Patented Apr. 4, 1944 2,345,632

UNITED STATES PATENT OF FICE 2,345,632 POLAM DES ) Edwin A. Robinson, Chatham, and Maurice J. Kelley, Newark, N.J., assignors to National Oil Products Company, Harrison, N.J., a corpora tion of New Jersey N. No Drawing. Application May 20, 1939, serial No. 274,808 13 Claims. (CL 260-404.5) This invention relates to textile lubricants and vide a process for the preparation of textile softeners, more particularly to textile lubricants lubricants and softeners from polyamines. and softeners comprising mixed fatty polyamides. We have now found that polyamides having It has been proposed to use higher fatty the general formula R1CO-NR3-X-COR2 in amides, such as amide, oleic acid which R1 stands for an alkyl radical containing methyl amide and oleic acid ethylene diamide from 7 to 21 carbon atoms, Ra stands for an alkyl as Softeners and lubricants for textile materials. radical containing from 1 to 4 Carbon atoms, ER3 Such amides are ordinarily prepared by reacting stands for or an acyl group containing a or fatty ester with a mono- or poly from 2 to 5 carbon atoms and X stands for the amine. The reaction of monoamines with higher O grouping (CRR-CR-R-NR) , Wherein R4 fatty acids or fatty esters yields products which and R5 stand for hydrogen or alkyl radicals, and n. are not readily dispersible in water, and since is a whole number, may be applied to textile these products contain no residual amino group, materials so as to impart thereto excellent soft they may not be solubilized to any substantial ness, drape and pliability without causing yellow extent by treatment with acids. Hence these s ing of the material. The preferred polyamides products may not be advantageously applied to of our invention may be prepared in a simple textile material. It has been proposed, there and inexpensive manner by reacting a readily fore, to react polyamines with higher fatty acids available polyamine such as ethylene diamine, or fatty esters to produce amides having free diethylene triamine, triethylene tetramine, etc., amino groups capable of reacting with weak 20 with a fatty acid containing from 8 to 22 carbon acids so as to solubilize the products and render atoms or an ester thereof, and with a short chain them readily dispersible or soluble in water. fatty acid containing from 2 to 5 carbon atoms However, the monoamides formed from such or an ester, anhydride or acid halide thereof. polyamines, by reaction thereof with higher fatty Preferably, the polyamides of our invention con acids or fatty esters cause yellowing of textile 25 tain one secondary amino group so that they material upon application thereto, and hence may be treated with weak acids for the produc are highly unsuitable for use as textile lubri tion of Solubilized modifications of the poly cants and softeners. On the other hand, poly amides. We have found that the presence of amides formed by the reaction of higher fatty substantially more than one secondary amino acids Or fatty esters with polyamines are much 30 group in the polyamides of our invention tends less desirable as Softeners and lubricants than to cause objectionable yellowing of the textile the corresponding monoamides because of their material to which the polyamide is applied; relatively poor softening and lubricating proper hence, if polyamines containing more than 3 ties. nitrogen atoms, e. g., triethylene tetramine ol 5 tetraethylene pentamine, are employed to pre It has also been proposed to prepare textile pre the products of our invention, preferably lubricants and softeners by reacting unsym stifficient amounts of the short chain fatty acid metrical dialkyl ethylene. diamine with higher are employed so as to acylate all but one of the fatty acids such as oleic acid. Such unsym Secondary amino groups. metrical dialkyl annines are, however, relatively 40 The products of our invention are preferably expensive and diffic lit to obtain, and hence, while prepared by reacting a polyamine with a higher the amides thereof have been used to some ex fatty acid containing from 8 to 22 carbon atoms, tent as textile lubricants and softeners, there is preferably from 12 to 18 carbon atoms, or an a great demand in the textile industry for ester thereof so as to form a monoamide, and cheaper products which may be used in place 46 then reacting the monoamide with suitable of these annides. amounts of an acid containing from 2 to 5 carbon It is the object of this invention to provide atoms. However, when employing diamines or inexpensive and highly effective textile lubri triamines in the practice of our invention, the cants and Softeners, s preparation of the amides may be carried out It is a further object of this invention to pro 50 by first reacting the polyamine with the short 3,868,682 chain acid and then seating he product with to 5 carbor atois; as above mentioned, anhy 3.he long chain fatty acid. Any polyainine may dides, ester's or acid halides of these acids may ise used in the practice of our invention; thus, also be employed. The amount of