JP3550248B2 - Purification method of nonionic surfactant - Google Patents

Description

表中、ＰＡＧは高分子量ポリアルキレングリコールを意味する（以下同じ）。
【００１９】
実施例１０
粗製物例２で得た粗製物〔Ａ〕を４００ｇにした以外は実施例１に準じて行い、Ｃ_１２アルコール＋７ＥＯ・２ＰＯの精製品を得た（ＥＯ：エチレンオキサイド、ＰＯ：プロピレンオキサイドを示す。）。
実施例１１
粗製物例３で得た粗製物〔Ａ〕を４００ｇにした以外は実施例１０に準じて行い、Ｃ_１２アルコール＋７ＥＯの精製品を得た。
実施例１２
粗製物例４で得た粗製物〔Ａ〕を４００ｇにした以外は実施例１０に準じて行い、ラウリン酸ポリオキシエチレンメチルエーテル（付加モル数 ５）の精製品を得た。
【００２０】
実施例１３
実施例１で粗製物例５ ４００ｇ、アクリル系重合体〔Ｂ〕にアルカリ金属塩として３０％ＮａＯＨ水溶液を用いて部分中和（ｐＨ２．５→３．７（１％水溶液））した以外は実施例２に準じて行った。
比較例１
撹拌器を備えた１リットルの四口フラスコに粗製物例１で得たアルキレンオキサイド付加物４００ｇを８０℃に加温した。次いで、ろ過助剤として、活性白土０．４ｇとＫＣフロック２．０ｇを添加し３０分保持し、セルロースとポリエステルの二層フィルターを取り付けた、内径４ｃｍの加圧ろ過器に投入して温度８０℃、窒素圧１Ｋｇ／ｃｍ^２．Ｇでろ過操作を行った。
比較例２
粗製物例３で得たアルキレンオキサイド付加物４００ｇ、イオン交換水７０．６ｇ（１５％／粗製物）及びろ過助剤としてＫＣフロック２．０ｇを８０℃で混合した。次いで、比較例１で用いた加圧ろ過器でアルコキシル化触媒と高分子量ポリアルキレングリコールを分離除去した。
実施例１０〜１３及び比較例１（表中１４）と比較例２（表中１５）の結果を表−２に示す。
【００２１】
【表２】表−２

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for purifying a nonionic surfactant capable of removing high-molecular-weight polyalkylene glycol and an alkoxylation catalyst by-produced by a simple separation operation.
[Prior art]
Alkylene oxide adducts such as higher alcohols and fatty acid alkyl esters are used as various nonionic surfactants in liquid detergents for clothing, shampoos, dishwashing detergents, household detergents, etc. It is useful as an intermediate for producing a corresponding anionic activator by carrying out the reaction, 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 molar distribution, for example, magnesium oxide to which aluminum, gallium, indium, thallium or the like is added (Japanese Patent Publication No. 6-15038), magnesium and aluminum are mainly used. As a component, calcined hydrotalcite (JP-A-2-71841) has been proposed.
[0002]
However, the crude product (alkylene oxide adduct) obtained using these alkoxylation catalysts has a narrow addition molar distribution range, a pour point, water solubility, a small amount of the active hydrogen-containing compound as a raw material and a small odor. (JAOCS, Vol. 63, 365-370, HAPPI 32-37, April, 1986, 52-54, May, 1986), but the reaction solution contains polyalkylene glycol or the like. Since by-products are generated, the catalysts and by-product polyalkylene glycols contained in the crude product of the alkoxylation reaction are used in applications such as liquid detergents for clothing, shampoos, dishwashers, and household detergents. Must be used after separation.
When separating and removing high-molecular-weight polyalkylene glycol by-produced by filtration or the like, filter paper or filter cloth is easily clogged, the filtration speed is slow, and not only industrially a large amount of filtration equipment is required, Since high molecular weight polyalkylene glycol remains in the filtrate, there are drawbacks such as affecting the liquid properties and product stability depending on the application.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for purifying a nonionic surfactant which is free from clogging of filter paper and filter cloth and excellent in separation operation and has high industrial value.
