US2410788A - Fatty amide polymers - Google Patents

Description

Patented Nov. 5, 1946 FATTY AMIDE POLYMERS Willard L. Morgan, Columbus, Ohio, and Earle D. McLeod, Rumford, R. I., assignors to Arnold, Hoffman & Co. Incorporated, Providence, R. 1., a corporation of Rhode Island No Drawing. Application April 5, 1944, Serial No. 529,687

16 Claims.

This application is a continuation in part of our copending application Serial #357,443, filed September 19, 1940.

This invention relates to new condensation products which are suitable as assistants for the modification of the properties of textile fibers.

Many materials have been used as textile assistants for altering the softness, the easy wetting or the repellency of textile fibers, or for increasing the stiffness or apparent weight, but each has been subject to some fault; thus, tallows, oils, and sulfonated oils or tallows have long been used in the finishing of textiles for softening effects, but these effects are not permanent and are lost the first time the goods are washed. These materials also suffer from rancidity or objectionable odor development in the goods. Fatty alcohols and fatty alkyd resins have also been used as textile softeners, but these also wash out. Fatty amides and the quaternary salts of these, as well as fatty quatemaries produced from pyridine or the betaines, and fatty imidazoles, have been suggested as textile modifying agents and in particular as textile softeners. While these materials are mostly fairly expensive and dark in color, these substances have shown the advantage of being somewhat resistant to washing. The quaternary salts of fatty acid condensations with aliphatic polyamines have also been used, particularly as these have shown a maximum resistance to washing up to this time. However, each of these types of materials has left considerable to be desired with regards to resistance to washing and as each of these materials 2 have been finished with these materials have frequently during a few monthsstorage become seriously yellow due to the softener being sensifatty alkyds, methacrylates, and vinyls which, due 7 to their general water insolubility and sticky nature, cause considerable difliculty as they must be applied in the form of dispersions which are generally unstable. These materials leave much to be desired in their permanency on cloth due to alteration on ageing and poor resistance to washing particularly in the case of the alkyds. Ureaformaldehyde resins have also been widely applied but these frequently impart odors to the cloth or tender it and the special high temperatures necessary for its baking call for expensive equipment.

It is an object of this invention to provide a new class of textile assistants such as wetting, softening, lubricating, waterproofing, and stiffening agents having improved properties. It is a further object to produce textile assistants which are resistant to heat and to oxidation which permit the finishing and storage of the finished goods for long periods without any yellowing, odor development, or tendering.

As further objects of our invention, we describe condensation products which may be easily applied from aqueous solutions or dispersions to give finishes on cloth of a maximum softness,

has been unstable with respect to heat and oxida- 5 tion, their use has been attended with the serious difliculty of the cloth being yellowed either by reason of the initially dark color of the product, or by its decomposition clue to the heat used in drying the fabric. Furthermore, goods which which effects are completely permanent to Washing and to dry cleaning.

A further object of our invention is to provide condensation products of resinous nature which give permanent bodying or stiffness effects coupled with desirable soft feel. These materials, because of high 'efiectiveness,.ca,n be economically used to replace sulfonated tallows in textile finishing.

A still further object of our invention is to describe new condensation products and resinous materials which may be applied permanently to textile materials from aqueous solution without any special heating or baking of the treated cloth.

The condensation products proposed by this invention are resinous or semi-resinous materials in which dialkylol substituted carbamido compounds carrying side chains containing polyamino acid amide radicals are linked together by reaction with polybasic acids.

These compounds are readily prepared by reacting the carbamyl derivatives such as urea, thiourea, guanidine salts, biuret, diguanidine, or guanyl urea with the acid amide condensation products secured from aliphatic polyamines carrying hydroxyl groups and acids or acid esters or acid chlorides and thereafter reacting the products thus secured with polycarboxylic acids.

