KR102315753B1 - Preparation method of secondary and tertiary polyetheramine compound - Google Patents

Abstract

The present invention relates to a catalyst for reductive amination reaction and a method for preparing secondary and tertiary polyetheramine compounds using the same. According to the present invention, secondary and tertiary polyetheramines with high symmetry with high yield that are self-condensed through reductive amination reaction using primary polyetheramine and hydrogen without using alcohol as a reaction raw material can be manufactured.

Description

Method for preparing secondary and tertiary polyetheramine compounds {PREPARATION METHOD OF SECONDARY AND TERTIARY POLYETHERAMINE COMPOUND}

The present invention relates to a catalyst for reductive amination reaction and a method for preparing secondary and tertiary polyetheramine compounds using the same.

Reductive amination, as known in the art (hereinafter referred to as 'the art') to which the present invention pertains, introduces an amine group through a catalytic amination reaction of an aliphatic alkane derivative under reducing conditions and in the presence of hydrogen. It is one of the methods for obtaining an aliphatic alkane derivative. Such reductive amination is used to prepare various kinds of amine compounds such as polyetheramines.

Conventional secondary and tertiary polyetheramine production is generally produced by using alcohol as a raw material, converting it to aldehyde through dehydrogenation of alcohol, and then reacting with primary amine, but symmetric secondary and tertiary polyetheramines There is a disadvantage in that it is difficult to prepare polyetheramines.

Accordingly, the present inventors have provided a novel catalyst for reductive amination reaction and secondary and tertiary polyetheramines using the same for preparing secondary and tertiary polyetheramines with high symmetry and excellent amine conversion and yield without using alcohol A method for manufacturing was developed.

US Patent No. 9688646

Tetrahedron, 2001, Volume 57, Issue 37, pp. 7785-7811]

The present invention provides a catalyst for reductive amination reaction for producing secondary and tertiary polyetheramines using primary polyetheramines having a large molecular weight and an alkyl branch without using alcohol as a reaction raw material.

In addition, the present invention provides a method for preparing secondary and tertiary polyetheramines using the catalyst.

The present invention provides a catalyst for reductive amination reaction in which an active ingredient including cobalt (Co) and scandium (Sc) is supported on a support in order to achieve the above object.

In addition, the present invention,

(A) producing a primary polyetherimine compound by dehydrogenating a primary polyetheramine compound including a repeating unit of Formula 1 and having at least one amine group at the terminal thereof;

(B) reacting the primary polyetherimine compound with the primary polyetheramine compound to produce a secondary polyetherimine compound; and

(C) contacting the secondary polyetherimine compound with hydrogen in the presence of the catalyst for the reductive amination reaction according to any one of claims 1 to 4 to produce secondary and tertiary polyetheramine compounds It provides a method for preparing secondary and tertiary polyetheramine compounds, comprising the step of:

[Formula 1]

In Formula 1,

L ¹ and L ² are each independently alkylene having 1 to 10 carbon atoms, alkenylene having 2 to 10 carbon atoms, alkynylene having 2 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms. (cycloalkylene), or arylene having 6 to 30 carbon atoms; n is an integer from 1 to 500;

According to the present invention, secondary and tertiary with high symmetry with high self-condensation (self-condensation) and yield through reductive amination reaction using primary polyetheramine and hydrogen without using alcohol as a reaction raw material Polyetheramines can be prepared.

The present invention provides a catalyst for a reductive amination reaction in which an active ingredient including cobalt (Co) and scandium (Sc) is supported on a support.

Generally, a copper (Cu)-nickel (Ni)-based catalyst, a nickel (Ni)-rhenium (Re)-based catalyst, and a cobalt (Co)-nickel (Ni)-copper (Cu)-based catalyst are used for the reductive amination reaction. There have been many attempts to improve catalytic activity by combining metal elements such as chromium (Cr), titanium (Ti), zirconium (Zr), zinc (Zn), and molybdenum (Mo).

However, the previous catalysts described above have a problem in that the activity is easily lost due to moisture generated in the middle of the reductive amination reaction, so that the amine conversion rate is rapidly decreased.

