JPH10168014A - Higher secondary alcohol alkoxylate adduct and its production, and cleansing agent and emulsifier containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject adduct excellent as a surfactant by further adding an alkylene oxide to a higher secondary alcohol alkoxylate obtained by adding a (poly)alkylene glycol to the double bond of a long chain olefin. SOLUTION: The objective adduct is obtained by adding 1-30mol alkylene oxide such as ethylene oxide to (D) 1mol alkoxylate obtained by reacting (A) an 8-30C long chain olefin having an ethylenically unsaturated bond, e.g. octene with (B) a (poly)alkylene glycol, e.g. monoethylene glycol in 0.05-20 molar ratio of the component A to the component A in the presence of (C) 1-50wt.% acid catalyst such as a BEA-type zeolite based on the amount of the component A at 50-250 deg.C under a pressure of a normal pressure to 20kg/cm<2> , and reacting the component D with the added alkylene oxide by adding 0.01-2.0wt.% alkali catalyst such as sodium hydroxide based on the amount of the component D under a condition the same as that of the reaction for forming the component D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a higher secondary alcohol alkoxylate adduct, a method for producing the same, and a detergent and an emulsifier containing the adduct.

[0002]

BACKGROUND OF THE INVENTION Nonionic surfactants include alkylphenol ethoxylates, higher primary alcohol ethoxylates, fatty acid ethoxylates and the like.

[0003] Of these, alkylphenol ethoxylates, especially nonylphenol ethoxylate, are in the direction of being regulated because they are poor in biodegradability and thus have an adverse effect on the environment.

[0004] Higher primary alcohol ethoxylates have a high pour point and not only solidify at room temperature,
The surface activity such as osmotic power is insufficient, and the detergency and emulsifying power are not sufficient.

[0005] Other nonionic surfactants also include
For example, fatty acid ethoxylates hydrolyze,
Some of them are restricted in use, such as being unusable due to alkalinity, and none of them have sufficient performance.

Higher secondary alcohol ethoxylates, which are nonionic surfactants, have a low pour point, are easy to handle, have good penetrating power, have good foam removal, are excellent in detergency and emulsifying power, and are useful. .

[0007] However, the conventional production method uses a Lewis acid catalyst for a random secondary alcohol obtained by subjecting a linear paraffin composed of one or a mixture of two or more carbon atoms having 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 further added using a basic catalyst.

As described above, it is necessary not only to add ethylene oxide once but also to remove the catalyst, distill, and further add ethylene oxide to produce ethoxylate.

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

[0010]

As a result of various studies, the present inventors have found that a new manufacturing method simplifies the manufacturing method, finds an economically advantageous manufacturing method, and completes the present invention. Was. Furthermore, the present inventors have found that a specific higher secondary alcohol alkoxylate obtained by the above-mentioned production method has a low pour point, is easy to handle, has good penetration, has good defoaming, and has excellent detergency and emulsifying power. In addition, they have found that a surfactant can be obtained, and have completed the present invention.

That is, an object of the present invention is to provide (i) further adding an alkylene oxide to a higher secondary alcohol alkoxylate obtained by adding a (poly) alkylene glycol to a double bond of a long-chain olefin. This is achieved by a method for producing a higher secondary alcohol alkoxylate adduct characterized by the following.

Another object of the present invention is attained by (ii) a higher secondary alcohol alkoxylate adduct obtained by the production method of (i).

Further, another object of the present invention is attained by a detergent characterized by containing (iii) the higher secondary alcohol alkoxylate adduct of the above (ii).

Further, another object of the present invention is attained by an emulsifier characterized by containing (iv) the higher secondary alcohol alkoxylate adduct of the above (ii).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a higher secondary alcohol alkoxylate adduct according to the present invention, a (poly) alkylene glycol is added to an unsaturated bond of a long-chain olefin in a first reaction step. In the present specification, such a first
The product obtained in the reaction step is referred to as a higher secondary alcohol alkoxylate. Next, in a second reaction step, an alkylene oxide is further added to the higher secondary alcohol alkoxylate obtained above. Thereby, a desired end product can be obtained. In the present specification, the final product obtained in the second reaction step is
It is called a higher secondary alcohol alkoxylate adduct.

