JPH08208539A - Catalytical hydration of olefin - Google Patents

Abstract

PURPOSE: To directly hydrate an olefin under mild conditions of a low temperature and a low pressure using a solid heterogeneous catalyst and thermally stably obtain alcohol by reacting the olefin with water in the presence of an organic polymeric siloxane containing sulfonic acid. CONSTITUTION: An olefin such as ethylene or propylene is reacted with water in the presence of an organic polymeric siloxane, having a sulfonic acid group such as an aromatic sulfonic acid or an alkylsulfonic acid group and further preferably carrying out the coating and/or silylating treatments of the siloxane with a silane compound of the formula (R)n SiX4-n [R is a 1-4C aliphatic hydrocarbon or a 6-15C aromatic hydrocarbon; X is an alkoxy, Cl, Br or I; Si is silicon; (n) is 0-3] to afford the objective alcohols.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing alcohols by hydration of olefins. More specifically, the present invention relates to a method for producing alcohols by direct hydration of olefins, which is characterized by using a solid heterogeneous catalyst.

[0002]

2. Description of the Related Art Conventionally, as a method for producing alcohols by a direct hydration reaction of an olefin, a method by a gas phase reaction and a method by a liquid phase reaction have been industrially carried out. As a production method by a gas phase reaction, for example, JP-A-3-2077
In No. 28, a macroporous cation exchange resin is used as a catalyst, and in JP-A-55-124541, an acidic layered clay compound is used as a catalyst. Further widely industrialized methods include JP-A-53-84906 and JP-A-52-1.
There is a method using a catalyst in which phosphoric acid is supported on a carrier, which is disclosed in No. 33095 and Japanese Patent Publication No. 51-44915.

In these production methods by the gas phase reaction, the reaction is generally carried out in a high temperature range, and the conversion rate of olefin is low. Therefore, the amount of alcohols produced per unit volume of the reactor is extremely low, and it is necessary to recycle a large amount of unreacted olefin, which is not an advantageous method in terms of equipment and energy. In addition to this, the method of producing a supported phosphoric acid catalyst which is widely used industrially has a problem that the performance of the catalyst is deteriorated due to scattering of phosphoric acid which is a catalyst component along with the reaction.

Therefore, as a method for overcoming the drawbacks such as low productivity of alcohols and large-scale circulation of unreacted olefins in the gas phase method, one raw material, water, is brought into contact with an olefin in a liquid state, so-called liquid phase. The reaction is also widely known. For example, JP-B-43-8104, JP-B-43-
No. 16123 describes a method using an aromatic sulfonic acid as a homogeneous catalyst. Heteropoly acids are described as catalysts in JP-B-49-166, JP-B-50-35051, JP-B-49-36204 and JP-A-53-9746.

However, these homogeneous catalysts have a drawback that the separation and recovery from the catalyst and the reaction product (particularly water, which is one of the raw materials) becomes complicated, and the energy related thereto becomes large. In addition, since these acid catalysts are homogeneously dissolved in the liquid phase, they come into liquid contact with devices such as reactors, which may cause corrosion of the inner walls of the devices, necessitating the use of expensive device materials and making them economical. It can not be said.

Therefore, in the liquid phase reaction, a solid heterogeneous catalyst is used to make up for the drawbacks of the homogeneous catalyst. For example, JP-B-44-26656 and JP-A-49-11741.
2, JP-A-61-230744, JP-B-58-7614, JP-B-SHO
In 63-27332, etc., a strongly acidic cation exchange resin is used as a catalyst. Also, Japanese Patent Publication No. 3-502321, Japanese Patent Publication No. 3-503175, Japanese Patent Laid-Open No. 1-246234, Japanese Patent Laid-Open No. 1-246233.
In JP-A-63-218251 and the like, a zeolite catalyst is used. The strongly acidic cation exchange resin catalyst has higher activity when used under reaction conditions of lower temperature and lower pressure (around 150 ° C., around 100 atm) as compared with the above liquid phase homogeneous catalyst. However, the heat resistant temperature of the cation exchange resin itself is 100 ° C.
In reality, use at 150 ° C means that the reaction proceeds with permanent catalyst deterioration, and acidic components such as sulfonic acid groups are decomposed and desorbed in the reaction solution. It is inevitable that it will be leaked to. Therefore, the catalytic activity is significantly reduced, and like the liquid phase homogeneous catalyst, there is a risk of equipment corrosion due to the outflowing acidic components, and the reaction equipment must use an expensive material with high corrosion resistance, which is economical. Is disadvantageous to In addition, the cation exchange resin has low mechanical strength and is easily broken.

On the other hand, the zeolite-based heterogeneous catalyst has insufficient catalytic activity and cannot be expected to have the catalytic activity as high as that of the strongly acidic cation exchange resin, and it is high in order to increase the yield of alcohols. Requires reaction temperature. However, when the zeolite compound is heated to a high temperature in the presence of water in a liquid phase state as in the olefin hydration reaction condition,
Dealumination clearly promotes decomposition. Therefore, it is practically impossible to produce alcohols at a favorable production rate.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention pay attention to high productivity in a liquid phase reaction in producing alcohols by direct contact hydration reaction of olefin and water, and As a result of paying attention to the advantage of the solid heterogeneous catalyst in the above, and as a result of diligent studies to overcome the drawbacks of the conventional liquid phase heterogeneous catalyst, the organic polymer siloxane compound having a sulfonic acid group is thermally stable, and To become a solid catalyst having high catalytic activity, in particular, to coat and / or silylate the organic polymer siloxane having sulfonic acid groups with silica, organic polymer siloxane, a silylating agent having a hydrocarbon group, etc. As a result, they have found to be extremely stable and highly active, and have completed the present invention.

By using the solid heterogeneous catalyst of the present invention, even if the catalytic hydration reaction in the liquid phase is carried out under high temperature conditions, there is no elution of acidic components into the liquid phase due to decomposition of the catalyst due to thermal decomposition or the like. The activity can be maintained for a long time, and alcohol can be efficiently produced without the problem of equipment corrosion due to acid. That is, the object of the present invention is to produce alcohols in a liquid phase with high efficiency in a direct hydration reaction of olefins, to easily separate a catalyst and a reaction solution, and to carry out without corroding the apparatus. To provide a method. Another object of the present invention is to provide a catalyst capable of carrying out the hydration reaction in a wide temperature range without activity reduction in both gas phase and liquid phase reaction modes.

[0010]

The present invention is a method for producing alcohols, which comprises reacting an olefin with water in the presence of an organic polymer siloxane having a sulfonic acid group. Hereinafter, the present invention will be described in detail. The olefin used in the present invention is an aliphatic hydrocarbon compound, and is a linear or branched monoolefin or polyolefin having at least one carbon-carbon double bond. In addition, these olefins, as a substituent, a halogen element, a hydroxyl group, a nitro group, an amino group, a cyano group,
It may have a carbonyl group, an acetoxy group, an aromatic group, a carboxyl group, a mercapto group, or the like. It is preferably an aliphatic olefin having 2 to 10 carbon atoms.

Specifically, ethylene, propylene, 1-
Butene, 2-butene, isobutene, 1-pentene, 2-
Penten, 2-methyl-1-butene, 2-methyl-2-
Examples include linear or branched pentenes such as butene, 1-hexene, 2-hexene, 3-hexene, linear or branched hexenes such as methylpentene, and polyolefins such as butadiene, pentadiene and hexadiene. . Furthermore, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cyclooctene, methylcyclooctenes, cyclopentadiene,
It is also possible to use alicyclic olefins such as cyclohexadiene and cyclooctadiene. More preferably, the olefin is at least one selected from the group consisting of lower olefins having 2 to 6 carbon atoms, such as ethylene, propylene, n-butenes, i-butene and cyclohexene. In the present invention, one type or two or more types are used in the reaction.

The purity of the olefin used in the present invention is not particularly limited, and general reagent purity, industrial purity, or olefin diluted with alkane or the like can be used. In the present invention, the above-mentioned olefin and water are brought into contact with each other in the presence of an organic polymer siloxane catalyst having a sulfonic acid group to produce water-added alcohols corresponding to olefins.

The organic polymer siloxane having a sulfonic acid group, which is a catalyst used in the present invention, means that a hydrocarbon group partially having a sulfonic acid group in a silica matrix composed of siloxane bonds directly has a silicon atom and a carbon-silicon. It is a high-molecular-weight siloxane having a structure bonded by bonding. These organic polymeric siloxanes have an average of 0.05 or more and 3 or less, preferably 0.1 or more and 2 or less, and more preferably 0.2 or more and 1 or less carbon-silicon bond per silicon atom forming the siloxane. It is a molecular siloxane.

Further, these hydrocarbon groups are preferably a substituted or unsubstituted alkyl group having a sulfonic acid group and a substituted or unsubstituted aromatic group having a sulfonic acid group. Especially when the hydrocarbon group having a sulfonic acid group has an aromatic group, the carbon-silicon bond is a bond between carbon and silicon of the aromatic hydrocarbon group directly,
It may be a bond between carbon and silicon of a hydrocarbon group having an aromatic group as a substituent.

