JP3222080B2 - Higher secondary alkyl ether sulfate, method for producing the same, and detergent and emulsifier containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a higher secondary alkyl ether sulfate, a method for producing the same, and a detergent and an emulsifier containing the same.

[0002]

BACKGROUND OF THE INVENTION Anionic surfactants include alkyl allyl sulfonates, higher primary alcohol sulfates, higher primary alkyl ether sulfates, and the like.

[0003] Of these, alkyl allyl sulfonates,
In particular, linear alkylbenzene sulfonates are being regulated because they have poor biodegradability and thus have an adverse effect on the environment.

[0004] Alkyl allyl sulfonates, higher primary alcohol sulfates, and the like are easily affected by the hardness of water and have poor water solubility.

[0005] Higher primary alkyl ether sulfates not only have high viscosities and tend to gel, but also have insufficient surface activity such as surface tension and osmotic power, and have sufficient detergency and emulsifying power. Absent.

[0006] Other anionic surfactants also include
There is not enough performance.

[0007] Higher secondary alkyl ether sulfates, which are anionic surfactants, are low in viscosity and difficult to gel, so that they are easy to handle, and have good surface tension and penetrating power.
It has good defoaming, excellent cleaning power and emulsifying power, and is useful.

However, the conventional production method uses a Lewis acid catalyst for a random secondary alcohol obtained by subjecting a linear paraffin comprising one or a mixture of at least 8 to 20 carbon atoms to liquid phase oxidation. Then, ethylene oxide is added to obtain a low EO adduct, unreacted alcohol is recovered from the reaction mixture, and ethylene oxide is added using a basic catalyst, and then chlorosulfonic acid or sulfuric anhydride is added. It is used for sulfation.

As described above, in order to produce a higher secondary alkyl ether sulfate, not only a single addition of ethylene oxide but also removal of a catalyst, distillation, addition of ethylene oxide, and then sulfation. It is necessary.

Therefore, as far as this manufacturing method is concerned, the process can be said to be very complicated.

[0011]

As a result of various studies, the present inventors have found that a long-chain olefin is used as a raw material, a new production method is used, thereby simplifying the production method and finding an economically advantageous production method. The present invention has been completed. Further, the present inventors have found that the specific higher secondary alkyl ether sulfate obtained by the above-mentioned production method has a low viscosity and is difficult to gel, so that it is easy to handle, has a good surface tension, has a good penetrating power, and has a good foam removal. The present inventors have found that a surfactant having excellent detergency, detergency and emulsifying power can be obtained, and have completed the present invention.

That is, an object of the present invention is to provide (i) adding an alkylene glycol to a double bond of a long-chain olefin.
When using crystalline aluminosilicate as a catalyst
A higher secondary alcohol alkoxylate obtained by adding an alkylene oxide, or a higher secondary alcohol alkoxylate obtained by further adding an alkylene oxide. Achieved.

Another object of the present invention is attained by (ii) a higher secondary alkyl ether sulfate salt obtained by the production method of the above (i).

Further, another object of the present invention is achieved by (iii) a detergent characterized by containing the higher secondary alkyl ether sulfate of the above (ii).

Further, another object of the present invention is attained by an emulsifier characterized by containing (iv) the higher secondary alkyl ether sulfate of the above (ii).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a higher secondary alkyl ether sulfate according to the present invention is characterized in that, when an alkylene glycol is added to a double bond of a long-chain olefin ,
As a catalyst, a higher secondary alcohol alkoxylate obtained by using a crystalline aluminosilicate or a higher secondary alcohol alkoxylate obtained by further adding an alkylene oxide is sulfated.

The higher secondary alcohol alkoxylate obtained by adding an alkylene glycol to a double bond of a long-chain olefin used as a raw material of a higher secondary alkyl ether sulfate used in the present invention has 8 carbon atoms. ~ 3
0 long-chain olefin and (poly) alkylene glycol are reacted (in the presence of an acid catalyst, appropriately adjusted to an appropriate molar ratio if necessary), and the obtained product is separated by distillation, extraction, or other methods. The higher secondary alcohol alkoxylate is obtained by further adding an alkylene oxide to the higher secondary alcohol alkoxylate.

The long-chain olefin used for obtaining the higher secondary alcohol alkoxylate is preferably a hydrocarbon having 8 to 30 carbon atoms having an ethylenically unsaturated bond, and preferably a carbon atom having an ethylenically unsaturated bond. Acyclic hydrocarbons of several 10 to 20 are mentioned. Specific examples include octene, decene, dodecene, tetradecene, hexadecene, octadecene, and eicosene. These may be used alone or as a mixture of two or more.

