DE1198555B - Process for the preparation of polyoxy-alkylated N- (tert-alkyl) -amines - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

C08g

German class: 39 c-13

1198 555
R28425IVd / 39c
July 28, 1960
August 12, 1965

It is already known that tertiary amines can be reacted with ethylene oxide or propylene oxide (USA patent 2 871266). The reaction of amines with propylene oxide and ethylene oxide has already been described.

The invention relates to a three-stage combination process for the preparation of polyoxyalkylated N- (tert-alkyl) -amines by reacting N- (tert-alkyl) amines of the general formula

R ₂ -C-NH ₂

R ₃

in which R ₁ , R ₂ and R _{3 are} alkyl radicals with a total of 7 to 23 carbon atoms, with ethylene oxide and then with propylene oxide, characterized in that one

a) the N- (tert-alkyl) -amines in a solution of water and methanol by reaction with Ethylene oxide converted into the corresponding mono- or dioxyethyl derivatives,

b) immediately thereafter the oxyethyl derivatives obtained in a known manner by further Reaction with ethylene oxide in the presence of basic catalysts converted into products, the 15 to 45 moles of ethylene oxide obtained, and

c) immediately afterwards the products obtained with 15 to 67.5 moles of propylene oxide in The presence of alkaline catalysts reacts, the ratio of the total propoxy groups adjusted to the total ethoxy groups in the end product to 1: 1 to 1.5: 1 will.

The invention is based on the combination effect of the three process steps a), b) and c). For the individual Independent protection is not claimed.

In the first stage, a solution of water and methanol is used, with either the monooxyethyl derivative of the formula

R ₁ R ₂ R ₃ CNH-CH ₂ CH ₂ OH I

or the dioxyethyl derivative of the formula

Process for the preparation of polyoxyalkylated N- (tert-alkyl) -amines

Applicant:

Rohm & Haas Company, Philadelphia, Pa.

(V. St. A.)

Representative:

Dr.-Ing. Dr. jur. H. Mediger, patent attorney,

Munich 9, Aggensteinstr. 13th

Named as inventor:

Fred Easterday Boettner,

Huntingdon Valley, Pa .;

Jean Dupre, Levittown, Pa. (V. St. A.)

Claimed priority:
V. St. v. America August 10, 1959
(832503)

or a mixture of both, possibly with any unreacted primary amines, is obtained.

In the latter case, the components can be separated and the mono- and bis-derivatives can be separated React with further amounts of ethylene oxide, or the crude> is oxethylated Reaction product immediately further. In both cases, basic catalysis is used and the final stage is the molar ratio Reached 15: 1 to 45: 1 from ethylene oxide to amine.

The intermediate product mixture obtained in this way consists mainly of tertiary amines the general formula

r ₂ —c — n:

R ₃

, (C ₂ H ₄ O) ₀ H
XC ₂ H ₄ O) ₆ H

R ₁ R ₈ R ₃ CN:

XH ₂ CH ₈ OH

CH ₂ CH ₂ OH

However, if the initial reaction product contains a relatively large proportion of

R ₁ R ₂ R ₃ CNHCH ₂ CH ₂ OH

509 630/443

so the intermediate product can largely consist of a body with a single polyglycol chain structure

R ₁ R ₂ R ₃ CNH (C ₂ H ₄ O ^ H
exist.

Propylene oxide is added to the reaction products thus obtained, and in the presence of one basic catalyst led the reaction to an end product which on average 15 to Contains 67.5 moles of propylene oxide per amino group.

In this way, polyoxylalkylated N- (tert-) amines of the formulas are obtained

R ₂ -C- NH (C ₂ H ₄ O) _n (C ₃ H ₆ O) ₆ H IV

j, (C ₂ H ₄ O) ₁₁ (C ₃ H ₆ O) ₆ H

R ₂ -CN ^ V

I ^X (C ₂ H ₄ O) ₀ (C ₃ H ₆ O) ₁ JH

In these formulas, R ₁ , R ₂ and R _{3 represent} alkyl groups containing a total of 7 to 23 carbon atoms; α is an integer from 15 to 45, b is a number from 15 to 67.5, while in the formula V a + c is an integer from 15 to 45, b + d is a number 3 <, from 15 to 67, 5 means.

