JP2764602B2 - Polyoxyalkylene polyol derivative and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyoxyalkylene polyol derivative and a method for producing the same, and more particularly, to reacting a polyoxyalkylene polyol with a cyanobenzyl halide. A method for producing a polyoxyalkylene polyol derivative having a benzonitrile skeleton at the molecular end, and a benzylamine skeleton at the molecular end characterized by catalytically hydrogenating a polyoxyalkylene polyol derivative having a benzonitrile skeleton at the molecular end. The present invention relates to a method for producing a polyoxyalkylene polyamine.

The polyether having an amino group at the terminal provides a polyurea by a polyaddition reaction with a polyisocyanate, and is used as a raw material for a polyurea-based RIM, elastomer, flexible foam, rigid foam and the like. Further, it is a compound useful as various plastic raw materials such as epoxy resin, polyamide, and polyimide.

[Conventional technology]

Many attempts have heretofore been made on polyoxyalkylene polyol derivatives having an amino group at a terminal, and unique ones have been provided.

The terminal hydroxyl group of the polyoxyalkylene polyol,
A method of producing by reacting with ammonia at a high temperature and a high pressure using a hydrogenation-dehydrogenation catalyst (eg, Belgian Patent No. 677124). (For example, Japanese Patent Publication No. 45-7289), a method in which a polyoxyalkylene polyol is reacted with acrylonitrile, the terminal of the polyoxyalkylene polyol is cyanoethylated, and then a catalytic reduction is carried out (for example, JP-B-53-95906), a method of producing a polyoxyalkylene polyol by transesterification with an amine benzoate (eg, JP-B-60-95906).
-38412), a method of reacting a polyoxyalkylene polyol with paranitrobenzoic acid chloride and then reducing the nitro group to produce (for example, US Pat. No. 4,32
No. 8,322), a method in which isatoic anhydride is reacted with a polyoxyalkylene polyol in the presence of a strong base (for example, Japanese Patent Publication No. 46-5245), benzyl is reacted by reacting a polyoxyalkylene polyol with benzyl halide. A method for producing a polyoxyalkylene polyamine having a benzylamine skeleton by converting it into an ether, followed by chloromethylation and then reacting with ammonia (for example, JP-A-63-238047) is known. Is complicated in the reaction step.

[Problems to be solved by the invention]

An object of the present invention is to provide a method for producing a polyoxyalkylene polyamine having a benzylamine skeleton at a molecular terminal in a high yield by a simpler method than before.

[Means for solving the problem]

The present inventors have diligently studied to achieve the above object,
Finally, the present invention has been achieved.

That is, the present invention provides a compound represented by the general formula (I): (Wherein n represents an integer of 2 to 8, R represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), and has a benzonitrile skeleton at the molecular terminal Polyoxyalkylene polyol derivatives. General formula (I) characterized in that a polyoxyalkylene polyol is reacted with a cyanobenzyl halide. (Wherein n represents an integer of 2 to 8, R represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), and has a benzonitrile skeleton at the molecular terminal Method for producing polyoxyalkylene polyol derivative (first step) and general formula (I) (Wherein n represents an integer of 2 to 8, R represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), and has a benzonitrile skeleton at the molecular terminal A method for producing a polyoxyalkylene polyamine having a benzylamine skeleton at a molecular terminal (second step), comprising catalytically hydrogenating a polyoxyalkylene polyol derivative.

The polyoxyalkylene polyol used in the present invention preferably has 2 to 8 functionalities and an average molecular weight of 400 or more. For example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, bisphenol A, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, dipropylene glycol, bisphenol F, dihydroxydiphenyl ether, dihydroxybiphenyl, hydroquinone , Resorcinol, naphthalene diol, aminophenol, aminonaphthol, phenol formaldehyde condensate, phloroglucin, methyldiethanolamine, ethyldiisopropanolamine, triethanolamine, ethylenediamine, hexamethylenediamine, bis (p-aminocyclohexyl) methane, tolylenediamine, Diphenylmethanediamine, naphthalene Such as an amine, ethylene oxide, propylene oxide, butylene oxide,
A polyoxyalkylene polyol obtained by adding one or more styrene oxides or the like. In addition to the above, examples include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

The cyanobenzyl halide used in the present invention includes o
-Cyanobenzyl chloride, p-cyanobenzyl chloride, m-cyanobenzyl chloride, o-cyanobenzyl bromide, p-cyanobenzyl bromide, m-cyanobenzyl bromide and the like.