[Means for Solving the Problems]
The present invention is based on the finding that, when a nonionic surfactant crude product is passed through after contacting with an acrylic polymer and water, high-molecular-weight polyalkylene glycol and an alkoxylation catalyst by-produced can be efficiently removed. It was done.
That is, the present invention provides a nonionic surfactant crude product obtained by an addition reaction of an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of an alkoxylation catalyst, by adding an acrylic polymer and water to Provided is a method for purifying a nonionic surfactant, which comprises contacting and separating and removing a polyalkylene glycol and an alkoxylation catalyst by-produced.
[0004]
BEST MODE FOR CARRYING OUT THE INVENTION
The crude nonionic surfactant to be purified in the present invention is obtained by an addition reaction of an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of an alkoxylation catalyst.
Examples of the alkoxylation catalyst include metal ion-added magnesium oxide (JP-B-6-15038, JP-A-7-227540, JP-A-6-198169, JP-A-6-182206, and JP-A-5-170688). ), Calcined hydrotalcite (JP-A-2-71841), Al-Mg-based composite oxide catalysts such as calcined aluminum hydroxide / magnesium (Japanese Patent Application No. 7-94417), or surface modification thereof Catalysts (Japanese Patent Application Nos. 6-33481 and 6-334772), oxides and hydroxides of barium (JP-A-54-75187), oxides and strontium oxides and hydroxides (JP-B-63-32055) and calcium compounds (JP-A-2-134336 and JP-A-2-135144). It is.
[0005]
The active hydrogen-containing compound may be any compound as long as it is alkoxylated, and is not particularly limited. Alcohols, polyols, amines, alkanolamides, and 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 of 8 to 22 or a branched alkyl primary alcohol such as 2-ethylhexanol or a Guerbet alcohol having 16 to 36 carbon atoms; And secondary alcohols such as 2-octanol, 2-decanol and 2-dodecanol, and benzyl alcohol.
Examples of the polyols include alcohols having two to eight functional groups such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, sorbitol, trimethylolpropane, and pentaerythritol.
[0006]
As amines, octylamine, dioctylamine, laurylamine, dilaurylamine stearylamine, primary or secondary amine having a saturated or unsaturated alkyl group having 8 to 36 carbon atoms such as distearylamine, Examples thereof include 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 linear or branched, saturated or unsaturated alcohol having 8 to 22 carbon atoms is preferred.
The fatty acid alkyl ester is represented by the general formula R ₁ COOR ₂ , and preferably has 6 to 22 carbon atoms of R ₁ and 1 to 30 carbon atoms of R ₂ . Here, the alkyl group is a concept including a so-called alkenyl group containing a double bond in a carbon chain.
In addition, triglyceride, which is a fatty acid ester of glycerin, is also included in this.
[0007]
As the alkylene oxide, an alkylene oxide having 2 to 4 carbon atoms is preferable. Specifically, ethylene oxide, propylene oxide, butylene oxide and the like can be used alone or as a mixture of two or more. In the present invention, it is preferable that 1 to 50 mol of alkylene oxide is added per 1 mol of active hydrogen-containing compound and / or fatty acid alkyl ester. The nonionic surfactant preferably has an HLB of 3 to 20.
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 from 80 to 230 ° C, and the reaction pressure is from 0 to 20 atm, preferably from 2 to 8 atm, depending on the reaction temperature. If necessary, the addition reaction of the alkylene oxide can be carried out under a condition diluted with nitrogen. The amount of the alkoxylation catalyst varies depending on the type of the alkylene oxide and the active hydrogen-containing compound to be subjected to the reaction, or the type of hydrophobic raw material such as fatty acid alkyl ester, and the number of moles added. % By weight is preferred.
The above reaction can be obtained, for example, by charging an active hydrogen-containing compound and / or a fatty acid alkyl ester and an alkoxylation catalyst in an autoclave, and introducing an alkylene oxide under a predetermined temperature and pressure condition under a nitrogen atmosphere to perform a reaction. it can.
[0008]
The acrylic polymer used in the present invention is preferably a polymer selected from the group consisting of an acrylic acid or methacrylic acid monomer or an alkali metal salt thereof and a copolymerizable monomer as a main component.
