JPS6286020A - Production of novel polyalkylene polyamine - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention involves reacting a tE-position dino-roalkane with ammonia in an aqueous system in the presence of a strong base to form an imine intermediate, and then adding a polyalkylene polyamine to form the intermediate. By obtaining a large amount of the next higher homologous polyalkylene polyamine in the product.

A novel method for improving selectivity of poly-alkylene polyamines.

The production of ethylenediamine from ethylene chloride and ammonia is known. In this process, in addition to ethylenediamine, 5-diethylenetriamine, triethylenetetramine, tetra-ethylenepentamine, pentaethylenehexamine, and small amounts of high-boiling amine residues are produced. In this case, it is not possible to separate into pure compounds, and the fine-framed compounds are worthless.

In some cases, the demand for ethylenediamine is exceeded by the demand for higher homologs, and efforts have been made to increase the relative production of higher components. One way to accomplish this is to reduce the molar ratio of ammonia to ethylene chloride used in the reaction. However, this method is undesirable because it increases the high boiling point cruelty from the process.

U.S. Patent A2,769. B 41 describes a method for reducing the amount of diethylenetriamine produced and increasing the amount of higher homologs produced. In this process, diethylene-triamine is recycled and fed to the reactor along with ethylene chloride and ammonia. However, this method increases the production of undesirable vinyl chloride and
And the amount of high boiling point residue? It is disadvantageous in that it increases

U.S. Pat. No. 3,372,129 discloses a method for producing polymeric polyamines that does not substantially contain cyclic structures in the product. This method involves adding a base, such as NaOH'e, to the reaction mixture containing the amine or ammonia and the alkylene dinolide during the last 60 to 70 hours of the reaction time to bring the total pH of the reaction mixture to about 8.0-8.0.
12.5.

Related processes are disclosed in US Pat. No. 3,356,294 for the preparation of alkyleneimines, and US Pat. No. 3,634,696 for improved methods thereof. The latter approach is described in which a base, such as N--OH, is gradually added to the reaction of ammonia and an alkylene diolide in increasing amounts. This method is reported to yield imines in higher yields than the former patent.

The present invention provides alkylene amide/
This method increases the selection of higher alkylene amines obtained as secondary products without increasing the amount of high-boiling point residues and/or cyclic structure amines produced. This amine is obtained in large quantities in the product. Therefore, by feeding one of the amine series to the process, the next higher amine series will be obtained in larger amounts in the product.

Improvement in the method for producing graded alkylene polyamines by reacting 1,2-dihaloalkane and excess ammonia with 1S in an aqueous system, and adding a strong base completely to the reaction system for at least a certain period of the δ step. The points are as follows.

(1) Carry out reaction 6 at a temperature of 50-70'C7).

Add a strong base to the reaction mixture to keep it on the base side of 12+pHk; (3) Add the hair alkylene polyamine to the reaction mixture; (4) Heat the entire reaction mixture to 10 degrees to 160°C; and (5) The reaction is continued until the 1,2-dihaloalkane is used up, thereby selectively obtaining the next higher amine than the added amine.

The reaction between ammonia and 1,2-dihaloalkane produces an alkylene S/intermediate, which reacts with ammonia to produce a diamine, which then reacts with a large amount of intermediate to produce various A mixture rich in polyalkylene/polyamine is produced. It is preferred to remove excess added alkylene polyamine and separate the desired polyamine product from the mixed product.

Now, if the reaction between ammonia and the intermediate alkylene/imine is diluted with a strong base such as N, OH and then added with certain amines as disclosed in U.S. Pat. The compositional distribution of the product's proboscis changes so that the product is dominated by higher amines, specifically alkylene-imines, and amines added as reactants, followed by MJ-class amines. This is what was discovered here. Therefore, if ethylenediamine (EDA) is added to the reaction of ethylene chloride (EDC) and ammonia (NH3), the dominant amine becomes diethylenetriamine (DETA).

1.2-Dihaloalkane and ammonia are reacted in an aqueous system at a ratio of ammonia to halogen compound of 5:1 to 2.
51]:1, preferably 15:1 to 6U:1. If the stiffness ratio is too small, selectivity will be lost, and if it is large, the cost will increase due to the need to recycle all of the excess ammonia.

