JPH0363538B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel polyoxylic acid produced by first adding propylene oxide and then adding ethylene oxide to a secondary alcohol obtained by boric acid oxidation of n-paraffin having 10 to 15 carbon atoms. This invention relates to a method for producing propylene polyoxyethylene alkyl ether. Ethoxylates of secondary alcohols have superior wetting power, penetrating power, solubility, emulsifying power, and detergency compared to ethoxylates of primary synthetic alcohols and natural alcohols, so they are used as general cleaning agents and in the textile industry. It is widely used in various fields such as , paper and pulp industry, and metal industry. Such secondary alcohol ethoxylates have different interfacial properties depending on the number of carbon atoms in their alkyl groups. For example, a secondary alcohol ethoxylate with an alkyl group having 10 to 12 carbon atoms has good penetration power, and a secondary alcohol ethoxylate with an alkyl group having 12 to 14 carbon atoms has good penetration power and detergency. This secondary alcohol ethoxylate has excellent detergency. Among these, alkyl group having 10 to 12 carbon atoms or 12 to 12 carbon atoms
Secondary alcohol ethoxylates with 14 carbon atoms are already on the market and are widely used, but those with alkyl groups of 15 or more carbon atoms have unique properties but are difficult to process. Due to constraints, commercialization has been postponed to this day. In other words, an increase in the number of carbon atoms in the alkyl group raises the boiling point of the secondary alcohol, so the distillation conditions essential for purifying and separating the secondary alcohol become stricter. Distilling alcohol requires a much higher degree of vacuum than conventional conditions to prevent decomposition at high temperatures, which increases equipment and utility costs, and most alcohols with a large number of carbon atoms cannot be distilled. I have a problem that makes it impossible. The present inventors have discovered that this alcohol has a high detergency equivalent to that of a secondary alcohol ethoxylate with an alkyl group having more than 15 carbon atoms, and has excellent wetting power, penetrating power, and solubility that are characteristic of secondary alcohols. As a result of intensive research to develop a nonionic surfactant with emulsifying power, propylene oxide was added at a specific ratio to a random secondary alcohol obtained by oxidizing n-paraffin with boric acid in the presence of an acid catalyst. After removing the acid catalyst and unreacted alcohol from the reaction solution, a product to which ethylene oxide is added in the presence of an acid or base catalyst has excellent detergency, and has excellent cleaning properties that are characteristic of secondary alcohol ethoxylates. The present invention has been completed by discovering that it has excellent wetting power, penetrating power, solubility, emulsifying power, etc., and can be used as a substitute for secondary alcohol ethoxylates having more than 15 carbon atoms, which are difficult to manufacture. The present invention is a method for producing polyoxypropylene polyoxyethylene alkyl ether obtained by adding propylene oxide and ethylene oxide to a secondary alcohol obtained by boric acid oxidation of n-paraffin having 10 to 15 carbon atoms. In the presence of a catalyst, 1.5 to 6.0 moles of propylene oxide are added to the secondary alcohol based on the average number of moles added after removing unreacted alcohol, then the acid catalyst contained in the reaction solution is removed, and then propylene oxide is added by distillation. A polyoxypropylene polyoxyethylene alkyl, characterized in that the unreacted alcohol is distilled off until the unreacted alcohol content in the product becomes 1.0 weight percent or less, and ethylene oxide is added to the obtained propylene oxide adduct. This invention relates to a method for producing ether. The starting material of the present invention is a secondary alcohol obtained by boric acid oxidation of n-paraffin having 10 to 15 carbon atoms. In the case of alcohols with an alkyl group having less than 10 carbon atoms, even if propylene oxide is added, the detergency will be poor and it will not be practical, and in the case of alcohols with more than 15 carbon atoms, there will be production problems and it will not be practical. isn't it. In order to obtain a propylene oxide adduct with a narrow distribution of addition moles necessary to achieve the object of the present invention, the catalyst used for the addition of propylene oxide is preferably an acid catalyst. When propylene oxide is added to a secondary alcohol in the presence of a base catalyst, the distribution of the number of moles added to propylene oxide becomes unnecessarily wide. The fluidity of the ether is poor and the detergency is also reduced, making it impossible to obtain a substitute for alcohol ethoxylates having more than 15 carbon atoms, which is the object of the present invention. Examples of acid catalysts used in the present invention include mineral acids such as sulfuric acid and phosphoric acid, and Lewis acids such as tin tetrachloride and boron trifluoride. From this point of view, tin tetrachloride, antimony pentachloride, boron trifluoride, or complexes thereof are particularly suitable as catalysts. The amount of acid catalyst used is 0.01 to 3.0% by weight, preferably 0.1 to 3.0% by weight, based on the secondary alcohol obtained by boric acid oxidation of n-paraffin having 10 to 15 carbon atoms.
