DE1090860B - Process for the preparation of quaternary ammonium compounds of polymeric fatty acid amines - Google Patents

Description

GERMAN

The invention relates to a method for production new quaternary ammonium compounds from amines of polymeric fatty acids.

Polymeric fatty acids are known, commercially available acids. In the present proceedings The amines of polymeric fatty acids used have the same structure, but instead of the - COOH groups —CHgNH ^ groups. You can directly from polymeric fatty acids by reacting these acids with ammonia with dehydration to form the corresponding nitrile and subsequent hydrogenation of the nitrile to the amine. Also can Similar amines of polymeric fatty acids by polymerization of suitable fatty acid nitriles and then Hydrogenation of the polymeric nitrile to the corresponding amine of the polymeric fatty acid can be prepared.

Fatty acids are used as the basic raw materials for the production of amines of polymeric fatty acids Formation of polymeric substances have sufficient functional double bonds. Such an ideal starting material for thermal polymerization, for. B. pure linoleic acid. The acids used mostly come in the Nature as. complex mixtures. Isolation of pure linoleic acid is technically not feasible. This is why raw materials with a high linoleic acid content (30 to 80%) are used as starting acids. An analytical method for characterizing mixtures of fatty acids with enough functional ones Double bonds is the determination of their iodine number, i. H. the number of grams of iodine given by a 100 g sample absorbed halogen. In general, acids with an iodine number of at least 120 have enough double bonds to to form polymers. Acids suitable as starting materials are, for example: soy, flax, tung, Perilla, cottonseed, corn, sunflower, safflower and dehydrated castor oil and tall oil. Fatty acids High linoleic acid content can be obtained from these various sources by crystallization and / or distillation be won.

Instead of thermal polymerization, any other process, e.g. B. the in U.S. Patent 2,793,219 can be used. Polymerization processes can also be used unsaturated acids are used.

The amines of polymeric fatty acids produced in this way can form various quaternary salts with Substances are converted into the quaternary compounds according to the invention. Such quaternary salts forming substances are for example: methyl chloride, methyl bromide, Methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, n-propyl chloride, n-propyl bromide, n-propyl iodide, Isopropyl bromide, n-butyl chloride, n-butyl bromide, Isobutyl bromide, sec-butyl bromide, n-amyl bromide, n-hexyl chloride, Benzyl chloride, benzyl bromide, methyl sulfate,

Method of manufacture

quaternary ammonium compounds

polymeric fatty acid amines

Applicant:

General Mills Inc.,
Minneapolis, Minn. (V. St. A.)

Representative ¹ :

Dr. W. Beil and A. Hoeppener, lawyers,
Frankfurt / M.-Höchst, Antoniterstr. 36

Stuart A. Harrison, Kirtland E. McCaleb

and William J. Ward, Minneapolis, Minn. (V. St. Α.),

have been named as inventors

Ethyl sulfate, methylbenzenesulfonate, methyl p-toluenesulfonate or the like. These compounds are directly linked to the amines of polymeric fatty acids described the following quaternary compounds: chloromethylate, bromomethylate, iodine methylate, chloroethylate, bromoethylate, Iodine ethylate, chlorine-n-propylate, bromine-n-propylate, iodine-propylate, Bromine isopropoxide, chlorine n-butoxide, bromine butoxide, Bromine isobutylate, bromine sec-butylate, bromine amylate, chlorine n-hexylate, chlorobenzylate, bromobenzylate, Methyl sulfate, ethyl sulfate, benzomethyl sulfonate, or p-toluene methyl sulfonate, etc. Preferred residues on the Nitrogen atoms are aliphatic hydrocarbon radicals with 1 to 6 carbon atoms.

