US2345632A

US2345632A - Polyamides

Info

Publication number: US2345632A
Application number: US274808A
Authority: US
Inventors: Edwin A Robinson; Maurice J Kelley
Original assignee: National Oil Products Co
Current assignee: National Oil Products Co
Priority date: 1939-05-20
Filing date: 1939-05-20
Publication date: 1944-04-04
Anticipated expiration: 1961-04-04
Also published as: GB657419A

Description

Patented Apr. 4, 1944 FICE Pommrnnas J Edwin A. Robinson, Chatliam, and Maurice J. Kelley, Newark, N. .L, minors to National Oil Products Company, Harrison, N. 1., a coupontion of New Jersey No Drawing. Application May 20. 1939,

- Serial No. 274,808

13 Claims. (c1. zoo-5104.5)

This invention relates to textile lubricants and softeners, more particularly .to textile lubricants methyl amide and oleic acid ethylene diamide as softeners and lubricants for textile materials. such amides are ordinarily prepared by reacting a fatty acid or fatty ester with a monoor polyi amine. The reaction of monoamines with higher fatty acids or fatty esters yields products which are not readily dispersible in water, and since these products contain no residual amino group. they may not be solubilized to any substantial extent by treatment with acids. Hence these products may not be advantageously applied to textile material. It has been proposed, therefore, to react polyamines with higher fatty acids or fatty esters to produce amides having free amino groups capable of reacting with weak acids so as to solubilize the products and render them readily dispersible or soluble in water. However, the monoamides formed from such polyamines, by reaction thereof with higher fatty acids or fatty esters cause yellowing of textile material upon application thereto, and hence are highly'unsuitable for use as textile lubricants and softeners. On the other hand, polyamides formed by the reaction of higher fatty acids or fatty esters with polyamines are much less desirable as softeners and lubricants than the corresponding monoamides because of their relatively poor softening and lubricating properties.

It has also been proposed to prepare textile lubricants and softeners by reacting unsymmetrical dialkyl ethylenediamine with higher fatty acids such as oleic acid. Such unsymmetrical dialkyl amines are, however, relatively expensive and difficult to obtain, and hence, while the 'amides thereof have been used to some extent as textile lubricants and softeners, there is a great demand in the textile industry for cheaper products which may be used in place of these amides.

It is the object of this invention to provide inexpensive and highly effective textile lubricants and softeners.

It is a further object of this invention to provide a process for the preparation of textile ,lubricants and softeners from polyamines.

We have now found that polyamides having the general formula R1CO-NRa-XCOR2 in which R1 stands for-an alkyl radical containing from 7 to 21 carbon atoms, Ra stands for an alkyl radical containing from 1 to 4 carbon atoms, R: 'stands for hydrogen or an acyl group containing from 2 to 5 carbon atoms and 2! stands for the grouping (-CR4 s-CR4Rs-NR:), wherein R4 and R5 stand for hydrogen or alkyl radicals, and n is a whole number, may be applied to textile materials so as to impart thereto excellent softness, drape and pliability without causing yellowing of the material. The preferred polyamides of our invention may be prepared in a simple and inexpensive manner by reacting a readily available polyamine such as ethylene diamine, diethylene triamine, triethylene tetramine, etc., with a fatty acid containing from 8 to 22 carbon atoms or an ester thereof, and with a short chain fatty acid containing from 2 to 5 carbon atoms or an ester, anhydride or acid halide thereof.

Preferably, the polyamides of our invention contain one secondary amino group so that they may be treated with weak acids for the production of solubilized modifications of the poly amides. We have found that the presence of substantially more than one secondary amino group in the polyamides of our invention tends to cause objectionable yellowing of the textile material to which the polyamide is applied: hence, it polyamines containing more than 3 nitrogen atoms, e. g., triethylene tetramine o1 tetraethylene pentamine, are employed to prepare the products of our invention, preferably sumcient amounts of the short chain fatty acid are employed so as to acylate all but one of'the secondary amino groups.

