METHOD FOR THE PREPARATION OF POLYAMINES FROM DINITRILES AND/OR AMINO NITRILES
20190218341 ยท 2019-07-18
Assignee
Inventors
- Thomas REISSNER (Ludwigshafen, DE)
- Ansgar Gereon Altenhoff (Ludwigshafen, DE)
- Christian Mueller (Ludwigshafen, DE)
- Rolf-Hartmuth FISCHER (US)
Cpc classification
International classification
Abstract
The present invention relates to a process for one-stage preparation of polyamines by reacting compounds comprising at least two nitrile groups (dinitrile) or at least one nitrile group and one amino group (amino nitrile) with hydrogen in the presence of heterogeneous transition metal catalysts.
Claims
1: A process for preparing polyamines, the process comprising converting compounds of formula (I)
NCZ.sub.m(X).sub.nY (I) where Z is CH.sub.2CH.sub.2NR, m=0 or 1, where in the case that m=0 NC is bonded directly to X, in the case that m=1 and n=1 NR is bonded to X and R=H or CH.sub.2CH.sub.2CN, and in the case that m=1 and n=0 either R or NR is selected from the group consisting of CH.sub.3, a phenyl group, CH.sub.2CH.sub.2CN and CH.sub.2CH.sub.2CH.sub.2NH.sub.2 or the nitrogen of the NR is part of a heterocycle selected from the group consisting of a piperazine, a (benz)imidazole, a pyrazole, a triazole, and a diazepane, in which another nitrogen of the heterocycle is bonded to Y, X is selected from the group consisting of an alkyl group-substituted or unsubstituted methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonanylene, decanylene, undecanylene, or dodecanylene group; an alkyl group-substituted or unsubstituted 1,2-, 1,3- or 1,4-benzyl group; a 1,4-bicarbonyl group; a 9,10-anthracenyl group; an alkyl group-substituted or unsubstituted 1,2-, 1,3- or 1,4-cycloalkyl group; and a substituted or unsubstituted phenyl-N group of a piperazine, (benz)imidazole, pyrazole, triazole, or diazepane, where the bond to CN or Z and Y or H in each case is via the two nitrogen atoms of the ring, one to two methylene groups may be substituted by linear or branched C.sub.1- to C.sub.12-alkyl, C.sub.6- to C.sub.10-aryl, C.sub.7- to C.sub.12-aralkyl, or C.sub.3- to C.sub.8-cycloalkyl, and at least one methylene group may be replaced by O, NH or NR, where R has the same definition as above and C.sub.1- to C.sub.12-alkyl, C.sub.6- to C.sub.10-aryl, C.sub.7 to C.sub.12-aralkyl, C.sub.3- to C.sub.8-cycloalkyl groups may in turn be substituted by alkyl groups, n is 0 or a natural number from 1 to 10, and Y in the case that m=0 and n=1 or higher is CN, CH.sub.2NH.sub.2 or CH.sub.2CH.sub.2CN, in the case that m=1 and n=1 or higher is NH.sub.2 or NRCH.sub.2CH.sub.2CN, in the case that m=1 and n=0 is H, CH.sub.2CH.sub.2CN, CH.sub.2CH.sub.2CH.sub.2NH.sub.2, alkyl group-substituted or unsubstituted benzyl or cycloalkyl group, and in the case that m=0 and n=0 is CH.sub.2CN, CH.sub.2CH.sub.2CN, CH.sub.2CH.sub.2CH.sub.2CN, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CN, CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CN, CH.sub.2NH.sub.2, CH.sub.2CH.sub.2NH.sub.2, or CH.sub.2CH.sub.2CH.sub.2NH.sub.2, in one stage at temperatures in a range f from 100 to 200 C. and pressures in a range of from 20 to 200 bar, in the presence of hydrogen and a heterogeneous catalyst comprising one or more elements of transition groups 8-10 of the Periodic Table, and in one or two or more reactors, to obtain the polyamines, wherein if the process is conducted in two or more reactors, then the heterogeneous catalyst is the same for each of the two or more reactors.
2: The process of claim 1, wherein the entire process is conducted in one reactor.
3: The process of claim 1, wherein each reaction stage of the process is conducted at the same pressure and the same temperature.
