WO2008089010A1 - Préparation de diamines secondaires - Google Patents

Préparation de diamines secondaires Download PDF

Info

Publication number
WO2008089010A1
WO2008089010A1 PCT/US2008/050662 US2008050662W WO2008089010A1 WO 2008089010 A1 WO2008089010 A1 WO 2008089010A1 US 2008050662 W US2008050662 W US 2008050662W WO 2008089010 A1 WO2008089010 A1 WO 2008089010A1
Authority
WO
WIPO (PCT)
Prior art keywords
diamine
ketone
aliphatic primary
carbon
aliphatic
Prior art date
Application number
PCT/US2008/050662
Other languages
English (en)
Inventor
John Y. Lee
Paul L. Wiggins
Original Assignee
Albemarle Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Albemarle Corporation filed Critical Albemarle Corporation
Publication of WO2008089010A1 publication Critical patent/WO2008089010A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to the preparation of secondary diamines from primary diamines.
  • This invention provides processes for preparing aliphatic secondary diamines under mild conditions.
  • An advantage of the relatively mild pressure and temperature conditions used in the processes of the invention is that ordinary process apparatus can be employed, so there is no need for specialized equipment, such as that required for high- pressure reactions.
  • An embodiment of this invention is a process for forming a secondary diamine.
  • the process comprises bringing together i) at least one aliphatic cyclic ketone, ii) at least one aliphatic primary diamine, iii) hydrogen, and iv) a hydrogenation catalyst.
  • the aliphatic primary diamine is isophoronediamine or an aliphatic primary ⁇ , ⁇ -diamine
  • the hydrogenation catalyst is selected from platinum on carbon, palladium on carbon, sulfided platinum on carbon, sulfided palladium on carbon, and a mixture of any two of the foregoing.
  • the process is conducted at a temperature in the range of about 2O 0 C to about 75 0 C and at a hydrogen pressure in the range of about 1 to about 95 pounds per square inch gauge (1.08xl0 5 to 7.56xlO 5 Pa), such that a secondary diamine is formed.
  • Diimines that are products of a reaction of a primary diamine and a carbonyl compound are sometimes called Schiff bases, and such diimines are formed by at least some of the processes of the invention.
  • the carbonyl compound used to form the diimine is a ketone, such a diimine is occasionally referred to as a ketimine or diketimine.
  • reductive alkylation The formation of a secondary diamine from a primary diamine and a ketone is often referred to as reductive alkylation or reductive amination, and the terms “reductive alkylation” and “reductive amination” can be used to describe the processes of this invention.
  • psig pounds per square inch gauge
  • the processes of the invention prepare aliphatic secondary diamines in one step via the bringing together of a ketone, an aliphatic primary diamine, hydrogen, and a hydrogenation catalyst.
  • the ketone is at least one aliphatic cyclic ketone
  • the aliphatic primary diamine is at least one aliphatic primary diamine which is isophoronediamine or an aliphatic primary ⁇ , ⁇ -diamine
  • the hydrogenation catalyst is selected from platinum on carbon, palladium on carbon, and a mixture thereof.
  • aliphatic cyclic hydrocarbyl ketones are used; these ketones include monoketones, diketones, and polyketones.
  • the hydrocarbyl portion of the ketone is a ring, which ring can be bicyclic, and there can be one or more substituents on the ring.
  • the ketones used in the practice of this invention preferably have from five to about twenty carbon atoms. More preferred are ketones having from five to about fifteen carbon atoms.
  • the substituent(s) on the ring are aliphatic, and can be cyclic, branched, or straight chain, and are preferably branched or straight chain. Preferred substituents have from one to about six carbon atoms. Suitable substituents include methyl, ethyl, propyl, isopropyl, 1,1-dimethylpropyl, n-butyl, sec-butyl, cyclobutyl, 2- ethylbutyl, n-pentyl, 2-pentyl, 2-methylpentyl, cyclopentyl, hexyl, cyclohexyl, methylcyclohexyl, menthyl, 2-ethylhexyl, heptyl, cyclooctyl, 5-nonyl, decyl, dodecyl, and the like.
  • Suitable monoketones include cyclobutanone, 2-dodecyl-cyclobutanone, 3- isopropyl-cyclobutanone, cyclopentanone, 2-methyl-cyclopentanone, 3-ethyl-cyclo- pentanone, 3-sec-butyl-cyclopentanone, 2,5-dimethyl-cyclopentanone, 2-pentyl-cyclo- pentanone, cyclohexanone, 2-methyl-cyclohexanone, 3-n-propyl-cyclohexanone, 3- cyclobutyl-cyclohexanone, 4-ethyl-cyclohexanone, 3-isopropyl-l -cyclohexanone, 4-tert- butyl-cyclohexanone, 2-(2-methylpentyl)-cyclohexanone, 2-(2-ethylhexyl)-cyclo- hexanone, 4-(l,l-dimethyl
