WO2007113985A1

WO2007113985A1 - Alkylene oxide adduct, method for production thereof, and surfactant composition

Info

Publication number: WO2007113985A1
Application number: PCT/JP2007/054636
Authority: WO
Inventors: Shingo Uemura; Ryusuke Mitomi
Original assignee: Lion Corporation
Priority date: 2006-03-30
Filing date: 2007-03-09
Publication date: 2007-10-11
Also published as: KR101367543B1; KR20080106565A; JP5203186B2; JPWO2007113985A1

Abstract

Disclosed is an excellent method for production of an alkylene oxide adduct which, despite using a composite metal oxide catalyst which is a solid catalyst, does not need any step for filtrating the solid catalyst (a solid-liquid separation step), and which has improved production efficiency. Also disclosed is an alkylene oxide adduct containing a composite metal oxide catalyst having a very fine particle size. Further disclosed is a surfactant composition which contains the alkylene oxide adduct and is excellent in applicability. The method for production of an alkylene oxide adduct comprises reacting at least one of an organic compound having an active hydrogen and a fatty acid alkyl ester with an alkylene oxide in the presence of a composite metal oxide catalyst and a polyhydric alcohol.

Description

Specification

Alkylene oxide adduct, method for producing the same, and surfactant composition

Technical field

[0001] The present invention relates to a method for producing an alkylene oxide adduct using a solid catalyst, an alkylene oxide adduct containing a solid catalyst having a fine particle diameter, and a surface activity containing the alkylene oxide adduct. The agent composition.

Background art

[0002] When an alkylene oxide adduct is produced using a solid catalyst, in the conventional catalyst suspension type reaction form, solid-liquid separation is used to remove the catalyst from the product after the reaction. A process is essential. Since this solid-liquid separation process is practically difficult to carry out industrially, various proposals have been made to reduce or improve the load.

[0003] For example, as a method for improving solid-liquid separation by suppressing the refinement of catalyst particles, an example of improving the method of introducing a catalyst into a reactor (see Patent Document 1) and a reaction system during the reaction There is an example (refer to Patent Document 2) in which the pressure in the inner vapor phase alkylene oxide is kept low.

In addition, there are examples in which the solid-liquid separability is improved by reducing the amount of by-product that deteriorates the solid-liquid separability and improving the fluidity of the activator (see Patent Documents 3 to 5).

[0004] The above prior art is intended to solve the problem by controlling the catalyst particles and by-products, which are to be filtered, to be in a state where they can be easily filtered. The separation process itself was essential.

Therefore, further improvement in production efficiency of alkylene oxide adducts has been demanded. Specifically, development of a method for producing alkylene oxide adducts that does not require a solid-liquid separation process has been an issue. .

Patent Document 1: JP 2000-51680 A

Patent Document 2: Japanese Patent Laid-Open No. 2002-201151

Patent Document 3: Japanese Patent No. 3312883 Patent Document 4: Japanese Patent Laid-Open No. 2000-15094

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2005-187415

Disclosure of the invention

[0006] An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention does not require a step of filtering the solid catalyst (solid-liquid separation step) despite the use of a composite metal oxide catalyst that is a solid catalyst, and is excellent in improved production efficiency. A method for producing an alkylene oxide adduct, an alkylene oxide adduct containing a composite metal oxide catalyst having a fine particle diameter, and a surfactant composition containing the alkylene oxide adduct and having excellent usability The purpose is to provide goods.

[0007] In devising a method for producing an alkylene oxide adduct that uses the solid catalyst but does not require a solid-liquid separation step, the present inventors have practically used catalyst particles as particles. The idea was that if the size could be reduced to a size that does not need to be handled, the catalyst particles would not settle or agglomerate.

[0008] According to the example of Patent Document 2 and the like, the degree of refinement of the catalyst obtained by the conventional technique is up to about 10 m as the catalyst particle diameter. In such a particle diameter, In this case, the sedimentation of the catalyst particles occurred within a few hours, which was far from the required state.

On the other hand, using a means such as mechanical force, it is economical to introduce special equipment for the method of obtaining the desired refined state by physically crushing the catalyst particles before the reaction. Disadvantages The significance of implementation is lost, it is difficult to properly handle extremely refined catalyst particles, and refinement before reaction promotes the exposure of active sites to the external environment, thereby improving catalyst performance. There are concerns that it will be lost, etc. Power is appropriate, etc.

[0009] Therefore, as a result of intensive studies, the present inventors have found that the above problems can be solved by using a polyhydric alcohol. In other words, in the presence of the composite metal oxide catalyst and the polyhydric alcohol, the reaction of at least the active hydrogen-containing organic compound and the fatty acid alkyl ester with alkylene oxide can reduce the size of the catalyst particles during the reaction. Proceeding remarkably, the catalyst particles are extremely fine to a size that does not need to be treated substantially as particles It can be refined, and it is found that no settling of catalyst particles is confirmed in the product after the reaction, that is, no solid-liquid separation step is required to remove the solid catalyst. The present invention has been completed.

The present invention is based on the above knowledge obtained by the present inventor, and means for solving the above problems are as follows. That is,

<1> A method for producing an alkylene oxide adduct in which at least one of an active hydrogen-containing organic compound and a fatty acid alkyl ester is reacted with an alkylene oxide in the presence of a composite metal oxide catalyst and a polyhydric alcohol. .

<2> After contacting the composite metal oxide catalyst with the polyhydric alcohol, at least one of the active hydrogen-containing organic compound and the fatty acid alkyl ester is reacted with the alkylene oxide according to the above <1>. This is a method for manufacturing an adduct.

<3> From the above <1>, the composite metal oxide catalyst and the polyhydric alcohol are brought into contact with each other under heating and reduced pressure conditions, and then at least one of an active hydrogen-containing organic compound and a fatty acid alkyl ester is reacted with an alkylene oxide. <2> A method for producing an alkylene oxide adduct according to any one of <2>.

<4> At least one of the active hydrogen-containing organic compound and the fatty acid alkyl ester, the composite metal oxide catalyst, and the polyhydric alcohol are brought into contact with each other, and then the alkylene oxide is brought into contact with each other to react. <3> is the process for producing an alkylene oxide adduct according to any one of the above.

