JPH02263828A - Polyoxyalkylene-polyamine and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject polyamine useful as a raw material for plastics by reacting respectively specific polyoxyalkylene-polyamine with halogen compound in the presence of a base. CONSTITUTION:The objective compound expressed by formula II is obtained by reacting a polyoxyalkylene-polyamine expressed by formula I (n is 2-8; A is n-valent group obtained by removing OH groups from n-valent polyoxyalkylene polyol) with a halogen compound (e.g. methyl chloride) expressed by the formula RX (R is 1-20C saturated hydrocarbon, 3-20C unsaturated hydrocarbon, 6-20C aromatic hydrocarbon or 7-20C aralkyl; X is halogen) in the presence of a base (e.g. sodium carbonate).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyoxyalkylene polyamine having a secondary amino group at the end of the molecule and a method for producing the same. A polyoxyalkylene polyamine having a T-aminopropyl ether group, a polyoxyalkylene polyamine having a T-aminopropyl ether group which is a primary amino group at the end of the molecule, and a halogen compound are reacted in the presence of a base. A method for producing a polyoxyalkylene polyamine having a T-aminopropyl ether group, which is a secondary amino group, at the molecular end, and a polyoxyalkylene polyol whose molecular end is cyanoethylated, which is characterized by A method for producing a polyoxyalkylene polyamine having a T-aminopropyl ether group, which is a secondary amino group, at the end of the molecule, characterized by carrying out reductive amination in the presence of a compound, hydrogen, and a hydrogenation-dehydrogenation catalyst. It is something.

A polyether having an amino group at the terminal provides polyurea through a polyaddition reaction with a polyisocyanate, and is used as a raw material for polyurea-based R1)1, elastomers, flexible foams, hard foams, and the like. It is also used as an initiator for ring-opening polymerization of epoxy compounds, and is a useful compound as a raw material for plastics, such as epoxy resin curing agents, heat-resistant, and fast-curing paints.

[Conventional technology]

Conventionally, many attempts have been made on polyoxyalkylene polyamines having amino groups at the terminals, and unique products have been provided.

■Produced by reacting the terminal hydroxyl group of a polyoxyalkylene polyol with ammonia at high temperature and pressure using a hydrogenation-dehydrogenation catalyst (for example, Belgian patent 677124)
(No.), ■Produced by reacting the terminal hydroxyl group of a polyoxyalkylene polyol with a primary amine under high temperature and pressure using a Raney metal catalyst (for example, Japanese Patent Publication No. 45-7289).
No.), (1) those produced by reacting polyoxyalkylene polyol and acrylonitrile to cyanoethylate the terminals and then catalytically reducing them (for example, Japanese Patent Publication No. 53-95906
No.), ■ Aminobenzoic acid ester derivatives of polyether polyols obtained by transesterification reaction between aminobenzoic acid esters and polyoxyalkylene polyols (for example, Japanese Patent Publication No. 38412/1983), ■ Varanitrobenzoic acid chloride and polyoxyalkylene polyols (U.S. Pat. No. 4,328,322), isatoic acid anhydride, which is obtained by reacting polyol with para-aminobenzoic acid ester (U.S. Pat. No. 4,328,322), and then reducing the nitro group. anthranyl ester of polyether obtained by reacting with an ether polyol (JP-A-46-5245); (2) reacting a polyoxyalkylene polyol with an excess amount of polyisocyanate to form a compound having isocyanate end groups; A polyamine produced by reacting an isocyanate compound with a ketimine, aldimine or enamine having a hydroxyl group formed by the reaction of hydroxylamine and an aldehyde or ketone and hydrolyzing the resulting polyketimine, polyaldimine or polyenamine ( Japanese Patent Publication No. 57-57051), etc. are known.

(Problems to be Solved by the Invention) Conventionally known polyoxyalkylene polyamines having an amino group at the end are those in which the terminal amino group is composed of an aliphatic primary amino group (conventional techniques ① and ②). ), the terminal amino group is composed of an aromatic amino group (sections ■, ■, ■, ■ of the prior art), and the terminal amino group is composed of an aliphatic secondary amino group. Oxyalkylene polyamines are manufactured under high temperature and high pressure. (Section (2) of the prior art) An object of the present invention is to provide a polyoxyalkylene polyamine having a γ-aminopropyl ether group, which is a secondary amino group, at the end of the molecule, and a relaxed method for producing the same.

