US3357785A - Shrinkproofing wool through serial impregnation with a diisocyanate having one or two terminal ester groups and a diamine - Google Patents

Description

United; States Patent Office 3,35?,785 Patented Dec. 12, i967 This invention relates to the treatment of fibers and textile materials made from them. More particularly it relates. to a method for shrinkproofing wool utilizing alipthatic diisocyanates of carboxylic and dicarboxylic acid esters, novel compositions containing the same, and

novel products obtained thereby.

There are at least two mechanisms by which the shrinkage of wool may occur. The first of these is known as relaxation shrinkage and occurs when wool is treated with water or other chemicals. The art has attempted to solve the relaxation shrinkage problem by submitting wool to preshrinking wherein the material is allowed to encounter the environment which it would normally encounter during use and thereby be preshrunk before being put into actual use. It is theorized that this shrinkage is due to a change in the internal structure of the wool fibers. Another important shrinkage phenomenon, designated felting shrinkage, occurs in consequence of the physical structure of wool fibers. Wool fibers, which are normally clad with scales, will shrink when friction is applied to the wetted wool. The fibers are apparently aligned in random directions and the movement induced in these fibers tends, by a mechanism involving differential friction, to shrink the material. The arthas attempted to control felting shrinkage mainly by three techniques. Two of these, the oxidative and hydrolytic methods, involve treating the wool chemically with such materials as hypochlorite or chlorine in the first case, or with proteolytic enzymes such as trypsin and papain in the second. These two processes both suffer the disadvantage of degrading the wool to a point where, in order to achieve effective shrinkproofing, the material is consequently weakened in strength. Both of these methods alter the scale formation on the wool fibers.

Another method which has been directed toward the control of felting shrinkage is the so-called polymer deposition method. This involves depositing upon the wool fibers a polymer which tends to decrease the shrinkage of the wool when the material is subjected to a normally shrinking environment. Heretofore, the conventional polymer deposition techniques have not been entirely satisfactory, all suffering from one or more disadvantages which seriously limit their commercial acceptance. For example, some polymer systems currently available to the art require the use of large amounts of solvents for the. deposition of the polymer. This is a very serious drawback to the Wool processor who is generally not equipped to handle solventsboth from the standpoints of safety and economy. Another disadvantage attending the polymer deposition process is the. relatively large amounts of.

polymer required to be deposited. This too, as can be readily appreciated, presents an economic barrier to the. wool processor. Further, conventional polymer .deposition techniquestend to stiffen and harshen the wool such that the material does not conform aesthetically to a de-;

sirable standard.

When the disadvantages of the prior processes are com sidered it is apparent that it would be extremely desirable does not require the use of organic solvents and large amounts of polymer deposition and which yields a wool which is not harsh to the touch or stiffened to any appreciable extent.

It is accordingly an object of this invention to provide a process for shrinkproofing wool which does not require the use of organic solvents.

It is a further object of the invention to compositions useful in shrinkproofing wool.

Yet. another object of the invention is to provide a process for shrinkproofing Wool whereby the wool so treated is not harsheued to any appreciable extent.

It is still a further objectof the invention to provide a process for shrinkproofing woolby the in situ formation and depoistion of a polyurea which does not tend to discolor upon prolonged exposure to light.

provide novel These and further objects will become more apparent.

when full consideration is given to the following detailed disclosure.

In accordance with the present invention it has been discovered that wool may be very effectively shrinkproofed by the in situ formation thereon of a polyurea formed from a water dispersible diarnine and a member of a particular class of diisocyanates. The invention contemplates novel processes for forming the novel polyurea, novel diisocyanate compositions used in the novel processes and novel shrinkproofed articles obtained thereby. The process involves serially impregnating wool with the diisocyanate and the diarnine, not necessarily, but preferably, in that order. The diarnine coming into. contact with the diisocyanate, reacts therewith forming the polyurea polymer as a coating on the wool fibers, though residual amino groups of the wool also co-react, yielding a grafted polymer structure.

It isan important feature of the invention that the for mation of the polyurea does not involve the use of an organic solvent but rather uses an aqueous system for the application to the wool fibers of the reactants which form: the polyurea. In this regard, it is critical that the diisocyanate be supplied to the wool in the form of an aqueous emulsion and the diarnine in the form of an aqueous dispersion. As used herein, dispersion is meant to include solutions.