4: The process of claim 1, wherein the compounds of formula I are dinitriles of formula Ia
NC(X).sub.nCN (Ia) or formula IIa
NCCH.sub.2CH.sub.2NR(X).sub.nNHCH.sub.2CH.sub.2CN (IIa) where R, n, and X are as defined in claim 1.
5: The process of claim 1, wherein the compounds of formula I are amino nitriles of formula Ib
NC(X).sub.nCH.sub.2NH.sub.2, (Ib) or formula Ib
NC(X).sub.n (Ib) or formula IIb
NCCH.sub.2CH.sub.2NR(X).sub.nNH.sub.3 (IIb) where R, n, and X are as defined in claim 1.
6: The process of claim 1, wherein the one or more elements of the heterogeneous catalyst is/are selected from the group consisting of Co, Ni, and Cu.
7: The process of claim 1, wherein the heterogeneous catalyst is an unsupported Co catalyst comprising up to 99% by weight of Co.
8: The process of claim 1, wherein the compounds of formula I are dinitriles selected from the group consisting of malononitrile, succinonitrile, glutaronitrile, adiponitrile, suberonitrile, 2-methylmalononitrile, 2-methylsuccinonitrile, 2-methylglutaronitrile, 1,2-, 1,3- and 1,4-dicyanobenzene, 9,10-anthracenodicarbonitrile, and 4,4-biphenyldicarbonitrile.
9: The process of claim 1, wherein the compounds of formula I are amino nitriles used-ee selected from the group consisting of 6-aminocapronitrile, 4-aminobutyronitrile, 3-aminopropionitrile and 2-aminoacetonitrile.
10: The process of claim 1, wherein an excess of hydrogen, based on the amount of hydrogen theoretically needed for hydrogenation of the nitrile groups, of 1 to 5 moles is introduced into a liquid or gas phase of a first reactor, and excess hydrogen together with ammonia formed in the converting is removed from a last reactor.
11: The process of claim 1, wherein ammonia is separated from a discharged ammonia/hydrogen mixture and discharged from the process, and hydrogen separated off is wholly or partly recycled into a reactor.
12: The process of claim 1, wherein an ammonia/hydrogen gas mixture is separated by distillation or after cooling by phase separation.
13: The process of claim 1, wherein a portion of ammonia separated off is recycled into a first reactor.
14: The process of claim 1, which is conducted batchwise or continuously.
15: The process of claim 1, wherein the one or two or more reactors reactor is/are tubular reactors or shell and tube reactors.
16: The process of claim 1, wherein unconverted nitriles and amino nitriles from a crude polyamine output and diamines and polyamine oligomers formed therefrom are separated off by distillation and recycled into a first reactor.
Description
[0246] Preferred Process Variants
[0247]
VARIANT D-1
[0248]
[0249] If the batchwise hydrogenation and polycondensation is conducted not in the presence of a fixed catalyst but of a suspended catalyst, the suspension catalyst is first removed, for example by filtration or centrifugation, when the product is discharged in the course of workup of the product of value.
[0250] The reaction output obtained in the batchwise polycondensation can be passed into a distillation column K1 in which a stream of dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof and oligomers of the dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof is removed at the top. Polyamine is obtained at the bottom of the column.
[0251] The reaction output obtained in the batchwise polycondensation can alternatively be passed into a distillation column K1 in which a stream of dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof is removed at the top, and a fraction consisting essentially of oligomers of the dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof as a side draw. At the bottom of the column, polyamine is drawn off.
VARIANT D-2
[0252]
VARIANT D-3
[0253]
VARIANT K-1
[0254]
[0255] The reaction output is passed to column K1. A mixture of ammonia and hydrogen is the overhead product from column K1, and this is discharged from the process. The bottom product of column K1 is conducted to a column K2. Unconverted dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof is the overhead product from column K2, and is recycled into the reactor R1. Oligomers are optionally drawn off from a side draw from column K2, and these are discharged and/or recycled into the reactor R1. The bottom product of column K2 comprises polyamine.
VARIANT K-2
[0256]
[0257] The reaction output is passed to column K1. The overhead product of column K1 is a mixture of ammonia and hydrogen, out of which the ammonia is condensed. Inert gas and/or hydrogen can be recycled into the reactor R1.