  • diketones or polyketones can be employed.
  • diketones that can be used in the practice of this invention include tetramethyl- ⁇ S-cyclobutanedione, 1,3-cyclopentanedione, 1,3-cyclohexanedione, 2-methyl-l,3-cyclopentanedione, 1,4-cyclohexanedione, 1,3-cycloheptanedione, 1,4- cycloheptanedione, 5-methyl- 1 ,3-cyclohexanedione, 4,4-dimethyl- 1 ,3-cyclohexanedione, 5-isopropyl- 1,3-cyclohexanedione, bicyclo[3.3.1]nonane-3,7-dione, bicyclo[3.3.1]nonane- 2,6-dione, l,5-di
  • the use of one or more diketones or polyketones may yield oligomeric or polymeric products.
  • the ketone is in liquid form when it is used in the processes of the invention.
  • elevated temperatures and/or increased pressure will liquefy the ketone. If such conditions are not used, a solvent may be used to provide the ketone in liquid form.
  • the aliphatic primary diamines used in the processes of this invention are isophoronediamine or aliphatic primary ⁇ , ⁇ -diamines.
  • the aliphatic primary ⁇ , ⁇ - diamines are primary diamines which are in the form of a straight chain, with a primary amino group bound to each of the two terminal carbon atoms.
  • the straight chain is either a hydrocarbyl straight chain or a secondary amino straight chain, where "secondary amino straight chain” means a straight chain in which one of the -CH 2 - moieties in a hydrocarbyl straight chain is instead an -NH- moiety.
  • Such secondary amino group of the aliphatic primary diamine does not become tertiary in the processes of this invention.
  • the aliphatic primary ⁇ , ⁇ -diamine has about three to about twenty carbon atoms; more preferably, the aliphatic primary ⁇ , ⁇ -diamine has about four to about ten carbon atoms.
  • Suitable aliphatic primary diamines include, but are not limited to, isophoronediamine and aliphatic primary ⁇ , ⁇ -diamines such as 1,3-diaminopropane, 1,4- diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, diethylenetriamine (N-(2- aminoethyl)-l,2-ethanediamine), norspermidine, spermidine, bis(hexamethylene)triamine, N-(3-aminopropyl)cadaverine, N-(3-aminopropyl)- 1 ,7-heptanediamine, triethylene- tetramine, and tetraethylenepentamine.
  • Preferred aliphatic primary diamines include 1,6- diaminohexane, isophoronediamine, and diethylenetriamine. Preferred combinations in the processes of this invention are the use of isophoronediamine with cyclohexanone, the use of 1,6-diaminohexane with cyclohexanone, and the use of diethylenetriamine with cyclohexanone.
  • the aliphatic primary diamine is in liquid form when it is used in the processes of the invention. For some primary diamines, elevated temperatures and/or increased pressure will liquefy the primary diamine. If such conditions are not used, a larger amount of ketone or a solvent may be used to provide the primary diamine in liquid form.
  • the mole ratio of ketone to aliphatic primary diamine is normally at least about one mole of ketone per mole of amino group, i.e., at least about two moles of monoketone per mole of diamine.
  • an excess of the ketone is used, preferably at least about a 10% molar excess of ketone relative to the primary diamine is used.
  • Mole ratios of monoketone to aliphatic primary diamine in the range of about 2.2:1 to about 10:1 are effective, and thus are preferred; more preferred are mole ratios of monoketone to aliphatic primary diamine in the range of about 2.5:1 to about 6:1.
  • ketone Large excesses of ketone are acceptable in the practice of the invention; the ketone can be, and for monoketones preferably is, present in enough quantity to also act as a solvent. In fact, a large excess of ketone is often considered beneficial because, as is well known in the art, the formation of a diimine (which is believed to be an intermediate in the formation of the secondary diamines in the processes of this invention) behaves as an equilibrium, and excess ketone often helps shift the equilibrium to favor diimine formation.
  • a diimine which is believed to be an intermediate in the formation of the secondary diamines in the processes of this invention
  • the mole ratio of ketone to aliphatic primary diamine is normally at least about one mole of ketone group per mole of amino group, i.e., at least about one mole of diketone per mole of diamine.
