KR100762862B1 - Method of oxidizing carbon-carbon double bond and process for producing oxidized compound - Google Patents

Abstract

A method of oxidizing a carbon-carbon double bond, which is used for the oxidation reaction after inhibiting the conversion of a compound having a carbon-carbon double bond, separating an unreacted compound from a product, and a method for decomposing an oxidized compound using the oxidation method. This makes it possible to obtain the target oxidizing compound with high selectivity or high productivity.

Description

METHOD OF OXIDIZING CARBON-CARBON DOUBLE BOND AND PROCESS FOR PRODUCING OXIDIZED COMPOUND}

The present invention is a compound having at least two functional groups, wherein at least one of the functional groups is a carbon-carbon double bond (hereinafter sometimes referred to as "compound A"). A method for oxidizing using a catalyst and a method for producing an oxidizing compound using the oxidizing method.

More specifically, the present invention provides a method for oxidizing a carbon-carbon double bond of Compound A, wherein the peroxide is used as an oxidizing agent, and the carbon-carbon double bond of Compound A is highly selectively oxidized in the presence of a titanosilicate catalyst, and It relates to a method for producing an oxidized compound (preferably an epoxy compound) using an oxidation method.

In general, "Zeolite" is a generic term for crystalline porous aluminosilicate since ancient times, and the basic unit of the structure is usually (SiO ₄ ) ^4- and (AlO ₄ ) ^5- having a tetrahedral structure. However, it has recently been discovered that zeolite-specific or zeolite-like structures also exist in many other oxides such as aluminophosphate.

In addition, the International Zeolite Society (hereafter referred to as "IZA") is referred to as "Atlas of Zeolite Structure Types" (W.Meier, DHMeier, DH0lson and Ch. Baerlocher, 4th.EdiTion, 1996,). Elsevier) (hereinafter referred to as "Atlas"), and in this atlas, as the target substance for defining the structure, a substance having the same structure in addition to the aluminosilicate, Is called Zeolite-like Materials (For details on this process, see Yoshio Ono, Tatsuaki Yashima, “Science and Engineering of Zeolites,” pages 1 and 2, Kodansha, July 2000). See the 10-day publication).

The definition of the term "zeolite" in the present specification is not only aluminosilicate, but also the above-mentioned "science and engineering of zeolite" stipulated that it contains not only aluminosilicate, but also a substance having a similar structure such as titanosilicate (Yo Ono Yoshio, Tatsuaki Yashima, Kodansha, pages 1 to 2, issued July 10, 2000).

In addition, regarding the description of the structure of a zeolite and a zeolite like substance in this specification, the structure code which consists of three capital letters of the alphabet approved by IZA (derived from the name of the reference material first used for the clarification of the structure) is used. do. Their structure codes include those listed in the Atlas, and those approved after the fourth edition.

In addition, the "aluminosilicate" and "titanosilicate" in this specification do not restrict | limit any property, such as a difference in crystallinity or amorphousness, a porous thing, etc., and unless otherwise indicated, all aluminium "alumina" Nosilicate "and" titanosilicate ".

In addition, the "molecular sieve" in this specification means the thing which has the effect | action and operation which select | select the molecule | numerator by the magnitude | size, and the function. The "zeolite" also includes the "molecular sieve" For more detailed description of the "Self-independent", see the section "Molecular sieve" in the Japanese Chemical Society edition "Standard Chemical Terminology Dictionary" Maruzen, published on March 30, 2016.

In addition, the "mesoporous body" in this specification means the porous material which has a pore diameter of 2-50 nm (in detail, "The science and engineering of zeolite", page 13-23 by Yoshio Ono and Tatsuaki Yashima, page 13-23). , Kodansha, issued July 10, 2000).

Since the synthesis method of TS-1, which is one kind of zeolite, has been disclosed by U.S. Patent No. 4,410,501, various oxidation reactions of organic compounds using titanosilicates as catalysts and peroxides as oxidants have been studied. As the specific example, for example, an olefin compound is obtained by using a crystalline titanosilicate-containing molecular sieve having a structure such as zeolite beta which does not contain aluminum having a crystal structure code of * BEA as a catalyst and hydrogen peroxide or an organic peroxide as an oxidizing agent. The method of performing the epoxidation reaction of Unexamined-Japanese-Patent No. 7-242649 is disclosed.

In the oxidation reaction of a compound having a carbon-carbon double bond using a titanosilicate as a catalyst, for example, an olefin compound, the ring-opening reaction of the epoxy group of the epoxy compound as a product is likely to occur, resulting in a decrease in the selectivity of the epoxy compound. have. In addition, in such a reaction, since the rate of catalyst deactivation is large, it is necessary to use a large amount of catalyst or to frequently regenerate the catalyst, and it is often difficult to industrially use a titanosilicate catalyst.

In contrast, Japanese Patent Application Laid-open No. Hei 10-25285 discloses using a crystalline titanosilicate (TS-1) catalyst having a structure code of ZSM-5 and epoxidizing an olefin compound with hydrogen peroxide in the reaction. A method of coexisting a mixture of ketones is disclosed.

The addition of the alcohol and the ketone mixture was expected to suppress the diol by-products caused by the ring-opening reaction of the epoxy compound (mainly proceeding in the water phase) in the olefin compound oxidation reaction using hydrogen peroxide as the oxidant. Indeed, in the above specification, there is an example that the catalytic activity is improved by the addition of an alcohol and a ketone mixture, but a soluble solvent reaction of an alcohol or a ketone compound and an epoxy compound occurs, and a decrease in the selectivity of the epoxide compound occurs. There is a problem that carbonyl compounds such as ketones are likely to by-produce explosive organic peroxides.

On the other hand, Japanese Patent Application Laid-Open No. 11-171880 discloses a method in which epoxidation of a halogenated allyl by a titanosilicate catalyst and hydrogen peroxide is carried out by irradiating ultrasonic waves to a reaction system and using ammonium carbonate as a semicatalyst. . In the above specification, it is exemplified that the ring-opening reaction of the epoxy compound can be suppressed when the reaction is carried out while irradiating ultrasonic waves in the presence of ammonium carbonate, but a large amount of ammonium carbonate to be added or recovery of ammonium carbonate There is a problem in industrial use such as difficulty. In addition, when ultrasonic waves are irradiated, there is a problem that the micronization of the catalyst becomes remarkable, and separation of the catalyst and the reaction mixture and recovery of the catalyst become difficult.

Thus, various proposals have been made for the oxidation reaction of an olefin compound using a titanosilicate as a catalyst and a peroxide as an oxidizing agent, but the technique which can be industrially carried out is limited. In the oxidation of carbon double bonds, there are no reports of obtaining desired oxidizing compounds with high selectivity yet.

SUMMARY OF THE INVENTION An object of the present invention is that in the selective oxidation reaction of a carbon-carbon double bond of a compound A having a peroxide as an oxidizing agent in the presence of a titanosilicate catalyst, it is possible to obtain the desired oxidizing compound at high selectivity and at high productivity. The present invention provides a method for oxidizing a carbon-carbon double bond of Compound A, and a method for producing an oxidized compound of Compound A using the oxidation method.

As a result of earnest examination, the present inventors have unreacted compounds separated from the product while suppressing the conversion ratio of Compound A to a certain extent in the oxidation reaction of the carbon-carbon double bond of Compound A having a peroxide in the presence of a titanosilicate catalyst as an oxidizing agent. The use of A (at least a portion of) in the oxidation reaction again and prevention of loss of compound A results in making the desired oxidation reaction more efficient and of high selectivity and extremely effective in achieving the above object. I found it.

That is, the present invention (I) is a method of oxidizing a carbon-carbon double bond of compound A, wherein the oxidation method includes the following first to third steps. Oxidation of bonds.

Step 1: A step of subjecting the oxidation reaction of the carbon-carbon double bond of Compound A to a peroxide in the presence of a titanosilicate catalyst as an oxidizing agent in a conversion ratio of Compound A of 50 mol% or less to obtain an oxidation reaction mixture,

Second step: separating compound A from the oxidation reaction mixture obtained in the first step,

Third Step: Returning Compound A obtained in the second step to the first step.

In addition, the present invention (II) is a method for producing an oxidized compound of Compound A, which uses the oxidation method of the present invention (I).

In addition, this invention consists of the following matters, for example.

[1] A method of oxidizing a carbon-carbon double bond of a compound having at least two functional groups, wherein at least one of the functional groups is a carbon-carbon double bond (hereinafter referred to as “Compound A”). The oxidation method includes the following first to third steps, wherein the carbon-carbon double bond of Compound A is oxidized.

1st step: the oxidation reaction of the carbon-carbon double bond of the compound A with a peroxide as an oxidizing agent in the presence of a titanosilicate catalyst, and the conversion rate of the compound A is 50 mol% or less, and the oxidation reaction mixture is obtained,

Second step: separating compound A from the oxidation reaction mixture obtained in the first step,

Third Step: Returning Compound A obtained in the second step to the first step.

[2] The oxidation method of carbon-carbon double bond of compound A according to [1], wherein the conversion ratio of compound A in the first step is in a range of 30 mol% or less.

