JPH0140049B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved method for producing polyoxyalkylene polyamines. In more detail,
The present invention relates to the reductive amination of high molecular weight hydroxy-terminated polyoxyalkylene compounds using a molybdenum-reinforced Raney nickel catalyst in the presence of ammonia and optionally hydrogen, resulting in polypolymers with good yield and selectivity. The present invention relates to a method of providing oxyalkylene amines. According to the present invention, Raney nickel reinforced with molybdenum such that the final Raney nickel catalyst contains 0.2 to 5 wt% molybdenum, more preferably 0.5 to 1.5 wt% molybdenum, (more preferably 230
Unexpected results were obtained when used to catalyze the reductive amination of hydroxy-terminated polyoxyalkylene compounds having a molecular weight of at least 230, such as those with a molecular weight of ~6000), using unreinforced Raney-nickel catalysts or Compared to the yields and selectivities typically obtained when reductively aminating hydroxy-terminated polyoxyalkylene compounds in the presence of Raney nickels reinforced with other metals,
It was an unexpected finding that there was a considerable improvement in yield and selectivity. The reductive amination process of the present invention can be carried out in batches using powdered molybdenum-enriched Raney nickel, or alternatively, a mass of molybdenum-enriched Raney nickel catalyst, e.g.
Particle size of mm, surface area of 25 m ² /g or less and 0.01 to 0.03
With a fixed bed of mass having a porosity of cm ³ /g,
It can be performed continuously. In a preferred embodiment of the invention, a hydroxy-terminated polyoxyalkylene compound, such as a diol or triol having a molecular weight of 500 to 10,000, is reacted with molybdenum as described above in anhydrous conditions in the presence of ammonia and optionally in the presence of hydrogen. The corresponding polyoxyalkylene polyamines were obtained in good yield and selectivity by continuous passage through a catalyst bed of reinforced Raney catalyst mass. US Patent No. 3,236,895 discloses a method for producing polyoxyalkylene polyamines such as polyoxyalkylene diamines by reacting polyoxyalkylene diols with ammonia in the presence of hydrogen. Examples 8-14 of that patent are specifically directed to reacting polypropylene glycol with ammonia in the presence of added hydrogen and a conventional Raney-nickel catalyst. The yield of desired product was 40-70%. U.S. Pat. No. 3,215,742 also discloses a method for producing alkylene diamine, and more particularly, a method for producing hexamethylene diamine from 1,6-hexane diol by reacting the diol with ammonia in the presence of Raney nickel. There is. US Pat. No. 3,347,926 discloses an ammonolysis process for producing aliphatic amines using a hydroxy-containing feedstock with an aminating agent in the presence of a Raney-Nickel catalyst containing trace amounts of chromium. U.S. Pat. No. 3,654,370 discloses a method for producing a polyoxyalkylene polyamine, in which a polyoxyalkylene polyol is mixed with hydrogen and nickel.
The object is a process which is characterized in that it is reacted with ammonia in the presence of a catalyst prepared by reduction of a mixture of oxides of copper and chromium. European Patent No. 0022532 discloses the use of pelletized Raney nickel in a continuous process for the reductive amination of low molecular weight compounds such as neopentyl alcohol. It has been reported that low yields and selectivities are usually expected. European Patent No. 0081701 discloses the use of conventional Raney nickel in the amination of polyether triols with a molecular weight of 6000.
