JPH09262456A - Purifying method of nonionic surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a purifying method of a nonionic surfactant which hardly causes a clogging of a filter paper and a filter cloth, is excellent in separating operation and high in utilization value industrially. SOLUTION: In this purifying method, a nonionic surfactant crude product obtained by subjecting alkylene oxide to additional reaction with a compd. containing an active hydrogen and/or fatty alkylate is brought into contact with acrylic polymer and water, and a polyalkylene glycol produced secondarily and an alkoxylation catalyst are separated and removed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for purifying a nonionic surfactant capable of removing by-produced high molecular weight polyalkylene glycol and an alkoxylation catalyst by a simple separation operation.

BACKGROUND OF THE INVENTION Alkylene oxide adducts such as higher alcohols and fatty acid alkyl esters are used as sulfuric acid as various nonionic surfactants to be mixed in liquid detergents for clothes, shampoos, dishwashing detergents, household detergents and the like. It is useful as an intermediate for producing a corresponding anion activator by esterification or carboxymethylation, or as an intermediate for other industrial products. In recent years, as an alkoxylation catalyst for obtaining a reactant having a narrow alkylene oxide addition mole distribution, for example, magnesium oxide to which aluminum, gallium, indium, thallium, etc. have been added (Japanese Patent Publication No. 6-1
No. 5038), calcined hydrotalcite containing magnesium and aluminum as main components (JP-A-2-7184).
No. 1) has been proposed.

However, the crude product (alkylene oxide adduct) obtained by using these alkoxylation catalysts has a narrow range of addition mole distribution, pour point, water solubility,
The residual amount of active hydrogen-containing compound in the raw material is small and it is advantageous in physical properties such as odor and quality (JAOCS, Volume 63, 365-370,
HAPPI 32-37, April, 1986, 52-54, May, 1986), since by-products such as polyalkylene glycol are produced in the reaction solution, liquid detergent for clothes, shampoo, dishwashing agent,
In order to use it as a household cleaning agent or the like, it is necessary to separate and remove the catalyst and the by-product polyalkylene glycol contained in the crude product of the alkoxylation reaction before use. When the high-molecular weight polyalkylene glycol by-product is separated and removed by a filtration operation or the like, it is easy to cause clogging of the filter paper or the filter cloth, the filtration speed is slow, and not only a large filtration facility is industrially required, Since high molecular weight polyalkylene glycol remains in the filtrate, there are drawbacks such as affecting the liquidity and the stability of the product depending on the application.

[0003]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a method for purifying a nonionic surfactant which is free from clogging of a filter paper or a filter cloth and which is excellent in separation operation and which has high industrial utility value. To do.

Means for Solving the Problems The present invention provides a high molecular weight polyalkylene glycol and an alkoxylation catalyst which are by-produced when a crude product of a nonionic surfactant is brought into contact with an acrylic polymer and water and then filtered. This was done based on the finding that it can be removed efficiently. That is, the present invention provides an active hydrogen-containing compound and / or an active hydrogen-containing compound in the presence of an alkoxylation catalyst.
Alternatively, a nonionic surfactant crude product obtained by addition reaction of alkylene oxide with fatty acid alkyl ester is brought into contact with an acrylic polymer and water to separate and remove by-produced polyalkylene glycol and alkoxylation catalyst. A method for purifying a nonionic surfactant is provided.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION A crude product of a nonionic surfactant to be purified in the present invention is obtained by adding an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of an alkoxylation catalyst. It was obtained. Here, as the alkoxylation catalyst, magnesium ion-added magnesium oxide (Japanese Patent Publication No. 6-15038, JP-A No. 7-227540, and No. 6-19816).
No. 9, No. 6-182206, No. 5-1706
88), calcined hydrotalcite (JP-A-2-7)
No. 1841), aluminum hydroxide / magnesium fired products (Japanese Patent Application No. 7-94417), and other Al-Mg.
-Based complex oxide catalysts or surface-modified catalysts thereof (Japanese Patent Application Nos. 6-334781 and 6-334782)
In addition, barium oxide, hydroxide (JP-A-54-75187), strontium oxide, hydroxide (JP-B-63-32055), calcium compound (JP-A-2). -134336 gazette, the same 2-
No. 135144).

