JPH09262478A - Complex consisting of specified metallic halide and quaternary salt type anion exchange resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a useful novel resin complex acting as a catalyst for production of unsatd. alcohol from olefin and aldehyde under mild conditions. SOLUTION: This complex consists of a metallic halide represented by the formula and a quat. salt type anion exchange resin. In the formula, M is at least one kind of metal selected from among Sn, Ga, In and Sc, X1 is halogen and (q) is an integer equal to the valance of M.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel complex of a specific metal halide and a quaternary salt type anion exchange resin, which is useful as a catalyst for producing an unsaturated alcohol from an olefin and an aldehyde.

[0002]

2. Description of the Related Art Heretofore, there have been known some examples in which a quaternary ammonium salt type anion exchange resin and a metal chloride are treated in concentrated hydrochloric acid. For example, quaternary ammonium salt type anion exchange resin (Dowex-1: Dow Chemical Company (USA))
It is known that chlorides of iron, molybdenum, tungsten and uranium are adsorbed in concentrated hydrochloric acid (J. Amer. Chem. Soc. ), 77, 3972 (1955)). It is also known that iron chloride (FeCl ₃ ) forms a complex with a quaternary ammonium salt type anion exchange resin in concentrated hydrochloric acid (Bulletin of the Chemical Society of Japan). of the Chem
ical Society of Japan), 42, p. 1760 (1969)). Further, it is known that various metal chlorides form a chlorine-containing negative charge complex in concentrated hydrochloric acid, and the complex is adsorbed by anion exchange resin, but this adsorption occurs only in concentrated hydrochloric acid. It is observed and does not occur in dilute hydrochloric acid or in water (Proceeding of the International Conference on the Peaceful Uses of Atomic Energy, Geneva). International
Conference on the Peaceful Uses of Atomic Energy,
Geneva), 1955, 11, p / 837, 113-125). However, a complex composed of a halide of tin, gallium, indium or scandium and a quaternary salt type anion exchange resin has not been known so far.

[0003]

It has long been known that a reaction for producing an unsaturated alcohol by reacting an olefin with formaldehyde proceeds in the presence of a Lewis acid catalyst. However, since the Lewis acid itself is easily hydrolyzed in the presence of water, formaldehyde raw materials containing no water, such as paraform, trioxane, and gaseous formaldehyde, had to be used. These are more expensive than formaldehyde aqueous solution and are not suitable as a raw material for producing an inexpensive unsaturated alcohol. Further, when a Lewis acid catalyst is used in the presence of water, the catalyst is hydrolyzed, and there is a problem that a target unsaturated alcohol and a large amount of a metaalkyldioxane, which is difficult to separate by distillation, are by-produced. . Further, these Lewis acid catalysts are difficult to separate and collect from the reaction solution after the reaction, and there is a problem that they must be thrown away. Therefore, the present inventors have tried to use the previously described complex of iron chloride and quaternary ammonium salt type anion exchange resin for the reaction of olefin and formaldehyde. It was found that the complex did not show sufficient catalytic activity for this reaction, since the target unsaturated alcohol was poorly selected.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have proposed a complex which can be used when an olefin is reacted with formaldehyde to produce an unsaturated alcohol and which has high activity and is easily separated and recovered from the reaction solution. As a result of earnest study,
General formula (I)

[0005]

Embedded image

(In the formula, M represents at least one metal selected from the group consisting of tin, gallium, indium and scandium, X ₁ represents a halogen atom, and q represents M.
Represents the same integer as the valence number of. The present invention has been completed by finding a complex consisting of a specific metal halide represented by the formula (4) and a quaternary salt type anion exchange resin.

The complex consisting of a specific metal halide and a quaternary salt type anion exchange resin found by the present invention acts as a highly active catalyst for the production of unsaturated alcohol by the reaction of olefin and formaldehyde. . Since the complex is more stable to water than the metal halide alone, an inexpensive formaldehyde aqueous solution can be used as the formaldehyde raw material. Since the complex is a solid, it can be separated and recovered from the reaction solution by a simple method such as decantation, and can be easily reused.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The quaternary salt type anion exchange resin used in the present invention may be any resin as long as it is an anion exchange resin containing a quaternary salt type substituent. The quaternary salt-type anion exchange resin is composed of an ion exchange resin polymer substrate, a quaternary salt-type substituent, and a linker connecting both of them. The ion-exchange resin polymer substrate has the general formula (II)

[0009]