First, the unsaturated bond of the long-chain olefin is
In the first reaction step of adding the (poly) alkylene glycol, for example, the long-chain olefin and the (poly) alkylene glycol are adjusted to an appropriate molar ratio and reacted in the presence of an acid catalyst, and the obtained product is distilled. , A secondary alcohol alkoxylate of higher secondary alcohol can be obtained.

The long-chain olefin used in the first reaction step has 8 to 8 carbon atoms having an ethylenically unsaturated bond.
30 hydrocarbons, preferably an acyclic straight-chain hydrocarbon having 10 to 20 carbon atoms and having an ethylenically unsaturated bond. 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 in the first reaction step include monoethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Examples include 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, para-xylene glycol, 1,4-cyclohexanemethanediol, and the like. However, from the viewpoint of reactivity,
Preferred are monoalkylene glycols such as monoethylene glycol and monopropylene glycol. These may be used alone or as a mixture of two or more.

Here, the molar ratio of the (poly) alkylene glycol to the long-chain olefin is not particularly limited, but is preferably from 0.05 to 20, more preferably from 0.1 to 10. When the molar ratio is less than 0.05, the yield of the higher secondary alcohol alkoxylate decreases, while when it exceeds 20, the volume of the reactor increases, which is not economical. . As the reaction conditions for adding the (poly) alkylene glycol to the unsaturated bond of the long-chain olefin, the reaction temperature is usually 50 to 250 ° C, preferably 100 to 200 ° C.
° C, and the reaction pressure may be any of reduced pressure, normal pressure or increased pressure, 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 becomes too slow. On the other hand, when the reaction temperature exceeds 250 ° C., polymerization of long-chain olefin, decomposition of (poly) alkylene glycol, polycondensation, etc. occur, resulting in a selectivity. Is unfavorable.

Specific examples of the acid catalyst include a strongly acidic ion exchange resin, crystalline aluminosilicate, dodecylbenzenesulfonic acid, and the like.
Preferably, it is a crystalline aluminosilicate, and 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. The catalyst amount is 1
If the amount is less than 50% by weight, sufficient catalytic activity cannot be obtained and the addition reaction cannot be promoted.
It is not preferable that the effect corresponding to the further addition cannot be obtained, and it becomes uneconomical.

Next, in the second reaction step of further adding an alkylene oxide to the higher secondary alcohol alkoxylate obtained in the first reaction step, for example,
Alkylene oxide is added to the higher secondary alcohol alkoxylate obtained in the first reaction step 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 this case, two or more kinds of alkylene oxides may be added at random or each may be added to a block. Good.

The alkylene oxide used in the second reaction step includes, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like.

Here, the molar ratio of alkylene oxide to higher secondary alcohol alkoxylate is not particularly limited, but is preferably 1 to 30, more preferably 4 to 20. As the reaction conditions for further adding an alkylene oxide to the above product, the reaction temperature is usually 50 to 250 ° C, preferably 100 to 200 ° C.
The reaction pressure may be either normal pressure or pressurization, 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 becomes slow,
On the other hand, if the temperature exceeds 250 ° C., it is not preferable because decomposition and an increase in by-products occur.

Examples of the alkali catalyst include hydroxides of elements belonging to alkali metals or alkaline earth metals, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide,
Although barium hydroxide and the like can be mentioned, sodium hydroxide, potassium hydroxide and the like are preferable in view of availability and reactivity. These may be powdered, granular, or added as an aqueous solution to perform dehydration. The amount of the alkali catalyst used is preferably from 0.01 to 2.0% by weight, and more preferably from 0.02 to 0.5% by weight, based on the starting alkoxylate.

The higher secondary alcohol alkoxylate adduct according to the present invention obtained by the above-mentioned production method,
As it is, it can be used as a nonionic surfactant.

