JPS609040B2 - Manufacturing method of nonionic surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a nonionic surfactant consisting of polyoxyalkylenated sucrose fatty acid ester.

Sucrose has eight hydroxyl groups in one molecule and is an industrially inexpensive raw material, so in recent years it has attracted attention as a hydrophilic raw material for surfactants. Many activators are also known. Up to now, a few methods are known for producing polyoxyalkylenated sucrose fatty acid esters (hereinafter referred to as POASE).

Attempts have been made to obtain POASE with high purity by uniformly dissolving sucrose in an organic solvent such as dimethylformamide, dimethylacetamide, or acylmorpholines, and reacting the sucrose with alkylene oxide in the presence of an alkali. polyoxyalkylenated sucrose (hereinafter referred to as POAS)
After obtaining POA, it is esterified using fatty acids, fatty acid esters, fatty acid halides, triglycerides, etc.
Methods of obtaining SE are known.

(Japanese Patent No. 300, 215). However, this method has the drawbacks that the solvent used in polyoxyalkylenation is toxic and expensive, and that it is difficult to completely remove the parenthesized solvent. Furthermore, a method for obtaining POASE by simultaneously reacting sucrose, fat and oil, and alkylene oxide in the presence of an alkali is also known (Tsubaki Kosho No. 46-11040).

However, in addition to POASE, what was obtained with this method was
It contains monoglycerides, diglycerides, fats and oils, sucrose fatty acid esters, oxylene alcohols of monoglycerides and diglycerides, and its performance is quite different from that of POASE alone. Furthermore, since it is a mixture, it is difficult to provide the desired performance, which is an extremely disadvantageous drawback in terms of the manufacturing method. Furthermore, ``a continuous addition reaction of sucrose and alkylene oxide in the presence of water or steam''
Report by JGW, Maistre et al.: J. big. Che
m. 13, 782 [1948]) or a two-step addition reaction (Japanese Patent No. 490-74), and a method of producing POAS by reacting a two-step addition reaction product with a fatty acid, a fatty acid ester, or a fatty acid halide. A method for producing it (Tsubaki Kaisho 49-108012) is also known.

However, according to this method, it is inevitable to create a large amount of alkylene glycol or polyalkylene glycol at the stage of producing POAS, and therefore POASE contains a large amount of alkylene glycol fatty acid ester or polyalkylene glycol fatty acid ester, The performance is also different from that of POASE alone. Furthermore, since the obtained product is a mixture, it is technically difficult to provide the desired performance, and furthermore, it is extremely difficult to separate POASE from these mixtures. Furthermore, according to this method, significant coloring is observed during the production of POAS. Furthermore, the reaction is also quite slow. The present inventors have conducted various studies to overcome these deficiencies in the production of POASE, and have found that ``no organic solvents are used and large amounts of alkylene glycol or polyalkylene glycol are generated during the production of POAS.'' According to this method, during the production of POAS, the amount of alkylene glycol or polyalkylene glycol created is extremely small, the reaction is completed in an extremely short time, and there is almost no coloration. I can't do it.

The present invention produces highly purified polyoxyalkylenated sucrose (POAS) by reacting rice bran and alkylene oxide in the presence of water and a small amount of alkylene glycol through a continuous addition reaction or a two-step addition reaction, This is a method for producing a nonionic surfactant, which is characterized in that this is then reacted with a fatty acid, a fatty acid halide, a fatty acid ester, or a triglyceride to obtain a highly purified polyoxyalkylenated sucrose fatty acid ester (POASE). According to the present invention, highly pure and high performance POASE can be produced industrially at low cost and in high yield.