Embedded image

(In the formula, R _a is a hydrogen atom or an optionally substituted lower alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group. R _b and R _c each represent a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted aryl group, an ester group or an amide group, and m and n represent the degree of polymerization of the ion exchange resin. Represents an integer corresponding to the ratio of 1: 9
It is in the range of 9 to 99: 1. ) Is a copolymer of substituted ethylene and divinylbenzene. The quaternary salt type substituent is usually represented by the general formula (III)

[0011]

Embedded image

(In the formula, K represents a nitrogen atom or a phosphorus atom, and R ¹ , R ² and R ³ are each a lower alkyl group which may be substituted, a cycloalkyl group which may be substituted, or a substituted alkyl group. Which represents an optionally substituted aryl group or an optionally substituted aralkyl group, and X ₂ represents a halogen atom or a hydroxyl group, and an ammonium salt-type or phosphonium salt-type substituent represented by the general formula (IV)

[0013]

Embedded image

(In the formula, Py represents a portion of the pyridine ring excluding a nitrogen atom, N represents a nitrogen atom in the pyridine ring, R ⁴ is an optionally substituted lower alkyl group, or an optionally substituted lower alkyl group. Which represents a good cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, and X ₂ is as defined above.) Is a pyridinium salt type substituent. The linker varies depending on the component of the monomer that is the constituent raw material of the ion exchange resin,

[0015]

[Chemical 6]

Or general formula (VI-1, VI-2)

[0017]

Embedded image

(In the formula, r represents an integer other than zero). Therefore, the quaternary salt type anion exchange resin has the general formula (VII)

[0019]

Embedded image (In the formula, R _a , R _b , R _c , m and n are as defined above, L represents a linker, and Q represents a quaternary salt type substituent.).

R ¹ , R ² and R ³ in the general formula (III) and R ⁴ in the general formula (IV) are each a lower alkyl group which may be substituted, a cycloalkyl group which may be substituted, and a substituted alkyl group. Represents an optionally substituted aryl group and an optionally substituted aralkyl group, and these lower alkyl group, cycloalkyl group and aryl group may each be substituted with, for example, a lower alkyl group or a hydroxyl group. The aromatic ring portion of the aralkyl group may be substituted with a lower alkyl group or a halogen atom. Specific examples of the ammonium salt-type or phosphonium salt-type substituent represented by the general formula (III) include, for example, trimethylammonium chloride chloride group, triethylammonium chloride chloride group, tributylammonium chloride chloride group, and dimethylbutylammonium chloride chloride group. Trimethylammonium bromide group, dimethyl (hydroxyethyl) ammonium chloride methyl group, dimethylbenzylammonium bromide group,
Examples thereof include tributylphosphonium methyl chloride group, triphenylphosphonium methyl bromide group, tricyclohexylphosphonium methyl bromide group, but are not limited thereto. The pyridinium salt-type substituent of the general formula (IV) is, for example, a substituent of the nitrogen atom in the pyridine ring, such as N-methyl chloride, N-ethyl chloride, N-butyl chloride, N-benzyl chloride. , N-methyl bromide, and the like, but are not limited thereto.

The metal halide used in the present invention is
It is a halide of at least one metal selected from the group consisting of tin, gallium, indium and scandium and having a valence of 3 or 4. Examples of the metal halide include stannic chloride (IV),
Stannous bromide (IV), stannous bromide (IV), gallium (III) chloride, gallium (III) bromide, indium (III) chloride, indium (III) bromide, scandium (III) chloride, Such as scandium bromide (III),
Also, hydrates of these metal halides can be used. Further, a mixture of the exemplified metal halides may be used, and other metal halides may be added if necessary.

The complex composed of the metal halide and the quaternary salt type ion exchange resin has a complex structure in which 0.1 to 1.0 unit of the metal halide is coordinated with one unit of the quaternary salt type substituent in the resin. With. The complex is a complex formed by an ionic bond consisting of a quaternary cation of the resin and a metal salt anion, in which a halogen ion or a hydroxyl ion in the quaternary salt type ion exchange resin is coordinated with a metal halide. It is estimated that

The complex can be prepared by mixing a liquid in which a metal halide is dissolved in water or an organic solvent and a quaternary salt type ion exchange resin, then impregnating and adsorbing and supporting, and distilling off the solvent. When preparing a solution of a metal halide, a hydrogen halide solution may be added if necessary, or a mixed solvent composed of two or more kinds of solvents may be used as the solvent. Further, after the impregnation treatment, excess metal halide may be washed with a solvent, if necessary. The treatment temperature is not particularly limited, but when a solvent containing water is used as a treatment solvent, it is preferable to perform the treatment at a temperature in the range of 0 ° C to 60 ° C. If it exceeds 60 ° C, the metal halide may be hydrolyzed.

