DE3608716A1 - METHOD FOR PRODUCING POLYOXYALKYLENE POLYAMINES - Google Patents

Description

Müller, Schupfner & Gauger Texaco Development Corp. Patent Attorneys T-004 86 DE S / H

D 80,45A-F (KRP)

Process for the preparation of polyoxyalkylene polyamines

description

The present invention relates to a process for the preparation of polyoxyalkylene polyamines by reaction an OH-terminated polyoxyalkylene compound that has a molecular weight of at least about 230, reductive with ammonia in the presence of a Raney nickel catalyst under anhydrous conditions Amination, if appropriate in the presence of hydrogen.

U.S. Patent 3,236,895 discloses a process for the preparation of polyoxyalkylene polyamines such as polyoxyalkylene diamines by reacting a polyoxyalkylene diol with ammonia in the presence of hydrogen. the Examples 8-14 of this patent are specific on the reaction of a polyoxypropylene glycol with ammonia in the presence of supplied hydrogen and a conventional one Raney nickel catalyst directed. The product yield ranges from about 40 to 70%.

In U.S. Patent 3,215,742 there is a method of manufacture

of alkylenediamines, and in particular the Her-30

provision of hexamethylenediamine from 1,6-hexanediol Reaction of the diol with ammonia in the presence of Raney nickel.

U.S. Patent 3,347,926 discloses an ammonolysis process for preparing aliphatic amines from OH-containing ones Feedstocks with an aminating agent in the presence

of Raney nickel catalyst, which is a smaller amount Contains chrome.

U.S. Patent 3,654,370 discloses a process for the preparation of polyoxyalkylene polyamines, wherein a polyoxyalkylene polyol with ammonia in the presence of hydrogen and a catalyst that is produced by reducing a mixture the oxides of nickel, copper and chromium obtained is converted.

European patent application 0022532 discloses the use of pelletized Raney nickel in a continuous Process of reductive amination of a low molecular weight compound such as Neopentyl alcohol] for the production of the corresponding neopentylamine. It gets there from low yields and Reported selectivities.

European patent application 0081701 discloses the use of conventional Raney nickel in the Amination of a polyether triol with a molecular weight of 6000. The conversion to the amino groups is only 80%.

The present invention is therefore based on the object to provide a process for the reductive amination, the preparation of the polyoxyalkylenepolyamines allowed in high yield and selectivity,

In solving this problem, a method is provided, which is characterized in that a Raney nickel or Raney nickel activated with molybdenum / Aluminum catalyst is used, which is about 0.2 to 5 wt.% Molybdenum, based on the total weight

35 of the catalyst contains.

_? ■ '■ "■■ -36087 Ί According to the invention was in fact surprisingly found that the Raney Mickel catalyst, which is activated with molybdenum in such a manner that the ready-catalyst system contains about 0.2 to 5 wt.% Molybdenum, and in particular about 0.5 to about 1.5 wt.% molybdenum, shows unexpected results when this catalyst is used in the reductive amination of OH-terminated polyoxyalkylene compounds having a molecular weight of about 230 or more, such as, for example, a molecular weight of about 230 to about 10,000 (and in particular from 230 to 6000) is used, which results in a significant improvement in yield and selectivity compared to the yields and selectivities usually obtained when OH-terminated polyoxyalkylene compounds are used in the presence of non-activated Raney nickel catalysts or Raney nickel catalysts, which are active with other metals such as chromium or iron, are aminated were ized.

The inventive method for reductive amination can be carried out in batches using molybdenum activated Raney nickel in powder form or continuously using a fixed bed of granules (nuggets) of the with Molybdenum activated Raney nickel catalyst carried out be, for example with granules with a particle size of about 1 to 10 mm in the longest prostitute

2 sion, a surface area of no more than about 25 m / g and a porosity of about 0.01 to about 0.03 ml / g.

According to a preferred embodiment of the process according to the invention, an OH-terminal polyoxyalkylene compound is such as a diol or a triol, having a molecular weight of about 5000 to 10,000 continuously through a bed of with molybdenum

35 activated Raney catalyst in granular form, such as

described above, under anhydrous conditions in the presence of ammonia and optionally in the presence of Hydrogen is passed through, the corresponding polyoxyalkyleneamines in good yield and selectivity

5 vity can be preserved.