The conversion rate to amino groups is only 80%. The present invention produces polyoxyalkylene polyamines by reductively aminating hydroxy-terminated polyoxyalkylene compounds with ammonia, optionally in the presence of hydrogen, using a Raney-nickel catalyst under anhydrous conditions; An improved process is directed to a molybdenum reinforced Raney nickel or Raney nickel/aluminum catalyst containing from 0.2 to 5% by weight of molybdenum based on the total weight of the catalyst. Catalyst Composition In general, reinforced Raney nickel catalysts are obtained by first preparing an alloy of nickel, aluminum, and metal reinforcement in the desired proportions. The alloy is then treated with a base such as sodium hydroxide to leach substantially all of the aluminum from the alloy, thereby yielding the desired strengthened Raney nickel catalyst. Typically, reinforced Raney nickel catalysts contain less than 10% aluminum by weight, usually from 1.5 to 7.5% aluminum. In the present invention, conventional molybdenum-reinforced Raney nickel catalysts, ie catalysts prepared as described above and containing less than 10% by weight aluminum, can be used. Alternatively, Raney nickel/aluminum catalysts of the type disclosed in co-pending application (D.80, 394) can be used, modified by the inclusion of the desired amount of molybdenum in the starting alloy. Thus, the Raney nickel/molybdenum/aluminum catalyst is prepared by treating a nickel/molybdenum/aluminum alloy with a base such as sodium hydroxide such that the final product, preferably in the form of lumps, contains up to 40% aluminum by weight. Alternatively, aluminum can be produced simply by partially leaching aluminum from the alloy. Thus, the catalyst used in the present invention contains, based on the total weight of the catalyst, 0.2 to 5% by weight of molybdenum, 0 (i.e., trace amounts) to 40% by weight of aluminum, and the remainder of the composition is nickel. More preferably, the Raney-nickel catalyst used in the present invention contains 0.5 to 1.5% by weight of molybdenum and 1 to 35% by weight of aluminum, based on the total weight of the catalyst.
The rest is nickel. The molybdenum-enriched Raney nickel and Raney nickel/aluminum catalysts can be used in powder form when the process of the invention is carried out in batches.
Molybdenum-enriched catalysts are either fixed beds of catalyst in the form of pellets or "nuggets" of molybdenum-enriched Raney nickel or Raney nickel/aluminum.
(i.e. the mass is at least 1 mm long in its longest dimension, preferably 1 to 10 mm in length in its longest dimension)
It can be used in the form of a fixed bed for continuous operation, such as a fixed bed containing molybdenum-reinforced Raney nickel or Raney nickel/aluminum (unpowdered large and small lumps) with a particle size of 1 to 20 mm. preferable. The surface area of powdered Raney nickel is usually 80 to 100 m ² /g, but
Molybdenum-reinforced Raney Nickel and Raney Nickel/Aluminum "nuggets" are typically 25
less than m ² /g. The molybdenum-reinforced Raney nickel and Raney nickel/aluminum lumps also have a relatively low porosity of 0.01-0.03 cm ³ /g. Polyoxyalkylene Polyol Feedstock The polyoxyalkylene polyol feedstock that can be used in the present invention is produced by reacting an epoxide such as ethylene oxide, propylene oxide or butylene oxide with an initiator to produce a hydroxy-terminated alkoxylated product. This is a produced hydroxy-terminated polyoxyalkylene compound. Preferred feedstocks include hydroxy-terminated polyoxypropylene and poly(oxyethylene-oxypropylene) compounds such as diols and triols, although the functionality of the feedstock is not critical to the practice of this invention. do not have. Thus, a wide variety of compounds can be used, such as polyoxypropylene glycols, monoalkyl ethers such as tetrols, hexols, and the like. However, the feedstock has an average molecular weight of at least 230, e.g.
