CS244560B1 - Desinfectant or desinfection component winning method - Google Patents

Abstract

Disinfectant or Component is obtained from crude products catalyzed decomposition of cumene hydroperoxide to phenol and acetose as their distillation residue called. phenol pitch containing cumylphenol [a mixture of 4-cumylphenol, respectively. phenol, 4- (l- -methyl-1-phenylethyl) with 2-cumylphenol, respectively. phenol 2- (1-methyl-1-phenylethyl) omega 16-50% wt. Of these, distillation at reduced pressure, the fraction containing the crystals is separated first mainly acetophenone, dimethylphenylcarbinol and ienol. The rest as such or after distilling under reduced pressure from the bee fraction mainly containing active cumylphenol a dimers of alpha-methylstyrene or after conversion to cumylphenates (sodium, potassium, ammonium) ap.j and their isolation is an effective means, preferably after isolating cumylphenol crystallization or extractive by crystallization with hydrocarbons, mainly n-alkanes Cs to C12 at a temperature of +10 to -30 ° C. Cumylphenols, respectively. cumylphenolates are odorless and substantially more effective disinfectant agents such as cresols, with high antibacterial properties antimycotic effect

Description

(54) Method for obtaining a disinfectant and / or disinfectant component

2

The disinfectant or component is obtained from crude products catalyzed by the decomposition of cumene hydroperoxide to phenol and acetone as their distillation residue, the so-called distillation residue. phenol pitch containing cumylphenol [mixture of 4-cumylphenol, resp. phenol-4- (1-methyl-1-phenylethyl) n-2-cumylphenol, respectively. % phenol-2- (1-methyl-1-phenylethyl) 16-50 wt. Of these, distillation under reduced pressure first separates the fraction containing mainly acetophenone, dimethylphenylcarbinol and ienol. The residue as such or after distillation under reduced pressure from a fraction mainly containing active cumylphenol and alpha-methylstyrene dimers or after conversion to cumylphenlates (sodium, potassium, ammonium, etc.) is an effective means for isolation of cumylphenol, preferably by crystallization or extractive isolation of cumylphenol crystallization with hydrocarbons, in particular Cs-C12 n-alkanes at a temperature of +10 to -30 ^° C.

Cumylphenols, respectively. cumyl phenolates are odorless and substantially more effective disinfectants than cresols, with a high antibacterial and antifungal effect.

244860

The invention relates to a process for obtaining a chemical disinfectant or disinfectant component having antibacterial, antifungal and anti-yeast activity on the basis of the available by-product from the petrochemical process.

It is known [Raška K. et al .: Disinfection, desinsection, deratisation. Statni zdravotnicke nakladatelstvi, Praha (1956)], that the chemical method of disinfection is carried out with organic or inorganic substances, the disinfectant effect of which besides the type of disinfectant depends on its concentration, duration of action and temperature at which disinfection is carried out. Inorganic disinfectants include mineral acids such as nitric acid (usually in the form of an aqueous solution of 2% by weight), sulfuric acid, hydrochloric acid, sodium hydroxide, calcium hydroxide, chlorine, chlorine lime, hydrogen peroxide, iodine, salts heavy metals etc. Disinfectants based on organic compounds are widespread. Such is formaldehyde, ethylene oxide, but their disadvantage is the short contact time during application. Then phenol, cresol, cresolates, mydlofenol solutions, chlorophenol, but their disadvantage is a relatively considerable and unpleasant odor. This problem is solved by benzylphenols and alkali metal benzylphenolates, dibenzylphenols, which are produced from petrochemical raw materials [Spaulding E. M .: J. Hosp. Res. 9, 5 (1972); MS. U.S. Pat. 150,889, 152,180 and 183,478; Schmidt B .: Pharm. Ind. 36, No 3, 179 (1974)] Among other bacteriostatic and antifungal agents, tert-butyl-m-cresol, pentachlorophenol laurate, ethoxylated chlorocresols, o-benzyl-p-chlorophenol and trichlorophenol are important [Linder K .: Tenzide- Téxtilhilfsmittel-Waschrohstoffe, page 2601. Wissenschaftliche Verlaggesselschaft MBH - Stuttgart (1971)] However, they require valuable starting chemical raw materials, high-tech and material-intensive production equipment, and many of these products have an unpleasant odor.

