DE1768990A1 - Process for the alkoxylation of amines - Google Patents

Description

The invention relates to a process for the alkoxylation of primary and secondary amines. ·

In the previously known alkoxylation processes for amines, the reaction is carried out in the presence of basic catalysts such as alkali hydroxides or bicarbonates at an elevated temperature, usually above 100.degree. The reaction products obtained in this procedure are more or less strongly discolored, so that a physical or chemical aftertreatment, which in some cases can be quite expensive , is necessary to improve the color quality of the amine-alkylene oxide adducts. For the purpose of color enhancement of alkylene oxide adducts, the proposal has also been made to carry out the base-catalyzed alkylene oxide with the addition of antioxidants.

This measure allows, in the case of alkpxylation of amines, to achieve a relative improvement in the color of the products of the process; Viewed in absolute terms, however, the color quality of the amine alkoxylation products remains unsatisfactory even with this process.

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It has now been found that products with significantly improved Color quality is maintained if tertiary oxonium salts are used as catalysts for the alkoxylation.

These tertiary oxonium salts are of open-chain or cyclic ethers and compounds containing carbonyl groups derived compounds of the general formula

R ₂ -YR ₁

Here Y mean an oxygen atom or a C = O group, X is a not or only slightly polarizable halogen com-

- - P-plex anion, such as B. BF ^, AlCl ₁ ^, FeCl ₁ ^, SbCIg, SnCIg; R ₁

a lower aliphatic radical with 1-4 carbon atoms. R ₂ is a hydrogen atom or R ₂ and R are alkyl radicals with 1-24 carbon atoms, aromatic, alicyclic or heterocyclic ring systems with 3-14 ring atoms, R ₂ and R, can also be joined together to form rings with 4-14 ring atoms.

The alkyl radicals described can be saturated or unsaturated, straight-chain or branched, substituted, interrupted by heteroatoms or bonded to Y via heteroatoms. The alicyelic or heterocyclic ring systems can be saturated or unsaturated. Are R ₂

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and R, joined together to form a ring, this can optionally contain heteroatoms and also be saturated or unsaturated. All ring systems mentioned can Carry substituents.

As an example of the tertiary oxohium salts to be used according to the invention, the following could be mentioned:

Trimethyloxoniumfluoborat, Triäthylo'xoniumf luoborat, Triäthyloxoniumhexachloroantimonat, 1-ethyl-1-oxa-cyclopentaniumhexachloroantimonat, Tributyloxoniumhexachloroantimonat, 1- (4-chlorobutyl) -1-oxa-cyclopentaniumhexachloroantimonat, Trimethyloxoniumtetrachloroferrat, Trimethyloxoniumtetrachloroaluminat, Triäthyloxoniumtetrachloroaluminat, bis - (trimethyloxonium) -hexachlorostannat, ■ Triphenyloxoniumfluoborat, O-Sthylcampheroxoniumfluoborat, 2-ethoxy-i-oxa-cyclopent-i-eniumfluoborat, O-Xthyldibenzalacetoniumtetrachloroaluminat, Triäthylcarbonat-acidium-fluoborate, O-Äthyldimethylformimidiumfluoborat, * 2-ethoxy-1-thia-cyclopent-1-eniumfluoborat, 1 -Methyl-2-ethoxy-1-aza-cyclopent-1-enium fluorate, 2, ^ - Benzo-e-ethoxy-pyrylium fluorate, 2-methyl-1,3-dioxolenium fluorate, 2-phenyl-1,3-dioxolenium hexachloroantimonate, 2 -Sthoxy-1-oxa-cyclotridec-1-enium fluoborate. . .

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The use of tertiary oxonium salts in which the Y of the above formula represents the C = O group and R ₁ , Rg, R, and X have the meaning set out above, for example O-ethylcampheroxonium fluorate, 2-ethoxy-1- oxa-cyclopent-1-enium fluorate, O-ethyl-dibenzalacetonium tetrachloroaluminate and dialkoxycarbonium salts such as diethoxycarbonium fluoroborate, diethoxycarbonium hexachloroantimonate. The tertiary oxonium salts can be prepared by methods known from the literature (cf. Houben-Weyl, Methods of Organic Chemistry, Volume 6/5, 4th edition).

Saturated tertiary oxonium salts, in which the Y of the above formula symbolizes an oxygen atom, are for example by the action of metal and non-metal halide atherates on epoxides, addition of alky! halides to metal and Non-metal halide etherates, alkylation of ethers with haloalkylenes and silver tetrafluoborate as well as action aliphatic diazo compounds obtained on primary and secondary oxonium salts. The unsaturated tertiary oxonium salts, in which the Y of the above Formula represents a C = O group, are essentially obtained by alkylating carbonyl compounds with trialkyloxonium salts or alkyl halide silver tetrafluoroborate and represented by the action of boron trifluoride or antimony pentachloride on acetals and ortho acid esters.