The products of our invention are preferably prepared by reacting a polyamine with a higher fatty acid containing from 8 to 22 carbon atoms,

preferably from 12 to 18 carbon atoms, or an chain acid and then treating ,the product with the long chain fatty acid. Any polyamine may be used in the practice of our invention; thus, for example, polyamlnes such. as ethylene di amine, diethylene triamine, triethylene tetramine, tetra ethylene pentamine and hydroxyethyl ethylenediamine may be employed. We

prefer to use diethylenc triamine since we have found that amides prepared from this polyamine in accordance with our invention are highly effective textile lubricants and softeners, do not yellow textile material to which they are applied and may be readily solubilized by treatment with weak acids; furthermore, diethylene triamine is relatively inexpensive and readily available.

The long chain fatty acid compound reacted with the polyamine in accordance with our in-. ventlou maybe any of the fatty acids containing from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, or the esters thereof the following higher fatty acids may be mentioned by way of examples: caprylic acid, nonylic acid.

capric acid, undecyllc acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, ricinoleic acid, mixtures of these acids, etc. In place of the higher fatty acids, derivatives thereof such as glycerides and other esters, may be employed. Actually, we prefer to use glycerides of the fatty acids since products are obtained having superior softening properties to e those resulting from the reaction of the polyamines with theiree fatty acids. Froducts par- The short chain acids employed in accordance Eli accuses to 5 carbon atoms: as above mentioned, armydrides, esters or acid halides of these acids may also be employed. The amount of short chain acid compound employed depends to some extent upon the number of amino groups to be acylated and the nature of the compound'used. Thus in the case oi diethylene triamine, we prefer to employ about 3. mol of a short chain fatty acid per mol of diethylene trlamine; however, in the case of triethylene tetramine, where it is desired to acylate not only the -NH2.gro1lp but also one of the secondary amino groups, approximately 2 mols oi the sgiort chain acid per mol of the polyamine may be employed. It is to be understood that if derivatives'oi the short chain acid are reacted with the monoamide, the amounts thereof will be adjusted accordingly; for example, approximately one-half mol of acetic anhydride is used where one mol of acetic acid isrequired. If desired, sumclent amounts of the short chain acid may be used so as to form two amido groups on the free NH2 group; the --NE group adjacent the long chain fatty group may also be acylated. Generally. it may be said that the number of mole of short chain fatty acid employed per mol of polyamine will be equivalent to the number of groups to be acylated in accordance with our invention. The conditions under which this'r'eaction is carried out may vary widely, but we have found that the constituents may be reacted at atmospheric pressure and at a temperature of about C. for about 3 to 5 hours, the mixture then raised to between about .C. and about C., and

the reaction continued for about 5 to about 8 additional hours with excellent results. However, it is to be understood that these conditions may be varied somewhat without afiecting the course of with our invention contain from 2. to 5 carbon accordance with procedures well known to the art. We prefer to use acetic acid or acetic anhydride in the preparation of our novel products because of their ready availability and the excellent softening properties of the amide-s prepared from these compounds.

in carrying out the reaction in accordance with our preferred method, approximately equimolecular quantities of a pclyamine and a fatty acid containing from etc 22 carbon atoms are mixed; if a glyceride of a fatty acid is employed, e. g., coconut oil, approximately moi ofthe glyceride per mol of polyamine' is used. The com-- pounds are then permitted to react at a temperature suficlently high to cause the formation of the monoamide; this temperature may vary from about 120 C. to about 200 (2., but preferably is between about 150 C. and about 170" C. The time of this reaction may vary widely dependme somewhat upon the particular reactants and somewhat upon the temperature: generally, 8 hours or more are required. The pressure under which the reaction is carried out is preferably at? mospheric: however, pressures above or below atmospheric may be employed. The product of the reaction is then mixed with a suitable quantity or a short chain fatty acid containingjrom 2 the reaction, e. -g., pressures above or below at- I j mospheric may be used, the temperatures may vary widely so long as they are suficiently high to eflect' acylation, and the time of reaction may difier from the time above set forth.