Further, all of these hydrocarbon groups may have one or more sulfonic acid groups, or some of the many hydrocarbon groups may have a sulfonic acid group.
It is preferable if all the hydrocarbon groups have sulfonic acid groups. However, the catalyst in the present invention is not limited by the amount of the sulfonic acid group contained therein.

The catalyst used in the present invention is as described above.
Although it is an organic polymer siloxane having a sulfonic acid group,
Further, an organic polymer siloxane having these sulfonic acid groups is silica-coated with an alkoxysilane, a halogenated silane, an alkyl group- and / or aromatic group-substituted alkoxysilane and an alkyl group- and / or aromatic group-substituted halogenated silane, and an organic compound. By applying a high molecular siloxane coating and / or silylation treatment,
It is a more preferable organic polymer siloxane catalyst having a sulfonic acid group. In the present invention, these organic polymer siloxanes having a sulfonic acid group are used as a catalyst.

In the present invention, the preparation method of these catalysts is not particularly limited, and any preparation method may be used as long as a hydrocarbon group having a sulfonic acid group having a carbon-silicon bond is present in the polymer siloxane matrix. Although it may be prepared by the method described above, it can be prepared, for example, by the following preparation method as an easy method. However, the present invention is not limited to only these preparation methods.

As a preparation method which is easy to carry out, for example, the general formula: (Ra) _n Si (X) _4-n (where Ra is a hydrocarbon group having at least one sulfonic acid group, and the same hydrocarbon group is used) Si is a silicon atom, X is at least one selected from the group consisting of an alkoxy group and a halogen atom, and n is 1 or more and 3 or less, preferably 1 or more. Or a silane compound represented by the general formula: Si (X) ₄ (where Si is a silicon atom, X is an alkoxy group and a halogen atom). It is obtained by a method of hydrolyzing a mixture with a silane compound represented by at least one selected from the group).

At this time, the sulfonic acid group possessed by Ra is converted into a sulfonic acid group by subjecting the polymer siloxane obtained by the above hydrolysis to the above-mentioned hydrolysis as a sulfonic acid salt whose proton is exchanged with a metal cation in advance. It doesn't matter. Further, a silane compound represented by the above general formula: (Ra) _n Si (X) _4-n immobilized on silica gel by silylation is also an effective catalyst in the present invention.

In addition, as another easy preparation method, a general formula: (Rb) _n Si (X) _4-n (where Rb is a hydrocarbon group capable of introducing a sulfonic acid group by subjecting it to a sulfonation treatment) It may be the same hydrocarbon group or different hydrocarbon groups.Si is a silicon atom, X is at least one selected from the group consisting of an alkoxy group and a halogen atom, and n is It is a positive integer of 1 or more and 3 or less, preferably 1 or more and 2 or less.), Or these silane compounds and the general formula:
After hydrolyzing a mixture with a silane compound represented by Si (X) ₄ (wherein Si is a silicon atom, X is at least one selected from the group consisting of an alkoxy group and a halogen atom), sulfonation is performed. It is treated to obtain an organic polymer siloxane having a sulfonic acid group. Further, after immobilizing the silane compound represented by the above general formula: (Rb) _n Si (X) _4-n on silica gel by silylation,
Those subjected to the sulfonation treatment are also effective catalysts in the present invention.

The hydrocarbon groups Ra and Rb represented by the above general formula will be described below. Ra is at least 1
It is possible to use a number of even present invention be any hydrocarbon group, if a hydrocarbon group having a sulfonic acid group (-SO ₃ H), preferably having 6 to 20 carbon atoms, more preferably Is a substituted or unsubstituted aromatic hydrocarbon group having at least one sulfonic acid group having 6 to 15 carbon atoms (including a group in which a sulfonic acid group is directly substituted in an aromatic group, or a carbon group in which an aromatic group is substituted). It may be a hydrocarbon group in which a sulfonic acid group is substituted for a hydrogen group) or has at least one sulfonic acid group, preferably having 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms.
It is at least one selected from the group of the following substituted or unsubstituted aliphatic and / or alicyclic saturated hydrocarbon groups.

Specifically, an aromatic group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group and the like, a benzyl group, a naphthylmethyl group and the like, which are nuclear-substituted with at least one or more sulfonic acid groups. Methyl group, ethyl group, n-propyl group, i-propyl group, n substituted with at least one sulfonic acid group such as group-substituted alkyl group
-Butyl group, i-butyl group, t-butyl group, straight-chain and branched pentyl group, straight-chain and branched hexyl group, straight-chain and branched heptyl group, straight-chain and branched octyl group, Examples thereof include a cyclohexyl group, a methylcyclohexyl group, an ethylcycle hexyl group and the like. Further, these aromatic or saturated aliphatic or alicyclic hydrocarbon groups are hydrocarbon groups having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group and a hydroxy group in addition to the sulfonic acid group. It doesn't matter.

Further, Rb may be any hydrocarbon group as long as it is a hydrocarbon group capable of introducing a sulfonic acid group by various sulfonation treatments, but if it is exemplified as a preferable hydrocarbon group, an aromatic group can be used. Having a hydrocarbon group, a hydrocarbon group having at least one mercapto (-SH) group, an alkyl group having at least one halogen atom, at least one carbon carbon, an olefinic hydrocarbon group having a double bond , A hydrocarbon group having at least one epoxy group, and the like. However, the present invention is not limited to these hydrocarbon groups.

As an example of the hydrocarbon group (Rb),
The hydrocarbon group having an aromatic group may be any hydrocarbon group having an aromatic group, but preferably has 6 to 20 carbon atoms, and more preferably has 6 carbon atoms.
And 15 or more aromatic groups or hydrocarbon groups substituted with at least one or more aromatic groups (for example, alkyl groups substituted with aromatic groups) and the like, and phenyl group, tolyl group, xylyl group, naphthyl group, methyl Examples thereof include an aromatic group such as a naphthyl group and an aromatic group-substituted alkyl group such as a benzyl group and a naphthylmethyl group. Further, these groups may be a hydrocarbon group having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group and a hydroxy group.

As the hydrocarbon group having at least one mercapto group, any hydrocarbon group may be used as long as it is a hydrocarbon group having one or more mercapto groups, but preferably, it has 1 to 15 carbon atoms. More preferably, it is a mono- or polymercapto-substituted alkyl group having 1 to 10 carbon atoms, and an aromatic mono- or polymercapto-substituted hydrocarbon group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. Specifically, mercaptomethyl group, 2-mercaptoethyl group, 3-mercapto-n-propyl group, 4-mercapto-n-butyl group, 4-mercaptocyclohexyl group, p-mercaptophenyl group, p-mercapto group. Methylphenyl group, p-mercaptobenzyl group, 4-mercaptonaphthyl group and the like can be mentioned. Further, these groups may be hydrocarbon groups having a substituent such as a halogen element, an alkoxy group, a nitro group, an amino group and a hydroxy group in addition to the mercapto group.

Further, the alkyl group having at least one halogen atom may be any alkyl group as long as it is an alkyl group substituted with a halogen atom. Further, the number of halogen atoms is not limited, and it is sufficient that at least one or more of hydrogens bonded to carbons of the alkyl group are replaced with halogen atoms.
Specifically, a halogenated alkyl group having 1 to 15 carbon atoms is preferable, a halogenated alkyl group having 1 to 10 carbon atoms is more preferable, and the halogen atom is selected from the group consisting of chlorine atom, bromine atom and iodine atom. It is recommended to be at least one selected. More specifically, chloromethyl group, bromomethyl group, dichloromethyl group, methyl iodide group, diiodomethyl group, 2-chloroethyl group, 1,2-dichloroethyl group, 2-bromoethyl group, 2-iodoethyl group, 3-chloro-n-propyl group, 3-bromo-n-propyl group, 4-chloro-n-
Examples thereof include a butyl group, a 4-bromo-n-butyl group, a 4-chlorocyclohexyl group and a 4-bromocyclohexyl group. Further, these groups may be a hydrocarbon group having a substituent such as an alkoxy group, a nitro group, an amino group and a hydroxy group in addition to the halogen atom.

The olefinic hydrocarbon group having at least one carbon-carbon double bond may be any hydrocarbon group as long as it is a hydrocarbon group having at least one olefinic double bond. Is preferably an aromatic hydrocarbon group having 8 to 20 carbon atoms, more preferably an olefinic hydrocarbon having 8 to 15 carbon atoms as a substituent, and preferably 2 to 15 carbon atoms, and more preferably a carbon number. It is an aliphatic or alicyclic olefinic hydrocarbon group of 2 or more and 10 or less, and specific examples of the aromatic hydrocarbon group having an olefinic hydrocarbon as a substituent include a 4-vinylphenyl group and 4- Vinylnaphthyl group, 4-allylphenyl group and the like, and as the aliphatic or alicyclic olefinic hydrocarbon group, a vinyl group,
Allyl group, n-butenyl groups, cyclohexenyl groups,
Examples include methylcyclohexenyl groups and ethylcyclohexenyl groups. In addition, these groups are other alkoxy groups,
It may be a hydrocarbon group having a substituent such as a nitro group, an amino group or a hydroxy group.