These olefins can be used without particular limitation, regardless of whether the position of the unsaturated bond is α-position, inner position, or both α-position and inner position. it can. of course,
Two or more of these olefins having different unsaturated bond positions may be used in combination.

Specific examples of the (poly) alkylene glycol used to obtain the higher secondary alcohol alkoxylate include, for example, monoethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, monopropylene glycol,
Dipropylene glycol, tripropylene glycol,
Polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, para-xylene glycol, 1,4-cyclohexanemethanediol, etc. Is mentioned. These may be used alone or as a mixture of two or more.

The molar ratio between the long-chain olefin and the (poly) alkylene glycol for obtaining the higher secondary alcohol alkoxylate is not particularly limited.
It is 0.05-20, preferably 0.1-10. In addition, the above-mentioned (poly)
The reaction conditions for adding the alkylene glycol include:
Reaction temperature is usually 50 to 250 ° C, preferably 100 to 250 ° C.
200 ° C. The reaction pressure may be any of reduced pressure, normal pressure or pressurized, but is preferably in the range of normal pressure to 20 kg / cm ² . When the reaction temperature is lower than 50 ° C., the reaction rate is too slow. On the other hand, when the reaction temperature is higher than 250 ° C.,
Polymerization of long-chain olefins, decomposition of (poly) alkylene glycols, polycondensation, etc. occur, and the selectivity is undesirably reduced.

The above-mentioned long-chain olefin and the above-mentioned (poly)
Specific examples of the acid catalyst used for the reaction of the alkylene glycol include a strongly acidic ion exchange resin, crystalline aluminosilicate, dodecylbenzenesulfonic acid, and the like.From the viewpoint of reactivity, preferably, crystalline aluminosilicate is used. Among them, BEA zeolite is particularly desirable. The amount of the acid catalyst is 1 to 50% by weight, preferably 2 to 30% by weight, based on the long-chain olefin. When the amount of the catalyst is less than 1% by weight, sufficient catalytic activity cannot be obtained and the addition reaction cannot be promoted. On the other hand, when the amount exceeds 50% by weight, the effect corresponding to further addition cannot be obtained. It is not preferable because it is uneconomical.

In the present invention, a higher secondary alcohol alkoxylate obtained by further adding an alkylene oxide to the above higher secondary alcohol alkoxylate may be used as a raw material for sulfation. In that case, the alkylene oxide is added to the higher secondary alcohol alkoxylate in an appropriate molar ratio and reacted in the presence of an alkali catalyst. The alkylene oxide may be only one kind or two or more kinds. In the latter case, two or more kinds of alkylene oxides may be added at random or each may be added to a block.

Examples of the alkylene oxide used to obtain the higher secondary alcohol alkoxylate adduct include ethylene oxide, propylene oxide, butylene oxide and styrene oxide.

As the alkali catalyst used at this time, hydroxides of elements belonging to alkali metals or alkaline earth metals, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, hydroxide Barium and the like may be mentioned, and these may be in the form of powder, granules, or further added as an aqueous solution for dehydration.

The amount of the catalyst for the addition of the alkylene oxide is 0.01 to 2.
0% by weight, preferably 0.02 to 0.5% by weight.

As the conditions for adding the alkylene oxide, the reaction temperature is usually 50 to 250 ° C., preferably 10 to 250 ° C.
0-200 ° C. The reaction pressure may be either normal pressure or pressurized, but is preferably in the range of normal pressure to 20 kg / cm ² . When the reaction temperature is lower than 50 ° C., the reaction rate is slow. On the other hand, when the reaction temperature is higher than 250 ° C., it is not preferable because decomposition and an increase in by-products occur.

In the manufacturing method of the present invention, the high-grade second
The desired higher secondary alkyl ether sulfate salt is obtained by sulfating a secondary alcohol alkoxylate, and the sulfation is performed using chlorosulfonic acid or sulfuric anhydride.

When chlorosulfonic acid is used, higher secondary
Chlorosulfonic acid is dropped into the secondary alcohol alkoxylate by a known method, for example, directly or accompanied by air, an inert gas, or the like, or JP-B1-36823.
According to the method described in Japanese Patent Application Laid-Open Publication No. H10-163, the mixture is mixed using a sulfation apparatus equipped with an external circulation equipped with a line mixer, thereby performing batch-type sulfation. The dropping time of chlorosulfonic acid is 1 to 2 hours, and the reaction temperature is -20 to 30C, particularly 0 to 20C.