short chain for example, polyai initias Such as ethylene dis acid compound employed depends to gone extent anize, diethylene tria Raine, tiethyiene tetrae s upon the number of amino groups to be acylated mine, tetra ethylene pentainine and hydroxy and the Eaature of the compound used. Thus in ethyl ethylene die nine may be employed. We the case of diethylene triainine, we prefer to en prefer to use diethylene trianine since we have pioy about inol of a short chain fatty acid per found that aridies prepared from this polyamine mol of diethylene triarmine; however, in the case in accordance with our invention are highly of triethylene tetramine, where it is desired to affective textile lubricants and softeners, do not acylate not only the -NHa group but also one of yellow textile materiai to which they are applied the secondary amino groups, approximately 2 mols and may be readily Solubilized by treatment, with of the short chain acid per mol of the polyamine weak acids; furtheriore, diethylene trainine is may be employed. It is to be understood that if relatively inexpensive and readily available, derivatives of the short chain acid are reacted The long chain fatty acid compound reacted with the monoamide, the amounts thereof will be with the polyamine in accordance with our in - adjusted accordingly; for example, approximately vention may be any of the fatty acids contain one-half no of acetic anhydride is used where iing from 8 to 22 C&rbon atoms, preferably from 12 one mol of is required. If desired, Sufi to i8 carton atons, or the esters thereof; the foll cient amounts of the short chain acid may be used ioning higher fatty acids may be entioned by so as to form two amido groups on the free -NH2 way of examples: , nonyi ic acid, group; the -NH-group adjacent the long chain , undecylic acid, , syristic fatty group may also be acylated. Generally, &cid, palnitic acid, searic acid, , it may be said that the number of nois of short oleic acid, ricinoleic acid, mixtures of these acids; 25 chain fatty acid employed per inol of polyamine etc. In place of the higher fatty acids, tieriva will be equivalent to the number of groups to tives thereof such as glycerides &nd other esters, be acylated in accordance with or invention. Inay he employed. Actually, we prefer to use The conditions under which this reaction is car glycerides of the fatty acids since products are tied out may Vary widely, but we have found the 8, obtained having Stiperior softening properties to the constituents may be reacted at atmospheric those resulting from the reaction of the poly. pressure and at a temperature of about 135 C. anines with the free fatty acids. Products par for about 3 to 5 hours, the mixture then raised ticularly suitable as textile lubricants and soft to between about 50 C. and about 170° C., and eners are obtained by employing coconut, oi! to the reaction continued for about 5 to about 8 addi react with the polyamines in accordance with our 35 tional hours with excellent results. However, it is invention, since these products are dispersible in to be understood that these conditions may be Water Without ifurther Solubilizing Greatment, and varied somewhat, without affecting the course of possess excellent lubricating and softening prop the ireaction, e.g., pressures above or below at eries. As ex82nples of other glycerides that may nospheric may be used, the temperatures may be employed is place of the long chain fatty acids, Very widely so long as they are sufficiently high to there may be mentioned teaseed oil, eastor oil, effect, acylation, and the time of reaction may hydrogenated eastor oil, etc. differ from the time above set forth. he short, chain acidis employed in accordiance The products of our invention ay be liquids of with our invention contain from 2 to 5 caron soids, but generally they are solids. The ins atoms; this, for example, acetic acid, actic acid, jority of these products are relatively insoluble propioic acid, butyric scid and valleric acid may in water; however, products somewhat soluble be exployed; derivatives hereof such as esters, or dispersible in water may be obtained. As above acid halides and 8.nihydrides Ray See eployed in sentioned, the coconut oil products are generally ScCordiance with procedures well known to the dispersible in water. The preferred products of &rt. Wife prefer to Ise acetic acid oy acetic an 8 or invention contain a free Seco diary anio hydride in the preparation of our novel products group so that they may be treated with weak acids because of their ready &vailability and the excei such as acetic acid or lactic acid to Sobilize the lent softening properties of the anides prepared a hide and render then more soilbie 0 iss froii these compounds. - persible in water. The solubilizing treatment is In carrying out the reaction in 20cordance with preferably carried out by fixing 8, dilute solution our preferred method, approximately equi of the weak acid with the molten polyanide, molecular quantities of a polyamine and a fatty stirring the mixture until