WO2006136682A2

WO2006136682A2 - Method for preparing fatty-chain branched triamines and ether diamines

Info

Publication number: WO2006136682A2
Application number: PCT/FR2006/001366
Authority: WO
Inventors: Jean-Philippe Gillet
Original assignee: Arkema France
Priority date: 2005-06-24
Filing date: 2006-06-16
Publication date: 2006-12-28
Also published as: FR2887546A1; WO2006136682A3

Abstract

The invention relates to preparing linear or C8 and more fatty chain branched triamines and ether diamines obtainable by hydrogenating aliphatic dinitrile derivatives, to the use of the thus obtainable products and, more specifically, to C8 and more fatty chain branched ether diamines.

Description

PROCESS FOR THE PREPARATION OF FATTY CHAIN GRANULATED TRIAMINES AND DERIVAAMINES

Field of the invention

The invention relates to the preparation of linear or branched C ₈ and higher branched chain or branched chain tri-amines and ethers, obtained by hydrogenation of aliphatic dinitrile derivatives, the applications of the products obtained and more particularly the fatty-chain branched ether-diamines. CG and more. Prior art and technical problem.

In the field of fatty amines used in particular as precursors of surfactants, there are complete ranges of mono, di, tri and polyamines.

These amines with linear structures are generally obtained by the repetition of Michael's condensation sequences with acrylonitrile and then hydrogenation.

There are also amines with branched structures obtained by Michael double condensation on acrylonitrile and hydrogenation to lead to amines having amine units separated by a propyl carbon chain of the following type:

wherein R may represent an alkyl chain in C] ₂ to C] _8.

The preparation of branched triamines without fatty chains of the following type

is described in JP101075925 by Michael's addition of ammonia to methyleneglutaronitrile to give 2-aminomethylglutarodinitrile and then the hydrogenation of the latter yields 2-aminomethyl-1,5-diaminopentane. The hydrogenation is carried out in the presence of Raney nickel and sodium hydroxide in an alcoholic solvent medium at 70 ° C. under 5 × 10 ⁶ Pa for 2 hours. The 2-aminomethyl-1,5-diaminopentane triamine obtained in a yield of 83% is used as a crosslinking agent for epoxy resins and in polyurethanes. In the field of fatty chain amines JP44023210 describes the condensation of laurylamine with methyleneglutaronitrile and the hydrogenation of the product obtained in the presence of Ni supported on Kieselguhr, under operating conditions which mainly result in yields of 90% to products of cyclization such as substituted piperidines. The document cites the presence of about 9% by-product in the form of the branched 2- (N-lauryl) aminomethyl-1,5-diaminopentane triamine.

Regarding the synthesis of dinitrile derivatives precursors of diamino derivatives, JP45028571 describes the addition of ammonia (in ammoniacal form) and short chain primary amines (methylamine, butylamine and cyclohexylamine) on methyleneglutaronitrile to yield the corresponding aminodinitriles. The reaction is generally carried out at room temperature in solution in methanol. The products are isolated by distillation under reduced pressure.

FR495198 discloses the preparation of dinitrile derivatives obtained by condensation of active hydrogen compounds such as alkylamines or alkyl alcohols with 2-methyleneglutaronitrile wherein the preferred alkyl chains comprise from 1 to 8 carbon atoms.

EP 261605 describes the synthesis of 1,5-diaminopentane-derived etheramines by hydrogenation of the corresponding alkoxymethylglutaronitriles. The hydrogenation step is carried out in the presence of a large excess of catalyst and in THF-type solvents, conditions which are hardly industrialized. JP 45-034456 discloses hydrogenations with raney cobalt to give short-chain (R methyl or butyl) branched diamines and their use as hardeners in epoxy resins.

Therefore, there is no reference in the prior art to a process for specifically obtaining linear or branched chain C ₈ or higher branched chain tri-amines or ethers of diamines from the corresponding dinitrile derivatives. Summary of the invention.

The object of the invention is to provide a process for the preparation of compounds of formula I

(I) wherein Z is a radical -OR or -NHR where R represents an alkyl radical having a carbon number greater than or equal to 8 or a mixture thereof, n is an integer of from 1 to 12, preferably n is equal to 2, by catalytic hydrogenation of the corresponding dinitrile derivatives of formula Ia

(the)

in the presence of Raney metal catalysts.

According to one embodiment, R represents an alkyl radical having a carbon number between 10 and 22 or a mixture thereof. According to one embodiment, the hydrogenation reaction is carried out in the presence of nickel or Raney cobalt.

According to one embodiment, the hydrogenation reaction is carried out under a hydrogen pressure of between 10 ⁶ Pa and 15 10 ⁷ Pa.