The catalyst used according to the invention is a Raney nickel catalyst activated with molybdenum.

Such an activated Raney nickel catalyst is obtained by first using a nickel / aluminum alloy with the desired content of molybdenum, based on the nickel content. The alloy is then with a base, such as

15 Sodium Hydroxide Treats to Essentially Everything

Dissolve aluminum from the alloy, thereby obtaining the desired activated Raney nickel catalyst usually contains the activated Raney nickel catalyst less than about 10 wt.% aluminum,

20 in particular about 1.5 to 7> 5% by weight of aluminum.

According to the invention, a known per se, with molybdenum activated Raney nickel catalyst can be used, which was prepared as described above.

2g According to a preferred embodiment, a Raney nickel / aluminum catalyst is used used as disclosed in patent application P 35 45 598, filed on December 21, 1985 with the title "Process for the preparation of polyoxyalkylene polyamines" is which one there-

^ ₀ was modified by that the desired amount of molybdenum was introduced into the starting alloy. In this way, a Raney nickel / molybdenum / aluminum catalyst can be produced by treating a nickel / molybdenum / aluminum alloy with a base, as in the case of

for example sodium hydroxide in such a way that the ob

Aluminum is only partially dissolved out of the alloy, so that the end product contains up to about 40% by weight of aluminum. The catalyst should preferably be in "nugget" form.
5

The catalysts used according to the invention can thus be used as Raney nickel catalysts activated with molybdenum are characterized, which about 0.2 to about 5 wt.% molybdenum, 0 (i.e. traces) to about 40 wt.% Aluminum with the remainder to 100% by weight of the composition containing nickel. Preferably, the inventive Raney nickel catalyst about 0.5 to about 1.5 wt.% Molybdenum, about 1 to about 35 wt.% aluminum with the remainder to 100 wt.% of the catalyst composition, essentially

IQ borrowed nickel, included.

Both Raney nickel and Raney nickel / aluminum are as well as products from W.R. Grace & Co. such as the corresponding activated Raney nickel and activated Raney nickel / aluminum catalysts. You will be on the manner described above by leaching the aluminum from an aluminum / nickel alloy, such as a molybdenum / aluminum / nickel alloy, made with an aqueous base such as sodium hydroxide.

The molybdenum activated Raney nickel and Raney nickel / aluminum catalysts can be used in powder form when the process of the present invention is carried out in batches. Preferably, the _o _ are used with molybdenum promoted catalysts in the form of a fixed bed for the continuous implementation, such as a fixed bed of pelleted catalyst or a fixed bed containing the catalyst in "nugget" shape (ie, pieces or chunks of

_._ catalyst with a particle size of about 1 to 20 mm, if

so that the length of the particles in their longest dimension is at least 1 mm and preferably about 1 to 10 mm).

The surface of the powdered catalyst is in

2
usually about 80 to 100 m / g while the surface area

5 of the catalyst in "nugget" form usually around

Is 25 m / g or less. The Raney-Niekel and Raney nickel / aluminum catalyst activated with molybdenum in particulate form also has a relatively low porosity of about 0.01 to 0.03 ml / g.

The polyoxyalkylene polyol starting materials used to carry out the process according to the invention are OH-terminated polyoxyalkylene compounds made by the reaction of an epoxy, e.g. Ethylene oxide, propylene oxide or butylene oxide with an initiator to form an OH-terminated alkoxylation product. Preferred starting materials include OH-terminated polyoxypropylene and poly (oxyethylene-oxypropylene) compounds, like diols and triplets. The functionality of the starting material is not critical for the use according to the invention. Compounds as different as monoalkyl ethers of polyoxypropylene glycols, -tetrols, -hexols, etc., are used. It is important, however, that the feed is a

average molecular weight of at least about 25

230, such as a molecular weight of about 230 to 10,000, and more preferably a molecular weight from about 500 to 8000.

The monoalkyl glycol ethers, which are used as starting materials are suitable for carrying out the process according to the invention can generally be given by the following formula can be characterized:

R '- [O-CH ~ -Ch | -OH (I) ² I.

