JPH11199531A - Production of trimethylolalkane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a trimethylolalkane, capable of easily producing the trimethylolalkane having a high quality in a high yield without lowering the yield due to the by-production of the formate ester of the trimethylolalkane. SOLUTION: This method for producing trimethylolalkane comprises reacting an n-alkanal with formaldehyde in the presence of a tertiary amine and water. Therein, the reaction mixture is heated at a temperature capable of thermally dissociating a by-produced formic acid-tertiary amine salt to distill out the tertiary amine and water, and the trimethylol alkane formate ester contained in the residue is reacted with water, ammonia, a primary amine or a secondary amine to produce the trimethylolalkane. The trimethylol alkane formate ester is reacted with the water to produce the trimethylolalkane and simultaneously hydrogen and carbon dioxide and/or water and carbon monoxide. The trimethylol alkane formate ester is also reacted with the ammonia, the primary amine or the secondary amine to produce the trimethylolalkane and simultaneously formaldehyde compounds. But the by-products can easily be separated from the trimethylolalkane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing trimethylolalkane by reacting n-alkanal with formaldehyde in the presence of a tertiary amine and water. Trimethylolalkanes are useful as raw materials for alkyd resins, polyurethane resins, (un) saturated polyester resins, synthetic lubricating oils, surfactants, reactive monomers and the like.

[0002]

2. Description of the Related Art As a method for producing trimethylolalkane, a method is known in which n-alkanal and formaldehyde are reacted in the presence of an alkali metal or alkaline earth metal hydroxide. In this method, alkali metal or alkaline earth metal formate is by-produced. Trimethylolalkane undergoes catalytic pyrolysis by its formate, so when performing distillation, which is a normal isolation and purification method for trimethylolalkane, avoid a decrease in the yield of trimethylolalkane due to its catalytic pyrolysis. Therefore, the separation between trimethylolalkane and alkali metal or alkaline earth metal formate must be sufficient. For this reason, the separation operation becomes complicated.

As an improved method of this production method, a method of producing trimethylolalkane by replacing a hydroxide of an alkali metal or an alkaline earth metal with a tertiary amine and water (West German Patent 1952738) has been proposed. ing. In the method using the tertiary amine, the formate as a by-product is a tertiary amine formate having no catalytic thermal decomposition action on trimethylolalkane, and the thermal decomposition of trimethylolalkane can be suppressed. This method uses a boiling point difference between a tertiary amine formate and a trimethylolalkane to separate and remove a tertiary amine formate.

[0004]

However, this improved method has the following disadvantages. That is, during the separation of the formic acid tertiary amine salt and the trimethylolalkane using the boiling point difference, formic acid and trimethylolalkane generated by thermal dissociation of the tertiary amine formate react with trimethylol Alkane formate is formed. As a result, the yield of trimethylolalkane decreases.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have intensively studied a method for producing trimethylolalkane by reacting n-alkanal with formaldehyde in the presence of a tertiary amine and water. . As a result, the reaction mixture is heated to a temperature at which by-product tertiary amine salt of formic acid contained in the reaction mixture after the reaction is thermally dissociated into formic acid and tertiary amine, and the tertiary amine and tertiary amine are removed from the reaction mixture. Distill water and then reacting the resulting residue with water, ammonia, primary amine or secondary amine,
The formate of trimethylolalkane formed in the process of distilling the tertiary amine and water and contained in the residue is easily and efficiently decomposed to form trimethylolalkane, and the formate of trimethylolalkane is formed. The present inventors have found that the yield of trimethylolalkane does not decrease, and have reached the present invention. Furthermore, the present inventors have found that the tertiary amine distilled off from the reaction mixture after the completion of the reaction can be reused in the production of trimethylolalkane, leading to the present invention.

That is, the present invention relates to (1) a method for producing a trimethylolalkane by reacting n-alkanal with formaldehyde in the presence of a tertiary amine and water; The tertiary amine and water are distilled out by heating the reaction mixture after completion of the reaction to a temperature at which the tertiary amine and water can be thermally dissociated, and the trimethylolalkane formed in the process of distilling the tertiary amine and water and contained in the residue is removed. A method for producing trimethylolalkane by reacting a formic acid ester with water, ammonia, a primary amine or a secondary amine to produce trimethylolalkane; (2) a third method of distilling from a reaction mixture after completion of the reaction. A method for producing a trimethylolalkane according to (1), wherein the secondary amine is reused for producing a trimethylolalkane.

