DE1495620A1 - Process for the preparation of monocarboxylic acid amides - Google Patents

Description

Esso Research and Eng. Co,

Esso xiesearch and Engineering Company Linden, New, Jersey

Process for the preparation of idonocarboxamides

Prior: Jan 13, 1964 U.S. 3 series. No. 337 187

The present invention relates to a method of manufacture of I.onocarboxamides by reacting an aliphatic monocarboxylic acid with an aliphatic polyamine.

A process for the preparation of reaction products from monocarboxylic acids is already known. It will be there however Acids are used that contain 18 to 3o carbon atoms. Such Relatively low molecular weight acids are iaht suitable as dispersants in petroleum fractions.

Another known process relates to the production of dispersants from dicarboxylic acids. Ea becomes a mixture of there Materials used, for example, from hemiamides, diamides and. Imiden consists

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In the process according to the invention, on the other hand, a high molecular weight acid, which has been prepared by reacting a C 4o - C25o ~ polymer from Ö2 to C ₁ monoolefins with an α, ß-unsaturated monocarboxylic acid containing 3 to 8 carbon atoms, is brought into a molar acid Ratio of polyamine to high molecular weight acid between Ί: 1 to 1: 5 for conversion.

alo / · ■

It is preferable to use / high molecular weight acid such as which one by reaction of an olefin polymer, which initially so halogenated that there are 1 to 2 halogen atoms per molecule of the Contains olefin polymer with an unsaturated monocarboxylic acid in a proportion of 1 to 2 moles of unsaturated monocarboxylic acid per mole of polymer

The high molecular weight acid used can also be one which is obtained by reacting the non-halogenated olefin polymer with the unsaturated monocarboxylic acid with simultaneous halogenation

But you can also use one made of acrylic acid and a polyisobutylene Use formed high molecular weight acid, tetraethylene pentamine being used as the polyamine. ■ - ■

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The preferred starting materials for the production of the homo-molecular monocarboxylic acids used according to the invention are polymers of C ₂ - We C ^ monoolefins, ZcB. Polyethylene, polypropylene or polyisobutyylene, the olefin polymers having an average molecular weight of about 600 to 1000. Particularly valuable products are obtained when the molecular weight of the polyolefins is around 800 to 19ΟΟ *. Such polymers contain about 40 to 250, preferably about 30 to 120 carbon atoms in the molecule. Such a polymer is halogenated with bromine or chlorine, preferably with chlorine, using a sufficient amount of halogen to include about 1 to 2 atoms of halogen in each molecule of the olefin polymer. The halogenation can be carried out in the range from room temperature to about 20 ° C. To facilitate the halogenation, the polymer can be dissolved in a solvent, such as carbon tetrachloride, in order to reduce its viscosity, even if the use of a solvent is not absolutely necessary.

The time required for halogenation depends on a certain «radο of the speed with which that Halogen is supplied. Usually about 2 to 5 hours are sufficient for this. With typical large-scale chlorination There are polyisobutylenes with a molecular weight of 830

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In an aneate of 45 kg polyisobutylene at a chlorination temperature of about 120 ° 0 in the course of τοη 3 1/2 hours 4 »5 kg Chlorine initiated.

The halogenated polymerizate obtained becomes old one. α-Unsaturated Munooarboxylic acid oils 1 oils 8 carbon atoms condensed. In general, monocarboxylic acids old 3 or 4 carbon atoms in NolekUl are used for this purpose, since they are more readily available bind. This subheading includes acrylic acid, α-methyl ayleic acid (ie 2-methylpropenoic acid) and crotonic acid or isoorotonic acid (ß-methylacrylic acid). Other α, β-unsaturated nonooarboxylic acids which can be used according to the invention are tiglinic acid (ec-methylorotonic acid), angelloaic acid (α-methyllsoorotonic acid), sorbic acid and cinnamic acid. If necessary, their esters such as β.B. can also be used instead of the free acids. Metheory acid ethy ester, can be used.

In the condensation of the halogenated polyolefins or the unsaturated monooarboxylic acid, the latter is used in an amount of at least 1 mol per hol halogenated polyolefins. Of course, the acid is used in excess of up to about 1.5 to 2 moles of carboxylic acid per mole of halogenated polyolefin. The condensation temperature is around 150 to 260 ° 0, Torsugswelse around 190 to 246 ° 0. 01s Condensation can last from 3 to 24 hours, but usually takes 6 to 18 hours.

■ even after the termination can be dsr 8äurettbersohuas from dea OMisoh s.B alt elaea Stiokstoffetio »bsi 204 to 260 ° ο be aborted.

