. The European lightweight portions including 2-ethylhexanol also contain n-butanol, isobutanol, and generally has 2-ethylhexanol, isoamyl alcohol, heptanone, and other oxygen compounds and heavies addition of 2-ethylhexanol also alcohols ^of which the most common dodecanol and C ₁₂ diol a'spravidla and admixtures of acetals, esters and ether alcohols. The crude 2-ethylhexanol, which is fed to the distillation and the distillation, respectively. the rectification may result from the aldolization of n-butyraldehyde (associated with separation by dehydration and hydrogelation), whether from the aldolization of acetaldehyde associated with dehydration and aelective hydrogenation or from the production of n-butyraldehyde (together with isobutyraldehyde) by oxonation of propylan. In this case, essentially after separation of the isobutyraldehyde, the aldolization of the n-butyraldehyde associated with dehydration to 2-ethylhexenal, this is hydrogenated to the crude 2-ethylhexanol, usually in the liquid phase at elevated pressure (usually 10 to 20 MPa) using hydrogenation catalysts mainly metal VIII. groups of the periodic system (e.g. Ni on silica), at temperatures of 100 to 190 ° C.

Less suitable is hydrogenation in the vapor phase, respectively. on scrubbed catalysts at a pressure of about 1 bar. The crude 2-ethylhexanol thus obtained is distilled, respectively. it may rectify and the by-products, i.e. both the bottoms and the distillation residues, may be a suitable raw material for the production of surfactants, in particular nonionic and anionic surfactants. In the case of the production of nonionic surfactants, the primary products of the addition, respectively. polyadditions of by-products with ethylene oxide, propylene oxide, optionally butene oxide and isobutene oxide, respectively after removal of unconverted olefin oxides and other unconverted low molecular weight moieties.

ABOUT

Otherwise, further treatment of nonionic surfactants can be made, especially if the purpose is to obtain anionic surfactants, e.g. phosphatization, sulfation, usually associated with subsequent neutralization.

More details of the surfactant manufacturing process of the present invention, as well as other advantages, are apparent from the examples.

Example 5

Into a 2.5 dm stainless steel autoclave equipped with a duplicator, anchor stirrer, and thermometer well, 350 g of heavy fractions from the rectification of crude 2-ethylhexanol (2-EHTP) were added. Crude 2-ethylhexanol is produced by aldolizing mainly n-butyraldehyde from propene oxonation coupled with dehydration to 2-ethylhexenal and its hydrogenation on a nickel catalyst (nickel on silica) at a temperature of 00 to 180 ° C and a hydrogen pressure of 10 MPa. The heavy fractions resulting from the rectification of the crude 2-ethylhexanol are essentially a distillation residue. Ich č. acidity = 0.9 mg KOH / g; no. saponification = 22.1 mg KOH / g; wt% OH = 12.9; bromine number = 4.7 g Brg / 100 g; density at 20 ° C = 901.9 kg.m ^- 1; n ^ ® = 1.4530. The diol content

_C12 = 44.1 wt%; 2-ethylhexanol = 36.3 wt. and butyraldehyde diisobutylacetal = 0.7 wt. and 7 other oxygen species in conc. %, up to 6 wt. The average molecular weight is 190. To these heavy fractions, 245 g of oxirane (ethylene oxide, i.e. 3 moles / 1 mol) and 5 g of potassium hydroxide catalyst are added under a nitrogen atmosphere. Under continuous stirring at a temperature of 125 to 40 ° C and a pressure of about 3 bar, polyaddition of ethylene oxide takes place for 6 hours. The product obtained is a water-insoluble viscous liquid. The antifoam effectiveness on sodium alkyl polyglycol ether sulfate as a foaming agent is 42%.

Example 2

In a 2.5 dm autoclave, as specified and as described in Example 1, 350 g of heavy fractions, respectively, were used. The distillation residues from the rectification of 2-ethylhexanol specified in Example 1 weigh 8.0 g of ethylene oxide (i.e., approximately 10 moles per mole).