As the hydrocarbon group having at least one epoxy group, any hydrocarbon group may be used as long as it is a hydrocarbon group having at least one epoxy bond (oxirane group), but it is preferable. 8 to 20 carbon atoms, more preferably 8 to 15 carbon atoms,
An aromatic hydrocarbon group having an epoxy group as a substituent, preferably an aliphatic or alicyclic hydrocarbon group having an epoxy bond having 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, Specific examples of the aromatic hydrocarbon group having an epoxy group as a substituent include p-epoxyethylphenyl group, 4-epoxyethylnaphthyl group and p-epoxyethylnaphthyl group.
(2,3-epoxypropyl) phenyl group, p- (3,
4-epoxycyclohexyl) phenyl group and the like, and as the aliphatic or alicyclic hydrocarbon group having an epoxy bond, epoxyethyl group, 2,3-epoxypropyl group, 3-glycidoxypropyl group, 3 , 4-epoxycyclohexyl group, 2- (3,4-epoxycyclohexyl) ethyl group and the like. Further, other than these hydrocarbon groups, a hydrocarbon group having a substituent such as an alkoxy group, a nitro group, an amino group and a hydroxy group may be used. Of course, these hydrocarbon groups are merely examples, and the hydrocarbon groups are not limited thereto.

When the catalyst is prepared using the silane compound represented by the general formula: (Rb) _n Si (X) _4-n , the silane compound alone or the silane compound represented by the general formula: SiX ₄ is used. Hydrolysis of a mixture of, or the general formula:
A silane compound represented by (Rb) _n Si (X) _4-n is subjected to silylation treatment on silica gel and immobilized, and then subjected to sulfonation treatment to obtain an organic polymer siloxane having a sulfonic acid group.

The sulfonation treatment in the present invention is not particularly limited with respect to its formulation, and any formulation can be used as long as it is a formulation in which the hydrocarbon group represented by Rb is a hydrocarbon group having a sulfonic acid group. You can use it. Further, it is natural that the prescriptions differ depending on the type of Rb.

As a concrete example of a method that can be easily carried out as the sulfonation treatment, for example, when Rb is an organic polymer siloxane obtained from a silane compound which is a hydrocarbon having an aromatic group, these organic siloxanes are used. The high molecular siloxane can be converted to an organic high molecular siloxane having a sulfonic acid group by a usual aromatic sulfonation by contact with sulfuric acid or chlorosulfonic acid.

If Rb is an organic polymer siloxane obtained from a silane compound in which Rb is a hydrocarbon group having at least one mercapto group, various oxidants (eg nitric acid, hydrogen peroxide, etc.) can be used. Oxidize by contact with.
Alternatively, an organic polymer siloxane having a sulfonic acid group can be obtained by addition reaction with an olefin compound having a sulfonic acid group (addition of SH to olefin).

At this time, the olefin compound having a sulfonic acid group used for sulfonation is an olefinic hydrocarbon compound having at least one sulfonic acid group and carbon and a carbon double bond, specifically, vinyl vinyl. Examples thereof include sulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, cyclohexenesulfonic acid and the like.

Further, in the case of an organic polymer siloxane obtained from a silane compound in which Rb is an alkyl group having at least one halogen element, the sulfone is heated by contact with a solution of a metal sulfite (eg sodium sulfite, potassium sulfite). It can be an organic polymer siloxane having an acid group. Further, in the case of an organic polymer siloxane obtained from a silane compound in which Rb is an olefinic hydrocarbon group having at least one carbon atom and a double bond, in the presence of an oxidizing agent (oxygen etc.), metal sulfite is present. The organic polymer siloxane having a sulfonic acid group can be obtained by contact with a solution of hydrogen salt (sodium hydrogen sulfite, potassium hydrogen sulfite, etc.). Furthermore, in the case of an organic polymer siloxane obtained from a silane compound in which Rb is a hydrocarbon group having at least one epoxy bond (oxirane group), metal bisulfite (sodium bisulfite, potassium bisulfite, etc.) An organic polymer siloxane having a sulfonic acid group can be obtained by contact with a solution.

Here, in the sulfonation using a metal bisulfite, it is recommended as a preferable sulfonation method to coexist with a metal sulfite and perform sulfonation. However, it goes without saying that the method of the present invention is not limited to only these sulphonated formulations.

The method of the present invention uses, as a catalyst, the organopolymer siloxane having a sulfonic acid group prepared by the method exemplified above. : (R) _n
SiX _4-n (wherein R is at least 1 selected from the group consisting of an aliphatic or alicyclic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 15 carbon atoms).
X represents at least one selected from the group consisting of an alkoxy group and a halogen atom, and Si represents a silicon atom. N is 0 or an integer of 1 or more and 3 or less. ) At least one of the silane compounds represented by
Depending on the species, it can be more effectively carried out by using a coated and / or silylated sulfonic acid group-containing organopolymer siloxane as a catalyst. By applying these coatings and / or silylation treatments, the life of the catalyst is extended and its activity is further improved.

Next, the coating and / or
Or describe silylation. As described above, in the present invention, the organic polymer siloxane catalyst having a sulfonic acid group is further coated and / or silylated with a silane compound represented by the above general formula: (R) _n SiX _4-n. This makes it a more suitable catalyst.

The silane compound represented by the above general formula: (R) _n SiX _4-n used for the coating and / or silylation treatment in the present invention is, as described above, R being an aliphatic group having 1 to 10 carbon atoms. Or at least one hydrocarbon group selected from the group consisting of alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 15 carbon atoms, and X is selected from the group consisting of alkoxy groups and halogen atoms. At least one kind.

Specific examples of R include methyl group, ethyl group, n-propyl group, i-propyl group, linear or branched butyl group, linear or branched pentyl group, linear or branched group. Branched hexyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, cyclohexyl group, 4-methylcyclohexyl group, phenyl group, naphthyl group, p-tolyl group Group, p-
Examples thereof include an ethylphenyl group and a 4-methylnaphthyl group. X represents an alkoxy group or a halogen atom, and n =
Also included are silane compounds that do not have an alkyl substituent of 0.

The coating treatment referred to in the present invention means that a siloxane compound having a sulfonic acid group, which is a catalyst, is mixed with a silane compound represented by the general formula: (R) _n SiX _4-n and the mixture is suspended. Hydrolysis is performed to form a polymer siloxane, which is a hydrolysis product of a silane compound represented by (R) _n SiX _4-n , on an organic polymer siloxane having a sulfonic acid group. The silylation treatment is a silane represented by the general formula: (R) _n SiX _{4-n in} which the silanol group contained in the organic polymer siloxane matrix having a sulfonic acid group, which is the catalyst prepared by the above-mentioned preparation method or the like, is used. The reaction is to directly react with the compound to form a siloxane bond and immobilize it on the catalyst.

At this time, as the silane compound used for the coating treatment, n is preferably 0 or 1 in the above general formula: (R) _n SiX _4-n , and the silane compound used for the silylation treatment has n of 1 It is preferably 3 or more and 3 or less. In the present invention, a catalyst obtained by performing coating and silylation treatment a plurality of times, such as a coating treatment, a silylation treatment, and then a silylation treatment, is also a suitable catalyst.

In carrying out these coating or silylation treatments, silane compounds represented by the general formula: (R) _n SiX _4-n , such as alcohol, hexane, heptane, benzene, and toluene, and sulfonic acid as a catalyst. It is also possible to use solvents which are inert towards the organopolymeric siloxanes which carry groups. In the coating treatment, it is preferable to use a solvent having a high mutual solubility with water, such as alcohol.

In the present invention, the amount of coating and / or silylation of the catalyst is not particularly limited, but preferably the coating amount is 5 to 2 by weight percent based on the organic polymer siloxane having a sulfonic acid group as a raw material.
It is 00 weight percent, more preferably 10 to 100 weight percent. The silylation amount is preferably 0.1 to 30% by weight, and more preferably 0.5 to 20% by weight, based on the weight percentage of the organic polymer siloxane having a sulfonic acid group as a raw material. Of course, the present invention is not limited to only these ranges.

X in the above general formulas represents an alkoxy group or a halogen atom in all the formulas, and the silicon-X bond is decomposed by carrying out the above-mentioned preparation method, for example, by hydrolysis. It is a group that makes it possible to form a high-molecular siloxane bond and further reacts with a silanol group on silica by a silylation treatment to form a siloxane bond.

The alkoxy group has 1 to 10 carbon atoms.
The following aliphatic alkoxy groups are preferable, and aromatic alkoxy groups having 6 to 15 carbon atoms are also preferable. Specific examples of the alkoxy group are methoxy group, ethoxy group,
Examples thereof include alkylalkoxy groups such as n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group and t-butoxy group, and aromatic alkoxy groups such as phenoxy group and naphthoxy group. As a halogen atom,
There are chlorine atom, bromine atom and iodine atom, and chlorine atom is preferable. Of course, X is not limited only to these, and further, mixed substituents thereof may be used.

