KR950015131B1 - Process for producing polyalkylen oxide-diamine - Google Patents

Abstract

The polyalkylene oxide diamine of formula (I) is prepd. by : reacting polyalkylene oxide of formula (II) and thionyl chloride in polar solvent; adding amine cpd. of formula (III) and reacting with ammonia gas at 50-100 deg.C under 5-10 kg/cm2. In the formulas, n is integer of 60-110; R is ethylene or propylene gp,; R' is C1-3 alkyl. Pref. the polar solvent is toluene, methylethylketone or xylene. The obtd. polyalkylene oxide diamine (I) is useful as a hardening agent for epoxy resin or urethane and a modifier for polyamide. The process reduces the cost of production , and gives good colorness of (I).

Description

Method for preparing polyalkylene oxide diamine

The present invention relates to a novel method for producing a polyalkylene oxide diamine represented by the following general formula (I).

Wherein n is an integer of 60-110 and R is an ethylene group or a propylene group.

The general formula (I) is a polyalkylene oxide diamine is a known compound used as a curing agent and polyamide modifier of epoxy resin, urethane, etc. for a special use. Unlike general low-molecular weight compounds, the technique of substituting a terminal group or a special functional group with another group in a high molecular compound is known as a very difficult technique.

As a conventional technique, Japanese Patent Publication No. 59-12660 discloses a method for producing polyethylene oxide diamine from polyethyleneolside using cyanoethylation reaction and high pressure hydrogen reaction. However, this method requires high pressure equipment of 100-150㎏ / ㎠ for high pressure hydrogen reduction reaction, and it is uneconomical because the reaction time is long due to two-stage reaction of high pressure hydrogen reduction reaction and cyanoethylation reaction. Discoloration is easy

On the other hand, the production method according to the present invention can shorten the reaction time by immediately replacing the chlorine group with the substitution of the amine group, and can economically obtain the target substance by relatively low pressure reaction (5-10 kg / cm 2). It is a method and is excellent also in the color of the product.

The structure of the manufacturing method of this invention is as follows. The polyalkylene oxide represented by the following general formula (II) is first reacted with thionyl chloride in a polar solvent to be firstly substituted with a chlorine group. At this time, the polar solvent used may be toluene, methyl ethyl ketone, xylene and the like, most preferably toluene, and reacted at 50-60 ° C. for 1 hour to prepare a polyalkylene oxide compound in which the sock end is substituted with a chlorine group. do. Subsequently, the amine compound of the following general formula (III) was added, ammonia gas was pressurized at 5-10 kg / cm 2, and reacted for 1-3 hours to prepare a polyalkylene oxide diamine of the following general formula (I).

Wherein n is an integer of 60-110, R is an ethylene group or a propylene group, and R 'is an alkyl group having 1-3 carbon atoms.

In this case, when n is 60 or less in the polyalkylene oxide of Formula (II), the side reaction becomes severe under the conditions of the present invention, and the color quality is lowered. If the pressure of the ammonia gas is 5 kg / cm 2 or less, or the reaction temperature is 50 ° C. or less, the substitution rate decreases, and the total amine value decreases. If the temperature of the ammonia gas is 100 ° C. or more, the side reaction proceeds to obtain a high molecular weight product. .

The reactor tool of the present invention is as follows.

Wherein n is an integer of 60-110, R is an ethylene group or a propylene group, and R 'is an alkyl group having 1-3 carbon atoms.

The reaction is a Nucleophilic Substitution, and is an easy reaction because it proceeds in a two-step reaction or in-situ. In the reactor operation of ii), (R ′) ₃ N acts as an Acid Capture.

The present invention is embodied by the following examples and comparative examples.

Example 1

100 parts by weight of polyethylene oxide 4000 (n = 90), 3 parts by weight of thionyl chloride, and 250 parts by weight of toluene were added to a reactor and reacted at 55 ° C for 1 hour. Then, 2.7 parts by weight of triethylamine was added and 7 kg / of ammonia at 80 ° C. After reacting at a pressure of cm 2 for 1.5 hours, a white wax (wax) solid having a melting point of 61 ° C. was obtained to recover the solvent.

Example 2

It proceeded in the same manner as in Example 1 except that polyethylene oxide 3000 (n = 60) was used.

Example 3

The same procedure as in Example 1 was carried out except that polystyrene oxide 5000 (n = 110) was used.

[Comparative Example]

Japanese Patent Publication No. 59-12660.

100 parts by weight of dicyanoethylate of polyethylene oxide having a molecular weight of 4000, 70 parts by weight of ethylene glycol and 25 parts by weight of lanicobalt were added to an autoclave and reacted at 120 ° C. and hydrogen pressure of 150 kg / cm 2 for 30 minutes. The catalyst was removed to give a pale yellow waxy solid.

Each characteristic measurement method of the said Example and a comparative example is as follows.

Melting point; Melting points were investigated by scanning between 0-100 ° C. at a rate of 10 ° C./min with DSC (differential scanning calorimetry). Unit: ℃.

* color ; The sample was placed in a colorimetric tube, heated to make it transparent, and then the standard colorimetric tube was placed from side to side and compared (Hagen method).

* Total amine number; After taking a sample and dissolving in methanol, it was calculated by titrating bromocresol red with hydrochloric acid standard solution as an indicator. unit ; Equivalent / g.

The results are shown in Table 1 below.

TABLE 1

As a result, the polyalkylene oxide diamine according to the production method of the present invention is more excellent in color at a similar level (Example 1, Example 4, Comparative Example), shorter reaction time and relatively low pressure reaction As a result, it was found that the production equipment can be easily manufactured economically.

Claims (2)

After reacting the polyalkylene oxide of the following general formula (II) with thionyl chloride under a polar solvent, the amine compound of the following general formula (III) was added thereto, and 5-10 kg of ammonia gas at a reaction temperature of 50-100 ° C. A method for producing a polyalkylene oxide diamine of the following general formula (I), characterized by reacting at a pressure of / cm 2. Wherein n is an integer of 60-110, R is an ethylene group or a propylene group, and R 'is an alkyl group having 1-3 carbon atoms. The method for producing a polyalkylene oxide diamine of the general formula (I) according to claim 1, wherein the polar solvent is toluene, methyl ethyl ketone or xylene.