GB2175910A - Process for the catalytic preparation of polyoxyalkylene polyamines - Google Patents
Process for the catalytic preparation of polyoxyalkylene polyamines Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
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- C08G65/3255—Ammonia
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Abstract
Reductive amination of hydroxy-terminated polyoxyalkylene compounds, by reaction with ammonia and optionally hydrogen, takes place under anhydrous conditions in the presence of molybdenum-promoted Raney nickel or Raney nickel/aluminium catalysts containing 0.2 to 5.0 wt % of molybdenum, based on nickel. The employment of molybdenum as promoter leads to higher yields and selectivities compared with unpromoted Raney nickel or Raney nickel/aluminium, or compared with catalysts promoted by other metals. Typical catalysts can comprise 0.2 to 5.0 wt % of molybdenum, and from trace amounts up to 40 wt % of aluminium, the balance being nickel.
Description
SPECIFICATION
Process for the catalytic preparation of polyoxyalkylene polyamines
This invention relates to an improved method for the manufacture of high molecular weight polyoxyalkylene amines. More particularly, this invention relates to a method wherein a high molecular weight hydroxy-terminated polyoxyalkylene compound is reductively aminated in the presence of ammonia, and in the optional presence of hydrogen, using a molybdenum-promoted
Raney nickel catalyst, whereby to provide polyoxyalkylene amines in good yield and selectivity.
It has been unexpectedly discovered, in accordance with the present invention, that Raney nickel promoted with molybdenum such that the final Raney nickel catalyst contains from 0.2 to 5 wt. % of molybdenum and, more preferably, from 0.5 to 1.5 wt. % of molybdenum, provides unexpected results when used to catalyze the reductive amination of hydroxy-terminated polyoxyalkylene compounds having a molecular weight of at least 230, such as a molecular weight of 230 to 10,000 (more preferably 230 to 6000); providing a significant improvement in yield and selectivity, as compared with the yields and selectivities normally obtained when reductively aminating hydroxy-terminated polyoxyalkylene compounds in the presence of unpromoted Raney nickel catalysts, or Raney nickel promoted with other metals such as chromium or iron.
The reductive amination process of the present invention can be conducted batchwise, using powdered molybdenum-promoted Raney nickel, or can be conducted on a continuous basis, using a fixed bed of nuggets of the molybdenum-promoted Raney nickel catalyst, for example, nuggets having a particle size of 1 to 10 mm in the longest dimension, a surface area of not more than 25 m2/g and a porosity of 0.01 to 0.03 cm3/g. In accordance with a preferred form of the present invention, a hydroxy-terminated polyoxyalkylene compound, such as a diol or triol having a molecular weight of 500 to 10,000, is continuously passed through a bed of molybdenum-promoted Raney catalyst nuggets, as described above, under anhydrous conditions in the presence of ammonia, and in the optional presence of hydrogen, to provide the corresponding polyoxyalkylene polyamines in good yield and selectivity.
US-A-3236895 discloses a process for producing polyoxyalkylene polyamines, such as polyoxyalkylene diamines, by reacting a polyoxyalkylene diol with ammonia in the presence of hydrogen. Examples 8 to 14 of that patent are specifically directed to the reaction of a polypropylene glycol with ammonia in the presence of added hydrogen and a conventional Raney nickel catalyst. The yield of desired product is from 40 to 70%.
US-A-3215742 also discloses the preparation of alkylene diamines, and more particularly, the preparation of hexamethylene diamine from 1,6-hexanediol, by reacting the diol with ammonia in the presence of Raney nickel.
US-A-3347926 discloses an ammonolysis process for preparing aliphatic amines, employing hydroxy-containing feedstocks with an aminating agent in the presence of a Raney nickel catalyst containing a minor amount of chromium.
US-A-3654370 is directed to a process for the preparation of polyoxyalkylene polyamines wherein a polyoxyalkylene polyol is reacted with ammonia in the presence of hydrogen and a catalyst prepared by the reduction of a mixture of the oxides of nickel, copper and chromium.
EP-A-0022532 discloses the use of pelleted Raney nickel in a continuous process for the reductive amination bf a low molecular weight compound, such as neopentyl alcohol, to provide the corresponding neopentyl amine. The normally to be expected low yields and selectivities are reported.
EP-A-0081701 discloses the use of conventional Raney nickel in the amination of a 6000 molecular weight polyether triol. Conversion to amino groups is only 80%.
This invention is directed to an improved method for the manufacture of high molecular weight polyoxyalkylene polyamines by the reductive amination of a high molecular weight hydroxyterminated polyoxyalkylene compound with ammonia, in the optional presence of hydrogen, using a Raney nickel catalyst under anhydrous conditions, the catalyst being a molybdenum-promoted
Raney nickel or Raney nickel/aluminium catalyst containing 0.2 to 5 wt. % of molybdenum, based on nickel content.
