JPH0395219A - Preparation of polyoxyalkylene polyamine having secondary amino group at molecular terminal - Google Patents

Abstract

PURPOSE:To facilitate the preparation of a polyoxyalkylene polyamine having secondary amino groups at the molecular terminals by reacting a polyoxyalkylene polyamine having gamma-aminopropyl ether groups at the molecular terminals with a specific halide. CONSTITUTION:After a polyoxyalkylene polyol is reacted with (meth) acrylonitrile, the nitrile groups in the reaction product are catalytically reduced to give a polyoxyalkylene polyamine (e.g. polyoxypropylene polyamine) having an average mol.wt. of 400 or higher and gamma-aminopropyl ether groups (that is primary amino groups) at the molecular terminals. The resulting polyoxyalkylene polyamine is reacted with a halide of the formula RX (wherein R is a 1-20C satd. hydrocarbon group, a 3-20C unsatd. hydrocarbon group, a 6-10C arom. hydrocarbon group, or a 7-10C aralkyl group; and X is F, Cl, Br, or I) (e.g. benzyl chloride) in an amt. of 5-200 equivalent % (based on the amino groups of the polyoxyalkylene polyamine) in the presence of a base (e.g. K2CO3) in an amt. of 1-10 equivalents (based on the halide) at room temp. to 150 deg.C under a pressure of 0-10kg/cm<2>G for 1-20hr.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a polyoxyalkylene polyamine having a secondary amino group at the end of the molecule. - a polyoxyalkylene polyamine having an anopropylether group, and a saturated hydrocarbon group of formula RX (R is C1 to C2),
~C2. unsaturated hydrocarbon group, C, ~COO aromatic hydrocarbon group, or C1-C20 aralkyl group; 2 at the end of the molecule.
The present invention relates to a method for producing a polyoxyalkylene polyamine having a grade amino group.

Polyethers having amino groups at the terminals provide polyurea through a polyaddition reaction with polyisocyanates, and are used as raw materials for polyurea-based RIMs, elastomers, flexible foams, rigid foams, and the like. It is also a useful compound as a raw material for plastics such as epoxy resin, polyamide, and polyimide.

[Conventional technology]

Conventionally, many attempts have been made to use polyoxyalkylene polyamines having amino groups at the terminals, and one unique product has been proposed.

■Produced by reacting the terminal hydroxyl group of polyoxyalkylene polyol with ammonia at high temperature and pressure using a hydrogenation-dehydrogenation catalyst (for example, Hergie Patent No. 677124)
No.), ■Produced by reacting the terminal hydroxyl group of polyoxyalkylene polyol with a primary amine using a Raney metal catalyst (e.g., Japanese Patent Publication No. 7289/1989), ■Reacting polyoxyalkylene polyol with acrylonitrile Those produced by cyanoethylating the terminal end and then catalytic reduction (for example, Japanese Patent Publication No. 53-95906), ■Aξ
Aminobenzoic acid ester derivatives of polyether polyols obtained by the transesterification reaction between nobenzoic acid ester and polyoxyalkylene boriol (e.g., Japanese Patent Publication No. 38412/1983), ■ Varanitrobenzoic acid chloride and polyoxyalkylene boliol para-aminobenzoic acid ester of a polyol obtained by reacting and then reducing the nitro group (U.S. Pat. No. 4.328
, No. 322), ■ Anthranyl ester of polyether obtained by reacting isatoic anhydride with a polyether polyol in the presence of a strong base such as sodium hydroxide (JP 46-5245), ■ Borioxyalkylene A polyol and an excess amount of polyisocyanate are reacted to form a compound having an isocyanate end group, and the isocyanate compound is transformed into a compound having a modified hydroxyl group by reacting a hydroxylamine with an aldehyde or a ketone. Polyamines produced by hydrolyzing polyketines, polyaldines, or polyenamines obtained by reacting with ketimines, aldimines, or enamines (Japanese Patent Publication No. 57-5
No. 7051), etc. are known.

[Problem to be solved by the invention]

Conventionally known polyoxyalkylene polyamines having an amino group at the end include those in which the terminal amino group is an aliphatic primary amino group (sections ■ and ■ in the prior art), and those in which the terminal amino group is aromatic. It is composed of amino groups (sections 1, 2, 2, and 2 of the prior art). In addition, when the present inventors conducted an experiment based on the method described in the section ① of the prior art, polyoxyalkylene polyamines which are isated with secondary 72 groups were indeed obtained, but secondary products resulting from intermolecular reactions It was found that the structure is different from that of the polyoxyalkylene polyamine targeted by the present invention.

An object of the present invention is to provide a simple method for producing a polyoxyalkylene polyamine having an aliphatic secondary ξ group at the end of the molecule.