<5> The following storus formula:

V = l / 18-(pp-p) g / μ-Dp ² (Stortus equation)

[In the stoichiometric formula,

V = settling rate of composite metal oxide catalyst after reaction (mZh),

PP = specific gravity of the composite metal oxide catalyst after reaction (kgZm ³ ),

P = specific gravity of the resulting alkylene oxide adduct (kg / m ³ ),

g = gravitational acceleration (mZs ² ),

μ = viscosity of the resulting alkylene oxide adduct (kgZm Dp = Average particle diameter of the composite metal oxide catalyst after reaction (m)

Show]

Sedimentation velocity V of the composite metal Sani匕物catalyst after the reaction sought is such that 4. 6 X 10 ^_5 (mZh) hereinafter in terms of sedimentation speed per hour, mixed metal after reaction The method for producing an alkylene oxide adduct according to any one of <1> to <4>, wherein an average particle diameter Dp of the oxide catalyst is controlled.

<6> The method for producing an alkylene oxide adduct according to any one of <1> to <5>, wherein the polyhydric alcohol is glycerin.

<7> The method for producing an alkylene oxide adduct according to any one of <1> to <6>, wherein the composite metal oxide catalyst is a magnesium-based composite metal oxide catalyst.

<8> The method for producing an alkylene oxide adduct according to any one of <1> to <7>, wherein the composite metal oxide catalyst has a specific surface area of 50 to 400 m ² Zg.

<9> An alkylene oxide adduct characterized by containing a composite metal oxide catalyst having an average particle size of 2 μm or less.

<10> The alkylene oxide adduct according to <9>, which is obtained by the method for producing an alkylene oxide-attached product according to any one of <1> to <8>. [10] A surfactant composition characterized by containing the alkylene oxide-containing caroten described in any one of [9] to [9] to [10].

<12> The surfactant composition according to <11>, which is a cleaning agent.

According to the present invention, the conventional problems can be solved and the object can be achieved, and the solid catalyst is filtered despite the use of the composite metal oxide catalyst that is a solid catalyst. An alkylene oxide adduct containing a composite metal oxide catalyst having a fine particle size, and a production method of an alkylene oxide adduct with improved production efficiency, which does not require a step for solid-liquid separation (solid-liquid separation step), In addition, a surfactant composition containing the alkylene oxide adduct and excellent in utility can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] (Method for producing alkylene oxide adduct)

The process for producing an alkylene oxide adduct of the present invention comprises a composite metal acid which is a solid catalyst. And a step of reacting at least one of active hydrogen-containing organic compound and fatty acid alkyl ester with alkylene oxide in the presence of a polyhydric alcohol, and, if necessary, other processes. Process.

[0013] Terms>

In the present specification, the composite metal oxide catalyst is sometimes referred to as “solid catalyst” or simply “catalyst”. In addition, at least one of the active hydrogen-containing organic compound and the fatty acid alkyl ester (the active hydrogen-containing organic compound and Z or the fatty acid alkyl ester) and the alkylene oxide may be collectively referred to as “reaction raw material”. is there. Further, the alkylene oxide adduct obtained by the reaction of the reaction raw materials may be referred to as “product”.

[0014] By reacting an active hydrogen-containing organic compound and Z or a fatty acid alkyl ester with an alkylene oxide in the presence of a composite metal oxide catalyst and a polyhydric alcohol.

During the reaction, the refinement of the catalyst progresses remarkably, and the sedimentation force S of the catalyst particles in the product after the reaction does not occur. Therefore, according to the method for producing an alkylene oxide adduct of the present invention, production efficiency is improved as a result of not having to perform a solid-liquid separation step for removing catalyst particles in the product. .

The above-mentioned “catalyst refinement” refers to the collapse of catalyst particles that can normally occur during the alkylene oxide addition reaction (for example, the accumulation of heat of reaction inside the catalyst particles and the generation of polymer by-products). To a stage where it cannot occur in a known phenomenon (e.g., due to sudden pressure difference, mechanical shearing by a stirring blade, etc.) Means no need to handle as

[0015] <Composite metal oxide catalyst>

The above-mentioned catalyst miniaturization is caused by the reaction of the polyhydric alcohol causing a temporary inactive state on the surface of the catalyst and then a rapid reaction, thereby promoting and progressing the miniaturization. it is conceivable that. Therefore, as the catalyst capable of remarkably obtaining the catalyst refinement effect, a catalyst having a high catalytic activity and a high catalytic activity up to the inside of the catalyst particles having a large specific surface area is preferable. Here, the composite metal oxide catalyst means two or more metal species. It is the above-mentioned acid catalyst.

[0016] Therefore, the composite metal oxide catalyst is not particularly limited and can be appropriately selected according to the purpose. However, even though the magnesium-based composite metal oxide catalyst is preferred, the hydroxide metal catalyst is used. Aluminium / magnesium fired product and its surface modification product power At least one non-layered composite selected is particularly preferred. Here, the magnesium-based composite metal oxide catalyst is a composite metal oxide catalyst containing magnesium.

[0017] The calcined product of aluminum hydroxide and magnesium can be appropriately selected according to the purpose without any limitation, and examples thereof include those described in JP-A-8-268919. Specifically, it is a coprecipitate of hydroxyaluminum and hydroxyammonium represented by the following formula (I), and it can be made into an aluminum magnesium based composite metal oxide catalyst by firing. it can.

nMgO -Al O · πιΗ O (I)

2 3 2

[In the formula (I), n can be appropriately selected according to the purpose without any restriction, but about 2.5 is preferred, and m can be appropriately selected according to the purpose without any restriction. . Here, the firing temperature is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of 1S catalytic activity expression and suppression of the amount of by-product produced, 400 to 950 ° C is preferred 400 to 800 ° C is more preferred.

Note that the description of the sintered aluminum hydroxide / magnesium in JP-A-8-268919 is included in the description of the present specification.

