WO1988006579A1 - Amination of polyoxyalkylene alcohols - Google Patents

Amination of polyoxyalkylene alcohols Download PDF

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Publication number
WO1988006579A1
WO1988006579A1 PCT/GB1988/000147 GB8800147W WO8806579A1 WO 1988006579 A1 WO1988006579 A1 WO 1988006579A1 GB 8800147 W GB8800147 W GB 8800147W WO 8806579 A1 WO8806579 A1 WO 8806579A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
group
alcohol
hydroxide
mixture
Prior art date
Application number
PCT/GB1988/000147
Other languages
French (fr)
Inventor
Zdzislaw Dudzinski
Phillip Adams
Original Assignee
Stepan Company
Holmes, Michael, John
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stepan Company, Holmes, Michael, John filed Critical Stepan Company
Publication of WO1988006579A1 publication Critical patent/WO1988006579A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

Definitions

  • This invention concerns improvements in or relating to the amination of polyoxyalkylene alcohols with secondary amines to yield polyoxyethylene tertiary amines.
  • the usual method of aminating polyoxyalkylene alcohols is to substitute chlorine for the terminal OH group using phosphorus trichloride and hydrogen chloride (as described in US Patent No. 3294847) , and then treating the resulting material with a primary or secondary amine.
  • an object of this invention is to find a method of treating a mixture of copper oxide and Group II metal hydroxide catalyst in such a manner that it would not be poisoned by amines when in suspension in hot polyoxyalkylene alcohols.
  • Another object of this invention is to prepare tertiary amines by polyoxyalkylenyleating secondary amines.
  • pre-treating, or "conditioning" the catalyst will keep it from becoming poisoned when heated in the presence of polyoxyalkylene alcohols and amines.
  • the polyoxyalkylene alcohol preferably has the general formula R(OA) OH, wherein R is an alkyl, aryl or aralkyl group and mixtures thereof having 1 to 20 carbon atoms, A is an alkylene chain having from 2 to 20 carbon atoms and n is an integer from 1 to 20. A is preferably C 2 _g and more preferably an ethylene grouping and n is preferably not greater than 9.
  • R is an alkyl, aryl or aralkyl group and mixtures thereof having 1 to 20 carbon atoms
  • A is an alkylene chain having from 2 to 20 carbon atoms and n is an integer from 1 to 20.
  • A is preferably C 2 _g and more preferably an ethylene grouping and n is preferably not greater than 9.
  • the polyoxyalkylene alcohol will normally be present as a mixture of related alcohols although use of pure polyoxyalkylene alcohols is also included and alkylpolyoxyalkylene alcohols are especially useful.
  • the secondary amine is advantageously a dialkylamine for example having 1 to 4 carbon atoms in each of the alkyl groups (which may be the same or different) . Dieth lamine is preferred.
  • the preferred catalyst used in practice of the present invention is a mixture of powdered copper oxide and calcium hydroxide. The substitution of barium hydroxide or magnesium hydroxide for the calcium hydroxide is also within the scope of this invention.
  • the mixture of copper oxide or hydroxide and Group II metal oxide or hydroxide is preferably in the weight ratio of about 2 to 6 parts of copper oxide or hydroxide to about one part of the Group II metal oxide or hydroxide.
  • Pre-treating, or "conditioning” or “activating” the catalyst comprises heating the catalyst, preferably at a temperature of between about 150°C to 250°C and more preferably between about 170°C to
  • the hydrogen is preferably substantially pure.
  • the amount of catalyst used is advantageously from about 2% to about 10% by weight based on the weight of polyoxyalkylene alcohol.
  • the secondary amine may be introduced. Where this is gaseous, it may advantageously be introduced with the hydrogen gas stream, which is preferably recirculated.
  • a ratio of 30% to 70% by volume of the secondary amine to 70% to 30% by volume of H 2 is useful in the gas stream.
  • dimethylamine a ratio of 30%-45% by volume of dimethylamine to 70%-55% by volume of hydrogen was found to be very effective and is a preferred composition of the gas mixture.