[Means for solving intelligence 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 polyamine having a γ-anopropylether group, which is a primary amino group, at the end of the molecule, and a polyoxyalkylene polyamine having the formula RX (R is a saturated hydrocarbon group of C1 to C2, C3 to C20). unsaturated hydrocarbon group, C1-C2
0 aromatic hydrocarbon group, or a C6-C20 aralkyl group; This is a method for producing a polyoxyalkylene polyamine having a secondary axi group at the end.

The polyoxyalkylene polyamine having a primary amino group at the molecular end used in the present invention can be obtained by a method such as reacting the terminal hydroxyl group of a polyoxyalkylene polyol with acrylonitrile or methacrylonitrile and then catalytically reducing the nitrile group. Here, borioxyalkyleneboriol is a compound obtained by ring-opening polymerization of alkylene oxide using a basic catalyst such as an alkali metal hydroxide in the presence of an appropriate initiator. It will be done. Initiators include propylene glycol, dipropylene glycol, tripropylene glycol, other polypropylene glycols, ethylene glycol, diethylene glycol, triethylene glycol, other polyethylene glycols, glycerin, diglycerin, bentaethritol, sorbitol, shakerose, and others. Examples include polyhydric alcohols, bisphenol A2, bisphenol S, resol, 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.

Used in the present invention, the formula RX (R is a saturated hydrocarbon group of C1 to C2, an unsaturated hydrocarbon group of C, to C!, C, to C
A halogen compound represented by an aromatic hydrocarbon group of IO or a C1-C20 aralkyl group; Ethyl bromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide, isopropyl chloride, isopropyl bromide, isopropyl iodide, butyl chloride, isobutyl chloride, t-butyl chloride, amyl bromide, octyl bromide, Halogenated saturated hydrocarbons such as decyl iodide, lauryl iodide, stillyl chloride, palutyl iodide, stearyl iodide, propenyl chloride, brobenyl bromide, bropenyl iodide, isobrobenyl chloride,
Halogenated unsaturated hydrocarbons such as allyl chloride, methallyl bromide, butenyl bromide, oleyl iodide, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene,
Halogenated aromatic hydrocarbons such as p-bromotoluene and p-bromo t-phthylbenzene, benzyl chloride, benzyl bromide, benzyl iodide, p-methylbenzyl chloride,
Examples include aralkyl halides such as 0-methylbenzyl chloride and isopropylbenzyl chloride.

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, Examples include tertiary amine compounds such as tributylamine.

The amount of the halogen compound to be used is determined depending on the desired secondary amine content of the raw material, but is usually 5 to 200 equivalent %, preferably 10 to 150 equivalent %, based on the amino group.
More preferably, 20 to 100 equivalent % is used. The halogen compound may be charged all at once, but it is preferably added sequentially or in portions depending on the progress of the reaction. Excessive presence of a halogen compound in the reaction system is undesirable because tertiary amines are produced due to side reactions and the selectivity of secondary amines becomes low.

Bases are used to scavenge hydrogen halides and are usually
Water and an organic solvent may or may not be present in the reaction system in which an equivalent to 10 times the amount of the halogen compound is used. The solvent is one that is inert under the reaction conditions, such as lower alcohols such as methanol and ethanol,
Examples include aromatic hydrocarbons such as toluene and xylene.

The reaction conditions 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 between room temperature and 150°C.
, reaction pressure is 0 ~ 10 kg/caG, reaction time is 1 ~
Do it in 20 hours. If the temperature is too low, the reaction rate will be low;
Moreover, if it is too high, side reactions etc. will occur, which is not preferable.

After the reaction is complete, excess base and by-product salts are removed by neutralization, washing with water, etc., and then drying, filtration, etc. are carried out to obtain the desired product, a secondary amino group at the end of the molecule. A polyoxyalkylene polyamine having the following properties can be obtained.

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

Production example of polyoxypropylene diol (difunctional, oil value 5)
6.1mgKOH/g, average molecular weight 2000) 150
0g, water 79.5g, potassium hydroxide 7.5g
79.5 g of acrylonitrile was added dropwise from the dropping funnel over 2 hours while stirring in the glass flask No. 1 and keeping the temperature at 30°C. After completion of the dropwise addition, the mixture was allowed to react at 30°C for 38 hours.

Hydrochloric acid was added to the reaction solution to adjust the pH to 5, and the mixture 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. 80 g of purified cyanoethylated product and 0.4 g of nickel diatomaceous earth catalyst were charged into a 200 d high-pressure autoclave, and after purging with nitrogen, 2.5 equivalents of liquid ammonia were added to the amino group. Raise the temperature to 120'C, charge hydrogen, and increase the initial pressure from 80kg/c+aG to the final pressure of 48k.
It reacted up to g/cdG. After repeated catalytic filtration and water washing, boroxypropylene diagonal was obtained by dehydration under reduced pressure.