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The isolated saturated or unsaturated tertiary oxonium salts are added to the amine to be alkoxylated in amounts of 0.05-5, preferably 0.1-1.5% by weight , based on the amount of amine used.

Serve as starting materials for the process according to the invention primary and secondary mono- or polyvalent aliphatic amines with preferably 2-22 carbon atoms, the alkyl radicals of which can be straight-chain, branched, saturated or unsaturated. Examples of such compounds include: monoethylamine, Diethylamine, n-propylamine, n-hexylamine, N-methylhexylamine, Hexamethylenediamine, n-dodecylamine, N-methyldodecylamine, Hexadeelamine, docosylamine, 3-aminooctane, 3-methyloctylamine-1, Oleylamine, eucylamine. The corresponding amine mixtures can also be used. As an example of this are in particular mention the amine mixtures obtained from natural fats in a known manner, e.g. B. cocoa amine, tallow amine.

Furthermore, they can contain cycloaliphatic or aromatic radicals Amines, for example cyclohexylamine benzylarain, can be used.

All substances containing epoxy groups are alkylene oxides suitable. Compounds with 2-4 carbon atoms are of particular interest. Examples of this are:

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Ethylene oxide, propylene oxide, butylene oxide. It can too substituted epoxides such as glycid and epichlorohydrin can be used.

These epoxides can be used individually or in a mixture with one another are attached to the amine. They can also be used one after the other in any order.

The amount of alkylene oxide to be deposited is arbitrary. For many purposes one will add so much epoxy that water-soluble products arise «whereby the amount of the to be deposited Alkylene oxides must be matched to the carbon number of the amine.

The alkoxylation process according to the invention can after addition of the tertiary oxonium salt to the amine to be reacted in the usual way Way to be carried out.

The temperatures to be used are in the range of O - 2oo C, preferably 3o - 160 ° C. Are unsaturated oxonium salts used as catalysts «so the implementation of the reaction at room temperature gives a high Degree of implementation

The response can as it be to shorten the response time is common to be carried out under increased pressure, wherein Press until loo atü are applied.

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However, it is also possible to work at normal pressure, since the reaction takes place at a satisfactory rate even at normal pressure runs.

The process can be carried out continuously.

The catalyst introduced can either remain in the end product or, after the reaction has ended, is hydrolytically cleaved and neutralized with alkali. After separation of about μ fallen salts and eingeschlepptem Removing water are crude products, which are virtually colorless and contained no undesirable by-products. In particular, the polyalkylene glycol ethers, which usually occur as a by-product in alkoxylations, are only present in the end product in minor amounts.

The process products can be used in many ways. You can e.g. B. as textile auxiliaries, as liquid or solid detergents
and detergents or as intermediates for various syntheses. ™

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example 1

In an autoclave, 59 g (1 mol) of n-propylamine were mixed with 0.12 g (0.2 percent by weight) of triethyloxonium fluoroborate under a nitrogen atmosphere offset. The autoclave was once again filled with nitrogen to remove residual oxygen from the air rinsed and the contents of the autoclave heated to 70 ° C. A second autoclave was then cooled with an ice-saline mixture 88 g (2 mol) of ethylene oxide pressed over with the aid of nitrogen. The pressures used were in the range of 2, ο to 5.6 atm. The pressure increase took place in stages so that the temperature could be kept in the range of 7 o to 1o5 C. The amount of ethylene oxide used had reacted after 4.5 hours. The process product was without further work-up practically colorless and resulted in the measurement in the Lovibond tintometer (4 cuvette, 2o ° C) the following parb numbers: yellow 1.1, red o, 4, blue 0. The color numbers of the Starting amines were yellow ο, 6, red ο, 1, blue 0. The polyethylene glycol content of the product, which was determined by separation via acidic ion exchangers in a known manner, was 0.2 wt .- ^.

Example 2

A mixture of 1o1 g (1 mol) of n-hexylamine and o, 2o g (0.2 percent by weight) triethyloxonium fluoroborate was in the manner described in Example 1 with a total of $ 2 g (2.1 mol) of ethylene oxide using pressures between o, 5 to 8.8 atmospheres reacted. The reaction temperature was in the range

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ο
Held at 70-92 C. The amount of ethylene oxide offered was absorbed after 3 hours. The reaction product had the Lovlbond Parb numbers (4 "cuvette, 45 ° C.): yellow 0.7, red 0.1, blue 0. The color numbers of the starting amine measured under the same conditions were: yellow 0.4, red 0, blue 0 The polyethylene glycol content of the product was 0.9 percent by weight.