[3] The oxidation method of carbon-carbon double bond of Compound A according to [1], wherein the conversion ratio of Compound A in the first step is in a range of 15 mol% or less.

[4] The peroxide in the first step is a limited reaction component, the concentration of the peroxide in the raw material mixture is 0% by mass to 50% by mass, and the conversion rate of the peroxide is 30 mol% to 100 mol%. The oxidation method of the carbon-carbon double bond of the compound A in any one of [3].

[5] The oxidation method of carbon-carbon double bond of compound A according to [4], wherein the conversion rate of the peroxide is 80 mol% to 100 mol%.

[6] The carbon-carbon double of compound A according to any one of [1] to [5], wherein the titanosilicate catalyst is at least one or more selected from the group consisting of crystalline titanosilicate and mesoporous titanosilicate. Oxidation of bonds.

[7] The crystal structure of crystalline titanosilicate is selected from the group consisting of MFI type, AEL type, EUO type, FER type, MEL type, AFI type, MWW type, ATO type, * BEA type, MOR type and CLO type. The oxidation method of the carbon-carbon double bond of the compound A as described in [6] which is at least 1 sort (s) and its composition is represented by following formula (1).

Formula (1)

xTiO ₂ ㆍ (1-x) SiO ₂

(Wherein x is 0.0001 to 0.2)

[8] The oxidizing agent is hydrogen peroxide, t-butyl hydroperoxide, t-aminohydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, methylcyclohexyl hydroperoxide, isobutylbenzene hydroperoxide A method of oxidizing a carbon-carbon double bond of Compound A according to any one of [1] to [7], which is at least one compound selected from the group consisting of oxides, ethylnaphthalene hydroperoxides and peracetic acid.

[9] Functional groups other than the carbon-carbon double bond in Compound A in the first step include alkenyl groups, alkynyl groups, aryl groups, alcohol groups, phenol groups, ether groups, epoxide groups, halogen atoms, carbonyl groups, Amide group, cyanate group, isocyanate group, thiocyanate group, amino group, diazo group, nitro group, nitrile group, nitroso group, sulfide group, sulfoxide, sulfone group, thiol group, orthoester group, urea group and already A method of oxidizing a carbon-carbon double bond of Compound A according to any one of [1] to [8], which is at least one or more functional groups selected from the group consisting of no groups.

[10] The compound A is at least one compound selected from the group consisting of allyl ethers, ethers of polyhydric alcohols, carboxylic acid esters, and other compounds having 3 to 10 carbon atoms. The oxidation method of the carbon-carbon double bond of the compound A in any one of 1]-[9].

[11] The allyl ether is at least one compound selected from the group consisting of allyl methyl ether, allyl ethyl ether, allyl propyl ether, allyl butyl ether, allyl vinyl ether and diallyl ether. Method for oxidation of carbon-carbon double bond of compound A.

[12] A method for oxidizing a carbon-carbon double bond of compound A according to [10], wherein compound A is diallyl ether or allyl alcohol, and the oxidant is hydrogen peroxide.

[13] ethers of polyhydric alcohols include ethylene glycol monoalkenyl ether, ethylene glycol dialkyl ether, 1,2-propanediol monoalkenyl ether, 1,2-propanedioldialkenyl ether, 1,3-propanediol Monoalkenylether, 1,3-propanedioldialkenylether, 1,2-butanediol monoalkenylether, 1,2-butanedioldialkenylether, 1,3-butanediol monoalkenylether, 1,3-butanedioldial Kenyl ether, 1,4-butanediol monoalkenyl ether, 1,4-butanediol dialkenyl ether, trimethylolpropane monoallyl ether, trimethylolpropanediallyl ether, trimethylolpropanetriallyl ether, pentaerythritol monoalkenyl ether And at least one compound selected from the group consisting of pentaerythritol dialkenyl ether, pentaerythritol trialkenyl ether, and pentaerythritol tetraalkenyl ether. Carbon compounds A - carbon oxidation of the double bonds.

[14] The carbon of compound A according to [10], wherein the carboxylic acid ester is at least one or more compounds selected from the group consisting of allyl formate, allyl acetate, allyl propionate, allyl tartarate and allyl methacrylate. -Oxidation of carbon double bonds.

[15] The compound according to [10], wherein the compound having 3 to 10 carbon atoms is at least one compound selected from the group consisting of allyl alcohol, allyl bromide, allyl chloride, acrolein, methacrolein, and acrylic acid. Oxidation method of carbon-carbon double bond of A.

[16] The carbon-carbon of Compound A according to any one of [1] to [15], wherein the oxidation reaction is carried out in the presence of at least one solvent selected from the group consisting of alcohols, ketones, nitriles and water. Oxidation of Double Bonds.

[17] The carbon-carbon double of compound A according to any one of [1] to [16], wherein the product obtained by the oxidation reaction is an epoxidized compound of a carbon-carbon double bond site of compound A as a raw material. Oxidation of bonds.

[18] A method for producing an oxidized compound of Compound A, wherein the method for oxidizing a carbon-carbon double bond of Compound A according to any one of [1] to [17] is used.

[19] As the compound A, at least one member selected from the group consisting of diallyl ether, allyl alcohol, and mixtures thereof is used, and the carbon-carbon double of compound A according to any one of [1] to [17]. A method for producing allylglycidyl ether, diglycidyl ether, or glycidol, characterized by using a method of oxidizing a bond.

[20] The method for producing allyl glycidyl ether, diglycidyl ether or glycidol according to [19], wherein hydrogen peroxide is used as the oxidizing agent.

1 is a process chart for explaining Example 8 and Comparative Example 4 in more detail.

In the above, each code | symbol has the following meanings.

1: Tank C

It is a tank which stores diallyl ether and methanol which are raw materials, and unreacted diallyl ether and methanol are collect | recovered in tank C.

2: tank A

Tank that stores diallyl ether as a raw material.

3: tank B

Tank for storing 60% by mass aqueous hydrogen peroxide solution.

4: mixer

An apparatus for mixing a methanol solution of diallyl ether fed from tank C, diallyl ether fed from tank A, and a 60% by mass aqueous hydrogen peroxide solution fed from tank B to prepare a solution uniformly.

5: oxidation reactor

It is a reactor filled with a titanosilicate catalyst, and an oxidation reaction of diallyl ether is performed.

6: Distillation column A

The distillation column which feeds the reaction mixture which flowed out from the oxidation reactor, and collect | recovers unreacted diallyl ether and methanol in the tower top.

7: Distillation column B

A distillation column for purifying crude allylglycidyl ether fed from the bottom of the column of distillation column A.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail, referring drawings as needed. In the following descriptions, "parts" and "%" meaning the ratios are based on mass unless otherwise specified.

The present invention (I) is a method of oxidizing a carbon-carbon double bond of compound A, wherein the oxidation method includes the following first to third steps. Oxidation method.

Step 1: A process for obtaining an oxidation reaction mixture by subjecting the carbon-carbon double bond of Compound A to a peroxide in the presence of a titanosilicate catalyst as an oxidizing agent in a conversion ratio of Compound A of 50 mol% or less.

Second Step: Separation of Compound A from the Oxidation Reaction Mixture Obtained in the First Step

Third Step: Returning Compound A obtained in the second step to the first step.

First, the first step will be described.

(Titanosilicate Catalyst)

The titanosilicate catalyst used in the first step of the present invention is not particularly limited, but specific examples thereof include crystalline titanosilicate and porous titanosilicate represented by the following formula (1).

Formula (1)

xTiO ₂ ㆍ (1-x) SiO ₂

    (Where x is 0.0001 to 0.2)

Here, part of the means of x is, the presence of TiO ₂ molar ratio of the titanosilicate, a further (1-x) are present as a molar ratio of SiO _2. In other words, x / (1-x) represents only the molar ratio of titanium / silicon, and does not deny the presence of other elements in the titanosilicate catalyst.

The range of x in the composition formula (1) is 0.0001 to 0.2, preferably 0.005 to 0.2, more preferably 0.01 to 0.1. In addition to titanium contained in the skeleton by substituting silicon, titanium species present at sites other than the skeleton, such as 6-coordinate titanium species or titanium oxide in anatase, may generally be present. Since the side reaction is promoted or the pore is narrowed to inhibit the diffusion of the reactant, the smaller amount is preferable.

The x defined in the above formula (1) assumes the proportion of titanium contained in the skeleton, but when titanium exists outside the skeleton in addition to the titanium in the skeleton, it is not practical to quantitatively quantitate titanium contained in the skeleton accurately. . In general, for example, absorption in the vicinity of 210 nm by the ultraviolet visible absorption spectrum is titanium in the skeleton, absorption in the vicinity of 260 nm is the sixth coordinate lattice other titanium species, absorption in the vicinity of 330 nm and anatase If it belongs to the same titanium species and there is absorption in the vicinity of 21O nm, it turns out that the titanosilicate has titanium in skeleton. In fact, the titanosilicate catalyst of the present invention (I) has an absorption around 220 nm and shows that titanium in the skeleton is present. However, when absorption is also present at other wavelengths, it is only evident that it is difficult to quantitatively discuss the proportion of these titanium species in combination with other methods such as nuclear magnetic resonance or infrared absorption. The molar ratio of titanium to silicon calculated from the ratio of titanium and silicon obtained by the compositional analysis is that the maximum value of the amount of titanium contained in the skeleton. As described above, since it is difficult to directly determine the molar ratio of titanium contained in the skeleton, in the present invention, the molar ratio of titanium and silicon calculated by composition analysis as x in the composition formula (1) is conveniently contained in the skeleton. It is used as molar ratio of.