1.0 weight percent used. The reaction pressure is from normal pressure to 20Kg/cm ² G, preferably from 1 to 10Kg/cm ²
G, and the reaction temperature is 20~130℃, preferably 30~
It is carried out at 100℃. The above propoxylation reaction can be carried out batchwise, continuously, or by any method. The acid catalyst contained in the reaction solution after propoxylation can be removed by washing the reaction solution after propoxylation with water or an alkaline aqueous solution in the catalyst removal step to transfer the acid catalyst to the aqueous layer. . The cleaning conditions are not particularly limited, but include cleaning at 20 to 150℃ in a stirring tank or line mixer;
It is preferably washed at a temperature of 50 to 100°C, and then allowed to stand to separate the organic and aqueous layers and remove the catalyst. The organic layer from which the catalyst has been removed is then subjected to a distillation step to remove unreacted alcohol. Here, it is necessary to keep the unreacted alcohol content in the propylene oxide adduct to 1.0 weight percent or less. If the amount of unreacted alcohol exceeds 1.0% by weight, the detergency will decrease, making it impossible to obtain a surfactant having the properties of the present invention. The main purpose of the present invention is to add propylene oxide to achieve a detergency equal to or greater than that of alcohol ethoxylate, which has a larger number of carbon atoms than the raw alcohol. However, even if the number of moles of propylene oxide added is too small, Further, if the amount is too large, the detergency will not be improved, and the average number of moles of propylene oxide added after removing unreacted alcohol is preferably in the range of 1.5 to 6.0 moles. When the average number of moles of propylene oxide added is less than 1.5, no improvement in detergency is observed, and when it exceeds 6.0, the detergency is still reduced and the object of the present invention cannot be achieved. In this way, propylene oxide is added to a random secondary alcohol having 10 to 15 carbon atoms in the presence of an acid catalyst, and the unreacted alcohol is distilled off, resulting in an average number of added moles of 1.5 to 6.0 moles.Propoxylate is produced as follows. The final product, a polyoxypropylene polyoxyethylene alkyl ether surfactant, can be obtained by adding ethylene oxide to the surfactant. The final product pass-through may be omitted if the salt concentration in the product is low. Ethylene oxide can be added to the propylene oxide adduct by a known method in the presence of an acid or base catalyst, and the number of moles added can be determined depending on the intended use. Ethoxylation conditions are not particularly limited, but generally NaOH or KOH is used and the pressure is 1 to 1.
30Kg/ ^cm2G , preferably 2-15Kg/ ^cm2G , temperature
It can be carried out at 100-180°C, preferably 120-160°C. After adding ethylene oxide, a solid acid such as sulfuric acid, acetic acid, or activated clay can be used as a neutralizing agent when the catalyst is neutralized to obtain a polyoxypropylene polyoxyethylene alkyl ether surfactant. The entire production process from random secondary alcohol to obtaining the final product polyoxypropylene polyoxyethylene alkyl ether may be carried out continuously, or some or all of the steps may be carried out in batches. Next, the method for producing polyoxypropylene polyoxyethylene alkyl ether according to the present invention will be explained with reference to FIG. In Figure 1, boron trifluoride is added as a catalyst from line 3 to the secondary alcohol supplied from line 1 and the recovered unreacted alcohol circulated from line 2, and the mixture is mixed into the propoxylation step 6 through line 4. On the other hand, propylene oxide is supplied from line 5 to propoxylation step 6, and the propoxylation reaction is carried out at a pressure of 1 to 5 kg/cm ² G and a temperature of 50 to 70°C. After the aging, the reaction solution is supplied to the catalyst removal step 8 through line 7, washed by supplying from line 9 an aqueous NaOH solution with a mole of 4 times that of boron trifluoride supplied as a catalyst from line 3, and then removed from line 10 as a catalyst. remove.