Next, as a use of the higher secondary alcohol alkoxylate adduct of the present invention, for example, it can be used as a raw material for producing anionic surfactants and cationic surfactants. It is particularly effective to use it as a detergent and an emulsifier because it is easy to use, has good penetration, good foam removal, and has excellent detergency and emulsification.

That is, another invention of the present invention is provided as a cleaning agent containing the above-mentioned higher secondary alcohol alkoxylate adduct.

In the detergent of the present invention, the above-mentioned higher secondary alcohol alkoxylate adduct may be used alone, or a conventionally known detergent surfactant may be used in combination. Such surfactants include, for example, alkyl benzene sulfonate, alkyl sulfate, α-
Olefin sulfonates, alkyl sulfonates, aliphatic amide sulfonates, dialkyl sulfosuccinates,
Examples include anionic surfactants such as alkyl ether sulfates, cationic surfactants such as alkylamine salts and quaternary ammonium salts, and amphoteric surfactants such as alkyl betaines.

Conventional nonionic surfactants, for example,
For higher primary alcohol ethoxylate, etc.
It is possible to use them together as long as the performance 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, miscellaneous goods, 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.

Another aspect of the present invention is an emulsifier comprising the above-mentioned higher secondary alcohol alkoxylate adduct. In the emulsifier of the present invention, the above-mentioned higher secondary alcohol alkoxylate adduct may be used alone, but may contain a conventionally known emulsifier. For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant or a zwitterionic surfactant generally used as an emulsifier can be used in combination.

There are no particular restrictions on the oily substances on which the emulsifier of the present invention can be used, and mineral oils, animal and vegetable oils,
It can be used for synthetic oils and the like. Examples of mineral oils include, for example, spindle oil, machine oil, liquid paraffin oil, and the like. Examples of animal and vegetable oils include:
Tallow, lard, fish oil, whale oil, rapeseed oil, sesame oil, coconut oil,
Examples include 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 and emulsifiers for emulsion polymerization.

[0036]

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

(Production method) Example 1 Secondary dodecanol ethoxylate adduct 1-dodecene was converted to a BEA type zeolite manufactured by PQ (trade name:
VALFOR CP811 BL-25) A dodecene isomer mixture (1-dodecene 25mo) obtained by reacting in a liquid phase at 5% by weight at 150 ° C for 10 hours.
1%, 75% by mole of inner decene)
0 g (4.82 mol), monoethylene glycol 9
00g (14.52 mol), and BEA type zeolite (trade name: VALFOR CP) manufactured by PQ as a catalyst.
811 BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser,
After the gas phase was replaced with nitrogen, the atmosphere was maintained at a normal pressure in a nitrogen atmosphere. Subsequently, 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. Thereafter, the reaction solution was cooled to room temperature, and the upper layer of the dodecene phase was separated and distilled. After distilling off unreacted dodecene, 155 g of secondary dodecanol monoethoxylate was obtained at a reduced pressure of 2 mmHg and a boiling point range of 129 to 131 ° C.

155 g (0.67 mol) of the obtained secondary dodecanol monoethoxylate and 0.2 g of sodium hydroxide as a catalyst were charged into a stainless steel autoclave, and after purging with nitrogen, the pressure in the reactor was raised to 1 with nitrogen. .
The pressure was adjusted to 0 kg / cm ² G, and after the temperature was raised to 150 ° C., 217 g (4.93 mol) of ethylene oxide was introduced into the autoclave in 3 hours. After the introduction, the temperature was kept at 150 ° C. for another hour, cooled to room temperature, and the internal pressure was purged.
A secondary dodecanol ethoxylate adduct having an average of 8.4 mol of oxyethylene groups was obtained.