(Specific example of titanosilicate)

Specific examples of the crystalline titanosilicates include crystalline titanosilicates and porous titanosilicates as described above. More specifically, crystalline titanosilicates whose crystal structures are MFI type, AEL type, EUO type, FER type, MEL type, AFI type, MWW type, ATO type, * BEA type, MOR type and CLO type are mentioned, for example. Can be. On the other hand, as a specific example of mesoporous titanosilicate, the symbol is, for example, FSM-16, MCM-41, MCM-48, MCM-50, SBA-1, SBA-2, SBA-3, HMS, MSU-1, And mesoporous titanosilicates which are MSU-2, SBA-15 and SBA-16.

Preferred titanosilicates as catalysts include MFI type, MEL type, MWW type, EUO type, crystalline titanosilicate or MCM-41, MCM-48 mesoporous titanosilicate, and in particular, MFI type, MWW type and crystalline titanosilicate. Silicates and MCM-41, mesoporous titanosilicates and the like. Of course, you may mix and use these different types of titanosilicates.

The titanosilicate catalyst used in the present invention can be prepared by a known method. Specifically, for example, MFI type crystalline titanosilicate (US Patent No. 4410501), * BEA type crystalline titanosilicate (JP-A-7-242649), MOR type crystalline titanosilicate (GJKim, BRCho, JHKim, Catalyst Letteres 259 (1993)), MCM-41 porous titanosilicate (T.Blasco, Journal of Catalysis, 156 (1995)), MCM-48 porous titanosilicate (Takashi Tatsumi, Chemi cal Communication 145 (1996)).

 The form of the titanosilicate catalyst used in the first step is also not particularly limited. In the present invention, a form in which the pressure loss in the reactor is small (for example, in a form of powder, microspheres, pellets, extruded articles, or carriers) when the reactor is filled is preferable. Although a binder may be used for molding, the preferred binder and carrier are essentially nonacidic or acidic weak substances and preferably do not promote the decomposition reaction of the peroxide or the decomposition reaction of the target oxidizing compound.

(Oxidation reaction)

In the oxidation reaction in the first step of the present invention, only the oxidation reaction of the carbon-carbon double bond can be selectively performed without substantially affecting the functional groups other than the carbon-carbon double bond of the compound A. Do. Of course, functional groups other than carbon-carbon double bonds can also be reacted at the same time to obtain completely different objects, and needless to say, such cases are also included in the present invention.

In the present invention, the reason why such excellent selectivity is obtained is that, according to the findings of the present inventors, in general, the titanosilicate used in the present invention has a high oxidation activity to a carbon-carbon double bond and a low oxidation activity of other functional groups ( TS-1, on the other hand, is exceptionally likely to oxidize other functional groups as well).

(peroxide)

Although the peroxide which can be used in the 1st process of this invention is not specifically limited, Specifically, hydrogen peroxide or an organic peroxide is mentioned, for example. Examples of the organic peroxide include t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, methylcyclohexyl hydroperoxide, isobutylbenzene hydroper Oxide, ethylnaphthalene hydroperoxide, and peracetic acid are mentioned, but it is not limited to this. Moreover, even if it mixes and uses two or more types of these peroxides, it does not mind.

In terms of ease of availability, treatment after reaction, and the like, hydrogen peroxide is most preferably used as the peroxide, and hydrogen peroxide in any concentration may be used, for example, 30 mass% or 60 mass commercially available. Hydrogen peroxide aqueous solution of concentration, such as% and 90 mass%, can be used.

(Compound A)

"Compound A" used in the first step of the present invention is a compound having at least two or more functional groups in one so-called molecule, and is not particularly limited as long as at least one of the functional groups is a compound having a carbon-carbon double bond. In this case, even if a carbon-carbon double bond is contained among the functional groups other than the carbon-carbon double bond (that is, at least one carbon-carbon double bond) essential for the compound A, or as the "other functional group", Do not.

Specific examples of other functional groups include, for example, alkenyl groups, alkynyl groups, aryl groups, alcohol groups, phenol groups, ether groups, epoxide groups, halogen atoms, carbonyl groups, amide groups, cyanate groups, isocyanate groups, thiocyanate groups, Amino groups, diazo groups, nitro groups, nitrile groups, nitroso groups, sulfide groups, sulfoxides, sulfone groups, thiol groups, orthoester groups, urea groups, and imino groups may be mentioned, but are not limited thereto. Moreover, even if it has two or more functional groups of the same kind, and has two or more functional groups, it does not interfere.

As a suitable functional group in this invention, an alkenyl group, an aryl group, an alcohol group, a phenol group is mentioned as a suitable other functional group ", for example.

(Example of Compound A)

More specific examples of the compound A include allyl ethers, ethers of polyhydric alcohols, carboxylic acid esters, and the like and other C3-C10 compounds. Of course, even if it is a mixture of two or more of these, it does not mind.

More specifically, for example, allyl ethers include allyl methyl ether, allyl ethyl ether, allyl propyl ether, allyl butyl ether, allyl vinyl ether, diallyl ether, and the like.

As ethers of polyhydric alcohols, ethylene glycol monoalkenyl ether, ethylene glycol dialkyl ether, 1,2-propanediol monoalkenyl ether, 1,2-propanedioldialkenyl ether, 1,3-propanediol monoalkenyl Ether, 1,3-propanedioldialkenyl ether, 1,2-butanediol monoalkenyl ether, 1,2-butanedioldialkenyl ether, 1,3-butanediol monoalkenyl ether, 1,3-butanedioldialkenyl ether, 1,4-butanediol monoalkenyl ether, 1,4-butanedioldialkenyl ethertrimethylolpropane monoallyl ether, trimethylolpropanediallyl ether, trimethylolpropanetriallyl ether, pentaerythritol monoalkenyl ether, pentaerythritol diallyl Kenyl ether, pentaerythritol trialkenyl ether, pentaerythritol tetraalkenyl ether, etc. can be illustrated.

Examples of the carboxylic acid esters include formic acid allyl, allyl acetate, allyl propionate, allyl stannate, allyl methacrylate, and the like.

As a C3-C10 compound, allyl alcohol, allyl bromide, allyl chloride, acrolein, methacrolein, acrylic acid, etc. can be illustrated.

(Preferred Compound A)

In view of many industrial uses among the oxidized compounds of Compound A, preferred compounds A include allyl chloride, diallyl ether, allyl acetate, allyl methacrylate or allyl alcohol. As most preferable compound A, diallyl ether, allyl alcohol, and mixtures thereof are mentioned. As mentioned above, a preferable oxidant is hydrogen peroxide, and the combination of this and diallyl ether, allyl alcohol, and mixtures thereof is mentioned as an example of the combination of the most preferable oxidizing agent and compound A of the said oxidation method.

In this case, when using diallyl ether as compound A, allyl glycidyl ether, diglycidyl ether, and a mixture thereof can be obtained as an oxidizing compound. In addition, when allyl alcohol is used as compound A, glycidol can be obtained as an oxidizing compound.

The range of the conversion rate of the compound A in 1st process is 50 mol% or less, Preferably it is 30 mol% or less, More preferably, it is 15 mol% or less. The "conversion ratio of compound A" herein refers to the ratio of the compound A consumed by the reaction with respect to the compound A which existed before the reaction. When the conversion ratio of compound A is larger than 50 mol%, the selectivity of compound A to oxidation products may deteriorate, which is not preferable.

(Regeneration of catalyst)

The titanosilicate catalyst used in the oxidation method of the carbon-carbon double bond of Compound A having a peroxide as an oxidizing agent has a time-lapse or repeated use, so that coke substances and the like adhere to the pores and exhibit no initial activity. do. The deterioration of activation due to coking matter is considered to be reversible degradation, and there are many reports that the degradation catalyst can be regenerated to the initial activity by aeration regeneration. For example, a method for regenerating a titanium-containing molecular sieve catalyst (Japanese Patent Laid-Open No. 8-309200), which is heated to a temperature lower than 400 ° C. but higher than 150 ° C., can be exemplified.

However, the titanosilicate catalyst whose activity is deteriorated due to the oxidation reaction of the first step of the present invention having a conversion rate of Compound A of 50 mol% or more does not exhibit initial activity even after performing a regeneration treatment by conventionally known aeration. . According to the findings of the present inventors, not only the pore occlusion due to coke adhesion was caused by the coke deposition but also the titanium atom, which is the active point of the catalyst, was released during the reaction, and the concentration of titanium in the catalyst was increased. It is estimated by the decrease. In other words, when the conversion ratio of Compound A is performed at 50 mol% or more, the titanosilicate catalyst tends to cause a phenomenon (permanent deterioration) in which initial activity is not exhibited even after aeration regeneration. Therefore, the conversion rate of the compound A in the 1st process becomes like this. Preferably it is 50 mol% or less, More preferably, it is 30 mol% or less, More preferably, it is 15 mol% or less.