Here, as the neutralized salt of the acrylic acid monomer, for example, a sodium salt, a potassium salt, an amine salt or the like can be mentioned, and a partially neutralized salt of 1 to 30 mol% is preferable. Incidentally, if the ratio of the neutralized salt is increased, the viscosity of the aqueous polymer solution becomes high, which is not preferable from the viewpoint of handling.
Examples of the copolymerizable monomer include (meth) acrylic acid alkyl ester (alkyl group having 1 to 18 carbon atoms), for example, methyl or ethyl methacrylate, methyl or ethyl acrylate, and 1 to 25 mol. % Is preferably used. Further, unsaturated polycarboxylic acids such as itaconic acid and maleic acid can be exemplified, and it is preferable to use them in an amount of 1 to 50 mol%.
[0009]
More specifically, polyacrylic acid homopolymer, polymethacrylic acid homopolymer, salts thereof (including partially neutralized salts), acrylic acid and / or methacrylic acid 99 to 75 mol% and (meth) acrylic acid alkyl ester 1 to 25 mol% of a copolymer, a salt thereof (including a partially neutralized salt), 98 to 49 mol% of acrylic acid and / or methacrylic acid, and 1 to 25 mol% of an alkyl (meth) acrylate and unsaturated Copolymers with 1 to 50 mol% of polyvalent carboxylic acid, and salts thereof (including partially neutralized salts).
The preferred weight average molecular weight of such an acrylic polymer is from 500 to 2,000,000, particularly preferably from 1,000 to 1,000,000. In the present invention, it is particularly preferable to use a water-soluble acrylic polymer.
As the water used in the present invention, it is preferable to use distilled water, ion-exchanged water, tap water, well water and the like.
[0010]
In the present invention, the crude nonionic surfactant can be brought into contact with the acrylic polymer and water in any manner. For example, an acrylic polymer and water or an aqueous acrylic polymer solution are added to and mixed with a crude nonionic surfactant. At this time, the temperature is preferably stirred at 40 to 100 ° C (preferably 60 to 90 ° C) for about 5 to 60 minutes. In addition, after stirring, it can also be left (rested). Here, the nonionic surfactant crude product [A] and water [C] are 97/3 to 70/30 (weight ratio), and the nonionic surfactant crude product [A] and water [C] It is preferred that the acrylic polymer [B] be 0.01 to 1 part by weight per 100 parts by weight in total. More preferably, the nonionic surfactant crude [A] and water [C] are 95/5 to 80/20 (weight ratio), and the nonionic surfactant crude [A] and water [C] are used. And the acrylic polymer [B] is 0.02 to 0.7 parts by weight per 100 parts by weight of the total.
Further, 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 separated by filtration by filtration. Before removal, a filter aid may be added, if necessary.
[0011]
As the filter aid, a well-known filter aid can be used. For example, a diatomaceous earth of amorphous silicate containing SiO ₂ as the main component 80% to 95%, for example Radiolite # 100, Radiolite # 200, Radiolite # 500, Radiolite # 600, Radiolite # 900 , Zemrite Super M, Zemlite Super 1, Zemlite Super 56, Zemlite Super 2, Celite 501, Celite 503, Celite 535, Celite 545, Hyflo Super Cell, Standard Super Cell, and Filter Cell. Examples of the aluminum silicate containing about 70% of SiO ₂ as a main component include Topco # 31 and Topco # 34, and examples of the cellulose-based filter aid include KC floc, SW40, BW20, BW40, BW100, and BW200. , BNB20 and the like.
Furthermore, examples of the activated carbon, synthetic zeolite, silica gel, activated alumina, and clay or clay mineral include acid clay, activated clay, and the like, and each can be used alone or as a mixture of two or more. 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 crude nonionic surfactant is thus brought into contact with the acrylic polymer and water, and then filtered by a conventional method. For example, it is preferable to use a two-layer filter of cellulose and polyester, a metal mesh filter, or the like as filter paper, and filter under reduced pressure or pressure at a temperature of 40 to 100 ° C.
Furthermore, filtration using a centrifuge such as a decanter or a centrifugal clarifier can also be performed.