In contrast, the supported catalyst according to an embodiment of the present invention contains cobalt (Co) and scandium (Sc) as active ingredients, and the balance of dehydrogenation and hydrogenation reactions accompanying reductive amination can be properly maintained.

In addition, as the supported catalyst according to an embodiment of the present invention contains cobalt (Co) and scandium (Sc) as active ingredients, dehydrogenation and hydrogenation accompanying the reductive amination reaction by their synergistic action A more stable balance can be maintained even in the (hydrogenation) reaction.

According to one embodiment of the present invention, the supported catalyst includes cobalt and scandium as active ingredients, and preferably includes cobalt oxide (CoO) and scandium oxide (Sc ₂ O ₃ ) (CoO—Sc _{2 )} O ₃ ) may be. _{The catalyst may have a composition of CoO-Sc 2} O ₃ after the sintering process, and may exhibit a composition including (Co metal)-(Scandium metal) through catalytic reduction conditions. As such, the active ingredients in the form of oxides or metals can be used as catalysts in the reductive amination reaction.

At this time, the catalyst is 1 to 30 parts by weight of scandium oxide based on 100 parts by weight of cobalt oxide; or 1 to 25 parts by weight of scandium oxide; Or 3 to 20 parts by weight of scandium oxide may be included. That is, while allowing the effect of the synergistic action of cobalt and scandium to be sufficiently realized, in consideration of the degree of improvement in catalytic activity according to the content ratio of cobalt and scandium, the catalyst is prepared by mixing cobalt oxide and scandium oxide in the above-described content ratio. It is advantageous to include

Meanwhile, according to another embodiment of the present invention, the supported catalyst may further include palladium (Pd) as an active ingredient.

The palladium (Pd) is hardly affected by moisture generated in the middle of the reductive amination reaction, and catalytic reduction in the activation process of the catalyst due to the synergistic action with cobalt (Co) and scandium (Sc) described above. By making it more smoothly, it is possible to finally further improve the amine conversion rate.

The palladium (Pd) may be included in the above-described catalyst in the form of palladium oxide (CoO-Y ₂ O ₃ -PdO).

In particular, according to the present invention, the catalyst may include 1 to 30 parts by weight of scandium oxide and 0.01 to 50 parts by weight of palladium oxide based on 100 parts by weight of cobalt oxide; or 0.01 to 45 parts by weight of palladium oxide; Or 0.1 to 45 parts by weight of palladium oxide may be included. That is, while allowing the effects of cobalt, scandium, and palladium to be sufficiently expressed, and in consideration of the degree of improvement in catalytic activity according to their content ratio, the catalyst contains the active ingredient in the above content ratio. it is advantageous

Meanwhile, the supported catalyst for reductive amination reaction according to the present invention includes a carrier on which the above-described active ingredient is supported.

That is, the catalyst may be a catalyst in which an active ingredient including cobalt and scandium is supported on a predetermined carrier, and palladium may be further included as the active ingredient. As described above, the catalyst in which the active ingredient is supported on the carrier can secure a wide specific surface area of the active ingredient, and thus an equivalent effect can be obtained even with a relatively small amount of the active ingredient.

Here, as the carrier, as long as it does not adversely affect the activity of the above-described active ingredient, conventional ingredients known in the art may be used. However, according to an embodiment of the present invention, the carrier is SiO ₂ , Al ₂ O ₃ , MgO, MgCl ₂ , CaCl ₂ , ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, bauxite, zeolite, starch , cyclodextrine or synthetic polymer.

The method of supporting the above-mentioned active ingredient on the carrier as described above is a method of directly supporting the active ingredient on a dehydrated carrier, or a method of mixing the active ingredient and the carrier and supporting it by sedimentation and then calcining. A conventional loading method known in the art may be applied.