(Control method of telephone rate)

The method for controlling the conversion rate of Compound A is not particularly limited, but the conversion rate can be controlled by, for example, the amount of the titanosilicate catalyst used for the reaction, the reaction temperature, and the concentration of the peroxide in the raw material composition. It is preferable to use the reaction method which makes it. The term "limited reactive content" as used herein refers to the ratio of the amount of material (moles) of each raw material component in the feedstock based on the raw material components in the reaction raw material supplied to the reactor, and compared it with the ratio required by the quantitative theory. When we refer to raw materials supplied at the least ratio (refer to the detailed description of this limited reactive ingredient, page 39 of Kenji Hashimoto "reaction engineering", Baifukan, September 30, 1993 revision publication) have). When the peroxide is defined as a limited reactive component, the maximum value of the conversion ratio of Compound A can be easily controlled by the amount of substance of the peroxide as the oxidizing agent.

The concentration in the peroxide raw material as the limited reactive component is not particularly limited, but preferably 30 mass% or less, more preferably 15 mass% or less, and further 10 mass% or less, based on the mass of all components supplied to the reactor. desirable. If the peroxide concentration is 30% by mass or more, the self-decomposition reaction of the peroxide tends to be remarkable, and it is not preferable because the risk of explosion due to the generation of oxygen increases.

Although the conversion rate of the oxidizing agent in this invention is not specifically limited, Preferably it is 50 mol% or more, More preferably, 75 mol% or more at the conversion rate based on the amount of increase and decrease of the oxidizing agent itself before and after reaction. More preferably, it is 90 mol% or more.

When the conversion rate of the oxidizing agent is 50 mol% or less, since unreacted peroxide tends to remain during the reaction, the self-decomposition reaction of the peroxide becomes remarkable, and it is necessary to separate and recover the peroxide from the mixture after the reaction is completed. I can't. When the separation of the peroxide is difficult, it is necessary to decompose the peroxide from the viewpoint of safety, but as a result, the selectivity of the peroxide deteriorates as a result. Therefore, the conversion rate of the oxidant is preferably set to 50 mol% or more.

(Amount of titanosilicate catalyst)

The amount of the titanosilicate catalyst used in the oxidation reaction of the first step is not particularly limited. The preferred range can be changed by the activity of the titanosilicate catalyst, the type of oxidation reaction, the reaction temperature, the reactivity of the substrate, the peroxide concentration, and the reaction mode (batch type or continuous type). When using in a slurry type | system | group, the range of 0.1 mass%-20 mass% is suitable normally (based on the mass of all the components supplied to a reactor) as a density | concentration in a reactant mixture, More preferably, it is 0.5 mass%-10 mass masses. Range of% In the fixed bed flow reaction system, it is preferable to use a catalyst amount larger than this apparently.

(menstruum)

The oxidation reaction in the 1st process of this invention (I) does not need to use a solvent, or may be performed in presence of a suitable solvent. Examples of suitable solvents include alcohols, ketones, nitriles, water and the like.

Specific examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, amyl alcohol, ethylene glycol, propylene glycol, 1,2-butanediol, acetone as ketones, Examples of methyl ethyl ketone, diethyl ketone and nitriles include acetonitrile, propionitrile and benzonitrile.

These solvents can be used alone or as a mixture. Acetone, methanol, acetonitrile and water are mentioned as a preferable solvent from a compound A, compatibility with an oxidizing agent, and stability in the solvent of an oxidizing agent, and methanol and water are especially preferable.

Although the usage-amount of a solvent may change with compound A, the kind, and combination of oxidizing agents, 0.5 times-100 times are preferable with respect to compound A on a mass basis.

(Reaction temperature of oxidation reaction)

The reaction temperature of the oxidation reaction in the first step of the present invention (I) is not particularly limited. This reaction temperature becomes like this. Preferably it is the range of 0 degreeC-150 degreeC, More preferably, it is the range of 10 degreeC-100 degreeC. When the reaction temperature is lower than 0 ° C., the reaction rate is slow and not practical. On the other hand, when the reaction temperature is higher than 150 ° C., the decomposition reaction of the peroxide becomes remarkable and the decomposition reaction of the target product may be promoted, which is not preferable. .

In general, since the oxidation reaction is exothermic, it is preferable to remove the heat of reaction by a suitable method in order to control the reaction temperature to a certain range. In addition, the reaction pressure is not particularly limited.

The oxidation reaction in the first step of the present invention uses a suitable reactor such as a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, a tank reactor, or a continuous stirred tank reactor, and uses a batch system and a continuous system. Or semi-continuous, and either method may be used. In addition, the mixture which consists of a titanosilicate catalyst, a compound A, and a peroxide may be mixed, you may mix all at once, or may mix sequentially.

In this way, in the first step of the present invention (I), the oxidation reaction of the carbon-carbon double bond of the compound A is carried out while pressing the conversion ratio of the compound A in the presence of a titanosilicate catalyst as the oxidizing agent. Obtained with high selectivity. In the general oxidation method, the production method in which the conversion rate of the raw material compound is low and the desired concentration of the oxidized compound in the reaction mixture is not obtained often leads to deterioration in productivity and is not preferable as an industrial method.

On the other hand, in this invention (I), the selectivity of the target oxidation reaction is included in the oxidation method of the carbon-carbon double bond of compound A by including the following 2nd process-3rd process following a 1st process. It is possible to carry out the desired oxidation reaction at high productivity without substantially damaging the.

Next, the second step and the third step will be described.

(2nd step)

The second step in the present invention (I) is a step of separating compound A from the reaction mixture obtained in the first step.

The method for separating Compound A from the reaction mixture in the second step of the present invention is not particularly limited. In the case where the reaction apparatus for the oxidation reaction in the first step is a stirred tank reactor, after recovering the titanosilicate catalyst by a suitable method such as filtration or centrifugation, the compound A is removed from the reaction mixture by any method. The compound A may be separated from the reaction mixture while the titanosilicate catalyst is contained without recovering the catalyst.

On the other hand, in the case where the reaction apparatus for the oxidation reaction in the first step is a fixed bed reactor, the reaction mixture containing no titanosilicate catalyst can be easily obtained from the outlet of the reactor while the titanosilicate catalyst is maintained in the reactor. Therefore, Compound A can be separated by any method in the reaction mixture which does not contain the titanosilicate catalyst obtained.

(Preferable separation method)

The preferred method for separating compound A from the reaction mixture of the first step is different depending on the boiling point of the compound A and its oxidized product, the type of functional group, and thermal stability. For example, when Compound A has a standard boiling point of 30 ° C. to 150 ° C. under atmospheric pressure, when separated from the reaction mixture of the first step, a fractional distillation method under atmospheric pressure having an operating temperature range of 30 ° C. to 200 ° C. as a separation method. This is preferable. Examples of the compound A having a boiling point of 30 ° C. to 150 ° C. under atmospheric pressure include allyl methyl ether, allyl ethyl ether, allyl propyl ether, allyl butyl ether, allyl vinyl ether, diallyl ether, allyl bromide, allyl chloride, methacrolein, and formic acid. Allyl, allyl acetate, allyl propionate, allyl tartarate, allyl methacrylic acid, etc. can be illustrated.

Further, in the case of allyl alcohol, acrolein, acrylic acid, ethylene glycol monoalkenyl ether, etc., in which compound A has high solubility in water, liquid extract separation using an organic solvent as the extractant is preferable, and the operating temperature at that time is 15 ° C. It is preferable that it is the range of -200 degreeC. When the operation is performed at a temperature higher than this, the decomposition of the oxidized compound as a product may occur, which is not preferable.

Moreover, when compound A has a boiling point of 150 degreeC or more under atmospheric pressure, distillation under reduced pressure or separation from the reaction mixture by liquid liquid extraction using an organic solvent as an extractant is preferable. The pressure range of a preferable vacuum distillation is 133 Pa-100 kPa, and a preferable operating temperature range is 20 degreeC-200 degreeC. Moreover, as an organic solvent used for liquid extraction, an acetate ester compound, an ether compound, an aromatic compound, and an aliphatic saturated hydrocarbon compound are preferable, and operation temperature range is 20 degreeC-150 degreeC.

Examples of the compound A having a boiling point of 150 ° C. or higher at atmospheric pressure include ethers of polyhydric alcohols, ethylene glycol dialkyl ether, 1,2-propanediol monoalkenyl ether, 1,2-propanedioldialkenyl ether, 1,3- Propanediol monoalkenyl ether, 1,3-propanediol alkenyl ether, 1,2-butanediol monoalkenyl ether, 1,2-butanedioldialkenyl ether, 1,3-butanediol monoalkenyl ether, 1,3- Butanedioldialkenyl ether, 1,4-butanediol monoalkenyl ether, 1,4-butanedioldialkenyl ethertrimethylolpropane monoallyl ether, trimethylolpropanediallyl ether, trimethylolpropanetriallyl ether, and pentaerythritol dialkyl ether , Pentaerythritol trialkenyl ether, pentaerythritol tetraalkenyl ether and the like can be exemplified.