1 wherein R ^{1 is} a C, - to C ^ -alkyl group,

R is hydrogen, methyl, ethyl, propyl and / or

Butyl, and

χ mean a positive number with a value from about k to 100,

provided that the minimum molecular weight is about 230.

The diol starting materials which are used to carry out the inventive Process suitable can generally be characterized by the following formula:

HO-CH-CH ₀ -Po-CH ₉ -CHI -OH (II) Ι ^{ά L} \ ^Λ

R R

wherein R is hydrogen and / or methyl, ethyl or butyl, and

χ a positive number with a value of about

3 to 170 mean

provided that the minimum molecular weight of the compound is at least about 230.

Examples of starting materials of this type are polyoxypropylene diols, such as those of the following formula:

HO-CH-CH ₀ - Fo-CH ₀ -CHl -OH

Ι ά L · d ι JX

(III)

CH ₃ CH ₃

wherein χ is a number with a value of about 3, preferably about 6, to about 100,

provided that the minimum molecular weight of the compound is at least about 230. Preferably χ is about 33.

Examples of starting materials with a structure of the formula II are polyoxypropylene diols with an average Molecular weight of about 230 or more, wherein χ is about 6 to 7, polyoxypropylene diols with a average molecular weight of about 2000, wherein χ means an average value of about 33, and

1 polyoxypropylene diols with an average molecular weight of about AOOO, wherein χ represents an average value of about 60.

5 As a further example, polyoxyalkylenediol starting materials with the following formula are mentioned:

CH-,

I ³

10 CH ₃ CH ₃

where b is from about 8 to 100 and a + c is from about 2 to about 3.

The following are mentioned as examples of starting materials of the formula IV:

Molecular weight value a + c nearly nearly 2.5 b 2.5 600 8.5 2.5 900 15.5 2.5 2000 AO AOOO 86

Another class of preferred starting materials are polyoxyalkylene triols, such as those with the following formula: J- -i
25 C- | OCH ₂ CH [ _x -0H

CH ₃ (V) R "-C-Γ-rI _n [ÖcH ₂ CH | -OH,

CH ₃

c- | o-ch ₂ ch] _z -oh

CH ₃

wherein R 'is a methylene group or hydrogen and R "is hydrogen or methyl, and

4 ■ '"-' "'3Έ08716 wherein η is 0 to 1; namely, η is O when R ^f and R "denote hydrogen and 1 when R 'denotes methylene and R" denotes methyl; and wherein the sum of x + y + z is a positive number having a value from about 5 to 170, and especially from about 5 to 100, the average molecular weight of the compound being about 230 or more.

Specific examples of compounds of the formula V are as follows:

Molecular weight

approximately RJ] _- FM_ η x + y + z

500 -CH-, -CHp- 1 7 5000 H H 0 85

Another class of for practicing the invention Process suitable feedstocks are tetrols, pentols, hexols and heptols of the following formula:

CH ₂ - [O _{-CH 2} -CH (CH ₃ )] _{x -0H}

(VI) (CH-Io-CH ₂ -CH (CH ₃ TIy-OH) _n , CH ₂ - JO-CH ₂ -CH (CH ₃ ) I _z -0H

where η is a positive number with a value of about 1

to 5, preferably 1, and

wherein the sum of x + y + z is about 7 to 170. 25th

As stated above, the polyoxyalkylenepolyamines according to the invention produced in that a Polyoxyalkylene polyol starting material under the conditions of reductive amination with ammonia, if appropriate in the presence of hydrogen, on a Raney nickel or Raney nickel / aluminum catalyst activated with molybdenum implemented.

It would be expected that the reaction rates would slow down as the molecular weight of the feed increases.

become saraer. Contrary to this expectation, it was found that when carrying out the invention Process, the reaction rates are surprisingly higher when the higher molecular weight P ο Iy oxy alkylene starting materials reductively under anhydrous conditions in the presence of ammonia and optionally aminated in the presence of hydrogen on a molybdenum-activated Raney nickel catalyst.

When carrying out the process according to the invention, it is expedient to use about 4 to 150 moles of ammonia per OH equivalent of the starting material. The presence of hydrogen is not essential for carrying out the process according to the invention. However, hydrogen is preferably used in an amount of ¹ ^ about 0.5 to about 10 molar equivalents per OH equivalent of the starting material.