The reaction liquid from which the catalyst has been separated is supplied to a distillation column 12 via a line 11, and unreacted alcohol is recovered by distillation and recycled to a propoxylation step 6 via a line 2. The propoxylate in the lower part of the distillation column 12 is introduced via line 13 and then through line 14.
It is mixed with NaOH or KOH and supplied to the ethoxylation step 15. In the ethoxylation step 15, ethylene oxide is supplied from the line 16 and the pressure is 2.
The ethoxylation reaction is carried out at ~10 Kg/cm ² G and a temperature of 130-150°C. The reaction solution that has been aged is supplied to a neutralization step 18 via a line 17, neutralized with acetic acid supplied as a neutralizing agent via a line 19, and the neutralized product is supplied to a secondary step 21 via a line 20. Polyoxypropylene polyoxyethylene alkyl ether is obtained through line 22 after passing through the salt. Further, Table 1 shows the detergency, foaming power, and penetration power of the surfactant according to the present invention. As is clear from Table 1, the polyoxypropylene polyoxyethylene alkyl ether obtained by the production method of the present invention has superior detergency compared to that without addition of propylene oxide, and has superior detergency to that of the ethoxylate of alcohol with a larger number of carbon atoms. Even if compared, it is more than the same. In addition, the surfactant of the present invention has excellent penetration power, solubility, and emulsifying power,
The characteristic that the alkyl group is secondary is not lost. Furthermore, the surfactant according to the present invention has a characteristic of being less foaming than the ethoxylate of raw alcohol, and can be used in many fields. For example, examples of industrial cleaning agents that utilize excellent cleaning power include scouring cleaning agents for textiles, cleaning agents for machinery and metals, deresin removal agents for paper and pulp, deinking agents, and degreasing agents for leather. In addition, other fields where good emulsifying power is utilized include use as an emulsifier or dispersant in the rubber/plastic industry, petroleum/coal industry, etc. Examples will be described below, but the present invention is not limited to the following examples. Example 1 Internal volume 1500ml with thermometer, pressure gauge and stirrer
Autoclave a random second carbon number 12-14
After charging 590 g of grade alcohol (hydroxyl value 279) and 3.2 g of boron trifluoride ether complex as an acid catalyst and sufficiently replacing the inside of the autoclave with nitrogen,
Heating it to ℃ and feeding 410g of propylene oxide,
Propoxylation was performed. Next, the reaction solution was mixed with 4 times the mole of boron trifluoride.
The catalyst was removed by heating and washing with an aqueous NaOH solution and then washing twice with water. After dehydration, the reaction solution was distilled under reduced pressure of 10 mmHg until the content of unreacted alcohol was 1.0 weight percent or less. The resulting propoxylate has a hydroxyl value
150, the average number of moles of propylene oxide added is 3.0
It was hot. Next, 486 g of the propoxylate and 1 g of KOH were placed in an autoclave similar to that used in the propoxylation reaction, and after the interior of the autoclave was sufficiently purged with nitrogen, the autoclave was heated to 140° C. to react with 514 g of ethylene oxide. The mixture was then neutralized with acetic acid to obtain a 9 mol ethylene oxide adduct. Table 1 shows the interfacial properties of the obtained product. Example 2 In Example 1, the second random number having 12 to 14 carbon atoms
The reaction was carried out under the same reaction conditions and operations as in Example 1, except that a propylene oxide adduct having an average addition mole number of 3.0 mols of alcohol was ethoxylated in the same manner as in Example 1 to obtain a 12 mol ethylene oxide adduct. Table 1 shows the interfacial properties of the obtained product. Comparative example 1 Internal volume 1500ml with thermometer, pressure gauge and stirrer
Autoclave a random second carbon number 12-14
After charging 740 g of grade alcohol (hydroxyl value 279) and 3.2 g of boron trifluoride ether complex as an acid catalyst and sufficiently purging the inside of the autoclave with nitrogen,
It was heated to 0.degree. C. and 260 g of ethylene oxide was supplied to carry out an ethoxylation reaction. Next, the reaction solution was mixed with 4 times the mole of boron trifluoride.
