JPH0436314A - Preparation of polyoxyalkylenepolyamine - Google Patents

Abstract

PURPOSE:To enable the recycling of an unreacted amine to a reaction system by reacting a polyoxyalkylene polyol with ammonia and/or an amine in the presence of a catalyst and a monohydric alcohol. CONSTITUTION:A polyoxyalkylene polyol (e.g. a polyoxypropylene polyoxyethylene polyol) is allowed to react with ammonia in an amt. of 0.5-50 equivalents and/or an amine comprising a primary amine (e.g. isopropylamine) in an amt. of 0.5-50 equivalents or a secondary amine in an amt. of 0.2-100 equivalents, each based on one equivalent of the hydroxyl group of the polyol, in the presence of pref. a nickel-carried catalyst, in an amt. of 0.1-20wt.% based on the polyol and a 1-10C primary or secondary monohydric alcohol (e.g. ethanol) in an amt. of 0.01-1 equivalent based on 1 equivalent of the amine under a pressure of 20-150kg/cm<2>G at 150-280 deg.C for 1-20hr, giving a polyoxyalkylenepolyamine contg. at least 30% secondary amino groups.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a polyoxyalkylene polyamine, and more specifically, the present invention relates to a method for producing a polyoxyalkylene polyamine, and more specifically, a method for producing a polyoxyalkylene polyol and an ammonia and/or amine compound in the presence of a catalyst. The present invention relates to a method for producing a polyoxyalkylene polyamine by reaction, characterized in that the reaction is carried out in the coexistence of a monohydric alcohol.

A polyether having an amino group at the terminal provides a polyurea through a polyaddition reaction with a polyisocyanate, and polyurea-based RI? It is used as a raw material for I + elastomers, soft foams, hard foams, etc. It is also a useful compound as a raw material for various plastics such as epoxy resins, polyamides, and polyimides.

[Conventional technology]

A method for obtaining a polyoxyalkylene polyamine having an amino group at the terminal by reacting a polyoxyalkylene polyol with ammonia or an amine compound is known. For example, Belgian Patent No. 677124 proposes a method of producing polyoxyalkylene polyol and ammonia by reacting them at high temperature and pressure using a Raney metal catalyst.

According to this method, all the polyoxyalkylene polyols produced become primary amines. Polyoxyalkylene polyamines with primary amino groups at the end have too high reactivity with isocyanates, which causes problems such as the need for special and expensive high-speed molding machines to control the urea reaction. has.

On the other hand, polyoxyalkylene polyamines having secondary amino groups have milder reactivity with isocyanates than primary amino groups, so they have the great advantage of being easier to control the ureation reaction and easier to mold. have

As a method for producing a polyoxyalkylene polyamine having a secondary amino group, JP-A No. 2-2251 describes a method for producing a polyoxyalkylene polyol and a secondary amine compound,
A method has been proposed in which a Co or Cu catalyst is used to react at high temperature and pressure. According to this method, a polyoxyalkylene polyamine with a high content of secondary amino groups can be obtained. However, a large excess of expensive secondary amine compounds must be present in the system, and for industrial production, it is necessary to recycle the recovered unreacted amine into the system. Here, there is a problem in that the recovered amine contains many by-products such as primary amine compounds and alcohol produced under these reaction conditions.

[Problems to be Solved by the Invention] An object of the present invention is to provide a polyoxyalkylene polyol,
In a method for producing polyoxyalkylene polyamines by reacting ammonia and/or amine compounds in the presence of a catalyst, unreacted amines can be recycled to the reaction system, and secondary amino groups can be produced using inexpensive raw materials. An object of the present invention is to provide a method for producing a polyoxyalkylene polyamine containing polyoxyalkylene polyamine.

[Means for Solving the Problems] The present inventors have made extensive studies to achieve the above object, and have finally arrived at the present invention.

That is, the present invention provides a polyoxyalkylene polyol;
This is a method for producing a polyoxyalkylene polyamine by reacting ammonia and/or an amine compound in the presence of a catalyst, and is characterized in that the reaction is carried out in the coexistence of a monohydric alcohol.