At this time, the content of the active ingredient supported on the carrier is not particularly limited, since it can be determined in consideration of the range above the extent to which the minimum activity can be expressed, and the effect of reducing the amount of the active ingredient according to the introduction of the carrier. However, preferably, the active ingredient may be included in an amount of 1 part by weight or more, or 1 to 200 parts by weight, or 10 to 150 parts by weight based on 100 parts by weight of the carrier. Here, when the active ingredient is included in 100 parts by weight based on 100 parts by weight of the carrier, it can be expressed as 'the active ingredient is supported in 50 wt%'.

In addition, the catalyst may further include a co-catalyst compound capable of further improving the activity of the above-described active ingredient. The promoter compound may be supported together on the aforementioned carrier, and conventional promoter compounds known in the art may be employed without particular limitation.

On the other hand, since the catalyst can be prepared according to a conventional method known in the art, the specific details of the preparation method are also not particularly limited.

However, according to the present invention, a catalyst including the above-described active ingredients can be prepared through a precipitation method or the like. As a non-limiting example, after dissolving cobalt nitrate and scandium nitrate in water, a predetermined carrier is added, and sodium carbonate solution is added thereto to include cobalt oxide and scandium oxide. Precipitation in which the salt is supported on a carrier can be obtained, and the catalyst of one embodiment can be prepared by washing, drying, and calcining the precipitated salt. Furthermore, a catalyst of another embodiment may be prepared by adding and mixing water in which palladium nitrate is dissolved in the catalyst that has undergone the calcination process, and drying it at a high temperature.

The catalyst according to the present invention as described above can be used for the preparation of secondary and tertiary polyetheramines through reductive amination of primary polyetheramines having an amino group at the terminal.

Meanwhile, according to another embodiment of the present invention, in the presence of the aforementioned catalyst for reductive amination reaction, a polyether derivative such as primary polyetheramine is brought into contact with hydrogen to undergo self-condensation through reductive amination reaction. ) A method for preparing secondary and tertiary polyetheramine compounds is provided.

As an example of the reductive amination reaction, the _{primary polyetheramine having an amino (-NH 2} ) group at the terminal is subjected to the following three-step reaction mechanism.

[reaction mechanism]

Step 1: Dehydrogenation of a primary amine to produce a primary imine

Step 2: reacting the primary imine produced in step 1 with a primary amine to produce the corresponding imine

Step 3: reacting the imine produced in step 2 with hydrogen to produce a secondary amine

In the reaction mechanism, a primary polyetheramine is converted to a primary polyetherimine through a dehydrogenation reaction, and the primary polyetherimine is reacted with a primary polyetheramine to produce a corresponding secondary polyetherimine; The secondary polyetherimine may be reacted with hydrogen to form a secondary polyetheramine.

According to one embodiment of the present invention,

(A) producing a primary polyetherimine compound by dehydrogenating a primary polyetheramine compound including a repeating unit of Formula 1 and having at least one amine group at the terminal thereof;

(B) reacting the primary polyetherimine compound with the primary polyetheramine compound to produce a secondary polyetherimine compound; and

(C) contacting the secondary polyetherimine compound with hydrogen in the presence of a catalyst for reductive amination reaction according to the present invention to produce secondary and tertiary polyetheramine compounds; A method for preparing a tertiary polyetheramine compound is provided.

[Formula 1]

In Formula 1,

L ¹ and L ² are each independently alkylene having 1 to 10 carbon atoms, alkenylene having 2 to 10 carbon atoms, alkynylene having 2 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms. (cycloalkylene), or arylene having 6 to 30 carbon atoms; n is an integer from 1 to 500;

According to one embodiment of the present invention, the primary polyetheramine compound may be a compound including a repeating unit of Formula 2 below and at least one amine group at the terminal thereof.

[Formula 2]

In Formula 2, R ¹ is each independently hydrogen or a C1-C4 alkyl group, and n is an integer of 4 to 500.

The primary polyetheramine compound may be a block polymer or a random polymer including one or more amine groups at the terminal and the repeating unit of Formula 1 above.

In one embodiment of the present invention, the primary polyetheramine compound may be a compound of Formula 3 below.