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The new high molecular weight monocarboxylic acids can also be prepared by what is known as a step process, in that the halation of the olefin polymer is carried out in the presence of the acid monocarboxylic acid. In this case, the monocarboxylic acid and the olefin polymer are mixed with one another in the reaction vessels in the specified proportions, and the temperature is kept below about 66 ° C. until the halogenation begins, in order to prevent the α, β-unsaturated mono-carboxylic acid from being polymerized . Once the halogenation has started, the temperature can be increased up to 120 ° C. After the introduction of the halogen a, the temperature can be increased to 150 ° 260 ° 0 so that the condensation reaction takes place.

The high molecular weight monooarboxylic acid obtained in this way can also be reacted with a polyalkylene polymer under reaction conditions which favor the formation of amides. In general, these Umsetiung is carried out at a molar ratio of Monooarboneäure to Folyanin in Bereioh of I ι 1 to 3 »1 i can jedooh AUOH at higher MoIverhältniesen bj.e. ^ about 5:) operate when the Po ty ami η sufficient amino groups .

Alkylene polyamines of the general formula _;

) _n - illH (OH ₂ ) J - MH ₂

can be used, in which η has the value 2 or 3 and 9 «in · Number of 0 ble iü means. Special connections of this

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are Dläthylentriäratn, Tetraäthylenpentamin, Di propylenediamine, Cotoathylennonamin and Tetrapropylenpentamln. Aüoh'V ₉ V-Dl- (2-aainoäthyl) ftthylon'Jiaeia can be used. Other aliphatic polyamino compounds which can be used are the V-aminoalkylpiperaalne of the general formula

CH ₂ - CH

CH p ¹ 'CH η

- ^H

in which η is a number from 1 to 3 and R is a hydrogen atom or an aminoalkyl radical with 1 to 3 carbon atoms ₉ V-Dl-2-aminoethyl) -piperasln.

In the context of the invention, the use of geoisohen from spilled alkylene polyamines, mixtures is also available various N-aminoalkyipiperasines and mixtures of alkyl · η-polyamines and N-aminoalkylpiperasines. The term "aliphatic polyamiri" encompasses all of these compounds and mixtures of connections.

J) Ie reaction temperatures for the amide formation reaction are generally in the range from about 93 to 204 ° C. Most one will in the narrower temperature range of about 120 to 177 ° 0 work. The response time depends in a certain way · * Depending on the temperature, the composition of the reaction mixture can be determined by measuring the amount during the conversion split off water beetimet werdon. If necessary, a

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WaaeereehDeppmittel, such as heptane, can be used to dae Absorb water in the form of an aiseotropic geology.

Example 1

Duron a solution of 2000 g of polyisobutylene (molecular weight 950) in 1000 g of carbon tetrachloride is 4 hours with stirring at room temperature Chi or passed. Then the Carbon tetrachloride is driven off by passing nitrogen through it at 140.degree. The chlorinated polyisobutylene has one

Chlorine content of 4.33 dew.

A mixture of 600 g of this chlorinated polyisobutylene and 55 g of acrylic acid is obtained at 232 ° C. for 18 hours, with hydrogen chloride develops. Then through the mixture 1/2 8 hours passed nitrogen at 232 ° 0, whereupon the mixture is gektthlt to 121 ° 0 and filtered through a filter aid ("Dicalitt") is filtered. The product identified as foIyJsobutenylpropionaäure contains 0.3 Qew.-1C chlorine and has a concentration of 52.1 ag KOU / g.

Example 2

A mixture of 555 g of the prepared according to Example 1 Polyisobutenylpropionic acid, 132 g mineral oil (viscosity 150 8U8 at 37.8 ° 0) and 44 g of tetraethylene pentamine is 5 hours under Stirring to 149 ° 0, with constant nitrogen through the The mixture is passed in order to drive off the Vasssr split off during the condensation of the monooarboxylic acid and the polyamine. The reaction product is filtered through the filter aid indicated above and contains 2.63 wt.% Of atioketoff.

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Example 3

A mixture of chlorinated polybutenes produced according to Example 1 from ViO g 'ines (chlorine content 6.4% by weight | produced except for a polyisobutylene with a molecular weight τοπ 830 by chlorination for 5 hours) and 88.6 g of methacrylic acid Heated at 232 ° C for 18 hours. Then 1 hour will go through the Reaction genisoh nitrogen passed over the excess Drive off methacrylic acid. Thereupon the reaction gen cooled to 121 ° C and filtered through the filter aid specified above. The product has a saponification grade of 39tO ag KOH / g. You structure as a carboxylic acid will duroh that Ultrared spectrum confirmed.