The active hydrogen-containing compound may be any compound that can be alkoxylated and is not particularly limited, and alcohols, polyols, amines,
Alkanolamides or mixtures thereof can be used. Examples of alcohols include carbons such as n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, oleyl alcohol, etocosanol, behenol, nonanol, undecanol and tridecanol. A higher aliphatic primary alcohol having a saturated or unsaturated linear alkyl group having a number of 8 to 22, or a branched chain alkyl primary alcohol such as 2-ethylhexanol or a Guerbet alcohol having a carbon number of 16 to 36; And secondary alcohols such as 2-octanol, 2-decanol, and 2-dodecanol, and
Benzyl alcohol and the like. Examples of the polyols include alcohols having a divalent to octavalent functional group such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, sorbitol, trimethylolpropane, and pentaerythritol.

Examples of amines include octylamine, dioctylamine, laurylamine, dilaurylamine stearylamine, distearylamine and the like having 8 to 36 carbon atoms.
And primary or secondary amines having a saturated or unsaturated alkyl group, and polyamines such as ethylenediamine and diethylenetriamine. Examples of the alkanolamide include alkanolamides having 12 to 18 carbon atoms such as lauryl monoethanolamide and lauryl diethanolamide. Among these active hydrogen-containing compounds, a straight-chain or branched saturated or unsaturated alcohol having 8 to 22 carbon atoms is preferable. The fatty acid alkyl ester is represented by the general formula R ₁ COOR ₂ , where R ₁ has 6 to ₁₀ carbon atoms.
No. 22 and R ₂ preferably have 1 to 30 carbon atoms. Here, the alkyl group is a concept including a so-called alkenyl group containing a double bond in a carbon chain. Also,
Triglyceride which is a fatty acid ester of glycerin is also included in this.

The alkylene oxide has 2 to 2 carbon atoms.
The alkylene oxide of 4 is mentioned as a preferable one. Specifically, it is ethylene oxide, propylene oxide, butylene oxide or the like, and these can be used as one kind or as a mixture of two or more kinds. In the present invention, it is preferable to add 1 to 50 mol of alkylene oxide per mol of the active hydrogen-containing compound and / or fatty acid alkyl ester. Further, as the nonionic surfactant, those having HLB of 3 to 20 are preferable. The target nonionic surfactant crude product can be easily prepared using the above-mentioned raw materials under well-known operating procedures and reaction conditions. The reaction temperature is preferably 80 to 230 ° C., and the reaction pressure depends on the reaction temperature, but is 0 to 20 atm, preferably 2 to
It is 8 atm, and the alkylene oxide can be subjected to the addition reaction under the condition of diluting with nitrogen if necessary. The amount of the alkoxylation catalyst to be used varies depending on the type of the alkylene oxide and the active hydrogen-containing compound used in the reaction, or the hydrophobic raw material such as fatty acid alkyl ester, and the number of added moles. Weight percent is preferred. The above reaction can be obtained by, for example, charging an active hydrogen-containing compound and / or a fatty acid alkyl ester and an alkoxylation catalyst in an autoclave and introducing alkylene oxide under a predetermined temperature and pressure conditions in a nitrogen atmosphere to carry out a reaction. it can.