In carrying out the present invention, the amount of olefin as a raw material and water used (amount ratio) is not particularly limited, but a water / olefin molar ratio of 0.1 to 50 is preferable, and 0 is more preferable. It is recommended to carry out in the range of 3 to 30. If the amount of water is too small, it is difficult to achieve a high conversion rate of the raw material olefin, and if the amount of water is too large, it is possible to increase the conversion rate of the olefin, but it is necessary to use more water than necessary so that the reaction This is because the vessel becomes too large and a large amount of water needs to be circulated, so that it cannot be manufactured efficiently.

Further, when carrying out the method of the present invention, the amount of catalyst used is not particularly limited, but, for example, when the reaction is carried out in a batch system, it is preferably a weight percentage relative to water as a raw material. At 0.001 to 100 weight percent, more preferably 0.1 to 50 weight percent.

The use of too little catalyst substantially slows down the reaction rate and causes a problem in efficiency.
Further, if too much catalyst is used, stirring efficiency of the reaction solution or the like may be lowered, which may cause trouble. Further, the catalyst may be used in a usual powder form, or the powder may be extruded, molded by pressing or the like and used in a granular form or the like.

The reaction temperature is not particularly limited, but is preferably in the range of 0 to 500 ° C, more preferably 30 to 300 ° C. If the reaction temperature is extremely low, the conversion rate of the olefin (reaction reagent) is low, in other words, the reaction rate extremely decreases, and the productivity of the reaction product decreases. on the other hand,
When the reaction temperature is 500 ° C. or higher, undesirable side reactions and the like proceed to increase the amount of by-products and the stability of the olefin as a raw material and the stability of alcohols as a product are not preferable, and the reaction selectivity It causes a decline and is not economical.

The reaction can be carried out under any of reduced pressure, increased pressure and normal pressure. From the viewpoint of reaction efficiency (reaction efficiency per unit volume), it is not preferable to carry out at a too low pressure. In addition, it is not preferable to carry out the reaction at an excessively high pressure from the viewpoint of the economical efficiency of the equipment such as a reactor. A generally preferred operating pressure range is 0.5 to 500 atmospheres,
More preferably, it is 1.0 to 300 atm. However, the invention is not limited to only these pressure ranges.

In carrying out the present invention, it is also possible to add a solvent or gas which is inert to the catalyst and the reaction reagent into the reaction system and carry out the reaction in a diluted state. Specifically, methane, ethane, propane, butane, hexane, cyclohexane and other saturated aliphatic hydrocarbons, nitrogen,
Examples thereof include inert gases such as argon and helium.
The reaction can be carried out in any of a liquid phase, a gas-liquid phase and a gas phase, but from the viewpoint of productivity and the scale of the reactor, at least a part of water is carried out in a liquid state. It is preferable. However, the present invention is not limited to this.

The present invention can be carried out in any reaction method such as a normal batch reaction, a semi-batch reaction in which a part of raw materials or a catalyst is continuously supplied, or a continuous flow reaction. Further, the order of addition of each component such as the reaction raw material and the catalyst and the addition method are not particularly limited. Further, as the catalyst filling method, a fixed bed, a fluidized bed, a suspension bed,
Various methods such as a fixed shelf floor are adopted, and any method may be used. The reaction time (residence time or catalyst contact time in flow reaction) is not particularly limited,
It is usually 0.1 seconds to 30 hours, preferably 0.5 seconds to 15 hours.

After the reaction, the reaction product can be separated and recovered from the catalyst or the like by a usual separation method such as filtration separation, extraction and distillation. Alcohols, which are the target products, are subjected to a sequential treatment method such as solvent extraction, distillation, alkali treatment, acid treatment or the like from the separated and recovered matter, or a usual separation or purification method such as an operation in which these are appropriately combined. It can be separated, purified and obtained. Further, the unreacted raw material can be recovered and recycled to the reaction system for use. In the case of a batch type reaction, the catalyst recovered by separating the reaction product after the reaction may be used as it is, or after regenerating a part or all thereof, it may be repeatedly used as a catalyst in the reaction again.

When the reaction is carried out in a fixed bed or fluidized bed flow continuous reaction system, the catalyst partially or wholly inactivated or reduced in activity by subjecting to the reaction is regenerated after interruption of the reaction and then used in the reaction. Alternatively, a part of the catalyst may be continuously or intermittently withdrawn, regenerated, recycled to the reactor, and reused. Further, fresh catalyst can be continuously or intermittently fed to the reactor. When the reaction is carried out in a moving bed flow continuous reaction or a homogeneous catalyst flow reaction system, the catalyst can be separated, regenerated and reused as in the batch reaction.

[0055]

EXAMPLES The present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Preparation of catalyst (1) Synthesis of organopolymer siloxane by hydrolysis of silane compound (1-1) Preparation of organopolymer siloxane partially having halogenated alkyl group by hydrolysis of silane compound (Preparation Method 1) 3- Chloropropyltrimethoxysilane ((ClPr) Si (OMe) ₃ ) and tetraethoxysilane (Si (OE
t) ₄ ) was mixed at a predetermined mixing ratio shown in Table 1, 62.5 ml of ethanol was further added, and the mixture was put into a 1-liter three-necked flask equipped with a stirrer and a cooling tube, and stirred at 60 ° C. for 1 hour. 16.7 ml of 0.01 N hydrochloric acid aqueous solution was added to the solution, and stirring was continued at 60 ° C. for 2 hours. (Note that when tetraethoxysilane was not mixed, the following operation was carried out without adding a hydrochloric acid aqueous solution.) Thereafter, this solution was heated at 60 ° C.
A mixture of 15 ml of hexane and 22.5 ml of ethanol was added while stirring at 2, and a solution of 25.0 ml of 28% aqueous ammonia solution in 135.0 ml of pure water was slowly added dropwise. After completion of dropping, stirring was further continued at this temperature for 10 hours to complete gelation. Desolvation of the resulting gelled mixture under reduced pressure,
After dehydration and drying of the gel, the dried gel was further washed thoroughly with water and then dried at 120 ° C. for 6 hours to obtain an organopolymer siloxane. Table 1 shows the organic polymer siloxane obtained by the above Preparation Method 1.

[0056]

[Table 1] Table 1 ────────────────────────────────────Organic polymer siloxane (ClPr) Si (OMe) ₃ : Si (OEt) ₄ Weight (molar ratio) ──────────────────────────────────── ─ Siloxane 1 99.38g: 0.0g (1: 0) Siloxane 2 49.68g: 52.08g (1: 1) Siloxane 3 29.81g: 72.92g (1: 2.3) Siloxane 4 9.94g: 93.75g (1: 9) ─ ───────────────────────────────────

(1-2) Preparation of Organic Polymer Siloxane Partially Having Phenyl Group by Hydrolysis of Silane Compound (Preparation Method 2) Phenyltriethoxysilane ((Ph) Si (OE
t) ₃ ) and tetraethoxysilane (Si (OEt) ₄ ) were mixed in the prescribed mixing ratio shown in Table 2, 62.5 ml of ethanol was further added, and the mixture was placed in a 1-liter three-necked flask equipped with a stirrer and a cooling tube. After stirring at 60 ° C for 1 hour, 0.01N aqueous hydrochloric acid solution (16.7 ml) was added to the solution and stirring was continued at 60 ° C for 2 hours. (Note that when tetraethoxysilane was not mixed, the following operation was performed without adding a hydrochloric acid aqueous solution.) Thereafter, while stirring at 60 ° C., a mixed solution of 15 ml of hexane and 22.5 ml of ethanol was added, Further, a solution prepared by dissolving 25.0 ml of 28% aqueous ammonia solution in 135.0 ml of pure water was slowly added dropwise. After completion of dropping, stirring was further continued at this temperature for 10 hours to complete gelation.
The resulting gelled mixture was desolvated under reduced pressure, dehydrated and dried to dry the gel, and the dried gel was further thoroughly washed with water,
It was dried at 120 ° C. for 6 hours to obtain an organic polymer siloxane.
Table 2 shows the organic polymer siloxane obtained by the above Preparation Method 2.