The products of our invention may be liquids or solids, but generally they are solids. The majority of these products are relatively insoluble in water; however, products somewhat soluble or dispersible in water may be obtained. As above mentioned, the coconut oil products are generally dispersible in water. The preferred products of our invention contain a free secondary amino group so that they may be treated with weak acids such as acetic acid or lactic acid to solubilize the amide and render them more soluble or dis= possible in water. The solubilizing treatment is preferably carried out by mixing a dilute solution of the weak acid with the molten polyamide, stirring the mixture until it is homogeneous, then permitting the mixture to cool and recovering the solubillzed amide. Our novel products may be marketed as such or in the form of an aqueous solution, dispersion or paste thereof. They may be applied to textile material by any of the well known methods, e. g., in the form of a dilute solution thereof, and in every case impart ex cellent softness, drape, flexibility and handle to the textile material.

The following examples are illustrative of our invention. Amounts are given in parts by weight.

Example I a,ses,esa I a 3 Example II 587 parts of coconut oil and 277 parts of dicthylene triamine were mixed in an open kettle and agitated at a temperature oi 150' C. for 8 hours. The mixture was then permitted to cool to just above the melting point 01 the reaction product (about 50 0.). 136 parts of acetic anbetween 150' C. and 170' C. and the reaction continued for! more hours. The 'product was a viscous brown liquid relatively insoluble in water. This product was melted, mixed with about 1400 parts oi a hot 3% acetic acid solution, the mixture stirred at a temperature above the melting oint of the amide until homogeneous, then cooled and a product soluble in water recovered.

Example VII 280 partsoi' oleic acid and 103 parts oi oiethylene triamine were mixed in an open kettle and the mixture agitated at temperatures bee hydride were added to the molten mass, and the mixture agitated at a temperature of 135' C. for

" 5 hours, the temperature then ralsed to 150' C. and the reaction continued for 3 more hours.

The product thus obtained was a light tan solid relatively dispersible in water. This product was then melted, mixed with approximately 5400 parts of a hot 3% solution oi acetic acid, the' mixture stirred at a temperature above the melting point 01 the amide until homogeneous. then cooled and a product soluble in water recovered.

I Example III 190 parts of tetraethylene pentamine and 230 parts of coconut oil were mixed in an open kettle and agitated at a temperature between 150' C. and 170 C. for 3 hours. 153 parts of acetic anhydride were'then added to the reaction product and the mixture agitated at a temperature of 135 C. for 3 hours, the temperature was then raised to between 150 C. and 170 C. and the reaction continued for 5 more hours. The product thus obtained was relatively soluble in water.

The product was then melted, mixed with about 2000 parts of a hot 3% solution of acetic acid,

the mixture stirred at a temperature above the melting point of the amide until homogeneous,

then cooled and a product soluble in water recovered. I

Example I V 60 parts of ethylene diamine and 230 parts of coconut oil were mixed in an open kettle and agitated at a temperature between 150 C. and 170' C. for 8 hours. parts of acetic anhydride were then added to. the reaction product and the mixture agitated at a temperature of 135 C. for 3 hours, the temperature raised to between 150 C. and 170 C.- and the reaction continued for an additional 5 hours. A solid product relalively insoluble in water was thereby obtained.

Example V Example VI 186 parts of teaseed oil and 65 parts of diethylene triarnine were mixed in an open kettle and agitated at temperatures between 150' C. and .170" C. for 8 hours. '32 parts of acetic anhydride were then addedto the reaction product and the mixture agitated at a temperature of 135 C. for 3 hours, the temperature raised to 75 260 parts tween 150 C. and 170 C. for about.12 hours. 51 parts of acetic anhydride were-then added to the reaction product and the mixture agitated at a temperature of 135 C.- !or 3 hours, the temperature raised to between 150 C. and 170 C. and the reaction continued for 7 more hours. The product was a viscous brown liquid relatively insoluble in water. This product was melted, mixed with about 2000 parts oi a hot 3% acetic acid solution.

the mixture stirred at a temperatureabove the melting point 01 the amide until homogeneous.

then cooled and a product soluble in water recovered.