These problems are solved by the method of obtaining a disinfectant and / or disinfectant component based on phenol derivatives and / or corresponding alkali metal and / or earth phenolates or ammonium phenolates, which is carried out by obtaining from the crude products catalyzed decomposition of cumene hydroperoxide into phenol and acetone. at least one of the processes which comprises isolating the distillation residue, so-called " phenol pitch with a cumylphenol content of 16 to 50% by weight, conversion of cumylphenols and phenol from phenolic pitch to phenollates, isolation by distillation from phenol pitch of a fraction of 30-80% cumylphenol, isolation of cumylphenol from this fraction by crystallization or extractive crystallization at +10 -30 ° C with the action of at least one saturated hydrocarbon Cs to C12, whereby crystallized cumylphenol is usually separated after washing with a cold extracting agent, or by converting cumylphenol to cumylphenol by treatment with at least one alkali metal or earth hydroxide or ammonia or ammonium hydroxide and . The isolated cumylphenol can also be converted to cumylphenolate, the final treatment being chosen depending on the intended application, most often as a powder or solution having a concentration of 0.01 to 20 prec. wt. of the active substance.

An advantage of the process according to the invention is its raw material availability and technical simplicity, while the byproducts from the production of phenol and acetone are greatly economically and economically utilized to obtain an effective yet practically odorless disinfectant or disinfectant component.

The least suitable procedure is to isolate the distillation residue from the acid-catalyzed decomposition of cumene hydroperoxide to phenol and acetone, since in addition to 16 to 50% cumylphenols (2-cumylphenol, 4-cumylphenol) contain relatively high amounts of odorous phenol and other odorous and more disinfectant acetophenone, dimethylphenylcarbinol, alpha-methylstyrene, and alpha-methylstyrene dimers, and is dark-colored and relatively inefficient.

A better disinfectant and / or disinfectant component is obtained by distilling off acetophenone, dimethylphenylcarbinol and phenol with an efficiency of at least 80%, which is preferably carried out under reduced pressure.

The most ^appropriate: The process of collecting, untying the front distilled off units in a remarkable reduction of pressure, e.g., at 2 to 10 kPa, which almost completely 'separated from tZvť fehólůvýčh pitches acetophenone, dimethyl phenyl and phenol, and at a higher temperature in another fraction? mainly the cumylphenol and the alpha-methylstyrene dimers are separated. From this fraction, cumylphenol can be separated by crystallization at reduced temperature and even more efficiently by extracting the crystallization agent at a temperature of +10 to -30 ° C. A temperature of about 0 ° C is usually sufficient. Extracting agents are preferably n-alkanes, respectively. hydrocarbon fractions containing mainly n-alkanes. A primary gasoline fraction is also suitable. However, since a disinfectant or component in water-soluble form is suitable for most applications, it is desirable to obtain it from a fraction containing at least 30% cumylphenol in the form of phenolates, thereby saving the extractant, reducing the number of process steps and energy consumption for extractant recovery and cooling extracted solution.

The disinfectant or component of the present invention for application in the form of aqueous solutions, emulsions, detergent components, and the like. it is preferable in the form of phenolates. For applications in organic solvents such as oil components etc. in the form of phenol, respectively. cumylphenols, while other components, so-called " phenolic pitch.

The method of recovering the disinfectant and / or disinfectant component of the present invention can be carried out continuously, semi-continuously and discontinuously. The disinfectant composition of the present invention may also be combined with other disinfectants.

Further details of the process as well as other advantages are evident from the examples.