That is, according to the production of the present invention, POAS is first produced by adding alkylene oxide to sucrose by Renji addition reaction or two-step addition reaction in the presence of water and a small amount of alkylene glycol, and then producing a yellow sticky rice liquid. However, both the continuous addition reaction and the staged addition reaction have extremely high reaction rates and are completed explosively in a short period of time. In the case of a continuous addition reaction and a two-stage addition reaction, the water used hardly reacts with the alkylene oxide during the addition reaction and remains in the system as water, and in the case of a continuous addition reaction, the addition reaction does not occur. After completion, in the case of a two-stage addition reaction, after addition of 1 to several moles of alkylene oxide per molecule of sucrose, the remaining water is completely removed. In the case of a two-stage addition reaction, a desired amount of alkylene oxide is further added after water is removed. The highly purified POAS thus obtained is reacted with fatty acids, fatty acid halides, fatty acid esters, or triglycerides to produce highly purified POAS.
Obtain ASE. The core of the present invention is to suppress the production of alkylene glycol or polyalkylene glycol in the created product by adding alkylene oxide to a small amount of alkylene glycol in an aqueous solution of sucrose when producing POAS. However, this method, which seems contradictory at first glance, is thought to be because the presence of a small amount of alkylene glycol increases the reactivity between sucrose and alkylene oxide, and as a result, side reactions between alkylene oxide and water are suppressed. .

In fact, ``When producing POAS, adding alkylene oxide to an aqueous sucrose solution without adding alkylene glycol as in the present invention requires an extremely long time compared to the method of the present invention. In the case of the present invention, it is possible to avoid the use of expensive and toxic organic solvents as disclosed in Japanese Patent Nos. 300 and 215. Deki, special public service 1977-1040
It is possible to prevent the production of large amounts of various by-products such as No. 9, and also J. W. Report by Hi Maistre et al., Japanese Patent No. 49
It is possible to prevent the production of large amounts of alkylene glycol or polyalkylene glycol during the production of POAS such as No. 074 and Samurai Publication No. 49-108012. More specifically, the production of the present invention is carried out as follows.

In the production process of POAS, firstly, sucrose is added to a reaction vessel, water is added at a ratio of 20 to 10% by weight to the sucrose, and 1% water is added to the sucrose.
To ~1% by weight of alkylene glycol and sucrose, 0.001 to 0.5% by weight of caustic soda, caustic potassium amine, and an alkali catalyst such as sodium methylate are added, and this is heated to 80 to 120 CO to make it transparent. Make a syrupy liquid.

The ratio of water to sucrose is preferably the minimum amount that turns sucrose into a transparent syrupy liquid when heated, and adding more water than this is unnecessary because the water will be removed after alkylene oxide addition is complete; 4 weight percent is preferred.

Also, the ratio of alkylene glycol to sucrose is 5
-7% by weight is preferred; if the proportion is less than this, the reaction rate of the alkylene oxide addition reaction decreases as the amount of alkylene glycol decreases, resulting in the production of a large amount of alkylene glycol or polyalkylene glycol.

In addition, when the proportion of alkylene glycol is 5 to 7% by weight or more, the reaction rate of alkylene oxide addition reaction is 5%.
It is almost the same as the case of ~7% by weight, and only increases the amount of alkylene glycol or polyalkylene glycol by-product in POAS. Alkylene oxide such as ethylene oxide or propylene oxide is added to the sucrose syrupy liquid at a temperature of 80 to 140°C under a pressure of 1.0 to 1.0.
Introduced at 7.0k9/ground.

The addition temperature of alkylene oxide is preferably as low as possible, and is preferably 80 to 120 oo since sucrose decomposes as the temperature increases. The reaction proceeds explosively in a very short time, but at the same time it also generates a large amount of heat, so it is necessary to use an additional device equipped with a cooling device, and during the addition reaction, the temperature should not exceed 140 qC. It must be controlled using water. As the reaction progresses, the pressure decreases, and when the pressure returns to normal, water is completely removed under reduced pressure.