As described above, the method of the present invention thermally dissociates the tertiary amine formate by-produced and decomposes the formate of trimethylolalkane contained in the residue to produce trimethylolalkane. Therefore, this is a method for producing trimethylolalkane which does not substantially produce formate or formate. In the present invention, the tertiary amine distilled from the reaction mixture after the completion of the reaction can be reused for producing trimethylolalkane.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a method for producing a trimethylolalkane by reacting an n-alkanal with formaldehyde in the presence of a tertiary amine and water comprises the following steps: Formation of aldol by the aldol condensation reaction of n-alkanal with formaldehyde under the following conditions: Consisting of generation.

After the above-mentioned aldol condensation reaction and cross-cannizzaro reaction, the resulting reaction mixture is heated to a temperature at which by-product tertiary amine formate can be thermally dissociated to distill the tertiary amine. Thermal dissociation of the tertiary amine salt of formic acid produces formic acid and a tertiary amine. The generated formic acid reacts with trimethylolalkane to form a formate of trimethylolalkane.

Taking, for example, the case of using triethylamine as the tertiary amine and n-butanal as the n-alkanal, the aldol condensation reaction, the cross-cannizzaro reaction, the thermal dissociation of the tertiary amine formate and the trimethylol of the present invention. The reaction for forming the formate of the alkane is shown by the following reaction formulas.

(1) Aldol condensation reaction CH ₃ CH ₂ CH ₂ CHO + 2HCHO → CH ₃ CH
₂ C (CH ₂ OH) ₂ CHO

(2) Cross-cannibalism reaction CH ₃ CH ₂ C (CH ₂ OH) ₂ CHO + HCHO +
N (C ₂ H ₅ ) ₃ + H ₂ O → CH ₃ CH ₂ C (CH ₂ O
^{_{H) 3 + HCOO - N +}} H (C 2 H 5) 3

(3) Thermal dissociation of tertiary amine formate and formation reaction of formate of trimethylolalkane HCOO ^- N ⁺ H (C ₂ H ₅ ) ₃ → HCOOH + N
(C ₂ H ₅ ) ₃ CH ₃ CH ₂ C (CH ₂ OH) ₃ + nHCOOH → C
H ₃ CH ₂ C (CH ₂ OCHO) _n (CH ₂ OH) _{3- n} (where n is 1, 2 or 3)

The tertiary amine produced by the reaction (3) is distilled off by heating. The formate of trimethylolalkane by-produced by the reaction (3) remains in the residue. In the present invention, the formate of trimethylolalkane contained in this residue is reacted with water, ammonia, a primary amine or a secondary amine to produce trimethylolalkane.

When the formate of trimethylolalkane is reacted with water, the formate of trimethylolalkane is decomposed to produce trimethylolalkane, hydrogen and carbon dioxide and / or water and carbon monoxide. Taking the case of using triethylamine as the tertiary amine and n-butanal as the n-alkanal as an example, this reaction is shown by the reaction formula as follows.

CH ₃ CH ₂ C (CH ₂ OCHO) _n (CH _{2
OH) 3-n + nH 2} O → CH 3 CH 2 C (CH 2 O
_{H) 3 + m (H 2} + CO 2) + l (H 2 O +
CO) (wherein n is 1, 2 or 3, l and m are 0 to 3, and 1 + m = n)

When the formate of trimethylolalkane is reacted with ammonia, primary amine or secondary amine, trimethylolalkane and formamides are formed. Triethylamine as a tertiary amine,
Taking the case where n-butanal and ammonia are used as the n-alkanal and dimethylamine as the primary amine or the secondary amine as an example, this reaction is represented by the following reaction formula.

CH ₃ CH ₂ C (CH ₂ OCHO) _n (CH _{2
OH) 3-n + n (} CH 3) 2 NH → CH 3 CH 2 C (C
H ₂ OH) ₃ + nHCON (CH ₃ ) ₂ (where n represents 1, 2 or 3)

Next, the aldol condensation reaction and the cross-Cannizzaro reaction in the present invention will be described. Examples of the n-alkanal in the present invention include propanal, n-butanal, n-pentanal, 3-methylbutanal, and n-alkanal.
-Hexanal, 3-methylpentanal, n-heptanal, 4-methylhexanal, n-octanal and the like.

Formaldehyde is usually 5 to 50% by weight.
An aqueous solution containing formaldehyde (i.e., formalin) is used, preferably 5 to 50% by weight formalin having a methanol content of 1% by weight or less.