[0058]

[Table 2] Table 2 ──────────────────────────────────── Organic polymer siloxane (Ph) Si (OEt) ₃ : Si (OEt) ₄ Weight (molar ratio) ──────────────────────────────────── ─ Siloxane 5 120.19g: 0.0g (1: 0) Siloxane 6 60.09g: 52.08g (1: 1) Siloxane 7 36.06g: 72.92g (1: 2.3) Siloxane 8 12.02g: 93.75g (1: 9) ─ ───────────────────────────────────

(1-3) Preparation of Organic Polymer Siloxane Partially Having Vinyl Group by Hydrolysis of Silane Compound (Preparation Method 3) Vinyltriethoxysilane (CH ₂ = CHSi (OE
t) ₃ ) and tetraethoxysilane (Si (OEt) ₄ ) were mixed in the prescribed mixing ratio shown in Table 3, 62.5 ml of ethanol was added, and the mixture was placed in a 1-liter three-necked flask equipped with a stirrer and a cooling tube. After stirring at 60 ° C. for 1 hour, 0.01 N hydrochloric acid aqueous solution (16.7 ml) was added to this solution, and stirring was continued at 60 ° C. for another 6 hours. Then, while stirring at 60 ° C, a mixed solution of 15 ml of hexane and 22.5 ml of ethanol was added to this solution, and 25.0 ml of 28% ammonia aqueous solution was further added to pure water 1
The solution dissolved in 35.0 ml was slowly added dropwise. After completion of dropping, stirring was continued at this temperature for 4 hours to complete gelation. The obtained gelled mixture was desolvated and dehydrated under reduced pressure to dry the gel, and the dried gel was further thoroughly washed with water and then dried at 120 ° C. for 6 hours to obtain an organopolymer siloxane. Table 3 shows the organic polymer siloxane obtained by the above Preparation Method 3.

[0060]

[Table 3] Table 3 ──────────────────────────────────── Organic polymer siloxane CH ₂ = CHSi (OEt) ₃ : Si (OEt) ₄ Weight (molar ratio) ──────────────────────────────────── ─ Siloxane 9 47.58g: 52.08g (1: 1) Siloxane 10 28.55g: 72.92g (1: 2.3) ────────────────────────── ───────────

(1-4) By hydrolysis of silane compound
Preparation of organo-polymer siloxane partially containing epoxy groups
Manufacturing (Preparation Method 4) 2- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane (C₆H₈OC ₂H₂Si (OMe)₃)as well as
Tetraethoxysilane (Si (OEt)_Four) Is shown in Table 4
Mix at the mixing ratio, add 62.5 ml of ethanol and stirrer.
And in a 1-liter three-necked flask equipped with a cooling tube
After stirring for 1 hour at 60 ° C, add pure water to this solution.
5 ml was added and stirring was continued at 60 ° C. for another 6 hours. So
After that, this solution is stirred at 60 ° C while stirring with 15 ml of hexane.
22.5 ml of ethanol and ethanol were added, and further anhydrous sulfite was added.
A solution prepared by dissolving 7 g of sodium in 200 ml of pure water is slowly added.
Dropped. After completion of dropping, stirring is continued for 4 hours at this temperature.
Then, gelation was completed. Depressurize the resulting gelled mixture
Desolventize and dehydrate the gel below and dry the gel.
After further thoroughly washing the resin with water, it is dried at 120 ° C for 6 hours to be organic
A high molecular siloxane was obtained. Obtained by the above Preparation Method 4
The organic high molecular siloxane is shown in Table 4.

[0062]

[Table 4] Table 4 ──────────────────────────────────── Organic polymer siloxane C ₆ H ₈ OC ₂ H ₂ Si (OMe) ₃ : Si (OEt) ₄ Weight (molar ratio) ─────────────────────────────── ────── Siloxane 11 61.60g: 52.08g (1: 1) Siloxane 12 36.96g: 72.92g (1: 2.3) ──────────────────── ────────────────

(1-5) Preparation of Organic Polymer Siloxane Partially Having Alkylthiol Group by Hydrolysis of Silane Compound (Preparation Method 5) 3-Mercaptopropyltrimethoxysilane (HS (CH ₂ ) ₃ Si (OMe ) ₃ ) and tetraethoxysilane (Si
(OEt) ₄ ) was mixed at a predetermined mixing ratio shown in Table 5, 62.5 ml of ethanol was further added, and a stirrer and a cooling pipe were attached 1
The mixture was placed in a liter three-necked flask and stirred at 60 ° C. for 1 hour, then 16.7 ml of 0.01N hydrochloric acid aqueous solution was added to the solution, and the stirring was continued at 60 ° C. for another 6 hours. Then, a mixture of 15 ml of hexane and 22.5 ml of ethanol was added to this solution while stirring at 60 ° C., and further, a solution of 25.0 ml of 28% aqueous ammonia solution in 135.0 ml of pure water was slowly added dropwise. After completion of dropping, stirring was continued at this temperature for 4 hours to complete gelation. The obtained gelled mixture was desolvated and dehydrated under reduced pressure to dry the gel, and the dried gel was further thoroughly washed with water and then dried at 120 ° C. for 6 hours to obtain an organopolymer siloxane. Table 5 shows the organic polymer siloxane obtained by the above Preparation Method 5.

[0064]

[Table 5] Table 5 ──────────────────────────────────── Organic polymer siloxane HS (CH ₂ ) ₃ Si (OMe) ₃ : Si (OEt) ₄ Weight (molar ratio) ───────────────────────────────── ──── Siloxane 13 49.09g: 52.08g (1: 1) Siloxane 14 29.45g: 72.92g (1: 2.3) ─────────────────────── ──────────────

(2) Synthesis of organic polymer siloxane by silylation on silica gel (2-1) Synthesis of organic polymer siloxane partially having halogenated alkyl groups by silylation on silica gel (Preparation method 6) commercially available 10 g of silica gel (MS gel: manufactured by Dokai Chemical Industry Co., Ltd.) was dried under reduced pressure at 100 ° C. for 4 hours, and then 1
It was put in a 00 ml eggplant-shaped flask, 25.0 g of 3-chloropropyltrimethoxysilane ((ClPr) Si (OMe) ₃ ) was added thereto, and the mixture was heated and stirred at 100 ° C. for 4 hours. After allowing to cool, filter,
The white solid was thoroughly washed with methanol and then dried at 120 ° C. to obtain Organic Polymer Siloxane 15.

(2-2) Synthesis of Organopolymer Siloxane Partially Having Phenyl Group by Silylation to Silica Gel (Preparation Method 7) 10 g of commercially available silica gel (MS gel: Dokai Chemical Industry Co., Ltd.) at 100 ° C. After drying under reduced pressure for 4 hours, 1
Put in a 00 ml eggplant flask, add 25.0 g of phenyltriethoxysilane ((Ph) Si (OEt) ₃ ) to this, and add 100 ° C.
The mixture was heated and stirred for 4 hours. After standing to cool, it was filtered, and the white solid was thoroughly washed with methanol and then dried at 120 ° C. to obtain organic polymer siloxane 16.

(2-3) Synthesis of Organic Polymer Siloxane Partially Having Vinyl Group by Silylation to Silica Gel (Preparation Method 8) 10 g of commercially available silica gel (MS gel: manufactured by Dokai Chemical Industry Co., Ltd.) at 100 ° C. After drying under reduced pressure for 4 hours, 100ml
25 g of vinyltriethoxysilane (CH ₂ = CHSi (OEt) ₃ ) was added thereto, and the mixture was heated and stirred at 100 ° C. for 4 hours. After standing to cool, it was filtered, and the white solid was thoroughly washed with methanol and then dried at 120 ° C. to obtain organic polymer siloxane 17.

(2-4) Synthesis of Organic Polymer Siloxane Partially Having Epoxy Group by Silylation to Silica Gel (Preparation Method 9) 10 g of commercially available silica gel (MS gel: manufactured by Dokai Chemical Industry Co., Ltd.) at 100 ° C. After drying under reduced pressure for 4 hours, 1
Place in a 00 ml eggplant flask and add 2- (3,4-
25 g of epoxycyclohexyl) ethyltrimethoxysilane (C ₆ H ₈ OC ₂ H ₂ Si (OMe) ₃ ) was added, and the mixture was heated with stirring at 100 ° C. for 4 hours. After standing to cool, it was filtered, and the white solid was thoroughly washed with methanol and then dried at 120 ° C. to obtain organic polymer siloxane 18.

(2-5) Synthesis of Organic Polymer Siloxane Partially Having Alkylthiol Group by Silylation on Silica Gel (Preparation Method 10) 100 g of commercially available silica gel (MS gel: Dokai Chemical Industry Co., Ltd.) After vacuum drying for 4 hours at ℃,
Put in a 100 ml eggplant-shaped flask and add 3-mercaptopropyltrimethoxysilane (HS (CH ₂ ) ₃ Si (OMe) ₃ ) 25
g was added and the mixture was heated with stirring at 100 ° C. for 4 hours. After cooling, the white solid was thoroughly washed with methanol and then filtered.
It was dried at ℃ and organic high-molecular siloxane 19 was obtained.

(3) Sulfonation of Organic Polymer Siloxane (3-1) Sulfonation of Organic Polymer Siloxane Partially Having Halogenated Alkyl Group (Sulfonation 1) Organic compound prepared by the above Preparation Method 1 or 6. High-molecular siloxane 10.0g and anhydrous sodium sulfite 1.5 times the molar amount of alkyl halide group, 100ml of pure water
Was placed in a 300 ml flask, heated under reflux with stirring for 50 hours, cooled to room temperature, and the solid was separated by filtration. The separated solid was further thoroughly washed with pure water and vacuum dried at 120 ° C. for 6 hours to obtain a white solid. Add 1 more of this white solid
After stirring in 100 ml of N-hydrochloric acid for 1 hour, the solid was separated by filtration, washed thoroughly with pure water, and dried at 120 ° C. for 6 hours to obtain a white solid. These were used as catalysts for hydration of olefins. Table 6 shows the sulfonic acid group-containing organic polymer siloxane catalyst obtained by the sulfonation method 1.