The ratio b: α or the ratio

(b + d): (a + c)

has a value from 1: 1 to 1.5: 1.

In formula V, α and c on the one hand and b and d on the other hand can represent the same or different numbers.

Preferred compounds of the general formula IV or V are those in which the carbon number of R ₁ + R ₂ + R _{3 is} 11 to 14 and a or (a + c) has a value of 20 to 35 and b or (b + d ) has a value from 20 to 45.

For the preparation of the polyoxyalkylated N- (tert .-) - amines all available on the market are suitable N-tert-alkylamines with a total of 8 to 24 carbon atoms. You can essentially choose from one single compound or predominantly mixtures of isomers, homologues or both be.

For example, tert-octylamine (primary), 2-amino-2,4,4-trimethylpentane, tert-tridecylamine, iso-C ₈ H ₁₇ (C ₂ H ₅ ) ₂ CNH ₂ and commercially available mixtures of tert. -Alkyl (primary) amines, such as C ₁₂ H ₂₅ NH ₂ to C ₁₅ H ₃₁ NH ₂ and C ₁₈ H ₃₇ NH ₂ to C ₂₄ H ₄₉ NH ₂ , which are derived from hydrocarbon fractions of corresponding orders of magnitude.

These tertiary amines correspond to the general formula

R ₁

R ₂ -C-NH ₂

VI

R ₁ , R ₂ and R ₃ have the meanings given above. The smallest tertiary amine is an octylamine, the largest a tetrakosylamine.

Between that disclosed in U.S. Patent 2,871,266 described method and the method according to the invention there are notable differences. For example, the patent only shows the preparation of a polyoxyalkyleneamine which is characterized by a monolinear chain of oxyalkylene groups. According to the invention Polyoxyalkyleneamines are made that have either a monolinear chain or di-linear chains of oxyalkylene groups or a mixture of both. The reaction of the alkylene oxide with the tertiary amine can be controlled by the choice of starting material and the concentration of the catalyst used so that predominantly either single-chain or double-chain polyglycol derivatives arise.

Another important difference compared to the prior art is that according to the Invention which products distinguished by surprising properties can only be obtained if you first add the ethylene oxide. One starts with the addition of propylene oxide or If a mixture of ethylene oxide and propylene oxide is used, products are obtained which are in the Compared to the products of the invention, they tend to foam much more and practically at all have no defoaming effect.

The determination of the foam suitability is carried out according to Hamilton-Beach in an electrically driven Mixing device inserted into a glass tube closed at the bottom. Four baffles stainless steel are arranged vertically in the pipe. The glass tube is immersed in a water bath, which is set to the respective test temperature (15 to 30 ° C) with an accuracy of 0.5 ° C is. The mixing blades are arranged centrally in the glass tube, with the upper blade approximately 12.5 mm above the surface of the solution. 200 ecm of a 0.1% test solution are applied to the Temperature set and then for three minutes at high speed (14500 revolutions per minute) mixed. Then stop the mixer and determine the after 15 seconds Foam height. Each test is carried out twice. A foam height of less than 5.5 cm is considered permissible, Products that give higher foam heights are discarded.

The stain test is carried out by a method commonly used in the industry. Five clean test drinking glasses with a capacity of 280 ecm and ten other glasses are treated several times in a dishwasher. The glasses are placed on the upper bar, while the lower bar is loaded with six dinner plates with a diameter of 22.5 cm, which are smeared with a total of 60 g of test soiling (made from 4 parts oleomargarine and one part milk powder). In addition, eight unsoiled salad plates with a diameter of 15 cm are placed on the lower bar. All plates and glasses are left in certain positions from test to test. At each washing cycle consists of 5 minutes of washing and twice one minute rinse, 40 g (0.45%) are added to the detergent recipe in 8.61 of water (hardness 250 x 10 ~ ⁶⁾ and connected to a hot air drying 25 minutes.

To evaluate the stain test, the stains are counted which have a larger diameter

have a diameter of more than 3 mm, and any deposits of fog or dirt are observed and judges the general appearance. The five test glasses are placed in a darkroom with fluorescent Investigated light. This procedure is considered to be one cycle. Each product comes in ten such Cycles tested using the same five glasses with no additional cleaning between cycles will. After each cycle, the test glasses are pushed one place on the bar and rotated by 90 ° of its axis. If all variables are carefully kept equal, such as pre-cleaning the Glasses, water temperature, production of test pollution, addition of detergent, etc., sufficiently reproducible test results can be obtained.