[Means for solving 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 - formula (1) % formula % ( (in the formula, % is an integer of 2 to 8, A is an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol, R is a saturated hydrocarbon group of CI-Ct., C1~
represents a C3° unsaturated hydrocarbon group, a C4 to Cf11 aromatic hydrocarbon group, or a C7 to cte aralkyl group)
A polyoxyalkylene polyamine represented by the formula (n) A (OCHg CHx CH!NHI)n
(If) (in the formula, n is an integer of 2 to 8, A represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol); (III)RX
(III) (R is a saturated hydrocarbon group of CI"'C1@, CI-C1l
A halogen compound represented by an unsaturated hydrocarbon group of l, an aromatic hydrocarbon group of Ch''-Cttr, or an aralkyl group of C7 to C!; X is fluorine, chlorine, bromine, or iodine), - Formula (1) % Formula % (1) (In the formula, n is an integer of 2 to 8, and A is an n-valent polyoxyalkylene polyol by removing a hydroxyl group from the polyoxyalkylene polyol. The n-valent group obtained, R is a C1-C8 saturated hydrocarbon group, C1-
C8, unsaturated hydrocarbon group, Ch~C! . A method for producing a polyoxyalkylene polyamine represented by (representing an aromatic hydrocarbon group or a C7-cte aralkyl group),
and - Formula (IV) A - (OCH-CHx CN)n
(■) (in the formula, n is an integer of 2 to 8, A represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), a cyanoethylated product of polyoxyalkylene polyol is subjected to reductive amination in the presence of a primary amine compound, hydrogen, and a hydrogenation-dehydrogenation catalyst. An integer, A is an n-valent group obtained by removing the hydroxyl group from an n-valent polyoxyalkylene polyol, R is a C1-C2° saturated hydrocarbon group, C3-
This is a method for producing a polyoxyalkylene polyamine represented by a C2° unsaturated hydrocarbon group, a C4-C2° aromatic hydrocarbon group, or a C1-C2° aralkyl group.

The polyoxyalkylene polyamine having a γ-aminopropyl ether group, which is a primary amino group, at the molecular end used in the present invention is obtained by reacting the terminal hydroxyl group of a polyoxyalkylene polyol with acrylonitrile to cyanoethylate it, and then catalytically reducing the cyano group. It was manufactured by Here, the polyoxyalkylene polyol is 2-
Those with B functionality and an average molecular weight of 400 or more are suitable and can be obtained by ring-opening polymerization of alkylene oxide using a basic catalyst such as an alkali metal hydroxide in the presence of a suitable initiator. Initiators include propylene glycol, dipropylene glycol, tribrobylene glycol, other polypropylene glycols, ethylene glycol, diethylene glycol, triethylene glycol, other polyethylene glycols, glycerin, diglycerin, pentaerythritol, sorbitol, shakerose, and others. polyhydric alcohol, bisphenol A,
Examples include bisphenol S luzole, novolak, other polyhydric phenols, triethanolamine, jetanolamine, and other alkanolamines. Further, as the alkylene oxide, propylene oxide, ethylene oxide, and butylene oxide are usually used alone or in any combination.

The halogen compounds used in the present invention include methyl chloride, methyl bromide, methyl wax, ethyl chloride, ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, isopropyl chloride, isopropyl bromide, and iodine. Isopropyl chloride, butyl chloride, isobutyl chloride, t-butyl chloride, amyl bromide, octyl bromide, decyl iodide, lauryl iodide, myristyl chloride, palmityl bromide, stearyl iodide, propenyl chloride, propenyl bromide, iodide Propenyl, isopropenyl chloride, allyl chloride, methallyl bromide, butenyl bromide, oleyl tatsuide, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, benzyl chloride, benzyl bromide, benzyl iodide, p-
Examples include methylbenzyl chloride and O-methylbenzyl chloride.

Halogen compounds are determined depending on the application, but usually
5 to 200 equivalent%, preferably 10 to 200% by weight based on the amino group
150 equivalent % is used, more preferably 20 to 100 equivalent %. The halogen compound may be added as appropriate or may be charged in bulk depending on the progress of the reaction.