The conversion to the quaternary compounds is expediently carried out in the presence of a solvent, z. B. an alcohol in which the amine corresponding to the polymeric fatty acid is soluble. Are solvents especially isopropyl and butyl alcohol, but numerous other solvents and combinations can be used of solvents, e.g. B. alcohol-hydrocarbon mixtures can be used. Solvent seem generally not noticeably influencing the implementation; their use is only appropriate because it achieves closer contact between the alkylating agent and the amide. The reaction can be carried out in the presence of bases, e.g. B. alkali hydroxides, alkaline earth hydroxides, alkali carbon

009 627/446

naten, alkali metal alkylates, etc., are carried out. These are used to record during the implementation too quaternary compounds released acid. If no such base is used, the amino groups serve of the amine as an uptake for the acid formed by the reaction. If z. B. no base is used and an alkyl halide is used, the acid compound consists of a hydrohalide which is with the amino groups present to form a salt. In this case there is only a partial transfer in quaternary compounds, as some amino groups convert to by-products. on in this way the conversion into quaternary compounds can be regulated, if one is not complete Implementation is to be achieved.

In the example, all "parts" are parts by weight and all "Percentages" percentages by weight.

example

200 parts of polymeric "fatty acid amines", which have been produced by the reaction of polymeric fatty acids, which mainly consist of dilinoleic acid, with ammonia to form the corresponding nitrile and hydrogenation of the nitrile to the amide, 107 parts of a 57% aqueous sodium hydroxide solution and 190 parts of isopropanol were placed in an autoclave. The autoclave was closed and stirring was started; Methylene chloride was added to the extent that the pressure was maintained from 5.6 to 8.4 kg / cm ² at a temperature between 105 and 13O ⁰ C. After 100 minutes the pressure remained constant without the addition of further methyl chloride. At this time, the vessel was cooled to 75 to 8O ⁰ C the gases vented. The reaction mixture was filtered to remove the NaCl formed during the reaction. The precipitated product was washed with 50 ecm isopropanol. The filtrate was with 50 cc of the isopropanol used for washing were combined, whereupon there was obtained a clear liquid which is approximately 50 ° ₀ of the quaternary ammonium compound contained / of the polymeric fatty acid amine.

The quaternary ammonium compounds of polymeric fatty acid amines, as they are prepared in the example, are suitable as plasticizers for paper. If they are added to the paper pulp before sheet formation, do so they soften the paper sheets, while at the same time certain difficulties encountered with other plasticizers turned off. The addition of these quaternary ammonium compounds to the paper pulp and the Conventional processing of the pulp into paper sheets does not cause any problems with regard to foam formation as when using a quaternary dimethylammonium chloride of a difatty acid. Also give the Leaves from the pulp containing quaternary ammonium compounds of amines of polymeric fatty acids, When handling them, no fluffy paper dust is produced, as was the case with the sheets with the quaternary dimethylammonium compound of a di-fatty acid had been treated.

Another major advantage is that the new, quaternary ammonium compounds reduce the bursting pressure do not decrease nearly to the extent to which this is the case with the compounds previously used.

The following data show the different effects on the cracking stress due to the two compounds.

0 Burst pressure, in arbitrarily set units 2.5 3.0 ° / _{0 of} the added reagent 115 88 82 Quaternary ammonium compounds of polymeric fat
acid amines Duaternary ammonium chloride in which two of
Tallow fatty acids derived by hydrogenation
remnants R are located CH ^CH3 ^ n ⁺ he
CH ^χ ' ^{18 37} CH ₃ 115 45 35 (R essentially corresponds to the groups C ₁₈ H ₃₇ ,
some C ₁₀ H ₃₃ groups of the palmitin
acid and unsaturated C ₁₆ and C ₁₈ groups
be able to handle) 0.5 1.0 84 83 69 56

The quaternary ammonium compounds produced from amines of polymeric fatty acids give a Burst pressure, which is relatively constant regardless of the amount of quaternary ammonium compounds remained, while through the other quaternary connections the bursting pressure of the paper sheets remained in almost proportional to the amount of material available.

Claims (1)

Claim: Process for the preparation of quaternary ammonium compounds of polymeric fatty acid amines, characterized in that amines of polymeric fatty acids are reacted with compounds which form quaternary salts. © 009 627/446 10.60