As the tertiary amine, one having a boiling point lower than that of trimethylolalkane and that of formate of trimethylolalkane is used. If such a tertiary amine is used, the tertiary amine can be easily distilled and recovered by heating the reaction mixture after the reaction. Preferred tertiary amines include trimethylamine, triethylamine, tri (n-propyl) amine, triisopropylamine, tri (n-butyl) amine, triisobutylamine, diethylmethylamine,
Aliphatic tertiary monoamines such as dimethylethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine and dimethylisobutylamine, triethylenediamine, N, N, N ',
N'-tetramethylethylenediamine, N, N, N ',
Aliphatic tertiary diamines such as N'-tetramethyl-1,3-propanediamine; nitrogen-containing heterocyclic tertiary such as N-methylmorpholine, N-ethylmorpholine, N-methylpiperidine, N-ethylpiperidine Amines and the like. These can be used alone or in combination of two or more.
A particularly preferred tertiary amine is triethylamine.

The molar ratio of n-alkanal, formaldehyde and tertiary amine is 3 to 4 mol, preferably 3. mol, per mol of n-alkanal.
2 to 3.6 moles and the tertiary amine is 1 to 2 moles, preferably 1.1 to 1.5 moles. If formaldehyde is used in an amount larger than the above range, it becomes difficult to recover the tertiary amine, which is not preferable. Further, even if the tertiary amine is used in an amount larger than the above range, the yield of trimethylolalkane will not be further improved, and the cost of the acid required for neutralization and the time required for the recovery of the tertiary amine will be rather long. Absent.

The amount of water used is 200 to 6 based on the total of n-alkanal, formaldehyde and tertiary amine.
00% by weight, preferably 250-500% by weight.

The reaction temperature of the aldol condensation reaction is -5 to 9
0 ° C, preferably 10 to 60 ° C. If the temperature is lower than −5 ° C., the reaction rate is extremely slow. Further, the reaction temperature of the cross cannizzaro reaction is 20 to 90 ° C, preferably 40 to 90 ° C.
80 ° C. If the temperature is lower than 20 ° C., a considerably long time is required for the reaction. In the present invention, since the aldol condensation reaction and the cross-cannizzaro reaction proceed sequentially, it is more preferable that the aldol condensation reaction is first performed mainly at 10 to 40 ° C, and then the cross-cannizzaro reaction is mainly performed at 40 to 80 ° C. Do.

After completion of the aldol condensation reaction and the cross-Cannizzaro reaction, the resulting reaction mixture is heated to a temperature at which by-product tertiary amine formate can be thermally dissociated to distill tertiary amine and water. If the reaction mixture is finally heated to 120 to 190 ° C., the formic acid tertiary amine salt is thermally dissociated into formic acid and tertiary amine, and the tertiary amine and water can be distilled from the reaction mixture. Heating of the reaction mixture may be performed under reduced pressure, normal pressure, or under pressure. The tertiary amine distilled off can be reused in the production of the trimethylolalkane of the present invention. Distillation of the tertiary amine and water by heating the reaction mixture is carried out such that the water content in the residue is less than 20% by weight. In this way, the tertiary amine can be recovered with a high yield. In particular, a method of distilling almost the entire amount of water is preferable because a tertiary amine can be recovered in a high yield. The residue obtained by distilling off the tertiary amine and water contains the formate of trimethylolalkane in which formic acid generated by thermal dissociation has reacted with trimethylolalkane.

Next, the obtained residue is reacted with water, ammonia, a primary amine or a secondary amine. When reacting with water, the mixture is heated in the presence of water to decompose the formate of trimethylolalkane contained in the residue into trimethylolalkane, hydrogen and carbon dioxide, and / or water and carbon monoxide. The amount of water is 10
5 to 50 parts by weight, preferably 7 to 0 parts by weight,
-30 parts by weight. If the amount of water is less than the above range,
When the formate of trimethylolalkane is hardly decomposed and the amount of water is larger than the above range, there is no particular problem in the decomposition reaction, but the above range is preferable because the efficiency of the container is lowered. The amount of water can be adjusted to the above range by controlling the amount of water distilled when distilling the tertiary amine and water from the reaction mixture by heating the reaction mixture. A method in which the amount of water in the above range is added to the residue obtained by distilling substantially all of the amine and water is preferable.

The reaction between the formate of trimethylolalkane and water can be carried out more easily and efficiently by heating under pressure. When a noble metal catalyst is not used, it is usually 6.9 MPa (70 kgf / cm ² )
Under the following pressure, preferably 3.4 to 5.9 MPa (35
加 圧 60 kgf / cm ² )
It is carried out at 300 ° C, preferably at 210-280 ° C. In this case, the decomposition of the formate of trimethylolalkane proceeds efficiently, and the trimethylolalkane can be produced from the formate of trimethylolalkane in high yield.

The reaction between the formate of trimethylolalkane and water can be carried out more easily and efficiently by heating in the presence of a noble metal catalyst.