(By-product with hydroxyl group)

In any operation of separating Compound A from the reaction mixture, if the by-product having a hydroxyl group resulting from a peroxide may react with Compound A or its oxidized compound, any of Compound A may be separated from the reaction mixture. Before phosphorus operation, it is preferable to remove the by-product which has a hydroxyl group which arises from a peroxide beforehand.

As by-products having hydroxyl groups resulting from peroxides, water, t-butyl alcohol, t-amyl alcohol, 2-phenyl-2-propanol, 1-phenylethanol, cyclohexenol, methylcyclohexenol, 2-methyl- 2-hydroxy-3- phenyl propane, acetic acid, etc. can be illustrated concretely. Although the removal method of the by-product which has a hydroxyl group resulting from a peroxide is not restrict | limited, Distillation, liquid extraction, liquid separation, and membrane separation can be illustrated as a removal method (For details of such a removal method, For more information, see Kyoto University Tarama Laboratory, "Responsive Catalytic Classification Table 2," pages 221 to 232, published May 1, 1984, and the Chemical Industries, Ltd.).

(Removal of water)

When the by-product having a hydroxyl group generated from the peroxide is water, the nucleophilicity of the water is high and the decomposition reaction of the oxidized product is likely to occur, so that water from the reaction mixture is removed before any operation of separating Compound A from the reaction mixture. It is desirable to remove. The method of removing water is not particularly limited, and examples thereof include liquid separation, liquid extraction, distillation, and membrane separation.

When the water is removed using the liquid separation, the liquid separation may be performed as it is without adding anything to the reaction mixture, but an inorganic salt may be added to the reaction mixture in order to lower the distribution ratio of the oxidation product in the aqueous phase. It is preferable to perform liquid-liquid separation after reducing the concentration in the aqueous phase of the oxidized compound. As inorganic salts added for this purpose, lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, potassium acetate, lithium chloride, sodium chloride, magnesium chloride, aluminum chloride, potassium chloride, lithium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, And potassium sulfate etc. can be illustrated.

The extractant which can be used as a method of removing water by using liquid extraction is not particularly limited, but in view of the separation coefficient and selectivity when extracting water and oxidation products, the preferred effluent is a carboxylic acid ester, More specifically, methyl formate, ethyl formate, formic acid propyl, butyl formate, formic acid allyl, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, allyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, propionic acid Allyl.

In the method of removing water by distillation, the method of distillation is not particularly limited, but since distillation of water usually requires enormous energy, azeotropic distillation can be exemplified as a preferable distillation method. Preferred compounds having an azeotropic composition with water in the azeotropic distillation method may be present in the reaction mixture in advance, or may be newly added to the reaction mixture as an azeotropic agent. You may add an agent. At the time of selecting an azeotropic agent, the azeotropic agent whose azeotropy temperature with water is 200 degrees C or less under atmospheric pressure is preferable, and the compound which does not show acidic acid in order to prevent decomposition | disassembly of an oxidizing compound is preferable.

(Unreacted peroxide)

When separating compound A from the reaction mixture, unreacted peroxide may be present in the reaction mixture, but to avoid the risk of explosion due to the concentration of unreacted peroxide, unreacted peroxide is removed from the reaction mixture. It is preferable to remove it before separation. There is no restriction | limiting in the removal method of an unreacted peroxide, You may remove a peroxide from a reaction mixture as it is, or remove it from a reaction mixture by decomposing a peroxide. Separation of the peroxide from the reaction mixture and decomposition of the peroxide can be performed by a conventionally known method.

As a method of separating a peroxide from the reaction mixture, for example, distillation, liquid separation and liquid extraction can be exemplified. Examples of the decomposition method of the peroxide include a method of adding an inorganic salt to the reaction mixture, and contacting the reaction mixture with a metal catalyst. Method and the like.

In the method for separating peroxides, in the case of hydrogen peroxide, peracetic acid, etc., in which the peroxide is easily dissolved in water, liquid extraction using water as the extractant is preferable, and the peroxide is t-butyl hydroperoxide, cumene hydroperoxide, ethyl In the case of peroxides which are hard to dissolve in water such as benzene hydroperoxide, distillation is preferred, and the preferred temperature for performing these liquid extraction operations is 20 ° C to 200 ° C, and the pressure is not particularly limited. It goes without saying that the recovered peroxide can be returned to the first step for reuse.

In the method of decomposing a peroxide by adding a reducing substance to the reaction mixture, the inorganic salt to be added is not particularly limited. Examples thereof include sodium thiosulfate, cerium sulfate, and potassium permanganate. The amount of the inorganic salt to be added is not particularly limited, but may be added to the molar amount of the remaining peroxide, or may be added in a small amount, but the preferred amount is 30 mol% to 200 mol%, more preferably 50 mol relative to the molar amount of the peroxide remaining. % To 120 mol%. In addition, arbitrary forms may be sufficient as the added inorganic salt, and it may add as a solid, or may add as an aqueous solution. Although the temperature of the reaction mixture at the time of adding an inorganic salt is not restrict | limited, Preferably since the decomposition reaction of a peroxide is exothermic reaction, Preferably it is 20 degreeC-180 degreeC, More preferably, it is 30 degreeC-150 degreeC.

(Metal catalyst)

The metal catalyst in the method for decomposing the peroxide by contacting the reaction mixture with the metal catalyst is not particularly limited, but is preferably at least one selected from the group of iron, copper, nickel, manganese, platinum, and palladium as the metal catalyst. And metals, chlorides, oxides, and sulfides. In addition, these metals may be used in any form, and may be used as particles, dissolved in a solution, or supported on a carrier (for details of these metal catalysts, for example, Literature: `` Catalyst Classification Table 2 for Reactions '', page 221-232, issued by May 1, 1984, Chemical Industries, Ltd., Tara Lab, Kyoto University).

(3rd step)

The 3rd process in this invention (I) is a process of returning the compound A obtained by the 2nd process to a 1st process.

The compound A obtained at the second step may be returned to the first step as it is, or the compound A obtained at the second step may be purified by an arbitrary method and then returned to the first step. Although the purity of the compound A returned to the 1st process is not specifically limited, When the component used as a catalyst poison of the titanosilicate catalyst in a 1st process is contained, it is preferable to refine | purify the compound A obtained by the 2nd process.

(Catalyst poison)

Although the component used as a catalyst poison of the titanosilicate catalyst in a 1st process is not specifically limited, In the point of affinity and coordination power with titanium, the epoxide ring-opening product by-produced in the method of manufacturing an epoxide compound in Compound A , Alcohol compounds, and aldehyde compounds.

More specifically, examples of the epoxide ring-opening product include diol compounds generated from epichlorohydrin, diol compounds generated from glycidol, diol compounds generated from glycidyl methacrylate, diol compounds generated from glycidyl acetate, and allyl. Diol compounds resulting from glycidyl ether can be illustrated.

Examples of the alcohol compound include methanol, ethanol, propanol, vinyl alcohol, allyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, trimetholpropane and pentaerythritol. have.

In addition, examples of the aldehyde compound include formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde and acrolein.

Particularly preferred catalytic poisoning components are diol compounds resulting from epichlorohydrin, diol compounds derived from glycidol, diol compounds derived from allylglycidyl ether, vinyl alcohol, allyl alcohol, 1,3-propanediol , 1,4-butanediol, trimetholpropane, formaldehyde, acetaldehyde, propionaldehyde, acrolein and the like.

As a method of removing the component used as the catalyst poison of the titanosilicate catalyst of a 1st process, liquid-liquid separation, liquid-liquid extraction, distillation, and membrane separation are mentioned, but it is not limited to this. In addition, there is no restriction | limiting in the form of the compound A obtained by the 2nd process and return to a 1st process, Any form of a gas state, a liquid state, and a solid state is not restrict | limited, and temperature and a pressure are not specifically limited.

(Recycle)

Although only Compound A obtained from the second step may be returned to the first step, it is preferable to form a so-called "recycle" as a chemical process to add new compound A and return to the first step. In general, a method of adding a new compound A in an amount equal to or in excess of the amount converted to the oxidized compound of the compound A by an oxidation reaction and returning the compound A obtained from the second step to the first step, More preferred.

When no new compound A is added, the concentration of compound A in the first step decreases, and it is difficult to obtain a sufficient reaction rate, which is not preferable. On the other hand, when the compound A obtained in the second step is returned to the first step by comparing at least the new compound A with the amount converted to the oxidized compound of the compound A, the compound A in the first step is not less than a certain concentration. It is easy to hold | maintain and to perform stable oxidation reaction.

(Method for Producing Oxidized Compound)

Next, this invention (II) is demonstrated. This invention (II) is a manufacturing method of the oxidized compound of the compound A characterized by using the oxidation method of this invention (I).

The method for producing the oxidized compound of the compound A of the present invention (II) is sufficient as long as it includes the first to third steps presented by the oxidation method of the present invention (I). It may include. For example, the method for producing this oxidized compound includes a step of decomposing and removing a peroxide used as an oxidizing agent as described in the description of the present invention (I), a step of purifying Compound A obtained in a third step, and the like. can do.

