US2385766A - Guanamines in textile finishing - Google Patents

Description

-Patented Sept. 25, 1945' GUANAMINEB IN TEXTILE FINISHING Jack '1. Thurston, Cos Cob, Coma, assignor to American Cyanamld Company, New York, N. Y., a corporation of Maine No Drawing. Application August 30, 1941, Serial No. 409,113

3 Claims. (01. 117-161) This invention relates to the treating and fluishing of textiles and textile forming materials such as cotton, linen, wool, viscose, cellulose acetate, spun rayon, and the like. More particularly the invention relates to textile finishing processes, to finishing compositions and to textiles finished with compositions consisting of or containing N-substituted guanamines and their aldehyde condensation products as will be subsequently described.

A wide range of softening agents, fulling agents, lubricants, creaseproofing agents and waterproofing agents have heretofore been applied to textile threads and fibers. The treatment of textiles for these and similar purposes such as shrinkproofing is known as textile finishing, and the agents employed for the purpose are known as textile finishing agents. It is a principal object of the present invention to provide a new class of textile finishing agents having improved softening, waterprooflng and other properties, and to provide new and improved textile finishing processes employing such materials. A further important feature of the invention resides in the provision of cotton, wool, silk, cellulose ester and other yarns, threads or fabrics finished with compositions containing N-substituted guanamines and their reaction products and having improved water-re-' sistance and a more desirable hand, and other properties.

In my eopending application Serial No. 409,112, filed concurrently herewith, I have shown that the 2-alkyl or cycloaliphatic 4,6-dia1nino-1,3,5- triazines, generally known as alkyl guanamines, are excellent softening agents and water-repellents for textiles when the alkyl group contains at least seven carbon atoms. The present invention is based on the discovery that the textile softening and water-repellent properties of the guanamines are not necessarily limited by the presence of a long alkyl chain or cycloaliphatic group on the 2 carbon atom, but that one or more substituent group or groups totalling seven carbon atoms may be located at any point or points about the guanamine nucleus with equally eifective results. Since the only groups capable of substitution other than the 2 carbon atom are amino groups it follows that the compounds in question are all N-substituted guanamines which may or may not contain substituents on the 2 carbon atom.

Many of the N-substituted guanamines of my present invention possess a number of distinct advantages over some of the higher alkyl guanamines for textile finishing, such as greater ease of preparation, improved compatibility with certain resins and other binding agents, and better softness of hand. Thus, for example, it is a known fact that the lower alkyl guanamines are more easily prepared, and with much better yields, than are the higher alkyl guanamines, and this also applies to N-substituted lower alkyl guanamines prepared from substituted biguanides and lower fatty acid esters. Moreover, the N-substituted guanamines are obtainable by fusing the corresponding unsubstituted guanamines with amine salts or with acid chlorides or anhydrides. My present invention therefore extends the field of guanamines available for textile finishing to include a large number that may be cheaply and easily prepared.

Although any N-substituted guanamine in which the substituent groups contain a total of seven carbon atoms may be used with success in practicing my invention I prefer those compounds in which at least one N-substituent contains at least four carbon atoms. This substituent may be an alkyl group, as in the N-butyl, N-amyl or N-decyl guanamines or an acyl group as in the N-butyryl and N-caproyl guanamines or it may be an aryl group as in the 4-N-phenyl guanamines, but in the latter case it is preferable to have an aliphatic or cycloaliphatic radical of at least 4 carbon atoms elsewhere in the guanamine. Although my invention is not limited to any theory of operation, I believe that these substituent groups extend the area covered by the guanamine when applied to textile fibers and assist in rendering the textile soft and water-repellent.

From what has been said it is evident that the N-substituted guanamines used in practicing my invention are compounds corresponding to the formula ing monovalent radical connected to the 2-carbon atom of the aminotriazine nucleus by a carfore; and X is a saturated or unsaturated aliphatic or cycloaliphatic group or any suitable bon-to-carbon bond, A and B may be hydrogen 'or-any suitable monovalent substitutent thereguanamines are'i'nost useful as textile finishing agents when combined with aldehydes. When dispersible resins are desired it is usually advisable to employ guanamines containing at least two replaceable amino hydrogen atoms and to use rather mild conditions for the aldehyde condensation, such as by agitating the aldehyde and guaoxy, oxyaryl, aryiolw. orcarboxyiic, sulionic, carbonyl, amino or amido or other groups as will subsequently be explained. A few. representative compounds illustrative of the large number which may be ,applied to textiles in accordance with the present invention are as follows:

(1) Representative N-substituted guanamines in which R is hydrogen or an alkyl group are 4- N-phenyi lauroguanamine, 4-N-phenyl (2'- namine solution at 50-70" C. until the reaction is complete,rand an inert solvent may be used to maintain-the guanamine in a dispersed form at these temperatures. The resulting resin solutions which are first formed can usually be diluted with 7 limited quantities of water, but upon continued heating or upon reaction at higher temperatures a hydrophobic resin is produced. Further polymerization is obtained upon heating the resin after its application to the textile fibers, and a V permanent laundry-resistant waterproofing effect ethyl) hexanoguanamine, 4-N-phenyl octanoguanamine, 4-N-phenyl hexanoguanamine, 4-N- phenyl butyroguanamine, 4-N-pheny1 acetoguanamine, 4-N-phenyl (Z-methoxy) propionoguanamine, 4-N-hydroxyphenyl butyroguanamine, 4-N-m-aminophenyl butyroguanamine, 4- N-cyclohexyll-ethyl) -hexanoguanamine, 4-N- lauroyl lauroguanamine, and 4-N-octanoyl octanoguanamine. Typical tormoguanamines that may be employed include -n-p-tertiary amylphenyl iormoauanamine and 4-N-butyl-4-N- phenyl formoguanamine.

(2) Typical compounds in which R is aromatic are 4-N-phenyl benzoguanamine, 4-N-cyclohexyl benzoguanamine and 4-N-butyl benzoguanamine. Other compounds typical of the large number that may be employed in practicing the invention include N,N'-disubstituted guanamines such as 4,6-N,N-dibutyl benzoguanamine, 4,6- N,N'-dimethyl hexanoguanamine, 4,6-N,N'-diamyl benzoguanamine, 4,6-N,N'-diethanol lauroguanamine, and 4-N-phenyl-6-N-myristoyl myristoguanamine.

The above and other guanamines falling within the scope of the invention may be prepared by reacting biguanide or substituted biguanides with unsubstituted or substituted aliphatic and cycloaliphatic carboxylic acids and their esters and halides. When the acid halides are used the reaction usually proceeds smoothly upon simple admixture of the reagents in the presence of inert solvents but when the esters are employed it is frequently desirable to carry out the reaction in the presence of alkaline catalysts. Metal alcoholates are particularly useful for this purpose, and sodium methylate is the preferred catalyst. The condensation product is usually recovered by filtration and purified by recrystallization from methanol, other alcohols, acetone, methyethyl ketone, hot water or other suitavle solvents. Many of the N-substituted guanamines may also be prepared from the corresponding unsubstituted guanamines by fusion with amine salts, preferably in the presence of a flux such as phenol and a condensation catalyst such as zinc chloride. N- acylguanamines may be prepared in similar manner by heating the unsubstituted guanamine with an acid anhydride or with an acid chloride, preferably in the presence of a strong trialkyl amine.

All of the N-substituted guanamines containing at least one free amino hydrogen will comblue with formaldehyde, acetaldehyde, butyraldehyde and other aldehydes to form condensation products. This is an important advantage of my invention, for many of the N-substituted is obtained when the fiber is first impregnated with the resin in its water-dispersible stage and then subsequently heated to further cure the resin to the water-insoluble stage.

Although other aldehydes may be employed I prefer to condense the guanamines with formaldehyde, which may be used in the form of ordinary 37% formalin solutions, or as strong aqueous formaldehyde solutions of 40-50% strength stabilized by the addition of 4-10% of melamine, or a paraformaldehyde. At least one mole of formaldehyde for each mole of guanamine shouldbe used, but two to ten moles of formaldehyde are preferred. When higher formaldehyde ratios of the order of 6-8 moles for each mole of the guanamine are employed the condensation product is more easily dispersible in water.

The guanamine-formaldehyde condensation .products, are quite easy to obtain in the form of substantially monomolecular products; that is to say, as methylol guanamines. These compounds can be alkylated by heating with primary alcohols such as methanol, ethanol and butanol with or without the addition of small amounts of phosphoric acid, oxalic acid or hydrochloride acid with azeotropic distillation of the water of condensation, and the resulting products may be applied to textiles from their solutions in organic solvents as creaseproofing agents and water-repellents.

