WO1995030666A1 - Tertiäres diamin, verwendung als katalysator und verfahren zur herstellung von tertiären diaminen - Google Patents
Tertiäres diamin, verwendung als katalysator und verfahren zur herstellung von tertiären diaminen Download PDFInfo
- Publication number
- WO1995030666A1 WO1995030666A1 PCT/EP1995/001773 EP9501773W WO9530666A1 WO 1995030666 A1 WO1995030666 A1 WO 1995030666A1 EP 9501773 W EP9501773 W EP 9501773W WO 9530666 A1 WO9530666 A1 WO 9530666A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- methylpiperidino
- dinitrile
- bis
- methylpentane
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
Definitions
- Tertiary diamine Use as a catalyst and process for the preparation of tertiary diamines
- the present invention relates to a process for the preparation of tertiary diamines with two saturated heterocyclic rings from aliphatic dinitriles connected by an aliphatic carbon chain, and to a new tertiary diamine and its use as a catalyst for the production of polyurethanes.
- Tertiary diamines such as 1,5-dipiperidinopentane are valuable compounds because of their high basicity and relatively low volatility, which can be used, for example, as hardeners in epoxy resins (DE-PS 1032 920).
- a more recent use of such compounds is the use as a starting material for the preparation of emulsion stabilizers for blood substitutes (EP-A 0415 263).
- the object of the present invention was therefore to provide a simple process which provides tertiary diamines with two saturated heterocyclic rings connected by an aliphatic carbon chain in good yield and without the production of large amounts of waste products.
- A has the meaning given above, can be prepared.
- 4 mol of ammonia are formed on 1 mol of diamine.
- the hydrogenation is expediently carried out at a temperature of 100-250 ° C. and under elevated pressure in the presence of a supported palladium catalyst.
- Palladium on aluminum oxide is preferably used as the supported palladium catalyst. Good results have been achieved with relatively low palladium contents of, for example, 1%.
- the hydrogen pressure in the hydrogenation is preferably greater than 10 bar and is, for example, approximately 50 bar.
- a temperature of 150 to 220 ° C. is preferably set as the reaction temperature, for example 180 ° C.
- the hydrogenation is preferably carried out continuously.
- the dinitrile together with hydrogen is passed over the catalyst in a suitable reactor.
- Suitable carbon chains A are preferably 1,2-ethanediyl, 1,3-propanediyl, 1,4-butanediyl or 1,3-butanediyl ( ⁇ l-methyl-l, 3-propanediyl), corresponding to the dinitriles of succinic acid dinitrile, glutaric acid dinitrile, Adiponitrile or 2-methylglutaronitrile.
- 2-methyl-glutaronitrile which as a new product is l, 5-bis (3-methylpiperidino) -2-methylpentane of the formula
- This compound is particularly suitable as a catalyst for the production of polyurethanes, polyurethane / polyurea mixtures and polyureas.
- the polymers can thus be produced both as elastomers and in the form of foams.
- the hydrogen flows are based on normal conditions, and the throughput is given in g starting material per g catalyst and hour.
- the product composition was determined by gas chromatography.
- Example 2 In a reactor (13 mm 0) 3 g of a Pd / MgCl2 / Al2 ⁇ 3 catalyst (grain size 0.315-1 mm) were filled, which contained 1% Pd and 1.2% Mg. A temperature of 170 ° C. and a pressure of 50 bar were set in a stream of hydrogen (120 ml / min). Then 99.8% 2-methylglutaronitrile (MGN) was added. The throughput was 2.1 g / (g h).
- MGN 2-methylglutaronitrile
- VL Desmodur® VL from Bayer, aromatic diisocyanate with approx. 32% - CO D550U: Desmophen® 550U, polypropylene glycol from Bayer, trifunctional with 10.5% —OH
- DBU served as a comparative catalyst. Desmophen was presented with the amine (DBU or BMPMP) and mixed well. A solution was found. In Examples 6 and 7, water was also added. An emulsion / solution was formed. A weighed-in amount of isocyanate (VL) was added at time t - * - * ⁇ 0 with vigorous stirring. The times at which were noted
- MPI and MGN were then passed over the catalyst in a molar ratio of 2: 1.