The polyoxyalkylene polyol used in the present invention is
Diols having 2 to 8 functional properties and an average molecular weight of 400 or more are suitable. For example, diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and 1,4-butylene glycol, glycerin, hexanetriol, and trimethylol. propane,
Polyols such as pentaerythritol, sorbitol, and sucrose; aromatic compounds such as bisphenol A, bisphenol F, dihydroxydiphenyl ether, dihydroxybiphenyl, hydroquinone, resorcinol, phloroglucin, naphthalene diol, aminophenol, aminonaphthol, and phenol formaldehyde condensates; Amine compounds such as tanolamine, ethyldiisopropanolamine, triethanolamine, ethylenediamine, hexamethylenediamine, bis(p-aminocyclohexyl)methane, aniline, toluidine, tolylenediamine, diphenylmethanediamine, naphthalenediamine, etc., or the above compounds. It is a polyoxyalkylene polyol obtained by adding one or more types of propylene oxide, butylene oxide, styrene oxide, etc. to a mixture of two or more types selected from among them.

In addition to the above, examples include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran. Furthermore, a mixture of two or more selected from the above polyoxyalkylene polyols can also be used.

The primary amine compound used in the present invention is usually an amine having about 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specifically, methylamine, ethylamine,
n-propylamine, isopropylamine, butylamine, isobutylamine, 5ec-butylamine, t-butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine (laurylamine), tetradecylamine (myristylamine) , hexadecylamine (palmitylamine), octadecylamine (stearylamine), alkylamines such as oleylamine, alkylamines having substituents such as β-aminopropyl methyl ether, β-aminopropylethyl ether, benzylamine, p-methyl Aralkylamines such as benzylamine,
Examples include alicyclic amines such as cyclopentylamine and cyclohexylamine. Furthermore, a mixture of two or more selected from the above primary amines can also be used.

The secondary amine compound used in the present invention is usually an amine having about 2 to 20 carbon atoms, and specifically, dimethylamine, diethylamine, diropropylamine, diisopropylamine, dibutylamine, cyamylamine, diethylamine, methylethylamine, methyl Examples include alkylamines such as propylamine, methylisopropylamine, ethylpropylamine, ethylisopropylamine, N-methyldodecylamine, and aralkylamines such as dibenzylamine and N-methylbenzylamine. Furthermore, a mixture of two or more selected from the above secondary amines can also be used.

As the catalyst used in the present invention, conventionally known catalysts can be used, such as supported catalysts in which Ni, Co, etc. are supported on a carrier such as diatomaceous earth or alumina, Ni,
Typical examples include Co-based Raney type catalysts and Cu-Cr-based catalysts. Among these, a supported catalyst is one of the particularly suitable catalysts.

The monohydric alcohol used in the present invention has 1 to 1 carbon atoms.
Examples include 0 primary or secondary alcohols. Specifically, methanol, ethanol, n-propertool,
Alkyl alcohols such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 5et-butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, β-hydropropyl methyl alcohol, β-hydropropyl Examples include alkyl alcohols having substituents such as ethyl alcohol, aralkyl alcohols such as benzyl alcohol, p-methylbenzyl alcohol, and O-methylbenzyl alcohol, and cycloalkyl alcohols such as cyclopentyl alcohol and cyclohexyl alcohol.
Although the monohydric alcohol used in the present invention is not particularly limited, it is particularly preferable that it has the same number of carbon atoms and the same carbon bonding mode as the primary amine compound.

The amount of the amine compound used in the present invention is determined depending on the application, but usually, the primary amine compound is 0.5 to 50 equivalents, and the secondary amine compound is 0.2 to 1 equivalent, relative to the hydroxyl group.
00 equivalents, preferably 1 to 10 equivalents for the primary amine compound, and 0.5 to 50 equivalents for the secondary amine compound.

The amount of monohydric alcohol used in the present invention is usually 0.00% relative to the amine compound. 1 to 1 equivalent of O, preferably 0.05
~0.7 equivalents are used, most preferably 0.1-0.5 equivalents. If the amount of monohydric alcohol is too small, there will be no effect of addition, and if it is too large, the conversion rate of the polyoxyalkylene polyol will decrease, which is not preferable.

In the present invention, the amount of ammonia used is determined depending on the application, the amount of the amine compound, and the amount of the -hydric alcohol used.
Usually, 0.5 to 50 equivalents, preferably 1 to 10 equivalents are used relative to the hydroxyl group. When using a large amount of a primary amine compound, it is not necessarily necessary to use it.