A detergent that does not leave more than five hundred stains after ten cycles in this test, is considered satisfactory.

Serious foam problems are caused by foods that contain protein, such as egg, milk and flour, caused because these contribute to the fact that relatively large amounts of air in the water sprays be included. At higher concentrations, foam can also be replaced by greasy or oily soiling.

The defoaming test for food soiling is done in a dish washer executed in which the Gseehwihdigkeit of the rotor functionally on the amount and type of foam depends. If foam is pumped into the rotor, the rotor is accelerated less than by air-free water and it therefore runs slower.

The cleaning agent with the surface-active agent to be tested is added to the machine, and one lets them fill up. As soon as the spraying starts, the machine is briefly stopped and switched on Whole fresh egg or other contamination added. Then you let the spraying keep walking. After the second, third and fourth minute, the spray rotor rotates each counted for a period of 30 seconds. On three such counts the average will be Circulation number calculated. For the test soiling mentioned in the table below, this rotation number can reach at least 95 for the surfactant to be useful. For Soiling with egg, flour or milk is sufficient with the specified concentrations of the surface-active With a minimum score of 45.

From the table it can be seen that the products prepared according to the invention (No. 1 to 11) characterized by the properties required for the present special purpose, while the Known products (Nos. 12 to 15) of one or the other not falling under the invention Basically all are unsuitable for this purpose. Because, for example, with products 12 and 13 the If the content of oxyethylene and oxypropylene groups is too low, both products fail in the defoaming test and the product 12 also in the stain test. Because the product 14 has too high a content of oxyethylene and oxypropylene groups, it fails in the stain test.

Because in product 15 the oxypropylene chain is in the middle and the oxyethylene chain is at the end it fails both in the foam test and in the defoaming test with egg.

The product 16 corresponds to a well-known commercially available ethylene oxide surfactant and propylene oxide, the oxypropylene chain representing the hydrophobic part. It's bad in the stain test and defoaming test, although its low foam development might suffice.

In the table and the examples means

t-amine = products according to formula IV and V,

E = oxyethylene,

P = oxypropylene,

a = predominantly monolinear,

b = predominantly dilinear,

c = commercial product made from block copolymers of ethylene oxide and propylene oxide, which has approximately 9 parts of units
E ₅ P ₃₀ E ₅ and 1 part E ₂ P ₃₀ E ₂ contains.

The test soil consists of 0.67% (60 g) of a mixture of 4 parts by weight of oleo margarine and 1 part by weight milk powder, and 0.45% (40 g) detergent, consisting of 2% of the test surfactant and an alkaline base of approximately 34% sodium tripolyphosphate, 43% sodium silicate pentahydrate and 23% sodium carbonate.

The contamination with egg or flour consists of 0.11% (10 g) whole egg or flour, 0.30 (27 g) a cleaning agent consisting of 1.25% of the surface-active agent to be tested and the alkaline base specified above.

The milk contamination consists of 0.22% (20 g) dry milk, 0.30% (27 g) a cleaning agent, consisting of 0.67% of the surface-active agent to be tested and the alkaline agent specified above Basis.

Primarily, the products of the invention are for use in automatic dish washing machines determined and suitable. They can also be used in conjunction with alkaline ones Detergents are very effective in removing oil from steel surfaces. Because of their extremely low They are also recommended for the alkaline spray cleaning of metals with a tendency to foam. Because of her defoaming effect they come into consideration wherever this property is meaningful, z. B. in connection with protein solutions, boiler feed water solutions, other surface-active substances Agents, resin-based coating compositions and the like.

The following examples illustrate the process of the invention. The parts are parts by weight.

Manufacture of the first stage products
Procedure

1 a) A stainless steel autoclave, 21 capacity, equipped with a heating coil, stirrer, pressure valve and inlet pipe is charged with 500 g of a commercially available mixture of tertiary amines with 12 to 15 carbon atoms (predominantly tert-C ₁₂ H ₂₅ NH ₂ and with Neutral equivalent 196) and connects a small cylinder with ethylene oxide to the inlet pipe via a valve.