In addition, the reaction conditions, such as the compound A, the oxidizing agent, a titanosilicate catalyst, and the temperature, pressure, and composition ratio of an oxidation reaction which are applicable to the manufacturing method of this invention (II), are all the same as the oxidation method of this invention (I). same. The product is also the same as in the present invention (I).

Example

Hereinafter, although an Example demonstrates this invention further more concretely, these Examples show the outline | summary of this invention, and this invention is not limited to these Examples.

[Explanation of terms in Examples and Comparative Examples]

Calculation of diallyl ether conversion rate :

The diallyl ether conversion rate is represented by the molar ratio of diallyl ether consumed in the reaction to diallyl ether injected before the reaction. The diallyl ether consumed by the reaction was calculated from the increase and decrease of diallyl ether before and after the reaction.

Allyl glycidyl ether

The allylglycidyl ether selectivity is represented by the molar ratio of the allylglycidyl ether produced | generated calculated from the analysis result of the filtrate after reaction, and the diallyl ether consumed by reaction.

Calculation method of hydrogen peroxide conversion rate

The hydrogen peroxide conversion rate is expressed by the ratio of hydrogen peroxide consumed in the reaction with respect to hydrogen peroxide injected before the reaction. The hydrogen peroxide consumed in the reaction was calculated by the increase and decrease of the hydrogen peroxide before and after the reaction.

Hydrogen peroxide-based yield of epoxide compound as the desired oxidation product after completion of oxidation reaction using hydrogen peroxide

The yield on this hydrogen peroxide basis is expressed as the molar ratio of the amount of epoxide compound produced relative to the injected hydrogen peroxide.

Calculation of the hydrogen peroxide effective rate

The hydrogen peroxide effective rate is expressed as the ratio of hydrogen peroxide excluding hydrogen peroxide consumed by decomposition to oxygen among hydrogen peroxide consumed in the reaction (that is, the ratio of hydrogen peroxide consumed in the epoxidation reaction among hydrogen peroxide consumed).

[Analysis apparatus in an Example and a comparative example]

Titanosilicate Elemental Analysis Method

Approximately 100 mg of the titanosilicate catalyst, dried at 90 ° C. for 6 hours, was accurately calculated in 100 ml of Teflon (polytetrafluoroethylene, PTFE) beaker. About 100 ml of a 50 mass% hydrofluoric acid (hydrofluoric acid) aqueous solution was added to a Teflon beaker with a catalyst. A teflon beaker to which hydrofluoric acid was added was placed on a hot plate and heated to a temperature of 150 ° C. for 3 hours. After heating for 3 hours, it was confirmed that the liquid component completely disappeared, and about 100 ml of 1: 1 hydrochloric acid (1: 1 mixture of 35% hydrochloric acid and distilled water by volume) was added. Then, it heated at 150 degreeC on the hotplate, and performed processing for 3 hours. The aqueous hydrochloric acid solution thus obtained was subjected to a mass up using 100 ml measfrasco, and was referred to as a sample for ICP measurement.

The sample was analyzed for titanium, silicon, and boron composition using a desk-type plasma emission spectrometer (SPS 1700) manufactured by Seiko Electronics Co., Ltd. In this measurement, titanium concentration used the wavelength of 334.9410 nm, silicon concentration used the wavelength of 251.611 nm, and boron concentration was performed using the wavelength of 249.7730 nm.

Analysis of Organic Compound Concentration in Filtrate of Reaction Mixture

It measured on the following gas chromatography analyzers and conditions.

The analysis was carried out by using an internal standard method, and adding 1 ml of 1,4-dioxane as an internal standard to 100 ml of the reaction solution as an assay solution, and 0.4 µl of the assay solution was injected into a gas chromatography analyzer.

Gas Chromatography: Shimazu Corporation GC-14B

Column: Capital Column TC-WAX (length 30m, inner diameter 0.25mm, film thickness 0.25㎛)

Carrier gas: nitrogen (split ratio 20, column flow rate 2 ml / min)

Temperature condition: The detector and vaporization chamber temperature is 200 ° C., the column temperature is maintained at 50 ° C. for 5 minutes from the start of the analysis, thereafter, the temperature is raised to 150 ° C. at a heating rate of 10 ° C./min, and maintained at 150 ° C. for 10 minutes. Furthermore, it heated up to 200 degreeC at the temperature increase rate of 10 degree-C / min after that, and hold | maintained for 25 minutes.

Detector: FID (H ₂ pressure 70kPa, air pressure 100kPa)

Analysis of hydrogen peroxide concentration in the filtrate of the reaction mixture

 The potentiometric titration of hydrogen peroxide was performed using the automatic potentiometric titration apparatus AT-012 made from Kyoto Electronics Co., Ltd., using a solution containing Ce (IV) as the titrant. More specifically, 40 ml of ion-exchanged water was added to a 100 ml glass beaker, and the weight of the filtrate (about 0.3 g) of the reaction mixture to be measured was then accurately measured in the beaker. Then, potentiometric titration was performed using the above-described automatic potentiometric titrator while slowly adding 0.1 mol / liter of a water solution prepared using cerium tetraammonium tetrahydrate (available from Wako Pure Chemical) to the beaker. The concentration of hydrogen peroxide was calculated from the amount of 0.1 mol / liter of aqueous solution of cerium tetraammonium sulfate required to the end point of titration and the weight of the filtrate of the reaction mixture used for the analysis.

Reference Example: Method for preparing MFI type crystalline titanosilicate catalyst

62.5 g of tetraethylorthosilicate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a 500 ml beaker with a magnetic stirrer, and then a 20% by mass aqueous solution of tetrapropylammonium hydroxide at a temperature of 30 ° C (Tokyo) 107 g of Kasei Kogyo Co., Ltd. product) was added for 10 minutes. After stirring for 1.0 hour, a mixture of 38 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) and 14 g of tetraortho titanate (manufactured by Tokyo Kasai Co., Ltd.) was added over 30 minutes.

After stirring the obtained mixture at 30 degreeC for 30 minutes, the said mixture was heated using the 80 degreeC water bath, and stirring was continued for 2 hours. 230 g of water was added to the mixture thus obtained, transferred to a teflon autoclave (an autoclave in which a teflon cylinder was arranged inside), and hydrothermal synthesis was performed at 175 ° C for 48 hours. After the end of hydrothermal synthesis, the contents were taken out of the autoclave and the solid product was separated by centrifugation. The solid product thus obtained was washed with distilled water. After the completion of washing, the mixture was calcined at 500 ° C. for 8 hours in the presence of air to remove organic matter. In addition, 1 g of a solid obtained by firing was subjected to pickling for 12 hours using 20 ml of 1.0 mol of acetic acid aqueous solution, and after the completion of pickling, the solid product was separated by filtration. This solid product was then calcined in the presence of air at 500 ° C. for 12 hours to obtain the desired MFI type titanosilicate catalyst 1 having a molar ratio of titanium / silicon of 0.0222.

Example 1 Preparation of Oxidation Compound Using Crystalline MFI Type Tianosilicate Catalyst 1

8.0 g (81.5 mmol) of diallyl ether was added to a 20 ml Erlenmeyer Frasco equipped with a thermometer, a reflux condenser, and a magnetic stirrer, followed by injecting an MFI type titanosilicate catalyst 1 (100 mg) shown in Reference Example, It heated in the 60 degreeC hot water bath, and stirred violently. Immediately after the temperature of the reaction mixture reaches 57 ° C, 2.0 g of 60% by weight aqueous hydrogen peroxide solution (35.3 mmol as hydrogen peroxide) is added to the system, and this time point is the start time of reaction, until 60 minutes have elapsed from the start of the reaction. Stirring was continued.

Immediately after 60 minutes from the start of the reaction, the reaction mixture was cooled with water to stop the reaction. Thereafter, the reaction mixture was filtered to separate a liquid (unreacted diallyl ether, unreacted hydrogen peroxide, water, product, and solvent) and a solid (catalyst). This separation was carried out by adding the reaction mixture to a 50 ml syringe (Telmo, Telmo syringe) equipped with a filter (Shodex DTMX-25k), applying pressure and filtering.

At this time, the organic substance concentration in the obtained filtrate was analyzed using gas chromatography, and the unreacted hydrogen peroxide concentration was determined by potentiometric titration using Ce (IV). Reactivity is shown in Table 1.

As shown in the reactivity of this Table 1, the conversion rate of diallyl ether was 4.42%, and the selectivity of allyl glycidyl ether which is the produced epoxy compound was 83.9%.

Diallyl ether * 1 conversion rate (%) Allyl glycidyl ether * 2 selectivity (%) Example 1 4.42 83.9 Example 2 9.07 82.7 Example 3 13.2 81.7 Example 4 15.8 79.2

* 1 diallyl ether conversion rate: consumed diallyl ether (mol) / raw diallyl ether (mol) x 100% (%)

* 2 allylglycidyl ether selectivity: allylglycidyl ether (mol) / {consumed diallyl ether (mol)} × 100 (mol%)

Example 2 Preparation of Oxidation Compound Using Crystalline MFI Type Tianosilicate Catalyst 1

The same operation as in Example 1 was performed except that 300 mg of MFI type titanosilicate 1 was used. Reactivity is shown in Table 1.