it is homogeneous, then acid, containing from 8 to 22 carbon atoms are permitting the mixture to cool and recovering nixed; if a glyceride of a fatty acid is employed, the solubilized amide. Our novel products may e.g., coconut oil, approximately 4, mol of the 60 be marketed as such or in the form of an aque glyceride permio of polyamine is used. The cois ous solution, dispersion or paste thereof. They pounds are then permitted to react, a 2, en may be applied to textile material by any of the perature sufficiently high to cause the formation Well known inethods, e.g., in the form of a dilute of the monoainide; this temperature may vary solution hereof, and in every case impart ex from about i20 C. to about 200 C., but prefer 55 cellent softness, drape, flexibility and handle to ably is between about 50° C. and about 20° C. the textile material. The time of this reaction may vary widely depend The following examples are illustrative of our ing somewhat upon the particular reactants and invention. Amounts are given in parts by Weight. &omewhat upon the temperature; generally, 8 o w Eacomple hours or iaore are required. The pressure under 300 parts of coconut oil and 143 parts of di which the reaction is carried out is preferably at ethylene trianine were mixed and the mixture mospheric; however, pressures above or below at agitated at temperatures between 50° C. and mospheric may be employed. The product of i0 C. for 8 hours. 312 parts of the reaction theity reactionof a short is chainthen mixedfatty acid with containing a suitable fromquan 2 75 product were then mixed with 50 parts of acetic 2,845,082 3 anhydride, the mixture agitated at a temperas between 150' C. and 170', C. and the reaction con ture of 135° C. for 4% hours, the temperature tinued for-7 more hours. The product was a vis then raised to 160 C. and the reaction con cous brown liquid relatively insoluble in water. tinued for 3 more hours. The product thus ob This product was melted, mixed with about 1400 tained was a solid relatively dispersible in water. parts of a hot 3% acetic acid solution, the mix Erample II ture stirred at a temperature above the of the amide until homogeneous, then 587 parts of coconut oil and 277 parts of di ethylene triamine were mixed in an open kettle cooled and a product soluble in water recovered. and agitated at a temperature of 150' C. for 8 10 Eacample VII r hours. The mixture was then permitted to cool to just above the melting point of the reaction ethylene280 parts triamine of oleic were acid mixed and in103 an parts open ofkettle di product (about 50° C.). 136 parts of acetic an and the mixture agitated at temperatures be hydride were added to the molten mass, and the tween 150° C. and 170° C. for about 12 hours, 51 mixture agitated at a temperature of 135C. for s parts of acetic anhydride were then added to the 5 hours, the temperature then raised to 150' C. reaction product and the mixture agitated at a and the reaction continued for 3 more hours. temperature of 135 C. for 3 hours, the tempera The product thus obtained was a light tan solid ture raised to between 150° C. and 170° C. and the relatively dispersible in water. This product was reaction continued for 7 more hours. The prod then melted, mixed with approximately 5400 20 luct was a viscous brown liquid relatively insoluble parts of a hot 3% solution of acetic acid, ther. in water. This product was melted, mixed with mixture stirred at a temperature above the melt about 2000 parts of a hot 3% acetic acid solution, ing point of the amide until homogeneous, then the mixture stirred at a temperature above the cooled and a product soluble in water recovered. melting point of the amide until homogeneous, Eacample III 25 then cooled and a product soluble in water re 190 parts of tetraethylene pentamine and 230 covered. Example VIII? parts of coconut oil were mixed in an open kettle and agitated at a temperature between 150' C. 256 parts of and 103 parts of di and 170° C. for 8 hours. 153 parts of acetic an ethylene triamine were mixed in an open kettle hydride were then added to the reaction product 30 and the mixture agitated at temperatures be and the mixture agitated at a temperature of tween 150° C. and 170° C. for 12 hours, 51 parts 135° C. for 3 hours, the temperature was then of acetic anhydride were then added to the raised to between 150° C. and 170° C. and the re action product and the mixture agitated at a action continued for 5 more hours. The product 35 temperature of 135 C. for 3 hours, the tempera thus obtained was relatively soluble in water. ture raised to between 150 C. and 170° C. and the The product was then melted, mixed with about reaction continued for 7 more hours. The prod 2000 parts of a hot 3% solution of acetic acid, luct was insoluble in water. It was melted, mixed the mixture stirred at a temperature above the with about 2000 parts of a hot 3% acetic acid so melting point of the amide until homogeneous, 40 lution, the mixture stirred at a temperature above then cooled and a product soluble in water re the melting point of the amide until homo covered. w geneous, then cooled and a product soluble in Eacample IV Water recovered. 