[0012]
[Effects of the present invention]
According to the purification method of the present invention, the alkoxylation catalyst and the by-product polyalkylene glycol can be easily separated and removed from the crude product without causing clogging of the filter paper or filter cloth during the filtration operation. Further, according to the purification method of the present invention, the content of by-product polyalkylene glycol contained in the filtrate can be extremely reduced, so that the purification method of the present invention has extremely large industrial value.
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. The percentages in the examples are on a weight basis unless otherwise specified.
【Example】
Reference Example I
The alkoxylation catalyst was prepared in the following manner.
Catalyst example 1
A commercially available hydrotalside having a chemical composition of Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O (trade name of Kyowa Chemical Industry Co., Ltd., Kyoward 500) is fired at 600 ° C. for 3 hours in a nitrogen atmosphere. Thus, a catalyst was obtained.
[0013]
Catalyst example 2
A commercially available aluminum / magnesium hydroxide having a chemical composition of 2.5 MgO Al ₂ O ₃ .nH ₂ O [Kyowa Chemical Industry Co., Ltd. product name Kyoward 300AS] was calcined according to Catalyst Example 1.
Catalyst example 3
By the method described in Example 4 of JP-A-7-227540 discloses, _Mg-Sb 2 _{O 3} catalyst (Mg: Sb (atomic ratio) = 1: 0.05) was obtained.
Reference Example II
A crude nonionic surfactant [A] was prepared by the following method.
Crude product example 1
In a 4 liter autoclave, 97.7 g (0.52 mol) of lauryl alcohol, 293.1 g (1.45 mol) of Diadol 13 (alcohol having 13 carbon atoms, manufactured by Mitsubishi Chemical Corporation) as an active hydrogen-containing compound, and Catalyst Example 2 0.39 g (0.1% / active hydrogen-containing compound) of the catalyst obtained in the above was charged, and the temperature was raised (160 ° C.) with stirring after nitrogen replacement. Next, while maintaining the temperature at 180 ° C. and the pressure at 3 atm, 608.9 g (7 mol) of ethylene oxide was introduced to carry out the reaction. After aging at the same temperature for 0.5 hour, the mixture was cooled to 80 ° C to obtain a crude product.
[0014]
Crude product example 2
Into a 4 liter autoclave, 376 g (2 mol) of lauryl alcohol and 0.38 g (0.1% / lauryl alcohol) of the catalyst obtained in Catalyst Example 2 were charged as active hydrogen-containing compounds, and after purging with nitrogen, the mixture was raised 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 to carry out the reaction. After aging at the same temperature for 0.5 hour, 232 g (2 mol) of propylene oxide was introduced under the same reaction conditions, then aging was performed at the same temperature for 1.5 hours, and then cooled to 80 ° C to obtain a crude product. .
Crude product example 3
A crude product was obtained in the same manner as the crude product 2 except that the amount of the catalyst obtained in Catalyst Example 1 was 1.14 g and propylene oxide was not introduced.
Crude product example 4
A crude product was obtained according to Crude Product Example 1 except that the active hydrogen-containing compound was 750 g of lauric acid methyl ester, 7.5 g of the catalyst obtained in Catalyst Example 2, and 772 g of ethylene oxide.
Crude product example 5
A crude product was obtained according to Crude Product 1, except that the catalyst obtained in Catalyst Example 3 was changed to 3.76 g.
[0015]
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. Next, as a treating agent, 81.9 g (corresponding to 17%) of ion-exchanged water [C] and an acrylic polymer [B] (an acrylic acid polymer, a solid content of 39.6%, a viscosity of 59 cps / 25 ° C., and a pH of 2. 5 (1% aqueous solution, molecular weight: about 6000), 1.52 g, and mixed at 75 ° C. for 1 hour. Then, the by-product polyalkylene glycol and the alkoxylation catalyst were removed by filtration by filtration to remove the purified product. Obtained.
The filtration device was a two-layer filter of cellulose and polyester, a pressure filter having an inner diameter of 4 cm, at a temperature of 80 ° C. and a nitrogen pressure of 1 kg / cm ² . G.
Example 2
After adding and mixing the treating agent, 1.44 g of activated clay and 2.41 g of KC floc were added as filter aids, and the process was performed in the same manner as in Example 1 except that the mixture was stirred for 30 minutes.