As the noble metal catalyst used, ruthenium catalyst, rhodium catalyst, palladium catalyst, osmium catalyst,
Yttrium catalysts, platinum catalysts and the like can be mentioned. Among them, a palladium catalyst is particularly preferable. Further, a noble metal catalyst obtained by modifying these noble metal catalysts with a Group 14 element of the periodic table may be used. In particular, a noble metal catalyst modified with a lead element is preferable. One or more of these noble metal catalysts can be used.

The noble metal catalyst is generally carbon, alumina,
In addition to a carrier such as silica, a carrier such as a polymer compound having a basic nitrogen atom group in which a noble metal is supported by 0.5% by weight to 10% by weight is used. The usage form is powder, granule, or pellet. A suspension method or a fixed bed method is used as a reaction method between trimethylolalkane formate and water in the presence of a noble metal catalyst.

The amount of the noble metal catalyst used is in the range of 1 to 15% by weight as a noble metal based on 100% by weight of formic acid (HCOOH) generated by hydrolysis of the formate of trimethylolalkane contained in the residue.

When a solid acid catalyst is used in combination with a noble metal catalyst to decompose the trimethylolalkane formate of the present invention, the time required for decomposing the trimethylolalkane formate can be reduced. Examples of the solid acid catalyst include γ-aluminum oxide, silica-alumina, acidic ion exchangers, natural and synthetic zeolites, heteropoly acids, and the like, and one or more of these can be used.

The amount of the solid acid catalyst used is 0.1 to 100% by weight of formic acid (HCOOH) generated by hydrolysis of the formate of trimethylolalkane contained in the residue.
-5 parts by weight.

When a noble metal catalyst is used, the reaction between the formate of trimethylolalkane and water is carried out under normal pressure or under a pressure of 1.96 MPa (20 kgf / cm ² ) or less.
Preferably 0.49 to 1.47 MPa (5 to 15 kgf
/ Cm ² ), 50-300 ° C, preferably 80-250
Perform at ° C. In this way, the decomposition of the formate of trimethylolalkane proceeds efficiently, and the trimethylolalkane can be produced from the formate of trimethylolalkane in high yield.

When the formic ester of trimethylolalkane in the residue is reacted with ammonia, primary amine or secondary amine, the residue is mixed with ammonia, primary amine or secondary amine. Reaction produces trimethylolalkane and formamides.

The primary amine and the secondary amine include 1
A compound having at least one nitrogen atom bonded to one or two hydrogen atoms in a molecule, preferably a primary compound having one nitrogen atom bonded to one or two hydrogen atoms in a molecule. Monoamines and secondary monoamines. That is, the ammonia, primary amine or secondary amine to be reacted with the formate of trimethylolalkane is preferably ammonia, primary monoamine or secondary monoamine.

Examples of the primary monoamine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine,
Aliphatic primary such as n-pentylamine, isopentylamine, neopentylamine, n-hexylamine, 2-methylpentylamine, 3-methylpentylamine, 2,2-dimethylbutylamine and 2,3-dimethylbutylamine Monoamines; cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and a methyl group at the carbon atom of the ring of these alicyclic amines;
An alicyclic primary monoamine such as an amine to which an aliphatic hydrocarbon group such as an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group is bonded; and aniline;
Benzylamine, α-phenethylamine, β-phenethylamine, and methyl, ethyl, n-propyl, isopropyl, n-
Primary monoamines such as amines to which an aliphatic hydrocarbon group such as a butyl group and an isobutyl group are bonded.

As the secondary monoamine, for example, a hydrogen atom bonded to the nitrogen atom of the above-mentioned primary monoamine further has one methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. , Isobutyl group, n
-Substituted with an aliphatic hydrocarbon group such as a pentyl group and an n-hexyl group. Specifically, fats such as dimethylamine, diethylamine, di (n-propyl) amine, diisopropylamine, di (n-butyl) amine, diisobutylamine, di (n-pentyl) amine and di (n-hexyl) amine Group secondary monoamines; N-methylcyclopropylamine, N-ethylcyclopropylamine, N-methylcyclobutylamine, N-ethylcyclobutylamine, N-methylcyclopentylamine, N
Alicyclic secondary monoamines such as -ethylcyclopentylamine, N-methylcyclohexylamine and N-ethylcyclohexylamine; N-methylaniline, N-ethylaniline, N-methylbenzylamine, N-ethylbenzylamine, N- Methyl-α-phenethylamine, N-
Aromatic secondary monoamines such as ethyl-α-phenethylamine, N-methyl-β-phenethylamine, N-ethyl-β-phenethylamine; and pyrrolidine, piperidine, homopiperidine, morpholine and methyl at the carbon atom of the ring of these compounds Group, ethyl group, n-propyl group,
Nitrogen-containing cyclic secondary monoamines such as a compound to which an aliphatic hydrocarbon group such as an isopropyl group, an n-butyl group and an isobutyl group are bonded.