As suitable: acids for forming the polyamino acid amides with the polyamines, we prefer those containing six ormore carbons and preferably saturated-aliphatic acids such as lauric, stearic, palm oil acids, although we may use the lower molecular weight aliphatic acids including acetic and we may use the unsaturated or substituted fatty acids, such as ricinoleic, oleic, sebacic or chlorostearic, or the cycloaliphatic, aromatic, or resin acids may'also be used, such as naphthenic, phthalic, benzolc, creosotinic, and a 'bietic, or the resin acid secured from rosin and maleic anhydride. These acids may be condensed with any The condensation-products of ,this invention are materials of high molecular weight in which units of the following general formula are linked together at the dotted line in large numbers:

In this formula just given for the side chains of the polyamino acid amide type, R1 corresponds preferably to a saturated aliphatic chain such as would result from the use of a saturated fatty acid or any of the other various types of acids already enumerated; thus, R1 may also represent other hydrocarbon radicals such as a cyclo alkyl, an unsaturated hydrocarbon, an aryl radical, or a residue from a terpene acid. In each case the .corresponding acid, acid chloride, or ester may be used as a source to introduce this radical into our condensation products as will be shown later.

The letters 6 and m represent small integers, with e varying from 0 to 4 and m from 2 to 3, and any of the hydrogen in the CH2 group may be substituted by a simple alkyl or hydroxy group.

It is evident from the two general formulas above that .the alkylol polyamine employed in producing the product has the following general formula:

in which X represents a simple alkylene group of from 2 to 3 carbon atoms and in which one of the hydrogens attached to one of the carbon atoms is replaced by hydroxyl and in which formula the integer e varies from 0 to 4 and m from 2 to 3.

The condensation products of this invention are in some cases directly water soluble or water dispersible. In most cases the condensations are readily dissolved after treatment with acids, such as acetic, lactic, boric, oxalic, benzoic, salicylic, furoic, citric, tartaric, formic, phthalic, succinic, or alkyl naphthalene sulphonic acids or after reaction with an alkylating agent, such as, ethyl chloride, benzyl chloride, ethylene oxide, ethylene chlorohydrin, diethyl sulphate, or dimethyl sulphate. The salts or alkylated products of our substituted new condensates are indicated in the general formula given where B represents the acid hydrogen or alkyl groups and X the acid radical or halogen group, while for our primary condensations B and X disappear from the formula.

The condensation products of this invention are readily prepared by heating equimolal quantitles of the acid and hydroxylated amine at temperatures from 130 to 200 C. until the reaction is complete as shown by the loss of one molecule of water. The mix is then cooled back to 180 and one-half mol or more of the urea or other carbamyl derivative added. Ammonia is rapidly liberated as the urea becomes substituted, the

5: temperature being held between 170 and200 C.

p In this formula R1 is a hydrocarbon residue re- I sulting from the dicarboxylic acid which has been used.

R: and R4 represent simple alkylene groups of from twotzo three carbon atoms. These groups and the adjacent nitrogen originate from the amine used in the condensation and attached to the carbons R: and R4 is the remaining part of fatty acid precondensed with the amine forms the terminal part of the side chain. The amino acid amide side chains residues are-of the following type in which the radicals may depend for their nature on the amine and the acid reacted therewith. g

After holding the product for a short period up to one-half hour during which time the ammonia is driven 011, preferably one mol of the polycarboxylic acid is added at temperatures above 150 59 C. and the temperature is rapidly raised to 200- C.

as the polybasic acid reacts and wateris liberated. Depending upon the number of hydroxyl groups present in the primary condensation, we

the fatty i o a 01 d amide as a side (mam. The may increase the molal proportions of the polybasic acid used in order that allor part of these may-be reacted with the polybasic acid. The product may be cooled, and used directly or at temperatures of so .to 140 C. the various solubilizing acid or alkylating agents may be added in quantities of .2 to .5 mol or more.