- concentrations were found in the product stream (GC): 18.9% MPI, 70.6% l, 5-bis (3-methypiperidino) -2-methylpentane, remainder: 10.5%.
- the test results show that MPI alone is not converted to 1,5-bis (3-methylpiperidino) -2-methylpentane. However, MPI, when added to the MGN, is incorporated into the desired product.
- Example 9 3 g of a Pd / A_2 ⁇ 3 catalyst (1% Pd, grain size 0.315-1 mm) were introduced into a reactor (13 mm 0). A temperature of 180 ° C. and a pressure of 50 bar were set in a stream of hydrogen (140 ml / min). Then glutaronitrile was added. The throughput was 2.1 g (g h). With a conversion of 98.6%, the product stream contained 34.6% 5-piperidinopentanenitrile, 32.4% 1,5-dipiperidinopentane and 5.5% piperidine (GC) after a reaction time of 4 h.
- GC piperidine
- the product stream contained 26% 6- (hexahydro-lH-azepin-l-yl) hexanitrile, 20% l, 6-bis (hexahydro-lH-azepin-l-yl) after a reaction time of 3 h hexane and 13% hexahydro-lH-azepine (GC).
- 6- hexahydro-lH-azepin-l-yl
- 6-bis hexahydro-lH-azepin-l-yl
- Examples 1 and 11-13 show that the highest selectivity for the formation of the bis (methylpiperidino) compound is achieved at a molar ratio MGN. ⁇ 2 of approximately 1: 5.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU25632/95A AU686387B2 (en) | 1994-05-10 | 1995-05-10 | Tertiary diamine, its use as catalyst and method for preparation of tertiary diamines |
DE59503712T DE59503712D1 (de) | 1994-05-10 | 1995-05-10 | Tertiäres diamin, verwendung als katalysator und verfahren zur herstellung von tertiären diaminen |
US08/737,309 US5698607A (en) | 1994-05-10 | 1995-05-10 | Tertiary diamine, its use as catalyst, and process for preparing tertiary diamines |
EP95920018A EP0759914B1 (de) | 1994-05-10 | 1995-05-10 | Tertiäres diamin, verwendung als katalysator und verfahren zur herstellung von tertiären diaminen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH146094A CH686134A5 (de) | 1994-05-10 | 1994-05-10 | Tertiores Diamin, Verwendung als Katalysator und Verfahren zur Herstellung von tertioren Diaminen. |
CH1460/94 | 1994-05-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995030666A1 true WO1995030666A1 (de) | 1995-11-16 |
Family
ID=4210996
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1995/001773 WO1995030666A1 (de) | 1994-05-10 | 1995-05-10 | Tertiäres diamin, verwendung als katalysator und verfahren zur herstellung von tertiären diaminen |
Country Status (6)
Country | Link |
---|---|
US (1) | US5698607A (de) |
EP (1) | EP0759914B1 (de) |
AU (1) | AU686387B2 (de) |
CH (1) | CH686134A5 (de) |
DE (1) | DE59503712D1 (de) |
WO (1) | WO1995030666A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0962447A2 (de) * | 1998-06-06 | 1999-12-08 | Basf Aktiengesellschaft | Verfahren zur Herstellung von sekundären bzw. tertiären 2-Methyl-1,5-pentandiaminen |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014215382A1 (de) * | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1032920B (de) * | 1956-09-24 | 1958-06-26 | Leuna Werke Iawalter Ulbrichti | Verfahren zum Haerten von Glycidylpolyaethern |
DE1034180B (de) * | 1955-08-11 | 1958-07-17 | Basf Ag | Verfahren zur Herstellung von gesaettigten cyclischen Diaminen |
US3787496A (en) * | 1971-04-29 | 1974-01-22 | Exxon Research Engineering Co | Preparation of aromatic compounds via benzyne intermediates |