Catalyst Composition
In general, a promoted Raney nickel catalyst is obtained by first preparing an alloy of nickel, aluminium and the desired percentage of the metal promoter. The alloy is then treated with a base, such as sodium hydroxide, in order to leach substantially all of the aluminium from the alloy, whereby the desired promoted Raney nickel catalyst is provided. Conventionally, the promoted Raney nickel catalyst will contain less than 10 wt. % of aluminium, normally from 1.5 to 7.5 wt. % of aluminium.
In accordance with the present invention, a conventional molybdenum-promoted Raney nickel catalyst may be used, i.e., a catalyst prepared as described above, and containing less than 10 wt. % of aluminium.
Alternatively, there may be used a Raney nickel/aluminium catalyst of the type disclosed in copending application (D. 80,394) which has been modified by the inclusion in the starting alloy of the desired amount of molybdenum. Thus, Raney nickel/molybdenum/aluminium catalysts can be prepared by treating a nickel/molybdenum/aluminium alloy with a base, such as sodium hydroxide, so as only partially to leach the aluminium from the alloy, such that the final product contains up to 40 wt % of aluminium, preferably in nugget form.
Thus, the catalysts to be used in accordance with the present invention may, for instance, contain from 0.2 to 5 wt % of molybdenum, and from 0 (i.e. trace amounts) to 40 wt % of aluminium, with the balance of the composition being nickel. More preferably, the Raney nickel catalysts to be used in accordance with the present invention will contain from 0.5 to 1.5 wt % of molybdenum, and from 1 to 35 wt % of aluminium, the balance being nickel.
Both Raney nickel and "Raney nickel/aluminium" are proprietary products manufactured by
W.R. Grace & Co., as are the corresponding promoted Raney nickel and promoted Raney
Nickel/aluminium catalysts. They are prepared by leaching aluminium from an aluminium/nickel alloy, with an aqueous base, such as caustic soda, in the manner described above.
The molybdenum-promoted Raney nickel and Raney nickel/aluminium catalysts may be used in powdered form when the process of the present invention is conducted batchwise. The molybdenum-promoted catalysts are preferably used in the form of a fixed bed for continuous operations, such as a fixed bed of pelleted catalyst or a fixed bed containing "nuggets" of molybdenum-promoted Raney nickel or Raney nickel/aluminium (i.e., unpowdered chunks or lumps of molybdenum-promoted Raney nickel or Raney nickel/aluminium having a particle size of 1 to 20 mm, such that the nuggets are at least 1 mm in length in their longest dimension, and preferably 1 to 10 mm in their longest dimension).The surface area of powdered Raney nickel is normally from 80 to 100 m2/g, whereas the surface area of the molybdenum-promoted Raney nickel and
Raney nickel/aluminium "nuggets" will normally be not more than 25 m2/g. The molybdenumpromoted Raney nickel and Raney nickel/aluminium nuggets also have a comparatively low porosity of 0.01 to 0.03 cm3/g.
The Polyoxyalkylene Polyol Feeds to ck The polyoxyalkylene polyol feedstocks to be used in accordance with the present invention are hydroxy-terminated polyoxyalkylene compounds prepared by the reaction of an epoxide such as ethylene oxide, propylene oxide, or butylene oxide, with an initiator to form a hydroxy-terminated alkoxylation product. Preferred feedstocks include hydroxy-terminated polyoxyalkylene and poly(oxyethylene-oxypropylene) compounds, such as diols and triols, but, the functionality of the feedstock is not critical to the practice of the present invention. Thus, compounds as diverse as monoalkyl ethers of polyoxypropylene glycols, tetrols, hexols, etc. may be used.It is important, however, that the feedstock have an average molecular weight of at least 230, such as an average molecular weight of from 230 to 10,000, and, more preferably, an average molecular weight of 500 to 8,000.
The monoalkyl glycol ethers that may be used as feedstocks in accordance with one embodiment of the present invention may be generally characterized by the formula: (I) R'-(OCH2CHR2)pOH wherein
R' is C1 to C12 alkyl
R2 is Hydrogen, methyl, ethyl, propyl and/or butyl, and
is 4 to 100, and sufficient to provide a molecular weight of at least 230.
The diol feedstocks to be used in accordance with another embodiment of the present invention may be generally characterized by the formula:
wherein
R3 is hydrogen, methyl, ethyl or butyl and 9 is 3 to 170, and sufficient to provide a molecular weight of at least 230.
Examples of feedstocks of this nature include polyoxypropylene diols, such as polyoxypropylene diols having the formula:
wherein is from 3 to 100, and sufficient to provide a molecular weight of at least 230, r can be 6 to 100, for example.