The diisocyanates contemplated for use in this inven-.

tion are diisocyanato substituted aliphatic monocarboxylic acid esters or dicarboxylic acid esters of the following either unsubstituted or substituted with halogen radicals,=

R is a lower alkylene or a lower alkylidene radical, R can be either hydrogen, or the radical.

Typical of the diisocyanates represented by the fore-1 going formula are: the esters of 2,6-diisocyanato caproic acid (lysine .diisocyanate) such :as the methyl, ethyl,

propyl, butyl, octyl, dodecyL stearyl, methoxymethyLfl methoxyethyl, 'y-ethoxypropyl, phenyl, benzyl, o-tolyl, o- (2 chlorotolyl), 2 bromoethyl, 1,2-dichloropropyl, 2,3- dichloropropyl, and isopropyl esters; the esters of 2,5-diisocyanato valeric acid (ornithine diisocyanate) such as.

ethyl, propyl, butyl, hexyl, octyl, dodecyl, stearyl, ethoxymethol, B-ethoxyethyl, phenyl, benzyl, o-tolyl, o-(2-chlorotolyl), 2-chloropropyl, 2,3-dichloropropyl and isopropyl esters;.the diesters of 2,4-diisocyanato glutaric acid, 2,5-.

diisocyanato adipic acid, 2,6-diisocyanato pimelic acid, 2,7-diisocyanato suberic acid, 2,9diisocyanato sebacic acid such as the dimethyl, diethyl, dipropyl, dibutyl, dioctyl, distearyl, diphenyl, dibenzyl, di(o-tolyl), di(o-(2- chlorotolyl) di(2 chloropropyl), di(2,3 dichloropropyl), and diisopropyl diesters and mixed diesters such as methyl-propyl diesters, phenyl-octyl diesters, and benzylstearyl diesters. The diisocyanates may be either the levo rotatory forms or the dextro rotatory forms, racemates or mixtures thereof. The diisocyanates preferred for use are the methyl and octyl esters of 2,6-diisocyanato caproic acid and most preferably the octyl ester.

The diamines contemplated for use in the invention are the water dispersible diamines or water dispersible salts of water insoluble diamines. In general, any diamine conforming to the above characteristics will be suitable but it is preferred to use diamines such as hexamethylencdiamine; alkyl esters of lysine or omithine in their water soluble dihydrohalide salt form such as n-octyl-L-lysinate dihydrochloride or n-hexyl ornithinate dihydrochloride; tetramethylene diamine, trimethylene diamine; piperazine, methyl and dimethylpiperazine; a,w-diamino polypropylene oxide; mixtures of the above; and the like. Most preferred among the foregoing is hexamethylenediamine.

Before embarking upon a discussion of the nature and characteristics of the diisocyanate emulsion and diamine dispersion, for purposes of clarity of presentation, the following, which is a description of the general mode of carrying out the process, is presented. In general, the wool is first impregnated with the diisocyanate emulsion so as to provide throughout the wool an amount of diisocyanate. The impregnated wool is then removed from the aqueous emulsion of the diisocyanate and pressed between rollers so as to remove excess moisture and materials. The thus obtained material is then introduced into the diamine dispersion, therein to come in contact with the diamine itself. The reaction between the diamine and the diisocyanate is very rapid at room temperature with the consequent formation of the polyurea corresponding to the diamine and diisocyanate.

After the polymerization reaction is complete the resultin g woolen material is wrung to recover unreacted diamine or diisocyanate as the case may be, and the impregnated piece then washed to remove any excess materials such as free polymer or any other diamine or diisocyanate not expressed in the wringing stage. The material is then ready for processing as desired, such as drying, dyeing, and the like.

In general, for effective shrinkproofing, it is desired to have on the wool and available for conversion to the polyurea between 0.1 and by weight of the diisocyanate and preferably from 0.5 to 4 weight percent based on the weight of wool. This can be obtained by proper adjustment of diisocyanate concentration in the emulsion. This concentration is approximately linearly related to diisocyanate takeup on the wool. In its preferred aspect the wool should take up between 80-100 weight percent of total emulsion based on weight of wool. Therefore, the concentration of the diisocyanate in the emulsion will be approximately the same as those given in connection with the desired amount to be impregnated, namely from 0.1 to 10% by weight and preferably from 0.5 to 4% by weight of the diisocyanate in water.