EP0415263A2 (de) * | 1989-08-30 | 1991-03-06 | Kali-Chemie Aktiengesellschaft | Stabilisierung von Perfluorcarbonemulsionen und als emulsionsstabilisierende Zusätze verwendbare perfluorierte heterocyclische Verbindungen |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL211157A (de) * | 1956-11-27 | |||
US3673251A (en) * | 1969-04-30 | 1972-06-27 | Nat Distillers Chem Corp | Process for the catalytic reductive amination of nitriles |
US3728284A (en) * | 1970-07-29 | 1973-04-17 | Eastman Kodak Co | Nitrile hydrogenation catalyst |
US3886193A (en) * | 1971-04-29 | 1975-05-27 | Exxon Research Engineering Co | Preparation of aromatic compounds via benzyne intermediates |
US3898286A (en) * | 1973-11-19 | 1975-08-05 | Phillips Petroleum Co | Catalytic hydrogenation of unsaturated dinitriles employing palladium and ruthenium as catalyst |
DE3104765A1 (de) * | 1981-02-11 | 1982-09-02 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von pyridinen oder pyrrolen aus (alpha),(omega)-dinitrilen |
US4885391A (en) * | 1988-01-14 | 1989-12-05 | E. I. Du Pont De Nemours And Company | Production of C4 to C12 amines |
WO1991003442A2 (de) * | 1989-08-30 | 1991-03-21 | Kali-Chemie Aktiengesellschaft | Verfahren zur auftrennung von gemischen partiell fluorierter oder perfluorierter kohlenwasserstoffverbindungen |
DE4019061A1 (de) * | 1989-08-30 | 1991-03-07 | Kali Chemie Ag | Verfahren zur herstellung perfluorierter heterocyclischer verbindungen und nach diesem verfahren hergestellte verbindungen |
-
1994
- 1994-05-10 CH CH146094A patent/CH686134A5/de not_active IP Right Cessation
-
1995
- 1995-05-10 US US08/737,309 patent/US5698607A/en not_active Expired - Lifetime
- 1995-05-10 AU AU25632/95A patent/AU686387B2/en not_active Ceased
- 1995-05-10 WO PCT/EP1995/001773 patent/WO1995030666A1/de active IP Right Grant
- 1995-05-10 EP EP95920018A patent/EP0759914B1/de not_active Expired - Lifetime
- 1995-05-10 DE DE59503712T patent/DE59503712D1/de not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1034180B (de) * | 1955-08-11 | 1958-07-17 | Basf Ag | Verfahren zur Herstellung von gesaettigten cyclischen Diaminen |
DE1032920B (de) * | 1956-09-24 | 1958-06-26 | Leuna Werke Iawalter Ulbrichti | Verfahren zum Haerten von Glycidylpolyaethern |
US3787496A (en) * | 1971-04-29 | 1974-01-22 | Exxon Research Engineering Co | Preparation of aromatic compounds via benzyne intermediates |
EP0415263A2 (de) * | 1989-08-30 | 1991-03-06 | Kali-Chemie Aktiengesellschaft | Stabilisierung von Perfluorcarbonemulsionen und als emulsionsstabilisierende Zusätze verwendbare perfluorierte heterocyclische Verbindungen |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0962447A2 (de) * | 1998-06-06 | 1999-12-08 | Basf Aktiengesellschaft | Verfahren zur Herstellung von sekundären bzw. tertiären 2-Methyl-1,5-pentandiaminen |
US6198002B1 (en) | 1998-06-06 | 2001-03-06 | Basf Aktiengesellschaft | Preparation of secondary and tertiary 2-methyl-1, 5-pentanediamines |
EP0962447A3 (de) * | 1998-06-06 | 2002-01-02 | Basf Aktiengesellschaft | Verfahren zur Herstellung von sekundären bzw. tertiären 2-Methyl-1,5-pentandiaminen |
Also Published As
Publication number | Publication date |
---|---|
EP0759914A1 (de) | 1997-03-05 |
AU2563295A (en) | 1995-11-29 |
DE59503712D1 (de) | 1998-10-29 |
EP0759914B1 (de) | 1998-09-23 |
AU686387B2 (en) | 1998-02-05 |
CH686134A5 (de) | 1996-01-15 |
US5698607A (en) | 1997-12-16 |
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