The catalyst was removed by heating and washing with an aqueous NaOH solution and then washing twice with water. After dehydration, the reaction solution was distilled under reduced pressure of 10 mmHg until the content of unreacted alcohol was 1.0 percent by weight or less. The resulting ethoxylate has a hydroxyl value of 168
The average number of moles of ethylene oxide added was 3.0. Next, 558 g of the ethoxylate and 1 g of KOH were placed in an autoclave similar to the one used in the ethoxylation reaction, the interior of the autoclave was sufficiently purged with nitrogen, and then heated to 140° C. to react with 442 g of ethylene oxide. The mixture was then neutralized with acetic acid to obtain a total of 9 moles of ethylene oxide adduct. Table 1 shows the interfacial properties of the obtained product. Comparative Example 2 In Comparative Example 1, a random second sample having 12 to 14 carbon atoms
The reaction was carried out under the same reaction conditions and operations as in Comparative Example 1, except that an ethylene oxide adduct with an average number of moles of ethylene oxide added of 3.0 was ethoxylated in the same manner as in Comparative Example 1, resulting in a total of 12 moles of ethylene oxide. . Table 1 shows the interfacial properties of the obtained product.
Shown below. Comparative example 3 Internal volume 1500ml with thermometer, pressure gauge and stirrer
Autoclave a random second carbon number 14-16
After charging 765 g of grade alcohol (hydroxyl value 245) and 3.2 g of boron trifluoride ether complex as an acid catalyst and sufficiently replacing the inside of the autoclave with nitrogen,
It was heated to 0.degree. C. and 235 g of ethylene oxide was introduced to carry out an ethoxylation reaction. Next, the reaction solution was mixed with 4 times the mole of boron trifluoride.
The catalyst was removed by heating and washing with an aqueous NaOH solution and then washing twice with water. After dehydration, the reaction solution was distilled under reduced pressure of 10 mmHg until the content of unreacted alcohol was 1.0 weight percent or less. The resulting ethoxylate has a hydroxyl value of 155
The average number of moles of ethylene oxide added was 3.0. Next, 579 g of the ethoxylate and 1 g of KOH were placed in an autoclave similar to the one used in the ethoxylation reaction, and after the interior of the autoclave was sufficiently purged with nitrogen, it was heated to 140° C. to react with 421 g of ethylene oxide. The mixture was then neutralized with acetic acid to obtain a total of 9 moles of ethylene oxide adduct. Table 1 shows the interfacial properties of the obtained product. Comparative Example 4 In Comparative Example 3, a random second carbon number of 12 to 14
The reaction was carried out under the same reaction conditions and operations as in Comparative Example 1, except that an ethylene oxide adduct with an average number of moles of alcohol added of 3.0 was ethoxylated in the same manner as in Comparative Example 3, resulting in a total of 12 moles of ethylene oxide adduct. . Table 1 shows the interfacial properties of the obtained product.
Shown below. 【table】

[Brief explanation of drawings]

The drawing is a system diagram showing one example of implementation of the present invention. 1... Secondary alcohol supply line, 2... Recovered unreacted alcohol circulation line, 3... Acid catalyst supply line, 5... Propylene oxide supply line, 6... Propoxylation process, 8... Catalyst removal process, 9... Alkali supply line, 12... Distillation column, 14... Alkali supply line, 15... Ethoxylation process, 16... Ethylene oxide supply line, 18... Neutralization process, 19...
Neutralizing agent supply line, 21... Passing process, 22... Polyoxypropylene polyoxyethylene alkyl ether take-out line.

Claims (1)

[Claims] 1. A method for producing polyoxypropylene polyoxyethylene alkyl ether obtained by adding propylene oxide and ethylene oxide to a secondary alcohol obtained by boric acid oxidation of n-paraffin having 10 to 15 carbon atoms. First, propylene oxide is added to the secondary alcohol in the presence of an acid catalyst in terms of the average number of moles added after removing unreacted alcohol.
1.5 to 6.0 mol of propylene oxide is added, then the acid catalyst contained in the reaction solution is removed, and the unreacted alcohol content in the propylene oxide adduct is reduced by distillation.
A method for producing polyoxypropylene polyoxyethylene alkyl ether, which comprises distilling off the unreacted alcohol until it becomes 1.0 weight percent or less, and adding ethylene oxide to the obtained propylene oxide adduct. 2. The method according to claim 1, wherein the acid catalyst contained in the reaction solution is removed by washing with water or an aqueous alkaline solution.