  • the by-product (water) may be distilled out of the reaction mixture during the reaction.
  • the temperature of the reactants at which the amination is carried out with such a gaseous mixture is preferably between about 200°C to 220°C. The higher temperature is preferred because it results in a slightly faster reaction.
  • the mother liquors may be purified, as by filtering and washing with hot salt water solution.
  • a hot solution is preferred because polyoxyalkylene compounds are less soluble in hot water than cold water.
  • the filtrate may thereafter be dried. Analysis may be by titration with perchloric acid in glacial acetic acid to ascertain the concentration of tertiary amine, or the "equivalent weight" of the product.
  • the final product will commonly consist of a mixture of the polyoxyalkylene tertiary amine, and the polyoxyalkylene alcohol. In the embodiments shown in the Example, no effort was made to separate the two materials. The quantity of other non-nitrogenous material in the product generally did not exceed about 1% by weight. The concentration of tertiary amine in the product was ascertained by determining the "equivalent weight" of the mixture and comparing it with the calculated theoretical equivalent weight. The desired tertiary amine product yields generally always fell between 75% and 85%, by weight, with the remainder of the product being mainly unreacted alcohol.
  • the tertiary amine product obtained using the method of the present invention may subsequently be converted into a quaternary salt.
  • quaternization may be effected by methods common in the art, for example using an alkylating agent such as methyl chloride in the presence of sodium hydroxide.
  • alkylating agent such as methyl chloride in the presence of sodium hydroxide.
  • Such quaternary salts are useful for example as surfactants or in some cases antimicrobials.
  • the apparatus used in the Example was that described in the United States Patent No. 4594455, although other suitable apparatus may also be utilised.
  • the alkylpolyoxyalkylene alcohol used was a commercial product having the aforesaid formula R(OA) OH in which the alkyl group R is a mixture of alkyl groups of 12 carbon atoms and 14 carbon atoms.
  • the alkylene group A is -CH 2 CH 2 -, n varies from about 1 to about 7 and the average is about 3.
  • This material under the trade name "Alfoni ⁇ 14-12-40", is produced by the Vista Chemical Co., Houston, Texas and is described as having about 40% ethylene oxide (actually -OCH 2 CH 2 ⁇ ) and an equivalent weight of 329.0.
  • the reactor was fitted with an inlet tube through which hydrogen gas, or a mixture of hydrogen and dimethylamine gases, could be introduced at a controlled rate/pressure to the bottom of the reactor, and excess gases recirculated.
  • a mechanical agitation means and means for heating were also part of the equipment, as was means for distilling out the by-product (water) .
  • the contents of the reactor were heated to about 220°C, which took about 1 hour, during which time pure hydrogen was recirculated through the materials in the reactor.
  • the composition of the recirculating gas was changed from pure hydrogen to about 65%-70% hydrogen, and about 30%-35% dimethylamine, and this gas mixture was then recirculated through the reactor, which was maintained at about 220°C for about 10 hours while the by-product (water) was distilled out.
  • reaction mixture was filtered, and the filtrate was then extracted twice with boiling hot 10% aqueous sodium chloride solution. It was then dried.
  • the amine content of the product was found to be about 99% tertiary amine, and less than 1% secondary amine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method of catalytic amination of at least one polyoxyalkylene alcohol with at least one secondary amine using a catalyst comprising a mixture of copper oxide or hydroxide and at least one Group II metal oxide or hydroxide characterised in that the catalyst is activated by heating in suspension in said polyoxyalkylene alcohol while hydrogen gas is passed therethrough.