The acrylic polymer used in the present invention is a polymer selected from the group consisting of acrylic acid or methacrylic acid monomer or its alkali metal salt and a copolymerizable monomer as a main component. Is preferred. Here, as the neutralized salt of acrylic acid monomer, for example, sodium salt,
Examples thereof include potassium salts, amine salts and the like, and those partially neutralized at 1 to 30 mol% are preferable. It should be noted that increasing the ratio of the neutralizing salt increases the viscosity of the polymer aqueous solution, which is not preferable in terms of handling. The copolymerizable monomer is a (meth) acrylic acid alkyl ester (alkyl group having 1 to 18 carbon atoms), for example, methyl or ethyl methacrylate,
Methyl or ethyl acrylate may be mentioned, and it is preferably used in an amount of 1 to 25 mol%. Further, unsaturated polyvalent carboxylic acids such as itaconic acid and maleic acid can be exemplified.
It is preferably used in an amount of 50 mol%.

More specifically, polyacrylic acid homopolymers, polymethacrylic acid homopolymers, salts thereof (including partially neutralized salts), acrylic acid and / or methacrylic acid 99 to 75 mol% and (meth) acrylic. Copolymers with 1 to 25 mol% of acid alkyl ester, salts thereof (including partially neutralized salts), acrylic acid and / or methacrylic acid 98 to 49
Mol%, (meth) acrylic acid alkyl ester 1 to 25
Examples thereof include copolymers of 1 mol% to 50 mol% of unsaturated polycarboxylic acid and salts thereof (including partially neutralized salts). A preferred weight average molecular weight of such an acrylic polymer is
500 to 2,000,000, particularly preferably 100
It is 0 to 1,000,000. In the present invention, it is particularly preferable to use a water-soluble acrylic polymer. The water used in the present invention is preferably distilled water, ion-exchanged water, tap water, well water, or the like.

In the present invention, the crude nonionic surfactant can be contacted with the acrylic polymer and water in any manner. For example, an acrylic polymer and water or an aqueous acrylic polymer solution is added to and mixed with a crude product of a nonionic surfactant. The temperature at this time is 40 to 100 ° C. (preferably 60 to 90 ° C.), and it is preferable to stir for about 5 to 60 minutes. It should be noted that it is possible to leave (stand still) after stirring. Here, the nonionic surfactant crude product [A] and water [C] are
7/3 to 70/30 (weight ratio), and 0.01 to 1 part by weight of the acrylic polymer [B] per 100 parts by weight of the total amount of the crude nonionic surfactant [A] and water [C]. It is good to have a part. More preferably, the nonionic surfactant crude product [A] and water [C] are 95/5 to 80/20.
(Weight ratio), and the acrylic polymer [B] is 0.02 to 0.7 parts by weight per 100 parts by weight of the total amount of the crude nonionic surfactant [A] and water [C]. Furthermore, after adding and mixing the acrylic polymer [B] and water [C] as a treating agent to the crude product [A], a high molecular weight polyalkylene glycol as a by-product and a specific alkoxylation catalyst are filtered off by a filtration operation. If necessary, a filter aid can be added before the removal.

As the filter aid, known filter aids can be used. For example, if the main component SiO ₂ is 80
As amorphous silicate diatomaceous earth containing ~ 95%,
For example, Radio Light # 100, Radio Light # 200,
Radio Light # 500, Radio Light # 600, Radio Light # 900, Gem Light Super M, Gem Light Super 1, Gem Light Super 56, Gem Light Super 2, Celite 501, Celite 503, Celite 53
5, Celite 545, high flow supercell, standard supercell, filter cell and the like. Examples of the aluminum silicate containing about 70% of SiO ₂ as the main component include Topco # 31 and Topco # 34. Cellulose-based filter aids include KC floc, SW40, BW20, BW40, BW100 and BW.
200, BNB20 and the like. Examples of the activated carbon, synthetic zeolite, silica gel, activated alumina, and clay or clay mineral include acid clay and activated clay, which can be used alone or as a mixture of two or more kinds. The amount of the filter aid used is preferably about 0.05 to 5% by weight based on the crude product [A]. In the present invention, the nonionic surfactant crude product is thus contacted with the acrylic polymer and water and then filtered by a conventional method. For example, using a two-layer filter of cellulose and polyester as a filter paper, a metal mesh type filter,
It is preferable to filter under reduced pressure or increased pressure at a temperature of 40 to 100 ° C. Furthermore, it is also possible to perform filtration by using a centrifugal separator such as a decanter or a centrifugal clarifier.