[0071]

[Table 6] Table 6 ──────────────────────────────────── Catalyst Organic polymer siloxane Sulfonation method Acid exchange equivalent (mmol / g) ──────────────────────────────────── Catalyst 1 Siloxane 1 Sulfonation Method 1 1.78 Catalyst 2 Siloxane 2 Sulfonation Method 1 1.20 Catalyst 3 Siloxane 3 Sulfonation Method 1 1.31 Catalyst 4 Siloxane 4 Sulfonation Method 1 0.41 Catalyst 5 Siloxane 15 Sulfonation Method 1 0.79 ─ ───────────────────────────────────

(3-2) Sulfonation of Organic Polymer Siloxane Partially Having Phenyl Group (Sulfonation 2) 10.0 g of the organic polymer siloxane prepared by the above Preparation Method 2 or 7 and 100 ml of concentrated sulfuric acid were added to a 300 ml flask. After heating and stirring at 80 ° C. for 3 hours, the mixture was cooled to room temperature, the mixed solution (slurry) was put into a large amount of pure water, and then a solid was separated by filtration. The separated solid was further thoroughly washed with pure water and vacuum dried at 120 ° C. for 6 hours to obtain a white solid. These were used as catalysts for hydration of olefins. Table 7 shows the sulfonic acid group-containing organic polymer siloxane catalyst obtained by the sulfonation method 2.

[0073]

[Table 7] Table 7 ──────────────────────────────────── Catalyst Organic polymer siloxane Sulfonation method Acid exchange equivalent (mmol / g) ──────────────────────────────────── Catalyst 6 Siloxane 5 Sulfonation Method 2 0.91 catalyst 7 siloxane 6 sulfonation method 2 0.68 catalyst 8 siloxane 7 sulfonation method 2 0.79 catalyst 9 siloxane 8 sulfonation method 2 0.34 catalyst 10 siloxane 16 sulfonation method 2 0.57 ─ ───────────────────────────────────

(Sulfonation 3) 10.0 g of the organic polymer siloxane prepared by the above Preparation Method 2 and 30 ml of chloroform, and 20 ml of chlorosulfonic acid (ClSO ₃ H) were added to 30 ml of chloroform.
The solution dissolved in was placed in a 500 ml flask and stirred at 80 ° C. for 3 hours for sulfonation. After the completion of the reaction, the mixed solution (slurry) cooled to room temperature was put into a large amount of ethanol and sufficiently stirred, and then pure water was added to the ethanol mixed solution, and then the solid was separated by filtration. The separated solid was further thoroughly washed with pure water and vacuum dried at 120 ° C. for 6 hours to obtain a white solid. These were used as catalysts for hydration of olefins. Table 8 shows the sulfonic acid group-containing organic polymer siloxane catalyst obtained by the sulfonation method 3.

[0075]

[Table 8] Table 8 ──────────────────────────────────── Catalyst Organic polymer siloxane Sulfonation method Acid exchange equivalent (mmol / g) ──────────────────────────────────── Catalyst 11 Siloxane 5 Sulfonation Method 3 1.54 Catalyst 12 Siloxane 6 Sulfonation Method 3 1.12. Catalyst 13 Siloxane 7 Sulfonation Method 3 1.25 Catalyst 14 Siloxane 8 Sulfonation Method 3 0.46 ────────────────────────

(3-3) Sulfonation of Organic Polymer Siloxane Partially Having Vinyl Group (Sulfonation 4) 15.0 g of the organic polymer siloxane prepared by the above Preparation Method 3 or 8 and the number of moles relative to the vinyl group In 2
Double amount of sodium bisulfite, 4-fold equivalent of anhydrous sodium sulfite, and 500 ml of pure water were put into a 1000 ml flask, heated and refluxed with stirring for 46 hours while blowing air into the solution, then cooled to room temperature and solid was separated by filtration. . The separated solid was further thoroughly filtered and washed with pure water and dried at 120 ° C. for 6 hours to obtain a white solid. In addition, 1N of this white solid
-After stirring in 200 ml of hydrochloric acid for 1 hour, the solid was separated by filtration, thoroughly washed with pure water, and dried at 120 ° C for 6 hours to obtain a white solid. These were used as catalysts for hydration of olefins. Table 9 shows the sulfonic acid group-containing organic polymer siloxane catalyst obtained by the sulfonation method 4.

[0077]

[Table 9] Table 9 ──────────────────────────────────── Catalyst Organic polymer siloxane Sulfonation method Acid exchange equivalent (mmol / g) ──────────────────────────────────── Catalyst 15 Siloxane 9 Sulfonation Method 4 1.39 Catalyst 16 Siloxane 10 Sulfonation Method 4 1.44 Catalyst 17 Siloxane 17 Sulfonation Method 4 0.58 ───────────────────────── ─────────────

(3-4) Sulfonation of Organic Polymer Siloxane Partially Having Epoxy Group (Sulfonation 5) 10.0 g of the organic polymer siloxane prepared by the above Preparation Method 4 or 9 and the number of moles relative to the epoxy group Then, 2 volumes of sodium bisulfite, 4 volumes of anhydrous sodium sulfite, and 250 ml of pure water were placed in a 1000 ml flask, and the mixture was heated under reflux with stirring for 6 hours, cooled to room temperature, and solids were separated by filtration. The separated solid is further thoroughly washed with pure water,
It was dried at 0 ° C. for 6 hours to obtain a white solid. The white solid was further stirred in 200 ml of 1N hydrochloric acid for 1 hour, and then
The solid was separated by filtration, washed thoroughly with pure water, and dried at 120 ° C. for 6 hours to obtain a white solid. These were used as catalysts for hydration of olefins. Table 10 shows the sulfonic acid group-containing organic polymer siloxane catalyst obtained by the sulfonation method 5.

[0079]

[Table 10] Table 10 ──────────────────────────────────── Catalyst Organic polymer siloxane Sulfonation method Acid exchange equivalent (mmol / g) ───────────────────────────────────── Catalyst 18 Siloxane 11 Sulfonation Method 5 0.74 Catalyst 19 Siloxane 12 Sulfonation Method 5 1.12. Catalyst 20 Siloxane 18 Sulfonation Method 5 0.52 ──────────────────────── ─────────────

(3-5) Sulfonation of Organic Polymer Siloxane Partially Having Alkylthiol Group (Sulfonation 6) 10 g of the organic polymer siloxane prepared by the above Preparation Method 5 or 10 was added to 30 ml of concentrated nitric acid. The mixture was gradually added and stirred at room temperature for 1 hour. After the reaction, the solid was separated by filtration, washed thoroughly with pure water, and dried at 120 ° C. for 6 hours to obtain a white solid. These were used as catalysts for hydration of olefins. Table 11 shows the sulfonic acid group-containing organic polymer siloxane catalyst obtained by the sulfonation method 6.

[0081]

[Table 11] Table 11 ──────────────────────────────────── Catalyst Organic polymer siloxane Sulfonation method Acid exchange equivalent (mmol / g) ──────────────────────────────────── Catalyst 21 Siloxane 13 Sulfonation Method 5 1.70 catalyst 22 siloxane 14 sulfonation method 5 1.78 catalyst 23 siloxane 19 sulfonation method 5 0.55 ──────────────────────── ─────────────

(4) Silica coating of organic polymer siloxane having sulfonic acid group 10 g of the above catalyst 2, 3, 7 or 8 and 25.0 m of ethanol
l was put in a 500 ml three-necked flask equipped with a stirrer and a cooling tube, stirred at 40 ° C. for 1 hour, tetraethoxysilane (Si (OEt) ₄ ): 34.67 g (SiO ₂ 10 g equivalent) was added, and further Stirring was continued for 1 hour at 40 ° C. After that, 28.8 ml of pure water was slowly added dropwise to this mixed solution, and 8
Stirring was continued at 0 ° C. for 20 hours to perform silica coating. After coating, the mixed solution was desolvated under reduced pressure and dehydrated to obtain a white solid, which was dried at 120 ° C. to obtain a silica-coated sulfonic acid group-containing organopolymer siloxane catalyst. Table 12 shows the catalysts thus obtained.

[0083]

[Table 12] Table 12 ────────────────────────────────── Catalyst Catalyst before treatment Acid exchange equivalent (mmol / g) ────────────────────────────────── Catalyst 24 Catalyst 2 0.68 Catalyst 25 Catalyst 3 0.75 Catalyst 26 Catalyst 7 0.40 Catalyst 27 Catalyst 8 0.42 ───────────────────────────────────

(5) Silylation of Organopolymer Siloxane Having Sulfonic Acid Group 10 g of the above catalyst 2, 3, 7 or 8 was dried under reduced pressure at 100 ° C. for 4 hours, then placed in a 100 ml eggplant flask, and triethyl was added thereto. Add 25.0 g of ethoxysilane (Et ₃ SiOEt),
The mixture was heated and stirred at 100 ° C. for 4 hours. After cooling, the white solid was thoroughly washed with methanol and dried at 120 ° C. to obtain a silylated sulfonic acid group-containing organic polymer siloxane catalyst. Table 13 shows the catalysts thus obtained.