When sulfuric anhydride is used, the higher secondary alcohol alkoxylate is allowed to flow down into a thin film using a co-current thin film reactor by a known method, for example, the method described in Japanese Patent Publication No. Sho 51-17538. By bringing sulfuric anhydride gas diluted with active gas into parallel flow and gas-liquid contact,
Sulfation is carried out continuously. Inert gas speed is 20 ~ per second
70 m, the concentration of sulfuric anhydride in gas is preferably 1 to 10% by volume, and the molar ratio of sulfuric anhydride to higher secondary alcohol alkoxylate is preferably 0.95 to 1.2. Reaction temperature is -2
0-60 degreeC, especially 0-30 degreeC are desirable.

In the present invention, the use of a solvent in the sulfation step allows a higher yield of higher quality secondary
It is also possible to produce higher alkyl ether sulfates. As the type of the solvent used, chloroform, carbon tetrachloride, ethyl chloride, ethylene chloride, 1,1,
Chlorine solvents such as 1-trichloroethane and 1,1,1,2-tetrachloroethane, hydrocarbon solvents such as n-pentane, n-hexane, n-heptane and cyclohexane, ether solvents such as diethyl ether and isopropyl ether And the like. The solvent concentration is desirably 10 to 90% by weight in the reaction solution. Solvent concentration is 10% by weight
If the amount is less than 90%, the effect of using a solvent cannot be obtained. If the amount exceeds 90% by weight, the reaction efficiency is deteriorated and the yield is lowered.

After the sulfation, the obtained reaction solution is neutralized with a basic substance, and when a solvent is used, the solvent is removed to obtain the desired higher secondary alkyl ether sulfate.

Suitable bases for the neutralization step are alkali metal hydroxides, more preferably sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal oxides and hydroxides, more preferably Magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, alkanolamines, more preferably mono-, di- and triethanolamine,
And primary, secondary and tertiary alkylamines containing from 1 to 4 carbon atoms per alkyl group.

The higher secondary alkyl ether sulfate according to the present invention obtained by the above-mentioned production method can be used as it is as an anionic surfactant.

Next, the higher secondary alkyl ether sulfate of the present invention may be used alone as a detergent, or may be used in combination with a conventionally known detergent surfactant. Such surfactants include, for example, nonionic surfactants such as alkylphenol ethoxylate, higher primary alcohol ethoxylate, higher secondary alcohol ethoxylate, fatty acid ethoxylate, alkylamine salts, and quaternary ammonium. Examples include cationic surfactants such as salts and zwitterionic surfactants such as alkyl betaines.

Conventional anionic surfactants such as, for example,
Alkyl allyl sulfonates, higher primary alcohol sulfates, higher primary alkyl ether sulfates, and the like can also be used in combination as long as the performance of the detergent of the present invention is not impaired.

Further, various additives used in ordinary cleaning agents can be added to the cleaning agent of the present invention. Such additives include, for example, alkaline agents,
Examples include builders, fragrances, optical brighteners, coloring agents, foaming agents, foam stabilizers, polishing agents, bactericides, bleaching agents, enzymes, preservatives, dyes, solvents, and the like.

The cleaning agent of the present invention can be used for clothing, textiles, tableware, containers, sundries, food, building maintenance products,
Cleaning agents for houses, furniture, cars, aircraft, metal products, etc.
It can be used effectively as shampoo, body shampoo and the like.

On the other hand, the higher secondary alkyl ether sulfate of the present invention may be used alone as an emulsifier, but may contain other conventionally known emulsifiers as needed. For example, a nonionic surfactant, a cationic surfactant or a zwitterionic surfactant generally used as an emulsifier can be used in combination.

The oily substance used in the emulsifier of the present invention is not particularly limited, and mineral oil, animal and vegetable oil, synthetic oil and the like can be used. These can be used alone or in combination of two or more. Examples of mineral oils include, for example, spindle oil, machine oil, liquid paraffin oil, and the like. Examples of animal and vegetable oils include beef tallow, lard, fish oil, whale oil, rapeseed oil, sesame oil, coconut oil, soybean oil, palm oil, camellia oil, castor oil and the like.

The emulsifier of the present invention can be used in agricultural chemicals, metalworking oils, paints, emulsifiers for emulsion polymerization, and the like.