The complex found in the present invention has the general formula (VI
II)

[0025]

Embedded image

(In the formula, R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.) An olefin represented by the formula (IX) is reacted with formaldehyde.

[0027]

Embedded image

It has a high activity as a catalyst for producing an unsaturated alcohol represented by the formula (wherein R ⁵ , R ⁶ and R ⁷ are as defined above).

Examples of the olefin represented by the general formula (VIII) include propylene, isobutene, and 2-wherein R ⁵ , R ⁶ or R ⁷ is a hydrogen atom, an alkyl group or an aryl group.
Methyl-1-butene, 2-methyl-1-pentene, 2-
Methyl-1-hexene, 2-methyl-1-heptene, 2
-Methyl-1-octene, 2,3-dimethyl-1-butene, α-methylstyrene, α-ethylstyrene, R ⁷ and an alkyl group of R ⁵ or R ⁶ are included in a part of the same cyclic structure. Methylene cyclohexane, camphene, methylene norbornane and the like can be mentioned. Also, R ⁵ , R ⁶
Or as an example of an alkyl group in which R ⁷ is substituted with a hydroxyl group, 3
-Methyl-3-buten-1-ol, 7-octene-1
-All. Also, as an olefin,
Not only a single compound but also a mixture of the above exemplified compounds can be used.

The formaldehyde used in the present invention is a 10 to 70% aqueous solution, anhydrous formaldehyde,
In addition to paraform, hemiacetal composed of formaldehyde and alcohol is also included.

The amount of olefin used is preferably 0.5 to 50 times by mole, and particularly preferably 1 to 20 times by mole, relative to formaldehyde. When the amount of olefin used is small, the selectivity of the target unsaturated alcohol decreases, and when the amount used increases, the reaction rate decreases and the utility required for olefin recovery increases,
The industrial value decreases.

The amount of the complex used for the production of the unsaturated alcohol is such that the amount of the metal halide in the complex is 0.001 to 2 mol, based on 1 mol of the formaldehyde used. It is appropriately determined depending on the composition ratio with the quaternary salt type anion exchange resin. When the amount of the complex used is small, the reaction progresses slowly, and when the amount of the complex used is large, the decomposition of the product is promoted, and the cost of the complex catalyst increases, which causes an economical problem.

In the production of unsaturated alcohols, the general formula (VI
By reacting the olefin represented by II) with formaldehyde in a solvent in which the formaldehyde is uniformly dissolved, the yield of the target unsaturated alcohol is increased and the deactivation of the catalyst can be suppressed. The solvent used is of the general formula (VIII)
Any solvent can be used as long as it is capable of uniformly dissolving the olefin represented by and the formaldehyde and is inert to the reaction. Examples of the solvent include nitriles such as acetonitrile, fumaronitrile and malononitrile; isopropyl alcohol, isobutyl alcohol,
Examples thereof include alcohols such as t-butyl alcohol; ethers such as tetrahydrofuran and 1,4-dioxane; but are not limited thereto.

The reaction can be carried out in either a batch system or a continuous system, for example, a suspension batch system or a fixed bed continuous system.

In the case of the suspension batch system, the complex after the reaction is separated and recovered from the liquid phase component by filtration or decantation and reused, while in the case of the fixed bed continuous system, the liquid phase component is discharged from the reaction vessel outlet. Only spillage, so reuse it continuously.

[0036]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (Trimethylammonium) Methyl Chloride Substituent (4.2
100 g of styrenedivinylbenzene copolymer resin having meq / g) was suspended in 1 liter of acetonitrile, and 70 g of tin tetrachloride (SnCl ₄ ) was added dropwise over 30 minutes under ice cooling, followed by stirring at room temperature for 2 hours. . After distilling off acetonitrile under reduced pressure, 500 ml of acetonitrile
The SnCl ₄ -impregnated resin was washed 3 times, and then dried under reduced pressure to obtain a resin containing 37.1 wt% SnCl ₄ . When the Sn structure of the obtained resin was examined by solid-state NMR, a signal was observed at -730 ppm. This is the signal of SnCl ₄ itself (-680 pp
m) and SnCl ₄ are adsorbed and supported on the polyvinylstyrenedivinylbenzene copolymer, and the signal (−680 ppm: just adsorbed on the polymer causes Sn
It was confirmed that the resin formed a resin complex because it was clearly different from the same signal as Cl ₄ alone). In addition, it was calculated that the complex was SnCl ₄ coordinated with 0.54 equivalent to 1 unit of the resin amino group.