Production example 2 Polyoxybrobylene triol (trifunctionality, OH value 3
3.7+agKOII/g, average molecular weight 5000) 1
500g, water 79.5g, potassium hydroxide 7.5g
The same operation as in Production Example 1 was performed using 239 g of acrylonitrile to obtain polyoxypropylene triamine. (Amine value: 32.6 mgKOH/g) Example 1 Polyoxypropylene diamine obtained in Production Example 1 (
250 g of potassium carbonate (difunctional, amine number 46.7 ing KOH/g, average molecular weight 12400), 28.8 g of potassium carbonate dissolved in 150 g of water were added to a 500-g. Pour into a glass Yotsuro flask and heat to 100°C, then add benzyl chloride 26. 4 g was added dropwise from the dropping funnel over 1 hour. Thereafter, the reaction was continued for an additional 5 hours.

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 polyoxybrobylene diamine. When the amine value was determined by the azumetine method, the total amine value was 45.2+*g K011/g
The secondary amine value was 33.8 mgKOH/g.

In addition, tertiary amines were quantified by the acetylated monoperchloric acid and acetic acid method, but no tertiary amines could be detected. 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 In Example 1, except that the equivalent ratio of amine, benzyl chloride, and potassium carbonate was changed to 1/0.5/0.5.
The reaction was carried out under the same conditions as in Example 1. The results are shown in Table 1.

Example 4 In Example 1, the reaction was carried out under the same conditions as in Example 1, except that isoprobyl iodide was used instead of benzyl chloride, 75 g of water was allowed to coexist, and the reaction temperature was changed to 95°C. 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 polyoxybrobylene triamine obtained in Production Example 2 was used instead of polyoxybrobylene diamine obtained in Production Example 1. . 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 iodide, 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 I.

Example 7 The reaction was carried out under the same conditions as in Example 6, except that the equivalent ratio of adanan, isopropyl iodide, and potassium carbonate was changed to 1/0.8/1, and the reaction temperature was changed to 95°C. went. 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.
Example s) was used, water was not present in the system, the equivalence ratio of amine, methyl iodide, and triethyl acetate was changed to 1/1/5, and the reaction temperature was changed to 4°C. The reaction was carried out under the same conditions as in 5. The results are shown in Table 1.

Example 9 A reaction was carried out under the same conditions as in Example 1, except that allyl chloride was used instead of benzyl chloride. The results are shown in Table 1.

Example 10 A reaction was carried out under the same conditions as in Example 1, except that benzyl chloride was charged in bulk at the same time as the amine base in Production Example 1. When the tertiary amine was quantified, it was 4.3 mgK.
It was OH/g. The results are shown in Table 1.

〔Effect of the invention〕

The present invention provides a simple method for producing a polyoxyalkylene polyamine having 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. be. 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)

[Scope of Claims] 1. A polyoxyalkylene polyamine having a γ-aminopropyl ether group, which is a primary amino group, at the end of the molecule;
C_3 to C_2_0 unsaturated hydrocarbon groups, C_6 to C_
2_0 aromatic hydrocarbon group, or C_7 to C_1_0
a halogen compound represented by an aralkyl group; How to manufacture. 2. After adding a polyoxyalkylene polyamine having a γ-aminopropyl ether group, which is a primary amino group, at the end of the molecule and a base, the formula RX (R is C_1 to C_2_0
a saturated hydrocarbon group of C_3 to C_2_0, an aromatic hydrocarbon group of C_6 to C_1_0, or an aralkyl group of C_7 to C_1_0; X is a halogen represented by fluorine, chlorine, bromine, or iodine) compound,
The method for producing a polyoxyalkylene polyamine according to claim 1, characterized in that the addition is carried out sequentially. 3. The method for producing a polyoxyalkylene polyamine according to claim 1 or 2, wherein the polyoxyalkylene polyamine having a primary amino group at the end of the molecule has an average molecular weight of 400 or more. 4. The method for producing a polyoxyalkylene polyamine according to claim 1 or 2, wherein the halogen compound is a benzyl halide. 5.Claim 1, wherein the halogen compound is methyl halide.
Or the method for producing the polyoxyalkylene polyamine described in 2. 6. The method for producing a polyoxyalkylene polyamine according to claim 1 or 2, wherein the halogen compound is isopropyl halide. 7. The method for producing a polyoxyalkylene polyamine according to claim 1 or 2, wherein the base is an alkali metal carbonate. 8. Claim 1 or 2, wherein the base is an alkali metal hydroxide.
A method of producing the described polyoxyalkylene polyamine. 9. The method for producing a polyoxyalkylene polyamine according to claim 1 or 2, wherein the base is a tertiary amine compound. 10. The method for producing a polyoxyalkylene polyamine according to claim 1 or 2, wherein the polyoxyalkylene polyamine having a γ-aminopropyl ether group, which is a primary amino group, at the end of the molecule is a polyoxypropylene polyamine.