Example 1

From the distillation residues from the production of phenol by acid catalyzed decomposition of cumene hydroperoxide, ie from the production of phenol and simultaneously acetone, so-called. the cumene method provides cumylphenol as a disinfectant or disinfectant component. The distillation residue from phenol distillation, phenolic pitch composition: 0.2 wt. alpha-methylstyrene; 21.6% wt. acetophenone; 4.6% w / w phenol; 22.8 wt. kumylfenolu; 11.5 wt. dimethyl phenyl; 31% wt. alpha-methylstyrene dimers and the remainder to 100%, mainly consisting of 1-phenyl-1,3,3-trimethylindane, acetylacetone, mesityl oxide and benzofurans, were subjected to distillation under reduced pressure. In the temperature range of 27 to 160 ° C / 2.67 kPa, a fraction of 31.6% by weight was obtained. (calculated on the startTable 1

Extracting agent Extraction temperature (° C) disc phenol pitch, of the following composition (% by weight): 0.7 alpha-methylstyrene, 43.5 acetophenone, 11.3 phenol, 2.2 cumylphenol, 25.7 dimethylphenylcarbinol, over a temperature range of 160 to 210 ° C / 2.67 kPa, a second fraction of 49.4% by weight of the following composition (% by weight) is obtained: 1,2 alpha-methylstyrene; 7-acetophenone, 38.2 cumylphenol (predominantly p-cumylphenol), 0.2 dimethylphenylcarbinol and the remainder up to 100% by weight are mainly dimers of alpha-methylstyrene and 1-phenyl-1,3,3-trimethylidane. % wt.

While in the default, so-called. % of phenolic pitch is 22.8 wt. of cumylphenol, in the first fraction calculated on the starting "phenolic pitch", only 0.69 wt. (in a 2.2 wt.% fraction) cumylphenol; in II. fractions

18.8 wt. (in fraction 38.2% by weight) and in the distillation residue 3.25% by weight. (17.02% by weight of the residue).

100 g of samples II are then collected. the fraction to which 200 g of extractant is added and the whole contents is brought to the necessary temperature with stirring, whereupon the cumylphenol precipitates, which is separated by filtration and dried at 45 ° C under reduced pressure (10 kPa) and the amount of cumylphenol obtained ( 93% (rel. 4-cumylphenol and 7% rel. 2-cumylphenol) are weighed. The results obtained, i.e. the absolute percentage of cumylphenol obtained, stamped on the starting phenol pitch ¹ 'as a function of the temperature of the extractive crystallization, are shown in Table 1.

Amount of recovered Purity of cumylphenol obtained, calculated as cumylphenol by weight [%] of 'phenolic pitch' [% by weight]

n-hexane 33 6.9 > 92 n-hexane 10 20.2 > 90 n-hexane 0 24.7 - n-hexane -18 28.6 82 n-heptane 10 22.2 - n-heptane 0 24.2 - petrolétsr (fr. 30 - 60 ° C / 101 kPa) 10 22.7 __ petroleum (fr. 30-60 ° C / 101 kPa) 0 28.1 n-alkanes Cn. —- C13 19 24.7 88 n-alkanes C11-C13 7 27.7 - n-alkanes C11-C13 -5 17.8 92 prim. petrol, fr. 51 - 65 ° C / 101 kPa gasoline fr. 51 - 65 ° C / 101 kPa -14 23.7 88.4 - (without extraction agent) 20 15.4 86.2

By using other extraction agents such as cyclohexane at 20 and –10 ° C, carbon tetrachloride between 20 and - 30 ° C, cyclohexene between 6 and - 10 ° C, and mixtures of n-butenes between 20 and - 20 ° C, cumylphenol does not fall out.

Example 2

Per 100 g II. fractions o t. in. 160 DEG-210 DEG C./20 mm Hg were treated with an aqueous sodium hydroxide solution of conc. 10% wt. at 20 ° C. After isolation and drying, 65 g of sodium cumylphenolate are obtained.