58 g of methanol and 46 g of water are added to the autoclave, it is closed, the stirrer is turned on and the temperature is increased to 80 ° C, the small cylinder is charged with 330 g of ethylene oxide, connected to the inlet pipe and heated in a warm water bath, so that a valve pressure of 9 to 13.5 kg per 6.25 cm ^{2 is} maintained.

To remove the air, the autoclave is ventilated once and then the valve from the cylinder to the autoclave is opened to allow the ethylene oxide to flow in. The feed rate is adjusted so that the temperature in the autoclave is from 80 to 85 ° C. and the pressure is from 4.5 to 9 kg per 6.25 cm ² . For this purpose, the autoclave must be cooled until after 2 hours the entire amount of ethylene oxide has been added. The valve on the cylinder is now closed, heated for a further 2 hours at 80 to 85 ° C., then cooled to room temperature and vented to normal pressure.

The autoclave is opened, its contents are placed in a distillation vessel, removed at a reduced rate Pressure methanol and water until no at a temperature of 100 ° C and a pressure of 15 mm Hg More distillate passes over, then cools to room temperature, filtered and receives 825 g of a light amber-colored Oil, which is a mixture of mono- and bis-oxyethyl-tert-alkylamines with the Neutral equivalent is 253.

Ib) 300 parts of the product obtained according to a) are distilled under vacuum in a fractionating column packed with glass screws and having a height of 20 cm and a diameter of 1.25 cm. A fraction of 94 parts of practically pure tC ₁₂ H ₂₅ NHCH ₂ CH ₂ OH is obtained, which boils at 0.25 mm Hg between 88 and 103 ° C, the neutral equivalent 238 (theoretical 230) and the refractive index «) 1.4630.

Ic) The distillation of b) is continued and, after various intermediate runs, 120 parts of a fraction which boils at 145 to 150 ° C. and 0.1 mm Hg are obtained. It is practically pure tC ₁₂ H ₂₅ N (CH ₂ CH ₂ OH) ₂ with the neutral equivalent 278 (theoretically 274) and the refractive index 1.4730.

example 1

tC _12-15 H _{25th 31} NHE ₅ P _;

15th

253 parts (1 mol equivalent) of the product from the first stage of process (la) are mixed in 2.0 parts of flaky sodium hydroxide, heated to 130 ° C. under nitrogen, ventilated the apparatus three times with nitrogen and introduces a slow stream of ethylene oxide. The temperature is left at 150 rise to 180 ° C, the ethylene oxide turns off as soon as 603 parts of ethylene oxide according to the increase in weight are added, and begins with the supply of propylene oxide at 140 to 150 ° C, to 870 parts of the same are included.

The reaction product is then cooled and the catalyst is neutralized by adding 12.2 parts 20% sulfuric acid, heated to remove the water and filtered through a pack of kieselguhr. A water-soluble, slightly amber-colored liquid is obtained. An old solution of the same in water is clear below 24 ° C and becomes cloudy above this temperature.

Example 2

You work according to example 2 with the following changes: The catalyst used is 5.6 parts of potassium hydroxide and drives the addition of Ethylene oxide up to the absorption of 1923 parts of ethylene oxide, then propylation with 3918 Parts of propylene oxide. It is neutralized with 9.8 parts of 50% sulfuric acid. Has in 1% solution the product has a cloud point of 25 ° C.

Example 3

The procedure is as in Example 2, but using 238 parts of the product of the first stage in accordance with (Ib) and leads to the addition of ethylene oxide up to the absorption of 616 parts, the addition of propylene oxide continued up to the inclusion of 1160 parts. Cloud point 16 ° C in 1% aqueous solution.

Example 4

, E ₀ P ₆

Example 4 is used with 280 parts of the product of the first stage according to (1c) and a product C ₁₂ H _{25 of} the above formula, where a + c is 16 and b + d is 20, is obtained.

Example 5

600 parts (2 parts by molecular weight according to analysis) of a commercial mixture of tertiary are mixed Amines with 18 to 24 carbon atoms with 36 parts of water and 500 parts of isopropyl alcohol, treated in the autoclave according to (la) with 106 parts (2.4 mol) of ethylene oxide and obtained 700 parts of reaction product.