60 parts of ethylene diamine and 230 parts of Eacample IX coconut oil were mixed in an open kettle and agi ' 200 parts of lauric acid and 103 parts of di tated at a temperature between 150 C. and 170' ethylene trianine were mixed in an open kettle C. for 8 hours. 50 parts of acetic anhydride and the mixture agitated at temperatures be were then added to the reaction product and tween 150° C. and 170° C. for 12 hours, 51 parts the mixture agitated at a temperature of 135 C. of acetic anhydride were then added to the for 3 hours, the temperature raised to between reaction product and the mixture agitated at a 150° C. and 170° C. and the reaction continued temperature of 135° C. for 3 hours, the tempera for an additional 5 hours. A solid product rela ture raised to between 150° C. and 170° C. and tively insoluble in water was thereby obtained. the reaction continued for 7 more hours. The Eacample V 55 product was insoluble in water. It was melted, 679 parts of coconut oil and 321 parts of hy mixed with about 2000 parts of a hot 3% acetic droxy ethyl ethylene diamine were mixed in an acid solution, the mixture stirred at a tempera open kettle and agitated at temperatures be ture above the melting point of the amide until tween 150° C. and 170° C. for 8 hours. 260 parts, homogeneous, then cooled and a product soluble of the reaction product were then mixed with 47 60 in water recovered. parts of acetic anhydride, the mixture agitated Eacample X at a temperature of 135 C. for 5 hours, the tem perature then raised to between 150' C. and 170' 284 parts of and 103 parts of di C. and the reaction continued for 5 more hours. ethylene triamine were mixed in an open kettle The product was a clear, reddish amber liquid 65 and the mixture agitated at temperatures be dispersible in water. tween 150° C. and 170° C. for 12 hours. 51 parts of acetic anhydride were then added to the re Eacample WI action product and the mixture agitated at a 186 parts of teaseed oil and 65 parts of di temperature of 135 C. for 3 hours, the tempera ethylene triamine were mixed in an open kettle 70 ture raised to between 150° C. and 170° C. and the and agitated at temperatures between 150' C. reaction continued for 5 more hours. The prod and 170° C. for 8 hours. 32 parts of acetic uct thus obtained was insoluble in water. It was anhydride were then added to the reaction prod melted, mixed with 2000 parts of a hot 3% acetic uct and the mixture agitated at a temperature of acid solution, the mixture stirred at a tempera 135° C. for 3 hours, the temperature raised to 75 ture above the melting point of the amide until 6. 2,846,383 horogeneous and 8, product. Soiuole in Water re a onions,fasty acy CORradicle stands containing for a fromfattyacy 8 to 22radicle car coversii.In place of the acetic anhydride, 90 parts of CoEtairing from 2 to 5 carbon atoms, 3 stands lactic acid may be added; in place of the hot for a, radical selected from the group consisting acetic acid solution, 3000 parts of a hot 3% lactic of hydrogen and acyl radicals containing frog 2 acid solution lay e.e. ployed. to 5 cairborn atoms, and 2 stands for the grouping The polyanides obtained as above described (-CR4R-CR4R5-NR3) is in which Ra and R5 have beer found to be excellent textile lubricants standi for radicals selected from the group con and softene's, they in part to the textile nate sisting of hydrogen and alleyi radicals, and it is rial treated therewith excellent softness, drape, 0. 8, whole nailer greater than one. flexibility and handle, but do not cause any ap 3. Polyanidies having the general formula, preciable yellowing of the material even after R1OO-NR3-3-COR2 in which R1CO stands for prolonged contact therewith. The products of a fatty acy radicle containing from 12 to 8 our invention have been found to give a softer carbon atoms, COR2 stands for a fatty acyl radicle finish when applied to textiles than the fatty 5. containing from 2 to 5 carbon atoms, R3 stands amides of unsyIn metricai dialkyl diamines here for & radical selected from the group consisting in above referred to; hence, snailer amounts of of hydroge) and acyl radicals containing fron 2 our products may be used to soften textiles than to 5 carbon atoms, and 2 stands for the group are necessary when the latter anides are ene ing (-CR4R5-CR4R5-NR3) it in which R4 and ployed. Furthermore, our products cause less dis 20 Rs. stand for radicals selected from the group - coloration of the textile material to which they consisting of hydisogen and alkyl radicals, and it are applied than do the amides of unsymmetrical is 8, wholent) mber greater than one. daikyi diaries. In addition, the products of 4. Folyerinides having the general formula our invention are such easier to use than the R1CO-NR3-2-CORain which R1CO stands for amides of the usyn metrical dialky diamines 25 a fatty acyl radice containing from 8 to 22 car since they may be dispersed or dissolved in water