After adding the desired amount of alkylene oxide in the case of a continuous addition reaction, or after adding 1 to several moles of alkylene oxide per molecule of sucrose in the case of a two-step addition reaction, the remaining water is completely removed. to be removed. In the case of a two-stage addition reaction, after water is removed, a desired amount of alkylene oxide is further added under exactly the same conditions as in the first-stage reaction. The reaction product remains a yellow viscous liquid even after water is removed.

In both the continuous addition reaction and the two-step addition reaction, the amount of alkylene oxide introduced can be freely changed depending on the desired performance of POASE, but it is
It is preferably less than mol.

If the amount of alkylene oxide introduced increases, the specificity and biodegradability as a POASE will tend to be compromised, so it is more preferable to introduce up to about 25 mol. The POASE reaction product obtained by the above reaction is subjected to alkali catalyst purification treatment such as acid neutralization and sieving, and is used in the next POASE production process.

The alkylene glycol used in the present invention is an alkylene glycol having an alkylene group having 2 to 5 carbon atoms, and includes ethylene glycol, propylene glycol,
Examples include hexylene glycol, but ethylene glycol is preferred in terms of economy and effectiveness.

The alkylene oxides used in the present invention are ethylene oxide and propylene oxide, but if only propylene oxide is used, the resulting POASE is not water-soluble and is therefore impractical.

However, in the present invention, the amount of created alkylene glycol or polyalkylene glycol when producing POASE is similarly small whether ethylene oxide or propylene oxide is used. P.O.A.S.
The manufacturing process of E includes adding a fatty acid or a fatty acid ester having a saturated or unsaturated alkyl group having 8 to 22 carbon atoms to the POAS in the presence or absence of a catalyst.
At a temperature of 18,000 ℃, normal pressure to reduced pressure (1 to 5 Hg
) The esterification reaction is carried out while removing the water or alcohol formed under As the catalyst used for esterification, any catalyst that is effective for general esterification and transesterification reactions can be used.

For example, hydroxides, carbonates, fluorides, acetates, alkoxides, chlorides, soaps, hydrochloric acid (hydrochloric acid, sulfuric acid, phosphoric acid), organic acids (valatluene sulfonic acid, 8-naphthalene sulfonic acid), etc. Although effective, when an acidic catalyst is used, coloration is significant, and it is preferable to use the Aruca IJ catalyst as much as possible. The amount of catalyst used is 0'05 to 3.0% relative to the reactants.
0% by weight is suitable. The esterification and transesterification reactions are carried out at a temperature of 80 to 180 DEG C., but if the temperature is high, the product will be extremely colored, especially when an acidic catalyst is used.

An acidic catalyst is effective for the esterification reaction between POAS and fatty acids, but due to the reasons mentioned above, POAS is markedly colored. More preferred. In the case of transesterification, the reaction proceeds at a temperature of 80 to 120 degrees Celsius and is completed in a very short time. Therefore, P
Almost no OASE coloration is observed. Since the reaction is an equilibrium reaction, water or alcohol generated in the system can be removed from the system by continuously blowing inert gas such as nitrogen under normal pressure, or removed from the system under reduced pressure. The reaction will proceed more smoothly if you do so.

In the case of esterification reactions, the acid value and hydroxyl value (OHV) of the reactants are measured, and in the case of transesterification reactions, the Song reaction fatty acid esters contained in the reactants are measured by gas chromatography using standard substances. The reaction can be tracked by conducting an analysis and measuring the hydroxyl value.

In both the esterification and transesterification reactions, it is not necessary to use an organic solvent, and the reactions proceed without solvent.
In the production of POASE, when fatty acid halides are used, a basic substance that absorbs by-product hydrogen halide is suitable as a catalyst, and the reaction temperature is 10 to 10 minutes.
300C is preferred.

Coloring becomes more pronounced at higher temperatures. The degree of esterification of POASE is independent of the number of moles of alkylene oxide added to POAS, and it is possible to produce from a 1-substituted product to an 8-substituted product.