[0258] The bottom product of column K1 is conducted to a column K2. Unconverted dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof and low-boiling oligomer are the overhead product from column K2, and are recycled into the reactor R1. Oligomers are optionally drawn off from a side draw of column K2, and these are discharged and/or recycled into the reactor R1. The bottom product of column K2 comprises polyamine.
VARIANT K-3
[0259]
[0260] Dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof are passed together with inert gas and/or hydrogen over a catalyst arranged in fixed bed form in an inertized pressure reactor R1. Under the reaction conditions, a reaction output is formed, which is passed to a column K1. Column K1 is operated in such a way that the top product obtained is a mixture of ammonia and inert gas and/or hydrogen mixture, a mixture of dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof and oligomers of the dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof is withdrawn from a side draw, and polyamine is withdrawn as bottom product. Column K2 in
[0261] Any unconverted dinitrile/trinitrile/amino nitrile of the formula (I) and the corresponding diamines thereof and oligomeric polyamines can be separated off by distillation and recycled into the polyamine synthesis stage.
6. WORKING EXAMPLES
6.1. One-Stage Preparation of Polyhexamethylenepolyamine from Adiponitrile (Batchwise Mode)
[0262] The experiments were conducted in a 300 mL steel pressure vessel stirred with a paddle stirrer. Hydrogen was fed in via an inlet tube. In the upper part of the pressure vessel, it was optionally possible to lead off offgas, which was conducted without cooling into the middle of a vertical steel tube (internal diameter 1.4 cm, height 16 cm). Liquid condensate obtained here was recycled into the lower part of the pressure vessel, and offgas was led off from the apparatus via the steel tube.
[0263] The catalyst used was a cobalt catalyst having a strand diameter of 4 mm. Preparation thereof is described in EP-A-0636409. The shaped catalyst bodies were reduced at 280 C. and standard pressure by means of a continuous hydrogen stream of 50 L (STP) per hour for 12 hours. As feedstock, 50 g of adiponitrile (ADN) were initially charged in the pressure vessel under nitrogen. 50 g of the activated catalyst were fixed in a metal cage, through which the stirred reaction mixture flowed. The polycondensation was effected at 160 C. and total pressure 60 bar for 4 hours. After the reaction time, the autoclave was cooled to room temperature and decompressed. The reaction mixture was removed from the autoclave. The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards).
Example 1a
[0264] The experiment was conducted as described above. In the pressure vessel, a total pressure of 60 bar was maintained by injection of hydrogen over the entire experimental period. No offgas was led out of the pressure vessel. Analysis of the reaction output (table 1) shows that just 11% polyamines (high boilers) had formed.
Example 1b
[0265] The experiment was conducted as described above. During the reaction time of four hours, however, 2.4 moles of hydrogen per mole of ADN per hour were passed continuously through the pressure vessel at a pressure of 60 bar and disposed of. Liquid condensate was recycled into the pressure vessel. The structures of the hexamethyleneimine (HMI), aminohexyl-HMI, HMI-HMD-HMI, bis-HMD and HMI-(HMD).sub.2 by-products are shown in
TABLE-US-00001 TABLE 1 HMI- T Amino- Bis- HMD- HMI- High Ex. [ C.] HMI HMD hexyl-HMI HMD HMI (HMD)2 Others boilers M.sub.w PDI 1a 160 13 47 1 23 5 11 1b 160 9 2 6 9 1 4 7 62 750 1.6
[0266]
##STR00002##
[0267] Analysis of the reaction output (table 1) demonstrates that the passage of hydrogen with removal of ammonia formed considerably increases the conversion and leads to average molar masses of 750 g/mol.
6.2. One-Stage Preparation of Polyhexamethylenepolyamine from Adiponitrile (Continuous Mode)
Example 1c
[0268] Adiponitrile was passed continuously from the bottom upward through a catalyst present in a tubular reactor. The catalyst used was 378 g of activated cobalt catalyst having a strand diameter of 4 mm, the preparation of which is described in EP-A-0636409 as catalyst A on page 3 lines 35-44. The pressure was 50 bar, the temperature 170 C. The catalyst hourly space velocity was 0.1 kg/Lh of adiponitrile. 5 moles of hydrogen per mole of adiponitrile were passed through the reactor (offgas mode). The crude output was a white, waxy solid. The composition of the crude discharge is summarized in Table 2. The molar mass was determined after distillative removal of HMI, HMD, aminohexyl-HMI and bis-HMD.