[0042]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Method) Example 1 Secondary dodecyl ether sulfate 1-dodecene was converted to a BEA type zeolite manufactured by PQ (trade name:
VALFOR CP811 BL-25) 5% by weight, obtained by treating at 150 ° C. for 10 hours.
Dodecene isomer mixture (1-dodecene 25 mol%,
810 g (consisting of 75 mol% of inner decene)
(4.82 mol), monoethylene glycol 900
g (14.52 mol), and PQ B as a catalyst
EA type zeolite (trade name: VALFOR CP 81)
1BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen.
Next, while stirring at a rotation speed of 600 rpm, 1
After the temperature was raised to 50 ° C., and the reaction was carried out at the same temperature for 3 hours, the reaction solution was cooled to room temperature, the upper layer of the dodecene phase was separated and distilled. After distilling off unreacted dodecene, the pressure was reduced to 2 mmH.
155 g of secondary dodecanol monoethoxylate was obtained in a boiling point range of 129 to 131 ° C.

The secondary dodecanol monoethoxylate was used in a reaction tube forming an annular reaction zone having an inner diameter of 5 mm and a length of 100 cm. 16.2 per minute along the inner wall of
It flowed down in a thin film at a speed of g. At the same time, sulfuric anhydride diluted with nitrogen gas was flowed in from a nozzle provided at the top of the reaction tube. The flow rate of the flowed total nitrogen gas in the reaction tube was 30 m / sec, and the concentration of sulfuric anhydride in the flowed total mixed gas was 4% by volume. The molar ratio of the sulfuric anhydride dropped and the secondary dodecanol ethoxylate dropped was 1.1. Reaction heat generated by the reaction between ethoxylate and sulfuric anhydride was removed by a refrigerant flowing outside the reaction tube, and kept at 15 ° C. The fluid exiting the reaction tube was separated into nitrogen gas and reaction products by a cyclone. The reaction product was immediately neutralized with an aqueous sodium hydroxide solution to obtain an approximately 25% aqueous solution of the desired secondary dodecyl ether sulfate.

Example 2 Secondary Dodecyl Ether Sulfate 155 g (0.67 mol) of secondary dodecanol ethoxylate, an intermediate product of Example 1, and 0.2 g of sodium hydroxide as a catalyst were charged into a stainless steel autoclave. After replacing with nitrogen, the pressure in the reactor was increased to 1.0 with nitrogen.
and kg / cm ² G, temperature was raised to 0.99 ° C., was introduced ethylene oxide 62g of (1.41 mol) to an autoclave at 3hrs. After the introduction, the temperature was further maintained at 150 ° C. for 1 hour, cooled to room temperature, and the internal pressure was purged. Thus, a secondary dodecanol ethoxylate having an average of 3.1 mol of oxyethylene groups was obtained.

This secondary dodecanol ethoxylate 2
17 g (0.67 mol) was charged into a 500 ml flask and cooled to 10 ° C. Chlorosulfonic acid 8
6.3 g (0.74 mol) was added dropwise over about 1 hour. During the dropwise addition, the liquid temperature was maintained at 10 to 15 ° C. After the chlorosulfonic acid was dropped, nitrogen gas was flowed into the reaction solution to remove hydrogen chloride gas as a by-product, and then the reaction solution was dropped into a sodium hydroxide solution while maintaining the temperature at 20 ° C or lower. To give an approximately 25% aqueous solution of the desired secondary dodecyl ether sulfate.

Example 3 Secondary hexadecyl ether sulfate 1-hexadecene was obtained by subjecting 5% by weight of BEA-type zeolite (trade name: VALFOR CP 811 BL-25) manufactured by PQ to 150 ° C. for 13 hrs. Hexadecene isomer mixture (1-hexadecene 2
810 g (3.62 mol), 900 g (14.52 mol) of monoethylene glycol, and BEA type zeolite manufactured by PQ (trade name: VALFO) as a catalyst.
RCP 811 BL-25) (100 g) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen. Then, the temperature was raised to 150 ° C. while stirring at a rotation speed of 600 rpm, and the reaction was carried out at the same temperature for 3 hours. After that, the reaction solution was cooled to room temperature, and the upper hexadecene phase was separated and distilled. After distilling off unreacted hexadecene, 95 g of secondary hexadecanol ethoxylate was obtained at a reduced pressure of 2 mmHg and a boiling point range of 160 to 165 ° C.