[0012]

EFFECTS OF THE INVENTION According to the purification method of the present invention, it is easy to separate and remove the alkoxylation catalyst and the by-product polyalkylene glycol from the crude product without causing clogging of the filter paper or the filter cloth during the filtration operation. Further, according to the purification method of the present invention, the content of by-produced polyalkylene glycol contained in the filtrate can be extremely reduced, so that the purification method of the present invention has an extremely great industrial utility value. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the examples,% is based on weight unless otherwise specified.

EXAMPLES Reference Example I An alkoxylation catalyst was prepared by the following method. Catalyst Example 1 Commercially available Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O
[Kyowa Chemical Industry Co., Ltd., trade name KYOWARD 500], the hydrotalside of the chemical composition, under nitrogen atmosphere, 6
The catalyst was obtained by calcining at 00 ° C for 3 hours.

Catalyst Example 2 Commercially available 2.5 MgO Al_TwoO_Three・ NH_TwoO [Kyowa Chemical Industry
Industry Co., Ltd. product name KYOWARD 300AS]
Made of aluminum and magnesium hydroxide
It was then fired. Catalyst Example 3 According to the method described in Example 4 of JP-A-7-227540.
From Mg-Sb_TwoO _ThreeCatalyst (Mg: Sb (atomic ratio) =
1: 0.05) was obtained.Reference example II Preparation of nonionic surfactant crude product [A] by the following method
did. Crude Product Example 1 A compound containing active hydrogen was added to a 4 liter autoclave.
Lauryl alcohol 97.7g (0.52mol), die
Yadol 13 (C13 alcohol: Mitsubishi Chemical Co., Ltd.)
293.1 g (1.45 mol) of the catalyst obtained in Catalyst Example 2
Charge 0.39 g (0.1% / compound containing active hydrogen), nitrogen
After the replacement, the temperature was raised (160 ° C.) with stirring. Then
While keeping the temperature at 180 ° C and the pressure at 3 atm,
Introduce 608.9 g (7 mol) of oxide and carry out the reaction.
Was. After aging for 0.5 hours at the same temperature, cool to 80 ° C and coarse
I got a product.

Crude Product Example 2 In a 4-liter autoclave, 376 g (2 mol) of lauryl alcohol as a compound containing active hydrogen and Catalyst Example 2 were used.
Charge 0.38 g (0.1% / lauryl alcohol) of the catalyst obtained in (1), replace with nitrogen, and then raise the temperature with stirring (160
° C). Then, while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 616 g (7 mol) of ethylene oxide was introduced and a reaction was carried out. After aging for 0.5 hours at the same temperature,
After introducing 232 g (2 mol) of propylene oxide under the same reaction conditions, the mixture was aged at the same temperature for 1.5 hours and then cooled to 80 ° C. to obtain a crude product. Crude Product 3 A crude product was obtained in the same manner as in Crude Product 2 except that 1.14 g of the catalyst obtained in Catalyst Example 1 was used and propylene oxide was not introduced. Crude Product Example 4 A crude product was obtained in accordance with Crude Product Example 1 except that 750 g of lauric acid methyl ester, 7.5 g of the catalyst obtained in Catalyst Example 2 and 772 g of ethylene oxide were used as the active hydrogen-containing compound. Crude Product 5 Crude Product 1 except that 3.76 g of the catalyst obtained in Catalyst Example 3 was used.
A crude product was obtained according to.