The linking by ureaor other carbamyl compounds of two or more acid polyamine amide groups which are thereafter linked into long continuous resin-like chains results in products of very large molecular weight which are found tov show high substantivi-ty to the various textile fibers, such as, cotton, viscose, cellulose acetate, linen, jute, wool, nylon, and protein fibers and to ive textile treatments which are permanent to washing and dry cleaning. This marked substantivit'y is found to arise from the presence of the urea or other similar carbamyl groups and particularly to the very high molecular weight of the products secured by the polymeric chains formed by the polybasic acid linkages. The urea group also increases the solubility in water which is very important since such large molecules which are desirable for substantivity are poorly soluble. Watersolubility is, also brought about by the formation of salts at the nitrogen groups. We have found that the sensitiveness to oxidation and to heat or light of the acid polyamine amide condensations and other proposed nitrogen containing textile assistants which results in yellowing either in processing, drying, storage, or'use of the treated fabrics is mainly caused by the presence of primary amino or NH2 groups in the compounds and to a much lesser extent by secondary amino (NH) groups. It is the primary amino group left in the acid polyamine amide condensations which is reacted upon by the urea or other carbamyl compound and removed during the formation of our new reaction products, and we are thus able to secure compounds free of these diihculties. Likewise, the urea and other carbamyl compounds will react with and eliminate secondary amino groups and the yellowing arising from such groups and it is an alternative under this invention to use suflicient urea or other carbamyl compound to combine with all the primary and secondary amino groups in the acid polyamine amide, as well as merely the single groups as shown in the general formula already given. The resistance to scorching under heat is also found .to be lowered to some degree by the use of unsaturated acids as the source of R1 and while we may usethem in many types of application, for products of maximum resistance we prefer the use of the saturated fatty acids.

Inasmuch as urea, thiourea, and guanidine are I each decomposed readily at temperatures below 180 C. or the reaction temperatures employed, it was impossible to foresee that the large molecule substituted urea condensations would be stable at these temperatures or could be formed. Thus, the heating of urea and fatty acids at 160 does not lead to substituted ureas, but decompositions occur yielding only fatty amides as shown in U. S. 1,989,968 and U. S. 2,109,941. In a similar way we have been unable to react urea with simple 6 fatty amides or fatty ethanol amides and we find that it is only when we use the amide of an acid and & lyamine containing either or both a primary or secondary amino group that reaction to our substituted ureas can be secured. The condensations go readily and are free of side reactions, thus,.leading to full yields of products which do not need to be purified.

In view of the fact that polyamino acid amides change rapidly at elevated temperatures and that urea compounds are relatively unstable, it could not be foreseen that the polyamino acid amide substituted carbamyl compounds could be heated. to the high temperature necessary for reaction or that in view of their large molecular size they would react further with polybasic acids. However, we have found that these reactions can be carried out smoothly with theoretical yields giv-. ing products which need no further purification.

The production of resinous like materials indicates the formation of long polymeric chains which due to equimolar quantities of polybasic acids used have one hydroxyl and one carboxyl end group between which lie one or more repeating units as set forth in the aforementioned general formula. By reason of the resinous nature of the products, many of these when applied to cloth show definite stiffening effects and the effects become permanently attached to the various textile fibers. As we have already indicated, despite the large molecular weight of these compounds, the solubilizing groupspresent permit us to apply these in aqueous solutions or dispersions and the materials become permanently fixed to the textile fibers by their substantivity on the same, thus not requiring any special curing or baking beyond the normal drying to develop stiffening and other effects. Where the side chains contain large fatty groups, various degrees of soft feel are permanently secured along with the stiffness or bodylng effects.

The invention will be further illustrated, but is not limited by the following examples in which the quantities are stated in parts by weight:

Example 1 568 parts (2 mols) of stearic acid were heated with 133 parts of N-3 amino-2 propanol ethylene diamine until 1 mol of water was collected after 50 which 30 parts (/2 mol) of urea was slowly added at; 180-185 C. and the temperature raised to 190 C. during which time ammonia was evolved. At 190 C. 101 parts (1 mol equivalent) of sebacic acid were slowly added and the temperature raised 55 to 200 C. while water was distilled off. The product had the following unit formula:

H, H: H3 H 1 111 H: H: NH (1:0 NH NH =0 "His I JuHu The acetate salt of this condensate when applied to cotton fabric in the ratio of 6 parts in 50 gallons, gave a permanent finish resistant to washing and dry cleaning. The fabric possessed 180 C. and the temperature gradually raised to 190C. during which time ammonia was liberated. 1142 parts (1 mol) of the above condensate having the formula:

increased weight with some stillness.