The product obtained is of a pasty consistency, well soluble in water. Product foaming by conc. 1 g.dm is zero. Surface tension value at conc. 1 g.dm = 36.1 mN.m.

Example 3

In the 2.5dm < 2 > autoclave specified in Example 1, 1,040 g of ethylene oxide are polyaddated to 300 g (i.e. approximately 15 moles per mole) of the heavy fractions from the rectification of 2-ethylhexanol under otherwise similar conditions to Example 1.

A pasty consistency product, readily soluble in water, is obtained. Product foaming —Ί - -3 -1 o conc. 1 g.dm is zero. Surface tension value at conc. 1 g.dm = 38.3 mN.m.

Example 4

In an autoclave of 2.5 dm < 2 > under otherwise similar conditions to Example 1, 1,390 g of oxirane (ethylene oxide) are polyaddated on 350 g (i.e., about 20 moles per mole) of the heavy fractions from the rectification of 2-ethylhexanol.

A pasty consistency product is obtained which is soluble in water. Product foaming by conc. 1 g.da ^- 1 is 6%. Under similar conditions, the foaming power of the alkyl polyglycol ether ♦. - 7 - 1 sodium sulphate is 287.5 Surface tension at conc. 1 g.dm ^J = 39.2 mN.m.

Example 5

Κ 166 g of light fractions falling off in the rectification of 2-ethylhexanol (2-EHLP) characterized by 19.4 56 wt. OH groups, bromine number 1,3 g / 100 g, acid number 1,3 mg KOH / g and saponification value 2,5 mg KOH / g (density at 20 ° C 818,2 kg.m “^; η ^ θ = = 1.4088, water = 0.45 wt.%, Isobutanol = 20.756 wt., 2-ethylhexanol = 15.3 wt.%, N-butanol with another unknown component = 51.756 wt., Isoamyl alcohol = 4.1 56 wt., 3-heptanone = 4.1 56 wt., 2-ethylhexanol = 2556 wt.) Are added 1.5 g of powdered sodium hydroxide and 2 g of aqueous sodium carbonate solution with conc. 50 56 wt. into an autoclave with vigorous stirring under a nitrogen atmosphere. The contents of the autoclave are heated to 140 ° C and evacuated three times, which also removes water from the reaction system. Subsequently, 3,480 g of propylene oxide (methyloxirane) are added from a pressure bottle over a period of 6 hours while maintaining a reaction temperature between 140 and 10 ° C and an operating pressure of 0.5 to 0.6 MPa.

Example 6

To 880 g of the light fractions resulting from the rectification of the crude 2-ethylhexanol from the propene oxonation, as described in Example 5, 8.8 g of potassium hydroxide catalyst are gradually charged with 2,200 g of ethylene oxide under otherwise similar conditions to Example 5. g of a surfactant product, in the form of a viscous liquid.

Example 7

To 880 g of light byproducts from the rectification of the crude 2-ethylhexanol specified in Example 5 and 9 g of potassium hydroxide are successively metered at 140-10 ° C at 4 400 g of ethylene oxide under similar conditions as in Examples 5 and 6. with 5 175 g of a surfactant.

example

The procedure is similar to that of Example 5, but with the difference that 166 g of a light fraction, from the rectification of 2-ethylhexanol, is first fed with 35 g of ethylene oxide and then with 4 640 g of propylene oxide containing 4656 wt. buténoxldov. 4,590 g of surfactants are obtained.

Example 9

The procedure is similar to that of Example 6, but instead of 2,200 g of ethylene oxide, only 1,320 g of ethylene oxide are used per 880 g of light fraction which is eliminated in the rectification of the crude 2-ethylhexanol. 2098 g of surfactants are obtained. Of these, 1,200 g are withdrawn into a separate glass flask equipped with a stirrer, a thermometer and a funnel, heated to 50 ° C and phosphorus pentoxide is added in portions in a total quantity of 143 g so that the temperature does not rise above 75 ° C. After all the phosphorus pentoxide has been added, the reaction mixture is stirred vigorously for 4 hours. The resulting mixture of predominantly alkyl polyglycol ether phosphoric acids is neutralized at 50-60 ° C with aqueous sodium hydroxide solution to pH = 7. A surfactant having a surface tension of 37.4 mN.m -1 (c = 1 g.dm -1) is obtained.