[Formula 3]

In Formula 3,

L ¹ and L ² are each independently alkylene having 1 to 10 carbon atoms, alkenylene having 2 to 10 carbon atoms, alkynylene having 2 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms. (cycloalkylene), or arylene having 6 to 30 carbon atoms;

R ² is an alkyl group having 1 to 18 carbon atoms, an alkyleneamine group having 1 to 18 carbon atoms, or an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms;

n is an integer from 1 to 500;

In one embodiment of the present invention, the primary polyetheramine compound may be a compound of Formula 4 below.

[Formula 4]

In Formula 4,

L ^{3 To} L ⁶ are each independently alkylene having 1 to 10 carbon atoms, alkenylene having 2 to 10 carbon atoms, alkynylene having 2 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms (cycloalkylene), or arylene having 6 to 30 carbon atoms;

R ³ is an alkyl group having 1 to 18 carbon atoms, an alkyleneamine group having 1 to 18 carbon atoms, or an aryl group having 6 to 30 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms;

a and b are each independently an integer from 1 to 500;

In one embodiment of the present invention, the primary polyetheramine compound may be a compound of Formula 5 below.

[Formula 5]

In Formula 5,

L ⁷ to L ¹² are each independently alkylene having 1 to 10 carbon atoms, alkenylene having 2 to 10 carbon atoms, alkynylene having 2 to 10 carbon atoms, cycloalkylene having 3 to 10 carbon atoms. (cycloalkylene), or arylene having 6 to 30 carbon atoms;

R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkyleneamine group having 1 to 18 carbon atoms, or an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms;

y is an integer from 2 to 500, and (x+z) is an integer from 2 to 100.

In one embodiment of the present invention, the primary polyetheramine compound may be a compound of Formula 6 below.

[Formula 6]

In Formula 6,

R ⁵ is an alkyl group having 1 to 18 carbon atoms, an alkyleneamine group having 1 to 18 carbon atoms, or an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms;

R ⁶ are each independently hydrogen or a C1-C4 alkyl group;

n is an integer from 4 to 500;

In addition, in the present invention, the primary polyetheramine compound may be selected from the group consisting of compounds represented by the following Chemical Formulas 7 to 14.

[Formula 7]

In the above formula, x is an integer from 0 to 200, y is an integer from 0 to 200, except that both x and y are O.

[Formula 8]

In the above formula, x is an integer from 0 to 200.

[Formula 9]

In the above formula, x is an integer from 0 to 200, y is an integer from 0 to 200, and z is an integer from 0 to 200, except that x, y and z are all 0.

[Formula 10]

In the above formula, x is an integer from 0 to 200.

[Formula 11]

In the above formula, x is an integer from 1 to 10 independently of each other.

[Formula 12]

In the above formula, R1, R2, R3, R4 are each independently hydrogen or a C1-C4 alkyl group, x is an integer from 0 to 200, y is an integer from 0 to 200, z is an integer from 0 to 200, and , except that x, y, and z are all O.

[Formula 13]

In the above formula, x is an integer from 0 to 200, y is an integer from 0 to 200, z is an integer from 0 to 200, provided that the sum of x+y+z is an integer from 3 to 200.

[Formula 14]

In the above formula, x is an integer from 0 to 200, y is an integer from 0 to 200, z is an integer from 0 to 200, provided that the sum of x+y+z is an integer from 3 to 200.

In the method for preparing the secondary and tertiary polyetheramine compounds according to the present invention, the weight ratio of the reactants may be determined in consideration of the reaction efficiency and the like within a range in which a series of reactions can be sufficiently performed, and thus is not particularly limited.

However, according to the present invention, according to the present invention, the production method is carried out in the presence of 0.05 to 5 parts by weight or 0.1 to 3 parts by weight or 0.1 to 2 parts by weight of hydrogen with respect to 100 parts by weight of the primary polyetheramine compound for reaction efficiency may be advantageous in terms of improvement of

In addition, in the manufacturing method according to the present invention, each step is performed at a temperature of 20 °C to 350 °C and a pressure of 1 bar to 300 bar (100 kPa to 30,000 kPa), or a temperature of 20 °C to 300 °C and 1 bar to 250 bar under the pressure of; More preferably, it may be carried out at a temperature of 20 °C to 250 °C and a pressure of 1 bar to 220 bar, which may be advantageous in terms of improvement of reaction efficiency.