In the present invention, the fatty acids, fatty acid halides, fatty acid esters, or triglycerides having a saturated or unsaturated alkyl group having 8 to 22 carbon atoms include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Oleic acid, linoleic acid, erucic acid, mixed fatty acids derived from coconut oil, mixed fatty acids derived from rapeseed oil,
isostearic acid, castor oil fatty acid, 12-hydroxystearic acid and the chlorides and furomides of these fatty acids and the methyl, ethyl, propyl,
Examples include butyl esters and glycerol triesters of these fatty acids, but in particular, in the present invention, compounds using lauric acid, palmitic acid, stearic acid, oleic acid and esters, halides, and glycerol triesters of these fatty acids are used. Practically preferred.

POASE obtained by the present invention is a nonionic surfactant with a sucrose polyoxyalkylene residue as a hydrophilic group and a fatty acid residue as a hydrophobic group. By changing the degree of esterification, it is possible to obtain POASE with desired performance, and it is expected that it will be used in a wide range of applications as a low-foaming, low-porous, and highly biodegradable surfactant. A representative example of the invention is shown below.Example 1 '11 Production contents of POAS 1 2749 sucrose in the electromagnetic autoclave
, 68.4 hours of water, 17.1 hours of ethylene glycol, and 0.7 hours of flaky caustic soda were charged and heated.

When the temperature reaches 11,000, 15 moles of ethylene oxide are introduced by continuous addition under a pressure of 1 to 7 k9'. The reaction is completed in an extremely short time (40 to 6 minutes), but at the same time it generates a large amount of heat, so the temperature reaches 140℃.
Make sure it doesn't exceed 00 ~ Control through cooling water. ...to do.
The pressure decreases during the reaction and when it returns to normal pressure, reduce the pressure (1
10°C/0.1-1 Hg) Completely remove remaining water. The amount of water remaining at this time is approximately 90% of the amount of water charged.
The amount corresponds to ~95%. After the removal operation, neutralize with hydrochloric acid,
The generated sodium chloride is removed by sieving. The product is a pale yellow clear viscous liquid. ■ Production of POASE In a four-necked flask (one neck is connected to a vacuum pump via a cold trap) equipped with a fly rod and a thermometer, add POAS501 obtained in step 11 and methyl laurate ester 107.
In the evening, add 0.6 ounces of sodium methoxylate, 11
Turn on the heating light at 0qo.

The pressure was gradually reduced using a vacuum pump, and the reaction was allowed to proceed for 1 hour at a reduced pressure of 2 Hg, taking care not to blow out the contents due to bubbling. The reaction was carried out by gasketing OHV and the husband reaction methyl ester contained in the reactants using a standard substance. Follow-up by performing matographic analysis. After cooling, the catalyst is neutralized with hydrochloric acid. The yield was 97% and the purity was 95%. The product was a pale yellow viscous liquid that was easily soluble in water and showed surface activity.
Example 2 ○} Manufacturing details of POAS 1 Into the electromagnetic light Azusa autoclave, 274 grams of sucrose, 34 grams of water, 17.1 grams of ethylene glycol, and 0.7 grams of flaked caustic soda are charged and heated.

When the temperature reaches 11 psi, 3 moles of ethylene oxide are introduced underground at a pressure of 1 to 7.times.9'. The pressure decreases during the reaction and when it returns to normal pressure, reduce the pressure (11 pi 0/0.1~1
．． (Hg) Completely remove remaining water. Subsequently, 12 mol of ethylene oxide is introduced at the same temperature and pressure as in the first stage addition reaction. The reaction is completed when the pressure returns to normal pressure. The sodium chloride produced by neutralization with hydrochloric acid is removed by sieving. The product is a pale yellow transparent viscous liquid. The P obtained from Example 1'11 and Example 2 [1}' is shown below.
The analysis value of OAS and the comparative example are as follows. W. Buddha Mai
A report by Stre et al. (J.○rg.Chem.13, 78
2, 1948), POAS produced by the method of Japanese Patent No. 49074
Shows the analysis value of

However, the polyethylene glycol (PEG) content was measured and determined by the following method.