EXAMPLE

The procedure is similar to Example 9, except that the neutralization of the mixture of predominantly alkyl polyglycol ether phosphoric acids to pH = 7 is carried out with triethanolamine. Obtained as a surface tension of 36.5 mN ^- (c = 1 g.dm ^- ^).

Example 11

The antifoaming efficacy of some types of surfactants characterized in the preceding examples is examined. An aqueous bentonite suspension of conc. 6 wt. % with addition of 1 wt. domestic lubricant additive (SAP). To the 300 cnP suspension, 3 cn? antifoams, MIEG suspension for 1 min at room miegačke 'at a rotational speed of 1400 min ^-' and provides the weight of the slurry directly after premieganí and tired after 24 hours (rest).

The results obtained are shown in Table 1. The results show that the foaming stability of the base suspension is considerable. Of the antifoam agents investigated, the most effective surfactants are prepared by the procedures of Examples 8, 5 and 6. However, the surfactant prepared by the method of Example 7 is superior to the known silicone antifoam.

Table 1

Defoamer added to base suspension bentonite Quantity of antifoam added (% w / v suspension) Suspension density (kg.m “3) immediately after mixing po 24 h - (base suspension) silicone defoamer 0.0 680 690 (Lukosan, A-311) 1.0 700 720 težzid according to example 5 0.2 760 800 the surfactant of Example 5 0.6 820 880 surfactant according to Example 5 1.0 900 910 the surfactant of Example 6 0.2 750 770 the surfactant of Example 6 0.6 810 830 surfactant according to prift.edu 6 1.0 860 880 the surfactant of Example 7 0.2 710 730 the surfactant of Example 7 0.6 760 770 of the thizide according to Example 7 1.0 790 800 the surfactant of Example 8 0.2 800 920 the surfactant of Example 8 0.6 820 960 the surfactant of Example 8 1.0 840 '970'

EXAMPLE 1 a d 12 »> _

In _the autoclave of a volume of 2.5 dm ^ specified in Example 1, 350 g ^ ns heavies from the rectification of 2-ethylhexanol polyadenylation 405 g of ethylene oxide (mol pfoáler 1: 5) using I0 g (Cgíljíg ⁰ · ^ / ² · CgH2O.CgH2O ^{as the} catalyser of the reaction, operating at Aeplote 70 [deg.] C., with the same conditions as in Example 1 [deg.].

A water-insoluble product with application possibilities as in Example 1 is obtained.

Claims (3)

Process for the preparation of surfactants by polyalkylene alkylene oxide and / or alkylene oxide copolyadium or mixtures of C 2 -C 4 alkylene oxides for organic oxy compounds containing active hydrogen in the form of hydroxyl groups at a temperature of 10 to 220 ° C, usually in the presence of a catalyst or catalyst mixture, optionally by further treatment polyaddition products, characterized in that the olefin oxide or a mixture of olefin oxides having 2 to 4 carbon atoms is polyaddied and / or copolyaded to by-products from the production of 2-ethylhexanol containing at least two different alcohols, preferably a monovalent and / or divalent alcohol with n, 2n and 3n with carbon atoms, wherein n = 4, in the presence of other oxygenated organic substances such as esters, acetates. acids. 2. The process according to claim 1, characterized in that the product formed from polyaddition or copolyaddition is further treated by sulphation or phosphatization and generally by neutralization of these products. 3. Process according to claim 1 or 2, characterized in that the olefin oxide or a mixture of olefin oxides having from 2 to 4 carbon atoms is treated with by-products from propene oxonation, subsequently treated by aldolization and hydrogenation, preferably on front streams and / or distillation residues. hydrogenation product of 2-ethylhexenal.