When carrying out the process according to the invention, the temperature is expediently about 160 to

25O ⁰ C and especially about 185 to 230 ° C.

The pressure is expediently in the range from about 35 to about 242 bar and in particular in the range from about 70 to 173 bar.

When carrying out the reaction in a batch process, the reaction time is expediently about 0.1 up to 6 hours and in particular about 0.15 to 2 hours.

For the continuous implementation of the process according to the invention, the catalyst is in pellet or Nugget form is used, and the response time is

expediently about 0.1 to 2.0 g of feed per hour per cm of catalyst and in particular about 0.3 to 1.6 g of feed per hour per cm of catalyst.

y \ '"3 b O 871'6

1 The following examples illustrate the invention.

Example 1 5868-69-28 (5868-30)

A commercially available Raney nickel catalyst (Grace 3000) activated with molybdenum (2% Mo) was rendered anhydrous by repeatedly washing the wet catalyst with tert-butylamine. A stirred autoclave with a volume of one liter was charged with 404.1 g of a polyoxypropylene triol with a molecular weight of 5000, 50.0 g of anhydrous catalyst and 104.9 g of ammonia. A pressure of 32 bar at room temperature was set using hydrogen. The autoclave was rapidly heated to 245 ⁰ C and the temperature maintained at 243-249 ° C (with an average of 246 ⁰ C) 25 minutes.

The pressure was 214.7 to 216.5 bar. The autoclave was then rapidly cooled to room temperature. Some of the contents were filtered and stripped off (by means of a rotary evaporator at 98 ^° C. and 25 mm Hg). The analysis resulted in 0.59 meq / g total acetylatable, 0.60 meq / g total amines and 0.59 meq / g primary amines (with an analytical accuracy of νοηί 0.01 meq / g).

Example 2

The runs were carried out according to the procedure of Example 1 2g and the conditions and results are compiled in Table I. The results obtained are commented on as follows:

a. At a certain temperature, the conversion depends on the catalyst concentration (see reference nos. 5868-69-51, 5868-69-52, and 5868-69-53 and 5868-69-49; compare also 5868-69-47 with 5868-69-48 and 5868-69-46).

b. Under certain reaction conditions the catalysts with 1% Mo are more active than the catalyst

_oc tor with 2% Mo (compare 5868-69-33 and 5868-69-38

with 5868-69-40 and 5868-69-46).

1 example 3 (5868-25 and 5868-28)

At the same time, 51 g / h of polyoxypropylene glycol with a molecular weight of 2000, 54 g / h of ammonia and 8 liters / h hydrogen fed. The reactor was kept at 200 ^° C. and a total pressure of 134 bar. A sample of the reactor effluent was stripped on a rotary evaporator at 98 ° C and 25 mm Hg

^ q and analyzed. The following values were obtained: 1.01 meq / g total acetylatable, 0.65 meq / g total amines, and 0.64 meq / g primary amines.

The reactor was operated essentially in the same way, but at temperatures of 210 ° C., 220 ° C. and 224 ^° C. The reaction conditions and the product analyzes are shown in Table II.

Example 4 (5914-61, 5914-63) The runs of this example essentially were

carried out like the approaches of Example 3, the Re-ο

However, the actuator contained approximately 100 cm of one with molybdenum activated Raney nickel catalyst granulate with 1% Mo and a particle size of (8 χ 1.2 mesh). The reaction conditions and results

are given in Table III. 25th

Example 5 (5914-47, 5914-51)

Comparative example with non-activated Raney nickel The procedure was carried out essentially as in Example 4, but using a non-active catalyst as the catalyst

fourth Raney nickel granules with a particle size

of (8 x 12 mesh) was used. the

Reaction conditions and the results are in table IV reproduced.

Comparing the results of Table III with the results

Comparing the results of Table IV, it is found that

the Raney nickel catalyst activated with 1% Mo was better Provides results, especially at the highest PPG-2000 space velocities.