[0018] The surface modified product of the aluminum hydroxide-aluminum magnesium fired product is not particularly limited and can be appropriately selected according to the purpose. For example, Japanese Patent Application Laid-Open No. 8-169860, Examples include those described in JP-A-8-169861. Specifically, the calcined hydroxyaluminum / magnesium product can be surface-modified with a metal hydroxide or metal alkoxide to obtain a modified calcined hydroxide / alumina / magnesium catalyst. Among the metal hydroxides, among them, alkali metal or alkaline earth metal hydroxides are preferred, and sodium hydroxide and potassium hydroxide are more preferred. Among the metal alkoxides, alkali alkoxides or alkaline earth metal alkoxides are preferred, and sodium alkoxides and potassium alkoxides are more preferred. In the case where a fatty acid alkyl ester is used as the active hydrogen-containing organic compound and z or fatty acid alkyl ester, the addition metal distribution of the resulting alkylene oxide adduct can be sharpened, so that the composite metal As the oxide catalyst, it is preferable to use a surface modified product of the above-mentioned hydrated aluminum hydroxide 'magnesium'

[0019] The composite metal oxide catalyst may be used alone or in combination of two or more.

In addition, the composite metal oxide catalyst is preferably a porous particle in that the catalyst is remarkably refined, and the specific surface area is preferably 50 to 400 m ² / g. Yes.

[0020] The amount of the composite metal oxide catalyst used is not particularly limited as long as the reaction proceeds appropriately and the amount of by-products such as polyethylene glycol is within the range where there is no problem. Although it can be suitably selected according to the activity of the catalyst, etc., 0.01 to 1 mass relative to the total mass of the reaction raw materials (the active hydrogen-containing organic compound and Z or fatty acid alkyl ester and the alkylene oxide) % Is preferred 0.05 to 0.2% by mass, more preferred. If the amount of the composite metal oxide catalyst used is less than the preferred range, the reaction does not proceed appropriately, leading to an increase in the reaction process time, which may be uneconomical. In addition, the amount of catalyst is too large, which is uneconomical, adversely affects the amount of by-products, and makes it difficult to make the catalyst finer.

[0021] <Polyhydric alcohol>

The polyhydric alcohol is not particularly limited as long as it has two or more hydroxyl groups in the molecule and the effect of refining the catalyst is obtained. For example, the active hydrogen-containing organic compound and Z or The compound can be appropriately selected from compounds that can be emulsified or dispersed in the fatty acid alkyl ester depending on the purpose, and preferred examples include glycerin, ethylene glycol, and diethylene glycol. However, polyhydric alcohols derived from alkylene oxide are excluded. Among these, glycerin is particularly preferable.

The polyhydric alcohols may be used alone or in combination of two or more.

[0022] The amount of the polyhydric alcohol used is appropriately selected depending on the purpose without any particular limitation. However, 0.02-0. 5% by mass is preferable based on the total mass of the reaction raw materials (the active hydrogen-containing organic compound and Z or fatty acid alkyl ester and the alkylene oxide). 0.25% by mass is more preferred. Further, 1.0 times or more is preferable with respect to the mass of the composite metal oxide catalyst, and 1.25 times or more is more preferable. If the amount of the polyhydric alcohol used is less than the preferred range, the catalyst may not be refined to a desired degree. In addition, the reaction process time may be extended, which may be uneconomical.

Active hydrogen-containing organic compounds

The active hydrogen-containing organic compound can be appropriately selected according to the purpose without any particular limitation, and examples thereof include alcohols, amines, amides, phenols, and thiols. Among these, alcohols represented by the following general formula (Π) are preferable.

R'OH (II)

[In the general formula (Π), R ¹ can be appropriately selected according to the performance required for the product to be obtained without particular limitation, and examples thereof include an alkyl group and an alkenyl group. . The alkyl group and alkenyl group may be linear or branched. The number of carbon atoms of the alkyl group and the alkenyl group is not particularly limited. A force that can be appropriately selected according to the purpose 1 to 40 forces S is preferable, 3 to 30 is preferable, and 6 to 22 is particularly preferable. ]

[0024] Fatty acid alkyl ester

The fatty acid alkyl ester is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include those represented by the following general formula (III).

R ² COOR ³ (III)

[In the general formula (m), R ² and R ³ can be appropriately selected according to the performance required for the product to be obtained without particular limitation. For example, an alkyl group, an alkenyl group, and the like. Group and the like. The carbon number of the alkyl group and the alkenyl group is not particularly limited, and the force R ² that can be appropriately selected according to the purpose is preferably 1 to 40 force S, more preferably 3 to 30. 6-22 is particularly preferred. As for R ³ , 1 to 20 is preferable, 1 to 10 is more preferable, and 1 to 4 is particularly preferable. ]

The active hydrogen-containing organic compound and Z or the fatty acid alkyl ester may be used alone or in combination of two or more.

[0025] The use amount of the active hydrogen-containing organic compound and Z or the fatty acid alkyl ester is not particularly limited, and the use amount of the product to be obtained, the use of the composite metal oxide catalyst, the polyhydric alcohol, or the alkylene oxide. It can be appropriately selected depending on the amount and the like.

[0026] <Anorekiren talented side>

The alkylene oxide is not particularly limited as long as it reacts with the active hydrogen-containing organic compound and Z or a fatty acid alkyl ester to obtain an alkylene oxide adduct, and can be appropriately selected according to the purpose. However, an alkylene oxide having 3 to 8 carbon atoms is preferable, and an alkylene oxide having 3 to 5 carbon atoms is particularly preferable. The alkylene oxides may be used alone or in combination of two or more.

[0027] The amount of the alkylene oxide to be used is not particularly limited, depending on the type of the active hydrogen-containing organic compound and Z or fatty acid alkyl ester used, the performance required for the product to be obtained, and the like. 1 to 50 mol is preferable, more preferably 3 to 30 monoreca, and particularly preferably 5 to 20 monoreca with respect to 1 mol of the active hydrogen-containing organic compound and Z or fatty acid alkyl ester. Better!/,.