With further regard to the diisocyanate emulsion it is preferred to provide a uniform distribution of diisocyanate through the aqueous system so that the resulting polyurea formed will be uniformly distributed over the surface of the wool and will thus not be heavier in concentration in one place than in another, which difference in concentration might be visually apparent and would, therefore, detract from the aesthetic quality of the material. This may be achieved by mechanically dispersing the diisocyanate in the water as by agitation, ultrasonic vibration, the addition of emulsifiers, hereinafter discussed, and the like.

The temperature of the emulsion is not critical and is only a factor to the extent that temperature affects the chemical stability of the emulsion. In this regard, it will be appreciated that since isocyanate groups react with water, there will be a finite time available to a processor during which a substantial amount of diisocyanate remains unreaeted. This time will vary depending on the particular diisocyanate employed. For the preferred diisocyanate herein, octyl 2,6-diisocyanato caproate, the time is sufliciently long so that the emulsion is conveniently handled within 12 hours after its preparation. Operating within this time, good results are obtained when the emulsion bath temperature is between room temperature and about 40 C. For diisocyanates having a higher rate of reactivity, such as methyl 2,6 liisocyanato caproate, lower bath temperatures are conveniently employed to retard the reactivity and allow the processor convenient time in which to impregnate the wool. Temperatures of the order of 5 to 15 C. are suitable for this purpose.

With regard to the length of time and the conditions under which the diisocyanate impregnates the wool, contact times in the ester bath are related to the physical state of the wool (fibers, yarn, fabric). Particular con sideration is given to the thickness of the weave and its density. In general, the more dense the material the longer the contact time necessary to impregnate the wool with a convenient amount of diisocyanate. In dealing with typical flannel suiting material good results are obtained when the contact time is between 10 and 60 seconds. Shorter contact times of the order of one second or less are suitable for treating yarns and less dense materials, and longer times may be necessary for heavy fabrics.

With respect to the aqueous diamine dispersion it will be appreciated, as indicated previously, that the reaction between the diisocyanate and the diamine is very rapid and occurs quite fast. at room temperature. For this reason the concentration of the diamine in the, aqueous solution thereof is not critical. Since a one-to-one molar ratio of diamine to diisocyanate is required by the, stiochiometry it is, of course, preferred to supply in the aqueous solution a sufficient amount of diamine to react with all the diisocyanate present in the wool. For reasons of economy it is not desired to have an amount of diamine less than the stoichiometrically required amount. Hence the concentration of the diamine may be any convenient level consistent with these aims. The temperature and the contact time are not at all critical. Maintaining the bath at a temperature of about room temperature to about 40 C. gives satisfactory results and as indicated above the reaction rate is very rapid. Hence, the contacttime is of no criticality. Although the discussion here has been provided with respect to carrying out the reaction in a batchwise operation it will be understood that the process as a whole is particularly amendable to continuous'operation and this is therefore the preferred mode of carrying it out.

Further, although the above description is directed to ward carrying out the process by first impregnating with diisocyanate followed by the polymerization reaction with the diamine, the process is not to be limited to such a sequence of operations. Indeed, the impregnation may first be with the diamine dispersion, followed by polymerization through the use of the diisocyanate emulsion. When this order is carried out it will be appreciated by those skilled in the art that a simple, straight-forward calculation will yield the amount of diamine present in the first solution in order to obtain a wool article desirably having between 0.1 and 10 weight percent of polyurea impregnated thereon. Thus, by working back from the amount of polyurea desired to be put on, one may obtain the concentration of the diamine starting solution. The two bath process, in either order, is referredto as a serial treatment herein.

In preparing the emulsion of the diisocyanate material the process is operative when the diisocyanate is uniformly distributed in the water system without the aid; of any additives. However, when this is done the ensuing operations should be carried outhastily so as to avoid settling of the emulsion in the bath. As indicated previously, an.

emulsion of this type might not give uniform polymer deposition upon subsequent reaction with diamine. For this reason it is preferred to add an emulsifying agent to aid in the emulsification of the diisocyanate inthe.

is not critical and will vary depending upon the particu lar diisocyanate employed as a starting, material. The

goal is to obtain a good emulsion which is non-settling within a convenient operating time and one which gives.