The base used in the present invention includes alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate,
Alkali metal hydrogen carbonates such as potassium hydrogen carbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, trimethylamine, triethylamine, tributylamine, etc. Examples include tertiary amine compounds.

Bases are used to scavenge hydrogen halides and are usually
An equivalent to 10 times the amount of the halogen compound is used.

The reaction conditions of the polyoxyalkylene polyamine and halogen compound of the present invention vary depending on the raw materials used, especially the boiling point and reactivity of the halogen compound, and are not particularly limited, but generally the reaction temperature is from room temperature to 150°C, The reaction pressure was O~lokg/ca"G.

The reaction time is 1 to 20 hours. If the temperature is too low, the reaction rate will be low (and if it is too high, side reactions will occur, so it is not recommended to coexist with water or an organic solvent in the reaction system.) It's fine, and you don't have to.

After the reaction is completed, excess base and by-product salts are removed by neutralization, washing with water, etc., and then drying, filtration, etc.
The desired polyoxyalkylene polyamine having a T-aminopropyl ether group, which is a secondary amino group, at the end of the molecule can be obtained.

The cyanoethylated polyoxyalkylene polyol used in the present invention is one obtained by cyanoethylating the terminal hydroxyl group of the polyoxyalkylene polyol described above by reacting with acrylonitrile.

The primary amine compounds used in the present invention include methylamine, ethylamine, isopropylamine, butylamine, isobutylamine, 5et-butylamine, t-butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine,
Examples include β-aminopropyl methyl ether, β-aminopropylethyl ether, aniline, O-toluidine, m-toluidine, p-)luidine, benzylamine, naphthylamine, cyclopentylamine, cyclohexylamine, and the like.

The amount of the primary amine compound used in the present invention is determined depending on the application, but is usually 0.5 to 5
0 equivalents are used, preferably 1 to 10 equivalents.

The amount of hydrogen used in the present invention is usually 0.0% relative to the cyano group.
The amount is 2 to 50 times equivalent, preferably 0.5 to 10 times equivalent. If the amount of hydrogen is too small, the reaction will be insufficient, and if it is too large, the pressure will become high, which is not preferable.

As the hydrogenation-dehydrogenation catalyst used in the present invention, conventionally known catalysts can be used, such as supported catalysts in which nickel, cobalt, etc. are supported on a carrier such as diatomaceous earth, alumina, or silica; , a cobalt-based Raney type catalyst, a copper-chromium-based catalyst, a copper-zinc-based catalyst, etc. are typical examples.

Among these, a supported catalyst is one of the particularly suitable catalysts.

In the present invention, the catalyst is usually 0.1 to 20 w per cyanoethylated polyoxyalkylene polyol.
t%, preferably 0.5 to 10 wt% is used.

The reaction conditions for the reductive anodication of the present invention are not particularly limited, but generally the reaction temperature is 30 to 200°C, preferably 50 to 150°C, and the reaction pressure is 1 to 90 kg/cm.
"(H1 preferably 10-50 kg/cm"G, reaction time 1-20 hours, preferably 5-IO hours) A solvent may or may not be present in the reaction system. is an inert substance under the reaction conditions, such as lower alcohols such as methanol and ethanol, and aromatic hydrocarbons such as toluene and xylene.Also, ammonia may be present in the reaction system. After the reaction is complete, by appropriately combining methods such as catalyst filtration, water washing, and drying, the desired product, which has a γ-aminopropyl ether group, which is a secondary amino group, at the end of the molecule can be obtained. A polyoxyalkylene polyamine can be obtained.

〔Example〕

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

Production example 1 of cyanoethylated polyoxyalkylene polyol and polyoxyalkylene polyamine Polyoxypropylene diol (difunctional, OH value 56)
．． 1m5KOH/g, average molecular weight 2000) 1500
g, 79.5 g of water and 7.5 g of potassium hydroxide were stirred in a 3 L glass flask, and while keeping the temperature at 30°C, 79.5 g of acrylonitrile was added dropwise from the dropping funnel over 2 hours. After 38 hours of reaction at 0.degree. C., hydrochloric acid was added so that the pH of the solution was 5, and the solution was washed with a large amount of water in a separatory funnel to separate the aqueous layer. After repeating the same operation twice, the polyether layer was dehydrated under reduced pressure and the cyanoethylated product (O) monovalence 2.13 gKO11/g)
I got it.