Example 3

The procedure is similar to that of Example 1, but for the extraction crystallization of cumylphenol from II. fraction at 0 ^° C, varying amounts of n-hexane were used as the extractant. Using 27.6 wt. of n-hexane to II. the 160 to 210 ° C / 2.67 kPa fraction of cumylphenol does not yet fall off; using 50 wt. 23.9 wt. cumylphenol, calculated on II. fraction, which constitutes 11.8% of the starting "phenolic pitch". When using 100 wt. n-hexane already precipitates 25.74 wt. % of cumylphenol, which is 12.7 wt. to 'phenolic pitch'; using 150 percent n-hexane, 30 wt. cumylphenol, which is 14.8% by weight of "phenolic pitch" and using 212% of n-hexane already 38.2% by weight. cumylphenol, which is virtually complete extraction efficiency from II. % fractions, calculated on the 'phenolic pitch', 18,9%

Example 4

To verify the possibility of recirculating the solvent to precipitate cumylphenol from II. a phenol pitch fraction is carried out in a series of attempts to extract cumylphenol with recirculation of n-hexane or a primary gasoline fraction of t. in. 60-80 ° C / 101 kPa. To proceed to 100 g II. The phenolic pitch fraction was added with 150 g of solvent, while cooling to 0 ° C with stirring and allowed to stir for 30 min. The crystallized cumylphenol is filtered off, washed with pure solvent, dried and weighed. The solvent was distilled off from the filtrate and used to extract further cumylphenol from II. fraction after addition of solvent losses to 150 g. This procedure is repeated ten times. Absolute extracts of cumylphenol II. the fractions amounted to 23 to 29% and calculated on the weight of the starting phenolic pitch 10 to 14% by weight. Example 5

Differential distillation under reduced pressure (2.67 kPa) yielded II. the fraction was cooled to -30 ° C, precipitating cumylphenol, which was filtered off and washed on the filter with cold n-heptane. 23% by weight are obtained. cumylphenol, calculated on weight II. fractions.

Example 6

For differential distillation under reduced pressure (2.67 kPa), crude, so-called " phenolic pitch of the following composition (% by weight): 0.2 alpha-methylstyrene; 13.3 acetophenone; 8.2 dimethylphenylcarbinol; 5.0 phenol; 36.2 cumylphenol; The 22.4 dimer of alpha-methylstyrene and the remainder are unidentified compounds. In the temperature range from 27 to 165 [deg.] C./36 psi, 28.3 wt. from a total batch of phenolic pitches, the fraction comprising (in% by weight): 3.5 alpha-methylstyrene; 30.9 acetophenone; 20.2 dimethylphenylcarbinol; 15.8 phenol; 12.3 dimer of alpha-methylstyrene and 3.9 cumylphenol. The distillation residue constituted 70.6% by weight. of the raw phenolic pitch floods having the following composition (% by weight): 0.6 alpha-methylstyrene; 1,2-acetophenone; 0.4 dimethylphenylcarbinol; 0.6 phenol; 47 cumylphenol and 31.1 dimers of alpha-methylsyrene.

Example 7

A portion of the fraction boiling at 165 to 210 ° C / 2.67 kPa distilled from phenolic pitch was treated with ethanolic sodium hydroxide at conc. 12% by weight to precipitate sodium cumyl phenolate, which is filtered off and dried at 40 ° C under reduced pressure. Sodium cumyl phenolate powder is then admixed as a disinfectant component in an amount of 0.25% by weight. in a detergent powder composition comprising sodium dodecylbenzenesulfonate, water glass, sodium perborate, sodium tripolyphosphate, a brightener, and a fragrance.

From the second fraction of boiling point 165 to 210 ° C / 2.67 kPa potassium cumyl phenolate is prepared as a bacteriostatic and antifungal agent by treatment with an aqueous potassium hydroxide solution with conc. 15 wt. with vigorous stirring. After the separation of the potassium cumyl phenolate, this is added in an amount of 0.6% by weight. % to a liquid detergent consisting of 26 wt. % sodium dodecylbenzenesulfonate, 12 wt. urea, 5 wt. % lauryl ethanolamide and 57 wt. water.