Method for measuring PEG content (T.LC. analysis) POAS
was made into a methanol and chloroform solution, and this was used as a developing solvent (methanol: chloroform: acetic acid: water = 12.6
:67.2:16.8:3.4 volume ratio).
Separate polyethylene glycol (R value 3.3-5.3) and polyethylene glycol (R value 7.5-3.3), and treat the polyethylene glycol portion with a modified Dragendorff reagent or iodine. Develop color with steam and quantify using a densitometer using standard reagents.

Silica gel G was used as the adsorption layer, and the development temperature was 20
It was so hot. '2} Production of POASE In a four-necked flask equipped with a neck rod and a thermometer, add POAS501 obtained in [1} and lauric acid methyl ester 214.
In the evening, add 1.0mg of sodium methoxylate, 11
The rope is heated to 0℃.

The reaction was carried out for about 1 hour under the same conditions as in Example 1 [2-]. After cooling, the catalyst is neutralized with hydrochloric acid. The yield was 95% and the purity was 95%. The product was a pale yellow viscous liquid that was dispersible in water and showed surface activity. Example 3 Production of 01POAS Same as Example 1m ■ Production of POASE In a four-necked flask equipped with a condensation rod, a thermometer, a water sample tube, and a gas injection tube, POAS501 obtained in '1' and 100% lauric acid were added. In the evening, boron trifutide etherate (30
% ether solution) 2.0% and 140-15%
The reaction was carried out for 2 hours while continuously blowing inert gas (nitrogen gas).

The reaction was monitored by acid value and OHV, and the mixture was cooled when the acid value and saponification value became constant. Yield 90%, purity 9
It was 5%. The product was a brown viscous liquid. Example 4 '11 Production of POAS Same as Example 1'1} Production of '21 POASE POAS250 obtained in '1} was placed in a four-necked flask equipped with a rope rod, a thermometer, a dropping funnel, and a reflux condenser. .5 evenings, triethylamine ether solution (253 evenings/100')
and cooled to 5-10°C in a water bath.

Oleic acid chloride ether solution (75
．． Gradually drop 200 ml of [) for 2 evenings and raise the reaction temperature to 5~5
Keep it at 10q0. After the dripping is completed, the temperature is flooded to 3500, and the
The reaction was completed by refluxing the mixture for 1 hour. After filtering the product, ether and triethylamine are removed under reduced pressure. The yield was 95% and the purity was 93%. The product was a brown viscous liquid. Example 5 Production of '1' POAS Propylene oxide was used in place of ethylene oxide in Example 1m.

The number of moles added was 15 moles, and the addition conditions were as in Example 1 [11
It is exactly the same. The product was a pale yellow transparent viscous liquid. {2- Manufacture of POASE Example 1) Produced using stearic acid methyl ester and {1' instead of lauric acid methyl ester.

The manufacturing conditions are exactly the same as in Example 1 {2). Yield 96
%, purity was 95%. The product was a pale yellow paste. Next, a surfactant test example of POASE obtained according to the present invention will be shown.

Note 1. The number of fatty acid components substituted in the POASE I molecule is shown.

Note 2. Measured by the 0uNouy method. Note 3. Measured by the Ross Miles method.

Claims (1)

[Scope of Claims] 1. Sucrose and alkylene oxide are reacted in the presence of alkylene glycol and water in an amount of 1 to 10% by weight based on sucrose by continuous addition reaction or two-step addition reaction to produce a highly pure polyester. Production of a nonionic surfactant characterized by producing oxyalkylenated sucrose and then reacting it with a fatty acid, a fatty acid halide, a fatty acid ester, or a triglyceride to obtain a highly purified polyoxyalkylenated sucrose fatty acid ester. (However, the above fatty acids refer to those having a saturated or unsaturated alkyl group having 8 to 22 carbon atoms.)