Example 3 Preparation of Oxidation Compound Using Crystalline MFI Type Tinosilicate Catalyst 1

 The same operation as in Example 1 was performed except that 500 mg of MFI type titanosilicate 1 was used. Reactivity is shown in Table 1.

Example 4 Preparation of Oxidation Compound Using Crystalline MFI Type Tinosilicate Catalyst 1

The same operation as in Example 1 was performed except that 800 mg of MFI type titanosilicate 1 was used. Reactivity is shown in Table 1.

Example 5 Continuous Use Experiment with Crystalline MFI Type Titanosilicate

 The MFI-type titanosilicate catalyst (molar ratio of titanium and silicon of 0.0233) prepared in the same manner as in Reference Example was molded into a cylindrical pellet having a diameter of 3.0 mm and a height of 7.0 mm, and a glass reactor (35 mm in diameter and 300 mm in height). 15.0g was charged. Then, the outside of the reaction tube was heated to 60 ° C., and a mixture of diallyl ether (concentration 40.0 wt%), hydrogen peroxide (2.84 wt%), water (6.63 wt%), and methanol (50.53 wt%) 25.0 at the bottom of the reaction tube. g was fed using a pump.

The reaction liquid which leaked out after 1.0 hour from the start of reaction was collected, the organic substance concentration was analyzed using gas chromatography, and the unreacted hydrogen peroxide concentration was determined by potentiometric titration using Ce (IV). This operation was repeated until 50 hours have elapsed, and the reaction results have been recorded.

The catalyst was taken out of the reaction tube at the time when 50 hours passed from the start of reaction, and it heat-processed at 300 degreeC for 3 hours in air atmosphere, and performed the catalyst regeneration process. After the completion of the regeneration treatment, the catalyst was cooled to 30 ° C, charged into the reaction tube again, the same as in the first time, and the second reaction was carried out until 50 hours had elapsed while recording the reactivity every hour. In addition, this catalyst was taken out similarly to the 1st time, and it heat-processed at 300 degreeC for 3 hours in air atmosphere, and performed the catalyst regeneration process. The operation after the third reaction was also conducted in the same manner as the first and second reactions, and the reaction was performed until the twelfth time that elapsed 600 hours after the first reaction start time.

The oxidation reaction results for 600 hours up to the 12th time range from 10.1 mol% to 10.8 mol% of diallyl ether conversion, the selectivity of allylglycidyl ether is 89.0 mol% to 90.5 mol%, and the conversion of hydrogen peroxide is 95 mol%. It was the range of -99 mol%, and the allyglycidyl ether produced in 600 hours of reaction time was 659g. The obtained reactivity is shown in Table 2 below.

Diallyl ether * 1 conversion rate (%) Allyl glycidyl ether * 2 selectivity (%) Hydrogen peroxide * 3 conversion rate (%) Hours Used (hr) AGE g produced Example 5 * 1 10.5 90 97 600 659 Comparative Example 1 * 2 26.2 70 95 300 640

* 1 diallyl ether conversion: consumed allyl ether (mol) / raw diallyl ether (mol) x 100 (%)

* 2 allylglycidyl ether selectivity: allylglycidyl ether (mol) / {consumed diallyl ether (mol)} x 100 (%)

* 3 hydrogen peroxide conversion rate: consumed hydrogen peroxide (mol) / raw material hydrogen peroxide (mol) × 100 (%)

The diallyl ether conversion rate, the allylglycidyl ether selectivity, and the hydrogen peroxide conversion rate in Example 5 are average values in the first to twelfth operations.

The diallyl ether charge rate, the allylglycidyl ether selectivity, and the hydrogen peroxide conversion rate in Comparative Example 1 are the average values in the first to sixth operations.

Example 6

The catalyst used in Example 5 for 600 hours was heat-processed at 300 degreeC for 3 hours in air atmosphere, 100 mg of it was added to 20 ml Frasco equipped with a thermometer, a reflux condenser, and a magnetic stirrer. Furthermore, after adding 3.14 g (32.0 mmol) of diallyl ether and 2.5 g of methanol to the said fresco, it heated in the 60 degreeC hot-water bath and stirred violently. Immediately after the temperature of the reaction mixture reaches 57 ° C., 1.81 g of 30% by weight aqueous hydrogen peroxide solution (16.0 mmol as hydrogen peroxide) is added to the system, and this time point is the start time of reaction, until 30 minutes have passed since the start of the reaction. Stirring was continued. Immediately after 30 minutes from the start of the reaction, the reaction mixture was cooled with ice and the reaction was stopped.

Thereafter, the reaction mixture was filtered to separate unreacted diallyl ether, unreacted hydrogen peroxide, water, product, solvent, and catalyst. At this time, the organic substance concentration in the obtained filtrate was analyzed using gas chromatography, and the unreacted hydrogen peroxide concentration was determined by potentiometric titration using Ce (IV). Reactivity is shown in Table 3.

As shown in the reactivity of Table 3, the conversion rate of diallyl ether was 19.2%, and the selectivity of allylglycidyl ether which is the produced epoxy compound was 86.4%. Moreover, the conversion rate of hydrogen peroxide was 54.1%.

Diallyl ether * 1 conversion rate (%) Allyl glycidyl ether * 2 selectivity (%) Hydrogen peroxide * 3 conversion rate (%) Allyl glycidyl ether * 4 yield (%) Example 6 19.2 86.4 54.1 33.2 Comparative Example 2 16.3 87.0 44.3 29.9

* 1 diallyl ether conversion: consumed allyl ether (mol) / raw diallyl ether (mol) x 100 (%)

* 2 allylglycidyl ether selectivity: allylglycidyl ether (mol) / {consumed diallyl ether (mol)} x 100 (%)

* 3 hydrogen peroxide conversion rate: consumed hydrogen peroxide (mol) / raw material hydrogen peroxide (mol) × 100 (%)

* 4 allyl glycidyl ether yield: allyl glycidyl ether (mol) / {raw material hydrogen peroxide (mol)} × 100 (%)

Example 7

The elemental analysis of the catalyst which heat-processed the catalyst used for 600 hours in Example 5 at 300 degreeC for 3 hours was performed in air atmosphere. The results are shown in Table 3. The titanium concentration in the catalyst was 2.1% by weight, and the molar ratio of titanium / silicon was 0.027. The obtained results are shown in Table 4.

Titanium Concentration Mass% in Catalyst Si / Ti ＊ 1 Example 7 2.1 37 Comparative Example 3 1.7 47

* 1 molar ratio

Example 8 Preparation of Allyl Glycidyl Ether

The MFI type titanosilicate catalyst (molar ratio of titanium and silicon of 0.0233) prepared in the same manner as in Reference Example was molded into a cylindrical pellet having a diameter of 3.0 mm and a height of 5.0 mm, and a glass reactor (35 mm in diameter and 800 mm in height). , 100.0g were charged, and the reaction tube exterior was heated to 60 degreeC. Next, in tank A shown in FIG. 1, diallyl ether was flowed at a flow rate of 7.0 g per hour, and in tank B, 60 mass% of hydrogen peroxide aqueous solution (60 mass% of hydrogen peroxide concentration, 40 mass% of water concentration) was added. At a flow rate of 4.15 g per hour, the methanol solution of diallyl ether (72% by weight of diallyl ether and 28% by weight of methanol concentration) was fed to the mixer at a flow rate of 38.9 g per hour, respectively. In the mixer, the reactor was charged at a flow rate of 50.0 g per hour in which the raw material mixture having a mass ratio of diallyl ether: hydrogen peroxide: water: methanol = 70.0: 5.0: 3.3: 21.7 has an LHSV (liquid space velocity) of 0.5 (/ hr). Feed was done at the bottom. The reaction mixture flowing out of the reactor was passed through a double tube structure cooler to cool, and the reaction mixture was collected.

Analysis of the organic concentration of the collected reaction mixture showed that, per hour, 6.92 g of allylglycidyl ether was produced, diallyl ether conversion was 20.0 mol%, and allylglycidyl ether selectivity based on diallyl ether. Was 85 mol%.

Next, the collected reaction mixture was fractionally distilled under atmospheric pressure, and the unreacted diallyl ether and methanol which were distilled off at the top of the column were recovered. Analysis of the mixture of recovered diallyl ether and methanol is carried out, and insufficient diallyl ether is used so that the methanol solution of diallyl ether becomes a predetermined concentration (72% by weight of diallyl ether, 28% by weight of methanol), or Methanol was supplemented, it recycled to the tank C, and was used for reaction again. In addition, the concentrated component was not distilled off by the top of the column by fractional distillation and distilled again under reduced pressure of 13.3 kPa to obtain allyl glycidyl ether on the top of the column.

This operation was repeated every hour, and a total of 30 operations were performed until 30 hours had elapsed since the time of starting the raw material PD. The consumption of diallyl ether up to 30 hours was 220 g, and the obtained allyl glycidyl ether was 199.3 g. The reaction results of 30 hours are shown in Table 5.