Many of the N-substituted guanamines are soiuble in such organic solvents as acetone, toluene, dioxane and ethers of ethylene glycol and may 'be applied as such to textiles as softening agents and Water-repellents. The aldehyde condensation products can also be applied as solutions in these and similar organic solvents. In addition to the dispersi'bility obtained by the use of mild temperature conditions during the condensation and by excess formaldehyde, referred to above, the condensation products can be dispersed in water containing equimolecular amounts of organic acidssuch as acetic, lactic and alpha-hydroxy isobutyric acids, and these acids will also act as curing accelerators for the resins after their aplication to the cloth. The resins are also solubilized by ammonia and other alkalis. Polymerization products obtained by heating glycidol and other alcohols containing an ethylene oxide ring are also good dispersing agents.

Another class of agents that are well suited for use as dispersing agents are aliphatic and cycloaliphatic substituted guanamines in which the allryl radical contains the sulfonic group, such as omega-sulfo decanoguanamine or one or more carboxylic acid groups such as omega-carboxy propionoguanamine, omega-carboxy pelargonoassures I which theB-aliphatic or cycloaliphatic substitalkyl guanamine resins is'the guanamine obtained by condensingbiguanidewith"Petrex which is a diene condensation product. of. pinene with maleic anhydride.

Additional solubilizing and dispersing agents are also described and claimed in the copending applications or Stiegler, 'l 'luck and Thurston, Se-

rial-No. 109;114 filed concurrently herewith. -As' is pointed out in-that application, such wetting and emulsifying agents assodium isopropyl naphthalene sulionate, sodiumlauryl sulfate, glycerine and other polyhydric alcohols, partially or completely neutralized sulfite cellulose liquor, so-

dium; ammonium and ethan'olamine stearate,

oleate' and other higher'fatty acid salts and ammonium caseinate may be used as dispersing agents for the preparation of textile ilnishin'g baths containing higher guanaminesand guanamine-aldehyde condensation products.

Iii-addition to the application of the N-substituted guanamines'and their aldehyde condensation products to textiles as the principal finishin8 agent thesecompounds maybe applied in admixture with resins, gums, balsams and other binders that will give increased permanency to the finish. ThuaYoi-"example, urea-formaldehyde resins, melamine-formaldehyde resins, phenolformaldehyde re'sinaalky'd resins and any other curing typ of resin may be used to assist in binding the guanamine' tosthe fiber. These additional binding agents canbe used in considerable excess over -the amount or guanamine or guanamine resin, and the retention of finish on the fiber aiter laundering is thereby greatly improved. I

, 'Ashas been stated above, one of the most useful methods of preparing textile treating baths containing' the N-substituted guanamine compounds is with the'aid oi dispersing agents. A typical procedure of this kind, which may be used for applying any oi'the compositions of my invention to; textiles, is as follows: g

'A solution of the N-substituted guan'amine or guanamine-aldehyderesin i'sprepared in methanol, ethanol, isopropanol, ethyl ether oi ethylene glycol or other suitable solventby heating with agitation. aqueous dispersion of a resin, gum

or other suitable binding agent is then prepared having a 'cencentration suitable for application to the iiberj' ior example, a solution "of 10-15 parts or more of water-soluble urea-formaldehyde resin or of methylated trimethylol or hexamethylol melamine in suilicient water tomake 100 parts.- About 5-40 parts by weight oi" a 5% solution of a suitable dispersingagent such as sodium i'sopropyl naphthalene sullonate is'added to this bath and the guanamine or guanamine'resin solution is poured in with stirring-while maintaining the temperature at about 115 F. A dispersion having an extremely nne particle size is thus obtained, to which a curing accelerator may be added to speed up the setting of the resin after its ap lication to the fiber if desired. Four. percent based on the: total resinsolids of a mixture of 4 parts hexamethylene tetramine and parts 0! diammonium phosphate has been used to advantage. The cloth to be treated'lsilnmersed in thi bath and then passed through squeezing rolls adjusted to a tension such that the quantity oi treating solution retained on the cloth is approximately equal to the weight of the ilber. The treated cloth is then-dried at about 250 1". and heated for a short time at higher temperatures to cure the: resin. A permanent and laundry-resistalntt 1:vaterproof finish is thereby imparted to the c o I It'should be understood that the above described aqueous dispersions of higher alkyl guan'amines in admixturewith urea-formaldehyde and particularly methylated, melamine-formaldehyde resins is not claimed as such in the present application. On the'contrary', these dispersions and their application to textiles are claimed in the application of Stiegler, 'Fluck and Thurston, referred to above.

The invention will be illustrated 1.. greater detail by the following specific examples, which show representative compositions included therein. It sbouldbe understood, however, that although these examples may describe in detail some of the more specific details of the invention they are. given primaril for illustrativepurposes and the invention in its-broader aspects is not limited thereto.