good dispersion of particles throughout the medium. Hence any emulsifier which does this will be suitable. Thus it is even possible to use an emulsifier which may not be inert with respect to thediisocyanate but is elfective to form a good emulsion, if the rate of reaction between the emulsifier and the diisocyanate is not too rapid. In this regard, it will be remembered that the diisocyanate, being in contact with water, itself undergoes some I reaction with the water. This is not detrimental to the r process provided that the impregnation be carried out in such timeas will provide within the wool lattice a convenient amount of unreacted diisocyanate. Withre-. gard to the amount of emulsifier used, it is convenient to use, for the preferred emulsifiers described hereinafter,

about -15% by weight based on the diisocyanate. For i other materials, the total amount of emulsifier should. be enough to produce the desirable emulsion and yet still be consistent with good reaction economics. The emulsifier may be added to, mixed, or blended with the diisocyanate prior to mixing with water. Such compositions of emulsifier and diisocyanate are novel.

In general, suitableemulsifying agents are as follows: Sodium lauryl sulfate,: Ivory soap, sodium-N-methyl-N- oleoyl taurate (available under the trade name Igepon T-77 from Antara Chemical Company), octyl phenyl polyethoxy ethanol (available under the trade name Triton Xl5 fromRohm & Haas Co.), isooctyl phenyl polyethoxy. ethanol (available under the trade name Triton X-45 from: Rohm& Haas Co.). Also useful are various other emulsifiers available under the Triton trade name such as Triton CF-Zl, Triton X 100, Triton X-405, Triton CF42, and Triton X-lS, many of which are alkyl aryl polyethers; those available under the trade name T ergitol from Union Carbide Chemical Co. such as TergitoltNP 1X, Tergitol,

NP-27, Tergitol NPX, andTergitol NP-35, all of which are nonyl phenyl polyethylene glycol ethers.

In addition to the diisocyanates above, which are preferred, other diisocyanates and their adducts may also be used. For example, where some degree or yellowing can be tolerated, tolylene diisocyanate, phenylene diisocyanate or methylene bis-phenyl isocyanate may be emulsified and used in the serial treatment with a diamine. With these more reactive isocyanates it is necessary to maintain the emulsion bath at low temperatures (5-10 C. preferred) and to work with a short hold-uptime to avoid premature polymer formation. Hexamethylene diisocyanate, which is a hazardous substanceto handle, is best converted to an isocyanate-terminated adduct (with butylene glycol, hexamethylene glycol and the like) before emulsification. Control of polymer rigidity is done via the choice of adductor choice of diamine.

In addition to their .efficacy as shrinkproofing :treatments, all the above may find use in other textile finishing operations. Thus, by proper choice of monomers, useful and more or less permanent antistatic, water resistance,

or wash-and-wear characteristics may be introduced.

The following examples are given for purposes of illustration only and are not to be considered as limiting the invention. In each of the following examples, unless;

otherwise indicated, the following test method is employed:

A wool cloth is dipped into,bath (1). After remaining in the bath for a period of timethe cloth is removed and passed twice through a hand-operatediwringer to remove excess material. It is then immersed in bath (2) and again i 1 passed twice through a wringer. The contact time for each of the above immersions may vary from 15 to 30m 60 seconds without any noticeable efi'ect in the shriukproofing obtained. The cloth is then rinsed with water to remove unreacted monomers, emulsifier and unbound polymer and allowed to dry.

The test for shrinkage involves washing three to six pieces of wool measuring about 4 to 6 inches in a bowl of 0.1% solutionof Triton X-lOO (isooctyl phenyl poly-' ethoxy ethanol) available from Rohm & Haas Co., at,40 C. for 20 minutes. The samples are oven dried at 60 C.

to constant weight. In each washing there is always at least one untreated piece included to serve as a control. Each of the pieces is measured before treatment and:after washing-drying for calculation of area shrinkage.

EXAMPLE 1 Octyl-1,6diisocyanato caproate g 2 Sodium lauryl sulfate g .25 Water ml 250 r Hexamethylenediamine g 5 Water; "ml". 250 Shrinkage(area) 13% (control 38%.).

EXAMPLE 2 Hexamethylenediamine g 5 Water -ml 250 Octyl-2,6-diisocyanato caproate -g 2 Sodium lauryl sulfate g .25 Water ml 250 Shrinkage 17% (control 40%).

EXAMPLE. 3

Octyl-2,6-diisocyanato caproate g 4 Sodium lauryl sulfate g .25 Water ml 250 Hexamethylenediamine g 5 Water ml 250 Shrinkage 6% (control 43%).

