JPH073009A - Catalyst for producing polyether polyamine and production of polyether polyamine with the same - Google Patents

Abstract

PURPOSE:To obtain a catalyst for producing a polyether polyamine enabling reactions under low pressures, not affected by water, and giving high conversion rates by making Ru and one kind or more of metals such as Pd, Pt, Rh, Os, Ir, Re, Tc, Mo and W supported with a carrier. CONSTITUTION:(A) Ruthenium and (B) one kind or more of metals such as palladium, platium, rhodium, osmium, iridium, rhenium, technetium, molybdenum, and tungsten are made to be supported with a carrier (e.g. gamma-alumina) to obtain a catalyst used for producing polyether polyamines, enabling the reactions under low pressures, having sufficient activities even at high LHSV, substantially not affected by catalytic poisons such as water, and giving high conversion rates under reaction conditions in which the molar ratios of hydrogen gas and ammonia to hydroxyl groups are relatively low. A polyether polyol, hydrogen gas and ammonia are brought into contact with the catalyst to produce a polyether polyamine in high yield.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing a polyether polyamine useful as a curing agent for paints and molding materials, and more particularly to a catalyst carrying ruthenium and a method for producing a polyether polyamine using the same.

[0002]

2. Description of the Related Art Polyether polyamines are widely used as a curing agent for epoxy resins and a raw material for polyamides. In this useful production method, a method in which a polyether polyol is directly reacted with ammonia and hydrogen using a catalyst is known. In the amination reaction of such a polyether polyol, (1) the production of a ketone group by dehydrogenation of the hydroxyl group, (2) the production of an amino group by the addition of ammonia to the ketone group, and (3) the imino group by the dehydration of the amino group. It is considered that the reaction proceeds by the mechanism of the formation of (1) and (4) formation of an amino group by hydrogen addition to the imino group.

In order to obtain a polyetheramine with high efficiency, all the steps (1) to (4) must be carried out well. In most cases, nickel is used as a catalytic reduction catalyst for increasing the reaction efficiency in these steps, and it can be regarded as an essential metal as a catalyst for producing a polyetheramine.

For example, British Patent No. 2175910 describes a Raney nickel catalyst whose activity is increased by adding molybdenum. However, this catalyst is still insufficient in activity, and a long reaction time (LHS
V (space-time velocity of liquid, the higher the reaction time, the shorter the reaction time) = 0.1 ~
2.0) and high pressure (pressure exceeding 13 MPa in continuous type) are required, and it is difficult to carry out on an industrial scale.

[0005] Also, in European Patent Application No. 0356047A2,
A catalyst for catalytic reduction in which nickel, ruthenium and other transition metals are supported on a γ-alumina carrier is described. However, since this catalyst also has insufficient activity, it takes a long time for the reaction, and it is difficult to carry out it on an industrial scale.

Furthermore, the catalysts disclosed herein are sensitive to catalyst poisons such as water, for example, when about 5% water relative to the starting polyol is present in the system, the conversion is about.
It has a problem of 50% reduction. When nickel is used as a catalyst in this way, the reaction time is short,
It has not been possible to construct a system that is suitable for industrialization and that can perform a low-pressure reaction.

[0007]

The present invention has been made in view of the above circumstances and can be applied to either a continuous system or a batch system, and has sufficient activity even in a low pressure reaction and a high LHSV. However, it is an object of the present invention to provide a catalyst for producing a polyether polyamine that is not easily affected by a catalyst poison such as water, and that provides a high conversion rate under a reaction condition in which the molar ratio of hydrogen and ammonia to a hydroxyl group is relatively small.

Another object of the present invention is to provide a method for producing a polyether polyamine with high conversion and selectivity using the above catalyst.

[0009]

The present invention is accomplished by combining ruthenium and certain transition metals.

That is, the present invention provides that on a carrier, a) ruthenium and b) at least one metal selected from the group consisting of palladium, platinum, rhodium, osmium, iridium, rhenium, technetium, molybdenum and tungsten. The present invention relates to a catalyst for producing a polyether polyamine, which is carried on a carrier, and a method for producing a polyether polyamine using the same.

The carrier used in the catalyst of the present invention is not particularly limited as long as it is a carrier usually used as a catalyst for catalytic reduction catalysts, and γ-alumina, carbon, silica-γ-alumina,
It is preferably selected from the group consisting of silica-titanium oxide and diatomaceous earth. Other than this, for example, α-alumina, silica, titanium dioxide and the like may be used.

