The method of obtaining alkoxyacetic acids or their salts

 

(57) Abstract:

The invention relates to an improved method for producing alkoxyacetic acids (AUC) or their salts, which are used as surface-active substances, intermediates for the synthesis of pharmaceuticals and plant protection products. Get APK interaction relevant oxicological esters of alcohols or phenols with oxygen-containing gas in an aqueous-alkaline medium in the presence of a heterogeneous catalyst is palladium on a carbon carrier, when the molar ratio of oxygen : the original broadcast at the entrance to the reactor is from 0.01 to 1.1, the temperature of 80-140oC and a pressure of 1-10 MPa. Preferably the process is carried out in a vertical tubular reactor when submitting the initial reagents in the top of the reactor and used as the oxygen-containing gas is air. The proposed method allows to increase the specific productivity with 0,0052-0,0423 (prototype) to 0,043-0,433 mol/(g d). 5 C.p. f-crystals, 1 Il., table 2.

The invention relates to an improved method for producing alkoxyacetic acids (AUC) and their salts, which are used as surface-active substances, intermediates DL oxide ethylene M.: Chemistry, 1982, S. 672; N. M. Golchin "New fungicides and their use" J. WMO them. D. I. Mendeleev, T. 29, 4074, 1984.)

A method of obtaining alkoxyacetic acids and their salts interact chloracetate sodium and sodium alcoholate. (Medical industry of the USSR, 1962, 12,S. 24).

The disadvantages of this method are the high consumption of reagents, the formation of large quantities of waste, low yield of the target product.

A method of obtaining alkoxyacetic acids and their salts by the interaction of the oxygen-containing gas with oxyalkylation esters (GE) in an aqueous-alkaline solution at 50-95oAnd 0-3 ATI catalyst 1-10 wt.% palladium on coal (Patent England 1590614, MKI 07 With 51/235, 1981).

The main disadvantages of this method are the difficulties associated with separating fine catalyst from the viscous reaction mass, as well as the relatively low conversion of the original polyoxide-loglikelihood ether.

The closest analogue of this method is the method of obtaining alkoxyacetic acids or their salts interaction oxyalkylene esters of oxygen-containing gas in an aqueous-alkaline solution in the presence of a catalyst, Pallady ationary layer of catalyst. When this process is carried out in 1,14-30,19-fold molar excess of oxygen with respect to the original oxyalkylene esters. (Patent Of Russia 2008305).

The main disadvantage of this method is the low specific productivity of the process characterizing eat product (axialkuglelejer ether) in moles to grams of palladium in h, and which does not exceed the values 0,0052-0,0423 mol/(g d).

The proposed method allows to increase the specific productivity of the process.

This result is achieved by interaction of the respective oxicological ethers of alcohols and phenols with oxygen-containing gas in an aqueous-alkaline medium in the presence of a catalyst is palladium on a carbon carrier, at elevated temperature, while the oxidation process is carried out at a molar ratio of oxygen/oxicological ether =0,011,1.

The process can be carried out at 80-140oWith atmospheric or increased pressure. However, preferably the process is carried out at 90-110oAnd atmospheric pressure, and the ratio of oxygen/oxicological ether equal 0,11,0.

As the oxygen-containing gas can be used with oxygen or mixtures thereof with furnishings which can be carried out in the bubbling chamber with an agitator. However, preferably the process is carried out in a vertical tubular reactor with a fixed bed of catalyst.

Submission of initial reagents in the reactor can be implemented in different ways:

- when separate feeding gas (oxygen gas) and liquid (aqueous-alkaline solution oxicological esters);

- in the form of a mixture of gas with liquid emulsion of gas in a liquid or foam.

Source materials can be submitted in the bottom or the top of a vertical tubular reactor. It is preferable to submit the original of the substance or mixture in the top of a vertical tubular reactor.

The following examples illustrate the method:

The process was carried out using a flow-circulation of the installation shown in the drawing. The installation consisted of a tubular reactor with jacket (1), tube space of which is filled with a heterogeneous catalyst, capacity (2), equipped with a stirrer and a bubbler, a circulation pump (3) and a Packed column (4). To obtain an emulsion of gas in the liquid oxygen-containing gas was applied through a bubbler in the tank 2, and to get the foam in the bottom of the column 4.