[0269] Table 2
TABLE-US-00002 TABLE 2 Amino- HMI- hexyl- Bis- HMD- HMI- High T [ C] HMI HMD HMI HMD HMI (HMD)2 Others boilers M.sub.w PDI 170 1 0 2 0 9 1 14 73 1996 1.7
6.3. One-Stage Preparation of Polyoctamethylenepolyamine from Suberonitrile (Batchwise Mode)
Example 2
[0270] The experiment was conducted analogously to example 1b. The starting material used was suberonitrile. Over the four hours of reaction time, 1.8 moles of hydrogen per mole of adiponitrile per hour were passed continuously through the pressure vessel and disposed of. Liquid condensate was recycled into the pressure vessel.
[0271] The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards). The analysis results are summarized in table 3.
TABLE-US-00003 TABLE 3 High T [ C.] 1,8-Diaminooctane Suberonitrile Dimer Others boilers Mw PDI 160 17 0 20 3 60 570 3.2
6.4. One-Stage Preparation of Polyhexamethylenepolyamine from 6-Aminocapronitrile (6-ACN) (Continuous Mode)
Example 3
[0272] The experiment was conducted analogously to example 1c. 6-Amlnocapronitrile was passed continuously from the bottom upward through a catalyst present in a tubular reactor. The catalyst used was 378 g of activated cobalt catalyst having a strand diameter of 4 mm, the preparation of which is described in EP-A-0636409 as catalyst A on page 3 lines 35-44. The pressure was 50 bar, the temperature 170 C. The catalyst hourly space velocity was 0.1 kg/Lh of 6-aminocapronitrile. 2 moles of hydrogen per mole of 6-aminocapronitrile were passed through the reactor (offgas mode). The crude output was a white, waxy solid. The composition of the crude output is summarized in table 4. The molar mass was determined after distillative removal of HMI, HMD, aminohexyl-HMI and bis-HMD.
TABLE-US-00004 TABLE 4 HMI- T Amino- Bis- HMD- HMI- High [ C.] HMI HMD hexyl-HMI HMD HMI (HMD)2 Others boilers M.sub.w PDI 170 3 1 4 1 5 3 8 75 1634 1.8
[0273] Analysis of the reaction output showed that, with complete 6-ACN conversion and virtually complete HMD conversion, polyhexamethylenepolyamine molar masses of around 1634 g/mol were attained.
6.5. One-Stage Preparation of Polyamine from Dicyanoethylated Isophoronediamine (IPDA) (Continuous Mode)
Example 4
[0274] The experiment was conducted analogously to the one-stage preparation of polyhexamethylenepolyamine in continuous mode (analogously to experiment 1c). For this purpose, dicyanoethylated IPDA was passed continuously from the bottom upward through a catalyst. The catalyst used was 378 g of activated cobalt catalyst having a strand diameter of 4 mm, the preparation of which is described in EP-A-0636409 as catalyst A on page 3 lines 35-44. The pressure was 50 bar, the temperature 160 C. The reaction was conducted in the presence of THF as solvent. The reactant was dissolved in 50% by weight of THF. The catalyst hourly space velocity was 0.1 kg/Lh of reactant dissolved in THF. 12 moles of hydrogen per mole of cyanoethylated IPDA were passed through the reactor (offgas mode). The crude output was viscous and clear. The composition of the crude output is summarized in table 5. The molar mass was determined after distillative removal of THF, 3,3,5-trimethyl-7-azabicyclo[3.2.1]octane (IPDA-ring) and IPDA.
##STR00003##
TABLE-US-00005 TABLE 5 High T [ C.] THF IPDA-Ring IPDA Others boilers Mw PDI 160 15 2 1 6 76 1096 1.8
6.6. One-Stage Preparation of Polyamines from Cyanoethylated Precursor Molecules (Batchwise Mode)
[0275] Examples 5 to 10 were conducted analogously to example 1b.
