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Publication numberUS2272466 A
Publication typeGrant
Publication dateFeb 10, 1942
Filing dateNov 3, 1938
Priority dateNov 22, 1937
Publication numberUS 2272466 A, US 2272466A, US-A-2272466, US2272466 A, US2272466A
InventorsGeorg Hummel Hans, Michael Jahrstorfer
Original AssigneeGen Aniline & Film Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Production of waxlike substances
US 2272466 A
Abstract  available in
Images(3)
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Claims  available in
Description  (OCR text may contain errors)

Patented Feb. 10, 1942 UNITED STAT 2,252,466 2 PRODUCTION or waxmm SUBSTANCES Hans Georg Hnmmel, Mannheim, and Michael Jahrstorier, Ludwigshaien-on-the-Rhine, Germany, assignors, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application November 3, 1938, Se-

rial No. 1937 12 Claims.

The present invention relates to a process for producing wax-like substances by condensing polycarboxylic acids and amines. I

We have found that wax-like substances which are very valuable industrially can be obtained by condensing aliphatic amines having at least one high molecular alkyl radical i. e. a radical containing at least 8 carbon atoms and at least one hydrogen atom attached to nitrogen with cyclic polycarboxylic acids which are not capable of forming inner, anhydrides. acids there may be mentioned-particularly such as are derived from the benzene series for example isophthalic acid, terephthalic' acid, diphenyl-4.4 dicarboxylic acid, naphthalene-1.4- (l.5-, -l.6- and 2.64 dicarboxylic acids. Furthermore polycarboxylic acids, such as trimesic acid, trimesic acid the nucleus of which is partially .or completely hydrogenated, symmetric benzene tribenzoic acid, diphenyl- 2.4.3-tricarboxylic acid and pyridine-1.3.5-tricarboxylic acid which can be obtained by oxidizing collidine may be used. The said polycarboxylic acids may also contain substituents, as for example halogen atoms or hydroxyl, ether, ester or nitro groups, such as chloror nitro-terephthalic acid. Instead of the carboxylic acids, their functional derivatives, as for example their chlorides or esters, may also be used.

Suitable amines for the process are for example octylamine, decylamine, dodecylamine, methyldodecylamine, N-cetylethvlenediamine, asymmetric N-dicetylethylene-diamine,

decylamine, cyclohexyldecylamine, beta-ethylhexylamine, N-methyl-cetyl-amine, N-propylricinolamine, and also amine mixtures such as are obtained for example by reduction of amides or nitriles of the carboxylic acid mixtures contained in fatty substances of vegetal origin such as oils or iats or carboxylic acid mixtures obtained by oxidation of high molecularweight paraiiin hydrocarbons, or by the reaction .of mineral acid esters of fatty alcohols with ammonia or primary amines.

Generally speaking the amines and polycarboxylic acids are used in equivalent amounts. Smaller or larger amounts of amine may, however, be used. In many cases it is preferable to replace a part of the amines by aliphatic polyamines, as for example ethylene diamine, diethylene triamine or triethylene tetramine or mixtures of the same. It may also be advantageous to replace a part of the cyclic polycarboxylic acids by monobasic or dibasic aliphatic As polycarboxylic 238,618. In Germany November 22,

(Cl. 260404)' v vcarboxylic acids or mixtures thereof. For exoctadecylamine or oleylamine, hyd'roxyethyldoample high-molecular fatty acids as are contained in fatty substances of vegetal origin such as oils, fats or waxes, such as caproic acid, lauric acid, stearic acid or montanic acid may be employed or acids obtained by oxidizing high-molecular paraiiinic hydrocarbons may be employed. Suitable dicarboxylic acids are for example malonic acid, succinic acid, adipic acid or mixtures of dibasic acids as are obtained by oxidizing high-molecular paraffin hydrocarbons with nitric acid.

The condensation takes place generally speak- I ing even by simple heating of the polycarboxylic acids with the amines to high temperatures, as for example temperatures above C. It is advantageous to work at temperatures between and 300 C. The heating of the mixture is preferably continued until water has distilled oil in an amount approximately corresponding to the amount of water theoretically calculated for amide formation from the initial materials used.

The condensation may also be carried out in the presence of solvents of high boiling point, as for example tetrahydronaphthalene, trichlorbenzene or nitrobenzene, or with an addition of oils, tats or waxes of the acids contained therein. When using acid halides, it is preferable to work in the presence of agents binding acids, as for example caustic soda solution, caustic potash solution, ammonia or soda.