5 Example 6 (5969-19)

Comparative example of a batch batch, using a Cr-activated Raney nickel catalyst. According to the process conditions of batch 5868-69-32 of Table I, batches with the following were run

"LQ Exceptions: There were only 336.8 g of the polyoxypropylenetriol with a molecular weight of 5000 were used, 108.9 g of ammonia (24% NH,) were added and 50.1 g of Grace 2400 catalyst (2% Cr, 2% Fe-activated Raney nickel) used. Analysis of the stripped and filtered product showed: 0.59 meq / g total acetylables, 0.34 meq / g total amines and 0.33 meq / g primary amines. This result is much worse than the results of the approaches in Table I using Raney nickel activated with molybdenum.

Example 7 (5868-36)

Comparative example of a batch approach with non-

activated Raney nickel

This example was made under the process conditions

of Example 6 with the following exceptions

leads to: 414.6 g of the polyoxypropylene triol with a molecular weight of 5000, 72.8 g of ammonia and 49.98 g Grace 2800 catalyst (unactivated Raney nickel) was used. The following analysis results

of the process product were obtained: 0.60 meq / g 30

Total acetylatable, 0.55 meq / g total amine and

0.54 meq / g primary amine. Comparison with the results in Table I shows that the non-activated catalyst is less active than the catalysts activated with molybdenum.
35

25th 30th

Table I. Reactor-
pressure
bar established
Catalytic
G Total-
Ammonia acetyl
Wt% meq / g 0.59 - 360871B 216 50 20.60 0.60 153 54 11.18 0.60 (with Mon) material
No. 137 60 7.85 0.60 sales 5868-69-28 139 60 7.61 0.59 101.70 5868-69-32 Batch approaches, activated Raney nickel 142 60 7.70 0.60 93.33 5868-69-33 Temp.
⁰ C 161 80 7.61 0.59 83.33 5868-69-34 246 294 80 5.77 0.58 81.67 5868-69-35 248 122 60 6.81 0.60 81.36 5868-69-36 244 142 61 7.60 0.58 81.67 5868-69-37 258 124 60 7.55 0.60 27.12 5868-69-38 258 145 60 7.80 0.60 82.76 5868-69-40 260 135 58 7.65 0.61 95.00 5868-69-42 208 130 30th 7.61 0.57 81.03 5868-69-43 247 125 15th 7.46 0.65 96.67 5868-69-46 244 109 50 7.23 0.58 95.00 5868-69-47 248 115 25th 7.39 0.59 85.25 5868-69-48 250 125 25th 7.29 0.60 54.39 5868-69-49 244 122 13th 7.10 0.60 77.78 5868-69-50 245 118 100 7.35 77.59 5868-69-51 245 55.93 5868-69-52 220 33.33 5868-69-53 220 90.00 221 220 220

35

ίο

20 25 30

Prim.
MLn
% 16 I (continued) 0.42 - 3-608716 100.00 Tabel established Reaction
Triol G-5000 time
gh 0.42 material
No. 91.67 BTW Prim.
& Ges.Am. 404.4 0.43 Raney
Catalytic
identity 5868-69-28 81.67 0.01 514.7 0.20 3000 5868-69-32 80.00 0.01 691.77 0.20 3000 5868-69-33 79.66 0.01 694.08 0.20 3000 5868-69-34 80.00 0.01 696.15 0.05 3000 5868-69-35 25.42 0.01 693.88 0.42 3000 5868-69-36 81.03 0.01 796.87 0.42 3000 5868-69-37 93.33 0.01 697.47 0.20 3000 5868-69-38 79.31 0.01 695.32 0.25 3000 5868-69-40 95.00 0.01 700.75 0.20 3200 5868-69-42 93.33 0.01 710.48 0.20 3200 5868-69-43 83.61 0.01 695.90 0.20 3200 5868-69-46 52.63 0.01 695.75 0.333 3100 5868-69-47 76.19 0.01 697.29 0.42 3100 5868-69-48 75.86 0.01 695.85 0.333 3100 5868-69-49 54.24 0.01 696.76 0.333 3100 5868-69-50 31.67 0.01 695.80 0.333 3100 5868-69-51 88.33 0.01 696.22 3100 5868-69-52 0.01 695.22 3100 5868-69-53 0.01 3100

Raney 3200 and Raney 3100 contain 1% Mo; Raney 3000 contains 2% Mo.

35

ω ω bo fco μ ι- *

cn ο cn ο σι ο cn

Table II
Raney Ni / Mo (2% Mo) catalyst - 0.6 cm

Polyol total "Total Prim.