EXAMPLE 4 1 ()ctyl-2,6-diisocyanatocaproate g.. Triton X-l5 (Octyl phenyl toxyethanol-Rohm &

Haas) g .5 Water ml 250 n-Octyl-L-lysinate.dihydrochloride: g 10 Sodium carbonate g 10 Water ml 250 Shrinkage 16% (control 42%).

EXAMPLE 5 I (1) Oc tyl-2,6-diisocyanato caproate g 2 Triton X-lS (octyl phenyl polyethoxy ethanol- Rohm & Haas) (orTriton CF-21 (alkyl aryl polyether) v .25 Water "n Water n-Octyl-L-lysinate-dihydrochloride g 5 Sodium carbonate g 5 Water ml' Shrinkage: 25% (control 41% EXAMPLE-6 Methyl-2,6-diisocyanato caproate g 2 Triton X15 (octylphenyl polyethoxy ethanol- Water I l 250 Hexamethylenediamine g 5 Water a ml 250 Shrinkage 3% (control 34%).

EXAMPLE 7 Methyl-2,6-diisocyanato caproate g 2 Triton X-lS (octyl phenyl colyethoxy ethanol- Rohm and Haas) g .25

Water ml- 2.50

N-octyl-L-lysinate.dihydrochloride, g 5 Sodium carbonate g 5' Water m1 250 Shrinkage 20% (control 38%).

EXAMPLES 8 THROUGHv 15 TABLE 1 .Shrinkage, Percent Emulsifier Treated Control .Aquarex D.(Sodiun1 sultatesof higher fatty alcohols, available from E, I. du Pont de Nemours & 00.).

Triton X-15 (octyliphenoxy ethano1).

. Sodium lauryl sulfate Trlton X-45 (isooctyl phenyl polyethoxy ethanol).

Triton (IF-32 (aminepolyglycol eondensate). Triton- X'100 (isoootyl phenyl poly ethoxy ethanol). I 1 Triton C'F-21 (alkyl' aryl'p'olyether)...

be H H H an O- ,0! fgwcncno w u emanate H 00 m @CDHNIO This. example shows the shringproofing ofi woolusing an. emulsion of octyl-2,6-diisocyanato caproate in water without the aid of an emulsifier.

System 1) below isv prepared by rapid agitation in a Waring Blendor, and used immediately after preparation as the first bath in treatment of wool. System (2) is used as the second bath. Results are shown.

Octyl 2, 6-diisocyanato caproate g Hexamethylenediamine g Water W ml Shrinkage 6% (control 44% Wool cloth showed some streaks of resin.

EXAMPLE 17 Following the procedure of Example 16, the following bath; components are employed. Shrinkage results are shown.

Octyl-2,6-diisocyanato caproate is mixed with the various emulsifiers shown in Table 2 below such that the emulsifier constitutes 10% by weight of the total mixture. The original isocyanate content is measured and compared with the final isocyanate content of the mixture after it has been allowed to stand for 76 days.

TABLE 2 Isooyanate Content in Weight Percent Time in Emulsifier Days Initial Final Sodium. lauryl sulfate 24. 4 i 22.0 76 Triton (IF-21 (alkyl aryl polyether)'. 24.4 21.9 76 Triton Ci -32v (amine, polyglyeol condensate) 24. 4 20. 2 76 Tergitol N P-IX (nonyl phenyl polyethylene glycol ether) 24. 4 22. 1 76 Tergitol N P-27 (nonyl phenyl polyethyleneglycol other) 24. 4 21. 7 76 Tergitol NPX (nonyl phenyl polyehtylone glycol ether) 24. 4 22. 0 76 Tergitol N P-35 (nonyl phonyl polyethylene glycol ether) 24. 4 20. 7 76 Eightydhtee days after initial formulation, each of the above mixtures is separately added to water (0.5 g. of mixture, 50g. water) and good emulsions are obtained.

The following examples are intended to be illustrative of the preparation of the. diisocyanato esters used in the present invention.