[0028] <Reaction>

As a method of reacting the alkylene oxide with the active hydrogen-containing organic compound and Z or the fatty acid alkyl ester in the presence of the composite metal oxide catalyst and the polyhydric alcohol (alkylene oxide addition reaction method), There is no particular limitation as long as an effect can be obtained. Force that can be appropriately selected according to the purpose After contacting the composite metal oxide catalyst and the polyhydric alcohol, the active hydrogen-containing organic compound and A method of reacting at least one of the fatty acid alkyl esters with the alkylene oxide is preferable. Here, the composite metal oxide catalyst and the multivalent catalyst The contact with alcohol means that the catalyst and the polyhydric alcohol are brought into contact by adding and mixing the polyhydric alcohol before the reaction between the composite metal oxide catalyst and the alkylene oxide. There is no particular limitation on the method, and any method such as addition alone, addition by mixing with the active hydrogen-containing organic compound and Z or the fatty acid alkyl ester, addition by mixing with a catalyst, etc. may be used.

Specifically, the preferable alkylene oxide addition reaction method includes, for example, the active hydrogen-containing organic compound and Z or the fatty acid alkyl ester, the complex metal oxide catalyst, and the polyhydric alcohol, respectively, in advance. After introducing into the reactor in an amount that falls within the range, charging, stirring, and mixing, the reactor is purged with nitrogen, followed by dehydration under heating and reduced pressure conditions. Next, the temperature and pressure in the reactor can be adjusted, and the alkylene oxide can be introduced (supplied) at a predetermined rate in such an amount as to be within the preferred range.

Further, after the introduction of the alkylene oxide, an aging reaction may be further carried out if necessary.

[0029] The reactor used for the reaction can be appropriately selected according to the purpose without any particular limitation, and examples thereof include a general stirred tank type batch reactor such as an autoclave. It is done.

[0030] The method for introducing each of the above-described components into the reactor can be appropriately selected according to the purpose without any particular limitation, but particularly for the composite metal oxide catalyst, the reactor The method of sucking and introducing the catalyst in a powder state while reducing the pressure is preferable in terms of further promoting the refinement of the catalyst particles from the generated pressure difference.

[0031] The active hydrogen-containing organic compound and Z or the fatty acid alkyl ester, the composite metal oxide catalyst, and the polyhydric alcohol are introduced into the reactor and charged, and the reaction is performed while stirring and mixing. The temperature at which the inside of the vessel is purged with nitrogen is not particularly limited, and a force that can be appropriately selected according to the purpose is preferably 0 to 90 ° C, more preferably 20 to 70 ° C. If the temperature is less than the preferred range, the catalyst is poorly fluidized and the physical contact between the polyhydric alcohol and the catalyst is poor. If it exceeds the above preferred range, In addition, the moisture contained in the charged raw material may interact with the surface of the solid catalyst, and the desired catalyst performance may not be obtained.

[0032] The active hydrogen-containing organic compound and Z or the fatty acid alkyl ester, the composite metal oxide catalyst, and the polyhydric alcohol are charged into the reactor, and the reactor is filled with nitrogen while stirring and mixing. The pressure at the time of replacement can be appropriately selected according to the purpose without any particular limitation.

[0033] In addition, the temperature at which dehydration is performed under heating and reduced pressure conditions can be appropriately selected according to the purpose for which there is no particular limitation. A force of 70 to 150 ° C is preferred, and a temperature of 90 to 130 ° C is more preferred. preferable. If the temperature is less than the above preferred range, a sufficient dehydration effect cannot be obtained, and the remaining water may cause by-product formation or deteriorate the reactivity of the catalyst. When the preferable range is exceeded, the charged raw materials may be distilled out of the reaction system.

[0034] The pressure at which dehydration is performed under heating and reduced pressure conditions can be appropriately selected according to the purpose for which there is no particular limitation, but is preferably 13 kPa or less, more preferably 4 kPa or less. When the upper limit pressure exceeds the preferable range, a sufficient dehydration effect cannot be obtained, and the remaining water may cause by-product formation or may deteriorate the reactivity of the catalyst.

[0035] Further, the reaction temperature when the alkylene oxide is introduced (supplied) into the reactor and the alkylene oxide addition reaction is performed is not particularly limited, depending on the activity of the catalyst used, etc. Although it can be selected as appropriate, 120 to 230 ° C is preferred, and 150 to 200 ° C is more preferable. If the reaction temperature is less than the preferred range, the reaction activity may be reduced, leading to an extended reaction process time. If the reaction temperature exceeds the preferred range, decomposition of the reaction raw materials and products may occur. is there.

[0036] Further, the reaction pressure when the alkylene oxide is introduced (supplied) into the reactor and the alkylene oxide addition reaction is performed depends on the reaction temperature, the activity of the catalyst to be used, and the like. Moreover, in the meaning of the upper limit pressure, the pressure can be appropriately selected within a publicly known range according to the pressure resistance design of the reactor to be used. For example, the upper limit pressure is preferably 0.1 to 2 OMPa, more preferably 0.2 to 1 OMPa.

[0037] In addition, when the alkylene oxide is introduced (supplied) into the reactor and the alkylene oxide addition reaction is performed, the alkylene oxide is introduced into the reactor. The speed (supply speed) is not particularly limited, and can be appropriately selected depending on the purpose. However, the F value represented by the following formula (IV) satisfies the above range from 0.01 to 0.07. It is preferable to control the supply rate _{Va of the} alkylene oxide.

F = Va / Mp (IV)

[In the formula (IV), Va is the supply rate of the alkylene oxide to be used for the reaction [unit: mol Z min], and Mp is the number of moles of the alkylene oxide adduct obtained by the reaction [unit: mol]. ]

If the value of F is less than the preferred range, the reaction process time may be extended, and if the value exceeds the preferred range, the alkylene oxide supply rate exceeds the catalytic activity, and the reactor pressure is preferably the upper limit. In addition to exceeding the value, the amount of by-product high molecular weight polyethylene glycol produced may increase.

[0038] According to the method for producing an alkylene oxide adduct as described above, it is not necessary to treat the catalyst substantially as particles while using a composite metal oxide catalyst that is a solid catalyst. Therefore, it is possible to obtain an alkylene oxide adduct that is stable over time without a filtration step (solid-liquid separation step). As a result, an alkylene oxide adduct can be produced efficiently.