It is important to have an average molecular weight of 10,000, more preferably 500-8,000. Monoalkyl glycol ethers that can _be used ^as raw ^materials in one embodiment of the present invention generally _{have the} ^formula _: an alkyl group, R ₂ is hydrogen, methyl, ethyl, propyl and/or butyl, and p is from 4 to 100, sufficient to give a molecular weight of at least 230). The diol feedstock used in other embodiments of the invention generally has the formula: (wherein R ³ is hydrogen, methyl or butyl,
and q is from 3 to 170, sufficient to give a molecular weight of at least 230). An example of this type of feedstock is the formula (wherein r is between 3 and 100, sufficient to give a molecular weight of at least 230; r is, for example, between 6 and 100)
There are polyoxypropylene diols such as polyoxypropylene diols represented by (which may be). Examples of feedstocks represented by formula () include polyoxypropylene diols having an average molecular weight of 230 or more and a value of q of 6 to 7;
There are polyoxypropylene diols having an average molecular weight of about 2000 and an average value of q of about 33, and polyoxypropylene diols having an average molecular weight of about 4000 and an average value of q of about 60. In other embodiments, the polyoxyalkylene diol has the formula: (wherein b is from 8 to 100 and a+c is from 2 to 3). An example of a feedstock having the formula is: approximate molecular weight b, approximate value a+c 600 8.5 2.5 900 15.5 2.5 2000 40 2.5 4000 86 2.5. Other types of preferred feedstocks have the formula: (wherein R ⁴ is hydrogen or methyl, n is 0 or 1, and the sum of x + y + z is 5 to 100
It consists of polyoxyalkylene triols such as polyoxyalkylene triols represented by For example, n can be 0 when R ⁴ is hydrogen and 1 when R ⁴ is methyl. A particular example of a compound having the formula is the approximate molecular weight ^R4nx +y+z500 - _{CH3175000H085} . Other types of feedstock that can be used in the present invention are: (In the formula, n is 1 to 5, and the sum of x+y+z is 7 to 170). Preparation of Polyoxyalkylene Polyamines As indicated above, the polyoxyalkylene polyamine products of the present invention are prepared using molybdenum reinforced Raney nickel or Raney nickel/aluminum catalysts under reductive amination conditions and optionally in the presence of hydrogen. It is produced by reacting an oxyalkylene polyol feedstock with ammonia under anhydrous conditions. The general expectation is that the reaction rate will become slower as the molecular weight of the feedstock increases. Contrary to this expectation, it has been found that for the process of the present invention, reaction rates are unexpectedly faster for higher molecular weight hydroxy-terminated polyoxyalkylene feedstocks. The reductive amination conditions to be utilized range from 4 to 4 ammonia per hydroxyl equivalent of the feedstock.
It is preferred to include the use of 150 moles. Although hydrogen is not an essential co-reactant in the present invention,
0.5-10 hydrogen per hydroxyl equivalent of feedstock
It has been found preferable to use molar equivalent amounts. The reaction conditions to be used are preferably 160-250°C;
More preferably, it can include a temperature of 185-230°C. The pressure can be suitably 3.5 to 25 MPa, more preferably 7 to 17.5 MPa. The contact time is preferably when the reaction is carried out in batches.
It can be from 0.1 to 6 hours, especially from 0.15 to 2 hours. When the reaction is carried out in continuous mode with pelleted or bulk catalyst, the reaction time is suitably between 0.1 and 2.0 grams of feedstock per cubic centimeter of catalyst per hour, preferably between 0.1 and 2.0 grams of feedstock per cubic centimeter of catalyst per hour. Feed material 0.3～
Can be 1.6 grams. The invention will be further illustrated using the following specific examples; all percentages are by weight unless otherwise indicated. Example 1 A molybdenum-enriched (2% Mo) commercial Raney nickel catalyst (Grace 3000) was made anhydrous by repeatedly washing the wet catalyst with t-butylamine. 404.4 g of polyoxypropylene triol with a molecular weight of 5000 and 50.0 g of anhydrous catalyst are placed in a stirred autoclave.
and 104.9 g of ammonia were charged. at room temperature
Sufficient hydrogen pressure was applied to achieve 3.20 MPa.
The autoclave was rapidly heated to 245°C and the temperature was maintained at 243-249°C (average 246°C) for 25 minutes.