Example 1* 4-N-phenyl stearoguanamine was prepared by reacting 35.4 parts by weight of phenyl biguanide with parts of methyl stearate in a mixture of 200 parts. methanol'and 50 parts, 01 cellosolve." The product was purii'ied by recrystallization from carbon tetrachloride.

I 40 parts by weight or 37% aqueous formaldehyde solution were adjusted to a pH of 8.0 by the addition of triethanolamine and 45 parts or the I i-N-phenyfstearoguan'amihe and an equal weight of methanol were added. The mixture was heated at 70 C, jfor one hour, cooled and-dehydrated. The resinous product was tested as a water-repellant for cotton and spun rayon cloth.

Emmple 2 43 parts by weight or benzoguanam lne, 22 parts or n-butylamine hydrochloride and 15 parts of phenol were heated .togetherfor 6 hours at 180- 225 C. The hot mixture was mixed with water, an excess of strong-alkali was Iaddedand the phenol was removed,"leaving' a granular solid The resulting 4+N-butyl benzoguanamine was recrystallized from a mixture of benzene and sol vent naphtha and a' pure product was obtained in the form-of minute, colorless crystals."

This product was tested as a. water-repellent for textiles. A formaldehydecondensation prodnot was also'prepared by-reacting 10 parts by weight of the product with 133 parts by weight of 37% aqueous formaldehyde solution, this constituting a molar ratio of 1:4. The mixture was heated to boiling during 30 minutes with agitation .and a small amount 01' a 1%:solutionof dihydrogen dimethyl pyrophosphate was then added as a catalyst. The mixture was refluxed'i'or 30 minutes, an excess of butanol was added, and the mixture was heated for an additional .30 minutes with distillation of a water-butane] mixture until a clear-resin solution was obtained. This resin solution was applied to spun rayon challis-i'rom a 1.5% solution in ethyl-alcohol which also contained 10% of urea-formaldehyde resin and 5%oi' a curing accelerator. After drying and curing the fabric was found to possess a full, soft hand and good water repellency.

Example 3 4,6-N,N'-dibutyl benzoguanamine was prepared by fusing 140 parts by weight of n-butylamine hydrochloride with 100 parts of benzoguanamine in the presence of 50 parts of phenol and 13.6 parts of zinc chloride. Upon recrystallization from methanol the product was obtained in the form of minute, colorless plates. It was tested as a water-repellent and softener for textiles.

4-N-dimethyl hexanoguanamine was prepared by fusing 103 parts of hexanoguanamine with 40.8 parts of dimethylamine hydrochloride followed by solution in benzene and precipitation with naphtha. 10.5 parts of the product were reacted with 162 parts of 37% formalin by heating the mixture to boiling, adding a small quantity of dihydrogen dimethyl pyrophospha-te catalyst, and refluxing for one-half hour. An excess of butanol was then added and the mixture boiled for one-half hour longer, whereupon a clear, water-white resin solution was obtained. This product was also tested as a textile finishing agent.

4,6'-N,N'-diacetyl decanoguanamine was prepared by refluxing 24 parts of decanoguanamine with 250 parts of acetic anhydride for 30 minutes followed by evaporation to dryness and re crystallization from ethyl acetate.

Example 4 To 31 parts of neutral l-butylbiguanide sulfate 3 guanamine was approximately 50%, the other 50% being the guanamine.

parts by weight of 37% formalin were neutralized to a pH of 8 by the addition of triethanolamine and 16.8 parts of 4-N-octanoyloctano guanamine and 100 parts of isopropanol were added. The mixture was heated with agitation, 100 parts of butanol were added, and the heating was continued under a reflux condenser for minutes. The isopropanol was then distilled off and the product was cooled and filtered. The resulting clear resin solution was tested as a textile finishing agent.

Example 6 A suspension of 21.8 parts by weight of biguanide sulfate in 200 parts of water was cooled to 5-10" C. and reacted with 16 parts of sodium hydroxide. 21.8 parts of lauroyl chloride were then added with stirring and the mixture was maintained at 05 C. for two hours. 1000 parts of water containing 10 parts of acetic acid were then added and after stirring for a short time the product was filtered. The wet solid remaining on the filter was dissolved in hot ethyl acetate and the resulting solution was filtered and cooled to low temperatures. Crystals of 4-N-lauroyl lauroguanamine were obtained which were further purified by recrystallization from chloroform and ethyl acetate. The purified product, which melted at 182-1835" C., was used as'a textile finishing agent.