Material Temp. Pressure Weight by Weight Ammonia Weight Nm H2 Mol H2 / Mol NH3 / Acetyl Conversion Amine

No. ° C bar g / ml / h Weight% g / ml / h kg Pole Eq -OH Eq -OH meq / g % % , 40 5868-25-1 200 139 0.53 51.30 1.11 0 , 148 7.00 61.90 1.01 6h, 40 63 , 40 5868-25-2 210 139 0.53 t> 1.70 1.12 0 , 1 ^ 8 7.00 62.90 1.02 80.40 79 , 30 58b8-25-3 220 139 0.53 51.30 1.11 0 , 148 7.00 61.90 1.02 88.20 87 , 20 5868-25-4 224 139 0.52 50.50 1.05 0 , 154 7.30 59.80 1.02 91.20 90 , 10 5868-28-1 210 135 0.53 50.20 1.07 0 , 0? 7 3.50 59.20. 1.01 86.10 85 , 70 5868-28-2 210 139 0.54 49.60 1.09 0 , 219 10.40 57.70 0.99 73.70 72 , 20 5868-28-3 210 139 0.53 48.90 1.05 0 , 113 5.30 56.10 1.01 80.20 79

ω
ο

to cn

to ο

cn

Table III

Raney Ni / Mo (1% Mo) catalyst - 8x12 mesh

Removed
material
No. Hot spot
Temp.
⁰ C pressure
bar ammonia
Weight% Polyol
Gew.sv
g / ml / h Nm ³ Hp
kg P-ol total
Acetyl
Meq / g sales Prim.
Amines Moles of H ₂ /
Iq - OH Moles of NH ₃ /
Kq - OH 5914-61-1 200 139 50.63 1.01 0.056 0.99 92.93 91.92 2.65 60.23 5914-61-2 210 139 51.02 0.97 0.059 1.00 96.00 85.00 2.76 61.16 5914-61-3 220 139 49.84 1.03 0.055 0.99 97.98 95.96 2.60 58.34 5914-61-4 230 139 48.30 1.07 0.053 0.98 96.94 94.90 2.51 54.87 5914-63-1 210 132 50.17 1.48 0.045 1.01 95.05 93.07 2.12 59.12 5914-63-2 220 132 49.66 1.48 0.044 1.00 97.00 96.00 2.10 57.93 5914-63-3 225 135 50.00 1.44 0.046 1.02 94.12 92.16 2.17 58.72

ω ο

to ο

Oil

ι- O

Table IV

Catalyst: Raney Ni, not activated - 8x12 mesh

Removed
material
No. Hot spot
Temp.
° C pressure
bar ammonia
Weight% Polyol
Gew.sv
g / ml / h Nm ³ H ₂ /
kg P-ol total
Acetyl
Meq / g sales
% Prim.
Amine
% Moles of H ₂ /
Eq - OH Moles of NH ₃ /
Eq - OH 5914-47-1 210 135 48.65 1.03 0.055 1.01 96.04 95.05 2.58 55.64 5914-47-2 220 139 49.90 0.96 0.059 1.02 96.08 95.10 2.79 58.48 5914-47-3 225 139 49.63 0.99 0.058 1.00 96.00 94.00 2.72 57.85 5914-47-4 220 137 50.09 0.99 0.057 0.98 97.96 95.92 2.70 58.94 5914-51-1 210 135 51.56 1.36 0.049 1.01 93.07 91.09 2.29 62.51 5914-51-2 220 135 50.68 1.45 0.0462 1.00 96.00 95.00 2.18 60.34 5914-51-3 227 135 50.25 1.46 0.0456 1.01 94.06 93.07 2.14 59.30

The reactor volume was a constant 100 cm.