Examples of feedstocks having the formula(ll) include polyoxypropylene diols having an average molecular weight of 230 or more, wherein g has a value of 6 to 7, polyoxypropylene diols having an average molecular weight of 2000 wherein g has an average value of about 33, and polyoxypropylene diols having an average molecular weight of about 4000 wherein g has an average value of about 60.
In another embodiment, the polyoxyalkylene diol may have the formula:
wherein
b is 8 to 100
and a+c is 2 to 3.
Examples of feedstocks having formula IV include:
Approximate Approximate Value
Mol. Wt. b a+c 600 8.5 2.5
900 15.5 2.5
2000 40 2.5
4000 86 2.5
Another class of preferred feedstocks comprises polyoxyalkylene triols, such as those having the formula:
wherein R4 is hydrogen or methyl, n is O or 1, and wherein the sum of x+y+z is 5 to 100.
For instance, n can be 0 when R4 is hydrogen and 1 when R4 is methyl. Specific examples of compounds having formula V are:
Approximate
Mol. Wt. R4 n x+y+z
500 -CH3 1 7
5000 H 0 85
Another class of feedstocks that may be used in accordance with the present invention are tetrols, pentols, hexols, and heptols having the following formula:
wherein n is 1 to 5, and the sum of x+y+z is 7 to 170.
Preparation of Polyoxyalkylene Polyamines
As indicated, the polyoxyalkylene polyamine products of the present invention are prepared by reacting the polyoxyalkylene polyol feedstock under reductive amination conditions with ammonia in the optional presence of hydrogen using the molybdenum-promoted Raney nickel or Raney nickel/aluminium catalyst.
The general expectation is that reaction rates would become slower as the molecular weight of the feed increases. Contrary to this expectation, it has been discovered that, with the process of the present invention, the reaction rates are unexpectedly faster for the higher molecular weight hydroxy-terminated polyoxyalkylene feedstocks.
The reductive amination conditions to be utilized will suitably include the use of from 4 to 150 moles of ammonia per hydroxyl equivalent of feedstock. It has been discovered, in accordance with the present invention, that hydrogen is not an essential coreactant, but it is preferably used in an amount from 0.5 to 10 mole equivalents of hydrogen per hydroxyl equivalent of feedstock.
Reaction conditions to be used may suitably include a temperature of 160 to 250"C. and, more preferably, from 185 to 230"C.
The pressure may suitably be from 3.5 to 25 MPa and, more preferably from 7 to 17.5 MPa.
Contact times, when the reaction is conducted on a batch basis, may suitably be from 0.1 to 6 hours and, more particularly, from 0.15 to 2 hours.
When the reaction is conducted on a continuous basis using catalyst pellets or nuggets, reaction time may suitably be from 0.1 to 2.0 grams of feedstock per hour per cubic centimeter of catalyst and more preferably, from 0.3 to 1.6 grams of feedstock per hour per cubic centimeter of catalyst.
The invention will be further illustrated by the following specific Examples in which all percentages are by weight, unless otherwise indicated.
Example 1
A molybdenum-promoted (2% Mo) commercial Raney Ni Catalyst (Grace 3000) was made anhydrous by repeated washing of the wet catalyst with t-butylamine. A one litre stirred autoclave was charged with 404.49 of a 5000 molecular weight polyoxypropylene triol, 50.09 of the anhydrous catalyst, and 104.99 of ammonia. Hydrogen pressure was applied sufficient to achieve 3.20 MPa at room temperature. The autoclave was heated rapidly to 245"C and temperature was maintained at 243-2490C (avg. 246"C) for 25 minutes. Pressure was 21.47-21.64 MPa. The autoclave was rapidly cooled to room temperature. A portion of the contents was filtered and stripped (rotary evaporator, 98"C 3330 Pa).Analysis indicated 0.59 meq/g total acetylatables, 0.60 meq/g total amines, and 0.59 meq/g primary amines. (Analyses accurate to +0.01 meq/g).
Example 2
Runs were conducted in accordance with the procedure of Example 1. Conditions and results are recorded in Table I. The following points can be noted:
a. At a given temperature, there is a dependence of conversion on catalyst concentration (see
Samples 17, 18, and 19, and 15; also compare Sample 13 with 14 and 12).
b. Under a given set of conditions, the catalyst with 1% Mo is more active than the catalyst with 2% Mo (compare Samples 3 and 8 with Sample 9 and 12).