Production example 2 Polyoxypropylene triol (trifunctionality, OH value 3
3.75g1 [OH/g, average molecular weight 5000) 15
00g, water 79.5g, potassium hydroxide 7.5g,
Using 239 g of acrylonitrile, the same operation as in Production Example 1 was carried out to obtain a cyanoethylated product (2.28 md
OH/g) was obtained.

Production Example 3 80 g of the cyanoethylated product obtained in Production Example 1 and 0.4 g of the nickel diatomaceous earth catalyst were charged into a 200 ml high-pressure autoclave, and after the autoclave was purged with nitrogen, 2.5 equivalents of liquid ammonia was added to the amino group. Raise the temperature to 120"C, charge hydrogen, and increase the initial pressure from 80 kg/dG to the final pressure of 4.
It reacted up to 8 kg/ejG. After filtering the catalyst and repeating water washing, polyoxypropylene diamine (amine value: 50.7 gKo/g) was obtained by dehydration under reduced pressure.

Production Example 4 Using the cyanoethylated product obtained in Production Example 2, the same operation as in Production Example 3 was performed to obtain polyoxypropylene triamine (amine value: 30.0 mgKOH/g).

Example 1 Polyoxypropylene diamine 2 obtained in Production Example 3
50 g, benzyl chloride 26.4. , potassium carbonate28.
8 g of water and 15 G of water were heated while stirring in a 500 ml glass autoclave. The reaction was carried out at a predetermined temperature for a predetermined time. The aqueous layer was separated by static liquid separation, and washing was repeated with a large amount of water. The mixture was dehydrated under reduced pressure and filtered to obtain secondary polyoxypropylene diamine. As a result of measuring the amine value by the azomethine method, the secondary amine value was 36.8 mg.
The secondary conversion rate was 75.6% in terms of KOR/g. The results are shown in Table 1.

Example 2 A reaction was carried out under the same conditions as in Example 1, except that sodium carbonate was used instead of potassium carbonate. The results are shown in Table 1.

Example 3 A reaction was carried out under the same conditions as in Example 1, except that the equivalent ratio of amine, benzyl chloride, and potassium carbonate was changed to 110.510.5. The results are shown in Table 1.

Example 4 In Example 1, isopropyl iodide was used instead of benzyl chloride, 75 g of water was allowed to coexist, and the reaction temperature was 95°C.
The reaction was carried out under the same conditions as in Example 1, except that the reaction conditions were changed.

The results are shown in Table 1.

Example 5 In Example 1, the reaction was carried out under the same conditions as in Example 1, except that polyoxypropylene triamine obtained in Production Example 4 was used instead of polyoxypropylene diamine obtained in Production Example 3. The results are shown in Table 1.

Example 6 In Example 5, isopropyl iodide was used instead of benzyl chloride, 75 g of water was allowed to coexist, and the equivalent ratio of amine, isopropyl wax, and potassium carbonate was 1/1.
/10, and the reaction was carried out under the same conditions as in Example 5, except that the reaction temperature was changed to 102°C. The results are shown in Table 1.

Example 7 In Example 6, the equivalent ratio of amine, isopropyl iodide, and potassium carbonate was 110.8/1, and the reaction temperature was 95°C.
The reaction was carried out under the same conditions as in Example 6, except that the reaction conditions were changed.

The results are shown in Table 1.

Example 8 In Example 5, methyl iodide was used instead of benzyl chloride, and triethylamine (NEt) was used instead of potassium carbonate.
s), the reaction was carried out under the same conditions as in Example 5, except that water was not present in the system, the equivalent ratio of amine, methyl iodide, and triethylamine was changed to 1/115, and the reaction temperature was changed to 40 ° C. went. The results are shown in Table 1.

Example 9 In a 20-liter high-pressure autoclave, 4 g of nickel diatomaceous earth catalyst (Kickel content 50%), 80 g of the cyanoethylated product obtained in Production Example 1, and 5.3 g of isopropylamine were placed in a 20-liter high-pressure autoclave.
were charged in this order, and after nitrogen substitution was performed 5 times (10 kg/am Snow G), hydrogen was charged at an initial pressure of 40 kg/cm"G. The temperature was raised to 120°C with stirring, and the pressure was lowered after 6 hours. After the reaction was completed, the catalyst was separated by filtration, the unreacted amine was recovered by distillation, and the reaction was completed.
By washing with water and drying, a polyoxypropylene diamine having a secondary amino group at the end of the molecule was obtained. As a result of measuring the amine value by the azomethine method, the total amine value was 48.9 mgK.
O) I/g, secondary amine value 40.4 gKOR/g, amination rate 96.5%, secondary amine selectivity 82.6%
Met. The results are shown in Table 2.