Depending on the nature of the initial materials used, wax-like substances of very high melting point are obtained which have valuable industrial properties and which if desired may be subjected to purification, as for example by treatment with adsorbent or bleaching sub-.

are soluble inhigher boiling' organic solvents,

such as xylene, oil or turpentine, mineral oil fractions and also in oils, fats, paraflin waxes, ozokerite, ceresine, natural or synthetic waves and similar products and may be used with advantage for many purposes in industries working up waxes. For example they are suitable alone or together with other substances for impregnating textiles, paper and the like. The products also have a very high binding power for the solvents usual in industries working up waxes. The good oil-binding power of the products oifers special advantages in the preparation and storage of wax finished products, such as shoe creams and polishing compositions.

The following examples will further illustrate how the present invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 100 parts of terephthalic acid and 325 parts of octadecylamine are heated until about 20 parts of water have distilled off, whereby the temperature rises from 180 to 300 within about 3 hours.

A rather hard, almost colorless, wax-like prod- 160 parts of terephthalic.acid dimethyl ester and 310 parts of dodecylamine are heated until about 50 parts of methyl alcohol have distilled oil". The residue is a hard, colorless wax-like product having a dropping point of 166 and a softening point of 164 C.

Example 3 100 parts of terephthalic acid and 230 parts of dodecylamine are introduced into about 1700 parts of tetrahydronaphthalene, the mixture then being heated to boiling under a reflux condenser provided with a water separator until water no longer passes over. After distilling off the tetrahydronaphthalene in vacuo, there remains a pale yellow, rather hard wax having a dropping point of 164 and a softening point of 163 C. It is well soluble in fused paraffin wax, in natural and synthetic ozokerite and in oils, as for example linseed oil.

Example 4 A mixture of 100 parts or terephthalic acid and 320 parts of oleylamine are heated under a descending condenser. The splitting oil of water commences at 225 C. and is completed after about 3 hours when a temperature of 320 C. is reached. The condensation product is a yellow soft wax having a dropping point of 124 and a softening point of 115 C. It is well soluble when hot in alcohols and aromatic hydrocarbons and in fats V and waxes.

Isophthalic acid may be used instead of terephthalic acid; a dark yellow soft wax having a dropping point of 91 C. is thus obtained.

Example 5 300 parts of diphenyl-414'-dicarboxylic acid and 700 parts of octadecylamine are heated for about an hour until the amount of water calculated from the formation of the dicarboxylic acid diamide has distilled off. The residue solidifies when cooled to form a yellow, hard wax-like mass having a dropping point of 199 and a softening point of 173 C.

. Example 6 270 parts of diphenyl-4.4-dicarboxy1ic acid dimethyl ester and 380. parts of dodecylamine are heated until methyl alcohol no longer distils over. A dark yellow wax-like mass is obtained which has a dropping point of 205 and a softening point of 195 C.

ylamine instead of the dodecylamine, a wax-like mass having a dropping point of 176 C. is obtained.

, Example 7 A mixture of parts of terephthalic acid, 178 parts of dodecylamine and 10 parts of ethylene diamine hydrate is heated. After distilling off 20 parts of water, there remains a pale yellow. hard wax-like mass having a dropping point of 251 and a softening point of 180 C. The prodnot is well soluble in paraffin wax, waxes and similar substances.

Example 9 A mixture of 166 parts of terephthalic acid, 146 parts of adipic acid and 740 parts of dodecylamine is heated for an hour at from 200 to 300 C. After distilling off 70 parts of water, a hard, pale brown, wax-like mass is obtained having a dropping point of 153 and a softening point or c. It is soluble in higher boiling organic solvents, such as xylene, and also in paraffin wax, ozokerite, oils, fats and waxes.

Example 10 Example 11 1 molecular proportion of isophthalic acid is heated with 2 molecular proportions of dodecylamine at from about 200 to 240 C. until about 2 molecular proportions of water have distilled off.

The condensation product is a hard yellow wax having a dropping point of 124 and a softeninz point of 123 C.

By using octadecylamine instead of dodecylamine, a wax having a dropping point of 119 .and a softening point of 118 C. is obtained.

Example 12 A mixture of 100 parts of trimesic acid and 400 parts of octadecylamine is heated to from about 200 to 250 C. until about 20 parts of water have distilled ofi. The residue forms after cooling 9.

pale brown hard wax-like mass having a dropping point of C.; it becomes plastic and flexible when heated.

What we claim is:

1. The process of producing a wax-like substance which comprises condensing an aliphatic amine having at least one alkyl radical with at least 8 carbon atoms and at least one hydrogen atom attached to nitrogen with a cyclic dicarboxylic acid from which an anhydride can be formed only by combination of two molecules 01 By using an equimolecular amount of octadec- 76 acid.

2. The process of producing a wax-like substance which comprises condensiiig an aliphatic amine having at least one alkyl radical with at least 8 carbon atoms and at least one hydrogen atom attached to nitrogen with a cyclic dicarboxylic acid of the benzene series from which an anhydride can be formed only by combination of two molecules of acid.