Description

"AMINATION OF POLYOXYALKYLENE ALCOHOLS"
This invention concerns improvements in or relating to the amination of polyoxyalkylene alcohols with secondary amines to yield polyoxyethylene tertiary amines. The usual method of aminating polyoxyalkylene alcohols is to substitute chlorine for the terminal OH group using phosphorus trichloride and hydrogen chloride (as described in US Patent No. 3294847) , and then treating the resulting material with a primary or secondary amine.
It has recently been proposed to aminate alcohols catalytically, and this method has been described in United States Patent No. 4251465, as well as in United States Patent No. 4594455. For example, when n-dodecanol is aminated with dimethylamine in the presence of a catalyst composed of copper oxide and a Group II metal hydroxide together with nickel supported on kieselguhr, a good yield of dodecyldimethylamine is obtained. However, when, in a similar reaction, typically using copper oxide and a Group II metal hydroxide as catalyst and polyoxyalkylene alcohols instead of alkanols, amination does not occur. This may be due to the fact that in the presence of hot polyoxyalkylene alcohols, the catalyst is poisoned by amines. The solid catalyst clumps, and sinks to the bottom of the reactor.
Since polyoxyalkylene tertiary amines are intermediates for the syntheses of polyoxyalkylene quaternary salts, which are very effective anti¬ microbials, and because catalytic amination is the commercially used method for preparing amines. an object of this invention is to find a method of treating a mixture of copper oxide and Group II metal hydroxide catalyst in such a manner that it would not be poisoned by amines when in suspension in hot polyoxyalkylene alcohols. Another object of this invention is to prepare tertiary amines by polyoxyalkylenyleating secondary amines.
In accordance with the present invention, it has been found that pre-treating, or "conditioning" the catalyst will keep it from becoming poisoned when heated in the presence of polyoxyalkylene alcohols and amines.
According to the present invention we provide a method of catalytic amination of at least one polyoxyalkylene alcohol with at least one secondary amine using a catalyst comprising a mixture of copper oxide or hydroxide and at least one Group II metal oxide or hydroxide characterised in that the catalyst is initially activated by heating in suspension in said polyoxyalkylene alcohol in the absence of said amine while a gas stream comprising hydrogen is passed therethrough.
In general, the polyoxyalkylene alcohol preferably has the general formula R(OA) OH, wherein R is an alkyl, aryl or aralkyl group and mixtures thereof having 1 to 20 carbon atoms, A is an alkylene chain having from 2 to 20 carbon atoms and n is an integer from 1 to 20. A is preferably C2_g and more preferably an ethylene grouping and n is preferably not greater than 9. The polyoxyalkylene alcohol will normally be present as a mixture of related alcohols although use of pure polyoxyalkylene alcohols is also included and alkylpolyoxyalkylene alcohols are especially useful.
The secondary amine is advantageously a dialkylamine for example having 1 to 4 carbon atoms in each of the alkyl groups (which may be the same or different) . Dieth lamine is preferred. The preferred catalyst used in practice of the present invention is a mixture of powdered copper oxide and calcium hydroxide. The substitution of barium hydroxide or magnesium hydroxide for the calcium hydroxide is also within the scope of this invention.
The mixture of copper oxide or hydroxide and Group II metal oxide or hydroxide is preferably in the weight ratio of about 2 to 6 parts of copper oxide or hydroxide to about one part of the Group II metal oxide or hydroxide.
Pre-treating, or "conditioning" or "activating" the catalyst comprises heating the catalyst, preferably at a temperature of between about 150°C to 250°C and more preferably between about 170°C to
220°C, while it is suspended in the polyoxyalkylene alcohol in the absence of the amine and while passing, e.g. recirculating, a gas stream containing hydrogen gas into the suspension. Temperatures between about 200βC and 220βC are particularly preferred. The hydrogen is preferably substantially pure.
The amount of catalyst used is advantageously from about 2% to about 10% by weight based on the weight of polyoxyalkylene alcohol. The larger the quantity of catalyst, the faster the subsequent amination, but the subsequent reaction rate of amination is not proportional to the concentration of the catalyst. In actual procedures about 5% of catalyst was used, based on the weight of the alcohol.