[0085]

[Table 13] Table 13 ─────────────────────────────────── Catalyst before treatment Catalyst acid exchange equivalent (mmol / g) ─────────────────────────────────── Catalyst 28 Catalyst 2 1.18 Catalyst 29 Catalyst 3 1 .35 catalyst 30 catalyst 7 0.71 catalyst 31 catalyst 8 0.79 ─────────────────────────────────── ─

(6) Silylation of Silica-Coated Sulfonic Acid Group-Containing Polymeric Siloxane For each of the catalysts 24 to 27, 10 g of the catalyst was dried at 100 ° C.
After drying under reduced pressure for an hour, the mixture was placed in a 100 ml round-bottomed flask, 25.0 g of triethylethoxysilane (Et ₃ SiOEt) was added thereto, and the mixture was heated and stirred at 100 ° C. for 4 hours. After allowing to cool, filter,
The white solid was thoroughly washed with methanol and then dried at 120 ° C. to obtain silylated sulfonic acid group-containing organic polymer siloxane catalysts 32 to 35. Table 14 shows the catalysts thus obtained.

[0087]

[Table 14] Table 14 ─────────────────────────────────── Catalyst Pretreatment Catalyst Acid exchange equivalent (mmol / g) ─────────────────────────────────── Catalyst 32 Catalyst 24 0.58 Catalyst 33 Catalyst 250 .59 catalyst 34 catalyst 26 0.31 catalyst 35 catalyst 27 0.32 ─────────────────────────────────── ─

Hydration Reaction Examples 1 to 23 In a 70 ml autoclave, 3.0 g of catalyst and 24.0 g of water (1.33 m
ol) was charged, 12.0 g (0.285 mol) of propylene was injected under pressure, and the mixture was heated and stirred at 140 ° C. for 5 hours to carry out a reaction. After completion of the reaction, the autoclave was cooled and the pressure was released, and the reaction solution was analyzed by gas chromatography. As a result, it was confirmed that isopropyl alcohol was produced in good yield as shown in Table 15. At this time, in all of the examples, formation of isopropyl ether as a by-product was not confirmed. Further, the catalyst after the completion of the reaction was all settled at the bottom of the reaction vessel and could be easily separated.

[0089]

[Table 15] Table 15 ──────────────────────────────────── Example No. Catalyst used Isopropyl alcohol yield (%) ───────────────────────────────────── Example 1 Catalyst 1 8.15 Example 2 Catalyst 2 4.86 Example 3 Catalyst 3 5.11 Example 4 Catalyst 4 2.12 Example 5 Catalyst 5 3.85 Example 6 Catalyst 6 8.70 Example 7 Catalyst 7 5. 51 Example 8 Catalyst 8 5.30 Example 9 Catalyst 9 3.40 Example 10 Catalyst 10 4.22 Example 11 Catalyst 11 17.40 Example 12 Catalyst 12 10.99 Example 13 Catalyst 13 12.80 Implementation Example 14 Catalyst 14 4.87 Example 15 Catalyst 15 6.76 Example 16 Catalyst 16 7.06 Example 17 Catalyst 17 2.52 Example 18 Catalyst 18 1.78 Example 19 Catalyst 19 5.28 Example 20 Catalyst 20 1.14 Example 21 Catalyst 21 8 01 Example 22 Catalyst 22 8.35 Example 23 Catalyst 23 2.64 ────────────────────────────────── ─── The yield of isopropyl alcohol is based on the charged propylene.

Examples 24-27 In a 70 ml autoclave, 6.0 g of catalyst (3.0 g of organic polymer siloxane containing sulfonic acid groups) and 24.0 g of water (1.33 m
ol) was charged, 12.0 g (0.285 mol) of propylene was injected under pressure, and the mixture was heated and stirred at 140 ° C. for 5 hours to carry out a reaction. After completion of the reaction, the autoclave was cooled and the pressure was released, and the reaction solution was analyzed by gas chromatography. As a result, as shown in Table 16, it was confirmed that isopropyl alcohol was produced in a higher yield than the catalyst before silica coating. At this time, in all of the examples, formation of isopropyl ether as a by-product was not confirmed.
Further, the catalyst after the completion of the reaction was all settled at the bottom of the reaction vessel and could be easily separated.

[0091]

[Table 16] Table 16 ──────────────────────────────────── Example No. Catalyst used Isopropyl alcohol yield (%) ──────────────────────────────────── Example 24 Catalyst 24 14.55 Example 25 Catalyst 25 15.02 Example 26 Catalyst 26 15.74 Example 27 Catalyst 27 15.56 ──────────────────────── ───────────── The yield of isopropyl alcohol is based on the charged propylene.

Examples 28-31 In a 70 ml autoclave, 3.0 g of catalyst and 24.0 g of water (1.33 m
ol) was charged, 12.0 g (0.285 mol) of propylene was injected under pressure, and the mixture was heated and stirred at 140 ° C. for 5 hours to carry out a reaction. After completion of the reaction, the autoclave was cooled and the pressure was released, and the reaction solution was analyzed by gas chromatography. As a result, as shown in Table 17, it was confirmed that isopropyl alcohol was produced in a higher yield than the catalyst before the silylation treatment.
At this time, in all of the examples, formation of isopropyl ether as a by-product was not confirmed. Furthermore, the catalyst after the reaction is all settled at the bottom of the reaction vessel,
It could be easily separated.

[0093]

[Table 17] Table 17 ──────────────────────────────────── Example No. Catalyst used Isopropyl alcohol yield (%) ───────────────────────────────────── Example 28 Catalyst 28 9.12 Example 29 Catalyst 29 9.96 Example 30 Catalyst 30 10.40 Example 31 Catalyst 31 10.65 ──────────────────────── ───────────── The yield of isopropyl alcohol is based on the charged propylene.

Examples 32-35 In a 70 ml autoclave, 6.0 g of catalyst and 24.0 g of water (1.33 m
ol) was charged, 12.0 g (0.285 mol) of propylene was injected under pressure, and the mixture was heated and stirred at 140 ° C. for 5 hours to carry out a reaction. After completion of the reaction, the autoclave was cooled and the pressure was released, and the reaction solution was analyzed by gas chromatography. As a result, as shown in Table 18, it was confirmed that isopropyl alcohol was produced in a higher yield than the catalyst before the silylation treatment, and the silylation treatment after silica coating is an effective method for improving the catalytic activity. I understand. At this time, in all of the examples, formation of isopropyl ether as a by-product was not confirmed. Further, the catalyst after the completion of the reaction was all settled at the bottom of the reaction vessel and could be easily separated.

[0095]

[Table 18] Table 18 ──────────────────────────────────── Example No. Catalyst used Isopropyl alcohol yield (%) ───────────────────────────────────── Example 32 Catalyst 32 16.70 Example 33 Catalyst 33 17.46 Example 34 Catalyst 34 18.32 Example 35 Catalyst 35 18.67 ──────────────────────── ───────────── The yield of isopropyl alcohol is based on the charged propylene.

Examples 36 to 41 All of Examples 3 and 8 except that the reaction temperature was 160 ° C.
The reaction was carried out under the same conditions as 25, 27, 33 or 35. The results are shown in Table 19.

[0097]

[Table 19] Table 19 ──────────────────────────────────── Example No. Catalyst used Yield (%) iPA DiPE ───────────────────────────────────── Example 36 Catalyst 3 12.73 0.10 Example 37 Catalyst 8 17.68 0.15 Example 38 Catalyst 25 33.98 0.31 Example 39 Catalyst 27 38.41 0.35 Example 40 Catalyst 33 36.98 0.44 Example 41 Catalyst 35 39.51 0.58 ──────────────────────────────────── iPA = isopropyl Alcohol; DiPE = diisopropyl ether Yields are expressed in% on the basis of propylene charged.

Examples 42 to 47 All of Example 36 except that the amount of water charged was 36.0 g.
The reaction was carried out under the same conditions as ~ 41. The results are shown in Table 20.

[0099]

[Table 20] Table 20 ──────────────────────────────────── Example No. Catalyst used Yield (%) iPA DiPE ───────────────────────────────────── Example 42 Catalyst 3 12.73 0.10 Example 43 Catalyst 8 17.68 0.11 Example 44 Catalyst 25 44.98 0.23 Example 45 Catalyst 27 48.51 0.27 Example 46 Catalyst 33 52.98 0.25 Example 47 Catalyst 35 60.36 0.32 ──────────────────────────────────── iPA = isopropyl Alcohol; DiPE = diisopropyl ether Yields are expressed in% on the basis of propylene charged.