Example 3 {Continuous)
A tubular reactor containing approximately 95 cm3 of molybdenum-promoted Raney nickel granules (2% Mo) of approximately 6.5 mm diameter, was simultaneously fed with polypropylene glycol of 2000 molecular weight at 50.859 hr-' ammonia at 53.57 g hr--1, and hydrogen at 8 litres/hr. The reactor was maintained at 200"C and 13.89 MPa total pressure. A sample of effluent, when stripped at 98"C/3330 Pa on a rotary evaporator, was analyzed as follows: 1.01 meq/g total acetylatables, 0.65 meq/g total amines, and 0.64 meq/g primary amines.
The reactor was operated in essentially the same manner, but at temperatures of 210, 220, and 224"C. Actual conditions and product analyses are shown in Table Il.
Example 4
The essential procedure of Example 3 was followed, except that the reactor contained approximately 100 cm3 of 8X12 mesh molybdenum-promoted Raney Nickel (1% Mo) catalyst granules.
Conditions and results are shown in Table Ill.
Example 5.
Comparative Example with Promoted Raney Nickel
The essential procedure of Example 4 was followed, except the catalyst was 8 X 12 mesh unpromoted Raney nickel granules. Conditions and results are shown in Table IV.
It can be noted by comparing results in Table III with those in Table IV that the 1% Mopromoted Raney nickel gives somewhat better results, particularly at the highest PPG-2000 space velocities.
Example 6 Comparative Example of Batch Run with Cr-Promoted Raney Nickel
The essential procedure delineated by Sample 2 of Table I was repeated with the following exceptions: only 336.89 of the 5000 molecular weight polyoxypropylene triol were used, 108.99 of NH2 (24.4% NH3) were charged, and 50.19 of Grace 2400 (2% Cr, 2% Fe-promoted Raney nickel) were used. Analysis of the stripped and filtered product indicated 0.59 meq/g total acetylatables, 0.34 meq/g total amines, and 0.33 meq/g primary amines. This result is much poorer than in those runs employing Mo-promoted Raney nickel (cf Table I).
Example 7 Comparative Example of Batch Run with Unpromoted Raney Nickel
The essential procedure of Example 6 was followed with the following exceptions: 414.69 of the 5000 molecular weight polyoxypropylene triol, 72.89 of NH3, and 49.989 of Grace 2800 (unpromoted Raney nickel) were used. Analysis of the product indicated 0.60 meq/g total acetylatables, 0.55 meq/g total amine, and 0.54 meq/g primary amine. Comparison with results in Table I indicates that the unpromoted catalyst is less active than the Mo-promoted catalysts.
TABLE 1A
Avg. Reactor Catalyst Total
Sample Temp Pressure Charged Wt.% Acetyl
No. "C MPa Grams Ammonia Meq/g % Conv
1 246 21.64 50 20.60 .59 101.70
2 248 15.27 54 11.18 .60 93.33
3 244 13.71 60 7.85 .60 83.33
4 258 13.89 60 7.61 .60 81.67
5 258 14.23 60 7.70 .59 81.36
6 260 16.09 80 7.61 .60 81.67
7 208 29.75 80 5.77 .59 27.12
8 247 12.16 60 6.81 .58 82.76
9 244 14.23 61 7.60 .60 95.00
10 248 12.37 60 7.55 .58 81.03
11 250 14.51 60 7.80 .60 96.67
12 244 13.54 58 7.65 .60 95.00
13 245 13.02 30 7.61 .61 85.25
14 245 12.51 15 7.46 .57 54.39
15 220 10.92 50 7.23 .65 77.78
16 220 11.47 25 7.39 .58 77.59
17 221 12.51 25 7.29 .59 55.93
18 220 12.16 13 7.10 .60 33.33
19 220 11.75 100 7.35 .60 90.00
TABLE I-B Spread between Triol G- Reaction Raney
Sample Prim Prim & 5000 Chgd Time Catalyst No.l Amine Tot Am Grams Hours Identity
1 100.00 0.01 404.4 0.42 3000
2 91.67 0.01 514.7 0.42 3000
3 81.67 0.01 691.77 0.43 3000
4 80.00 0.01 694.08 0.20 3000
5 79.66 0.01 696.15 0.20 3000
6 80.00 0.01 693.88 0.20 3000
7 25.42 0.01 796.87 0.05 3000
8 81.03 0.01 697.47 0.42 3000
9 93.33 0.01 695.32 0.42 3200
10 79.31 0.01 700.75 0.20 3200
11 95.00 0.01 710.48 0.25 3200