The amount of cyanobenzyl halide used in the present invention is
Although it is determined according to the application, it is usually 0.
2-20 equivalents, preferably 0.5-10 equivalents, more preferably 1 equivalent
~ 5 equivalents are used.

Examples of the base used in the first step of the present invention include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate,
Examples thereof include alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; and tertiary amine compounds such as trimethylamine, triethylamine and tributylamine. In addition, an alkoxide of a polyoxyalkylene polyol prepared in advance from a polyoxyalkylene polyol and the above-described alkali metal hydroxide or metal sodium or metal potassium can also be used.

The base used in the first step of the present invention is used as a hydrogen halide scavenger, and is usually used in an equivalent amount to 10-fold equivalent to cyanobenzyl halide.

As the catalyst used in the second step of the present invention, a conventionally known catalyst can be used. For example, a supported catalyst in which nickel, cobalt or the like is supported on a carrier such as diatomaceous earth, alumina, or silica, nickel, cobalt Typical examples thereof include a Raney type catalyst, a supported catalyst in which a noble metal such as palladium, platinum and ruthenium is supported on a carrier such as carbon, alumina and silica. Among them, a supported catalyst is one of particularly suitable catalysts.

The catalyst used in the second step of the present invention is usually used in an amount of 0.1 to 20% by weight, preferably 0.3 to 10% by weight, based on the polyoxyalkylene polyol derivative.

Although the reaction conditions of the present invention are not particularly limited, the first step is generally carried out at a reaction temperature of 50 to 250 ° C, preferably 100 to 200 ° C, and a reaction time of 1 to 20 hours, preferably 5 to 20 hours.
Perform in ~ 10 hours. The reaction pressure may be reduced pressure or may be performed under pressure. A solvent may be present in the reaction system,
You don't have to. As the solvent, those which are inert under the reaction conditions and which are polar solvents are particularly preferred,
For example, dimethylformamide, dimethylsulfoxide, dimethylimidazolidinone, sulfolane and the like can be exemplified. After completion of the reaction, neutralization, recovery by evaporation of unreacted cyanobenzyl halide, washing with water, drying and the like can be appropriately combined to obtain the target polyoxyalkylene having a benzonitrile skeleton at the molecular terminal. it can.

In the second step, the reaction temperature is generally 30 to 200 ° C., preferably 50 to 150 ° C., and the reaction pressure is 1 to 90 kg / cm ² G, preferably 10 to 90 kg / cm ² G.
~ 50 kg / cm ² G, reaction time 1-20 hours, preferably 5-10
Do it in time. A solvent may or may not be present in the reaction system. Examples of the solvent include those inert under the reaction conditions, for example, lower alcohols such as methanol and ethanol, and aromatic hydrocarbons such as toluene and xylene. Further, ammonia may or may not be present in the reaction system. After completion of the reaction, a target polyoxyalkylene polyol derivative having a benzylamine skeleton at the molecular terminal can be obtained by appropriately combining a method such as filtration with a catalyst, washing with water, and drying.

〔Example〕

 Hereinafter, the present invention will be described with reference to examples.