Example 8

Of phenolic pitch (13-417) containing

16.7% wt. % acetophenone, 8.3 wt. % dimethylphenylcarbinol, 4.9 wt. phenol,

20.8% wt. alpha-methylstyrene dimers; and

36.7 wt. cumylphenol containing 94% rel. p-cumylphenol [2-cumylphenol, respectively. phenol-4- (1-methyl-1-phenylethyl)] and 6% rel. o-cumylphenol [4-cumylphenol, respectively. phenol-2- (1-methyl-1-phenylethyl) u), the first fraction of m.p. in. 27 to 165 degrees Celsius / 2.67 kPa in an amount of 28.3% by weight, calculated from the starting phenolic pitch. This fraction contains 0.9 wt. % alpha-methylstyrene, 35.4 wt. % acetophenone, 27.0 wt. % dimethylphenylcarbinol, 17.5 wt. % phenol, 7.8 wt. % of alpha-methylstyrene dimers, 3.2 wt. cumylphenol and the remainder are unidentified organic compounds.

Further distillation gave II. a fraction of 165 to 205 ° C / 2.67 kPa in an amount of 49.1 wt. and the distillation residue is 20.3%. Earned II. the fraction has the following composition (% by weight): alpha-methylstyrene = 0.2; alpha-methylstyrene dimers = 34.9; acetophenone equals 0.1; dimethylphenylcarbinol - 0.4; phenol = 0.4 and cumylphenol = - = 39.7. From this II. fractions were collected 50 g, was added to 75 g of n-hexane and stirred, the sample is cooled to 0 C ^c, which falls cumylphenol which is filtered, washed on the filter with cold n-hexane and dried. 21 g of cumylphenol of 99% purity are obtained, consisting of 5% o-cumylphenol (2-cumylphenol) and 94% of p-cumylphenols (4-cumylphenol), the impurities being 0.03% by weight. acetophenone, 0.01 wt. % dimethylphenylcarbinol, 0.05 wt. % phenol and 0.4 wt. dimers of alpha-methylstyrene.

In a second variant, 70 g II is taken. fractions, allowed to cool to 0 ° C and the precipitated cumylphenol was filtered off, washed with cold n-hexane on the filter, dried and weighed. 18.2 g of cumylphenol are obtained.

In the third variant, 70 g II. 100 g of aqueous sodium hydroxide solution with conc. 10% wt. The precipitated mainly sodium cumyl phenolate is filtered off, washed on the filter with an organic solvent and dried. 55 g of sodium cumylphenolate are obtained.

Example 9

The antibacterial and antifungal effect of cumylphenol, tricresol (cresolum detergents), phenolic pitches and the phenolic pitch distillation residue with a boiling point above 165 ° C / 2.67 kPa is investigated. % specified in Example 6, forming 70.6 wt. from raw phenolic pitch floods containing 47% by weight cumylphenol (1.2% acetophenone; 0.4% dimethylphenylcarbinol; 0.6 percent alpha-methylstyrene and 31% dimers. alpha-methylstyrene). The substances are prepared in the form of a detergent (sodium cumylphenolate) containing 15% of the active ingredient. For experiments, solutions of concentration 1 are used; 2.5 and 5%. The potency is expressed as a value of at least 1 inhibitory concentration (MIC) in µg of active ingredient per ml of medium. As the preparations have a strong alkaline character, the established methodologies (dilution - dilution and diffusion - disk method) cannot be used. Therefore, a modified method is used in which the inoculum of microorganisms and a certain concentration of the substance are added to the prepared warm (42 O agar) and this is poured onto an agar layer on Petri Nile.

The effect is. SPEECH! so that the cells do not grow and remain valid sterile. The last agar plate, which is sterile in a series of dilutions, is the last concentration with inhibitory effect. The MIC values of two disinfectants (in ng / ml) on bacteria, fungi and yeast are shown in Table 2 and so-called " phenolic pitch, as specified in Example 6, as well as the fraction thereof boiling above 265 ° C / 2.67 kPa in Table 3.