The pressure was 21.47-21.64 MPa. The autoclave was rapidly cooled to room temperature. Stripping a portion of the contents (rotary evaporator,
98℃ and 3330Pa). Analysis shows total acetylatables 0.59meq/g, total amines
0.60meq/g and primary amines 0.59meq/g. (The analytical value has an accuracy of ±0.01 meq/g) Example 2 The operation was performed according to the method of Example 1. Conditions and results are recorded in Table 1. Please note the following points. a At a given temperature, there was a dependence of conversion on catalyst concentration (see samples 17, 18 and 19, and 15; also compare sample 13 with samples 14 and 12). b Under the given set of reaction conditions, the 1% Mo catalyst is more active than the 2% Mo catalyst (compare samples 3 and 8 with samples 9 and 12). Example 3 (continuous type) In a tubular reactor containing about 95 cm ³ of molybdenum-reinforced Raney nickel granules (2% Mo) with a diameter of about 6.5 mm, polypropylene glycol with a molecular weight of 2000 was simultaneously added at 50.85 g/hour and ammonia. At 53.57 g/h, hydrogen was fed at 8/h. The reaction vessel is
The temperature was maintained at 200°C and a total pressure of 13.89 MPa. A sample of the effluent was heated at 98℃/3330Pa on a rotary evaporator.
When stripped and analyzed with
g, and primary amines 0.64 meq/g. The reaction vessels were operated in essentially the same manner, but at temperatures of 210, 220 and 224°C. Actual conditions and product analysis values are shown in the table. Example 4 The procedure of Example 3 was essentially followed, except that the reaction vessel was filled with about 100 cm ³ of molybdenum-reinforced Raney nickel (1% Mo) catalyst granules in 8 x 12 meshes. The conditions and results are shown in the table. Example 5 Comparative Example Using Unreinforced Raney Nickel The method of Example 4 was essentially followed except that the catalyst was an 8 x 12 mesh of unreinforced Raney nickel granules. The conditions and results are shown in the table. By comparing the results in the table with the results in the table, it can be seen that the 1% Mo reinforced Raney nickel produces somewhat better results, especially at the maximum PPG-2000 space velocity. Example 6 Comparative example of batch operation using Cr-reinforced Raney nickel Essentially, the method illustrated by sample 2 in the table was repeated: using only 336.8 g of polyoxypropylene triol with a molecular weight of 5000, NH ₃ ( 24.4
%NH ₃ ) 108.9g and Grace
2400 (2% Cr, 2% iron-reinforced Raney nickel) 50.1
g was used. Analysis of the stripped product revealed total acetylatable content.
0.59 meq/g, total amines 0.34 meq/g, and primary amines 0.33 meq/g. This result is
much worse than in operation with Mo-reinforced Raney nickels (compare with table). Example 7 Comparative example of batch operation using deactivated Raney nickel Essentially the method of Example 6 was followed but: Molecular weight
5000 polyoxypropylene triol 414.6g,
72.8 g of NH ₃ and 49.98 g of Grace 2800 (unreinforced Raney Nickel) were used. Analysis of the product revealed 0.60 meq/g total acetylatables, 0.55 meq/g total amines, and primary amines.
It was 0.54meq/g. Comparison with the results in the table shows that the unreinforced catalyst is less active than the Mo-reinforced catalyst.

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[Table] Example 8 (comparison) Amination of triol on supported Ni/Cu/Cr/Fe 165.54 g of polyoxypropylene triol with a molecular weight of 5000 and pulverized calcixate supported on diatomaceous earth were placed in an autoclave ( Calsicat)
It was filled with 65.09 g of Ni/Cu/Cr/Fe. The autoclave was replaced with hydrogen and pressurized to 1.48MPa with hydrogen.
