US3523750A - Process for treatment of proteinaceous materials - Google Patents

Description

United States Patent Oflice 3,523,750 Patented Aug. 11, 1970 3,523,750 PROCESS FOR TREATMENT OF PROTEINACEOUS MATERIALS Giuliana C. Tesoro, Dobbs Ferry, N.Y., assignor to J. P. Stevens & Co., Inc., New York, N.Y., a corporation of Delaware No Drawing. Continuation-in-part of application Ser. No. 569,016, Aug. 1, 1966, which is a continuation-in-part of application Ser. No. 481,094, Aug. 19, 1965. This application Nov. 8, 1968, Ser. No. 774,508

Int. Cl. D06n 13/48 U.S. Cl. 8-127.6 26 Claims ABSTRACT OF THE DISCLOSURE This invention concerns a novel process for modifying proteinaceous substrates comprising treating said substrates with polyfunctional aziridine reagent, and heating the treated substrate until the desired modification takes place.

The present invention is a continuation-in-part of my copending application Ser. No. 569,016, filed Aug. 1, 1966 now abandoned, which is a continuation-in-part of my application Ser. No. 481,094, filed Aug. 19, 1965, now abandoned.

The present invention relates to novel processes for treatment of proteinaceous materials and more particularly processes for enhancing the properties and characteristics of textiles containing wool fibers and improved products obtained thereby.

Various methods have been devised for the treatment of textile fabrics containing wool in order to improve certain properties thereof. Particularly important to the wool industry are methods and compositions to bring about improvements in the dimensional stability and the felting characteristics of textiles containing wool fibers. Although many methods have been developed for W001 treatment, relatively few give satisfactory results from the standpoint of improvement in dimensional stability and felting. Moreover, prior known methods frequently may deleteriously and adversely aflfect the appearance, handle, strength and other properties of the woolen textiles.

Accordingly, it is the object of the present invention to provide novel processes for imparting improved properties to proteinaceous materials, particularly wool-containing textile materials, which overcome the shortcomings and disadvantages associated with prior methods and compositions.

It is a further object of the present invention to provide novel processes for imparting excellent properties and characteristics to wool-containing textiles which avoid the drawbacks of prior methods and compositions.

It is a further object of the present invention to pro vide novel processes for imparting to wool-containing textile material excellent properties of dimensional stability and resistance to felting.

It is a further object of the present invention to provide woolen textiles having improved properties, particularly dimensional stability.

It is a further object of the present invention to provide processes for treating wool-containing textile materials without. adversely affecting the appearance, handle, strength and other desirable properties of the textile.

It is a further object of the present invention to provide processes for treating wool-containing fabrics which have desirable surface appearance after laundering, particularly minimal fuzziness.

In attaining the above objects, one feature of the present invention resides in imparting excellent properties and characteristics to proteinaceous materials by treating textile materials containing wool fibers with a selected group of polyfunctional compounds of a specified structure whereby the improvements in dimensional stability and other physical properties are achieved without adversely affecting the appearance, hand, strength and other desir able properties of the textile.

More particularly, a proteinaceous textile substrate such as wool and its blends is treated with a solution of polyfunctional composition represented by the structural formula:

o H H 0 wherein A is selected from the group consisting of Az,

NHC,,H ,,Az, and OC,,H Az

a is an integer from 1 to 4, m is an integer from 2 to 4, Az is N R -O CR R1; R2

where R R R are selected from the group consisting of H and alkyl having from 1 to 4 carbon atoms,

J which has the valence of m is the residue of a polyol having at least 2 to 8 hydroxyl groups,'after 2 to 4 hydroxyl groups have been removed, and

Q is selected from the group consisting of divalent aromatic and alkyl-su-bstituted aromatic groups having 6 to 18 carbon atoms,

to deposit an amount sufficient to obtain the enhancement of properties sought, dried and cured at elevated temperatures until the properties of the substrate are enhanced.