Example 4

2 ^ 0 g of chlorinated polybutene (chlorine content 4.18 Oew.-jC, produced by chlorinating polyisobutylene bit with a molecular weight of 950) and 27.5 g of crotonic acid are 20 hours heated to 232 ° C. The product is used for 1/2 hour at 232.degree Passed nitrogen, whereupon the product is cooled to 121 ° C and filtered duroh a filter aid (Moalite). That Product has a saponification value of 18.3 ng KOH / g and will by identifying its ultra-red spectrum as a carboxylic acid.

Example 5

800 g of polyisobutylene (Nolekulargewioht 830) and 80 g of acrylic acid are heated to 38 ° C. In the reaction, too becomes chlorine at a rate of 400 al / mln. initiated, and the temperature is increased to 121 ° 0, fold

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Let the chlorination stop for 2 hours and let the temperature rise Maintained at 2t8 ° C for 18 hours. Naoh 1-atUndigem Hinduohleitan of nitrogen at 2 ^ 8 ° C, the reaction mixture is brought to 121 ° C cooled and filtered through the filter aid specified above. The product has a saponification number of 38 ag KOB / g. Bas ultraredspekurum let the same as that of the naoh dao Carboxylic acid produced in two step processes. The product has a chlorine content of 0.42 wt. £

Example 6

500 g (0.4 Hol) of the polyisobutenylproponaic acid prepared in Example 1 with a silvering number of 48 ag KOH / g, 38 g (0.2 mol) of tetraethylene pentamine, 228 g of neutral Mineral oil (viscosity 150 SUS to 37.8 ° C) and 80 g of heptane are heated to the flux temperature of 145 to i48 ° C for 6 hours heated, whereby in a gate position near Dean and Stark 9.5 »1 waaeer are caught. The heptane becomes duroh Hindu-Rohleitan driven off by nitrogen on the steam bath and the product filtered through a filter aid (Dioalite). Daa product beeltst a nitrogen content of 1.65 wt .-> (Theoretically 1.76 ow.-Jt) · The structure as laid out is confirmed by the ultra-red spectrum.

Example 7

Following the procedure of Example 2, 443 β (0.34 mol) a polyisobutenylpropionic acid prepared according to Example t with a saponification number of 43 mg IOH / g and 19 g (0.1 KoX) Tetraäthylenptntamin In 194 g neutral Kineralöl «la evaporative

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nungsolttel implemented. The product contains 1.02% by weight of nitrogen (theoretically, 02% by weight).

Example 8

540 g (0.5 Ho;) of the polyisobutenylpropionic acid prepared in Example 1, 100 g neutral mineral oil as solvent and 5 ^ν g (0.5 mol)! wherein nitrogen is passed through the reaction gel to drive off the reaction water. The product is filtered through a filter aid and contains 2.5% by weight of nitrogen.

Example 9

540 g (0.5 mol) of the polyisobutenylpropionic acid prepared according to Example 1, 256 g of neutral mineral oil as solvent and 64.5 g (0.5 mol) of H-Aninoäthyjipiperasin are 3 to Heated to 149 ° C for 6 hours, during which time the reaction zone was aleoh Nitrogen is passed over the Eeaktionewaeser to drive off. The product is filtered through a filter aid and contains 2.47 Qew .- * nitrogen,

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Claims (2)

U95620 August 26, 1968 Dr. He / zo E 28 246 IVd / 39c P 14-95 62O.8 Esso Research and Eng · Go. Claims 1. A process for the preparation of monocarboxamides by reacting an aliphatic monocarboxylic acid with an aliphatic polyamine, characterized in that a high molecular weight acid, which is obtained by reacting a C ^ - hie 0pc _o polymer from G ₂ - to CL monoolefins with an α , ß-unsaturated monocarboxylic acid, which contains 3 to 8 carbon atoms, in a molar ratio of polyamine to high molecular acid between 1: to 1: 5 to implement 2. The method according to claim 1, characterized in that there is used as a high molecular weight acid which by reacting an olefin polymer which has first been halogenated so that there are 1 to 2 halogen atoms contains per molecule of the olefin polymer, with one unsaturated monocarboxylic acid in a proportion of 1 to 2 moles of unsaturated monocarboxylic acid per mole Has received polymer. 90981 3 / U 8 4 New Ualerfayen «ml ι § ι μ. ζ «w. ι sm 3 H95620 Ί '■ -e-. 3. Method according to claim 1, characterized in that that the high molecular weight acid used is one which is obtained by reacting the non-halogenated Olefin polymer with the unsaturated lionocarboxylic acid with simultaneous halogenation M-, process according to claims 1 to 3, characterized in that the high molecular weight acid used is one which was formed from acrylic acid and a polyisobutylene, and that the polyamine used is tetraethylene pentamine 909813/1484