Example VIII 258 parts of palmitic acid and 103 parts of diethylene triamine were mixed in an open kettle and the mixture agitated at temperatures between 150 C. and 170 C. for 12 hours. 51 parts of acetic anhydride were then added to the action product and the mixture agitated at a temperature 01 135' C. for 3 hours, the temperature raised to between 150' C. and 170' C. and the reaction continued for 7 more hours. The product was insoluble in water. It was melted, mixed with about 2000 parts 01' a hot 3% acetic acid solution, the mixturestirred at a temperature above the melting point oi the amide until homogeneous, then cooled and a productv soluble in water recovered. l

Example IX 200 parts of lauric acid and 103 parts of diethylene triamine were mixed in an open kettle and the mixture agitated at temperatures between 150" C. and 170 C. for 12 hours. 51 parts oi acetic anhydride were then added to the reaction product and the mixture agitated at a temperature of 135 C. for 3 hours, the temperature raised to between 150 C. and 170 C. and the reaction continued for 7 more hours. The product was insoluble in water. It was melted, mixed with about 2000 parts oi a hot.3% acetic acid solution, the mixture stirred at a temperature above-the melting point of the amide until homogeneous, then cooled and a product soluble in water recovered.

Example X 284 parts of stearic acid and 103 parts of diethylene triamine were mixed in an open kettle and the mixture agitated at temperatures between 150 C. and 170 C. for 12 hours. 51 parts of acetic anhydride were then added to the reaction product and the mixture agitated at a temperature of C. for 3 hours, the temperature raised to between C. and C. and the reaction continued for 5 more hours. The product thus obtained was insoluble in water. It was melted, mixed with 2000 parts of a hot 3% acetic acid solution, the mixture stirred at a temperature above the melting point of the amide until homogeneous and a product soluble in water re covered.

In place of the acetic snhydride, 90 parts of lactic acid may he added; in place of the hot acetic acid solution, 3000 parts of a hot 3% lactic acid solution may heemployed.

The polyainldes ohtained as alcove described have been found to be excellent textile lubricants and softeners. They impart to the textile material treated therewith excellent softness, drape, flexibility and handle, but do not cause any appreciable yellowing of the material even after prolonged contact therewith. The products of our invention have been found to give a softer I finish when applied-to textiles'than the fatty amides oi unsymmetrical diallzyl diamines "here-= inabove referred to; hence, smaller amounts of our products may be used to soften textiles than are necessary when'the latter amides are employed. Furthermore, our products cause less discoloration of the textile material to which they accuses a fatty acyl radicl'e containing ironed to 22 carbon atoms, CORQ stands for a tattyacyl radicle coataining from 2 to carbon atoms, R: stands for a radical selected from the group consisting of hydrogen and acyl radicals containing from 2 to 5 carbon atoms, and X stands for the grouping (GMRt-CR4R5NR3M in which R4 and R5 stand for radicals selected from the group consisting oi hydrogen and alkyl radicals, and n is a whole number greater than one.

3. Polyamides having the general formula RiCO-NRo-XCORz in which RrCO stands for a fatty acyl radicle containing from 12 to 18 carbon atoms, COR: stands'fol a fatty acyl radicle containing from 2 to 5 carbon atoms, R3 stands for a radical selected froin the group consisting containing from 2; to 5 carbon atoms, R3 stands of hydrogen and aeyl radicals containing from 2 to 5 carbon atoms, and X stands for the grouping (CR4R5CR4R5NR3)1: in which R4 and Rs stand for radicals selected from the group consisting of hydrogen and alkyl radicals, and n is a whole number greater than one.

s. Polyamides having the general formula RrCO-INRz-XCOR2 in which R160 stands for a fatty acyl radicle containing froni' 8 to 22 carbon atoms, CORz stands for a fatty acyl radicle tor a radical selected from the group consisting of hydrogen and acyl radicals containing irom2 to 5 carbon atoms, and X stands for the grouping CRiRsCRcRsNH(CR4RsCR4R5-NR3) I in which R4. and R5 stand for radicals selected it is evident that the products of our invention display a marked superiority over lubricants and softeners heretofore used in the textile industry, and hence will he of great value to textile manufacturers:

In addition to their use as textile lubricants and softeners, the products of our invention may be employed for article variety of other purposes; for example, they may he used as lubricants and softeners for other fibrous material such as leather, paper, etc. They may [be added to viscose spinning baths to prevent clogging of the spinnerets, and may he used as defoaming agents, assistants in dyein printing'and otherwise treating textilesv and the like, andior the preparation of detergents and wetting, dispersing and emulsifying agents.