12 93.33 0.01 695.90 0.20 3100
13 83.61 0.01 695.75 0.20 3100
14 52.63 0.01 697.29 0.20 3100
15 76.19 0.01 695.85 0.333 3100
16 75.86 0.01 696.76 0.42 3100
17 54.24 0.01 695.80 0.333 3100
18 31.67 0.01 696.22 0.333 3100
19 88.33 0.01 695.22 0.333 3100
Raney 3200 and Raney 3100 contain 1% Mo;Raney 3000 contains 2% Mo TABLE II
Polyol Total H2/polyol Total %
Sample Temp Pressure wt sv Wt% wt sv ratio Mol H2/ Mol NH3/ Acetyl % Prim
No. C MPa g/cc/hr Ammonia g/cc/hr (m /Kg) Eq -OH Eq -OH Meg/g Conv. Amine 20 200 13.89 0.53 51.30 1.11 0.155 7.00 61.90 1.01 64.40 63.40 21 210 13.89 0.53 51.70 1.12 0.155 7.00 62.90 1.02 80.40 79.40 22 220 13.89 0.53 51.30 1.11 0.155 7.00 61.90 1.02 88.20 87.30 23 224 13.89 0.52 50.50 1.05 0.161 7.30 59.80 1.02 91.20 90.20 24 210 13.54 0.53 50.20 1.07 0.081 3.50 59.20 1.01 86.10 85.10 25 210 13.89 0.54 49.60 1.09 0.230 10.40 57.70 .99 73.70 72.70 26 210 13.89 0.53 48.90 1.05 0.118 5.30 56.10 1.01 80.20 79.20 TABLE III
Hot Spot Reactor Polyol H2/polyol Total %
Sample Temp Pressure Wt. % wt sv ratio Acetyl % Prim Mol H2/ Mol NH3
No. C MPa Ammonia g/cc/hr (m /Kg) Meq/g Conv.Amine Eq -OH Eq -OH 27 200 13.89 50.63 1.01 0.059 .99 92.93 91.92 2.65 60.23 28 210 13.89 51.02 .97 0.061 1.00 96.00 85.00 2.76 61.16 29 220 13.89 49.84 1.03 0.058 .99 97.98 95.96 2.60 58.34 30 230 13.89 48.30 1.07 0.056 .98 96,54 94.90 2.51 54.87 31 210 13.20 50.17 1.48 0.047 1.01 95.05 93.07 2.12 59.12 32 220 13.20 49.66 1.48 0.046 1.00 97.00 96.00 2.10 57.93 33 225 13.54 50.00 1.44 0.048 1.02 94.12 92.16 2.17 58.72 TABLE IV (comparison)
Hot Spot Reactor Polyol H2/polyol Total %
Sample Temp Pressure Wt. % wt sv ratio Acetyl % Prim Mol H2/ Mol NH3
No. C MPa Ammonia g/cc/hr (m /Kg Meq/g Conv.Amine Eq -OH Eq -OH 34 210 13.54 48.65 1.03 0.058 1.01 96.04 95.05 2.58 55.64 35 220 13.89 49.90 .96 0.062 1.02 96.08 95.10 2.79 58.48 36 225 13.89 49.63 .99 0.061 1.00 96.00 94.00 2.72 57.85 37 220 13.71 50.09 .99 0.060 .98 97.96 95.92 2.70 58.94 38 210 13.54 51.56 1.36 0.051 1.01 93.07 91.09 2.29 62.51 39 220 13.54 50.68 1.45 0.048 1.00 96.00 95.00 2.18 60.34 40 227 13.54 50.25 1.46 0.048 1.01 94.06 93.07 2.14 59.30
The reactor volume was constant at 100 cm Example 8 (Comparison)
Amination of Triol over Supported Ni/Cu/Cr/Fe
An autoclave was charged with 165.54g of a 5000 molecular weight polyoxypropylene triol and 65.099 of finely ground Calsicat Ni/Cu/Cr/Fe supported on kieselguhr.It was flushed with hydrogen, pressurised to 1.48 MPa with H2, and to 10.09 MPa with nitrogen at 27"C. It was heated to 235"C over 46 minutes and repressurised from 15.96 to 20.78 MPa. It was held at 234-250"C (average 240"C) for 1.8 hours. The pressure dropped to 20.09 MPa during the first 0.8 hours. It was repressurised to 20.78 MPa; thereafter pressure steadily rose to 21.82 MPa.
The autoclave was cooled, and the gas was sampled while venting; it contained traces of isopropylamine, ethylamine and methylamine, and 22.9% of methane.
Analysis of a filtered stripped sample of the autoclave contents indicated 0.19 meq/g total acetylatables and t0.01 meq/g each of total and primary amines.
Example 9. -A mination of Triol over Mo-Promoted Raney Nickel
The procedure of Example 8 was essentially followed except that 167.299 of the 5000 molecular weight polyoxypropylene triol and 49.96 of anhydrous Raney 3000 were used. Initial pressures were 1.82 MPa and to 10.44 psig of hydrogen and nitrogen respectively. Heating to 283"C was accomplished over 53 minutes. It was cooled within two minutes to 2420C and pressurised with H2 from 19.06 to 20.78 MPa. It was maintained at 240 C and 20.78 MPa of
H2 supplied for 2 hours. Pressure rose to 21.82 MPa.