After "conditioning" or "activating" the catalyst, the secondary amine may be introduced. Where this is gaseous, it may advantageously be introduced with the hydrogen gas stream, which is preferably recirculated. A ratio of 30% to 70% by volume of the secondary amine to 70% to 30% by volume of H2 is useful in the gas stream. In the case of dimethylamine a ratio of 30%-45% by volume of dimethylamine to 70%-55% by volume of hydrogen was found to be very effective and is a preferred composition of the gas mixture.
The by-product (water) may be distilled out of the reaction mixture during the reaction.
The temperature of the reactants at which the amination is carried out with such a gaseous mixture is preferably between about 200°C to 220°C. The higher temperature is preferred because it results in a slightly faster reaction.
When the reaction is complete, the mother liquors may be purified, as by filtering and washing with hot salt water solution. A hot solution is preferred because polyoxyalkylene compounds are less soluble in hot water than cold water.
The filtrate may thereafter be dried. Analysis may be by titration with perchloric acid in glacial acetic acid to ascertain the concentration of tertiary amine, or the "equivalent weight" of the product. The final product will commonly consist of a mixture of the polyoxyalkylene tertiary amine, and the polyoxyalkylene alcohol. In the embodiments shown in the Example, no effort was made to separate the two materials. The quantity of other non-nitrogenous material in the product generally did not exceed about 1% by weight. The concentration of tertiary amine in the product was ascertained by determining the "equivalent weight" of the mixture and comparing it with the calculated theoretical equivalent weight. The desired tertiary amine product yields generally always fell between 75% and 85%, by weight, with the remainder of the product being mainly unreacted alcohol.
The tertiary amine product obtained using the method of the present invention may subsequently be converted into a quaternary salt. Such quaternization may be effected by methods common in the art, for example using an alkylating agent such as methyl chloride in the presence of sodium hydroxide. Such quaternary salts are useful for example as surfactants or in some cases antimicrobials.
The apparatus used in the Example was that described in the United States Patent No. 4594455, although other suitable apparatus may also be utilised.
The following Example is illustrative of the invention:
Example 1
The alkylpolyoxyalkylene alcohol used was a commercial product having the aforesaid formula R(OA) OH in which the alkyl group R is a mixture of alkyl groups of 12 carbon atoms and 14 carbon atoms. The alkylene group A is -CH2CH2-, n varies from about 1 to about 7 and the average is about 3. This material, under the trade name "Alfoniσ 14-12-40", is produced by the Vista Chemical Co., Houston, Texas and is described as having about 40% ethylene oxide (actually -OCH2CH2~) and an equivalent weight of 329.0.
Into a 1 liter reactor was placed 700gm of "Alfonic 14-12-40", 35.0gm of powdered copper oxide, and 7.0gm of calcium hydroxide.
The reactor was fitted with an inlet tube through which hydrogen gas, or a mixture of hydrogen and dimethylamine gases, could be introduced at a controlled rate/pressure to the bottom of the reactor, and excess gases recirculated. A mechanical agitation means and means for heating were also part of the equipment, as was means for distilling out the by-product (water) .
While being stirred, the contents of the reactor were heated to about 220°C, which took about 1 hour, during which time pure hydrogen was recirculated through the materials in the reactor. At this point, the composition of the recirculating gas was changed from pure hydrogen to about 65%-70% hydrogen, and about 30%-35% dimethylamine, and this gas mixture was then recirculated through the reactor, which was maintained at about 220°C for about 10 hours while the by-product (water) was distilled out.
After cooling, the reaction mixture was filtered, and the filtrate was then extracted twice with boiling hot 10% aqueous sodium chloride solution. It was then dried.
The amine content of the product was found to be about 99% tertiary amine, and less than 1% secondary amine.
The product had an "equivalent weight" of 459. The theoretical equivalent weight of the
"Alfonic 14-12-40" dimethylamine is 356. Therefore, the product was about 77.6% "Alfonic 14-12-40" dimethylamine, and about 22.4% non-nitrogenous material. Similar procedures in which the reaction mixture was not treated with hydrogen gas, but was immediately subjected to a mixture of hydrogen and dimethylamine, resulted in the poisoning of the catalyst shortly after the onset of the reaction. The catalyst agglomerated and clumped to the bottom of the reactor.