The amount of ammonia, primary amine or secondary amine used is usually 1 mol or more, preferably 1.1 to 2.0 mol, per 1 mol of formic acid component in the formate of trimethylolalkane. is there. If the amount of ammonia, primary amine or secondary amine is less than the above range, formate of trimethylolalkane remains.

The reaction temperature at which the formate of trimethylolalkane contained in the residue is reacted with ammonia, a primary amine or a secondary amine is not lower than ordinary temperature, preferably from ordinary temperature to 130 ° C. May be any of normal pressure, reduced pressure, and increased pressure. Since the reaction is an exothermic reaction, it is preferred that ammonia, a primary amine or a secondary amine be added dropwise to the residue while maintaining the above-mentioned temperature with stirring. Ammonia, primary or secondary amine can be dissolved in a solvent and mixed with the residue, the preferred solvent being water.

The method of the present invention may be carried out in any of a batch system and a continuous system. A method for carrying out a preferred embodiment of the present invention batch-wise will be described. Formaldehyde (3.2 to 1 mol of n-alkanal)
3.6 mol) and water (250-500 based on the total amount of n-alkanal, formaldehyde and tertiary amine).
Wt%), the reaction temperature is set to 10 to 40 ° C.
N-alkanal and tertiary amine (n-
1 to 1.5 mol per mol of alkanal)
And then complete the aldol condensation reaction in 1 to 3 hours at 40 to 60 ° C.
Complete the cross-canizallo reaction in 2 hours. After completion of the reaction, an excess of tertiary amine is added to the excess formaldehyde, if necessary, and treated with a copper oxide catalyst at 60 to 80 ° C. for 1 to 4 hours to obtain a tertiary amine salt of methanol and formic acid. The copper oxide catalyst is used in an amount of 0.5 to 5% by weight, preferably 1%, based on the reaction mixture.
Use up to 3% by weight. After treatment with a copper oxide catalyst, excess tertiary amine is neutralized with formic acid, methanol and water are distilled off from the reaction mixture under reduced pressure, and then most of the water is distilled off. Distilled and recovered as an azeotrope with Distillation of methanol, water and tertiary amine
Finally, heating is performed to 140 to 250 ° C. The tertiary amine and water mixture recovered as an azeotrope with water can be reused as it is or by circulating the tertiary amine separated from water to the reaction system.

In the case where the formate of trimethylolalkane is reacted with water to form trimethylolalkane, and when no noble metal catalyst is used, the tertiary amine and water are distilled off and the residue is removed. 5 to 50 parts by weight of water is added to 100 parts by weight, and 3.4 to 5.9 MPa.
(35-60 kgf / cm ² ) under pressure of 210-2
Heat to 80 ° C. to decompose the formate of trimethylolalkane into trimethylolalkane and hydrogen and carbon dioxide and / or water and carbon monoxide, and remove hydrogen and carbon dioxide and / or water and carbon monoxide out of the system. Remove.

In the case where the formate of trimethylolalkane is reacted with water to produce trimethylolalkane, and in the case where a noble metal catalyst is used, the tertiary amine and water are distilled off, and the residue 100 After adding 5 to 50 parts by weight of water with respect to parts by weight and adding a noble metal catalyst or a solid acid catalyst, 1.96 MPa (20 kgf /
While heating to 80 to 250 ° C. under a pressure of not more than ² cm ² ), the formate of trimethylolalkane is decomposed into trimethylolalkane and hydrogen and carbon dioxide and / or water and carbon monoxide, and hydrogen and carbon dioxide and / or
Alternatively, water and carbon monoxide are removed from the system.

The residue obtained by decomposing the formate of trimethylolalkane and removing hydrogen and carbon dioxide and / or water and carbon monoxide out of the system is used as it is or when the noble metal catalyst is not used. When used, it is filtered and then distilled, so that high-quality trimethylolalkane can be easily isolated.

When the formate of trimethylolalkane is reacted with ammonia, primary amine or secondary amine to form trimethylolalkane and formamides, the residue obtained by distilling tertiary amine and water is used. Ammonia, primary amine or secondary amine (1 mol or more per 1 mol of formic acid component in the formate of trimethylolalkane) at room temperature to 130 ° C under stirring.
Is reacted dropwise with the formate of trimethylolalkane in the residue to produce trimethylolalkane and formamides. From the reaction mixture obtained, trimethylolalkane and formamides can be separated and recovered by distillation or the like.