Since certain changes may he made in the above products and different embodiments of the invention may he made without departing from the scope thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and-not in a limiting sense.

Having described our invention, what we claim as new and. desire to smure by Letters Patent, is:

l. A compound selected from the group consisting of polyamide's having the general formula R1CO-NR3XCOR2 in which R180 stands for a fatty acyl radicle containing from 8 to 22 car'- bon atoms, COR: stands for a fatty acvl radicle containing from 2 to 5 carbon atoms, R: stands for a radical selected from the group consisting of hydrogen and acyl radicals containing from 2 to 5 carbon atoms and X stands for the grouping (-CR4R5-cR-iR5=-NR3)11 in which R4 and R5 stand for radicals-selected from the group consisting of hydrogen and alkyl radicals and n is a whole number greater than one, and salts of said polyamides with weak. acids.

2. Polyamides having the general formula Rlc-NR3'XCOR-2 in which R100 stands for from the group consisting or hydrogen and alkyl groups, and n is asvhole number.

5. Weak acid. salts of and polyamicies having the general formula R1CO-NRaX-C0R2 in which R stands for a fatty acyl radicle eontaiuing from 8 to 22 carbon atoms, COR/3 stands tor a fatty acyl radicle containing from 2 to 5 carbon atoms, Rs stands for a radical selected from the group consisting of hydrogen and acyl radicals containing from 2 to 5 carbon atoms.

- and X stands for the grouping mtr-CR .R:,NH-(msCRrRrNRc) 1:

in which Re and R5 stand for radicals selected from the group consisting of hydrogen and alkyl radicals, and n is a whole number.

6. Polyamides having the general formula R1CO-NHXCOR; in. which R1 stands for the mixture of the alkyl radicals of coconut fatty acids, CORa stands for a fatty acyl radicle containing from Z'to 5 carbon atoms, and X stands ,for the grouping (CHPCHPNRUI: in which R3 stands for a radical selected from the group consisting of hydrogen and acyl radical containing from 2 to 5 carbon atoms, and n is a whole number greater than one. 7

Z. Polyamides :having the general formula RICONHCH2CH2NHCH2CH2NHCOR 2 in which R1 stands for the mixture of the alkyl radicals of coconut fatty acids and COBB stands for a fatty acyl. radicle containing from 2 to 5 carbon atoms.

8. A. polyamide having the general formula RiCONI-ICHrCHzNHCHzCHzNHCOCrh in which R1 stands for the mixture of the alkyl radicals of v coconut fatty acids. I

9. An acetic acid salt of a polyamide having the general formula.

RrCONHCHsCI-IzNLlICI-IzCI-IzNI-ICOCHz 10. An acetic acid salt of a polyamide having and coconut oil to form a monoamide, and then the general Ionnula reacting the monoamide with acetic anhydride cnwmmcouncmcmmcmcnmncocm. firmadimida n A f h t 1 1y id 13. Polyamides having the general formula process or e prepara ono po 9. es 5 CH CH which comprises condensing a poiyamine with a RICO-NH EL M401, compound selected from the group consisting of fatty acids containing from 8 to 22 carbon atoms in which RICO stand for wand the esters thereof, and with a compound 4111113 1mm 8 23 COR! selected from the group consisting of fatty acids 10 5 fatty mammal 2 5 containing from 2 to 5 carbon atoms and the 05113011 esters, anhydrides and acid halides thereof. EDWIN ROBINSON- 12. A process for the preparation of polyamides MAURICE which comprises condensing diethylene triamine