[0039] Further, when a magnesium-based composite metal oxide catalyst such as an aluminum hydroxide / magnesium fired product is used as the composite metal oxide catalyst, as a secondary effect of catalyst miniaturization, unit There is also an effect that the catalytic activity per catalyst mass is improved. This is because, as the catalyst becomes finer, the surface of the catalyst, which did not contribute to the activity in the conventional reaction method, is exposed as an active point, and as a result, the catalyst effectiveness factor is increased, thereby improving the catalyst activity. Inferred to be connected.

Further, when a magnesium-based composite metal oxide catalyst such as a hydroxide-aluminum 'magnesium fired product is used as the composite metal oxide catalyst, the glycerin and the like used for the refinement of the catalyst The polyhydric alcohol also acts as a modifier on the catalyst surface, and has the effect of suppressing the production of high molecular weight polyethylene glycol as a by-product. As a result, the liquid viscosity of the resulting alkylene oxide adduct can be lowered, and a good effect can be given also in the handling surface. [0040] (Carotenized with alkylene oxide)

Despite the inclusion of the composite metal oxide catalyst in the alkylene oxide adduct obtained by the method for producing the alkylene oxide adduct, the composite metal oxide catalyst is substantially Therefore, the catalyst particles do not substantially settle, and are stable over time and can be handled as a liquid.

[0041] Here, the sedimentation speed of the composite metal oxide catalyst in the alkylene oxide adduct is not particularly limited, and can be appropriately selected according to the purpose. The following Stokes equation is used. :

V = l / 18-(pp-p) g / μ-Dp ² (Stortus equation)

[In the stoichiometric formula,

V = settling rate of composite metal oxide catalyst after reaction (mZh),

P = specific gravity of the resulting alkylene oxide adduct (kg / m ³ ),

g = gravitational acceleration (mZs ² ),

μ = viscosity of the resulting alkylene oxide adduct (kgZm

Dp = average particle diameter of the composite metal oxide catalyst after reaction (m)

Show]

The sedimentation rate V of the composite metal oxide catalyst after the reaction determined in (1) is preferably 4.6 X 10 " ⁵ (m / h) or less in terms of the sedimentation rate per hour. .

The sedimentation velocity V is 4. When it is 6 X 10 ^_5 (mZh) hereinafter, the relationship between the physical properties of the product and the physical properties of the fine catalyst particles under storage temperature envisaged, the precipitation of 10cm Since it takes about 3 months (90 days) or more, when the carbonate with alkylene oxide is handled as a liquid, there is substantially no problem of sedimentation of the composite metal oxide catalyst. Can be evaluated. Here, the storage temperature is not lower than the melting point of the alkylene oxide adduct to be stored and not higher than 80 ° C., preferably not lower than room temperature and not higher than 60 ° C.

[0042] The average particle diameter D p (m) of the composite metal oxide catalyst in the alkylene oxide adduct is not particularly limited and may be appropriately selected depending on the intended purpose, but 2 μηι The following is preferred: L m or less is more preferred 0.6 m or less is particularly preferred. When the average particle diameter exceeds 2 m, sedimentation of the composite metal oxide catalyst may become a problem in the alkylene oxide adduct.

The average particle diameter Dp (m) of the composite metal oxide catalyst after the reaction can be measured by, for example, the method described in Examples described later.

Therefore, the present invention also relates to an alkylene oxide adduct characterized by containing a composite metal oxide catalyst having an average particle diameter of 2 μm or less. As described above, the alkylene oxide adduct of the present invention can be preferably obtained by the production method of the alkylene oxide adduct of the present invention.

Since the composite metal oxide catalyst in the alkylene oxide adduct of the present invention is extremely refined to a size that is substantially not required to be handled as particles, the alkylene oxide adduct is used. Is stable over time, and does not cause catalyst particle settling during storage, transport, etc., and can be handled as a liquid.

In addition, since the alkylene oxide adduct of the present invention contains the composite metal oxide catalyst, when used as various surfactant compositions, as described later, antibacterial properties, lubricity, It has advantages in terms of residual fragrance and the like.

In addition, as described above, according to the method for producing an alkylene oxide adduct, a magnesium-based composite metal oxide catalyst such as an aluminum hydroxide / magnesium fired product is used as the composite metal oxide catalyst. In this case, the amount of by-products such as polyethylene glycol in the alkylene oxide adduct becomes very small and the liquid viscosity becomes low, so that the handling is excellent.

[0045] (Surfactant composition)

The alkylene oxide adduct can be used as various surfactant compositions in fields such as household use, industrial use, and agricultural use. Among these, the surfactant composition is suitable as a cleaning agent, an emulsifier, a dispersant, an oil phase component modifier, a penetrant, a used paper deinking agent, an agricultural spreading agent, and the like.

[0046] The surfactant composition contains the alkylene oxide adduct, and further contains other components as necessary. [0047] Products with alkylene oxide>

The content of the alkylene oxide adduct in the surfactant composition is not particularly limited, and a force that can be appropriately selected according to the purpose is 0.1 to 80% by mass, preferably 1 to 60% by mass. 2 to 40% by mass is particularly preferable.

[0048] <Other ingredients>

The other components can be appropriately selected according to the purpose without any particular limitation, and examples thereof include surfactants such as an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.

The anionic surfactant can be appropriately selected according to the purpose without any particular limitation, and examples thereof include carboxylic acid type surfactants, sulfate type surfactants, sulfonic acid type surfactants, and phosphate esters. Type surfactants and the like.

The cationic surfactant can be appropriately selected according to the purpose without any particular limitation. For example, higher amine salt, higher alkyl (or alkenyl) quaternary ammonium salt, higher alkyl (or alkke). -Le) Pyridium quaternary ammonia salt.

The amphoteric surfactant can be appropriately selected according to the purpose without any particular limitation. For example, alkylbetaine surfactant, alkylamide betaine surfactant, imidazoline surfactant, alkylamino Examples thereof include sulfonic acid type surfactants, alkylaminocarboxylic acid type surfactants, alkylamide carboxylate type surfactants, amidoamino acid type surfactants, and phosphoric acid type surfactants.