In the present invention, the catalyst is usually 0.1-20-t%, preferably 0.1-t%, based on the polyoxyalkylene polyol.
3-10 wt% is used, most preferably 0.5-5 wt%.

Although the reaction conditions of the present invention are not particularly limited,
Generally, the reaction temperature is 150 to 280°C, preferably 1
80~250℃, reaction pressure 20~150kg/cdG,
Preferably 30-100 kg/cjG, reaction time 1-
Hydrogen may or may not coexist in the reaction system, which is carried out for 20 hours, preferably 5 to 10 hours.The lower the reaction temperature, the lower the reaction rate, and if it is too high, the polyoxyalkylene This is not preferable because the polyol will decompose.

After the reaction is completed, the target polyoxyalkylene polyamine can be obtained by appropriately combining methods such as recovery by evaporation of unreacted amine compounds and alcohol, catalyst filtration, water washing, and drying. Further, the unreacted recovered amine containing alcohol can be used in the next reaction after adjusting the molar ratio of amine and alcohol.

In the polyoxyalkylene polyamine obtained by the present invention, primary and secondary amines can be determined separately and quantitatively by the azomethine method. The secondary amino group content can be freely adjusted depending on the composition of the raw material system, but a secondary amino group content of 30% or more is particularly preferable because the ureation reaction can be easily controlled.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 In a 200 d high-pressure autoclave, 4 g of nickel diatomaceous earth catalyst (Kickel content 50%) and polyoxypropylene triol (hydroxyl value 33.4 mg KOH/g) obtained by addition polymerizing propylene oxide to glycerin were placed in a 200 d high-pressure autoclave.
, an average molecular weight of 5040 i or less is abbreviated as polyol P. ), 11.0 g of ethanol were charged, nitrogen substitution was performed five times (10 kg/cdG), and after charging 6.8 m of liquid ammonia, hydrogen was charged at an initial pressure of 50 kg/cj.
Prepared with G. While stirring, raise the temperature to 220°C,
A time reaction was performed. At this time, the maximum pressure is 82kg/cj
After the completion of the reaction G, the polyoxyalkylene polyamine was purified by filtering off the catalyst and drying under reduced pressure. The obtained product had a total amine value of 27.6 mgKOH/g,
The primary amine value was 11.9 mgKOH/g, the secondary amine value was 15.7 mgKOH/g, and no tertiary amine was detected. The results are shown in Table 1.

Example 2 In a high-pressure autoclave of 11, 20 g of nickel diatomaceous earth catalyst (50% nickel content), polyol P 400
g, 7.1 g of isopropyl alcohol, and 70.4 g of isopropyl amine, and nitrogen substitution was performed 5 times (10 k
g/cdG), then hydrogen at an initial pressure of 50kg/cj
The reaction was carried out in the same manner as in Example 1, using G.

At this time, the maximum pressure was 8Q kg/c+j G.

The component composition of the unreacted amine recovered in the vacuum drying step was 4.82 wt% isopropylamine, 89.52 wt% diisopropylamine, and 5.47 wt% isopropyl alcohol. The results are shown in Table 1.

Example 3 7.7 g of isopropylamine was added per 100 g of recovered amine to the unreacted amine recovered in Example 2, so that the equivalent ratio of isopropylamine to diisopropylamine was 2.
．． Adjusted to be 4/10.

In a 200d high-pressure autoclave, 2.5 g of nickel diatomaceous earth catalyst (50%), polyol P5
0 g, and 36.2 g of the adjusted recovered amine were charged, and after nitrogen substitution was performed five times (10 kg/c+jG), hydrogen was charged at an initial pressure of 50 kg/cjG. The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 5 hours.

At this time, the maximum pressure was 71 kg/dG.

The results are shown in Table 1.

Example 4 31.9 g of isopropylamine was added per 100 g of recovered amine to the unreacted amine recovered in Example 2, and the equivalent ratio of isopropylamine to diisopropylamine was adjusted to 4.015.7. .