Example 3
The same procedure as in Example 1 was carried out except that the acrylic polymer [B] was an acrylic acid polymer, a solid content of 40.2%, a viscosity of 35 cps / 25 ° C., a pH of 1.6 (1% aqueous solution), and a molecular weight of about 3000. went.
[0016]
Example 4
Example 1 except that the acrylic polymer [B] was an acrylic acid polymer, a solid content of 39.8%, a viscosity of 1430 cps / 25 ° C., a pH of 2.7 (1% aqueous solution), and a molecular weight of about 20,000 to 30,000. It went according to.
Example 5
As the acrylic polymer [B], 0.78 g of an acrylic acid polymer, a solid content of 20.3%, a viscosity of 32,000 cps / 25 ° C., a pH of 3.3 (1% aqueous solution), and a molecular weight of about 200,000 to 300,000 The procedure was as in Example 1, except that 2.41 g of KC floc was added and mixed as a filter aid.
Example 6
As the acrylic polymer [B], 2 g of an acrylic acid polymer having a solid content of 39.6%, a viscosity of 59 cps / 25 ° C., a pH of 2.5 (1% aqueous solution) and a molecular weight of about 6,000 was added, and a filter aid was added. Example 2 was repeated except that 1.44 g of activated clay and 2.41 g of KC floc were added and mixed.
Example 7
Example 6 was repeated except that the amount of the acrylic polymer [B] was changed to 3 g.
[0017]
Example 8
Example 2 was repeated except that 65.5 g (corresponding to 14%) of ion-exchanged water [C] was added as a treating agent, 1.4 g of activated clay and 1.4 g of KC floc were added as filter aids.
Example 9
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 speed and the amount of polyalkylene glycol in the filtrate in Examples 1 to 12. The content of the high molecular weight polyalkylene glycol was measured by the following method.
Column: GS-310 φ7.6mm × 0.5m, 30 ° C
Mobile phase: CH ₃ CN / H ₂ O = 45/55 (vol / vol ratio), 1 ml / min
Detector: RI
Model: RID-6A (Shimadzu Corporation)
[0018]
[Table 1]

In the table, PAG means high molecular weight polyalkylene glycol (the same applies hereinafter).
[0019]
Example 10
The crude product obtained in crude Example 2 [A] except that the 400g is carried out according to Example 1 _to obtain a purified product of _{C 12} alcohol + 7EO · 2PO (EO: shows the propylene oxide: ethylene oxide, PO .).
Example 11
Except that the crude product obtained in crude Example 3 [A] was 400g is carried out according to Example 10 to obtain a purified product of C ₁₂ alcohol + 7 EO.
Example 12
A crude product of polyoxyethylene methyl ether laurate (5 moles added) 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.
[0020]
Example 13
Example 1 was carried out in the same manner as in Example 1 except that 400 g of the crude product Example 5 was partially neutralized (pH 2.5 → 3.7 (1% aqueous solution)) using an aqueous 30% NaOH solution as an alkali metal salt for the acrylic polymer [B]. Performed according to Example 2.
Comparative Example 1
400 g of the alkylene oxide adduct obtained in Crude Product Example 1 was heated to 80 ° C. in a 1-liter four-necked flask equipped with a stirrer. Next, 0.4 g of activated clay and 2.0 g of KC floc were added as filter aids, and the mixture was held for 30 minutes. ° C, nitrogen pressure 1Kg / cm ² . The filtration operation was performed with G.
Comparative Example 2
400 g of the alkylene oxide adduct obtained in the crude product example 3, 70.6 g of ion-exchanged water (15% / crude product), and 2.0 g of KC floc as a filter aid were mixed at 80 ° C. Next, the alkoxylation catalyst and the high molecular weight polyalkylene glycol were separated and removed by the pressure filter used in Comparative Example 1.
Table 2 shows the results of Examples 10 to 13 and Comparative Example 1 (14 in the table) and Comparative Example 2 (15 in the table).
[0021]
[Table 2]

Claims (1)

In the presence of an alkoxylation catalyst, a crude nonionic surfactant obtained by adding an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester is brought into contact with an acrylic polymer and water to produce by-products. A method for purifying a nonionic surfactant, comprising separating and removing a polyalkylene glycol and an alkoxylation catalyst.