On the other hand, the method for preparing the polyetheramine compound according to the present invention may be performed by further including conventional steps known in the art before or after each step, in addition to the steps described above.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in various various forms and is not limited to the embodiments described herein.

First, the catalysts of Examples and Comparative Examples were prepared in the following manner (Example 1, Comparative Examples 1 and 2), and polyetheramine compounds were prepared using each catalyst (Examples 2 and 3, Comparative Example) Examples 3 and 4).

In addition, the contents of Examples and Comparative Examples are summarized in Table 1 below.

In this case, the 'conversion rate' refers to the ratio (weight ratio) in which the starting material polyether derivative is converted to a polyether amine compound through reductive amination, and the weight of the polyether amine compound is measured in Total amine value (ASTM D2074) According to the titration method, it was measured.

And, 'secondary and tertiary amine selectivity' refers to the ratio (weight ratio) of secondary and tertiary amine compounds in the product, and titration according to secondary amine value measurement method and tertiary amine value measurement method (ASTM D2074) ) was measured.

Example 1

CoO-SC ₂ O ₃ -Preparation of PdO/Molecular sieve 13X catalyst

At room temperature, 44.034 g of cobalt nitrate and 0.525 g of scandium nitrate, and 0.056 g of palladium nitrate are dissolved in 400 g, and then, Molecular sieve 13X is administered as a carrier. A precipitation method was performed by injecting a 15 wt% aqueous solution of sodium carbonate at a rate of 0.08 ml/s.

After 1 hour had elapsed, the resulting salt was washed several times using 500 ml of distilled water, filtered, and dried at 110° C. for 15 hours.

The dried salt was put into the kiln, and the temperature of the kiln was raised to 600 °C at 300 °C/hr and calcined at 600 °C and air atmosphere for 4 hours. CoO-Sc ₂ O ₃ -PdO/Molecular sieve 13X _{A catalyst (containing 6.03 parts by weight of SC 2} O ₃ and 0.13 parts by weight of PdO based on 100 parts by weight of CoO) was obtained. This catalyst was reduced so that Cobalt became a metal state.

Example 2

Preparation of polyetheramine compounds

In a batch reactor having a capacity of 200 ml, 2.5 g of the catalyst according to Example 1 and 50 g of a primary polyethermiane (product name: D-2000, manufacturer: HUNTSMAN, molecular weight: 2,000) were added.

Subsequently, nitrogen was purged 5 times to remove oxygen in the reactor, and hydrogen was injected at room temperature by 20 bar. After that, the reactor temperature was raised to 220 °C and reacted for 2.5 hours under a pressure of 30 bar to obtain 29.40 g of secondary and tertiary polyetheramine compounds (conversion of secondary and tertiary amines relative to the starting material about 58.8%).

Example 3

Preparation of polyetheramine compounds

In a batch reactor having a capacity of 200 ml, 2.5 g of the catalyst according to Example 1 and 50 g of a primary polyethermiane (product name: D-2000, manufacturer: HUNTSMAN, molecular weight: 2,000) were added.

Subsequently, nitrogen was purged 5 times to remove oxygen in the reactor, and hydrogen was injected at room temperature by 20 bar. After that, the reactor temperature was raised to 220 ° C and reacted for 12 hours under a pressure of 30 bar to obtain 37.80 g of secondary and tertiary polyetheramine compounds (conversion rate of secondary and tertiary amines compared to the starting material about 75.6%)

Comparative Example 1

Preparation of CoO/Molecular sieve 13X catalyst

At room temperature, 44.034 g of cobalt nitrate is dissolved in 400 g of water, and then, Molecular sieve 13X is administered as a carrier. A precipitation method was performed by injecting a 15 wt% aqueous solution of sodium carbonate at a rate of 0.08 ml/s.

After 1 hour had elapsed, the resulting salt was washed several times using 500 ml of distilled water, filtered, and dried at 110° C. for 15 hours.