Reference Example 1 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 7.0 obtained in Example 1.
g (SnCl ₄ : 0.01 mol content) was added, and the mixture was stirred at 60 ° C. for 2 hours. The reaction pressure at this time is 8.0 kg / cm.
^{Was 2} . After cooling the reactor, the pressure of isobutene was released, and the resin complex was separated and recovered from the reaction solution by decantation. As a result of analyzing 43.2 g of the obtained reaction liquid,
1.65 g (0.055 mol) of formaldehyde remained and 2.8% of 3-methyl-3-buten-1-ol.
3 g (0.033 mol), 4,4-dimethyl-1,3-
0.03 g (0.27 mmol) of dioxane had formed. The conversion based on formaldehyde was 45%, the selectivity to unsaturated alcohol was 73%, and the selectivity to alkyl-m-dioxane was 1.2%.

Reference Example 2 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and 7.5 g of the resin complex recovered in Reference Example 1 were added, and the mixture was stirred at 60 ° C. for 2 hours. Post-treatment was carried out in the same manner as in Example 1, and the obtained reaction solution was analyzed. As a result, the conversion rate based on formaldehyde was 43%, the selectivity to unsaturated alcohol was 72%, and the alkyl-m-dioxane was selected. The selectivity to was 1.5%, and it was confirmed that the activity was retained even after repeated use.

Reference Example 3 A stainless steel reaction tube (internal volume: 10 ml) having an inner diameter of 4 mm and a length of 80 cm was filled with 6.3 g of the resin complex prepared in Example 1 and kept at 60 ° C. Isobutene 56.1g
(1.0 mol), 50% formaldehyde aqueous solution 6.0
g (0.10 mol), t-butanol 37.0 g (0.
A mixed solution of 50 mol) and 16 mg (0.16 mmol) of hydrochloric acid was sent to the reaction tube at a rate of 10 ml per hour. After 2 hours, the reaction liquid flowing out from the reaction tube was recovered, isobutene was released, and the components were analyzed. As a result, formaldehyde was not observed and 3-methyl-3-butene-
1-ol and 4,4-dimethyl-1,3-dioxane were 71% and 1.0% in yields based on formalin, respectively.
Had been generated. Subsequently, the reaction was continuously carried out, and after 50 hours, the same analysis was carried out. As a result, formaldehyde was not observed again, and 3-methyl-3-buten-1-ol and 4,4-dimethyl-1,3-dioxane were found. Since 70% and 1.2% were produced in the yield based on formalin, respectively, it was confirmed that the catalytic activity did not decrease until after 50 hours.

Example 2 100 g of a vinylpyridinedivinylbenzene copolymer resin having an N-propyl chloride substituent (3.8 meq / g) was suspended in 1 L of acetonitrile, and SnCl ₄ was cooled with ice.
After 70 g was added dropwise over 30 minutes, the mixture was stirred at room temperature for 2 hours. After distilling off the acetonitrile under reduced pressure, the SnCl ₄ -impregnated resin was washed 3 times with 500 ml of acetonitrile and then dried under reduced pressure to obtain 32.1 wt% SnCl 4.
A resin complex containing ₄ was obtained. The complex composition was found to have 0.48 equivalent of SnCl ₄ coordinated to 1 unit of the resin amino group. When the Sn structure was investigated by solid-state NMR, a signal was observed at -728 ppm in the complex obtained above, and it was revealed that SnCl ₄ was adsorbed and supported on a non-functional polyvinylstyrenedivinylbenzene copolymer (-680 ppm). It was found that the complex was formed by giving different signals. In addition, it was determined by calculation that this was a complex in which 0.48 equivalent of SnCl ₄ was coordinated to 1 unit of the resin amino group.