Pressurized to 10.09 MPa at 27°C with nitrogen. 46
Heat to 235℃ over 15.96MPa
The pressure was re-pressurized to 20.78MPa. 234-250℃ (average 240
°C) for 1.8 hours. pressure in the first 0.8 hours
The pressure dropped to 20.09MPa. This is further increased to 20.78MPa
After that, the pressure gradually increased to 21.82MPa. The autoclave was cooled and the gas was sampled during degassing; it contained trace amounts of isopropylamine, ethylamine and methylamine, and 22.9% methane. A filtered and stripped sample of the autoclave contents was analyzed to have 0.19 meq/g total acetylatables and <0.01 meq/g each of total and primary amines. Example 9 Amination of Triols on Molybdenum-Reinforced Raney Nickel Polyoxypropylene Triol with a Molecular Weight of 5000
The method of Example 8 was essentially followed except that 167.29 g and 49.96 g of anhydrous Raney 3000 were used. The initial pressure was 1.82 MPa, up to 10.44 psiq for each of hydrogen and nitrogen. Heating to 283°C was achieved over 53 minutes. It was cooled to 242° C. within 2 minutes and pressurized with hydrogen from 19.06 MPa to 20.78 MPa. The temperature was maintained at 240°C, and hydrogen at 20.78 MPa was supplied for 2 hours. The pressure rose to 21.82MPa. After cooling, the contents of the filter-stripped autoclave were analyzed and found to be 0.20 meq/g total acetylatables, 0.06 meq/g total amines, and 0.03 meq/g primary amines. Example 10 (Comparative) A reaction vessel containing chromium-reinforced Raney nickel granules approximately 6.5 mm in diameter was operated according to the conditions listed in the table. The results in the table show that this catalyst is also effective in aminating polypropylene glycol with a molecular weight of 2000. Example 11 A reaction vessel containing 6.5 mm diameter molybdenum reinforced Raney nickel granules was operated according to the conditions listed in the table. The results show that this catalyst is effective for PPG-2000 amination. After use, it contained an estimated 3-5% fine particles.

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[Table] It was.
Example 12 (Comparative) A commercially available Raney nickel catalyst (Grace 2800, an unreinforced Raney nickel containing less than 10% aluminum by weight) was rendered anhydrous by repeated washing of the wet catalyst with t-butylamine. 417.79 g of triol with a molecular weight of 5000 and the anhydrous catalyst were placed in a stirred autoclave.
50.16 g and 88.4 g of NH ₃ were charged. The autoclave was purged with hydrogen and sufficient hydrogen pressure was applied to achieve 3.20 MPa at room temperature. The autoclave was rapidly heated to 245°C and the temperature was maintained at 242-250°C (average 248°C) for 26 minutes. Pressure is 18.64~
It was 18.71MPa. The autoclave was rapidly cooled to room temperature. A portion of the contents was filtered and stripped (rotary evaporator; 98°C,
3330Pa). When analyzed, total acetylatables
0.59 meq/g, total amines 0.57 meq/g, and primary amines 0.56 meq/g. Example 13 The catalyst was 54.0 g of anhydrous Raney nickel-molybdenum [Grace 3000], and the triol
Except that 514.7g and 63.8g of ammonia were used.
Essentially the method of Example 12 was followed. The maximum pressure is
It was 15.27MPa. Analysis of the filter-stripped effluent reveals total acetylatables.
0.60 meq/g, total amines 0.56 meq/g, and primary amines 0.55 meq/g. Example 14 (comparative) The procedure of Example 12 was essentially followed, except that the catalyst was water-wet Raney molybdenum. Analysis of the product reveals total acetylatables
0.59 meq/g, total amines 0.07 meq/g, and primary amines 0.60 meq/g.

Claims (1)

[Claims] 1. In the presence of a Raney-nickel catalyst, under anhydrous conditions,
A process for producing a polyoxyalkylene polyamine by reductively aminating a hydroxy-terminated polyoxyalkylene compound having an average molecular weight of at least 230 with ammonia, wherein the catalyst contains molybdenum based on the total weight of the catalyst.
A method characterized in that the molybdenum-reinforced Raney nickel or Raney nickel/aluminum contains 0.2 to 5% by weight. 2. The method according to claim 1, wherein the reductive amination is carried out in the presence of added hydrogen. 3 The catalyst has a weight of 0.2 based on the total weight of the catalyst.
3. A method according to claim 1 or 2, comprising ~5% by weight of molybdenum, a trace amount of ~40% by weight of aluminum, and the remainder nickel. 4 The catalyst has a particle size of 1 to 10 mm in the longest dimension, 25
4. A method according to claim 1, comprising a mass having a surface area of less than or equal to ^m2 /g and a porosity of from 0.01 to 0.03 ^cm3 /g.