3. The process of producing a wax-like substance which comprises condensing an aliphatic amine derived from a fatty acid of vegetal origin having at least 8 carbon atoms and at least one hydrogen atom attached to nitrogen with a cyclic dicarboxylic acid from which an anhydride can be formed only by combination of two molecules of acid.

4. The process of producing a wax-like substance which comprises condensing an aliphatic amine with at least one alkyl radical containing at least 8 carbon atoms and at least one hydrogen atom attached to nitrogen with terephthalic acid.

5. The process of producing a wax-like substance which comprises condensing an aliphatic amine with at least one alkyl radical containing at least 8 carbon atoms and at least onehydrogen atom attached to nitrogen with a cyclic dicarboxylic acid from which an anhydride can be formed only by combination or two molecules of acid and an aliphatic carboxylic acid selected from the class consisting of aliphatic monoand dicarboxylic acids.

amide each CO is combined with the N of the radical of an aliphatic amine having at least one alkyl radical with at least 8 carbon atoms.

8. A diamide of a cyclic dicarboxylic acid of the benzene series, from which an anhydride can be formed only by combination of two molecules of acid, in which diamide each CO is combined with the N of the radical of an aliphatic amine having at least one alkyl radical with at least 8 carbon atoms.

9. A diamide of a cyclic dicarboxylic acid, from which an anhydride can be formed only by com-v binatlon of two molecules of acid, in which di- 6. The process of producing a wax-like sub stance which comprises condensing a mixture of an aliphatic amine with at least one alkyl radical containing at least 8 carbon atoms and an allphatic polyamine each of the said amines containing at least one hydrogen atom attached to nitrogen with a cyclic dicarboxylic acid from which an anhydride can be formed only by combination of two molecules of acid.

7. A diamide of a cyclic dicarboxylic acid, from which an anhydride can be formed only by combination of two molecules of acid, in which diamide each CO is combined with the N of a the radical of an aliphatic amine derived from a fatty acid of vegetal origin having at least one alkyl radical with at least 8 carbon atoms.

10. A diamide of terephthalic acid, in which diamide each CO is combined with the N of the radical of an aliphatic amine having at least one alkyl radical with at least 8 carbon atoms.

11. A wax-like condensation product from a cyclic dicarboxylic acid from which an anhydride can be formed only by the combination of two molecules of acid, an aliphatic carboxylic acid selected from the class consisting of aliphatic monoand dicarboxylic acids, and an aliphatic amine having at least one alkyl radical containing at least 8 carbon atoms and at least one hydrogen atom attached to nitrogen.

12. A wax-like condensation product from a cyclic dicarboxylic acid from which an anhydride can be formed only by the combination of two molecules of acid, an aliphatic carboxylic acid selected from the class consisting of aliphatic monoanddicarboxylic acids, and a mixtur of an aliphatic amine having at least one alkyl radical containing at least 8 carbon atoms and an aliphatic polyamine each of the said amines containing at least one hydrogen atom attached to nitrogen.

HANS GEORG HUMMEL. MICHAEL JAHRSTORFER.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2438200 *Mar 4, 1946Mar 23, 1948Du PontN, n'-bis (3-diethylaminopropylamide) of dibasic aliphatic acids
US2742496 *Sep 19, 1952Apr 17, 1956California Research CorpProcess for separating hexamethylene diamine salts of isophthalic and terephthalic acids
US2863857 *Oct 6, 1954Dec 9, 1958Ici LtdTrimesic acid modified polyamide
US2902475 *Apr 13, 1956Sep 1, 1959Gen ElectricLinear polyamide resins
US2937203 *Sep 27, 1957May 17, 1960Du PontNu-tertiary-alkyl amides of terephthalic, isophthalic, and trimesic acids
US2971027 *Sep 23, 1957Feb 7, 1961California Research CorpDiamides of terephthalic acid
US3264270 *Feb 20, 1963Aug 2, 1966Ici LtdPolyimides
US4499153 *Feb 15, 1983Feb 12, 1985Bayer AktiengesellschaftSizes
US4737239 *Sep 9, 1985Apr 12, 1988Ciba-Geigy CorporationProcess for the manufacture of paper or cardboard which is sized under alkaline or neutral conditions with anionic hydrophobic sizing agents and cationic retention aids
EP0174911A1 *Sep 9, 1985Mar 19, 1986Ciba-Geigy AgProcess for preparing alkaline or neutral sized paper or cardboard with anionic sizing agents and cationic retention aids
Classifications
U.S. Classification554/51, 554/56, 528/347, 564/134, 528/339, 564/139
International ClassificationC08L91/00, C08L91/06
Cooperative ClassificationC08L91/06
European ClassificationC08L91/06