According to a preferred embodiment, the hydrogenation reaction is carried out in the presence of ammonia at a partial pressure of 10 ⁴ Pa to 10 ⁷ Pa.

According to one embodiment, the amount of catalyst is between 0.01% and 10%, preferably between 0.01 and 5% by weight of the starting dinitrile.

According to one embodiment, the amount of catalyst is strictly less than 1%, preferably in the range from 0.01% to 0.99% by weight of the starting dinitrile Ia.

According to one embodiment, the reaction is carried out without a solvent or in the presence of a solvent chosen from the group of linear or cyclic aliphatic hydrocarbons, aromatic hydrocarbons or their mixture.

According to one embodiment, the dinitrile derivatives of formula Ia are prepared by reacting a compound of formula ZH with a compound of formula II

(M)

According to one embodiment, the molar ratio of the compound of formula ZH with respect to the dinitrile of formula II is from 0.5 to 1.5 and preferably from 0.9 to 1.1. According to another object the invention relates to compounds of formula I

(I)

wherein Z is an OR radical and R is a linear or branched alkyl radical having a carbon number greater than or equal to 8 or a mixture thereof, preferably a carbon number of between 10 and 22; n is an integer from 1 to 12, preferably 2.

Preferably, in the compound of formula I, R represents a linear or branched alkyl radical having a carbon number ranging from 14 to 22 carbon atoms, or a mixture thereof and preferably n = 2.

More preferably in compounds of formula I, R represents a linear alkyl or branched C ₆ or C ₈ or a mixture thereof.

According to another object the invention relates to the use of the compounds of formula I

(I)

as defined above, in the field of the crosslinking of epoxy resins, anticorrosion, detergency, as polycondensation monomers or as surfactant precursors, or as additives for bitumen, flotation agent or cryptant.

The advantages lie in the fact that this process makes it possible to obtain triamine derivatives and fatty chain branched ether-diamine derivatives with very good yields, a low level of cyclization by-products and an industrial scale implementation. .

The advantage also lies in the fact that it is thus possible to prepare, according to the same process, triamine derivatives and branched chain fatty ether derivatives from the corresponding dinitrile precursors. DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

According to the process of the invention, the compound of formula Ia is subjected

(the)

wherein Z is -OR or -NHR where R is an alkyl radical having a carbon number greater than or equal to 8 or a mixture thereof and n is an integer of 1 to 12, at a reaction temperature of catalytic hydrogenation under operating conditions making it possible to obtain predominantly non-cyclized derivatives of formula I which is the subject of the invention

(I)

The process makes it possible to obtain yields of triamine derivatives and fatty chain branched ether-diamine derivatives of formula I greater than 50%, preferably greater than 80%.

The reaction is carried out in the presence of a catalyst chosen from Group 8 metals, in particular finely divided Raney type metals, with a preference for catalysts based on nickel and cobalt and mainly catalysts in the form of nickel and Cobalt from Raney. The amounts used are from 0.01% to 10% by weight relative to the starting reagent and preferably from 0.02% to 3% or from 0.1% to 5% by weight. They are still preferably less than 1% or the amounts of catalyst used are in the range of 0.01% to 0.99% by weight of the starting dinitrile Ia.

The temperature may range from 50 ° C. to 250 ^° C. and preferably from 75 ° C. to 200 ° C.

The hydrogen pressure is 10 ⁵ Pa to 25 10 ⁶ Pa and preferably 10 ⁶ Pa to 15 10 ⁶ Pa or 3 10 ⁶ Pa to 10 ⁷ Pa.

The ammonia partial pressure is 10 ⁴ Pa to 10 ⁷ Pa and preferably 10 ⁵ Pa to 7 10 ⁶ Pa or 5 10 ⁵ Pa to 5 10 ⁶ Pa.

This hydrogenation reaction is carried out with or without a solvent. In order to limit production costs while improving productivity, it is preferred to carry out the reaction without solvent. However, when the reaction is carried out with a solvent, it is possible to use linear or cyclic aliphatic hydrocarbons, aromatic hydrocarbons or their mixture, which have the particular advantage of allowing the reaction to be carried out on an industrial scale.

According to the invention, to obtain the compound of formula Ia, it is first reacted with a compound of formula II,

(H)

a compound of formula ZH such as an amine of formula RNH ₂ or an alcohol of formula ROH in which R represents a linear or branched fatty chain comprising a carbon number greater than or equal to 8.

According to a preferred embodiment the compound of formula II is methyleneglutaronitrile (MGN) where n = 2. According to a preferred embodiment, the group R is a C ₁ -C ₂₂ alkyl chain, or a mixture of alkyl chains comprising from 10 to 22 carbon atoms.