Reference Example 4 A stainless steel reaction tube (internal volume: 10 ml) having an inner diameter of 4 mm and a length of 80 cm was filled with 6.2 g of the resin complex prepared in Example 2 and kept at 60 ° C. Isobutene 56.1g
(1.0 mol), 50% formaldehyde aqueous solution 6.0
g (0.10 mol), t-butanol 37.0 g (0.
A mixed solution of 50 mol) and 16 mg (0.16 mmol) of hydrochloric acid was sent to the reaction tube at a rate of 10 ml per hour. After 2 hours, the reaction liquid flowing out from the reaction tube was recovered, isobutene was released, and the components were analyzed. As a result, formaldehyde was not observed and 3-methyl-3-butene-
The yields of 1-ol and 4,4-dimethyl-1,3-dioxane were 77% and 1.3%, respectively, based on formalin.
Had been generated. Subsequently, the reaction was continuously carried out, and after 50 hours, the same analysis was carried out. As a result, formaldehyde was not observed again, and 3-methyl-3-buten-1-ol and 4,4-dimethyl-1,3-dioxane were found. Since the yields based on formalin were 76% and 1.3%, respectively, it was confirmed that the catalytic activity did not decrease until 50 hours later.

Example 3 (Triethylammonium) Methyl Chloride Substituent (3.8
100 g of styrenedivinylbenzene copolymer resin having meq / g) was suspended in 1 L of acetonitrile, 70 g of SnCl ₄ was added dropwise over 30 minutes under ice cooling, and the mixture was stirred at room temperature for 2 hours. After the acetonitrile was distilled off under reduced pressure, the SnCl ₄ -impregnated resin was washed 3 times with 500 ml of acetonitrile, and subsequently dried under reduced pressure to obtain a resin complex containing 35.8 wt% SnCl ₄ . Solid NM
When the Sn structure was examined by R, a signal was observed at -730 ppm in the complex obtained above, which is clearly different from the one in which SnCl ₄ was adsorbed and supported on a non-functional polyvinylstyrenedivinylbenzene copolymer (-680 ppm). A signal was given and it was found that the complex was formed. In addition, SnCl for 1 unit of resin amino group
It was calculated that ₄ was a 0.56 equivalent coordination complex.

Reference Example 5 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 7.3 obtained in Example 3.
g (SnCl ₄ : 0.01 mol content) was added, and the mixture was stirred at 60 ° C. for 2 hours. The reaction pressure at this time is 8.0 kg / cm.
^{Was 2} . The same post-treatment as in Reference Example 1 was carried out, and the obtained reaction solution was analyzed. As a result, formaldehyde was 1.50 g.
(0.050 mol) remaining, 3.23 g (0.038 mol) of 3-methyl-3-buten-1-ol, 4,
4-dimethyl-1,3-dioxane 0.03 g (0.3
0 mmol) had formed. The conversion rate based on formaldehyde is 50%, and the selectivity to unsaturated alcohol is 75.
%, The selectivity to alkyl-m-dioxane was 1.2%.

Example 4 (Trimethylammonium) Methyl Chloride Substituent (4.2
100 g of styrenedivinylbenzene copolymer resin having meq / g) was suspended in 800 ml of acetonitrile, and a solution of 45 g of scandium chloride (ScCl ₃ ) in 200 ml of acetonitrile was added dropwise over 30 minutes under ice-cooling, followed by room temperature. It was stirred for 2 hours. After distilling off acetonitrile under reduced pressure, S with 500 ml of acetonitrile
The cCl ₃ -impregnated resin was washed 3 times and then dried under reduced pressure to obtain a resin complex containing 24.2% by weight of ScCl ₃ . In addition, ScC for 1 unit of resin amino group
It was calculated that l ₃ was coordinated in 0.50 equivalents.

Reference Example 6 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 6.2 obtained in Example 4.
Add 6 g (ScCl ₃ : 0.01 mol content), 60 ℃
For 2 hours. The reaction pressure at this time is 8.0 kg / c.
m ² . Post-treatment is performed in the same manner as in Reference Example 1,
As a result of analyzing the obtained reaction liquid, 1.71 g (0.057 mol) of formaldehyde remained, 2.35 g (0.027 mol) of 3-methyl-3-buten-1-ol, 4,4 -Dimethyl-1,3-dioxane 0.06
0 g (0.52 mmol) had formed. The conversion based on formaldehyde was 43%, the selectivity to unsaturated alcohol was 63.5%, and the selectivity to alkyl-m-dioxane was 2.4%.

Example 5 (Trimethylammonium) Methyl Chloride Substituent (4.2
100 g of styrenedivinylbenzene copolymer resin having meq / g) was suspended in 800 ml of acetonitrile, and a solution of 50 g of gallium chloride (GaCl ₃ ) dissolved in 200 ml of acetonitrile was added dropwise over 30 minutes at room temperature. It was stirred for 2 hours. After distilling off acetonitrile under reduced pressure, GaC was added to 500 ml of acetonitrile.
l ₃ impregnated resin was washed three times, followed by obtaining a resin complex containing GaCl ₃ 26.2 wt% dried under reduced pressure. In addition, one unit of resin amino group makes GaCl ₃
Was calculated to be 0.48 equivalent.