Example 2 90 parts (1 moi) of 1 3 diamine isopropanol were heated with 284 parts (1 mol) of stearic acid until one moi of water was driven oil. 30

was heated to 190 C. at which point 202 parts 20 (1 mol) of sebacic acid was added and the temparts (/2 mol) of urea were then slowly added 25 sisted of rep t n unitsasfollowsz at 180485 C. and the temperature'raised to 190 C. during which'time ammonia was evolved. At 190 C. 101 parts (1 mol equivalent) of sebacic acid was slowly added and the temperature raised to 200 'C. The product was a sticky resin which was soluble in water after treatment with acetic acid and had the following formula:

282 parts (1 mol) of oleic acid was heated with 204 parts (1 mol) of 1 amino 3 dipropylene triamine isopropanol until one moi of water was 5 driven oil. At 180 C. 30 parts (/2 mol) of urea was slowly added and the temperature gradually increased to 190 C. during which time ammonia H: H: 2 13 v 1 111 u nHu Example 3 284 parts (1 mol) of stearic acid was heated with 262 parts (1 mol) of 1 amino 3 tetraethylene pentamine isopropanol until one mol of water was i evolved. 30 parts moi) of urea was added at was evolved. To the above condensate at 190 C., 74 parts (1 moi equivalent) phthalic anhydride was added and the temperature raised to 7 200 C. during which time water was removed.

The product obtained was soluble'in water after treatment with acids or aikylating agents and 50 gallons or water possessed a soft handle with had the following unit formula:

was resistant to washing and dry cleaning proc- /-OCECH;NHP1NKCHg-CH-O- tL/ I 5 esses. 4 'm A v Example 6 1 m H g 1 284 parts (1 mol) of stearic acid was heated g m with 204 parts (1 mol) 01' 1 amino 3 dipropylene triamine isopropanol until one moi of water was driven 011'. At 180 C. 30 parts We mol) of urea NH E was added and the temperature gradually raised ira Hi I to 190 C. during which time ammonia was tn. H l5 evolved. To the above condensate at 190 c. 73 H: parts (1 mol equivalent) of adipic acid was added t 11m and the temperature raised to 200 0. during J 5 which time water was liberated. The condensate NH "Ha v obtained was water soluble atter treatment with Example 5 acids or alkylating agents and had the following 9 parts 1 p of -3 diammo lsopropanol unit formula after treatment with dimethyl sulwas heated with 200 parts (1 mol) of lauric acid fate.

Ha Ha I'm NH H, H: Ha Ha +HI +3: NH NH HI 6H1 HI iHs H H: r r-soicm n cm =0 J7= Hid "Ha until one mol of water was driven oil. parts Equimolal quantities oi. linoleic, ricinoleic or soya mol) of urea was then added at 180-185 C. bean fatty acids maybe substituted for the stearic and the temperature raised to 190 C. during acid illustrated above which time ammonia was evolved. At 190 C. Example 7 107 parts (1 mol equivalent) of petrex acid,

a polybasic acid which is defined by its producer parts (1 moi) of 1-3 diamine isopropanol Hercules Powder (20., as 3-isopropy1-6-methyl- 5 were heated with 284 parts (1 mol) of stearic acid 3,6-endoethylene A tetra hydro phthalic anhyuntil one mol of water was driven oil. 30 parts dride, was slowly added and the temperature /2 mol) of urea was then slowly added at raised to 200 C. The condensate was a sticky C. and the temperature raised to C. durresin soluble in water after treatment with acetic ing which time ammonia was evolved. At 190 acid.- Its acetate salt had the following repeating 55 C. '74 parts (1 mol equivalent) of phthalic anunit formula: hydride was slowly added and the temperature 0' o o -/OCH-OHeNH- NH-OHsCHOp 1L- 0 H1 H] onr- -o-i i-n 1 m 0 E IE E 5 0 OH: nHu H Rayon fabric impregnated with a solution of the raised to 200 C; The condensate was a waxy above acetate salt in the ratio of 3 pounds per solid, resinous innature and soluble in water after considerable increased weight noticeable which 12 treatment,- with acetic acid. It had the follow- Example 10 ing unit formula: 60 parts (1 mol) of acetic acid was heated with I i l) 104 parts (1 mol) of 1,3 diamino 2 methylol Dro- CH pane to 180 C. until one mol of water was driven 1 CH 1 5 n, At 180 0. 30 parts we mol) of urea was slowly added and the temperature raised to 190 NE NH C. during which time ammonia was evolved. To