Example 3

A mixture of 185 g (1 mol) of n-dodecylamine and 0.37 g ( 0.2 wt% weight percent) triethyloxonium fluoroborate was prepared analogously to Example 1 with 88 g (2. o mol) of ethylene oxide at pressures between 0.8 and 11, 5 atü implemented. The reaction temperature was in the range 73 - 78 ⁰ C maintained. The reaction was over after 5 * 3 hours.

The Lovibond color numbers of the reaction product were measured at 45.degree (V-cuvette) and had the values: yellow 2.9, red 0.7, blue 0. The corresponding values of the starting amine were: yellow 1.6, red 0.5, blue 0. The product contained 0.1 percent by weight

Polyethylene glycol. Ä

Example 4

Example 3 was repeated with the exception that the amount of ethylene oxide used was reduced to 44 g (1 mol). Pressure and temperature had practically the same values as in Example 3 (0.6-11.5 atüj 70-76 ° C). The specified amount of ethylene oxide was in Course recorded for 4.5 hours. The reaction product had

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- 1ο -

the Lovibond color numbers (4 "cuvette, 55 ° C) yellow 0.8, red 0.3 blue O. The Parb numbers of the starting amine measured in the same way were: yellow 0.6, red 0, blue 0. The product contained 0.7 percent by weight polyethylene glycol.

Example 5

Example 3 was repeated with the exception that the amount of ethylene oxide used was increased to 237 * 6 g (5 # 4 mol). At pressures between 0.5 and 6.5 atmospheres and temperatures between Jo and 75 ° C P, the amount of ethylene oxide mentioned was absorbed in the course of 4.5 hours. The reaction product had the Lovibond color numbers (^ "cell, 40 ° C.): yellow 8.7, red 1.7, blue 0. The color numbers of the starting amine measured in the same way were: yellow 1.2, red 0.3 , blue 0. The product contained 2.4 percent by weight of polyethylene glycol ether.

Example 6

In a manner analogous to the previous examples, | 93 g (1 mol) of aniline ethoxylated in the presence of 0.19 g (0.2 percent by weight) triethyloxoniurafluoroborate. At pressures between 0.9 and 10 atmospheres and temperatures between 74 and 79 ° C., a total of 92 g (2.1 mol) of ethylene oxide were added on in the course of 2.8 hours. The Lobibond color numbers (4 ^M cuvette) of the product measured at 50 ° C. were: yellow 27, ο, red 7.4, blue 0. The color numbers of the starting amine measured in the same way were: yellow 27, o, red 13, o, blue 0. The reaction product contained 0.2 percent by weight of polyethylene glycol.

209812/170 "2 ¹¹ "

Example 7

A mixture of 116 g (1 mole) 1,12-diaminododecane and 0.23 g (0.2 percent by weight) Triethyloxoniumfluoroborat was analogous to Example 1 with 176 g (4 mol) of ethylene oxide at pressures between 0.6 and 8 atü and temperatures between 75 and 78 ° C implemented. The amount of ethylene oxide mentioned was absorbed after 3.8 hours. The reaction product had the Loyibond color numbers (4 "cuvette, 80 ° C.) yellow 5.7, red 2.2, blue O. Those measured in the same way Color numbers of the starting amine were: yellow 3 * 6, red 0.8, blue 0. The product contained 0.2 percent by weight of polyethylene glycol.

Example 8

Analogously to Example 1, a mixture of 146.2 g (1 mol) of triethylenetetramine was added and 0.29 grams (0.2 percent by weight) of triethyloxonium fluoroborate using pressures between 0.6 and 13 atmospheres 268.4 g (6.1 mol) of ethylene oxide added on. The temperature was maintained in the range between 73 and 95 ° C. The amount of ethylene oxide mentioned was recorded over 6.5 hours. The reaction product had the Lovibond color numbers (4 "cuvette, 20 ° C) yellow 27.9 * red 11, o, blue 0. Those measured in the same way The color numbers of the starting amine were: yellow 23.0, red 1.5 * blue 0. The reaction product contained 0.5 percent by weight of polyethylene glycol.