When cool, analysis of filtered and stripped crave contents indicated 0.20 meq/g total acetylatables, 0.06 meq/g total amines, and 0.03 meq/g primary amines.
Example 10 (Comparison)
The reactor containing chromium-promoted Raney Ni granules of approximately 6.5 mm diameter was run in accord with conditions listed in Table V. The results shown indicate that this catalyst also is effective for amination of a 2000 mol. wt. polypropylene glycol.
Example 11.
The reactor containing molybdenum-promoted Raney nickel granules of approximately 6.5 mm in diameter was run in accord with conditions listed in Table VI. The results indicate this catalyst is effective for PPG-2000 amination. After use, it contained an estimated 3-5% of fine particles. TABLE V (Comparision)
Polyol Total H2/polyol Total %
Sample Temp. wt sv Wt% wt sv ratio Mol H2/ Mol NH3/ Acetyl % Prim
No. C g/cc/hr Ammonia g/cc/hr (m /Kg) Eq -OH Eq -OH Meq/g Conv.Amine 41 200 .64 50.40 1.30 0.124 5.60 59.60 1.01 62.40 61.40 42 210 .62 51.30 1.27 0.130 5.80 61.70 1.01 77.20 76.20 43 220 .62 50.70 1.26 0.130 5.80 60.40 1.01 88.10 87.10 44 225 .66 50.00 1.32 0.118 5.40 58.70 1.01 91.10 90.10 45 210 .64 50.00 1.27 0.062 2.80 58.70 1.03 82.50 81.60 46 210 .65 50.50 1.33 0.180 8.20 59.90 1.02 70.60 69.60
Pressure was 13.89 MPa for all runs TABLE VI
Polyol Total H2/polyol Total %
Sample Temp. wt sv Wt% wt sv ratio Mol H2/ Mol NH3/ Acetyl % Prim
No. C g/cc/hr Ammonia g/cc/hr (m /Kg) Eq -OH Eq -OH Meq/g Conv.Amine 47 200 .53 51.30 1.11 0.155 7.00 61.90 1.01 64.40 63.40 48 210 .53 51.70 1.12 0.155 7.00 62.90 1.02 80.40 79.40 49 220 .53 51.30 1.11 0.155 7.00 61.90 1.02 88.20 87.30 50 224 .52 50.50 1.05 0.161 7.30 59.80 1.02 91.20 90.20 51 210 .53 50.20 1.07 0.080 3.50 59.20 1.01 86.10 85.10 52 210 .54 49.60 1.09 0.230 10.40 57.70 .99 73.70 72.70 53 210 .53 48.90 1.05 0.118 5.30 56.10 1.01 80.20 79.20
Pressure was 13.89 MPa for all runs except sample 51, for which it was 13.54 MPa.
Example 12. (Comparison)
Commercial Raney Ni catalyst (Grace 2800 unpromoted Raney nickel containing less than 10 wt.% of aluminium) was made anhydrous by repeated washing of the wet catalyst with tbutylamine. A one litre stirred autoclave was charged with 417.799 of the 5000 mol. wt. triol, 50.1 6g of the anhydrous catalyst, and 88.49 of NH3. The autoclave was flushed with hydrogen and hydrogen pressure applied at room temperature sufficient to achieve 3.20 MPa. The autoclave was heated rapidly to 245"C and temperature was maintained at 242-250"C (average 248"C) for 26 minutes. Pressure was 18.64-18.71 MPa. The autoclave was cooled rapidly to room temperature. A portion of contents was filtered and stripped (rotary evaporator, 98"C, 3330 Pa). Analysis indicated 0.59 meq/g total acetylatables, 0.57 meq/g total amines, and 0.56 meq/g primary amines.
Example 13.
The essential procedure of Example 12 was followed, except the catalyst was 54.09 of anhydrous Raney Ni-Mo (Grace 3000), and 514.79 of the triol and 63.89 of ammonia were used. Maximum pressure was 15.27 MPa. Analysis of a portion of filtered and stripped effluent indicated 0.60 meq/g total acetylatables, 0.56 meq/g total amines, and 0.55 meq/g primary amines.
Example 14. (ComparisonJ
The procedure of Example 12 was essentially repeated, except the catalyst was Raney Ni-Mo wet with water. Analyses of the product indicated 0.59 meq/g total acetylatables, 0.07 meq/g total amines, and 0.06 meq/g primary amines.