Example 1 400 g of the crude product [A] obtained in the crude product example 1 was placed in a 1 liter four-necked flask equipped with a stirrer and heated to 80 ° C. Then, as a treating agent, ion-exchanged water [C] 81.9
g (equivalent to 17%) and acrylic polymer [B] (acrylic acid polymer, solid content 39.6%, viscosity 59 cps / 25)
℃, pH 2.5 (1% water solution), molecular weight about 6000)
After adding 1.52 g and mixing at 75 ° C. for 1 hour, the by-product polyalkylene glycol and the alkoxylation catalyst were removed by filtration to obtain a purified product. The filtration apparatus used was a two-layer filter of cellulose and polyester, a pressure filter having an inner diameter of 4 cm, and a temperature of 80 ° C. and a nitrogen pressure of 1 kg / cm ² .G. Example 2 After adding and mixing a treating agent, activated clay 1.44 was used as a filter aid.
g and 2.41 g of KC floc were added and the same procedure as in Example 1 was performed except that the mixture was stirred for 30 minutes. Example 3 As an acrylic polymer [B], an acrylic acid polymer, solid content 40.2%, viscosity 35 cps / 25 ° C., pH 1.6
(1% aqueous solution), the molecular weight was about 3000 except that the procedure was the same as in Example 1.

Example 4 As an acrylic polymer [B], an acrylic acid polymer, solid content 39.8%, viscosity 1430 cps / 25 ° C., pH 2.7.
(1% aqueous solution), the molecular weight was about 20,000 to 30,000. Example 5 As an acrylic polymer [B], an acrylic acid polymer, solid content 20.3%, viscosity 32000 cps / 25 ° C., pH
3.3 (1% aqueous solution), molecular weight of about 200,000 to 300,000
0.78g added, KC floc 2.41g as a filter aid
The same procedure as in Example 1 was performed except that addition and mixing were performed. Example 6 As an acrylic polymer [B], an acrylic acid polymer, solid content 39.6%, viscosity 59 cps / 25 ° C., pH 2.5.
(1% aqueous solution) having a molecular weight of about 6000 (2 g) was added, and as a filter aid, 1.44 g of activated clay and 2.41 g of KC floc were added and mixed. Example 7 Example 7 was repeated except that the amount of the acrylic polymer [B] added was changed to 3 g.

Example 8 65.5 g (equivalent to 14%) of ion exchanged water [C] as a treating agent, 1.4 g of activated clay as a filter aid, KC floc
Example 2 was repeated except that 1.4 g was added. Example 9 The procedure of Example 8 was repeated except that the amount of ion-exchanged water [C] was changed to 44.4 g (corresponding to 10%). Table 1 shows the filtration rates of Examples 1 to 12 and the amount of polyalkylene glycol in the filtrate. The content of high molecular weight polyalkylene glycol was measured by the following method. Column: GS-310 φ7.6mm × 0.5m, 30
Mobile phase: CH ₃ CN / H ₂ O = 45/55 (vol / vol ratio),
1 ml / min Detector: RI Model: RID-6A (Shimadzu)

[0018]

[Table 1] Table-1 Example Crude product Acrylic ion-exchange filter aid Filtration rate PAG [A] polymer [B] water conversion [C] activated clay KC floc (g / 10 minutes) (%) 1 Example 1 1.52g 81.9g − − 338.2g 0.03 400g (Mw = 6000) (Moisture 17%) 2 Example 1 1.52g 81.9g 1.44g 2.41g 442.4g 0.02 400g (Mw = 6000) (Moisture 17%) 3 Example 1 1.52g 81.9g − − 396.9 0.04 400g (Mw = 3000) (Moisture 17%) 4 Example 1 1.52g 81.9g − − 286.5 0.03 400g (Mw = 20,000 to 30,000) (Moisture 17%) 5 Example 1 0.78g 81.9g − 2.41g 304.1 0.09 400g (Mw = 200,000-300,000) (water content 17%) 6 Example 1 2.0g 81.9g 1.44g 2.41g 440.1 trace 400g (Mw = 6000) (water content 17%) 7 Example 1 3.0g 81.9g 1.44g 2.41g 429.8 trace 400g ( Mw = 6000) (moisture 17%) 8 Example 1 1.52g 65.5g 1.4g 1.4g 248.6 0.07 400g (Mw = 6000) (moisture 14%) 9 Example 1 1.52g 44.4g 1.4g 1.4g 219.9 0.10 400g (Mw = 6000) (water content 10%) In the table, PAG means high molecular weight polyalkylene glycol (the same applies hereinafter).