Examples 48 to 53 The amount of propylene charged was 6.0 g, and the reaction temperature was 200.
The reaction was carried out under the same conditions as in Examples 42 to 47 except that the temperature was changed to 0.5 hours. As a result,
The yields of isopropyl alcohol and diisopropyl ether were as shown in Table 21.

[0101]

[Table 21] Table 21 ──────────────────────────────────── Example No. Catalyst used Yield (%) iPA DiPE ──────────────────────────────────── Example 48 Catalyst 3 34.24 0.31 Example 49 Catalyst 8 28.09 0.29 Example 50 Catalyst 25 71.39 0.49 Example 51 Catalyst 27 76.18 0.41 Example 52 Catalyst 33 80.74 0.53 Example 53 Catalyst 35 77.02 0.50 ──────────────────────────────────── iPA = isopropyl Alcohol; DiPE = diisopropyl ether Yields are expressed in% on the basis of propylene charged.

Examples 54 to 55 The reaction was carried out under the conditions of Examples 48 and 49, and after the completion of the reaction, only the catalyst was left in the reactor and only the reaction solution was separated and collected for analysis. Then, the catalyst left in the reactor was newly charged with the same amount of water and propylene as in each Example, and the reaction was repeated under the same reaction conditions. This operation was repeated 5 times in total. As shown in Tables 22 and 23, the results show that the reaction results were not deteriorated due to the repetition, and the catalyst is stable at this temperature and conditions.

[0103]

[Table 22] Table 22 ──────────────────────────────────── Catalyst used Reaction reaction yield (% ) IPA DiPE ──────────────────────────────────── Catalyst 3 1st time 33.85 0.29 2 3rd 34.10 0.30 3rd 34.22 0.31 4th 34.06 0.30 5th 33.98 0.28 ──────────────────── ───────────────── iPA = Isopropyl alcohol; DiPE = Diisopropyl ether The yields are expressed in% on the basis of the charged propylene.

[0104]

[Table 23] Table 23 ──────────────────────────────────── Catalyst used Reaction yield (% ) IPA DiPE ──────────────────────────────────── Catalyst 8 1st time 28.15 0.29 2 Time 28.36 0.31 3rd time 27.12 0.28 4th time 29.00 00 0.31 5th time 28.74 0.29 ──────────────────── ───────────────── iPA = Isopropyl alcohol; DiPE = Diisopropyl ether The yields are expressed in% on the basis of the charged propylene.

Examples 56 to 57 The reaction was carried out under the conditions of Examples 50 and 51, and after the reaction was completed, only the catalyst was left in the reactor and only the reaction solution was separated and collected for analysis. Then, the catalyst left in the reactor was newly charged with the same amount of water and propylene as in each Example, and the reaction was repeated under the same reaction conditions. This operation was repeated 5 times in total. As shown in Tables 24 and 25, the results showed that the reaction results were not deteriorated by the repetition, and the catalyst was stable at this temperature and conditions.

[0106]

[Table 24] Table 24 ──────────────────────────────────── Catalyst used Reaction reaction yield (% ) IPA DiPE ──────────────────────────────────── Catalyst 25 1st time 71.68 0.49 2 7th 30.02 0.52 3rd 72.22 0.50 4th 71.69 0.50 5th 71.25 0.49 ──────────────────── ───────────────── iPA = Isopropyl alcohol; DiPE = Diisopropyl ether The yields are expressed in% on the basis of the charged propylene.

[0107]

[Table 25] Table 25 ──────────────────────────────────── Catalyst used Reaction yield (% ) IPA DiPE ──────────────────────────────────── Catalyst 27 1st time 76.78 0.41 2 7th time 76.90 0.40 3rd time 75.64 0.39 4th time 76.77 0.39 5th time 76.03 0.40 ──────────────────── ───────────────── iPA = Isopropyl alcohol; DiPE = Diisopropyl ether The yields are expressed in% on the basis of the charged propylene.

Examples 58 to 59 The reaction was carried out under the conditions of Examples 52 and 53, and after the reaction was completed, only the catalyst was left in the reactor, and only the reaction solution was separated and collected for analysis. Then, the catalyst left in the reactor was newly charged with the same amount of water and propylene as in each Example, and the reaction was repeated under the same reaction conditions. This operation was repeated 5 times in total. As shown in Tables 25 and 26, the results show that the reaction results were not deteriorated due to the repetition, and the catalyst was stable at this temperature and conditions.

[0109]

[Table 26] Table 26 ──────────────────────────────────── Catalyst used Reaction yield (% ) IPA DiPE ──────────────────────────────────── Catalyst 33 1st time 81.23 0.52 2 Time 81.39 0.54 3rd time 80.01 0.54 4th time 83.65 0.55 5th time 80.47 0.51 ──────────────────── ──────────────── iPA = Isopropyl alcohol; DiPE = Diisopropyl ether The yields are expressed in% on the basis of the charged propylene.

[0110]

[Table 27] Table 27 ──────────────────────────────────── Catalyst used Reaction reaction yield (% ) IPA DiPE ──────────────────────────────────── Catalyst 35 1st time 76.92 0.50 2 74th 25.45 0.45 3rd 73.59 0.50 4th 75.64 0.51 5th 76.39 0.49 ──────────────────── ───────────────── iPA = Isopropyl alcohol; DiPE = Diisopropyl ether The yields are expressed in% on the basis of the charged propylene.

Comparative Example 1 Amberlyst 15 which is a cation exchange resin was used as a catalyst.
The procedure was repeated as in Example 48 except that the amount was 0 g. As for the reaction results of the fifth repetition, the yield of isopropyl alcohol was very small and was below the analytical measurement limit.
Apparently, it can be seen that the catalyst deteriorated in the repeated reaction under these conditions.

Examples 60 to 71 Propylene was replaced with ethylene or 1-butene, and 0.285
Example 3, 8, 25, 27, 3 except that mol was charged.
The reaction was performed under the same conditions as 3 or 35. The results are shown in Table 2.
As shown in 8, each olefin has a good yield,
Alcohol was produced. The yields in the table are all based on the charged olefin. The alcohols produced are ethanol from ethylene and 2-from 1-butene.
It is butanol.

[0113]

Table 28 Table 28 ──────────────────────────────────── Example No. Catalyst used Olefin Yield of alcohols (%) ───────────────────────────────────── Example 60 Catalyst 3 ethylene 4.95 Example 61 catalyst 3 1-butene 6.88 Example 62 catalyst 8 ethylene 5.01 Example 63 catalyst 8 1-butene 7.41 Example 64 catalyst 25 ethylene 11.69 Example 65 catalyst 25 1-Butene 15.98 Example 66 Catalyst 27 Ethylene 12.03 Example 67 Catalyst 27 1-Butene 16.14 Example 68 Catalyst 33 Ethylene 12.05 Example 69 Catalyst 33 1-Butene 16.01 Example 70 Catalyst 35 ethylene 13.98 Example 71 catalyst 35 1-butene 17.85 ─────────────────────────────────── ──

[0114]

According to the present invention, (1) an olefin can be directly hydrated to produce an alcohol with good yield and selectivity. (2) Compared to the conventional method, alcohols can be directly hydrated even under mild conditions of low temperature and low pressure. In addition, the reaction can be carried out under the condition that the reactor or the like is hardly corroded. (3) It is possible to produce industrially important alcohols significantly in terms of safety, process, and economy. (4) The alcohols can be produced by preventing thermal decomposition of the catalyst and omitting the neutralization treatment of the reaction solution. (5) A stable heterogeneous solid catalyst for alcohol production can be provided. INDUSTRIAL APPLICABILITY As described above, the present invention can provide an industrially excellent method for producing alcohols by hydration of olefins.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C07C 31/12 9155-4H // C07B 61/00 300

Claims (7)

[Claims] 1. A method for producing alcohols, which comprises reacting an olefin with water in the presence of an organic polymer siloxane having a sulfonic acid group. 2. The method according to claim 1, wherein the organic polymeric siloxane having a sulfonic acid group is an organic polymeric siloxane having an aromatic sulfonic acid group. 3. The method according to claim 1, wherein the organopolymeric siloxane having a sulfonic acid group is an organopolymeric siloxane having an alkylsulfonic acid group. 4. The organic polymer siloxane having a sulfonic acid group has the general formula: (R) _n SiX _4-n (wherein R is an aliphatic hydrocarbon group having 1 to 4 carbon atoms and 6 to 6 carbon atoms). 15 is at least one hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups, X is at least one selected from the group consisting of alkoxy groups, chlorine atoms, bromine atoms and iodine atoms, Si Represents a silicon atom, and n
Is 0 or an integer of 1 or more and 3 or less. 2. A coating and / or silylation treatment with at least one silane compound represented by the formula 1.).
The described method. 5. The method according to claim 1, 2, 3 or 4, wherein the reaction between the olefin and water is carried out under the condition that water exists in a liquid state. 6. The method according to claim 1, wherein the olefin is a lower olefin having 2 to 6 carbon atoms. 7. The method according to claim 6, wherein the olefin is ethylene or propylene.