[0046]

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

Example 1 3822.4 g (8.91 mol of formaldehyde) of a 7% aqueous solution of formaldehyde were charged into a 5-liter reactor equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel, and the internal temperature was lowered to 20 ° C. N-butanal 1
94.7 g (2.70 mol) and triethylamine 30
3.6 g (3.00 mol) of 1. g from a separate dropping funnel.
It was added dropwise over 5 hours. Then, the temperature was raised to 40 ° C.
After reacting for 5 hours, the temperature was raised to 60 ° C. and reacted for 1 hour, and further raised to 80 ° C. and reacted for 1 hour. After completion of the reaction, 100 g of a copper oxide catalyst was added, and 53.5 g (0.53 mol) of triethylamine was further added, followed by stirring at 70 ° C. for 2 hours to treat excess formaldehyde. The reaction solution was filtered to remove the copper oxide catalyst, and the pH was adjusted to 5 by adding 14.0 g of formic acid. Reaction solution 438 with pH adjustment
8.2 g was heated to 60 ° C. under a reduced pressure of 18.66 kPa (140 mmHg), and 17.9 g of methanol and 3
Distill 60 g and then 33.32 kPa (250 mm
Under reduced pressure of Hg), the mixture was heated to 80 ° C. to distill out 720 g of water, and further heated to 180 ° C. under normal pressure to distill and collect 355 g (3.51 mol) of triethylamine as a mixed solution with 2470 g of water. Then the residue 465.3
80 g of water, and 4.9 MPa (50 kgf / c
m ² ) under pressure and heated to 240 ° C. for 2.5 hours to decompose the formate of trimethylolpropane in the residue into trimethylolpropane and hydrogen, carbon dioxide, water and carbon monoxide. Carbon dioxide, water and carbon monoxide were removed out of the system. 440 g of residue were obtained, which did not contain formic acid and formate of trimethylolpropane. The obtained residue was subjected to 33.32 kPa
(250 mmHg) under reduced pressure and heated to 80 ° C.
5.5 g were distilled off. Then 0.4 kPa (3 mmH
g) Distillation under reduced pressure of trimethylolpropane 311
g (2.32 mol) was obtained (yield based on n-butanal: 86%).

Example 2 A mixed solution of triethylamine and water recovered in Example 1 was separated at 40 ° C. to separate triethylamine. 151.8 g (1.50 mol) of triethylamine separated
And the production of trimethylolpropane was carried out in the same manner as in Example 1 except that the scale of the reaction was reduced to half. As a result, 152 g of trimethylolpropane (1.
13 mol) (yield based on n-butanal: 84)
%). The residue after decomposition of the formate of trimethylolpropane did not contain formic acid or formate of trimethylolpropane.

Comparative Example 1 Reaction solution 43 adjusted to pH 5 obtained in the same manner as in Example 1.
Using 88 g, the reaction solution was charged at 18.66 kPa (1
Under reduced pressure of 40 mmHg), the mixture was heated to 60 ° C. to distill off 18 g of methanol and 375 g of water.
a (250 mmHg) under reduced pressure and heated to 80 ° C. to distill 828 g of water.
Under the reduced pressure of g), at 50 ° C., 2301 g of water, 71 g (0.70 mol) of triethylamine and 364 g (2.47 mol) of triethylamine formate were distilled off. 429 g of the obtained residue [266 g of trimethylolpropane (1.98 g)
Mol, yield 73% based on n-butanal), formic ester of trimethylolpropane 110 g (monoester 104 g: 0.64 mol, diester 6 g: 0.03 mol, triester: trace amount), triethylamine formate 5
2 g (0.35 mol)] at 0.4 kPa (3 mm
Hg) under reduced pressure to give 150 g of formate of trimethylolpropane (133 g of monoester: 0.82
Mol, 8 g of diester: 0.04 mol, triester:
Traces) and 246 g of trimethylolpropane (1.83)
Mol; yield based on n-butanal 68%).

Example 3 Reaction solution 43 adjusted to pH 5 obtained in the same manner as in Example 1
88.2 g was heated to 60 ° C. under a reduced pressure of 18.66 kPa (140 mmHg) to distill 17.9 g of methanol and 360 g of water, and then distilled at 33.32 kPa (250 mHg).
The mixture was heated to 80 ° C. under reduced pressure of mHg) to distill out 720 g of water, and further heated to 180 ° C. under normal pressure to distill and collect 355 g (3.51 mol) of triethylamine as a mixed solution with 2470 g of water. The residue 465.
72 g of water was added to 3 g, 16 g of 5% palladium / carbon powder (50% water-containing product) was added, and 0.98 MPa (10 k
gf / cm ² ) under pressure and heated to 200 ° C. for 2.5 hours to decompose the formate of trimethylolpropane in the residue into trimethylolpropane, hydrogen, carbon dioxide, water and carbon monoxide, Hydrogen, carbon dioxide, water and carbon monoxide were removed out of the system. 450 g of the residue was filtered to obtain 4
38 g of filtrate were obtained. The filtrate contained no formic acid and no formate of trimethylolpropane. The obtained filtrate was heated to 80 ° C. under a reduced pressure of 33.32 kPa (250 mmHg) to distill 73.5 g of water. Then, distillation under reduced pressure of 0.4 kPa (3 mmHg) gave 311 g (2.32 mol) of trimethylolpropane (yield based on n-butanal: 86%).