[0049] Further, as the other components, oily components, polymers, silicones, detergent builders, enzymes, anti-staining agents, bleaching agents, fluorescent agents, fragrances, dyes, solvents, hair conditioning agents, Also included are various additives such as ultraviolet absorbers, bactericides, preservatives, anti-dandruff agents, pastes, idrotropes, emulsions, thickeners, zeolites, phosphates, sulfates and sulfites.

[0050] The content of the other components in the surfactant composition is not particularly limited.

Can be appropriately selected according to the purpose.

[0051] The alkylene oxide adduct in the surfactant composition, as described above, The composite metal oxide catalyst is stably contained in a state of being miniaturized to such an extent that the problem of sedimentation of the catalyst does not occur.

Here, as an advantage that the composite metal oxide catalyst is stably contained in the alkylene oxide adduct, for example, when the surfactant composition is used as a cleaning agent, it is derived from the metal oxide. Since antibacterial properties can be obtained, the use of preservatives incorporated in the cleaning agent can be reduced, and lubrication can be obtained by entering submicron-order fine particles into the gaps in the fibers of clothing that is to be cleaned. In addition, it is possible to prevent wrinkles due to fiber warp and the like and to impart flexibility.

In addition, since the fragrance can be retained in the crystal structure of the composite metal oxide catalyst, it is possible to impart a long-lasting effect to the cleaning agent, and chlorine ions in tap water can be added to the crystal structure when washing clothes. Since it can be trapped, the ability to prevent clothing from fading is another advantage.

For these reasons, the surfactant composition is particularly suitable as a cleaning agent. Example

[0052] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0053] (Example 1)

2. 5MgO-Al O · πιΗ Aluminum hydroxide with different chemical composition 'Magnesium (Kyowa

2 3 2

A Kiyoword 300) manufactured by Kagaku Kogyo Co., Ltd. was calcined at 800 ° C. for 3 hours to obtain a magnesium-aluminum composite metal oxide catalyst powder. At this time, the average particle diameter of the catalyst particles (before the reaction) was 75 μm. The specific surface area was 270 m ² / g.

Next, 440g (2.06 mol) of methyl laurate (Nostel M12 manufactured by Lion Chemical Co., Ltd.) and 40% by weight aqueous solution of potassium hydroxide and potassium (manufactured by Kanto Chemical Co., Ltd.) were placed in a 4L autoclave. 0.23 g (pure KOH content: 1.6 mmol), 1.8 g of the composite metal oxide catalyst, glycerin as a polyhydric alcohol (manufactured by Kanto Chemical Co., Ltd.) 2 The autoclave was purged with nitrogen while stirring and mixing with 25 g, and then heated and dehydrated at 100 ° C. under reduced pressure (1.33 kPa or less) for 30 minutes. Next, at 180 ° C, the upper limit of the reaction pressure was 0.3 MPa, and 1,361 g (30.9 mol) of ethylene oxide (Mitsubishi Chemical Co., Ltd.) was added as described above. The introduction rate was introduced (supplied) at a rate such that the value of F in the introduction rate equation (formula (IV)) was F = 0.045. After further aging reaction, the mixture was cooled and extracted to obtain fatty acid polyoxyethylene lauryl ether as a product (alkylene oxide adduct).

[0054] (Example 2)

As a catalyst, 0.9 g of the composite metal oxide catalyst described in Example 1, 0.12 g of 40% by weight potassium hydroxide aqueous solution (KOH pure content 0.8 mmol), and 0.9 g of glycerin as a polyhydric alcohol. Fatty acid polyoxyethylene lauryl ether was obtained as a product in the same manner as in Example 1 except that it was used. However, since the reaction pressure reached the upper limit (0.3 MPa) during the reaction, the introduction rate of ethylene oxide was appropriately adjusted.

[Example 3]

As a catalyst, 3.6 g of the composite metal oxide catalyst described in Example 1, 0.48 g of 40% by mass potassium hydroxide aqueous solution (pure KOH content: 3.2 millimonoles), and 4.5 g of glycerin as a polyhydric alcohol. Fatty acid polyoxyethylene lauryl ether was obtained as a product in the same manner as in Example 1 except that it was used.

[0056] (Example 4)

As a catalyst, 0.9 g of the mixed metal oxide catalyst described in Example 1, 0.12 g of 40% by mass aqueous potassium hydroxide solution (0.8 mmol of KOH), and ethylene glycol (polyhydric alcohol) ( Fatty acid polyoxyethylene lauryl ether was obtained as a product in the same manner as in Example 1 except that 4.5 g of Kanto Chemical Co., Ltd. was used. However, since the reaction pressure reached the upper limit (0.3 MPa) during the reaction, the introduction rate of ethylene oxide was appropriately adjusted.

[0057] (Example 5)

As a catalyst, 0.9 g of the mixed metal oxide catalyst described in Example 1, 0.12 g of 40% by weight aqueous potassium hydroxide solution (0.8 mmol of KOH), diethylene glycol (Kanto) as the polyhydric alcohol Fatty acid polyoxyethylene lauryl ether was obtained as a product in the same manner as in Example 1 except that 4.5 g of Chemical Co., Ltd. was used. However, since the reaction pressure reached the upper limit (0.3 MPa) during the reaction, the introduction rate of ethylene oxide was appropriately adjusted.

[Example 6]

Methyl oleate in 4L autoclave (Lion Chemical's Pastel M181) The 570 g (l. 9 mol), 40 mass ^_0/0 Mizusani匕aqueous potassium. . 23 g (KOH pure content: 1.6 mmol), 1.8 g of the composite metal oxide catalyst described in Example 1 and 2.25 g of dallyserine as a polyhydric alcohol were charged, and nitrogen was added to the autoclave while stirring and mixing. Then, the temperature was raised and dehydration was performed at 100 ° C under reduced pressure (1.33 kPa or less) for 30 minutes. Then 180. At C, the upper limit of the reaction pressure was 0.3 MPa, a mixture of 1,009 g (22.9 monole) ethylene oxide and 222 g (3.8 mol) of propylene oxide (manufactured by Kanto Chemical Co., Ltd.) It was introduced (supplied) at such a speed that the value of F in the introduction speed equation (formula (IV)) was F = 0.047. After further aging reaction, the mixture was cooled and extracted to obtain fatty acid polyoxyethylene polyoxypropylene glycol ether as a product.