The dried salt was put into the kiln, and the temperature of the kiln was raised to 600 °C at 300 °C/hr and calcined at 600 °C and air atmosphere for 4 hours to obtain a CoO/Molecular sieve 13X catalyst.

This catalyst was reduced so that Cobalt became a metal state.

Comparative Example 2

CoO-SC ₂ O ₃ /Molecular sieve 13X catalyst preparation

At room temperature, 44.034 g of cobalt nitrate and 0.525 g of scandium nitrate are dissolved in 400 g of water, and then, Molecular sieve 13X is administered as a carrier. A precipitation method was performed by injecting a 15 wt% aqueous solution of sodium carbonate at a rate of 0.08 ml/s.

After 1 hour had elapsed, the resulting salt was washed several times using 500 ml of distilled water, filtered, and dried at 110° C. for 15 hours.

The dried salt was put into the kiln, and the temperature of the kiln was raised to 600 °C at 300 °C/hr and calcined at 600 °C and air atmosphere for 4 hours. CoO-SC ₂ O ₃ /Molecular sieve 13X catalyst ( Based on 100 parts by weight of CoO, SC ₂ O ₃ containing 6.03 parts by weight) was obtained. This catalyst was reduced so that Cobalt became a metal state.

Comparative Example 3

Preparation of polyetheramine compounds

In a batch reactor having a capacity of 200 ml, 2.5 g of the catalyst according to Comparative Example 1 and 50 g of primary polyethermiane (product name: D-2000, manufacturer: HUNTSMAN, molecular weight: 2,000) were added.

Subsequently, nitrogen was purged 5 times to remove oxygen in the reactor, and hydrogen was injected at room temperature by 20 bar. After that, the reactor temperature was raised to 220 °C and reacted for 2.5 hours under a pressure of 30 bar to obtain 6.6 g of secondary and tertiary polyetheramine compounds (conversion of secondary and tertiary amines relative to the starting material about 13.2%).

Comparative Example 4

Preparation of polyetheramine compounds

In a batch reactor having a capacity of 200 ml, 2.5 g of the catalyst according to Comparative Example 2 and 50 g of primary polyethermiane (product name: D-2000, manufacturer: HUNTSMAN, molecular weight: 2,000) were added.

Subsequently, nitrogen was purged 5 times to remove oxygen in the reactor, and hydrogen was injected at room temperature by 20 bar. Then, 14.2 g of secondary and tertiary polyetheramine compounds were obtained by raising the reactor temperature to 220 °C and reacting for 2.5 hours under a pressure of 30 bar (conversion of secondary and tertiary amines relative to the starting material about 28.4%).

starting material catalyst reaction
Temperature reaction
pressure reaction time 2+tertiary amine
transference number Example
2 D-2000 Example 1
(CoO-SC ₂ O ₃ -PdO/Molecular sieve 13X) 220℃ 30 bar 2.5 hours 58.7% Example
3 D-2000 Example 1
(CoO-SC ₂ O ₃ -PdO/Molecular sieve 13X) 220℃ 30 bar 12 hours 75.5% comparative example
3 D-2000 Comparative Example 1
CoO/Molecular sieve 13X 220℃ 30 bar 2.5 hours 13.2% comparative example
4 D-2000 Comparative Example 2
CoO-SC ₂ O ₃ /Molecular sieve 13X 220℃ 30 bar 2.5 hours 28.4%

As can be seen from the Examples and Comparative Examples, the preparation methods of Comparative Examples 3 and 4 using the catalysts of Comparative Example 1 or Comparative Example 2 showed low amine yields of 13.2% and 28.4%, respectively. In contrast, the preparation methods of Examples 2 and 3 using the catalyst of Example 1 showed high amine yields.

In particular, as can be seen from Example 2, when the catalyst according to the present invention was used, a high amine yield of 58.7% was exhibited even with a short reaction time of 2.5 hours.