Example 10 The same procedure as in Example 1 was carried out except that the amount of the crude product [A] obtained in the crude product example 2 was changed to 400 g. C ₁₂ alcohol + 7EO · 2P
A purified product of O was obtained (EO: ethylene oxide, PO:
Indicates propylene oxide. ). Example 11 A purified product of C ₁₂ alcohol +7 EO was obtained in the same manner as in Example 10 except that the amount of the crude product [A] obtained in the crude product example 3 was changed to 400 g. Example 12 A purified product of lauric acid polyoxyethylene methyl ether (number of moles added: 5) was obtained in the same manner as in Example 10 except that the amount of the crude product [A] obtained in the crude product example 4 was changed to 400 g.

Example 13 400 g of the crude product example 5 in Example 1 and partial neutralization (pH 2.5 → 3.7 (1% aqueous solution) with the acrylic polymer [B] using 30% NaOH aqueous solution as an alkali metal salt. )) Was performed according to Example 2. Comparative Example 1 Crude product example 1 in a 1-liter four-necked flask equipped with a stirrer
400 g of the alkylene oxide adduct obtained in 1. was heated to 80 ° C. Next, 0.4 g of activated clay and 2.0 g of KC floc were added as a filter aid and held for 30 minutes, and a two-layer filter of cellulose and polyester was attached.
cm pressure filter, temperature 80 ℃, nitrogen pressure 1Kg
The filtration operation was performed at / cm ² .G. Comparative Example 2 Alkylene oxide adduct 400 obtained in Crude Product Example 3
g, ion-exchanged water 70.6 g (15% / crude product), and KC floc 2.0 g as a filter aid were mixed at 80 ° C. Then, the alkoxylation catalyst and the high molecular weight polyalkylene glycol were separated and removed by the pressure filter used in Comparative Example 1. The results of Examples 10 to 13 and Comparative Example 1 (14 in the table) and Comparative Example 2 (15 in the table) are shown in Table-2.

[0021]

[Table 2] Table-2 Example Crude product Acrylic ion exchange filter aid Filtration rate PAG [A] polymer [B] water conversion [C] activated clay KC flocs (g / 10 min) (%) 10 Example 2 1.52g 81.9g − − 411.2 0.03 400g (Mw = 6000) Moisture 17% 11 Example 3 1.52g 81.9g − − 424.8 0.02 400g (Mw = 6000) Moisture 17% 12 Example 4 1.52g 81.9g − − 438.3 0.01 400g (Mw = 6000) Moisture 17% (g / 6 minutes) 13 Example 5 1.52g 81.9g 1.44g 2.41g 394.7 0.03 400g (Mw = 6000) Moisture 17% Partially neutralized Na salt * 1 14 Example 1 − − 0.4g 2.0g 28.6 − 400g 15 Example 3 − 70.6 g-2.0g 197.8 0.28 400g (water content 15%) * 1 Acrylic polymer [B] adjusted to pH 3.7 by adding 30% NaOH aqueous solution

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Itsuo Hama 1-3-7 Honjo, Sumida-ku, Tokyo Lion Corporation

Claims (1)

[Claims] 1. A nonionic surfactant crude product obtained by addition reaction of an alkylene oxide with an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of an alkoxylation catalyst is contacted with an acrylic polymer and water. A method for purifying a nonionic surfactant, characterized in that the by-produced polyalkylene glycol and the alkoxylation catalyst are separated and removed.