  • an excess of the ketone is used, preferably at least about a 10% molar excess of ketone relative to the primary diamine is used.
  • Mole ratios of diketone to aliphatic primary diamine in the range of about 1.1:1 to about 5:1 are effective, and thus are preferred; more preferred are mole ratios of diketone to aliphatic primary diamine in the range of about 1.2:1 to about 3:1. These ratios can be adjusted as necessary for polyketones, e.g., for triketones.
  • a diketone or polyketone can be present in enough quantity to also act as a solvent.
  • the hydrogenation catalyst used in this invention is platinum on carbon, palladium on carbon, sulfided platinum on carbon, sulfided palladium on carbon, or a mixture of any two of the foregoing. Use of one type of catalyst rather than a mixture of catalysts is preferred. Platinum on carbon and palladium on carbon are preferred hydrogenation catalysts in the practice of this invention. The presence of a strong acid with platinum on carbon or palladium on carbon is generally unnecessary. When platinum on carbon or palladium on carbon is used, it can be in either powdered form or in granular form.
  • Suitable amounts of hydrogenation catalyst can be relatively low, i.e., in the range of about 1 wt% to about 10 wt% relative to the primary diamine. More suitably, in the range of about 3 wt% to about 5 wt% hydrogenation catalyst can be used relative to the primary diamine.
  • a diimine is formed as an intermediate, producing water as a by-product, which water is thought to shift the equilibrium toward the ketone and the primary diamine; therefore, large amounts of water are normally not desired in such processes.
  • a water removal agent may be included in the reaction mixture to remove water as the water is produced in the process. The only requirement is that the water removal agent not adversely affect the reaction or its products. Suitable water removal agents include molecular sieves, silica gel, calcium chloride, and the like. Molecular sieves are a preferred water removal agent in the practice of this invention.
  • a water removal agent An alternative to the use of a water removal agent is the inclusion of a solvent or enough excess ketone to act as the solvent to effectively dilute the water is recommended and preferred.
  • a solvent When a solvent is used, a solvent that is able to azeotrope with water and thereby remove water as it is produced during a process is a preferred way of operating.
  • Preferred solvents that remove water are hexanes and toluene.
  • Another preferred way of operating when using a solvent is to use a solvent which takes water into a phase separate from that in which the reaction is occurring; preferred solvents for this way of operating include toluene and dichloromethane.
  • water is not present as an ingredient in the processes of the invention at the start of the process, except for adventitiously present water (e.g., less than about 1 wt% water relative to the total weight of the reaction mass). In this connection, it should be noted that anhydrous conditions are not necessary to the successful conduct of the processes of this invention.
  • solvent types that can be used in the processes of this invention include, but are not limited to, liquid aromatic hydrocarbons, liquid aliphatic hydrocarbons, liquid halogenated aliphatic hydrocarbons, liquid halogenated aromatic hydrocarbons, ethers, esters, alcohols, and a mixture of two or more solvents.
  • an alcohol especially a C 1-4 alcohol, is present during the process.
  • Such an alcohol is typically about 25 wt% to about 75 wt% of the total weight of the reaction mixture; preferably, the alcohol is 45 wt% to about 65 wt% of the total weight of the reaction mixture.
  • Suitable liquid hydrocarbons include benzene, toluene, xylenes, mesitylene, cumene, cymene, pentane, hexane, isohexane, cyclohexane, methylcyclohexane, heptane, octane, cyclooctane, nonane, and the like.
  • liquid halogenated aliphatic hydrocarbons examples include dichloromethane, trichloromethane, 1,2- dichloroethane, 1 -bromo-2-chloroethane,(chloromethyl)cyclopropane, 1 -bromobutane, cyclobutyl chloride, neopentyl chloride, l-bromo-5-chloropentane, cyclopentyl bromide, 1,6-dibromohexane, rr ⁇ ws-l,2-dichlorocyclohexane, 1-chloroheptane, 1,8-dichlorooctane, and the like.