80 g (0.28 mol) of this secondary hexadecanol ethoxylate and 400 g of ethylene chloride as a solvent were charged into a 1-liter flask and cooled to 10 ° C. 36 g of chlorosulfonic acid (0.31
mol) was added dropwise over about 1 hour. During dropping, the liquid temperature is 1
Maintained at 0-15 ° C. After dropping chlorosulfonic acid, a nitrogen gas is flowed into the reaction solution to remove by-product hydrogen chloride gas,
Then, while maintaining the temperature at 20 ° C. or lower, the reaction solution is dropped into sodium hydroxide solution to neutralize the solution, ethylene chloride is removed, and an approximately 25% aqueous solution of a desired secondary hexadecyl ether sulfate salt is removed. I got

(Physical Properties / Interface Properties) Examples 4 to 6 The following measurements were carried out on the substances obtained in Examples 1 to 3 (Examples 4 to 6). The results of these measurements are shown in Table 1 below.

Measuring method (1) Liquid range The viscosity was determined from the aqueous solution viscosity measured with a Brookfield-type rotational viscometer at 25 ° C. (2) Surface tension The surface tension was measured at 25 ° C using a surface tensiometer manufactured by Kyowa Kagaku based on the Wilhelmy method.
(Activator concentration: 0.1% by weight) (3) Penetration cotton: canvas 6 at 25 ° C by the campus disk method.
No. was measured. (Activator concentration: 0.25% by weight) (4) Foam property According to JIS K-3362 (Rosmiles method), 2
It was measured at 5 ° C. (Activator concentration: 0.1% by weight)

[0051]

[Table 1]

Examples 7 to 9 The substances obtained in Examples 1 to 3 were evaluated for the following detergency (Examples 7 to 9). The results are shown in Table 2 below.

(Evaluation method) In accordance with JIS K-3362, a stirring type detergency tester (Terg-O-tome) was used.
ter) was tested under the following conditions. <Washing condition> Soiled cloth: size 5 × 5 cm Soil (%) Oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 1.6 Cholesterol 7.0 Gelatin 29.8 Carbon Black 0.5 Water used: Tap water Temperature: 25 ° C Time: Washing 5 minutes / Rinse 5 minutes Bath ratio: 3 sheets / 1 pot (1 L) Activator concentration: 0.03% <Evaluation method of detergency> Reflectance meter The reflectance of the original cloth, the artificially-contaminated cloth, and the washed cloth after cleaning are measured at three locations for each cloth of each test piece, and the detergency (%) is calculated from the average value using the following formula. did.

[0054]

(Equation 1)

In the above formula, R _O represents the reflectance of the original cloth, R _S represents the reflectance of the artificially contaminated cloth, and R _W represents the reflectance of the cleaning cloth.

[0056]

[Table 2]

Examples 10 to 12 The substances obtained in Examples 1 to 3 were evaluated for the following emulsifying power. The results are shown in Table 3 below.

(Evaluation method) 5 ml of the synthesized sample was added to a mixture of 55 ml of water and 40 ml of oil, mixed well, and allowed to stand. After 5 minutes, the state of separation of the water or oil layer is observed. Evaluation was made as follows according to the emulsified state. ：: Good emulsified state △: Slightly separated ×: Completely separated

[0059]

[Table 3]

[0060]

The process for producing a higher secondary alkyl ether sulfate according to the present invention is extremely simple, highly practical, and economically advantageous.

Further, the higher secondary alkyl ether sulfate salt of the present invention obtained thereby has a low viscosity and is hardly gelled, so that it is easy to handle, has good penetrating power, has good foam removal, and has good detergency. Excellent emulsifying power.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshiyuki Onda 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (56) References JP-A-54-63009 (JP, A) JP-A Sho 62-265258 (JP, A) JP-A-2-295941 (JP, A) JP-B-1-36823 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 305/10 C07C 303/24 C07C 43/11 C07C 41/06

Claims (4)

(57) [Claims] The present invention relates to a method for adding an alkylene glycol to a double bond of a long-chain olefin , using a crystalline alcohol as a catalyst.
A higher secondary alkyl ether sulfate salt obtained by sulfating a higher secondary alcohol alkoxylate obtained by using a minosilicate or a higher secondary alcohol alkoxylate obtained by further adding an alkylene oxide. Manufacturing method. 2. A higher secondary alkyl ether sulfate obtained by the production method according to claim 1. 3. A cleaning agent comprising the higher secondary alkyl ether sulfate salt of claim 2. 4. An emulsifier comprising the higher secondary alkyl ether sulfate salt of claim 2.