EXAMPLE 19 2,6.-diisocyanato methyl caproate 250 g. oflysine monohydrochloride suspended in 2500 ml. ofl absolute methanol is dissolved by passing into the stirred. suspension dry hydrogen chloride. The reaction temperature, immediately goes up to 47 C. and in 10 minutes. all the solids are dissolved. The gas is passed in for five minutes longer. The reaction mass is then permitted to cool slowly to room temperature with stirring. Crystals start to form in 2.5 hours. The reaction mass is stirred for a period of 15 hours at a temperatue, of 25 C. The product is precipitated by adding 1.5 liters of diethyl ether over a period of 15 minutes. After one hour of stirring, the product is isolated by filtration and washing with three parts of ether dissolved in two parts of methanol, followed by a diethyl ether wash. The product lysine dihydrochloride methyl ester is dried to constantweight at 65 C. in a vacuum oven.

The lysine methyl ester dihydrochloride is finely ground in a. mortar and 186 grams is suspended in 2100 ml. of

freshly dried and redistilled o-dichlorobenzene in a 3-neck flask.

Phosgene is passed into the reaction vessel at a rapid rate while raising the temperature of the suspension to 150-155 C. As the reaction proceeds the solution becomes clearer and darker. Hydrogen chloride evolution is indicated by fuming from the condenser as it hits the moist atmosphere. After twelve hours, no more hydrogen chloride evolves. Phosgene is passed in for one more hour and nitrogen is then bubbled through the reaction vessel as the solution temperature drops to 25 C. to remove residual phosgene and hydrogen chloride. The remaining solids are removed by filtration and washed. The filtrate is then distilled under reduced pressure. O-dichlorobenzene, the solvent, is distilled at 44 C. and 2 mm. pressure. The product, 2,6-diisocyanato methyl caproate, is distilled at 123 C., at 0.45 mm. pressure. A clear, colorless liquid product is obtained having a refractive index of 1.4565 at 24.5 C.

In an analogous manner, the ethyl, propyl, butyl, or pentyl esters of 2,6-diisocyanato caproic acid are prepared by substituting equivalent amounts of ethanol, propanol, butanol or pentanol for methanol in the foregoing procedure.

Similarly, when equivalent amounts of the monohydrochloride of 2,5-diarnine valeric acid are substituted for lysine monohydroehloride and equivalent amounts of methanol, ethanol, propanol, butanol or pentanol are employed as the alcohol in the foregoing procedure, the corresponding methyl, ethyl, propyl, butyl or pentyl ester of 2,5-diisocyanato valeric acid is obtained.

EXAMPLE 20 2,6-diisocyanato-n-ctyl caproate 18.2 g. (0.1 mole) of l-lysine monohydrochloride is suspended in 140 ml. of n-octanol containing 0.24 mole of p-toluenesulfonic acid. The mixture is heated until water and octanol begin to distill and the reaction temperature is then maintained at l20130 C. by addition of n-octanol. After 240 ml. of n-octanol are added and removed over a two hour period, the residual alcohol is removed by vacuum stripping. The waxy product, the di-p-toluenesulfonate salt of 2,6-diamino-n-octyl caproate, is recrystallized from a mixture of ethanol and diethyl ether.

A solution of 73 grams of this product in 150 ml. methanol is adsorbed on a column of 500 ml. of a strongly basic styrene-divinylbenzene anion exchange resin (Dowex 1-X8) which had previously been activated on the hydroxyl cycle with aqueous ammonia, washed to neutrality, and had its water displaced with methanol. The product is eluted from the column with methanol. The free base ester is not isolated but converted to the dihydrochloride recovered by precipitation with diethyl ether. The dihydrochloride is suspended in 275 ml. of toluene and 0.45 mole of phosgene added at 60-70" C. When evolution of HCl ceases, the temperature of the reaction mass is gradually increased to strip out the solvent. The product, 2,6-diisocyanato-n-octyl caproate is recovered by vacuum fractionation, B.P. 137-142 C. at 0.2 mm.

When the foregoing procedure is repeated using equivalent amounts of hexanol, decanol, dodecanol, or tetradecanol in place of octanol, the corresponding hexyl, decyl, dodecyl, or tetradecyl ester of 2,6-diisocyanato caproic acid is obtained.

Similarly, when the foregoing procedure is repeated using equivalent amounts of the monohydroehloride of 2,5-diamino valeric acid in place of the lysine monohydrochloride and equivalent amounts of hexanol, octanol, decanol, dececanol, or tetradecanol are employed as the alcohol, the corresponding hexyl, octyl, decyl, dodecyl or tetradecyl ester of 2,5-diisocyanoto valeric acid is obtained.