Claims

CLAIMS :
1. A method of catalytic amination of at least one polyoxyalkylene alcohol with at least one secondary amine using a catalyst comprising a mixture of copper oxide or hydroxide and at least one Group II metal oxide or hydroxide characterised in that the catalyst is initially activated by heating in said polyoxyalkylene alcohol in the absence of said amine while a gas stream comprising hydrogen is passed therethrough.
2. A method as claimed in claim 1 in which the hydrogen gas used in the activation of the catalyst consists of substantially pure hydrogen.
3. A method as claimed in claim 1 or claim 2 in which the polyoxyalkylene alcohol has the general formula R(OA) OH, wherein R is an alkyl, aryl or aralkyl group or mixtures thereof having 1 to 20 carbon atoms, A is an alkylene chain having from 2 to 20 carbon atoms and n is an integer from 1 to 20.
4. A method as claimed in any of the preceding claims in which the activation of said catalyst is carried out at a temperature between 150° and 250°C.
5. A method as claimed in any of the preceding claims in which the catalyst comprises a mixture of copper oxicje or hydroxide and a Group II metal oxide or hydroxide in a ratio of 2-6 parts by weight of copper oxide to 1 part by weight of the Group II metal hydroxide.
6. A method as claimed in any of the preceding claims in which the Group II metal hydroxide is selected from the group consisting of the hydroxides of calcium, barium and magnesium and mixtures thereof.
7. A method as claimed in any of the preceding claims in which the amination is carried out by reacting said secondary amine with the polyoxyalkylene alcohol containing the activated catalyst in suspension.
8. A method as claimed in claim 7 wherein the secondary amine is dimethylamine.
9. A method as claimed in claim 8 in which the dimethylamine is introduced as a gaseous mixture with hydrogen in the ratio 30-70% by volume of dimethylamine to 70-30% by volume of hydrogen.
10. A method as claimed in any of the preceding claims in which, after completion of the amination reaction, the reaction mixture is purified.
11. A method as claimed in any of the preceding claims in which the amount of catalyst is between
2-10% by weight based on the weight of the polyoxy¬ alkylene alcohol reactant.
12. A method as claimed in any of claims 1 to
9 in which the product is converted into a quaternary salt thereof.
13. A method as claimed in any of the preceding claims in which the alcohol is an alkylpolyoxyalkylene alcohol.
14. A method of aminating alkylpolyoxyalkylene alcohol with dimethylamine to yield an alkylpolyoxy¬ alkylene dimethylamine which comprises pre-treating the catalyst by heating it at a temperature of between about 170βC to about 220βC in the alcohol while recirculating a stream of pure hydrogen gas through the suspension, said catalyst comprising a mixture of copper oxide and a Group II metal hydroxide in a ratio of about 2-6 parts by weight copper oxide to about 1 part by weight of the Group II metal hydroxide, then changing the composition of the recirculating gas to a mixture of hydrogen and dimethylamine at a temperature of between 200°C and 220°C, then purifying the reaction products.
PCT/GB1988/000147 1987-03-02 1988-03-01 Amination of polyoxyalkylene alcohols WO1988006579A1 (en)

Applications Claiming Priority (2)

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US2039187A 1987-03-02 1987-03-02
US020,391 1987-03-02

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356046A2 (en) * 1988-08-18 1990-02-28 BP Chemicals Limited The reductive amination of hydroxy-containing compounds
FR2785607A1 (en) * 1998-11-09 2000-05-12 Rhodia Chimie Sa PROCESS FOR THE PREPARATION OF TRIS (ETHER-AMINE)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2928877A (en) * 1957-05-10 1960-03-15 Wyandotte Chemicals Corp Process for preparing oxyalkyleneamines
EP0057884A2 (en) * 1981-02-11 1982-08-18 BASF Aktiengesellschaft Process for the preparation of permethylated oligomeric amines and alkanol amines
US4404404A (en) * 1981-12-09 1983-09-13 Millmaster Onyx Group, Inc. Process for producing aliphatic amines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2928877A (en) * 1957-05-10 1960-03-15 Wyandotte Chemicals Corp Process for preparing oxyalkyleneamines
EP0057884A2 (en) * 1981-02-11 1982-08-18 BASF Aktiengesellschaft Process for the preparation of permethylated oligomeric amines and alkanol amines
US4404404A (en) * 1981-12-09 1983-09-13 Millmaster Onyx Group, Inc. Process for producing aliphatic amines

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356046A2 (en) * 1988-08-18 1990-02-28 BP Chemicals Limited The reductive amination of hydroxy-containing compounds
EP0356046A3 (en) * 1988-08-18 1990-10-03 BP Chemicals Limited The reductive amination of hydroxy-containing compounds
US5015773A (en) * 1988-08-18 1991-05-14 Bp Chemicals Limited Reductive amination of hydroxy-containing compounds
FR2785607A1 (en) * 1998-11-09 2000-05-12 Rhodia Chimie Sa PROCESS FOR THE PREPARATION OF TRIS (ETHER-AMINE)
WO2000027796A1 (en) * 1998-11-09 2000-05-18 Rhodia Chimie Method for preparing tris(ether-amine)
US6403834B1 (en) 1998-11-09 2002-06-11 Rhodia Chimie Method for preparing tris(ether-amine)

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