[Example 7]

In a 4 L autoclave, 500 g (2.5 mol) of lauryl'myristyl alcohol (FPG CO1270), 0.54 g of the mixed metal oxide catalyst described in Example 1, and 1.34 g of glycerin as a polyhydric alcohol After the inside of the autoclave was replaced with nitrogen while charging and stirring and mixing, dehydration was carried out at 100 ° C under reduced pressure (1.33 kPa or less) for 30 minutes. Next, at 180 ° C, the upper limit of the reaction pressure was 0.3 MPa, 573 g (13 mol) of ethylene oxide was used, and the value of F in the introduction rate equation (formula (IV)) was F = Introduced (supplied) at a speed of 0.0.38. After further aging reaction, the mixture was cooled and extracted to obtain polyoxyethylene lauryl myristyl ether as a product.

[0060] (Comparative Example 1)

Fatty acid polyoxyethylene lauryl ether was obtained as a product in the same manner as in Example 1 except that glycerin, which is a polyhydric alcohol, was not used.

[0061] (Comparative Example 2)

Fatty acid polyoxyethylene lauryl ether was obtained as a product in the same manner as in Example 2 except that glycerin, which is a polyhydric alcohol, was not used. However, as in Example 2, since the reaction pressure reached the upper limit (0.3 MPa) during the reaction, the introduction rate of ethylene oxide was appropriately adjusted.

[0062] (Comparative Example 3)

Do not use glycerin, which is a polyhydric alcohol, ethylene oxide In the same manner as in Example 1 except that the introduction rate equation (the above formula (IV)) was introduced at a rate such that the value of F was F = 0.063, and the upper limit of the reaction pressure was 0.4 MPa, Fatty acid polyoxyethylene lauryl ether was obtained as a product.

[0063] (Comparative Example 4)

Fatty acid polyoxyethylene polyoxypropylene glycol ether was obtained as a product in the same manner as in Example 6 except that glycerin, which is a polyhydric alcohol, was not used.

[0064] (Comparative Example 5)

A polyoxyethylene lauryl myristyl ether was obtained as a product in the same manner as in Example 7 except that glycerin, which is a polyhydric alcohol, was not used.

[0065] Table 1 below shows reaction conditions (reaction raw materials, catalyst concentration, polyhydric alcohol concentration), catalyst properties (true specific gravity, pre-reaction catalyst average particle size, post-reaction catalyst average particle size) in each Example and Comparative Example. ) And evaluation results of catalyst refinement (sedimentation rate, sedimentation suppression degree). Table 2 below shows the reactivity (alkylene oxide (AO) supply time, amount of by-products) and product properties (viscosity, specific gravity) in each Example and Comparative Example.

In addition, the evaluation method of each item is as describing below.

[0066] [Measuring method of average particle diameter of catalyst]

The pre-reaction catalyst average particle size and the post-reaction catalyst average particle size (average particle size of the catalyst contained in the alkylene oxide adduct) were measured using a laser light scattering particle size distribution analyzer under the following conditions. The median diameter based on the number was calculated.

Measuring device: LA-920 (HORIBA)

Dispersion medium: Acetonitrile

[0067] [Calculation method of sedimentation velocity]

By applying the stoichiometric formula shown below, the sedimentation velocity V of the catalyst particles in the product was calculated and converted into the sedimentation velocity per hour (mZh).

V = l / 18-(pp-p) g / μ-Dp ² (Stortus equation)

In addition, each code | symbol in the said stochastic formula shows the following meaning, respectively.

V = settling rate of composite metal oxide catalyst after reaction (mZh),

PP = specific gravity of the composite metal oxide catalyst after reaction (kgZm ³ ), P = specific gravity of the resulting alkylene oxide adduct (kg / m ³ ),

g = gravitational acceleration (mZs ² ),

μ = viscosity of the resulting alkylene oxide adduct (kgZm

[0068] [Evaluation method of sedimentation suppression degree]

In the physical properties of the relationship between product properties and fine catalyst particles under storage temperature contemplated, about 3 months to precipitation of 10 cm (90 days) is the speed required 4. 6 X 10 ^_5 (mZh) If the sedimentation rate per hour (mZh) of the catalyst particles in the product obtained using the stoichiometric equation is less than this, the product is treated as a liquid. At this time, it was evaluated that the sedimentation rate of the catalyst particles was such that substantially no problem occurred. In Table 1, ○ X represents the following meanings.

○: sedimentation velocity 4. is ^{6 X 10- 5 (m / h} ) or less (no problem substantially the degree of sedimentation). X: (there is a problem to the degree of sedimentation) that sedimentation rate is more than ^{4. 6 X 10 _5 (mZh)} .

[0069] [Measurement method of by-product amount (high molecular weight polyethylene glycol (PEG) amount)]

Gel permeation chromatography measurement was performed under the following conditions, and the content of high-molecular-weight polyethylene glycol (PEG) as a by-product in the product was determined.

Detector: RID— 6A (manufactured by Shimadzu Corporation)

Column: AsahipackGF—310HQ (diameter 7.5 mm X length 0.3 m; manufactured by Showa Denko KK) Mobile phase: Acetonitrile Z water = 45 Z55 (volume ratio)

Flow rate: 0.6 mL / mm

Temperature: 30 ° C

[0070] [Method of measuring viscosity]

The viscosity of the product was measured under the following conditions.

Measuring instrument: RE 80 type viscometer

Rotor: 3 ° 1 ^ 12 and 1 ° 34 'X R24

Time: 2 minutes

Temperature: 60 ° C for Examples 1-5 and Comparative Examples 1-3

40 ° C for Examples 6 and 7 and Comparative Examples 4 and 5 [0071] [Method for measuring true specific gravity of catalyst]

The true specific gravity of the catalyst was measured under the following conditions by a pressure comparison method using a gas phase substitution method (pitometer method).