Source oxicological esters, sodium hydroxide and water in tadpole temperature of the reaction mixture, equal to the temperature of the heat carrier, launched the circulation pump and the flow of oxygen-containing gas. The pressure in the reactor was maintained by a valve 8. The oxidation process led up to the desired degree of conversion of the original oxicological ethers.

Example 1

The process was carried out on the installation shown in the drawing. As reactor 1 used a vertical tubular reactor with a volume of 356 ml (d=36 mm, l=350 mm), tube space which was filled with a heterogeneous catalyst: 0.3 wt.% Pd on carbon storage Sibunit. The amount of catalyst, 300 ml, weight 180, the Total content of palladium in the reaction zone of 0.54, the atmospheric Pressure (the valve 8 is fully open).

As starting substances used oxicological esters of isononylphenol General formula: X-O(CH2CH2O)nN, where X=Ar-R, a R is a primary alkyl group WITH9. Hydroxyl number (MS) - 112,9, average molecular mass (MM) - 497, which corresponds to the average number of hydroxyethyl groups (n), equal 6,29.

In tank 2 was downloaded 181,2 g (0,365 mol) GE, 16,35 g (0,409 mol) of NaOH and 798,25 g ( 44,35 mol ) of water. The concentration of GE in the original charge 0,367 mol/kg Included a stirrer, feed teplosetstroy in the initial moment of time the molar feed rate at the inlet of the reactor source GE - 0,257 mol/H. After reaching the initial charge temperature equal to the temperature of the heat carrier, included the supply of oxygen-containing gas (oxygen) in the top of the reactor (valve 5 is opened, the valves 6 and 7 are closed) speed 0,224-5,22 l/h (0.01 to 0,233 mol/h), while maintaining the molar ratio of the flows of oxygen and GE at the entrance to the reactor in the range of 0.91 -1,1 and the temperature in the reactor in the range of 90-100oC. the oxidation Process was carried out for 15 hours the reaction mass was analyzed for salt content alkoxyacetic acids (AUC) method nonaqueous potentiometric titration (Siggia S., Hanna, Quantitative analysis of functional groups, M , Chemistry, 1983,S. 136). Received 0,352 mol sodium salt APK. The conversion of GE (X)-96,4%. Specific productivity (Gy) was: Gy=0,352/(150,54)= 0,0434 mol/(g Pd4).

The resulting reaction mass may be used directly for the preparation of detergent compositions.

To obtain alkoxyacetic acid reaction mass was acidified with concentrated hydrochloric acid and was extracted with chloroform. From the obtained chloroformate hood drove chloroform. Received 0,336 mol auctions with an acid number of 108. The output APK to 92.1 used a vertical tubular reactor volume to 150.7 ml (d= 20 mm, l = 480 mm), tube space of which is filled with a heterogeneous catalyst: 0.3 wt.% Pd on carbon storage Sibunit. The amount of catalyst 131 ml, weight 78,6 the Total palladium content 0,236, the atmospheric Pressure (the valve 8 is fully open).

As starting substances used oxicological esters of isononylphenol General formula: X-O(CH2CH20)nN, where X=Ar-R, a R is a primary alkyl group WITH9. The average number of hydroxyethyl groups (n) is equal 6,29, hydroxyl number (MS) - 112,9 and average molecular mass (MM)-497.

In tank 2 was downloaded 202,6 g (0,408 mol) GE, 16,26 g (0,406 mol) of NaOH and 798,4 g (44,34 mol) of water. The concentration of GE in the original charge 0,401 mol/kg Included a mixer, the flow of the coolant in the jacket of the reactor and the circulation pump 3 speed circulation of the mixture of 0.7 kg/h, which corresponds to the initial moment of time the molar feed rate at the inlet of the reactor source GE - 0,281 mol/H. After reaching the initial charge temperature equal to the temperature of the heat carrier, included the supply of oxygen-containing gas (oxygen) in the top of the reactor (valve 5 is opened, the valves 6 and 7 are closed) speed 0,63-of 1.26 l/h (0,0281-0,0563 mol/h)while maintaining the molar sootnoshenie is carried out with during 14,62 PM The resulting reaction mass was analyzed for salt content alkoxyacetic acids (AUC) method nonaqueous potentiometric titration. Received 0,368 mol sodium salt APK. The conversion of FF X=90,3%. The specific productivity was: Gy=0,107 mol/(g d).