L one mol of the above condensate at 190 C. was "H" "Ha 10 added 118 parts (1 mol) of succinic acid and the temperature raised to 200 (1., water being re- Cotton fabric impregnated with a bath containmoved. The condensate obtained was resinous ing 5 pounds to 50 gallons of the above cominnature and had the following unit formula:

NH NH HI H:

pound in the form of its acetate salt possessed Example 11 resinous type hand which was resistant to wash 282 parts (1 mol) of oleic acid was heated with mg amid cleaning 204 parts (1 mol) of 1 amino 3 dipropylene tri- Example 8 amine isopropanol until one mol of water was driven off. At 180 C. 90 parts (1% mol) of v urea was slowly added and the temperature inwere heated with 284 parts (1 mol) of stearie creased to 1900 Q during which time ammonia acid until one moi of water was driven off. 0 parts (A mol) of urea was then slowly added at 10 was evolved- To the above C(mdensate at 190 o o C. '74 parts (1 mol equivalent) of phthalic an-' an m 1 g g g g ggfg z gzi g 2 hydride was added and the temperature raised to 200 C. during which time water was removed. 190 C. '73 parts (1 mol equivalent) of adipic acid was slowly added and the temperature raised to Ihe condensate Dbtamed was water soluble after The condensate was a sticky resin SOL treatment with acids or alkylating agents and 90 parts (1 mol) of 1-3 diamine isopropanol uble in water after treatment with acids or 2.1- had the following formula: kylating agents. It had the following unit for- 0 mula: -l--OCH-CHg-NH-Pl-NE-Clh-GH-O- -l o o o 0 o .1w-onmm-Nn-ii-m-cm-On-o-ii-mfifli;. m 15:. 4m, 7 8m fin 5: (EH: (1H1 o (2a, 0 m

"Ha Anna a H y Example 9 Am, A 282 parts (1 mol) of oleic acid was heated with E B 104 parts (1 mol) 01' 1,3 diamino 2 methylol pro- E l a H:

pane to C. during which time one mol of water was obtained. .At 180 C. 30 parts (A mol) NE NE of urea was slowly added and the temperature 5: J =o raised to C. during which time ammonia was H w A H evolved. To one mol of the above condensate 98 parts (1 mol) of maleic anhydride was added As many apparently widely difierent embodiand the temperature raised to 200 (3., water bements of this invention may be made without ing removed. The condensate obtained was 501- departing from the spirit and scope thereof, it

uble in water after treatment with acids or aiis understood that we do not limit ourselves to kylating agents and had the following unit for- 60 the specific embodiments thereof except as demula: fined in the appended claims.

"Ha Ha repeatingi units of the following general formula:

wherein R1 is a hydrocarbon residue resulting from a polycarboxylic acid and in which R3 and R4 represent simple alkylene groups of from 2 to m 3 carbon atoms and in which there is attached to one of the carbons in R: and R4 acid amide side chains of the following general formula:

in which R1 represents a hydrocarbon radical resulting from an organic acid and in which the letters e and m represent small integers with e varying from to 4 and m from 2 to 3.

2. The salt of an acid with a condensation compound described by the general formula in claim 1.

3. The alkylated product of the condensate described in claim 1 obtained by alkylating with a compound selected from the group consisting of ethyl chloride, ethylene oxide, benzyl chloride, diethyl sulfate and dimethyl sulfate.