Reference Example 7 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 6.7 obtained in Example 5.
Add ₃ g (GaCl ₃ : 0.01 mol content), 60 ℃
For 2 hours. The reaction pressure at this time is 8.0 kg / c.
m ² . Post-treatment is performed in the same manner as in Reference Example 1,
As a result of analyzing the obtained reaction liquid, 1.44 g (0.048 mol) of formaldehyde remained, 2.43 g (0.028 mol) of 3-methyl-3-buten-1-ol, 4,4 -Dimethyl-1,3-dioxane 0.15
g (1.2 mmol) had formed. The conversion based on formaldehyde was 52%, the selectivity to unsaturated alcohol was 54.3%, and the selectivity to alkyl-m-dioxane was 5.2%.

Example 6 (Trimethylammonium) Methyl Chloride Substituent (4.2
100 g of styrenedivinylbenzene copolymer resin having meq / g) was suspended in 800 ml of acetonitrile, and a solution of 63 g of indium chloride (InCl ₃ ) in 200 ml of acetonitrile was added dropwise over 30 minutes under ice-cooling, followed by room temperature. It was stirred for 2 hours. After distilling off the acetonitrile under reduced pressure, In
The Cl ₃ -impregnated resin was washed 3 times and then dried under reduced pressure to obtain a resin complex containing 32.2% by weight of InCl ₃ . In addition, one unit of resin amino group is used for InCl
It was calculated that ₃ was coordinated at 0.51 equivalent.

Reference Example 8 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 6.8 obtained in Example 6.
7g (InCl _3: 0.01 molar content) was placed, 60 ° C.
For 2 hours. The reaction pressure at this time is 8.0 kg / c.
m ² . Post-treatment is performed in the same manner as in Reference Example 1,
As a result of analyzing the obtained reaction solution, 1.53 g (0.051 mol) of formaldehyde remained, 2.17 g (0.025 mol) of 3-methyl-3-buten-1-ol, 4,4 -Dimethyl-1,3-dioxane 0.17
g (1.5 mmol) had formed. The conversion based on formaldehyde was 49%, the selectivity to unsaturated alcohol was 49.4%, and the selectivity to alkyl-m-dioxane was 6.1%.

Comparative Example 1 Bulletin of the Chemical Society of
Japan (Bulletin of the Chemical Society of Japa
n), 42, p. 1760 (1969), a complex composed of iron (III) chloride (FeCl ₃ ) and a quaternary ammonium salt type ion exchange resin was prepared by the following operation. Methyl chloride (trimethylammonium) chloride substituent (4.2 me
The column was packed with 100 g of styrenedivinylbenzene copolymer resin having q / g). FeCl ₃ 65g 40
After pouring the solution dissolved in 0 ml of 7M hydrochloric acid solution into the column, excess solution was washed out with 7M hydrochloric acid solution and removed. Remove the treated ion-exchange resin from the column,
Drying under reduced pressure gave a resin complex containing 40.9 wt% FeCl ₃ .

Reference Example 9 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 3.9 obtained in Comparative Example 1.
Add 7 g (containing FeCl ₃ : 0.01 mol) at 60 ° C.
For 2 hours. After the same post-treatment as in Reference Example 1, the reaction solution obtained was analyzed and as a result, formaldehyde was 1.9.
6 g (0.065 mol) remains, 3-methyl-3-
0.56 g (6.45 mmol) of buten-1-ol, 0.21 of 4,4-dimethyl-1,3-dioxane
g (1.8 mmol) had formed. The conversion based on formaldehyde was 34.8%, the selectivity to unsaturated alcohol was 18.5%, and the selectivity to alkyl-m-dioxane was 10.4%.

[0053]

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a novel complex consisting of a specific metal halide and a quaternary salt type ion exchange resin, which is useful as a catalyst for the production of unsaturated alcohol by the reaction of olefin and formaldehyde. did. Since the complex is a solid, it can be reused after separation and recovery from the reaction solution by a simple method such as filtration or decantation.

Claims (2)

[Claims] 1. A compound of the general formula (I) (In the formula, M represents at least one metal selected from the group consisting of tin, gallium, indium, and scandium, X ₁ represents a halogen atom, and q represents an integer equal to the valence number of M.) A complex comprising a specific metal halide represented by and a quaternary salt type anion exchange resin. 2. The complex according to claim 1, wherein the metal halide is SnCl ₄ .