Using the method of Example 2, 70 parts (0.2 mol) of this product and 0.8 parts are used NaOH with 176 parts of ethylene oxide and 348 parts of propylene oxide. The product yields at temperatures below 30 ° C a slightly hazy solution, which becomes very cloudy above 30 ° C.

Example 6

A mixture of 6 parts of 2-amino-2,4,4-trimenthylpentane, 80 parts, is treated according to (la) Water and 280 parts of menthanol with Etayleribxyd until 368 parts of the same are added drives off water and methanol and distilled in a fractionation column, the following Fractions are caught:

fraction

link

Parts by weight

Boiling range
(° C / mm)

Neutral equivalent
found theoretically

tC ₈ H ₁₇ NHCH ₂ CH ₂ OH
^ C ₈ H ₁₇ N (CH ₂ CH ₂ OH ₂ )

66 to 92 / 0.5
122 to 125 / 0.25

179
219

179
223

Fraction A is a liquid with a refractive index of 1.4580, fraction B is solid and melts at 50 to 51 ° C.

As in Example 2, 219 parts of fraction B are reacted with 1540 parts of ethylene oxide and 2030 parts of propylene oxide, and the above-mentioned product in which a + c is 35 and b + d is 45 is obtained.

Example 7.

^t - ^C 12-15 ^H 25-31 ^NHE 35 ^P 45

235 parts of the product of the first stage according to (la) and 5.6 parts of KOH are processed according to Method of Example 2 with 1483 parts of ethylene oxide and 2610 parts of propylene oxide. The product obtained of the formula given above has a cloud point of 21.5 ° C. in 10% aqueous solution.

Surface active agent

Hamilton

Beach foam test

(0.1% /

15 seconds /

50 ⁰ C)

Defoaming test (52 to 5 ' egg flour ' ⁰ C) Test ver
pollution 46 45 milk 101 47 95 107 95 71 68 108 72 73 104 106 75 108 93 91 105 93 86 102 91 93 106 70 73 38 37 91 83 44 100 18th 28 39 58 40

Stain test

1. t-amine E ₁₅ P ₁₅

2. t-amine E ₁₅ P ₂₀

3. t-amine E ₁₅ P ₂₀ (a)

4. t-amine E ₁₅ P ₂₀ (b)

5. t-amine E ₂₀ P ₂₀

6. t-amine E ₂₀ P ₃₀

7. t-amine E ₂₅ P ₂₅

8. t-Amine E ₃₅ P ₃₅

9. t-Amine E ₃₅ P ₄₅

10. t-amine E ₃₅ P _52s2

11. t-amine E ₄₅ P ₆₇ , ₅

12. t-Amine E ₈₄ P _9i3

13. t-amine E _12i5 P ₁₂

14. t-AminE ₆₀ P ₈₀

15. t-amine P ₁₉ E ₂₀

16. E-P block copolymers (c)

Claims (1)

Claim: 0.0 0.0 0.0 0.0 0.0 0.1 0.0 1.8 1.6 11.0 1.0 35 Process for the preparation of polyoxyalkylated N- (tert-alkyl) -amines by reaction of N- (tert-alkyl) amines of the general formula R ₂ -C-NH ₂ 45 in which A ₁ , R ₂ and R _{3 are} alkyl radicals with a total of 7 to 23 carbon atoms, with ethylene oxide and then with propylene oxide, characterized in that one a) the N- (tert-alkyl) amines in a solution of water and methanol are satisfactory by reaction
satisfactory
satisfactory
satisfactory Well Well Well Well Well Well
satisfactory unsatisfactory satisfactory
unsatisfactory unsatisfactory converted with ethylene oxide into the corresponding mono- or dioxyethylene derivatives, b) immediately afterwards the oxyethyl derivatives obtained in a known manner further reaction with ethylene oxide in the presence of basic catalysts converted into products that 15 to 45 mol Contain ethylene oxide, and c) immediately afterwards the products obtained with 15 to 67.5 mol of propylene oxide in the presence of alkaline catalysts, the ratio of the total Propoxy groups to the total ethoxy groups in the end product to 1: 1 to 1.5: 1 is set. Considered publications:
U.S. Patent No. 2,871,266;
British Patent No. 443,632. 509 630/443 8.65 © Bundesdruckerei Berlin