Example 2 Secondary tetradecanol ethoxylate adduct 1-tetradecene was added to 5% by weight of BEA type zeolite (trade name: VALFOR CP 811 BL-25, manufactured by PQ) in a liquid phase at 150 ° C. for 13 hours. A tetradecene isomer mixture (1-tetradecene 20 mol%, inner tetradecene 80 mol) obtained by the reaction
%), 810 g (4.13 mol), 900 g (14.52 mol) of monoethylene glycol, and a BEA-type zeolite manufactured by PQ (trade name: VA) as a catalyst.
100 g of LFOR CP 811 BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser. After the gas phase was replaced with nitrogen, the atmosphere was kept under a nitrogen atmosphere at normal pressure. Subsequently, 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. Thereafter, the reaction solution was cooled to room temperature, and the upper tetradecene phase was separated and distilled. After distilling off unreacted tetradecene, 102 g of secondary tetradecanol monoethoxylate was obtained at a reduced pressure of 5 mmHg and a boiling range of 170 to 174 ° C.

A stainless steel autoclave was charged with 102 g (0.40 mol) of the obtained secondary tetradecanol monoethoxylate and 0.2 g of sodium hydroxide as a catalyst, and after replacing with nitrogen, the pressure in the reactor was changed to nitrogen. After the temperature was raised to 150 ° C. and the pressure was adjusted to 1.0 kg / cm ² G, 150 g (3.42 mol) of ethylene oxide was introduced into the autoclave over 3 hours. After the introduction, the temperature was further maintained at 150 ° C. for 1 hour, then cooled to room temperature, and the internal pressure was purged. Thus, a secondary tetradecanol ethoxylate adduct having an average of 9.6 mol of oxyethylene groups was obtained.

Examples 3 and 4 The following physical properties and interface properties of the substances obtained in Examples 1 and 2 (higher secondary alcohol alkoxylate adducts) were measured.

The results of these measurements are shown in Table 1 below.

Measurement method (1) Pour point Measured according to JIS K-2269 (Petroleum product pour point test method). (2) Penetration wool: 2 in accordance with JIS K-3362-1955
Nippon woolen 20 oz roller cross wool piece at 5 ° C 9
It measured using 0x10mm. (Activator concentration: 0.1
Cotton): Canvas 6 at 25 ° C by the campus disk method.
No. was measured. (Activator concentration: 0.25% by weight) (3) Foam JIS K-3362 (Rosmiles method)
It measured at 25 degreeC according to. (Activator concentration: 0.1% by weight)

[0044]

[Table 1]

Examples 5 and 6 With respect to the substances (higher secondary alcohol alkoxylate adducts) obtained in Examples 1 and 2, the following detergency was evaluated.

(Evaluation method) Referring to JIS K-3362, a stirring type detergency tester (Terg-O-tom) was used.
eter) under the following conditions. <Washing conditions> Soiled cloth: Size 5 × 5 cm Soil (%) Oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 2.5 Cholesterol 1.6 Gelatin 7.0 Red Yellow soil 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> Using a reflectometer, the reflectance of the original cloth before contamination, the artificially-contaminated cloth, and the cleaning cloth after cleaning were measured at three locations for each cloth of each test piece, and the average value was used to perform cleaning using the following formula. Force (%) was calculated.

[0047]

(Equation 1)

[0048]

[Table 2]

Examples 7 and 8 The substances obtained in Examples 1 and 2 (higher secondary alcohol alkoxylate adducts) 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

[0052]

[Table 3]

[0053]

The process for producing a higher secondary alcohol alkoxylate adduct of the present invention has the effects of being extremely simple, having high practicality, and being economically advantageous.

The higher secondary alcohol alkoxylate adduct of the present invention and the detergent and emulsifier containing the same, which are obtained thereby, have a particularly low pour point, are easy to handle, and have good penetrability. In addition, it has the characteristics of good foam removal, excellent cleaning power and emulsifying power.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiyuki Onda 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (4)

[Claims] 1. The method according to claim 1, wherein (poly) is added to the double bond of the long chain olefin.
A method for producing a higher secondary alcohol alkoxylate adduct, further comprising adding an alkylene oxide to a higher secondary alcohol alkoxylate obtained by adding an alkylene glycol. 2. A higher secondary alcohol alkoxylate adduct obtained by the production method according to claim 1. 3. A cleaning agent comprising the higher secondary alcohol alkoxylate adduct of claim 2. 4. An emulsifier comprising the higher secondary alcohol alkoxylate adduct of claim 2.