The ratio of polyamine to haloalkane is typically 0.25:1
~20:1, but this depends on the anti-Ccl', amine. If this ratio is small, the selectivity to the desired amine will be reduced, and if it is large, it will be necessary to recycle all of the excess polyamine. Therefore, triethylenetetramine (T
The molar ratio of ETA) to 1,2-dino-loalkanes is usually L1.25:1 to 5:1, preferably 1:1 to 2:1. In the case of ethylenediamine, usually 1:1 to 20:1
The ratio is preferably 4:1 to 8:1.

The degree of reaction between halogen compounds and ammonia is 40 to 10
The temperature is 0°C, preferably 5Q to 70°C.

If the degree of soybean is low, the reaction rate will be too low, and if it is high, the selectivity to the desired imine will be reduced. The reaction t = degree of alkylene/polyamine and imine is 50-2 (JO C) preferably 100-15 [J'C. If the temperature is low, the reaction is too slow, if it is high, the vapor pressure is high. Appropriate containers and equipment are required.

The cost will be high.

Although the reaction time is a function of the degree of reaction, it is 15 minutes to 10 hours for the production of imines, and is approximately the same time for polyamine reactions.

The pressure is required to be at a certain level because the reaction takes place in the e-phase. 50 to 2,000 psig (345 psig)
~13,789 kpa) preferably about 200-600
psig (1,379-4,157 kpa).

For neutralization of amine hydrochloride, the base added is preferably caustic soda, but other bases, such as caustic potassium %i and calcium hydroxide, are also effective. Also, gold @j shunkamono can also be used conveniently.

The strong base is applied intermittently or continuously during at least one period of the counterattack process between ammonia and the halogen compound.
It is suitable to add. The rate of loading is controlled by the rate of progress of this reaction, which is a function of temperature. This pH of 6 should be kept on the base side so that the imine intermediate is active, but if too much base is added, undesirable hydrogen halide products such as vinyl chloride is generated.

Although all examples of 1,2-dichloroethane have been shown so far, other 1,2-dihaloalkanes can also be used. For example 1, 2
-dichloropropane and 1,2-dibromopropane,
2,6-di-bromobutane, 1,2-dichlorobutane,
Other 4-dihaloalkanes, such as 1,2-dichloropentane, 2,6-dichloropentane, 1,2-cyclo2-methylpropane, and other 4-position dihaloalkanes such as It is an alkane.

For polyamine reactants, an alkylene polyamine having the general formula: where R is hydrogen, methyl or ethyl, and n is an integer from 1 to 4, is used in the reaction so that the dominant amine is The next highest integer polyamine, a mixed product, can be created. Therefore, ethylenediamine, diethylenetriamine/, triethylenetetramine.

Tetraethylenepentamine (TEPA) i-
Useful are homologous polyamines of and propylene and butyne/. For example, anti-uni-core hediethylenetriamine (DET
When added to A)', triethylenetetramine (TE
TA) becomes the dominant amine, and triethylenetetramine (
If TETA)k is added, tetraethylenepentamine (TEPA) will predominate. There is no doubt that Honjo produces fewer impactions than conventionally known methods.

The following examples show the conventional method (comparison column) and the method of the present invention.

(Example) A 21 stainless steel autoclave reactor, equipped with a heating device, a cooling device, a stirring device, and a heating device, was prepared.

(Comparison DAIA) A reactor was charged with 64U9 of water at room temperature. Then, 20 mol (,540 OS') of ammonia was added.

Stirring was started and the mixture was heated to 160°C for 77°C.

Then 1rnol k of ethylene chloride (EDC) was added.

The mixture* was allowed to react until complete conversion of EDC (60 minutes).

(Comparative example B) Water 2727, ammonia 272 f (16 mol), E
The operation of Comparative Example A above was repeated except that DC1985' (2 mol)'ff was used.

Excess ammonia was carefully evaporated at 40° C. for product analysis. Then 50 liters of NaOHt was slowly added to the reaction. Then, N, (JH
of Beretsu If was added. The amine layer was analyzed by gas chromatography.

The results are shown in the table.

(Example 1) Ethylene chloride 7 (EDC) LJ, 5 mol (49,
5r).

A7 Monia 1 Omol (170f) bf Water 5.1
6 mol (93r) was charged into a warper (room temperature).