Reactor outlet performance Grades in 30 hours Diallyl ether * 1 conversion rate (%) Allyl glycidyl ether * 2 selectivity (%) Diallyl ether consumption (g) Allyl glycidyl ether acquisition amount (g) Example 8 20 85 220 199.3 Comparative Example 4 50 28 458 139.1

* 1 diallyl ether conversion: consumed diallyl ether (mol) / raw diallyl ether (mol) x 100 (%)

* 2 allylglycidyl ether selectivity: allylglycidyl ether (mol) / {consumed diallyl ether (mol)} x 100 (%)

The MFI-type titanosilicate catalyst (molar ratio of titanium and silicon of 0.0233) prepared in the same manner as in the reference example was molded into a cylindrical pellet having a diameter of 3.0 mm and a height of 7.0 mm, and a glass reactor (diameter 35 mm, height 300 mm). 15.0g was charged. Next, the outside of the reaction tube was heated to 60 ° C., and a mixture of diallyl ether (concentration 40.0% by weight), hydrogen peroxide (5.68% by weight), water (2.84% by weight) and methanol (51.48% by weight) 25.0 at the bottom of the reaction tube. g was fed using a pump. The reaction liquid which leaked out after 1.0 hour from the start of reaction was collected, the organic substance concentration was analyzed using gas chromatography, and the unreacted hydrogen peroxide concentration was determined by potentiometric titration using Ce (IV). This operation was repeated up to 50 hours and the reactivity was recorded.

When 50 hours passed, the catalyst was removed from the reaction tube, and heat treatment was performed at 300 ° C. for 3 hours under an air atmosphere to perform catalyst regeneration. After the completion of the regeneration treatment, the catalyst was cooled to 30 ° C, charged into the reaction tube again, the reaction was carried out in the same manner as the first time, and the second reaction was performed until 50 hours had elapsed while recording reactivity every hour. In addition, this catalyst was taken out similarly to the 1st time, and it heat-processed at 300 degreeC for 3 hours in air atmosphere, and performed the catalyst regeneration process. The operation after the third reaction was also performed in the same manner as the first and second reactions, and the reaction was carried out up to the sixth time that elapsed for 300 hours from the time of the first reaction start.

The oxidative reactivity of 300 hours until the sixth time ranges from 25.5 mol% to 26.lmol% of diallyl ether conversion, the selectivity of allylglycidyl ether is 74.8mol% to 75.5mol%, and the conversion of hydrogen peroxide is 95.0. It was the range of mol%-96.0 mol%, and the allyl glycidyl ether produced in 300 hours of reaction time was 640g. The obtained results are shown in Table 2.

Comparative Example 2

The same operation as in Example 6 was performed except that the catalyst used in Comparative Example 1 for 300 hours was used. The results are shown in Table 3.

Comparative Example 3

The same operation as in Example 7 was performed except that the catalyst used in Comparative Example 1 for 300 hours was used. The results are shown in Table 4.

Comparative Example 4

The MFI-type titanosilicate catalyst (molar ratio of titanium and silicon of 0.0233) prepared in the same manner as in Reference Example was molded into a cylindrical pellet having a diameter of 3.0 mm and a height of 5.0 mm to a glass reactor (35 mm in diameter and 800 mm in height). , 100.0g were charged, and the reaction tube exterior was heated to 60 degreeC. Next, in tank A shown in FIG. 1, diallyl ether was flowed at 15.0 g per hour, and in tank B, 60 mass% of hydrogen peroxide aqueous solution (60 mass% of hydrogen peroxide concentration, 40 mass% of water concentration) was 1 At a flow rate of 9.15 g per hour, in a tank C, a methanol solution of diallyl ether (58% by weight of diallyl ether concentration and 42% by weight of methanol concentration) was fed to the mixer at a flow rate of 25.85g per hour. In the mixer, the raw material mixture consisting of diallyl ether: hydrogen peroxide: water: methanol = 60.0: 11.0: 7.3: 21.7 was fed at the bottom of the reactor at a flow rate of 50.0 g per hour in which the LHSV became 0.5 (/ hr). . The reaction mixture flowing out of the reactor was passed through a double tube structure cooler to cool, and the reaction mixture was collected.

Analysis of the organic concentration of the collected reaction mixture showed that, per hour, 4.88 g of allylglycidyl ether was produced, diallyl ether conversion was 50.0 mol%, and allylglycidyl ether selectivity based on diallyl ether was determined. Was 28 mol%.

Next, the collected reaction mixture was fractionated and distilled under atmospheric pressure, and the unreacted diallyl ether and methanol which were eluted from the tower top were collect | recovered. Analysis of the mixture of the recovered diallyl ether and methanol is carried out, and insufficient diallyl ether is used so that the methanol solution of diallyl ether becomes a predetermined concentration (58% by weight of diallyl ether, 42% by weight of methanol), or Methanol was supplemented, it recycled to the tank C, and was used for reaction again. Further, the concentrated component was not distilled off from the top of the column by fractional distillation again under reduced pressure of 13.3 kPa to obtain allyl glycidyl ether on the top of the column. This operation was repeated every hour, and a total of 30 operations were performed until 30 hours had elapsed from the time when the raw material feed was first started. The diallyl ether consumed until 30 hours passed was 458 g, and the obtained allyl glycidyl ether was 139.1 g. Table 5 shows the reactivity of 30 hours.

As described above, in the production of an oxidized compound of Compound A having peroxide in the presence of a titanosilicate catalyst as an oxidizing agent, the production method of the present invention which actively recycles by suppressing the conversion ratio of Compound A as a raw material to a range of 50 mol% or less. Is a very useful method in that it is the selectivity of the reaction.

Claims (20)

A method of oxidizing only one carbon-carbon double bond of a compound having two or more carbon-carbon double bonds (hereinafter referred to as "Compound A"), ; The oxidation method includes the following first to third steps. First step: a step of obtaining an oxidation reaction mixture by performing a oxidation reaction of a carbon-carbon double bond of Compound A in the presence of a titanosilicate catalyst with a peroxide as an oxidizing agent in a range of 30 mol% or less, Second step: separating compound A from the oxidation reaction mixture obtained in the first step, Third Step: Returning Compound A obtained in the second step to the first step. delete 2. The method for oxidizing a carbon-carbon double bond of Compound A according to claim 1, wherein the conversion ratio of Compound A in the first step is in a range of 15 mol% or less. The peroxide in a 1st process is a limited reactive component, the peroxide concentration in a raw material mixture is 0 mass%-50 mass%, and the conversion rate of a peroxide is 30 mol%-100 mol%. A method of oxidizing a carbon-carbon double bond of Compound A. The method for oxidizing a carbon-carbon double bond of Compound A according to claim 4, wherein the conversion rate of the peroxide is 80 mol% to 100 mol%. 4. The method of claim 1 or 3, wherein the titanosilicate catalyst is at least one member selected from the group consisting of crystalline titanosilicates and mesoporous titanosilicates. 7. The crystal structure of crystalline titanosilicate according to claim 6, wherein the crystal structure of the crystalline titanosilicate comprises MFI type, AEL type, EUO type, FER type, MEL type, AFI type, MWW type, ATO type, * BEA type, MOR type and CLO type. The oxidation method of the carbon-carbon double bond of the compound A which is at least 1 sort (s) chosen from the group, and whose composition is represented by following formula (1). Formula (1) xTiO ₂ ㆍ (1-x) SiO ₂ (wherein x is 0.0001 to 0.2) The method of claim 1 or 3, wherein the oxidizing agent is hydrogen peroxide, t-butylhydroperoxide, t-aminohydroperoxide, cumene hydroperoxide, ethylbenzene hydroperoxide, cyclohexyl hydroperoxide, methylcyclohexyl hydroper A method of oxidizing a carbon-carbon double bond of Compound A, characterized in that it is at least one compound selected from the group consisting of oxides, isobutylbenzenehydroperoxide, ethylnaphthalene hydroperoxide and peracetic acid. delete delete The method for oxidizing a carbon-carbon double bond of compound A according to claim 1 or 3, wherein compound A is diallyl ether or allyl vinyl ether. delete delete delete delete The method for oxidizing a carbon-carbon double bond of Compound A according to claim 1 or 3, wherein the oxidation reaction is carried out in the presence of at least one solvent selected from the group consisting of alcohols, ketones, nitriles and water. The method for oxidizing a carbon-carbon double bond of Compound A according to claim 1 or 3, wherein the product obtained by the oxidation reaction is an epoxidized compound of the carbon-carbon double bond site of Compound A as a raw material. A method for producing an oxidized compound of Compound A, comprising oxidizing Compound A using the method for oxidizing a carbon-carbon double bond according to claim 1. A method for producing allyl glycidyl ether, wherein diallyl ether is used as compound A, and a method of oxidizing a carbon-carbon double bond of compound A according to claim 1 or 3 is used. 20. The method for producing allyl glycidyl ether according to claim 19, wherein hydrogen peroxide is used as the oxidizing agent.

Images