Claims (11)
1. A method for the production of polyoxyalkylene polyamines by the reductive amination of a hydroxy-terminated polyoxyalkylene compound having a molecular weight of at least 230 with ammonia under an hydros conditions in the presence of a Raney nickel catalyst, characterized in that the catalyst is molybdenum-promoted Raney nickel or Raney nickel/aluminium containing 0.2 to 5 wt % of molybdenum, based on nickel content.
2. A method according to claim 1 characterized in that the reductive amination is conducted in the presence of added hydrogen.
3. A method according to Claim 1 or 2, characterized in that the catalyst comprises 0.2 to 5 wt % of molybdenum, and from a trace amount to 40 wt % of aluminium, the balance being nickel.
4. A method according to any preceding claim characterized in that the catalyst comprises nuggets having a particle size of 1 to 10 mm in longest dimension, a surface area of not more than 25 m2/g, and a porosity of 0.01 to 0.03 cm3/g.
5. A method according to any preceding claim characterized in that reductive amination is carried out at a temperature of 160 to 250"C. and a pressure of 3.5 to 25 mPa.
6. A method according to any of claims 1 to 5 characterized in that the polyoxyalkylene has the formula: (I) R'-(OCH2CHR2)pOH wherein
R' is C1 to C2 alkyl
R2 is hydrogen, methyl, ethyl, propyl and/or butyl, and
is 4 to 100, and sufficient to provide a molecular weight of at least 230.
7. A method according to any of claims 1 to 5 characterized in that the polyoxyalkylene compound has the formula:
wherein
R3 is hydrogen, methyl, ethyl or butyl and 9 is 3 to 170, and sufficient to provide a molecular weight of at least 230.
8. A method according to any of claims 1 to 5 characterized in that the polyoxyalkylene compound has the formula:
wherein
r is 6 to 100.
9. A method according to any of claims 1 to 5 characterized in that the polyoxyalkylene compound has the formula:
wherein
b is 8 to 100, and a+c is 2 to 3.
10. A method according to any of claims 1 to 5 characterized in that the polyoxyalkylene compound has the formula:
wherein
R4 is hydrogen or methyl, n is O to 1, and wherein the sum of x+y+z is 5 to 100.
11. A method according to any of claims 1 to 5 characterized in that the polyoxyalkylene compound has the formula:
wherein
n is 1 to 5 and
the sum of x+y+Z is 7 to 170.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73959585A | 1985-05-31 | 1985-05-31 |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8608710D0 GB8608710D0 (en) | 1986-05-14 |
GB2175910A true GB2175910A (en) | 1986-12-10 |
GB2175910B GB2175910B (en) | 1989-06-28 |
Family
ID=24973003
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8608710A Expired GB2175910B (en) | 1985-05-31 | 1986-04-10 | Process for the catalytic preparation of polyoxyalkylene polyamines |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPS61278528A (en) |
DE (1) | DE3608716A1 (en) |
GB (1) | GB2175910B (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0273545A1 (en) * | 1987-01-02 | 1988-07-06 | Texaco Development Corporation | Novel reaction product and ORI-inhibited motor fuel composition |
EP0356047A2 (en) * | 1988-08-18 | 1990-02-28 | BP Chemicals Limited | Primary or secondary amine terminated polyethers |
US5015773A (en) * | 1988-08-18 | 1991-05-14 | Bp Chemicals Limited | Reductive amination of hydroxy-containing compounds |
EP0433777A2 (en) * | 1989-12-19 | 1991-06-26 | Bayer Ag | Process for preparing amino polyalkylene oxides |
EP0496145A1 (en) * | 1989-10-02 | 1992-07-29 | Texaco Chemical Company | Polyoxyalkylene polyamines having internal tertiary nitrogen atoms |
EP0647472A1 (en) * | 1993-10-07 | 1995-04-12 | Rhone-Poulenc Chimie | Composition of matter as Raney catalyst for hydrogenating halonitroaromatic compound and process using the same |
WO2000044812A2 (en) * | 1999-01-26 | 2000-08-03 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Amino-functionalised polyoxyalkanes |
US7161038B2 (en) | 2003-07-30 | 2007-01-09 | Kao Corporation | Process for producing polyoxyalkylene triamine |
US7696385B2 (en) | 2005-06-28 | 2010-04-13 | Clariant Produkte (Deutschland) Gmbh | Polyetheramine production method |
US8071814B2 (en) | 2006-12-06 | 2011-12-06 | Clariant Finance (Bvi) Limited | Process for preparing polyetheramines |