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Example 9

59 S (1 mol) of n-propylamine were placed in an autoclave and 12 g (0.2 percent by weight) of triethyloxonium fluoroborate were added under a nitrogen atmosphere. After removing the remaining oxygen from the air by flushing with nitrogen, the contents of the autoclave were heated to γ1 ° C. 116 g (2 mol) of propylene oxide were then injected from a second autoclave with the aid of nitrogen, a pressure of 2.1 atmospheres being applied initially, which was increased to 17 atmospheres in the course of the reaction. The pressure was increased in stages in order to keep the reaction temperature in the range 71-1o4 ° C. The stated amount of propylene oxide was absorbed in the course of 12.5 hours. The Lovibond Parb numbers of the reaction product were measured using a 4 "cuvette at 20 ° C. and had the values: yellow 5.7, red 1.2, blue O. The color numbers of the starting amine measured in the same way were: yellow o, 6, red 0.1 , blue 0. The product contained 0.2 percent by weight of poly propylene glycol.

Example 1o

107 g (1 mol) of benzylamine were mixed with 0.21 g (0.2 percent by weight) of O-ethylcampheroxonium fluoroborate in an autoclave under a nitrogen atmosphere. After three times of evacuation and flushing with nitrogen, the autoclave was heated to 47 ° C. Then a second, with ice-cream cooking

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salt mixture cooled autoclave 92 g (2.1 mol) of ethylene oxide with the aid of nitrogen, pressures of initially 0.5 to 7> 4 a tu were applied. The pressure increase took place in stages, so that the reaction temperature could be kept in the range kj-90 ° C. The stated amount of ethylene oxide was absorbed after 3 * 1 hours. The Lovibond color numbers of the reaction product were measured using a 4 "cuvette at 20 ° C. They had the values: yellow 3.1, red 0.5, blue 0. The color numbers of the starting amine measured in the same way were: yellow o , 8, red o, 1, blue 0. The reaction product contained 0.2 percent by weight of polyethylene glycol.

Example 11

1o1 g (1 mol) of n-hexylamine were mixed with 0.3o g (0.3 percent by weight) of O-ithylcampheroxonium fluoroborate in an autoclave under a nitrogen atmosphere and the contents of the autoclave were heated to 41.degree. 116 g (2 moles) of propylene oxide with the aid of nitrogen were handed over t presses then a second autoclave, wherein the pressure of initially o, 5 up to 16.5 atm was increased and the temperature range was 41-55 C. The stated amount of propylene oxide was absorbed after 15 hours. The Lovibond color numbers of the reaction product measured using a V-cell at 20 ° C. were: yellow ο, 3, red 0, blue 0. The color numbers of the starting amine measured in the same way were: yellow 0.4, red 0, blue 0 The reaction product contained 0.2 percent by weight polypropylene glycol.

209812 / 1702.4 _m

- 14 Example 12

A mixture of 185 g (1 mol) n-dodecylamine and 0.37 g (0.2 Weight percent) O-ethylformimidium fluoroborate was analogous Example 1 reacted with 88 g (2 mol) of ethylene oxide at pressures between 2.3 and 9.2 atu and temperatures between 68 and 74 ° C. The reaction was over after 8.5 hours. The Parb numbers measured using a 4 "cuvette at 45 ° C of the reaction product were: yellow 3.1, red 0.8, blue O. The Color numbers of the starting amine measured in the same way were: yellow 1.6, red 0.5 * blue 0. The reaction product contained 0.3 weight percent polyethylene glycol.

Example 1 ^ (comparative tests)

The same substances as in the previous examples were in the usual manner in the presence of basic catalysts reacted with ethylene oxide or propylene oxide.

In each case 1 mol of the amine in question was placed in an autoclave and treated with as much 30 # sodium methylate solution assumes that ο.2 percent by weight sodium, based on the amount of amine used, was present in the reaction mixture. The ins Methanol introduced into the reaction mixture was removed by evaporation in vacuo. In the parts where the boiling points of If the amine and methanol used were too close together, the catalyst was used in the form of solid sodium methylate. The reaction mixture was then heated to the respective reaction temperature and the alkylene oxide to the same

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Way fed as in previous examples. The temperatures and pressures used in the implementation, as well as the The implementation time and the properties of the respective reaction product are summarized in the following overview:

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Starting amine

Reaction conditions

Alkylene oxide MoI alkylene temp. C oxide per mole amine pressure atU

Reaction product

Lovibond color 4 "Ku numbers vette time yellow red blue measurement weight%

Hrs. ° C Poly-

glycol content

n-Propylamine (Lovibond FZ 2o ° C: yellow ο, 6, red o, 1 blue O)

n-Propylamine (Lovibond-FZ 2o ° C: yellow ο, 6, red o, 1 blue O)

n-Hexylamine (Lovibond FZ 45 ° C: yellow ο, 4, red O, blue O)

n-Hexylamine (Lovibond FZ 2o ° C: yellow ο, 4, red O, blue 0)