244569 11 Table 2 12 MIC values in µg / ml of active substance tribe ^: Disinfectant cumylphenol cresol bacteria Bacillus cereus 500 500 Sarcina lutea 175 500 Sarcina subflava 32 250 Bacillus pumilis 320 320 Bacillus subtilis 32 135 Staphylococus epidemis 500 500 Escherichia coli 62 320 Proteus mirabilis 250 500 Proteus vulgaris 250 500 Streptococus pyogenes 320 500 Staphylococus aureus 175 320 Proteus aeruginosa 175 320 Yeast and mold Candida albicans 150 500 Sacaromyces cerevisiae 75 500 Candida crusei 75 320 Candida pseudotropicalis 50 320 Clockera apikulata 50 500 Aspergillus niger 125 200 Trichophyton mentagrophyíes 40 320 Trichophyton rubrum 50 T a b u Ϊ k a 3 500

MIC values in μν / ml of the active substance. Fen pitches and extracts thereof boiling above 165 ° C / 2.67 kPa.

Claims (3)

244569 11 Table 2 12 MIC values in µg / ml active substance Strain: Disinfectant cumylphenol cresol Bacillus cereus bacterium 500 500 Sarcina lutea 175 500 Sarcina subflava 32 250 Bacillus pumilis 320 320 Bacillus subtilis 32 135 Staphylococus epidemis 500 500 Escherichia coli 62 320 Proteus mirabilis 250 500 Próteus vulgarls 250 500 Streptococus pyogenes 320 500 Staphylococus aureus 175 320 Proteus aeruginosa 175 320 Yeast and mold Candida albicans 150 500 Sacaromyces cerevisiae 75 500 Candida crusei 75 320 Candida pseudotropicalis 50 320 Clockera apikulata 50 500 Aspergillus niger 125 200 Trichophyton mentagrophyíes Trichophyton rubrum 50 T abu 3 500 MIC values in μ / ml of the active layman, the so-called feo + cms, and their leaching with a temperature above 165 ° C / 2.67 kPa. Strain / '' Phenolic resin disinfectant fraction above 165 ° C / 2.67 kPa from phenol pitch Próteus mirabilis 640 320 Escherichia coli 320 160 Próteus aeruginosa 640 320 Staphylococus aureus 160 160 Bacillus subtilis 320 320 Proteus vulgaris 640 320 Streptococus pyogenes 320 320 PRE DMET A method for obtaining a disinfectant composition and / or a disinfectant composition based on phenolic derivatives and / or corresponding alkali metal and / or earth phenolates, or ammonium phenolates, characterized in that it is obtained from crude products catalysed decomposition of hydroperoxide to phenol and acetone, and one of the processes including isolation of the distillation residue, so-called phenolic salts, with a cumene phenol content of 16 to 50% by weight, conversion of cumylphenols and phenol from phenol pitch to phenolates, isolation by distillation from phenol a pitch fraction of 30 to 80% cumylphenol, isolation of the phenol from this fraction by crystallization or extractive crystallization at a temperature of + 10 to -30 ° C with the addition of at least one saturated C 5 to C 12 hydrocarbon the crystallized cumylphenol, usually after washing with a cold extractant, is separated or converted to cumylphenol to cumene by treating at least one alkali metal hydroxide or earth, optionally ammonia or ammonium hydroxide, and separating cumylphenolate or converting already isolated cumylphenol cumylphenolate, the final treatment being dependent upon the application being determined; a powder or solution having a concentration of 0.01 to 20 wt. active ingredient. 2. A method for obtaining a disinfectant composition and / or a disinfectant composition according to claim 1, wherein the 4-cumylphenol and the 2-cumylphenol are also transferred, optionally also phenol to the corresponding phenols, by the action of at least one from alkali metal or earth metal hydroxides, preferably in the form of an aqueous and / or alcoholic solution, and with effective stirring. 3. A method for obtaining a disinfectant and / or disinfectant composition according to claim 1, wherein the cumylphenol is isolated from the phenol pitch containing 30-80% cumylphenol by extractive crystallization with at least one activity. n-alkanes C 5 to C 12, preferably n-alkan C 6 to C 8, or a mixture of hydrocarbons having an n-alkane content of 50 to 100%, preferably the extractant is recovered by distillation.