Example 7 The hydrophobic properties of cloth treated with water-repellant compositions containing N- substituted guanamines of the type described in the foregoing examples were determined quantitao tively by a standard spray test, which is applied as was concentrated to about one-third of its orig inal volume and diluted with about 400 parts of water. After removing the water-insoluble 4-H- butyl-2-ethylhexanoguanamine, it was dried and yield of a product melting at 131-132 C. was about 30% 10 parts of the 4-N-butyl-2-ethylhexanoguanamine were added to 30 parts of 37% aqueous formaldehyde containing sufilcient NaOH to adjust the pH to about 8.5. The mixture was heat ed to a clear solution after which an excess of n-butanol was added and a butanol-water mixture distilled off until a water-free resin solution was obtained.

1 Example 5 To 145 parts of biguanide suspended in 1200 parts of acetone cooled to about 30 C. was added rapidly 117 parts of caprylic acid chloride. The reaction mixture was stirred in the cold for several hours and finally heated to reflux and filtered. From the cold acetone filtrate there was obtained 56 parts of octanoguanamine melting at 166-167 C. The acetone insoluble residue was extracted with about 1500 parts of cold water in order to remove the biguanide hydrochloride. Alter filtering and drying, there was obtained 85 parts of crude 4-N-octanoyloctano guanamine melting at 184 C. This product was recrystallized from a 2:1 mixture oftoluene and methanol and the purified material melted at 197-198 C. The yield of the acylated recrystallized from naphtha (90-125 0.) The I follows:

A six-inch square of cloth treated with the waterproofing agent, dried and cured is weighed and then suspended 10 inches from a horizontal spray nozzle supplied with water at 70 F. under a head of exactly 6 feet. The cloth is sprayed for one minute, during which time 1.5 gallons of water are discharged through the nozzle, drained for 10 seconds, rolled between pieces of absorbent paper to remove surface water, and again weighed. The increase in weight is expressed as percent water absorbed, based on the original dry weight of the cloth.

In order to measure the resistance of the finish to laundering, samples of the treated cloth were washed in an 0.5% soap solution at 160 F. for

80 minutes, rinsed and dried, and again subjected a mixture of 4 parts hexamethylene tetramine and 30 parts diammonium phosphate. x 80-4 yard cotton percale was padded in the bath, passed through squeeze rolls, dried at 250 F. and cured in the manner previously described. The

results obtained are summarized in the following table:

Percent water Mom! absorbed Compound r ti oi OHIO 4 An Original Bowing i-N-ghenyl stearoguanamine 1:2. 6 36. 1 25. 4-N- utyi benzoguanamine None 55.6 40 4,6-N,N-dibutyi benzoguanamine None 54. 3 38. 4-N-butyi-2-(2-ethyi) hexanoguanamine 1:1 46.8 42. 4-N-octanoyl ootanoguanamine. 1:5 31. 0 26. i-N-lauroyi lauroguanamine None 39. 3 28. 4,6-N,N'-diacetyl decanoguanamine None 59.

What I claim is f l. A method of finishing textiles which comprises the steps 01' applying thereto a formaldehyde condensation product of an N-substituted guanamine of the formula B N/ x in which R is a member of the group consisting of hydrogen and carbon-containing monovalent radicals connected to the 2-carb0n atom of the aminotriazine nucleus by a carbon-to-carbon bond, IA and B are members of the group consisting of hydrogen and monovalent substituents for hydrogen and X is a member of the group consisting of aliphatic, cycloaliphatic and mononuclear aromatic radicals and in which a total of at least '7 carbon atoms is contained in the groups R, x, A and B, and then heating the textiles to cure the guanamine-formaldehyde condensation product thereon.

2. A method of finishing textiles which comprises the step of app ying thereto an N-substituted guanamine as defined in claim 1 together with a heat-curing resin other than an N-substituted guanamine-formaldehyde resin.

3. A method of finishing textiles which comprises the steps or preparing a liquid finishing composition containing an aqueous dispersion of a formaldehyde condensation product of an N- substituted guanamine of the formula in which R is a member of the group consisting of hydrogen and carbon-containing monovaient radicals connected to the 2-carbon atom of the aminotriazine nucleus by a carbon-to-carbon bond, A and B are members of the group consisting of hydrogen and monovalent substitutents for hydrogenand x is a member of the group consisting of aliphatic, cycloaliphatic and mononuclear aromatic radicals and in which a total of at least 7 carbon atoms is contained in the groups R, X, A and B, impregnating the textiles with said composition, and heating the impregnated textiles to dry the same and set the finish on the'fibers thereof. i I

JACK T. T'HURS'I'ON.