Example 10 The reaction was carried out under the same conditions as in Example 9, except that the equivalent ratio of cyanoethylated product/amine was changed to 115. The results are shown in Table 2.

Example 11 In Example 9, n-
The reaction was carried out under the same conditions as in Example 9 except that butylamine was used. The results are shown in Table 2.

Example 12 In Example 9, the equivalent ratio of cyanoethyl compound/amine was changed to 1/2, and instead of the nickel diatomaceous earth catalyst,
The reaction was carried out under the same conditions as in Example 9, except that a Raney nickel catalyst was used and the reaction temperature was changed to 150°C. At this time, the reaction time was 6.5 hours. The results are shown in Table 2.

Example 13 In Example 9, the reaction was carried out under the same conditions as in Example 9, except that the cyanoethylated product of Production Example 2 was used instead of the cyanoethylated product of Production Example 1.

The results are shown in Table 2.

〔Effect of the invention〕

The present invention provides a polyoxyalkylene boria amine having a T-aminopropyl ether group, which is a secondary amino group, at the end of the molecule, which has a structure different from conventionally provided polyoxyalkylene polyamines having an amino group at the end; The present invention also provides a method for manufacturing the same under mild conditions.

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.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. General formula (I) A-(OCH_2CH_2CH_2NHR)_n(I
) (In the formula, n is an integer of 2 to 8, A is an n-valent group obtained by removing the hydroxyl group from an n-valent polyoxyalkylene polyol, R is a saturated hydrocarbon group of C_1 to C_2_0, and C_3 to C_2_0 Unsaturated hydrocarbon group, C_4-C
_2_0 aromatic hydrocarbon group, or C_7 to C_2_
0 aralkyl group). 2. General formula (II) A-(OCH_2CH_2CH_2NH_2)_n(I
I) (in the formula, n is an integer of 2 to 8, A represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), and a polyoxyalkylene polyamine represented by the general formula ( III) RX (III) (R is a saturated hydrocarbon group of C_1 to C_2_0, C_3 to
A halogen compound represented by C_2_0 unsaturated hydrocarbon group, C_6 to C_2_0 aromatic hydrocarbon group, or C_7 to C_2_0 aralkyl group; X is fluorine, chlorine, bromine, or iodine) in the presence of a base General formula (I) A-(OCH_2CH_2CH_2NHR)_n(I
) (In the formula, n is an integer of 2 to 8, A is an n-valent group obtained by removing the hydroxyl group from an n-valent polyoxyalkylene polyol, R is a saturated hydrocarbon group of C_1 to C_2_0, and C_3 to C_2_0 Unsaturated hydrocarbon group, C_6-C
_2_0 aromatic hydrocarbon group, or C_7 to C_2_
0 aralkyl group)). 3. General formula (II) A-(OCH_2CH_2CH_2NH_2)_n(I
I) A polyoxyalkylene polyamine represented by (in the formula, n is an integer of 2 to 8, A represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol) is a polyoxypropylene polyamine The method for producing a polyoxyalkylene polyamine according to claim 2. 4. General formula (IV) A-(OCH_2CH_2CN)_n(IV) (n in the formula
is an integer of 2 to 8, A represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), a cyanoethylated polyoxyalkylene polyol, a primary amine compound, hydrogen , and general formula (I) A-(OCH_2CH_2CH_2NHR)_n(I
) (In the formula, n is an integer of 2 to 8, A is an n-valent group obtained by removing the hydroxyl group from an n-valent polyoxyalkylene polyol, R is a saturated hydrocarbon group of C_1 to C_2_0, and C_3 to C_2_0 Unsaturated hydrocarbon group, C_6-C
_2_0 aromatic hydrocarbon group, or C_7 to C_2_
0 aralkyl group)). 5. The method for producing a polyoxyalkylene polyamine according to claim 4, wherein the polyoxyalkylene polyol is a polyoxypropylene polyol.