Example 4 5% palladium / carbon powder (50%) used in Example 3
% Hydrous product) was replaced with 16 g of 5% palladium-1% lead / carbon powder (50% hydrous product) in the same manner as in Example 3, and finally trimethylolpropane 31 was used.
1 g (2.32 mol) was obtained (yield based on n-butanal: 86%). The decomposition of the formate of trimethylolpropane was completed in 0.5 hours, and the residue after the decomposition did not contain formic acid and formate of trimethylolpropane.

Example 5 The 5% palladium / carbon powder (50%) used in Example 3 was used.
% Hydrous product) and 16 g of 2% palladium / carbon powder (50% hydrous product) and a silica-alumina catalyst [N-
631HN: product of Nikki Chemical Co., Ltd.], and finally 311 g (2.32 mol) of trimethylolpropane was obtained (yield based on n-butanal: 86%) except that 5 g was used. The decomposition of the formate of trimethylolpropane was completed in 2.0 hours, and the residue after the decomposition contained no formic acid or formate of trimethylolpropane.

Example 6 A mixed solution of triethylamine and water recovered in Example 3 was separated at 40 ° C. to separate triethylamine. Example 3 with the exception that 151.8 g (1.50 mol) of triethylamine separated were used and the scale of the reaction was halved.
Production of trimethylolpropane was performed in the same manner as described above.
As a result, 152 g of trimethylolpropane (1.13
Mol) was obtained (yield based on n-butanal: 84)
%). The residue after decomposition of the formate of trimethylolpropane did not contain formic acid or formate of trimethylolpropane.

Example 7 A reaction solution 43 adjusted to pH 5 obtained in the same manner as in Example 1
Under reduced pressure of 88.2 g to 18.66 kPa (140 mmHg), the mixture was heated to a temperature of 60 ° C. and heated to 17.9 g of methanol.
And 360 g of water are distilled off, and then 33.32 kPa (25
Under reduced pressure of 0 mmHg) to a temperature of 80 ° C.
Then, the residue was heated to 180 ° C. under normal pressure, and 355 g (3.51 mol) of triethylamine was added to 2470 of water.
g and distilled off and collected. To 465.3 g of the obtained residue, 370.2 g of a 47% by weight aqueous dimethylamine solution was maintained while maintaining the temperature at 50 ° C. or lower while stirring and cooling.
The reaction was carried out while dropping (dimethylamine, 3.86 mol) over a period of 1 hour, and the reaction was terminated by maintaining the same temperature for 1 hour. After the completion of the reaction, no formic acid or formate of trimethylolpropane was found in the reaction mixture.
835.5 g of this reaction mixture was added to 101.3 kPa (7
Under normal pressure of 60 mmHg), heat to 120
6 g and 16 g of dimethylamine are distilled off and then 4 kP
a, heated to 80 ° C. under reduced pressure of 30 mmHg,
256 g of N-dimethylformamide were distilled off. The obtained residue was distilled under reduced pressure of 0.4 kPa (3 mmHg) to obtain 315 g (2.35 mol) of trimethylolpropane.
Was obtained (yield based on n-butanal: 87%).

Example 8 A mixture of triethylamine and water recovered in Example 7 was separated at 40 ° C. to separate triethylamine. 151.8 g (1.50 mol) of triethylamine separated
And trimethylolpropane was produced in the same manner as in Example 7 except that the scale was reduced to 1/2. As a result, 156 g (1.16 mol) of trimethylolpropane was obtained (yield based on n-butanal: 86%).
The reaction mixture after the reaction with dimethylamine did not contain formic acid and formate of trimethylolalkane.

Example 9 In Example 7, piperidine 3 was used in place of dimethylamine.
Example 7 except that 28.1 g (3.86 mol) was used.
The same was done. Formic acid and trimethylolpropane formate were not found in the reaction mixture after piperidine was added and reacted. The reaction mixture 793.
4 g was heated to 120 ° C. under normal pressure of 101.3 kPa (760 mmHg) to distill 30.5 g of piperidine, and then 120 g under reduced pressure of 4 kPa (30 mmHg).
The mixture was heated to 70 ° C. to distill 395.7 g of N-formylpiperidine. The obtained residue was treated with 0.4 kPa (3 mmH
g) Distillation under reduced pressure of trimethylolpropane 311
g (2.32 mol) was obtained (yield based on n-butanal: 86%).