Ruthenium is an essential component as the metal supported on the carrier (hereinafter referred to as the catalyst metal).
Ruthenium catalyzes dehydrogenation and hydrogenation reactions very effectively. Surprisingly, nickel, which has hitherto been considered to be essential as a catalyst for producing polyether polyamines, rather reduces its activity when combined with ruthenium.

Ruthenium is 0.1 to 30% by weight, preferably 0.5 to 10% by weight, based on the total weight of the catalyst composition.
Include. If the amount is less than 0.1% by weight, sufficient catalytic activity cannot be obtained. Further, even if ruthenium is added in an amount of more than 30% by weight, further improvement in conversion cannot be expected.

As the catalyst metal to be supported in combination with ruthenium, it is preferable to use at least one selected from the elements of Periodic Tables VIA, VIIA and VIII of the 5th and 6th Periods. Specifically, palladium, platinum,
Preference is given to using rhodium, osmium, iridium, rhenium, technetium, molybdenum and tungsten. More preferably, it is selected from palladium, platinum, rhodium, osmium and rhenium. These catalytic metals have the functions of promoting the activity of ruthenium and preventing the loss of activity due to catalyst poisons. The most preferred metal to support in combination with ruthenium is palladium.

The metal supported in combination with the ruthenium is contained in an amount of 0.1 to 30% by weight, preferably 0.5 to 10% by weight, based on the total weight of the catalyst composition. If the amount is less than 0.1% by weight, sufficient catalytic activity cannot be obtained. On the other hand, if it is added in an amount of more than 30% by weight, the carrier is covered with the metal particles and the function of the carrier is hindered, and the catalytic activity is rather lowered.

The total amount of ruthenium and the above catalytic metal is 0.2 to 60% by weight, preferably 1 to 20% by weight, more preferably 1 to 20% by weight, based on the total weight of the catalyst composition.
It is desirable that the carrier be supported in the range of 10% by weight. If the amount is less than 0.1% by weight, the catalytic activity cannot be sufficiently obtained, and even if the amount is more than 60% by weight, the carrier is covered with metal particles and the action of the carrier is hindered. . In any case, if the amount used is outside the above range, a sufficient catalytic function cannot be obtained.

In the present invention, it is preferable to support at least ruthenium and palladium as catalytic metals, and it is particularly preferable to support ruthenium in an amount of 0.5% by weight or more.

As a method for supporting the catalyst metal on the carrier, a method usually used in this technical field can be used. These include, for example, precipitation methods, impregnation methods and ion exchange methods.

After supporting the supporting metal on the carrier, the catalyst composition of the present invention can be prepared in a desired size and shape by a conventional means such as grinding. The size and shape of the catalyst particles are not particularly limited, but for example, a granular or pelletized form of 2 to 3 mm is preferable.

Another aspect of the present invention is a method of making a polyether polyamine which comprises the step of contacting a polyether polyol with hydrogen and ammonia with the above catalyst composition.

The polyether polyol used as a raw material is used in various fields and is not particularly limited, but alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran are subjected to ring-opening polymerization. It is something that can be obtained. The molecular weight is not specified, but 20000
It is effective in the following. Where the molecular weight exceeds 20,000, the concentration of hydrogen and ammonia per molecule of polyol becomes low in the reaction, so that diffusion control is likely to occur,
A high conversion rate cannot be obtained. In consideration of carrying out the flow reaction, it is preferable that the polyol is liquid at room temperature. The number of functional groups is preferably 2 to 8. Although monofunctional synthesis is possible, its industrial value is low. If it exceeds 8, it tends to become solid, which is not preferable for the reason mentioned above.

When the polyether polyol is reacted with ammonia and hydrogen, the reaction ratio is OH (in the polyether polyol) / NH ₃ / H ₂ from 1/10 to 4
Molar ratio of 0 / 0.5-10, especially 1 / 15-30 / 1
It is preferable to use a molar ratio of ˜5.

When the molar amount of hydrogen is less than 0.5 mol with respect to the hydroxyl group, the hydrogenation reaction is difficult to proceed and the conversion rate and selectivity are lowered. Further, even if the amount is increased over 10 mol, not only the conversion rate and selectivity cannot be improved, but on the contrary, it tends to be slightly decreased, which makes it difficult to carry out the low pressure reaction, which is not preferable.

If the molar amount of ammonia is less than 10 mols with respect to the hydroxyl groups, the conversion rate and the selectivity are lowered for unclear reasons, and even if the amount is more than 40 mols, the conversion rate and the selectivity are improved. Not only that, but it also becomes difficult to carry out a low-pressure reaction, which is not preferable.

The term "low pressure reaction" as used herein means that the reaction is carried out at a pressure of up to 20 MPa in a batch type reaction and up to 10 MPa in a flow type reaction.