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CN102389802A (en) * | 2011-09-20 | 2012-03-28 | 中国石油化工集团公司 | Amine-terminated polyether synthetic catalyst and preparation method thereof |
CN102408559A (en) * | 2011-07-07 | 2012-04-11 | 中国石油化工集团公司 | Preparation process of amine terminated polyether |
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JP2756000B2 (en) * | 1989-08-25 | 1998-05-25 | 花王株式会社 | Tertiary amino alcohol and method for producing the same |
CN108003041A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of method for separating Aethoxy Sklerol and polyetheramine |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3847992A (en) * | 1973-03-12 | 1974-11-12 | Jefferson Chem Co Inc | Partially aminated polyoxyalkylene polyols |
-
1986
- 1986-03-15 DE DE19863608716 patent/DE3608716A1/en not_active Withdrawn
- 1986-04-10 GB GB8608710A patent/GB2175910B/en not_active Expired
- 1986-05-15 JP JP10971686A patent/JPS61278528A/en active Granted
Cited By (29)
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EP0273545A1 (en) * | 1987-01-02 | 1988-07-06 | Texaco Development Corporation | Novel reaction product and ORI-inhibited motor fuel composition |
US4810261A (en) * | 1987-01-02 | 1989-03-07 | Texaco Inc. | Reaction product additive and ori-inhibited motor fuel composition |
EP0356047A2 (en) * | 1988-08-18 | 1990-02-28 | BP Chemicals Limited | Primary or secondary amine terminated polyethers |
EP0356047A3 (en) * | 1988-08-18 | 1990-10-03 | BP Chemicals Limited | Primary or secondary amine terminated polyethers |
US5015773A (en) * | 1988-08-18 | 1991-05-14 | Bp Chemicals Limited | Reductive amination of hydroxy-containing compounds |
EP0496145A1 (en) * | 1989-10-02 | 1992-07-29 | Texaco Chemical Company | Polyoxyalkylene polyamines having internal tertiary nitrogen atoms |
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EP0433777A2 (en) * | 1989-12-19 | 1991-06-26 | Bayer Ag | Process for preparing amino polyalkylene oxides |
EP0647472A1 (en) * | 1993-10-07 | 1995-04-12 | Rhone-Poulenc Chimie | Composition of matter as Raney catalyst for hydrogenating halonitroaromatic compound and process using the same |
FR2710856A1 (en) * | 1993-10-07 | 1995-04-14 | Rhone Poulenc Chimie | Material composition useful as a Raney type catalyst, for the hydrogenation of halonitroaromatic to haloaminoaromatic and process by applying. |
US5554573A (en) * | 1993-10-07 | 1996-09-10 | Rhone-Poulenc Chimie | Raney-type catalysts for the hydrogenation of halonitroaromatic compounds |
US5689021A (en) * | 1993-10-07 | 1997-11-18 | Rhone-Poulenc Chimie | Raney-type catalysts for the hydrogenation of halonitroaromatic compounds |
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US8071814B2 (en) | 2006-12-06 | 2011-12-06 | Clariant Finance (Bvi) Limited | Process for preparing polyetheramines |
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CN102408559A (en) * | 2011-07-07 | 2012-04-11 | 中国石油化工集团公司 | Preparation process of amine terminated polyether |
CN102389802B (en) * | 2011-09-20 | 2013-08-28 | 中国石油化工集团公司 | Amine-terminated polyether synthetic catalyst and preparation method thereof |
CN102389802A (en) * | 2011-09-20 | 2012-03-28 | 中国石油化工集团公司 | Amine-terminated polyether synthetic catalyst and preparation method thereof |
CN102964586A (en) * | 2012-12-06 | 2013-03-13 | 盘锦科隆精细化工股份有限公司 | Preparation method of catalyst used for polyether amine |
CN104099069A (en) * | 2013-04-12 | 2014-10-15 | 中国石油化工股份有限公司 | Anti-temperature clay anti-swelling agent and preparation method thereof |
CN104099069B (en) * | 2013-04-12 | 2017-02-08 | 中国石油化工股份有限公司 | Anti-temperature clay anti-swelling agent and preparation method thereof |
WO2019102087A1 (en) | 2017-11-21 | 2019-05-31 | Arkema France | Rheology additives based on di- or tri-amides and mixtures thereof |
CN107964094A (en) * | 2017-11-28 | 2018-04-27 | 中国科学院长春应用化学研究所 | A kind of catalyst, its preparation method and application for being used to synthesize end primary amino radical polyethers |
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Also Published As
Publication number | Publication date |
---|---|
GB2175910B (en) | 1989-06-28 |
GB8608710D0 (en) | 1986-05-14 |
DE3608716A1 (en) | 1986-12-04 |
JPS61278528A (en) | 1986-12-09 |
JPH0140049B2 (en) | 1989-08-24 |
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Legal Events
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PE20 | Patent expired after termination of 20 years |
Effective date: 20060409 |