V 3ο0871δ

1 example 8 (5868-70)

Amination of triol over Ni / Cu / Cr / Fe supported catalyst An autoclave was charged with 165.54 g of polyoxypropylene triol with a molecular weight of 5000 and 65.09 g of finely ground calsicat Ni / Cu / Cr / Fe on a Kieseiguhr. The reactor was flushed with hydrogen, brought to a pressure of 14.8 bar with hydrogen and then with nitrogen to a pressure of 101 bar at 27 ° C. The autoclave was heated to 235 ° C. over a period of 46 minutes and from 160 bar brought to 208 bar. The autoclave was kept 1.8 hours at 234 to 25O ⁰ C (on average 240 ⁰ C). Over a period of 0.8 hours the pressure fell to 201 bar. The pressure was brought to 208 bar and then rose steadily to 218 bar. The autoclave was cooled and the venting gas examined. It contained traces of isopropylamine, ethylamine, methylamine and a substantial amount (22.9%) methane.

Analysis of a filtered _} stripped sample of the autoclave contents showed: 0.19 meq / g total acetylatable and <0.01 meq / g total amines and primary amines, respectively.

Example 9 (5868-79)

Amination of triol on Mo-activated Raney nickel

The process conditions of Example 8 were essentially followed. 167.29 g of the polyoxypropylenetriol with a molecular weight of 5000 and 49.96 g of anhydrous xianey nickel 3000 were used. The initial pressures were 18.2 bar for hydrogen and 104 bar for nitrogen. It was ^{heated to 283 °} C. over a period of 53 minutes. ^{It was then cooled to 242 °} C. in the course of 2 minutes and the pressure was increased from 191 bar to 208 bar with hydrogen. The reactor was then held at a temperature of 24O ⁰ C and detected bar hydrogen for 2 hours available 208th

35 The pressure rose to 218 bar.

After cooling and analyzing the filtered and stripped contents of the autoclave, the following values were obtained: 0.20 meq / g total acetylatable, 0.06 meq / g total amines and 0.03 meq / g primary amines.

Example 10 (5868-18, 5868-21)

The reactor contained chromium-activated Raney / nickel granules with a diameter of approximately 0.6 cm. The reactions were conducted under the conditions of Table V throughput IQ. The results show that this catalyst is also effective for the amination of polyoxypropylene glycol with a molecular weight of 2000.

Example 11 (5868-25, 5868-28)

The reactor contained Raney nickel granules activated with molybdenum with a diameter of approximately 0.6 cm. The process conditions are given in Table VI. The results show that this catalyst can be used to aminate polyoxypropylene glycol having a molecular weight from 2000 is effective. After use, the catalyst contained about 3 to 5% finely divided Material.

Example 12 (5868-23)
_o _ Commercially available Raney nickel catalyst (Grace 2800,

non-activated Raney nickel with less than 10% by weight Aluminum) was rendered anhydrous by repeatedly washing the wet catalyst with tert-butylamine. A A stirred autoclave with a volume of one liter was

with 417.79 g triol (molecular weight 5000), 50.16 g was-30

anhydrous catalyst and 88.4 g of ammonia charged. Of the

The autoclave was flushed with hydrogen and brought to a pressure of 32 bar with hydrogen at room temperature. The autoclave was then quickly heated to 245 ° C. and the temperature increased to 242 to 250 ° C.

ω ω to fco * -> ι- ¹

cn ο cn ο cn ο cn

Table V
Catalyst: Cr-Ni

Polyol total ~ total prim.

Material temp. Pressure wt. Sv ammonia wt. Sv Nm H ₂ / mole Hp / mole NH3 / acetyl conversion amine
No. ⁰ C bar g / ml / h wt.% G / ml / h kg P-ol eq - OH eq - OH Mäq / g%%

5868-18-1 200 139 0.64 50.40 1 , 30 0.118 5.60 59.60 i, 01 62.40 61.40 5868-18-2 210 139 0.62 51.30 1 , 27 0.124 5.80 61.70 1.01 77.20 76.20 5868-18-3 220 139 0.62 50.70 1 , 26 0.124 5.80 60.40 1.01 88.10 87.10 5868-18-4 225 139 0.66 50.00 1 , 32 0.113 5.40 58.70 1.01 91.10 90.10 5868-21-1 210 139 0.64 50.00 1 , 27 0.059 2.80 58.70 1.03 82.50 81.60 5868-21-2 210 139 0.65 50.50 1 , 33 0.172 8.20 59.90 1.02 70.60 69.60