  • Ethers that are suitable for use in this invention include diethyl ether, di-n- propyl ether, diisopropyl ether, di-w-butyl ether, butyl ethyl ether, cyclohexylmethyl ether, tetrahydrofuran, 1,3-dioxane, 1,3-dioxolane, glyme (the dimethyl ether of ethylene glycol), 2-methoxyethyl ether (diglyme), and the like.
  • Suitable liquid halogenated aromatic hydrocarbons include chlorobenzene.
  • esters examples include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, and the like.
  • Alcohols including C 1-4 alcohols, that can be used in the practice of the invention include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-l- propanol, 1 -methyl- 1-propanol, cyclopropylmethanol, cyclobutanol, cyclopentanol, cis-2- methylcyclohexanol, and the like.
  • Preferred solvents include dichloromethane, ethyl acetate, toluene, and especially methanol and/or ethanol.
  • the processes of the invention are conducted at a temperature in the range of about 2O 0 C to about 75 0 C and at a hydrogen pressure in the range of about 1 to about 95 pounds per square inch gauge (1.08xl0 5 to 7.56xlO 5 Pa).
  • temperatures are in the range of about 4O 0 C to about 75 0 C
  • pressures are in the range of about 50 to about 95 pounds per square inch gauge (4.46x10 5 to 7.56x10 5 Pa).
  • the ketone, primary diamine, catalyst, and hydrogen may be brought together in any order. It is believed that the hydrogenation catalyst is necessary to obtain the secondary diamine in better yield and/or in shorter periods of time.
  • a particularly preferred method for preparing a secondary diamine is to place the primary diamine, hydrogenation catalyst, and solvent in a reaction vessel, and then to seal the reaction vessel under hydrogen gas pressure. The vessel is then heated as desired while the reaction mixture is stirred. On the laboratory scale, reaction times are typically about five hours to about twenty hours. [0030] In the practice of the invention, this process has yielded predominately secondary diamines.
  • Tertiary diamines when observed, have been seen in amounts of about 5% or less, and often in amounts of about 3% or less, where the percentage is a gas chromatograph (GC) area percent of an unpurified product mixture produced by the processes of this invention.
  • GC gas chromatograph
  • unpurified product mixture refers to the secondary aliphatic diamine in admixture with co-products and/or impurities resulting from preparation by bringing together an aliphatic cyclic ketone, an aliphatic primary diamine, hydrogen, and a hydrogenation catalyst selected from platinum on carbon, palladium on carbon, and a mixture thereof.
  • the composition of the product is process determined and not the result of use of downstream purification techniques, such as recrystallization, chromatography, distillation, or like procedures that can affect the chemical composition of the product mixture.
  • the secondary diamines produced by the processes of this invention are usually liquids. Methods for separating liquids that are well known in the art can be employed to separate at least a portion of the diamine from the other components of the reaction mixture. Such methods include, for example, recrystallization, chromatography and distillation. Distillation is a preferred separation method.
  • the secondary diamine produced is a solid
  • standard solid-liquid separation methods such as centrifugation, filtration, or recrystallization can be used to separate at least a portion of the product from the liquid portion of the reaction mixture.
  • the secondary diamines can be used in non-isolated form.
  • Products of the processes of this invention are aliphatic secondary diamines which include, but are not limited to, N,N'-dicyclopentyl-isophoronediamine, N,N'-dicyclohexyl- isophoronediamine, N,N'-di(4-ethyl-cyclohexyl)-isophoronediamine, N,N'-dicyclobutyl- 1 ,3-diaminopropane, N,N'-di(3-isopropyl-cyclobutyl)- 1 ,4-diaminobutane, N,N'-di(2,5- dimethyl-cyclopentyl)-l,4-diaminobutane, N,N'-dicyclopentyl-l,5-diaminopentane, N,N'- di(3-ethyl-cyclopentyl)- 1 ,5-diaminopentan
  • GC showed at least 98% yield of N,N'-dicyclohexyl- 1,6-diaminohexane, less than 1% of the intermediate, and less than 1% over- alkylated byproducts. No tertiary amines were found.
  • IPDA isophoronediamine
  • cyclohexanone 49 g, 0.5 mol
  • Pd/C 0.85 g, 5 wt% relative to IPDA
  • IPDA isophoronediamine
  • cyclohexanone 58.8 g, 0.6 mol
  • Pt/C 0.64 g, 5 wt% relative to IPDA