Example 3

The process was carried out on the installation shown in the drawing. As reactor 1 used a vertical tubular reactor with a volume of 190 ml (d=24 mm, l= 420 mm), tube space of which is filled with a heterogeneous catalyst (0.3 wt.% Pd on charcoal brand AG-3. The amount of catalyst 174 ml, weight 80,1 the Total palladium content of 0.24, the atmospheric Pressure (the valve 8 is fully open).

As starting substances used oxicological esters of isononylphenol General formula: X-O(CH2CH2O)nN, where X=Ar-R, a R is a primary alkyl group WITH9. The average number of hydroxyethyl groups (n) 12,78, hydroxyl number (MS) - 71,6 and average molecular mass (MM)-783,1.

In tank 2 was downloaded 201,7 g (0,258 mol) GE, 13,15 g (0,329 mol) of NaOH and 789,05 g (43,84 mol) of water. The concentration of GE in the original charge 0,258 mol/kg Included a mixer, the flow of the coolant in the jacket of the reactor and the time the molar feed rate at the inlet of the reactor original GE -0,181 mol/H. After reaching the initial charge temperature equal to the temperature of the heat carrier, included the supply of oxygen-containing gas (oxygen) in the top of the reactor (valve 5 is opened, the valves 6 and 7 are closed) at a rate of 2.28 l/h for 10 h was gradually reduced the rate of oxygen supply to 0.4 l/h, maintaining the ratio of the molar flow O2/FF at the entrance to the reactor in the range of 0.56 to 0.60. After that he switched the oxygen flow through the bubbler in the tank 2, i.e., directly in the reaction mass (valves 5 and 7 are closed; the valve 6 is opened), and was applied to the reactor inlet 1 emulsion of gas (oxygen) in the liquid. Continued gradually over 2 h to reduce the feed rate of oxygen from 0.4 to 0.14 l/h, while maintaining the molar ratio of threads ABOUT2/FF at the entrance to the reactor at 0.5. The total synthesis time is 12 hours, the temperature in the reactor 80-130oC. the resulting reaction mass was analyzed for salt content alkoxyacetic acids (AUC) method nonaqueous potentiometric titration. Received 0.24 mol sodium salt APK. X = 93,02%. The specific productivity was: Gy=0,083 mol/(g d).

Example 4

The process was carried out analogously to example 3, but after 10 h oxidation off the rest is nitrogen) at a rate of 2 l/h in the bottom of the Packed column 4 (valve 7 is opened, the valves 5 and 6 are closed). Thus obtained in column 4 foam was sent to the inlet of the reactor. The molar ratio of flows O2/FF inlet in the reactor was maintained at a level of 0.01 to 0.3. The total synthesis time is 20 hours, the temperature in the reactor 90-140oC. Received 0.25 mol of sodium salt APK. X = 96.9 percent. The specific productivity was: Gy=0,052 mol/(g d).

Examples 5-17

The process was carried out in the reactor described in example 3, feeding on the oxidation of other oxicological esters. Conditions and results are shown in tables 1 and 2.

Thus the process in this way allows you to increase the specific productivity with 0,0052-0,0423 (prototype) to 0,043-0.433 mol/(g Pd).

1. The method of obtaining alkoxyacetic acids or their salts of General formula

HO(CH2CH2O)nCH2CO2A,

where a is a hydrogen atom, sodium, potassium;

X is a primary or secondary alkyl group containing from 1 to 20 carbon atoms, an aromatic group (-ArR), containing as substituent R is hydrogen or primary or secondary or tertiary alkyl group with the number of carbon atoms from kislorodsodyerzhascimi gas in an aqueous-alkaline medium in the presence of catalyst palladium on a carbon carrier, at elevated temperature, characterized in that the process is carried out at a molar ratio of oxygen : the original broadcast at the entrance to the reactor is from 0.01 to 1.1.

2. The method according to p. 1, characterized in that as the oxygen-containing gas using the air.

3. The method according to p. 1, wherein the process is carried out in a vertical tubular reactor with a fixed bed of catalyst.

4. The method according to p. 3, characterized in that the source reagents are served at the top of the reactor.

5. The method according to p. 3, characterized in that the source reagents are served in the form of an emulsion of gas in the liquid.

6. The method according to p. 3, characterized in that the source reagents are served in the form of foam.

 

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