The amination reaction can be carried out by a conventional method regardless of whether it is carried out batchwise or continuously. At that time, it is preferable to carry out at a pressure in the range of 10 to 20 MPa in the batch type reaction and in the range of 4 to 10 MPa, particularly 5 to 10 MPa in the flow type reaction. If the reaction pressure is lower than the above range, the conversion rate and the selectivity are lowered, and if the reaction pressure is higher than the above range, the conversion rate and the selectivity are not further improved, and the low pressure reaction which is one of the features of the present invention is deviated. Is not preferable. The reaction temperature is preferably 170 to 250 ° C, particularly preferably 200 to 220 ° C. If the reaction temperature falls below 170 ° C, the conversion rate will decrease and
If the temperature exceeds 50 ° C, the decomposition reaction of the polyol occurs and the deterioration of the catalyst proceeds, which is not preferable. LHSV is preferably 10 or less, more preferably 2 to 10. LHSV is 10
If it exceeds, the conversion rate and the selectivity are lowered, which is not preferable.

The amount of the catalyst of the present invention used in the amination reaction depends on the catalyst composition, the polyol to be aminated, the reaction method and the like. Generally, in the case of a batch system, it is used in an amount of 1 to 50% by weight of the polyol to be reacted. If the amount of the catalyst is too small, the conversion rate and the selectivity decrease. Further, even if the amount is used more than necessary, it is not possible to achieve the improvement in conversion rate and selectivity corresponding to the increased amount.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

A. Batch-type reaction method 1) Charge and activation of catalyst: A predetermined amount of catalyst (5.0 g unless otherwise specified in the following comparative examples) was charged into a reaction vessel having a capacity of 500 ml, and nitrogen was sufficiently supplied with air. After removal, it was activated at 200 ° C. or higher, reduced under hydrogen for about 2 hours, and cooled to room temperature. 2) Preparation of polyol: Subsequently, 100 g of polypropylene glycol having a molecular weight of 2000 was put into a 150 ml cylinder connected to a reactor through a valve. After thoroughly degassing, use nitrogen to
The pressure was increased to 10 atm, and then the valve was opened and the reaction vessel was charged. 3) Ammonia and hydrogen charge: A predetermined amount of ammonia was put into a 150 ml cylinder connected through a valve to the reaction kettle, heated to about 70 ° C and charged into the reaction kettle. Similarly, hydrogen was charged into the reaction vessel from a hydrogen cylinder connected through a valve until a predetermined pressure was reached.

The amounts of ammonia and hydrogen charged are
The molar ratio of OH / NH ₃ / H ₂ = 1/30/5 was set. After the completion of charging, the temperature of the stirrer attached to the reaction kettle was raised to the reaction temperature while maintaining the rotation speed at about 1200 rotations. After maintaining as it was for 1 hour, it was cooled to room temperature and returned to normal pressure. A sample was taken out and filtered to remove the catalyst, and then dissolved ammonia and water were removed by distillation to obtain a polyether polyamine. The conversion rate from hydroxyl groups to amino groups and the selectivity were determined by measuring the amine value.

Here, the conversion rate and selectivity are defined according to the following (Equation 1).

[Equation 1]

[0032]

Examples 1 to 7 and Comparative Examples 1 to 12 Conversion and Selectivity when Using a Catalyst Composition Combining Ruthenium with Palladium and Other Metals in the Batch Reaction
The results of (primary amination ratio) are shown in Table 1. Further, the same reaction as in Comparative Examples 1 to 7 was carried out using a catalyst containing ruthenium alone and a catalyst containing nickel as catalyst species.
The results are shown in Table 1. From these results, the reactivity is improved by supporting palladium, molybdenum, platinum, and rhenium as the second component on the ruthenium metal-supported catalyst, and nickel conventionally known as a metal catalyst for amination reaction is It can be seen that the ruthenium-palladium-based supported catalyst suppresses the reaction.

[0033]

[Table 1]

[0034]

[Example 8 and Comparative Examples 13 to 16]
The same operation as in Example 1 was performed except that g was added. The results are shown in Table 2. In addition, the influence of the presence of water was investigated using Raney nickel and ruthenium supported catalysts as catalyst species, and the results are shown in Table 2. From these results, it was found that the catalyst composition of the present invention showed a small decrease in conversion rate even when water was present in the system.