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de diamines secondaires. Le procédé comprend l'association de i) au moins une cétone cyclique aliphatique, ii) au moins une diamine primaire aliphatique, iii) de l'hydrogène et iv) un catalyseur d'hydrogénation. La diamine primaire aliphatique est l'isophoronediamine ou une a,w-diamine primaire aliphatique, et le catalyseur d'hydrogénation est choisi parmi du platine sur du carbone, du palladium sur du carbone, du platine sulfuré sur du carbone, du palladium sulfuré sur du carbone et un mélange de deux quelconques de ce qui précède. Le procédé est réalisé à une température dans la plage d'environ 200 °C à environ 750 °C et à une pression d'hydrogène dans la plage d'environ 1 à environ 95 livres par pouce carré, de sorte qu'une diamine secondaire est formée.
PCT/US2008/050662 2007-01-16 2008-01-09 Préparation de diamines secondaires WO2008089010A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88515307P 2007-01-16 2007-01-16
US60/885,153 2007-01-16

Publications (1)

Publication Number Publication Date
WO2008089010A1 true WO2008089010A1 (fr) 2008-07-24

Family

ID=38511421

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/050662 WO2008089010A1 (fr) 2007-01-16 2008-01-09 Préparation de diamines secondaires

Country Status (2)

Country Link
TW (1) TW200844078A (fr)
WO (1) WO2008089010A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111909039A (zh) * 2020-09-07 2020-11-10 江苏湘园化工有限公司 一种高位阻效应的脂肪族二元仲胺的制备方法
CN111995529A (zh) * 2020-09-07 2020-11-27 江苏湘园化工有限公司 一种脂环族二元仲胺的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2497292A (en) * 1946-05-07 1950-02-14 Du Pont Preparation of n-isobutyl hexamethylenediamines
DD264014A1 (de) * 1987-08-27 1989-01-18 Zeiss Jena Veb Carl Epoxid/amin-(meth)acrylat-klebstoffe
WO2004009529A1 (fr) * 2002-07-22 2004-01-29 Huntsman Petrochemical Corporation Elaboration d'amines secondaires

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2497292A (en) * 1946-05-07 1950-02-14 Du Pont Preparation of n-isobutyl hexamethylenediamines
DD264014A1 (de) * 1987-08-27 1989-01-18 Zeiss Jena Veb Carl Epoxid/amin-(meth)acrylat-klebstoffe
WO2004009529A1 (fr) * 2002-07-22 2004-01-29 Huntsman Petrochemical Corporation Elaboration d'amines secondaires

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 22 April 2001 (2001-04-22), A. KLEBANSKII ET AL.: "Synthesis and Polycondensation of N-Alkyl Derivatives of Hexamethylenediamine. I. Synthesis of N,N'-Dialkyl Derivatives of Hexamethylenediamine", XP002452121, retrieved from STN Database accession no. 1958:103796 *
ZHURNAL OBSHCHEI KHIMII, vol. 28, 1958, pages 1066 - 1072 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111909039A (zh) * 2020-09-07 2020-11-10 江苏湘园化工有限公司 一种高位阻效应的脂肪族二元仲胺的制备方法
CN111995529A (zh) * 2020-09-07 2020-11-27 江苏湘园化工有限公司 一种脂环族二元仲胺的制备方法

Also Published As

Publication number Publication date
TW200844078A (en) 2008-11-16

Similar Documents

Publication Publication Date Title
JP4797063B2 (ja) ジイミンおよび第二級ジアミン
JP5291630B2 (ja) アルデヒドおよびケトンの還元アミノ化方法
JP5237800B2 (ja) 大環状ポリイミン（ｍａｃｒｏｃｙｃｌｉｃｐｏｌｙｉｍｉｎｅｓ）中間体の形成を介した、アルデヒドおよびケトンの還元性アミノ化方法
JP2005532401A (ja) Ｎ−アルキル−４，４′−ジアミノジフェニルメタンの存在での４，４−ジアミノジフェニルメタンの４，４′−ジアミノジシクロヘキシルメタンへの水素化の選択率を増大する方法
CN104817460B (zh) 用于氢化芳族二-和多胺的方法
WO2008089010A1 (fr) Préparation de diamines secondaires
WO2010101560A1 (fr) Bis[(alkylamino)alkyl]amines
JPS5826902B2 (ja) 炭素原子数４〜１８を有する脂肪族又は脂環式ジアミンの製法
EP1321453A2 (fr) N-Aminopropyl-toluènediamines et leur utilisation comme durcisseurs pour des résines époxydes
WO2008130721A1 (fr) Préparation de diamines secondaires
EP0309980A1 (fr) Polyalcoylène-polyamines alcoylées et procédé pour l'alcoylation sélective
JPH0428253B2 (fr)
JPH0528215B2 (fr)
WO2012173735A1 (fr) Procédé pour la préparation d'alkyldiamines

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08705824

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08705824

Country of ref document: EP

Kind code of ref document: A1