Ethylene oxide

Propylene * oxide

Ethylene oxide

Propylene oxide

n-Dodecylamine (Lovibond FZ Ethylen-55 C: yellow 0.6, oxid red 0, blue 0)

1.9

1.9

1.8

2.0

1.1

128-160 5.8-16.5 3, o 2.1 0.6 0 2o

1.1- 9.0 3.0 27.0 5.4 0 2o 0.6

128-156 0 - 5.6 2.2 6.7 1.2 0 45 0.8

15Ο-154 1.5- 8.8 9.8 12, o 2, ο Ο 2ο ο, 2

150-156 1.2- 8.5 2.2 5.7 ο.8 O 55. 2.7

Q6689U

Reaction conditions reaction product

Starting amine

Alkylene oxide moles of alkylene temp. C oxide per mole of amine

Lovibond-Parb- 4 "Kü
pay vette

Pressure atu time yellow red blue measurement wt. % Hrs. ⁰ C poly-

glycol content

1-dodecylamine
(Lovibond PZ ethylene-45 ° C yellow 1.6, oxid
red 0.5 blue

L-dodecylamine

Lovibond PZ ethylene-4o ° C, yellow 1.2, oxide red 0.5, blue
0)

3enzylamine

(Lovibond FZ ethylene-2o ° C yellow 0.8, oxide red o, 1, blue 0)

aniline
(LovibondPZ
5o C: yellow
27, ο, red 15, o,
blue 0)

Ethylene oxide

1,12-diamino

dodecane ethylene

(Lovibond FZ oxid

80 ⁰ C: yellow 5.6,

red 0.8, blue 0)

rriäthylenetetra- ethylene, -min (Lovibond FZ ^oxld 2o yellow 25, ο, red
1.5, blue 0)

2, o

6.0

, 9

2.0

4, o

5.9

128-152, 1-1o, 1 5.0. 9.0. 1.6 0 45 2.4

150-155 1, o-12.5 5, o 27.9 16.2 1, o 4o

152-154 o, 6-11, o 5.0 6.0 0.6 0 2o

120-156 1.1-1o, 5 2.8 27, o 17.0 1.5

152-155 1.4-1o, o 4.5 7.0 2.2 1.2 80 0.5

150-154 1.1-15.2 6.0 27, o 24, o 1.1 2o 0.6

Q6689U

.18-17G8990

The advantages that can be achieved with the invention are, in particular, that the alkoxylation products of amines are of good color quality can be obtained without the need for special purification operations or further apart from the catalyst chemical substances must be present in the reaction medium. Particularly noteworthy is the low polyalkylene glycol content the process products, which are usually more favorable than that achieved in the customary base-catalyzed alkoxylation.

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Claims (1)

PATENT CLAIMS 1. Process for the alkoxylation of primary and secondary Amines, characterized in that tertiary oxonium salts are used as catalysts. 2. The method according to claim 1, characterized in that alkylene oxides having 2-4 carbon atoms are used. J. The method according to claim 1-2, characterized in that tertiary oxonium salts of the formula R ₂ -YR ₁ in which Y is an oxygen atom or the C = O group, X is a halogeno complex anion, R _{1 is} a lower aliphatic radical with 1-4 carbon atoms, R _{2 is} hydrogen or R ₂ and R, alkyl radicals with 1-24 carbon atoms, aromatic , all- λ mean cyclic or heterocyclic ring systems with 3-14 ring atoms or are joined together to form rings with 4-14 ring atoms, can be used. - 2o - 209812/1702 - 2ο - 4. The method according to claim 1 - Z> » characterized in that tertiary oxonium salts of the formula R ₂ - C = O - in which X is a halogeno complex anion, R .. a lower ali-P phatic radical with 1-4 carbon atoms, Rp hydrogen or Rp and R ^ alkyl radicals with 1-24 carbon atoms, aromatic, alicyclic or heterocyclic ring systems with 5-14 ring atoms or to rings with 4-14 ring atoms are grouped together. 5. Method according to claims 1-4, characterized in that the catalyst in amounts of 0.05-5 *, preferably 0.1-1.5 Percentage by weight, based on the amount of amine, is used. 6. The method according to claim 1-5 *, characterized in that the starting materials preferably have primary and secondary amines Are 2-22 carbon atoms. - 21 - 209812/1702 7. The method according to claim 1-6, characterized in that the implementation at temperatures between 0 and 2oo ° C, preferably 3o - 16o ° C is carried out. HSNKSL & CIS. (Dr. Ha »·) (Zuriegl) 209812/1702