4. The condensation products having one hydroxyl and one carboxyl end group and consisting of repeating units of the following general formula:

wherein n ranges from 1 toul'? and R1 is the hydrocarbon residue from a dicarboxylic acid.

5. A new chemical compound having one hydroxyl and one carboxyl end group and consisting of repeating units of the following formula:

' 8. A process for forming a condensation product as defined in claim 1 in which equimolar quanmula 130170 C. and thereafter reacted with one-half I mol of urea at 170-200 C. and thereafter reacted with equimolar quantities of a polycarboxylic acid at temperatures from 150-200 C.

9. A process for forming a condensation product as defined in claim 1 in which equimolar quantities of an organic monocarboxylic acid and an alkylol polyamine of the following general formula in which X represents a simple alkylene group of from 2 to 3 carbon atoms and in which one of the hydrogens attached to one of the carbon atoms is replaced by hydroxyl and in which formula the integer e varies from 0 to 4 and m from 2 to 3 are condensed at temperatures between 130-170 C. and thereafter reacted with one half mol of urea at 170-200 C. and thereafter further reacted with sufllcient polycarboxylic acid to react with all of the hydroxyl groups present.

10. A process for forming a condensation product as defined in claim 1 in which equimolar quantities of an organic monocarboxylic acid and an alkylol polyamine of the following general formula NHa-rwmm-mmP-cm-x-Nm of the hydrogens attached to one of the carbon Hg H! NE NH "Ha "Has 6. A new chemical compound having one hy droxyl and one carboxyl end group and consisting of repeating units of the following formula:

p and thereafter further reacted with an equimolar NH 1 quantity of a polycarboxylic acid at temperatures =0 =0 from 150200 C. and thereafter solubiiized by "H" "H" adding one mol of acid.

. A new chemical compound having one 11. A process for forming a condensation prodand one carboxyl end group and consist not as defined in claim 1 in which equimolar ing of repeating units of the following formula: quantities of an organic monocarboxylic acid and 55 atoms is replaced by hydroxyl and in which formula the integer e varies from 0 to 4 and m from 2 to 3 are condensed at temperatures between -1'70 C. and thereafter reactedwith one-half mol of urea at temperatures between 200 C.

an alkylol polyamine of the following general in which X represents a simple aikylene group of from 2 to 3 carbon atoms and in which one of the hydrogens attached to one of the carbon atoms is replaced by hydroxyl and in which formula the integer e varies from to 4 and m from 2 to 3 are condensed at temperatures between 130-170" C. and thereafter reacted with one-half mol of urea at 170-200 C. and thereafter reacted with an equimolar quantity of polycarboxylic acid at ISO-200 C. and solubilized by the addition of one moi of a water soluble acid.

12. 'A process for forming a condensation product as defined in claim 1 in which equimolar quantities of an organic monocarboxylic acid and an alkyklolpolyamine of the following general formula .in which X represents a simple aikylene group quantities of an organic monocarboxylic acid and an alkylol polyamine of the following general formula in which X represents a simple alkylene group of from 2 to 3 carbon atoms and in which one. of the hydrogens attached to one of the carbon atoms is replaced by hydroxyl and in which formula the integer e varies from 0 to 4 and m from 2 to 3 are condensed at temperatures between -170 C. and thereafter reacted with one-half moi of urea at 170-200 C. and thereafter reacted with an equimolar quantity of polycarboxylic acid at -200" C. and soiubilized by reacting with one moi of an aikylating agent as selected from the group consisting of ethyl chloride, ethylene oxide, benzyl chloride, diethyl sulfate and dimethyl sulfate.-

14. A textile material impregnated with a condensation product as described in claim 1.

15. A textile material impregnated with an alkylated condensation product obtained by a]- kylating a condensation product as described in claim 1 with a compound selected from a group consisting of ethyl chloride, ethylene oxide, benzyl chloride, diethyl sulfate and dimethyl sulfate.

16. A textile material impregnated with the salt which is the addition product of an acid to a condensation product as described in claim 1.

WILLARD L. MORGAN. EARLE D. MOLEOD.