Example 1 300 g of polyoxypropylene triol (having a hydroxyl value of 33.4 mgKOH / g, an average molecular weight of 5040; hereinafter abbreviated as polyol P) obtained by addition polymerization of glycerin with propylene oxide in a 1000 ml glass four-necked flask. p-
35.3 g of cyanobenzyl bromide, 7.2 of sodium hydroxide
g, 300 ml of dimethylformamide, while stirring
The temperature was raised to 100 ° C., and the reaction was performed for 6 hours. After completion of the reaction, neutralization with hydrochloric acid, washing with water, drying, and evaporation of the solvent and unreacted p-cyanobenzyl bromide were performed. From the IR spectrum of the obtained polyoxyalkylene, the absorption of cyano group (2310
cm ^-1 ). Nitrogen content by elemental analysis is 0.76%
Met. Further, when the hydroxyl value was quantified according to JIS K1557, it was 2.0 mgKOH / g, and the conversion of the hydroxyl group was 94%. (First Step) Next, 4 g of a nickel diatomaceous earth catalyst (nickel content: 50%) and 80 g of the obtained polyoxyalkylene polyol derivative having a benzonitrile skeleton were charged into a 200-ml high-pressure autoclave, and nitrogen replacement was performed 5 times (10 kg) / cm ² G), followed by ammonia at 23 kg / cm ² G and then hydrogen at an initial pressure of 4
It was charged at 0 kg / cm ² G. While stirring, heat up to 120 ° C,
After 5 hours, the reaction was terminated because no pressure drop was observed. After completion of the reaction, the target product, polyoxyalkylene polyamine having a benzylamine skeleton at the molecular terminal, was purified by filtering off the catalyst and drying under reduced pressure. (Second Step) The results are shown in Table 1.

Example 2 In the first step of Example 1, sodium carbonate was used instead of sodium hydroxide, the equivalent ratio of polyol P / o-chlorobenzonitrile / potassium carbonate was changed to 1/1/10, and dimethyl was used as a solvent. The reaction was carried out at 130 ° C. using sulfoxide. In the second step, the catalyst was changed to Raney nickel, and the reaction was carried out at a reaction temperature of 150 ° C. The results are shown in Table 1.

Example 3 In the first step of Example 1, polyoxypropylene polyoxyethylene triol obtained by addition polymerization of glycerin with propylene oxide and then ethylene oxide instead of polyol P (ethylene oxide content 15 wt%, hydroxyl value 33.0 mg KOH / g, average molecular weight 5100; hereinafter abbreviated as polyol Q).
The reaction was carried out under the same conditions as described above. The results are shown in Table 1.

Example 4 In the first step of Example 1, instead of polyol P, polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran (having a hydroxyl value of 112 mgK
OH / g, average molecular weight 1000; hereinafter abbreviated as polyol R)
The reaction was carried out under the same conditions as in Example 1 except that was used.
The results are shown in Table 1.

Example 5 A reaction was performed under the same conditions as in Example 1 except that the reaction temperature was changed to 140 ° C. in the second step of Example 1 without coexisting ammonia. The results are shown in Table 1.

[Effects of the Invention] According to the present invention, it is possible to obtain a polyoxyalkylene polyamine having a benzylamine skeleton at a molecular terminal with a high yield and a high conversion rate by a simpler method than before.

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

Claims (8)

(57) [Claims] 1. The compound of the general formula (I) (Wherein n represents an integer of 2 to 8, R represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), and has a benzonitrile skeleton at the molecular terminal Polyoxyalkylene polyol derivatives. 2. The general formula (1) wherein a polyoxyalkylene polyol is reacted with a cyanobenzyl halide. (Wherein n represents an integer of 2 to 8, R represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), and has a benzonitrile skeleton at the molecular terminal A method for producing a polyoxyalkylene polyol derivative. 3. A compound of the general formula (I) (Wherein n represents an integer of 2 to 8, R represents an n-valent group obtained by removing a hydroxyl group from an n-valent polyoxyalkylene polyol), and has a benzonitrile skeleton at the molecular terminal A process for producing a polyoxyalkylene polyamine having a benzylamine skeleton at a molecular terminal, comprising subjecting a polyoxyalkylene polyol derivative to catalytic hydrogenation. 4. The method for producing a polyoxyalkylene polyol derivative according to claim 2, wherein the polyoxyalkylene polyol is a polyoxypropylene polyol. 5. The method for producing a polyoxyalkylene polyol derivative according to claim 2, wherein the polyoxyalkylene polyol is a polyoxypropylene polyoxyethylene polyol. 6. The method according to claim 2, wherein the polyoxyalkylene polyol is polytetramethylene ether glycol. 7. The method for producing a polyoxyalkylene polyol derivative according to claim 2, which is carried out in the presence of a base. 8. The method for producing a polyoxyalkylene polyamine according to claim 3, which is carried out in the presence of a metal catalyst and hydrogen.