According to another preferred embodiment the group R is an alkyl chain -C ₄ -C _22, or -C ₄ -C _9, or an alkyl chain Ci Cj ₆ or ₈ or a mixture thereof.

This step of preparation of dinitrile derivatives, in particular that starting from methyleneglutaronitrile can be carried out in a conventional reactor at atmospheric pressure. And this, unlike the methods of the prior art starting from acrylonitrile because methyleneglutaronitrile has a boiling point higher than that of acrylonitrile.

In addition, methyleneglutaronitrile has a more favorable HSE profile than carcinogenic acrylonitrile. Finally, there is no risk of rearrangement of the dinitrile during the hydrogenation step which can occur on the compound derived from the Michael double condensation on acrylonitrile.

This reaction is carried out with or without a solvent at temperatures ranging from 20 ^° C. to 150 ° C. and preferably from 50 ° C. to 100 ^° C. In order to limit production costs while improving productivity, it is preferred to carry out the reaction. reaction without solvent. However, when the reaction is carried out with a solvent, it is possible to use linear or cyclic aliphatic hydrocarbons, or aromatic hydrocarbons or their mixture. Thus, advantageously industrially, the two successive reactions until the compounds of formula I can be obtained in the same solvents.

The amine or alcohol molar ratio relative to the dinitrile of formula II is from 0.5 to 1.5 and preferably from 0.9 to 1.1.

In the case of alcohols, a catalyst chosen from alkali and alkaline earth alkali and potassium hydroxide bases is preferably added. The amount of catalyst is from 0.01% to 5% by weight and preferably from 0.1% to 2% by weight relative to dinitrile or methyleneglutaronitrile.

The method according to the invention therefore applies equally well to the C ₈ and higher fatty chain derivatives in which Z is RO and to linear or branched C ₈ and higher fatty chain derivatives in which Z is NHR. Another subject of the invention relates to the ether diamines of formula I in which Z is OR with R which represents a linear or branched C ₈ and higher fatty chain. According to one preferred embodiment, the fatty chains are a mixture of alkyl chains whose carbon numbers are between C ₀ and C ₂₂ . Preferably, R represents a linear fatty chain or branched Ci to C ₄ -C ₂₂ or ₄ to _9. According to a still Ci preferred embodiment R represents specifically a linear fatty chain or branched C] ₆ or C ₈ or their mixed. According to a particular embodiment n = 2 in formula I of these compounds.

These products are obtained according to the same process as that of the triamine derivatives as described above. According to another object the invention also relates to the applications of the compounds of formulas I.

In fact, the triamines and ether diamines obtained according to the invention can be used in a broad spectrum of application: _"

di and triamines for crosslinking epoxy resins;

polycondensation monomers; surfactant precursor polyamines;

- field of F anticorrosion; - field of detergency;

- bitumen additives; flotation agent; encrypting agent.

EXAMPLES The following examples illustrate the present invention without, however, limiting its scope. EXAMPLE 1

Synthesis of a triamine derivative of formula I wherein R is a tallow chain (Cj mixture _6, Body and unsaturated ^'). Step 1: Synthesis of aminodinitrile

In a stirred reactor equipped with a dropping funnel, an ascending condenser, a nitrogen inerting system and a jacket for heating, 309.7 g (1.1 MI ) a tallow amine base (Noram S type) having an alkalinity of 3.6 and 4 g of water. The reaction medium is brought to 70-75 ° C with stirring and inerting with nitrogen.

118.2 g (1.1 IM) of methyleneglutaronitrile are then poured in approximately 2H. It is then maintained for 1 h 30 at 80-85 ° C.

The final alkalinity is 2.6 and the analysis of the crude reaction gives a yield of 86%. Step 2: Synthesis of the triamine

In an Autoclave Engineers autoclave equipped with regulatory safety devices, a hollow shaft turbine agitation system, a cooling coil, and temperature control, 375 g (MI) of dinitrile obtained in Example 1 with 9 g of Raney nickel. The autoclave is closed and then purged with nitrogen. The reaction medium is brought to 75 ^° C. with stirring of 1300 rpm. Ammonia is then introduced so as to have a partial pressure of 7 10 ⁵ Pa. The autoclave is then heated to 120 ^° C. and the hydrogen is then admitted to a total pressure of 3 × 10 ⁶ Pa. Pa. The reaction is carried out between 120 and 150 ⁰ C until there is no longer any hydrogen consumption. At the end of the reaction, the reactor is drained and the catalyst recovered by filtration.

The analysis leads to a 90% yield of branched triamine based on tallow. EXAMPLE 2

Synthesis of an etherdiamine derivative of formula I wherein R is a group in Q _R.

Step 1: Synthesis of Etherdinitrile

In a stirred reactor equipped with a dropping funnel, an ascending condenser, a nitrogen inerting system and a jacket for heating, 270 g (1 L) are charged. octadecanol and 50% sodium hydroxide in aqueous solution. The reaction medium is brought to 70-75 ° C with stirring and inerting with nitrogen. Then 106 g (1M) of methyleneglutaronitrile are poured in approximately 2H. It is then maintained for 2 hours at 80-85 ° C. Analysis of the crude reaction gives a yield of 95%.

Step 2: Synthesis of Etherdiamine

In an Autoclave Engineers autoclave equipped with regulatory safety devices, a hollow shaft turbine agitation system, a cooling coil, and temperature control, 376 g (MI) of the ether-dinitrile obtained in Example 3 with 9 g of Raney nickel. The autoclave is closed and then purged with nitrogen. The reaction medium is brought to 75 ^° C. with stirring of 1300 rpm. Ammonia is then introduced so as to have a partial pressure of 7 10 ⁵ Pa. The autoclave is then heated to 120 ° C. and then the hydrogen is admitted to a total pressure of 3 × 10 ⁶ Pa. Pa. The reaction is carried out between 120 and 150 ° C until no more hydrogen consumption is observed. At the end of the reaction, the reactor is drained and the catalyst recovered by filtration.

The analysis leads to a yield of 90% of branched ether-diamine Cj ₈ .

Claims

CLAIMS.

1. Process for the preparation of compounds of formula I

(I) wherein Z is a radical -OR or -NHR where R represents an alkyl radical having a carbon number greater than or equal to 8 or a mixture thereof, n is an integer of from 1 to 12, by hydrogenation catalytically corresponding dinitrile derivatives of formula Ia

(the)

in the presence of Raney metal catalysts.

2. The method of claim 1 wherein n is 2.

3. A process according to claim 1 or 2 wherein R represents an alkyl radical having a carbon number of from 10 to 22 or a mixture thereof.

4. Method according to one of claims 1 to 3 wherein the hydrogenation reaction is carried out in the presence of nickel or cobalt Raney.

5. Method according to one of claims 1 to 4 wherein the hydrogenation reaction is carried out under a hydrogen pressure of between 10 ⁶ Pa and 15 10 ⁶ Pa.

6. Method according to one of claims 1 to 5 wherein the hydrogenation reaction is carried out in the presence of ammonia at a partial pressure of 10 ⁴ Pa to 10 ⁷ Pa. _l

7. Method according to one of claims 1 to 6 wherein the amount of catalyst is between 0.01% and 10%, preferably between 0.01 and 5% by weight of the starting dinitrile.

8. Method according to one of claims 1 to 7 wherein the amount of catalyst is strictly less than 1%, preferably in the range of 0.01% to 0.99% by weight of the starting dinitrile Ia.

9. Method according to one of claims 1 to 8 wherein n is equal to 2.

10. Method according to one of claims 1 to 9 wherein the reaction is carried out without a solvent or in the presence of a solvent selected from the group of linear or cyclic aliphatic hydrocarbons, aromatic hydrocarbons or their mixture.

11. Method according to one of claims 1 to 10 wherein the dinitrile derivatives of formula Ia are prepared by reaction of a compound of formula ZH on a compound of formula II

(H)

12. The method of claim 11 wherein the molar ratio of the compound of formula ZH relative to the dinitrile of formula II is 0.5 to 1.5 and preferably 0.9 to 1.1.

13. Compounds of formula I

(I) wherein Z is an OR radical and R is a linear or branched alkyl radical having a carbon number greater than or equal to 8 or a mixture thereof, preferably a carbon number of between 10 and 22; n is an integer from 1 to 12, preferably 2.

14. Compounds of formula I according to claim 13 wherein R represents a linear or branched alkyl radical having a carbon number ranging from 14 to 22 carbon atoms, or a mixture thereof, and preferably n = 2.

Compounds of formula I according to claim 13 or 14 wherein R represents a linear or branched C ₁₆ or C ₁₈ alkyl radical or a mixture thereof

16. Use of compounds of formula I

(I)

wherein Z is an OR or NHR radical and R is a linear or branched alkyl radical having a carbon number greater than or equal to 8 or a mixture thereof, preferably a carbon number of between 10 and 22; n is an integer from 1 to 12, preferably 2; in the field of the crosslinking of epoxy resins, anticorrosion T, detergency, as polycondensation monomers or as precursors of surfactants, or as additives for bitumen, flotation agent or cryptant .