Example 10 The procedure of Example 7 was repeated, except that 234.8 g (3.86 mol of ammonia) of a 28% by weight aqueous ammonia solution was used instead of dimethylamine. Formic acid and formate of trimethylolpropane were not confirmed in the reaction mixture after the reaction by adding the aqueous ammonia solution. 700.1 g of this reaction mixture was added to 101.
The mixture was heated to 120 ° C. under normal pressure of 3 kPa (760 mmHg) to distill 169 g of water and 6 g of ammonia, and then heated to 120 ° C. under reduced pressure of 4 kPa (30 mmHg) to distill 158 g of formamide. The obtained residue was distilled under reduced pressure of 0.4 kPa (3 mmHg) to obtain 315 g (2.35 mol) of trimethylolpropane (yield based on n-butanal: 87%).

[0058]

According to the method for producing trimethylolalkane of the present invention, the yield of trimethylolalkane does not decrease due to the formation of formate of trimethylolalkane, and high-yield and high-quality trimethylolalkane can be easily and efficiently obtained. Methylol alkanes can be produced. Also, since tertiary amines can be recovered and the tertiary amines recovered can be reused in the production of trimethylolalkane, a great advantage can be expected as compared with conventionally known production methods. The process for producing alkanes is a very advantageous industrial process.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 29/80 C07C 29/80 29/92 29/92 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Shingo Uji Chiba No. 25, Kita-sode, Sodegaura-shi Koei Chemical Industry Co., Ltd.

Claims (16)

[Claims] In producing trimethylolalkane by reacting n-alkanal with formaldehyde in the presence of a tertiary amine and water, a temperature at which by-product tertiary amine salt of formic acid can be thermally dissociated is used. The reaction mixture after completion of the reaction is heated to distill the tertiary amine and water, and the formate of trimethylolalkane generated in the process of distilling the tertiary amine and water and contained in the residue is converted to water, ammonia,
A process for producing trimethylolalkane, which comprises reacting with a primary amine or a secondary amine to produce trimethylolalkane. 2. The formate of trimethylolalkane contained in the residue is reacted with water under heating to produce trimethylolalkane, hydrogen and carbon dioxide, and / or water and carbon monoxide. A method for producing the described trimethylolalkane. 3. The process for producing trimethylolalkane according to claim 2, wherein the reaction between the formate of trimethylolalkane and water is carried out under a pressure of 6.9 MPa or less. 4. The process for producing trimethylolalkane according to claim 3, wherein the reaction between the formate of trimethylolalkane and water is carried out at 200 to 300 ° C. 5. The process for producing trimethylolalkane according to claim 2, wherein the reaction between the formate of trimethylolalkane and water is carried out in the presence of a noble metal catalyst. 6. The method for producing trimethylolalkane according to claim 5, wherein the noble metal catalyst is a palladium catalyst. 7. The method for producing trimethylolalkane according to claim 5, wherein the noble metal catalyst is a noble metal catalyst modified with a lead element. 8. The method for producing trimethylolalkane according to claim 6, wherein the palladium catalyst is a palladium catalyst modified with a lead element. 9. The process for producing a trimethylol alkane according to claim 5, wherein the reaction between the formate of trimethylol alkane and water is carried out in the presence of a solid acid catalyst. 10. The process for producing a trimethylol alkane according to claim 5, wherein the reaction between the formate of trimethylol alkane and water is carried out at normal pressure or under a pressure of 1.96 MPa or less. 11. The process for producing trimethylolalkane according to claim 10, wherein the reaction between the formate of trimethylolalkane and water is carried out at 50 to 300 ° C. 12. The process for producing trimethylolalkane according to claim 2, wherein 5 to 50 parts by weight of water is added to 100 parts by weight of a residue obtained by distilling water and a tertiary amine. 13. The method according to claim 1, wherein the formate of trimethylolalkane contained in the residue is reacted with ammonia, a primary amine or a secondary amine to form trimethylolalkane and formamides. 1
A method for producing the described trimethylolalkane. 14. The method for producing trimethylolalkane according to claim 13, wherein the ammonia, primary amine or secondary amine is ammonia, primary monoamine or secondary monoamine. 15. The process for producing a trimethylolalkane according to claim 1, wherein the tertiary amine distilled off from the reaction mixture after the completion of the reaction is reused for producing a trimethylolalkane. 16. The method for producing trimethylolalkane according to claim 1, wherein the tertiary amine is triethylamine.