After starting stirring, the mixture was quickly heated to 55°C (1
2 minutes]. The mixture was reacted at 55°C for 1.5 hours. Then, 60 N-(')H aqueous solution f [J
, 75 rnl/min. 60 weight 417) N-OH in total is 1079 (0.8 mol
) kFj5 was added. Na0I (triethylenetetramine (TETA) Ll, 75 mo
L(109,5f) was added all at once. Then anti(
The mixture was heated to 110°C and allowed to stand for 2 hours until all the EDC had reacted. Then anti(
The mixture was cooled and analyzed by gas chromatography.

For analysis of raw FM, T ETA 0.65 mol (9
5iP), tetraethylenepentamine (TjiPA) LJ
, 1 mol (195'), and ethylenediamine (E
DA) 0.14 mol (8,4f)'. The other amine produced was diethylenetriamine (DETA)
, piperazine (PIP), aminoethylpiperazine (A
EP), a polyamine with a larger molecular weight than vinyl chloride and TEPA.

(Example 2) Amount of TETA used kt3.75mol (109,51)
Instead of 1. The procedure of Example 1 was repeated except that Omol (1469) was changed. Product analysis was carried out by TE
PAo, 11mol (2U, 8f), TETA Ll,
828 mol (127 r) -j, - and EDA O
, 13 mol (7,87).

(Example 6) EDA instead of TETA O, 75 mol (109,5S') 3. The procedure of Example 1 was repeated except that Omol (180f) 41 was used. Analysis of the product consisted of DETA O, 13 mol (13,4r), T
ETA O, 041 mol (6ji') and EDA2
．． It showed 56 mol (153,6S'). The selectivity for vinyl chloride was 7.2 = 1. All EDCs were responding.

(-4 treatments?Nri 4) The operation of 112 was repeated, but about 1 of the ammonia
0mol (170f) tri, N, OH
It was evaporated using a 0-neck filter before adding TETA. All the conditions of the song were virtually exceeded. The analysis of the proboscis is
TEPAO, 1215mol (23f),
TETA O, 794 mol (116j) and EDA
Ll, LI76mol (4,9f)? Indicated.

The analysis of the remaining product from the wheat after separating the product from the excess chewing agent polyamine is shown in the table. The product composition of the four batches using the conventional method is the same as the comparison column shown in Comparison Column A. The molar ratio of NH3/E o c is 20:1 and is the same in all Examples including Comparative Example A. The pond test, ie comparative IJB, was carried out at a NHs/EDC ratio of 8:1.

Claims (1)

[Claims] 1. Production of higher alkylene polyamines by reacting a vicinal dihaloalkane with excess ammonia in an aqueous system, in which case a strong base is added to the reaction medium during at least part of the reaction process. In the process, the improvements include (1) carrying out the reaction at a temperature of 40 to 100°C; (2) adding a strong base to the reactants so that the pH is kept on the basic side; (3) alkylene polyamines. (4) heating the reaction mixture to a temperature between 50 and 200°C; (5) continuing the reaction until the 1,2-dihaloalkane is exhausted, thereby reducing the added amine. A method for producing a higher alkylene polyamine, comprising: selectively producing a next higher amine. 2. Process according to claim 1, characterized in that excess added alkylene polyamine is removed. 3. Claim 1 or 2, characterized in that the desired polyamine product is separated from the mixed product.
The method described in section. 4. The method according to claim 1, wherein the strong base is added intermittently or continuously. 5. The molar ratio of ammonia to 1,2-dihaloalkane is 5.
5. The method according to claim 1 or claim 4, wherein the ratio is 1 to 50:1. 6. The molar ratio of polyamine to 1,2-dihaloalkane is
The method according to claim 5, characterized in that the ratio is between 0.25:1 and 20:1. 7. Alkylene polyamine has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R is hydrogen, methyl or ethyl, and n
is an integer from 1 to 4). 8. The method of claim 7, wherein R is hydrogen and the 1,2-dihaloalkane is 1,2-dichloroethane. 9. The method according to claim 8, wherein n is 1, 2 or 3. 10. The method according to claim 1, characterized in that step (1) is carried out at a temperature of 50 to 70°C and step (4) is carried out at a temperature of 100 to 130°C.