boI2 atoms, COR2 stands for a fatty acy radicle with great ease, is contrast to the difficulties ex containing from 2 to 5 carbon atoms, R3 stands countered in dispersing or dissolving the latter for a radical selected from the group consisting amides. As arove pointed out, our novel products of hydrogen and 3cyl radicals containing from 2 nay be prepared from readily available and ine 30. to 5 carbon atoms, and 25 stands for the grouping expensive amines, and hence are inch cheaper than the fatty & rides of the unsynaetrical di -CR4RSCRR-NH-(CR4R5-CR4R5-NR3). ally diagnixeS. herefore, in view of the above, in which Ra and Rs stand for radicals selected i& is evident that the products of our invention . from the group consisting of hydrogen and alkyl display a narked Superiority over lubricants and grotips, and 2 is a whole nurther. softeers heretofore used in the textile industry, 5. Weak acid salts of and polyanides having and hence Willi be of great value to textile manu the general formula, RCO-NR3-3.--COR2 in facturers. which R1CO stands for a fatty acyl radicle con In addition to their use as textile lubricants taining from 8 to 22 carbon atoms, CORa stands and softeers, the products of our invention may or a fatty acyl radicle containing from 2 to 5 be employed for a wide variety of other pur Carson atons, R3 stands for a radical selected poses; for ex8ingle, they lay be used as lubri son the group consisting of hydrogen and acyl cants and softeners for other fiorous material Eadicals containing from 2 to 5 carbon atoms. . such as leather, paper, etc. hey gay be added & Eids stands for the grouping to viscose spinning baths to prevent clogging of 45 the spi Enerets, and may be used as defoaming agents, assistants in dyeing, printing and other in Which R4 and R5 stand for radicals selected Wise treating textiles and the like, and sor the from the group consisting of hydrogen and alkyl preparation of detergents and Wetting, dispersing and erulsifying agents. 50 radicals,6. Polyanides and n is ahaving whole number.the general formula Since certain changes may be made in the R1CO-NH-X-CORain which R1 stands for above products and different encodinents of the the mixture of the alkyl radicals of coconut fatty invention may be made without departing fron acids, COR2 stands for a fatty acyl radicle con the scope thereof, i, is intended that all in atter taining from 2 to 5 carbon atoms, and X stands contained in the above description shall be in for the grouping (CH2-CH2-NR3) in in which R3 terpreted 8s illustrative and not in a limiting stands for a radical selected from the group con sease. sisting of hydrogen and acyl radicals containing Having described our invention, what we claim from 2 to 5 carbon atoms, and r2 is a whole num as new and desire to secure by Letters Patent, is: ber greater than one. - i. A compound selected from the group con 60 7. Polyanides having the general formula sisting of polyamides having the general formula, R1CONH-CH2CH2NHCH2CH2NHCOR in which R1CO-NR3-X-COR2 in which R100 stands for R1 stands for the mixture of the alkyl radicals of a fatty acyl radicle containing from 8 to 22 car coconut fatty acids and COR2 stands for a fatty born atoms, COR2 stands for a fatty acy radicle 65 acy radicle containing from 2 to 5 carbon atoms. containing from 2 to 5 carbon atons, Ra stands 8. A polyamide having the general formula, for a radical selected from the group consisting of hydrogen and acyl radicals containing from 2 to 5 RCONHCH2CHNHCH2CH2NHCOCH3 in which carbon atoms and X stands for the grouping R1 stands for the mixture of the alkyl radicals of (-CR4R5-CR4R5-NR3) in in which R4 and R5 COCOnu, fatty acids. stand for radicals selected from the group con 70 9. An acetic acid salt of a polyamide having sisting of hydrogen and alkyl radicals and n is the generaliformula, a whole number greater than one, and salts of said polyanides with weak acids. RCONHCH2CH2NHCH2CH2NHCOCHs 2. Polyamides having the general formula in which R1 stands for the mixture of the alkyl RCO-NR3-X-COR2 in which RCO stands for . radicals of coconut fatty acids. 2,845,682 S 10. An acetic acid salt of a polyamide having and coconut oil to form a monoamide, and then the general formula. reacting the monoamide with acetic anhydride CE (CH2)6CONHCHCHNECECH-NHCOCE. so 13.as toPolyamides form a diamide. having the general formula 11. A process for the preparation of polyamides is an compoundwhich comprises selected condensing from the agroup polyamine consisting with ofa Rico-NH-CH-CH-i- i-NH-CORa fatty acids containing from 8 to 22 carbon atoms in which RCO stands for a fatty acyl radicle con and the esters thereof, and with a compound taining from 8 to 22 carbon atos, COR stands selectedcontaining from from the 2group to 5 consistingcarbon atoms of fatty and acids the no carbonfor a fatty atoms. acyl radicle containing from 2 to 5 esters, anhydrides and acid halides thereof. OWN A ROBINSON. 12. A process for the preparation of polyanides MARC. J. K.Y. which comprises condensing diethylene triamine