Example 5
[0276] As feedstock, 70 g of N,N-bis(2-cyanoethyl)piperazine dissolved in 70 g of THF were initially charged under nitrogen in the pressure vessel. 50 g of the activated catalyst were fixed in a metal cage, through which the stirred reaction mixture flowed. The polymerization was effected at 160 C. and total pressure 50 bar for 5 hours. The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards). The composition of the crude output is summarized in table 6.
##STR00004##
TABLE-US-00006 TABLE 6 N-(3- N,N-Bis(3- Aminopropyl)- aminopropyl)- T [ C.] THF piperazine piperazine Others High boilers Mw PDI 160 35 1 7 5 52 930 1.8
Example 6
[0277] As feedstock, 60 g of N-(2-cyanoethyl)piperazine dissolved in 60 g of THF were initially charged under nitrogen in the pressure vessel. 50 g of the activated catalyst were fixed in a metal cage, through which the stirred reaction mixture flowed. The polymerization was effected at 160 C. and total pressure 50 bar for 5 hours. The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards). The composition of the crude output is summarized in table 7.
##STR00005##
TABLE-US-00007 TABLE 7 N-(3- T Aminopropyl)- High [ C.] THF piperazine Dimer Others boilers Mw PDI 160 32 10 19 7 32 400 1.6
Example 7
[0278] As feedstock, 70 g of N,N-bis(2-cyanoethyl)phenylene-1,3-diamine dissolved in 70 g of THF were initially charged under nitrogen in the pressure vessel. 50 g of the activated catalyst were fixed in a metal cage, through which the stirred reaction mixture flowed. The polymerization was effected at 160 C. and total pressure 50 bar for 5 hours. The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards). The composition of the crude output is summarized in table 8.
##STR00006##
TABLE-US-00008 TABLE 8 N-(3- N,N-Bis(3- aminopropyl)- aminopropyl)- phenylene-1,3- phenylene-1,3- T [ C.] THF diamine diamine Others High boilers Mw PDI 160 31 12 8 9 40 440 1.8
Example 8
[0279] As feedstock, 70 g of N,N-bis(2-cyanoethyl)tolylene-2,4-diamine dissolved in 70 g of THF were initially charged under nitrogen in the pressure vessel. 50 g of the activated catalyst were fixed in a metal cage, through which the stirred reaction mixture flowed. The polymerization was effected at 160 C. and total pressure 50 bar for 5 hours. The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards). The composition of the crude output is summarized in table 9.
##STR00007##
TABLE-US-00009 TABLE 9 N,N-Bis(3- aminopropyl)-2,4- T [ C.] THF tolylenediamine Others High boilers Mw PDI 160 30 28 22 20 350 1.7
Example 9
[0280] As feedstock, 70 g of N,N-bis(2-cyanoethyl)aniline dissolved in 70 g of THF were initially charged under nitrogen in the pressure vessel. 50 g of the activated catalyst were fixed in a metal cage, through which the stirred reaction mixture flowed. The polymerization was effected at 160 C. and total pressure 50 bar for 5 hours. The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards). The composition of the crude output is summarized in table 10.
##STR00008##
TABLE-US-00010 TABLE 10 N,N-Bis(3- aminopropyl)- T [ C.] THF aniline Others High boilers Mw PDI 160 35 33 27 5 1097 2.6
Example 10
[0281] As feedstock, 70 g of N,N-bis(2-cyanoethyl)methyldiaminecyclohexane dissolved in 70 g of THF were initially charged under nitrogen in the pressure vessel. 50 g of the activated catalyst were fixed in a metal cage, through which the stirred reaction mixture flowed. The polymerization was effected at 160 C. and total pressure 50 bar for 5 hours. The reaction outputs were analyzed by gas chromatography (% by weight) and by gel permeation chromatography (absolute calibration by measurement of defined polyamine standards). The composition of the crude output is summarized in table 11.
##STR00009##
TABLE-US-00011 TABLE 11 N,N- Bis(3-aminopropyl)- methyl- High T [ C.] THF diaminocyclohexane Others boilers Mw PDI 160 31 33 16 53 593 1.7