. EXAMPLE 21 2,6-di'isocyanato phenyl caproate The acid chloride of lysine dihydrochloride is prepared by passing phosgene through a suspension of lysine dihydrochloride in dioxane for several hours at 50 C. The oily product is added to dimethyl formamide containing the calculated amount of sodium phenoxide to form the phenyl esters of lysine dihydrochloride. This ester is suspended along with a small amount of sodium chloride, in o-dichlorobenzene (0.1 mole in 200 ml.) and phosgenated with gaseous phosgene at C. The resulting carbamyl chloride is decomposed at C. and the solution is filtered, concentrated, treated with absorbent carbon, and the solvent removed to yield yellow 2,6-diisocyanato phenyl caproate which was then purified by molecular distillation.

When the foregoing procedure is repeated using equiva' lent amounts of the sodium salt of either o-cresol or 2,4,6 trichlorophenol in place of the sodium phenoxide, the o-tolyl or 1,3,5 trichlorophenyl ester of 2,6-diisocyanato caprioc acid is obtained respectively.

Similarly, when equivalent amounts of ornithine dihydrochloride are substituted for the lysine dihydrochloride in the above procedure, the corresponding 2,5- diisocyanato valeric acid esters are obtained.

It will be apparent to those skilled in the art that a wide variety of combinations and variations may be employed in preparing the compositions of the present invention without departing from the spirit and scope of the invention. All such modifications, changes and variations, departing from the above description are intended to be encompassed within the scope of the appended claims.

What is claimed is:

1. A process for the shrinkproofing of wool which comprises serially impregnating wool with an aqueous emulsion and an aqueous diamine dispersion, said emulsion comprising water and a diisocyanate of the formula:

wherein R is selected from the group consisting of alkyl, alkoxy alkyl, aryl, alkaryl, aralkyl, and halogenated derivatives thereof, R is selected from the group consisting of lower alkylene or lower alkylidene and R is selected from the group consisting of hydrogen and the radical 2. The process according to claim 1 wherein the aqueous emulsion of the diisocyanate additionally contains an emulsifier.

3. The process according to claim 1 wherein the diisocyanate is octyl-2,6-diisocyanato caproate.

4. The process according to claim 3 wherein the diamine is hexamethylenediamine.

5. The process according to claim 4 wherein the aqueous emulsion of octyl-2,6-diisocyanato caproate additionally contains an emulsifier.

6. The process according to claim 5 wherein the emulsifier is selected from the group consisting of sodium lauryl sulfate and alkyl aryl polyethers.

7. The process according to claim 6 wherein the emulsifier is sodium lauryl sulfate.

8. The process according to claim 1 wherein the diisocyanate is methyl-2,6-diisocyanato caproate.

9. The process according to claim 8 wherein the diamine is hexamethylenediamine.

1 1 1.2 10. The process according to claim 9 wherein the aque- References Cited ous emulsion of methyl-2g6-diisocyanato caproate addi- UNITED STATES PATENTS tionally contains an'emulsifier.

3;,084 ,019 4/1963: Whitfield ct al. 8-128 11. The process according to claim 10 wherein the emulsifier is selected from the group consisting of sodium. 5 V lauryl sulfate and alkyl aryl polyethers. NORMAN TORCHIN" Pnmary Exammer' 12. The process according to claim 10 wherein the I. CANNON Assistant Examiner.

emulsifier is sodium lauryl sulfate.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,357,785 December 12, 1967 John D. Garber et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. a a

Column 1, line 15, for "al1pthat1c read aliphatic column 2, line 14, for "depoistion" read deposition line 70, for "methol" read methyl column 6, line 23, for "Octyl-l,6-diisocyanato caproate" read Octyl-2,6diiso cyanato caproate column 7, line 24, for "Triton X-lS (octyl phenyl colyethoxy ethanol" read Triton X-lS (octyl phenyl polyethoxy ethanol line 65, for "shringproofing" read shrinkproofing column 9, line 72, for "dececanol" read dodecanol Signed and sealed this 14th day of January 1969.

(SEAL) Attest: Edward M. Fletcher, Ir. EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A PROCESS FOR THE SHRINKPROFFING OF WOOL WHICH COMPRISES SERIALLY IMPREGNATING WOOL WITH AN AQUEOUS EMULSION AND AN AQUEOUS DIAMINE DISPERSION, SAID EMULSION COMPRISING WATER AND A DIISOCYANATE OF THE FORMULA: