WO2021114166A1

WO2021114166A1 - Process for preparing n-substituted alkanolamines and/or n-substituted diamines from glycolaldehyde

Info

Publication number: WO2021114166A1
Application number: PCT/CN2019/124791
Authority: WO
Inventors: Bright KUSEMA; Zhen YAN; Stephane Streiff
Original assignee: Rhodia Operations
Priority date: 2019-12-12
Filing date: 2019-12-12
Publication date: 2021-06-17

Abstract

A process for preparing a N-substituted alkanolamine of formula (I) and/or a N-substituted diamine of formula (II) from glycolaldehyde is provided, which comprises reacting glycolaldehyde with an aminating agent of formula (III) in a solvent comprising at least one C1-C3 alkanol and/or tetrahydrofuran in the presence of hydrogen and a supported noble metal catalyst, wherein in formulas (I) - (III) : R and R', independently from each other, represent hydrogen, linear or branched C1-C20 alkyl, C3-C12 cycloalkyl, C2-C30 alkoxyalkyl, or C3-30 dialkylaminoalkyl, provided that at least one of R and R' is not hydrogen.

Description

Process for preparing N-substituted alkanolamines and/or N-substituted diamines from glycolaldehyde

TECHNICAL FIELD

The present invention relates to a process for preparing alkanolamines and/or diamines from a hydroxyl-substituted aldehyde. In particular, the present invention relates to a process for preparing N-substituted alkanolamines and/or N-substituted diamines from glycolaldehyde.

BACKGROUND ART

Industrially, (N-substituted) alkanolamines are produced almost exclusively by reacting ethylene oxide with ammonia or primary, secondary or tertiary amines.

For example, N, N-dimethylethanolamine is produced industrially by reacting ethylene oxide and dimethylamine. Ethylene oxide is fossil-based, toxic, carcinogenic and mutagenic. During this process, high molecular weight byproducts with more than 1 EO unit are generated as waste.

The reaction of hydroxyl-substituted aldehydes with aminating agents is already known from the prior art.

Glycolaldehyde (GA) , the smallest molecule containing both an aldehyde group and hydroxyl group obtainable from biomass, creates a versatile platform for ethanolamine derivatives potentially replacing current pathways via toxic ethylene oxide.

U.S. Pat. No. 8772548B2 discloses a one-step reaction of glycolaldehyde with an aminating agent in the presence of hydrogen, a catalyst comprising of Ni, Co, and/or Cu and an inert solvent. Preferential solvents are water and THF, and preference is given to ammonia as an aminating agent. In a reaction at 100℃ and 100 bar of hydrogen pressure for 8 hours, glycolaldehyde was contacted with ammonia at a molar ratio (NH ₃: GA) of 35. A conversion of 100%is obtained, with maximum selectivity of 82%for monoethanolamine (MEOA) and 17%of ethylenediamine (EDA) . It is said that a solvent used must be inert under the reaction conditions and has to have sufficient solubility for reactants and products.

CN107011194B discloses a method for carrying out catalytic reductive amination reaction on glycolaldehyde and an amination agent in the presence of hydrogen gas and a catalyst. The catalyst is a reduced supported noble metal catalyst containing rare-earth metal oxides; the reaction is carried out in an aqueous solution or an organic solution of the amination agent, in order to selectively obtain alkanolamine and diamine. In particular, the reductive amination of glycolaldehyde with NH ₃ over Ru/ZrO ₂ catalyst to ethanolamine and ethylenediamine is demonstrated.

WO2019193117A1 discloses a two-step one-pot process for reacting glycolaldehyde with an aminating agent in the presence of a reactive organic fluid for instance a reactive solvent. The first step comprises of contacting glycolaldehyde with an aminating agent in the presence of a reactive fluid for instance a reactive solvent under inert atmosphere to produce unsaturated intermediates, and reacting the reaction mixture obtained in step 1 with hydrogen in the presence of a supported hydrogenation catalyst in a second step.

Faveere et al., Glycolaldehyde as Bio-based C2 Platform Chemical: Catalytic Reductive Amination of vicinal Hydroxyl Aldehydes, ACS Catal. 2019, discloses the reductive amination of glycolaldehyde with aqueous amine solutions at a temperature of 100℃ and a hydrogen pressure of 70 bar to obtain N, N-dimethylethanolamine and N, N, N’, N’-tetramethylethylene diamine, wherein the weight ratio of the catalyst to glycolaldehyde is 50%.

Thus there is still a need for an improved method for the amination of glycolaldehyde which has a higher selectivity towards preferred products such as N-substituted alkanolamines, for example, dimethylethanolamine (DMEA) , and N-substituted diamines, for example, N, N, N’, N’-tetramethylethylene diamine (TMEDA) under relatively mild reaction condition (temperature lower than 100 ℃ and pressure lower than 70 bar) .

SUMMARY OF THE INVENTION

The aim of the present invention is to provide an improved method for the amination of glycolaldehyde, which has a higher selectivity towards N-substituted alkanolamines and/or N-substituted diamines under relatively mild reaction conditions, i.e. at a temperature lower than 100℃ and a pressure lower than 70 bar.

Upon diligent research, the inventors have discovered surprisedly that such an aim can be achieved by selecting a combination of specific aminating agent, specific solvent and specific catalyst during the amination process of glycolaldehyde.

Thus, the present invention provides a process for preparing a N- substituted alkanolamine of formula (I) and/or a N-substituted diamine of formula (II) from glycolaldehyde:

in formula (I) and formula (II) :

R and R’, independently from each other, represent hydrogen, linear or branched C1-C20 alkyl, C3-C12 cycloalkyl, C2-30 alkoxyalkyl, or C3-30 dialkylaminoalkyl, provided that at least one of R and R’ is not hydrogen,

comprising reacting glycolaldehyde with an aminating agent of formula (III) in a solvent comprising at least one C1-C3 alkanol and/or tetrahydrofuran in the presence of hydrogen and a supported noble metal catalyst,

in formula (III) :

R and R’ have the same meanings as defined above.

With the process according to the present invention, the amination of glycolaldehyde with a higher selectivity towards N-substituted alkanolamines and/or N-substituted diamines under relatively mild reaction condition, i.e. at a temperature lower than 100℃ and a pressure lower than 70 bar, can be realized.

With the process according to the present invention, the total yields towards N-substituted alkanolamine and N-substituted diamine can be more than 70%.

In addition, it is much easier to control EO unit to only 1 by using glycolaldehyde. Since glycolaldehyde is derived from biomass, the N-substituted alkanolamines and/or N-substituted diamines produced are bio-based products.

Other subjects and characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the detailed description and the examples that follow.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, unless otherwise indicated, the limits of a range of values are included within this range, in particular in the expressions "between…and…" and "from…to…” .

As used herein, the term “comprising” is to be interpreted as encompassing all specifically mentioned features as well optional, additional, unspecified ones.

As used herein, the use of the term “comprising” also discloses the embodiment wherein no features other than the specifically mentioned features are present (i.e. “consisting of” ) .

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the field the present invention belongs to. When the definition of a term in the present description conflicts with the meaning as commonly understood by those skilled in the field the present invention belongs to, the definition described herein shall apply.

Should the disclosure of any patents, patent applications and publications which are incorporated herein by reference conflict with the description of the present application in the extent that it may render a term unclear, the present description shall take precedence.

Unless otherwise specified, all numerical values expressing amount of ingredients, reaction conditions and the like used in the description and claims are to be understood as being modified by the term “about” . Accordingly, unless indicated to the contrary, the numerical values and parameters described herein are approximate values which are capable of being changed according to the desired performance obtained as required.

The present invention provides a process for preparing a N-substituted alkanolamine of formula (I) and/or a N-substituted diamine of formula (II) from glycolaldehyde:

in formula (I) and formula (II) :

in formula (III) :

R and R’ have the same meanings as defined above.

The reaction for the amination of glycolaldehyde is illustrated in the following scheme.

Glycolaldehyde is commercially available and can be prepared, for example, by oxidizing ethylene glycol (see, for example, JP 3246248 and JP3279342) .

Glycolaldehyde is preferably synthesized by reaction of formaldehyde with carbon monoxide and hydrogen, as described, for example, in US 2009012333, US 2008081931, US 2007249871, etc.

In some embodiments, R and R’, independently from each other, represents hydrogen, linear or branched C1-C4 alkyl, provided that at least one of R and R’ is not hydrogen.

In some embodiments, R and R’, independently from each other, represent linear or branched C1-C20 alkyl, C3-C12 cycloalkyl, C2-30 alkoxyalkyl, or C3-30 dialkylaminoalkyl.

In some embodiments, R and R’, independently from each other, represent linear or branched C1-C4 alkyl.

As examples of an aminating agent, preference is given to monomethylamine, dimethylamine, monoethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisoropylamine, isopropylethylamine, n-butylamine, di-n-butylamine, isobutylamine, cyclopropylamine, cyclopropylmethylamine, cyclobutylamine, cyclobutylmethylamine, cyclopentylamine, cyclopentylmethylamine, methoxyethylamine, ethyoxymethylamine, dimethylaminomethylamine, diethylaminomethylamine, and dimethylaminopropylamine, and the like.

Advantageously, the molar ratio of the aminating agent to glycolaldehyde is within a range from 1: 1 to 10: 1, preferably, 1: 1 to 5: 1.

The hydrogen is preferably used in technical grade purity. The hydrogen can also be used in a form of a hydrogen-comprising gas, i.e. in mixtures with other inert gases, such as nitrogen, helium, neon, and argon.

According to the present invention, the reaction of glycolaldehyde with the aminating agent in the presence of hydrogen takes place in a solvent.

The solvent used is inert under the reaction conditions and has a sufficient solubility for reactants and products.

In some embodiments, the solvent is selected from methanol, ethanol, isopropyl alcohol, and tetrahydrofuran (THF) .

In some embodiments, the solvent is substantially free of water.

As used herein, the term "substantially free of water" when used with reference to the solvent means that the solvent comprises no more than 0.5 wt. %, preferably no more than 0.2 wt. %of water, based on the total weight of the solvent.

In some embodiments, the solvent is completely free of water.

As used herein, the term "completely free of water" when used with reference to the solvent means that the solvent comprises no water at all.

In some embodiments, the solvent is a mixed solvent comprising (i) at least one C1-C3 alkanol and/or tetrahydrofuran; and (ii) a co-solvent selected from water, dioxane and butanol. Preferably, the co-sovent is present in an amount no more than 80 wt. %, or no more than 50 wt%, based on the total weight of the solvent.

In some embodiments, the co-solvent is present in an amount ranging from 10 wt. %to 70 wt. %, or from 20 wt. %to 60 wt. %, or from 30 wt. %to 50 wt. %, based on the total weight of the solvent.

In some embodiments, the solvent is a mixed solvent of a C1-C3 alkanol and water, wherein the water may be present in an amount ranging from above 0.5 wt. %to 30 wt. %, or from 10 wt. %to 30 wt. %, or from 10 wt. %to from 20 wt. %, or from above 0.5 wt. %to 10 wt. %, based on the total weight of the solvent.

In some embodiments, the solvent is a mixed solvent of tetrahydrofuran and water, wherein the water may be present in an amount ranging from above 0.5 wt. %to 30 wt. %, or from 10 wt. %to 30 wt. %, or from 10 wt. %to from 20 wt.%, or from above 0.5 wt. %to 10 wt. %, based on the total weight of the solvent.

The solvent can be used in a proportion of 10 wt. %to 95 wt. %by weight, preferably 75 wt. %to 95 wt. %, based in each case on the total weight of the reaction mixture including glycolaldehyde, the aminating agent and the solvent used.

According to the present invention, the amination of glycolaldehyde takes place in the present of a supported noble metal catalyst.

As used herein, the term “supported noble metal catalyst” means a catalyst comprising a noble metal on a support.

Preferably, the noble metal is selected from Pd, Pt, Rh and Ru, and the support is selected from carbon black, graphite, activated carbon, aluminium oxide, silicon dioxide or other supports known in the art.

Advantageously, the noble metal is present in amount from 0.5 wt. %to 10 wt.%in the supported noble metal catalyst, relative to the total weight of the supported noble metal catalyst.

The supported noble metal catalyst can be commercial available or prepared with a method known in the art.

In some embodiments, the solvent is methanol, the noble metal is selected from Pd, Pt, Rh and Ru.

In some embodiments, the solvent is ethanol, the noble metal is selected from Pd, Pt, Rh and Ru.

In some embodiments, the solvent is isopropyl alcohol, the noble metal is selected from Pd, Pt, Rh and Ru.

In some embodiments, the solvent is THF, the noble metal is selected from Pd, Pt, Rh and Ru.

As an example for the supported noble metal catalyst useful for the present invention, mention can be made to A102023-5 from Johnson Matthey, an Pd/C catalyst containing 5 wt. %Pd.

In a particular embodiment, the aminating agent is dimethylamine, the solvent is methanol or ethanol, the supported noble metal catalyst is Pd/C.

The amination of glycolaldehyde can be carried out at a temperature from 0℃ to 80℃ and a hydrogen pressure from 1 bar to 65 bar for 1-20 hours.

Advantageously, the amination of glycolaldehyde can be carried out at room temperature and a hydrogen pressure from 10 bar to 40 bar for 3-20 hours.

According to the present invention, room temperature is between 15℃ and 25℃.

Preferably, glycolaldehyde is added into a mixture of an aminating agent and a catalyst in a solvent gradually. More preferably, glycolaldehyde in a solvent is added into a mixture of an aminating agent and a catalyst in the same solvent gradually.

The amination of glycolaldehyde according to the present invention can be carried out in a catalyst effective mode. For example, the molar ratio of the noble metal in the catalyst to glycolaldehyde can be in the range of 0.01%-0.6%.

Examples

The technical features and technical effects of the present invention will be further described below in conjunction with the following examples so that the skilled in the art would fully understand the present invention. It will be readily understood by the skilled in the art that the examples herein are for illustrative purposes only and the scope of the present invention is not limited thereto.

Example 1

0.24 g of glycolaldehyde, 0.54 g of dimethylamine, 3 mL ethanol and 20 mg of 5 wt. %Pd/C catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was cooled to 0℃ under stirring and maintained at the same temperature for 6 hours. Next, the reaction was continued at room temperature (T=25℃) for 12 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to N, N-dimethylethanolamine (DMEA) and N, N, N’, N’-tetramethylethylene diamine (TMDEA) based on glycolaldehyde was 76%and 4%, respectively.

Example 2

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL ethanol and 20 mg of 5 wt. %Pd/C catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was heated under stirring at 80℃ for 3 hours. Then reaction mixture was cooled to room temperature (T=25℃) and the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 35%and 40%, respectively.

Example 3

0.12 g of glycolaldehyde, 0.21 g of dimethylamine, 2 mL ethanol and 20 mg of 5 wt. %Pd/C catalyst were added into a 30 mL stainless steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 10 bar of hydrogen. The mixture was kept at 25℃ under stirring for 3 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 65%and 9%, respectively.

Comparative Example 1

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL water and 20 mg of 5 wt. %Pd/C catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was kept at 25℃ under stirring for 3 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 50%and 20%, respectively.

Example 4

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL ethanol and 20 mg of 5 wt. %Pt/C catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was kept at room temperature (T=25℃) under stirring for 12 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 84%and 8%, respectively.

Example 5

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL ethanol and 20 mg of 5 wt. %Pd/C catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was kept at room temperature (T=25℃) under stirring for 3 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 94%and 2%, respectively.

Example 6

1.26 g of dimethylamine, 36 mL ethanol and 240 mg of 5 wt. %Pd/C catalyst were added into a 100 mL stainless steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 20 bar of hydrogen. The mixture was heated under stirring at 25℃and 1.41 g of glycolaldehyde and 24 mL of ethanol were added to the reactor at 0.067 mL/min for 6 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 82%and 4%, respectively.

Example 7

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL ethanol and 22 mg of 5 wt. %Rh/Al ₂O ₃ catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was cooled to 0℃ under stirring and maintained at the same temperature for 6 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMDEA based on glycolaldehyde was 72%and 4%, respectively.

Example 8

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL methanol and 23 mg of 5 wt. %Pd/C catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was kept at room temperature (T=25℃) under stirring for 3 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 83%and 4%, respectively.

Example 9

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL isopropanol and 20 mg of 5 wt. %Rh/Al ₂O ₃ catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was kept at room temperature (T=25℃) under stirring for 3 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 68%and 4%, respectively.

Example10

0.12 g of glycolaldehyde, 0.22 g of dimethylamine, 2 mL isopropanol and 20 mg of 5 wt. %Pd/C catalyst were added into a 30 mL stainless-steel autoclave at room temperature (T=25℃) . The autoclave was closed, flushed with nitrogen three times and then charged with 40 bar of hydrogen. The mixture was kept at room temperature (T=25℃) under stirring for 3 hours. Then the pressure was released, the reaction mixture was filtered and analyzed by GC.

The yield to DMEA and TMEDA based on glycolaldehyde was 89%and 2%, respectively.

The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims

A process for preparing a N-substituted alkanolamine of formula (I) and/or a N-substituted diamine of formula (II) from glycolaldehyde:

in formula (I) and formula (II) :

R and R’, independently from each other, represent hydrogen, linear or branched C1-C20 alkyl, C3-C12 cycloalkyl, C2-C30 alkoxyalkyl, or C3-30 dialkylaminoalkyl, provided that at least one of R and R’ is not hydrogen,

comprising reacting glycolaldehyde with an aminating agent of formula (III) in a solvent comprising at least one C1-C3 alkanol and/or tetrahydrofuran in the presence of hydrogen and a supported noble metal catalyst,

in formula (III) :

R and R’ have the same meanings as defined above.
The process according to claim 1, wherein R and R’, independently from each other, represents hydrogen, linear or branched C1-C4 alkyl, provided that at least one of R and R’ is not hydrogen.
The process according to claim 1 or 2, wherein the molar ratio of the aminating agent to glycolaldehyde is within a range from 1: 1 to 10: 1.
The process according to any of claims 1-3, wherein the solvent is selected from methanol, ethanol, isopropanol, and tetrahydrofuran.
The process according to any of claims 1-4, wherein the solvent is substantially free of water.
The process according to any of claims 1-3, the solvent is a mixed solvent comprising (i) at least one C1-C3 alkanol and/or tetrahydrofuran; and (ii) a co-solvent selected from water, dioxane and butanol.
The process according to any of claims 1-3, wherein the solvent is a mixed solvent of a C1-C3 alkanol and water, and the water is present in an amount ranging from above 0.5 wt.%to 30 wt.%, or from 10 wt.%to 30 wt.%, or from 10 wt.%to from 20 wt.%, or from above 0.5 wt.%to 10 wt.%, based on the total weight of the solvent.
The process according to any of claims 1-3, wherein the solvent is a mixed solvent of tetrahydrofuran and water, and the water is present in an amount ranging from above 0.5 wt.%to 30 wt.%, or from 10 wt.%to 30 wt.%, or from 10 wt.%to from 20 wt.%, or from above 0.5 wt.%to 10 wt.%, based on the total weight of the solvent.
The process according to any of claims 1-8, wherein the noble metal is selected from Pd, Pt, Rh and Ru, and the support is selected from carbon black, graphite, activated carbon, aluminium oxide, and silicon dioxide.
The process according to any of claims 1-9, wherein the noble metal is present in amount from 0.5 wt.%to 10 wt.%in the supported noble metal catalyst, relative to the total weight of the supported noble metal catalyst.
The process according to any of claims 1-10, wherein the aminating agent is dimethylamine, the solvent is methanol or ethanol, the supported noble metal catalyst is Pd/C.
The process according to any of claims 1-11, wherein the solvent is used in a proportion of 10 wt.%to 95 wt.%by weight based in each case on the total weight of the reaction mixture including glycolaldehyde, the aminating agent and the solvent used.
The process according to any of claims 1-12, wherein the molar ratio of the noble metal in the catalyst to glycolaldehyde can be in the range of 0.01%-0.6%.
The process according to any of claims 1-13, wherein the reaction is carried out at a temperature from 0℃ to 80℃ and a hydrogen pressure from 1 bar to 65 bar for 1-20 hours.