In a 200d high pressure autoclave, 2.5 g of nickel diatomaceous earth catalyst (50% nickel content), polyol P
After charging 50 g and 25.3 g of tJR-conditioned recovered amine and performing nitrogen substitution five times (10 kg/edG), hydrogen was charged at an initial pressure of 50 kg/cdG. reaction time 5
The reaction was carried out in the same manner as in Example 1 except that the time was changed. At this time, the maximum pressure was 86 kg/dG.

The results are shown in Table 1.

Example 5 In Example 3, instead of polyol P, polyoxypropylene polyoxyethylene triol (ethylene oxide content 15-1%) obtained by addition polymerizing propylene oxide and then ethylene oxide to glycerin was used.
, hydroxyl value 33. OtgKOH/g, average molecular weight 51
The reaction was carried out under the same conditions as in Example 3 except that 00; hereinafter abbreviated as polyol Q) was used. At this time, the maximum pressure was 70 kg/c+JG.

The results are shown in Table 1.

Example 6 In Example 4, polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran (hydroxyl value 112 dOH/
The reaction was carried out under the same conditions as in Example 4, except that polyol R (hereinafter abbreviated as polyol R) was used. At this time, the maximum pressure was 83 kg/cjG. The results are shown in Table 1.

Example 7 The reaction was carried out under the same conditions as in Example 1, except that benzyl alcohol was used instead of ethanol and the reaction time was changed to 10 hours.

At this time, the maximum pressure was 64 kg/cjG. The results are shown in Table 1.

Comparative Example 1 In Example 1, except that ethanol was not used and the equivalent ratio of polyol P and ammonia was changed to 1710,
The reaction was carried out under the same conditions as in Example 1.

At this time, the maximum pressure was 63 kg/cjG. The results are shown in Table 1.

Comparative Example 2 In Example 2, the equivalent ratio of polyol P and isopropylamine was changed to 1/1 without using isopropyl alcohol.
The reaction was carried out under the same conditions as in Example 2, except that the concentration was changed to 10. At this time, the maximum pressure was 88 kg/aj G. The results are shown in Table 1.

[Effects of the Invention] Many effects can be expected by allowing a monohydric alcohol to coexist in the method of producing a polyoxyalkylene polyamine by reacting a polyoxyalkylene polyol with ammonia or an amine compound. For example, when using ammonia as an aminating agent, conventionally 1
Although it has only been possible to produce polyoxyalkylene polyamines consisting only of secondary amino groups, by using alcohol, it becomes possible to obtain polyoxyalkylene polyamines containing secondary amino groups. In addition, when using a primary amine compound as an aminating agent,
By allowing alcohol to coexist, it becomes possible to produce a polyoxyalkylene polyamine with a higher content of secondary amino groups than before. Furthermore, when a primary amine compound and/or a secondary amine compound is used as an aminating agent, disproportionation of the amine compound and other side reactions occur within the reaction system, resulting in the formation of by-products in the recovered amine compound. (alcohol, etc.) cannot be avoided. When recycling this into the reaction system, it is extremely difficult to purify it, but if the method of the present invention is applied, there is no need for purification. When considering raw material costs, alcohol is cheaper and more economical than amine compounds for boat fishing.

The compound obtained by the method of the present invention can be effectively used as a raw material for plastics, such as by reacting with isocyanate to obtain a polyurea resin with urea bonds.

Claims (1)

[Claims] 1. A method for producing a polyoxyalkylene polyamine by reacting a polyoxyalkylene polyol with ammonia and/or an amine compound in the presence of a catalyst, in which the reaction is carried out in the presence of a monohydric alcohol. A method for producing a polyoxyalkylene polyamine, which is carried out as follows. 2. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein the polyoxyalkylene polyamine contains 30% or more of secondary amino groups. 3. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein the polyoxyalkylene polyol is a polyoxypropylene polyol. 4.Claim 1 wherein the polyoxyalkylene polyol is polyoxypropylene polyoxyethylene polyol.
A method for producing the polyoxyalkylene polyamine described. 5. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein the polyoxyalkylene polyol is polytetramethylene ether glycol. 6. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein the amine compound is a primary amine compound having 1 to 10 carbon atoms. 7. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein the amine compound is a secondary amine compound having 2 to 20 carbon atoms. 8. The method for producing a polyoxyalkylene polyamine according to claim 1, wherein the catalyst is a nickel-supported catalyst.