[0035]

[Table 2]

B. Continuous reaction method A continuous reaction kettle filled with a catalyst activated by the same operation as the batch reaction method (reaction kettle capacity; 250 ml, catalyst amount; 100 ml, upper and lower filled with Raschig rings) Nitrogen gas at a pressure of 2.5MPa per hour converted to atmospheric pressure of 60L
The temperature was raised to 150 ° C over about 45 minutes while flowing at the flow rate of.
Subsequently, while flowing hydrogen, the temperature was raised to 200 ° C. or higher and kept at that temperature for about 30 minutes. After that, the pressure was raised to a predetermined level while flowing only hydrogen, and then ammonia and polypropylene glycol having a molecular weight of 2000 were pumped into the reaction vessel to OH / NH ₃ / H ₂
Distribution was carried out with a predetermined LHSV so that the ratio became a predetermined number of moles. The sample after the circulation was filtered to remove the catalyst, and then water and ammonia contained in the sample were removed by distillation to obtain a polyether polyamine. The same analysis as the batch reaction method was performed.

[0037]

Examples 9 to 13 and Comparative Examples 17 to 21 Ruthenium
-A continuous reaction was carried out using a palladium-supported catalyst. The results are shown in Table 3. Table 3 shows the results of the reaction performed using a catalyst in which ruthenium was supported alone instead of the catalyst supporting ruthenium-palladium. From these results, it was found that the catalyst composition of the present invention shows a high conversion rate even at a high LHSV of 3 or more.

[0038]

[Table 3]

[0039]

Examples 14 to 20 and Comparative Examples 22 to 28 Reactions were carried out in a continuous reaction using a ruthenium-palladium supported catalyst at 2 levels of LHSV and changing the system pressure in four stages. The results are shown in Table 4. In addition, Table 4 shows the results obtained by using the catalyst in which ruthenium was solely supported. From these results, it was found that the catalyst composition of the present invention shows a high conversion rate even at a low pressure.

[0040]

[Table 4]

[0041]

[Examples 21 to 35 and Comparative Examples 29 to 40] A ruthenium-palladium-supported catalyst was used to carry out the reaction in a continuous reaction by changing the molar ratio of hydrogen and ammonia to hydroxyl groups at two levels of LHSV. The results are shown in Table 5.
Further, the reaction was carried out in the same manner as in Examples 21 to 29, except that the catalyst which supported ruthenium alone was used. The results are shown in Tables 5 and 6. From these results, it was found that the catalyst composition of the present invention has a high conversion rate even when the molar ratio of hydrogen and ammonia to hydroxyl groups is low.

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

Examples 36 and 37 The reaction was carried out in the same manner as in Example 7 except that the ruthenium-palladium-platinum supported catalyst was used. The results are shown in Table 7 below.

[0045]

[Table 7]

[0046]

Example 38 The reaction was carried out in the same manner as in Example 1 except that carbon was used as the carrier. The results are shown in Table 8 below.

[Table 8]

[0047]

EFFECTS OF THE INVENTION It has a sufficient activity even in a low pressure reaction and a high LHSV in a continuous system or a batch system, is hardly affected by a catalyst poison such as water, and has a relatively small molar ratio of hydrogen and ammonia to hydroxyl groups. Provided are a catalyst composition for producing a polyether polyamine that gives a high conversion rate under reaction conditions, and a method for producing a polyether polyamine using the same with a high conversion rate and selectivity.

Front page continued (72) Inventor Julius Joan Bati 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Brian Lewis Booth 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Within Japan Paint Co., Ltd.

Claims (6)

[Claims] 1. On a carrier, a) ruthenium and b) at least one metal selected from the group consisting of palladium, platinum, rhodium, osmium, iridium, rhenium, technetium, molybdenum and tungsten are supported on the carrier. A catalyst for producing a polyether polyamine, which is supported on. 2. The catalyst according to claim 1, wherein the ruthenium metal is contained in an amount in the range of 0.1 to 30% by weight, based on the total weight of the catalyst. 3. At least one metal selected from the group consisting of palladium, platinum, rhodium, osmium, iridium, rhenium, technetium, molybdenum and tungsten is 0.1 to 30% by weight based on the total weight of the catalyst.
The catalyst according to claim 1, which is contained in an amount in the range of. 4. A) ruthenium and b) palladium, platinum,
At least one metal selected from the group consisting of rhodium, osmium, iridium, rhenium, technetium, molybdenum and tungsten is contained in a total amount of 0.2 to 60% by weight based on the total weight of the catalyst. The catalyst according to claim 1, which is 5. A method for producing a polyether polyamine, which comprises the step of contacting a polyether polyol with hydrogen and ammonia together with the catalyst according to any one of claims 1 to 4. 6. The method for producing a polyether polyamine according to claim 5, wherein the production method is a continuous method.