As described above in detail a specific part of the content of the present invention, for those of ordinary skill in the art, it is clear that this specific description is only a preferred embodiment, and the scope of the present invention is not limited thereby. something to do. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (8)

delete delete delete delete (A) producing a primary polyetherimine compound by dehydrogenating a primary polyetheramine compound including a repeating unit of Formula 1 and having one or more amine groups at the terminal thereof;
(B) reacting the primary polyetherimine compound with the primary polyetheramine compound to produce a secondary polyetherimine compound; and
(C) the secondary polyetherimine compound, in the presence of a catalyst for reductive amination reaction in which an active ingredient including cobalt (Co), scandium (Sc) and palladium (Pd) is supported on a support, hydrogen and contacting to produce a mixture comprising secondary and tertiary polyetheramines;
The catalyst for the reductive amination reaction contains 1 to 30 parts by weight of scandium oxide and 0.01 to 50 parts by weight of palladium oxide based on 100 parts by weight of cobalt oxide,
Method for preparing secondary and tertiary polyetheramine compounds, which does not use alcohol as a reaction raw material:
[Formula 1]

In Formula 1,
L ¹ and L ² are each independently (C ₁ ~C ₁₀ )alkylene, (C ₂ ~C ₁₀ )alkenylene, (C ₂ ~C ₁₀ )alkynylene, (C ₃ ~ C ₁₀ ) cycloalkylene (cycloalkylene), or (C ₆ ~ C ₃₀ ) arylene (arylene); n is an integer from 1 to 500; The method according to claim 5, wherein the primary polyetheramine compound is selected from compounds represented by the following Chemical Formulas 3 to 5, Secondary and tertiary polyetheramine compounds:
[Formula 3]

In Formula 3,
L ¹ and L ² are each independently (C ₁ ~C ₁₀ )alkylene, (C ₂ ~C ₁₀ )alkenylene, (C ₂ ~C ₁₀ )alkynylene, (C ₃ ~ C ₁₀ ) cycloalkylene (cycloalkylene), or (C ₆ ~ C ₃₀ ) arylene (arylene);
R ² is (C ₁ ~ C ₁₈₎ alkyl, (C ₁ ~ C ₁₈₎ alkylene amine group, or a (C ₁ ~ C ₁₈₎ substituted or unsubstituted alkyl groups (C ₆ ~ C ₃₀₎ aryl group;
n is an integer from 1 to 500,

[Formula 4]

In Formula 4,
L ^{3 To} L ⁶ are each independently (C ₁ ~C ₁₀ ) Alkylene (alkylene), (C ₂ ~ C ₁₀ ) Alkenylene, (C ₂ ~ C ₁₀ ) Alkynylene, (C ₃ ~ C ₁₀ ) cycloalkylene (cycloalkylene), or (C ₆ ~ C ₃₀ ) arylene (arylene);
R ³ is a (C ₁ ~C ₁₈ )alkyl group, a (C ₁ ~C ₁₈ )alkyleneamine group, or _{a (C 6} ~C ₃₀ )aryl group unsubstituted or substituted with a _{(C 1} ~C _{18 )alkyl group;}
a and b are each independently an integer from 1 to 500,

[Formula 5]

In Formula 5,
L ^{7 To} L ¹² are each independently (C ₁ ~C ₁₀ ) Alkylene (alkylene), (C ₂ ~ C ₁₀ ) Alkenylene (alkenylene), (C ₂ ~ C ₁₀ ) Alkynylene, (C ₃ ~ C ₁₀ ) cycloalkylene (cycloalkylene), or (C ₆ ~ C ₃₀ ) arylene (arylene);
R ⁴ is a (C ₁ -C ₁₈ )alkyl group, a (C ₁ -C ₁₈ )alkyleneamine group, or _{a (C 6} -C ₃₀ )aryl group unsubstituted or substituted with a _{(C 1} -C _{18 )alkyl group;}
y is an integer from 2 to 500, and (x+z) is an integer from 2 to 100. The method of claim 5, wherein the weight ratio of the reactant is 0.05 to 5 parts by weight of hydrogen based on 100 parts by weight of the primary polyetheramine compound. The method of claim 5, wherein the steps (A) to (C) are carried out at a temperature of 20 °C to 350 °C and a pressure of 100 kPa to 30,000 kPa.