Measuring device: True density measuring device (micro pycnometer)

Carrier gas: He gas

Sample amount: lg

Temperature: Room temperature

[0072] [Method of measuring specific gravity of product]

Standard oil analysis method 2. 2. 2— The specific gravity of the product was measured using a specific gravity bottle with a thermometer according to 1996 “Specific gravity”.

[0073] [Specific surface area measurement method]

It measured using the BET surface area measuring apparatus ("RINT2100" by Shibata Kagaku Co., Ltd.).

[0074] [Table 1]

Reaction conditions Catalytic properties Evaluation results of catalyst refinement Polyhydric alcohol Before reaction After reaction

Catalyst concentration True specific gravity Sedimentation rate

Catalyst particle size Catalyst particle size

Sedimentation suppression Reaction raw material

Degree

[Mass% / anti [mass% / reaction crude

/ cm3] [m / h] Coarse product] Product]

Methyl ester clean

Example 1 0.1 0 3.1 75 0.31 1 .3E-05

EO 0.125 o Methyl ester gericin

Example 2 0.05 3.1 75 0.28 7.1 E-06

EO 0.05 o Methyl ester gericin

Example 3 0.20 3.1 75 0.56 4.4E-05

EO 0.25

Methyl ester ethylene gericol

Example 4 0.05 3.1 75 0.60 3.5E-05

EO 0.25 o Methyl ester ヅ Ethylene gel

Example 5 0 05 3.1 75 060 3.9 E-05 ○

EO 0.25

Methyl ester gericin

Example 6 0.1 0 3.1 75 025 1 .3E-05

EO PO 0.125 o Alcohol Gericin

Example 7 0.05 3.1 75 0.40 4.4E-05

EO 0.125 o Methyl ester

Comparative Example 1 0.1 0 Not used 3.1 75 1 7.90 2.5E-02

EO

Methyl ester

Comparative Example 2 0.05 Not used 3.1 75 7 50 3 5E-03

EO

Methyl ester

Comparative Example 3 0.1 0 Not used 3.1 75 1 2.50 7.9E-03

EO

Methyl ester

Comparative Example 4 0.1 0 Not used 3.1 75 1 5.20 3.4E-02

EO / PO

Alcohol

Comparative Example 5 0.05 Not used 3.1 75 1 0.90 2.8 E-02

EO [0075] [Table 2]

40 ° C for Comparative Examples 4 and 5

[0076] From Table 1, according to the method for producing an alkylene oxide adduct of the present invention, when the product is handled as a liquid, the solid catalyst can be substantially treated without performing the step of filtering the solid catalyst (solid-liquid separation step). It was confirmed that the sedimentation rate of the catalyst particles can be delayed to the extent that no problem occurs, that is, the catalyst particles can be extremely refined (to 2 m or less). Also, by comparing Example 2 with Examples 4-5, when using a polyhydric alcohol other than glycerin, use more polyhydric alcohol to obtain the desired sedimentation rate. It was confirmed that it was necessary to do.

Further, from Table 2, according to the method for producing an alkylene oxide adduct of the present invention, in particular, a magnesium-based catalyst such as a magnesium aluminum composite metal oxide catalyst as a catalyst is used. In the case of using a composite metal oxide catalyst, it is also possible to suppress the production of high molecular weight polyethylene glycol, which is a by-product, and thus an alkylene oxide adduct having a low liquid viscosity and excellent handling is obtained. It was confirmed that it was possible.

Industrial applicability

The alkylene oxide adduct obtained by the method for producing an alkylene oxide adduct can be used as various surfactant compositions in fields such as household use, industrial use, and agricultural use. The surfactant composition is suitable as, for example, a detergent, an emulsifier, a dispersant, an oil phase component modifier, a penetrating agent, a waste paper recycling deinking agent, an agricultural spreading agent, and the like. Particularly suitable as a cleaning agent.

Claims

The scope of the claims

[1] A method for producing an alkylene oxide adduct in which at least one of an active hydrogen-containing organic compound and a fatty acid alkyl ester is reacted with an alkylene oxide in the presence of a composite metal oxide catalyst and a polyhydric alcohol.

[2] The alkylene oxide according to claim 1, wherein at least one of the active hydrogen-containing organic compound and the fatty acid alkyl ester is reacted with the alkylene oxide after contacting the composite metal oxide catalyst with the polyhydric alcohol. Method for producing adducts.

[3] The stochastic formula:

V = l / 18-(pp-p) g / μ-Dp ² (Stortus equation)

[In the stoichiometric formula,

V = settling rate of composite metal oxide catalyst after reaction (mZh),

P = specific gravity of the resulting alkylene oxide adduct (kg / m ³ ),

g = gravitational acceleration (mZs ² ),

μ = viscosity of the resulting alkylene oxide adduct (kgZm

Show]

Sedimentation velocity V of the composite metal Sani匕物catalyst after the reaction sought is such that 4. 6 X 10 ^_5 (mZh) hereinafter in terms of sedimentation speed per hour, mixed metal after reaction 3. The method for producing an alkylene oxide adduct according to claim 1, wherein the average particle diameter Dp of the oxide catalyst is controlled.

[4] The process for producing an alkylene oxide adduct according to any one of claims 1 to 3, wherein the polyhydric alcohol is glycerin.

5. The method for producing an alkylene oxide adduct according to any one of claims 1 to 4, wherein the complex metal oxide catalyst is a magnesium-based complex metal oxide catalyst.

6. The method for producing an alkylene oxide adduct according to any one of claims 1 to 5, wherein the specific surface area of the composite metal oxide catalyst is 50 to 400 m ² Zg.

[7] It contains a composite metal oxide catalyst having an average particle size of 2 μm or less Alkylene oxide adduct.

[8] The alkylene oxide adduct according to claim 7, obtained by the method for producing an alkylene oxide adduct according to any one of claims 1 to 6.

[9] A surfactant composition comprising the alkylene oxide adduct according to any one of claims 7 to 8.