Table VI

Catalyst: Mo-Ni

material
No. Temp.
⁰ C pressure
bar Polyol
Gew.sv
g / ml / h ammonia
Weight% total
Gew.sv
g / ml / h Nm ³ Hp /
kg P-ol Moles of H ₂ /
Eq - OH Moles NHo /
Eq - OH total
Acetyl
Meq / g sales Prim.
Amine 5868-25-1 200 139 0.53 51.30 1.11 0.148 7.00 61.90 1.01 64.40 63.40 5868-25-2 210 139 0.53 51.70 1.12 0.148 7.00 62.90 1.02 80.40 79.40 5868-25-3 220 139 0.53 51.30 1.11 0.148 7.00 61.90 1.02 88.20 87.30 5868-25-4 224 139 0.52 50.50 1.05 0.154 7.30 59.80 1.02 91.20 90.20 5868-28-1 210 135 0.53 50.20 1.07 0.077 3.50 59.20 1.01 86.10 85.10 5868-28-2 210 139 0.54 49.60 1.09 0.219 10.40 57.70 0.99 73.70 72.70 5868-28-3 210 139 0.53 48.90 1.05 0.113 5.30 56.10 1.01 80.20 79.20

cut 248 C) held for 26 minutes. The pressure was 186.5 to 187.2 bar. The autoclave was quickly cooled to room temperature. A portion of the contents was filtered and stripped off (rotary evaporator, 98 ^° C., 25 mm Hg). Analysis values: 0.59 meq / g total acetylatable, 0.57 meq / g total amines and 0.56 meq / g primary amines.

Example 13 (5868-38)

IQ The process conditions were substantially the same as in Example 12 with the following exceptions: The catalyst used were 54.0 g of anhydrous Raney-nickel-molybdenum (Grace 3000) and 514.7 g of triol and 63.8 g of ammonia used. The maximum pressure was 153 bar.

] _g Analysis of a fraction of the filtered and stripped Reactor contents gave 0.60 meq / g total acetylatable, 0.56 meq / g total amines and 0.55 meq / g primary amines.

Example 14 (5838-86)

The procedure of Example 12 was essentially repeated except that the same catalyst was used was used, but in the water-moist state. The analysis of the process product showed 0.59 meq / g total acetylatable, 0.07 meq / g total amines

25 and 0.06 meq / g primary amines.

Claims (3)

Claims 1. Process for the preparation of polyoxyalkylene polyamines by reacting an OH-terminated polyoxyalkylene compound which has a molecular weight of at least about 230, with ammonia in the presence of a Raney nickel catalyst under anhydrous conditions reductive amination, if appropriate in the presence of hydrogen, characterized,
that a Raney nickel or Raney nickel / aluminum catalyst activated with molybdenum is used which contains about 0.2 to 5% by weight of molybdenum, based on the total weight of the catalyst. 2. The method according to claim 1, g e'k is indicated by the implementation of an OH-terminated polyoxyalkylene compound that has a molecular weight of about 230
to 10,000, with about A to 150 molar equivalents of ammonia and about 0.5 to 10 molar equivalents
Hydrogen under anhydrous conditions in a reactor containing a fixed catalyst bed, at a temperature of about 175 to 25O ⁰ C and one
Pressure of about 35 to 242 bar for a time in order to convert at least a portion of the compound used to the corresponding polyoxyalkylene-polyamine ³⁵ zen. 1 3. The method according to claim 1 or claim 2, characterized in that that the molybdenum activated catalyst consists of Raney nickel and aluminum and about 0.2 Up to 5% by weight of molybdenum and aluminum in trace amounts up to about 40% by weight and the remainder to 100 Contains% nickel by weight. k. Method according to claim 3, 10 characterized that the catalyst is present in granulated form or in the form of nuggets, made from activated with molybdenum Raney nickel / aluminum consists, namely about 0.5 to 1.5 wt.% Molybdenum, about 1 to 35 wt.% Contains aluminum and the remainder to 100% by weight nickel, whereby the nuggets have a surface area of no more than about ρ
25 m / g, a porosity of about 0.01 to 0.03 ml / g and a particle size of about 1 mm to 20 mm. 5. The method according to any one of the preceding claims, characterized in that the OH-terminal polyoxyalkylene compound is made from derivatives of ethylene oxide, propylene oxide, Butylene oxide or mixtures thereof.