While all of the above polyfunctional compositions function effectively as modifiers and enhancers of proteinaceous substrates, as in any large group, some members of the group, for various reasons, function more effectively than the others and for this reason are preferred. Thus, in the instant case, a more restricted group of compositions included within the above broad group, cornprise the preferred compositions of this invention. These compositions are included within the structural formula:

wherein m is a number from 2 to 4, A2 is R1 Ree-Me R and R are independently selected from the group consisting of H and alkyl having from 1 to 4 carbon atoms,

3 I which has the valence of m is the residue of an aliphatic or alicyclic polyol having from 2 to 4 hydroxyl groups after 2 to 4 hydroxyl groups have been removed, and

Q is methylphenylene.

In the preferred process embodiment a woolen or wool blend substrate is contacted with an amount of one or more of the preferred treating agents, in the form of a liquid solution, sulficient to deposit a modifying or enhancing amount of agent and cured until the desired enhancement of properties is obtained. Ordinarily the concentration of treating agent required varies between about 0.25 to by weight with the true upper limit determined primarily be economics. The mode of application is not critical; padding, spraying, dipping or the like being applicable. Depending upon the initial concentration of agent utilized, the pickup varies between about 50% to about 300%. Normally the treated substrate is dried and cured at about 100 C. to 200 C. for about 3 to 6 minutes, longer times being acceptable.

A further feature of the present invention resides in treating Wool-containing textile materials with a group of polyaziridinyl compounds and with selected co-reactants in order to further enhance and improve the dimensional stability and other physical properties of the textile without adversely affecting the appearance, hand, strength and other desirable properties thereof.

A more specific feature of the present invention resides in treating Wool-containing textile materials according to a process hereinafter defined with a certain group of relatively high molecular weight polyaziridinyl compounds in the presence of selected polybasic acids of polyamino compounds whereby excellent properties are imparted to the textile.

The above, as well as other objects, features and advantages of the present invention will become apparent from the following detailed description thereof.

According to the present invention, novel processes are provided whereby wool-containing textile materials, particularly Woven and knitted fabrics containing wool fibers, are treated with selected polyfunctional compounds to impart dimensional stability and other desirable properties to the textile product without substantially adversely affecting the appearance, handle, strength and other mechanical properties thereof.

It has been observed that the dimension properties of wool-containing textile materials are considerably enhanced as a result of the novel processes of the present invention and further that the desired properties are obtained without causing undesirable discoloration, harshening or other undesirable side effects. Moreover, in accordance with a further aspect of the present invention, novel processes are provided whereby an enhancement in the physical properties of wool-containing textile materials, particularly dimensional stability, are obtainedwhen the above-defined aziridine compounds are used in conjunction with co-reactants to be defined hereinafter which bring about an even greater improvement than was heretofore possible.

A detailed description of the substituents included within the formulae defining the polyfunctional compounds of this invention follows:

The compounds that are preferred for the present invention are polyfunctional compounds defined by Formula I, supra.

Aziridinyl compounds as defined by the symbol A2 in the various formulas which are suitable for purposes of the present invention may be obtained by several means such as, for example, the methods disclosed in British Pat. No. 919,861, the entire disclosure of which is relied on and incorporated herein by reference. Briefly described, the aziridinyl compounds defined by Formula I, supra, may be prepared by reacting an organic polyisocyanate with, preferably, an organic compound containing at least two hydroxyl groups to produce an intermediate having at least two isocyanate groups. Then the intermediate compound is reacted with a 1,2-alkylenimine to obtain the desired product. It has been determined that compounds falling Within the scope of the Formula 1, supra are exceptionally suitable for the treatment of wool-containing textile materials. It will be apparent from a consideration of the compounds encompassed by the present invention that the average molecular weight of the preferred compounds will range from about 1000 to about 6000. Such compounds are commercially available or can be prepared by known methods from commercially 7 available raw materials.

GROUPS REPRESENTATIVE OF Q Name: Composition Phenylene (o, m, or

P) s 4 Methylphenylene (various isomers such as 4-methyl-m-phenylone) -C6H3(CH3)- (o, m, or p)-Phenylenedimethylene H CC H OH Biphenylylene C H C H Methylenedi-(o, m, or

p)-phenylene C H CH C H Benzylphenylene C H (CH C H Naphthylene --C 'H The residue I can be (a) divalent, (b) trivalent, or (c) tetravalent.

(a) Illustrative of the residue J in the form of a divalent radical are the following:

(II) (CH where x is a number from 1 to 100.

(III) (C,,H ,,O) C H where a is a number from 1 to 4, and x is a number from about 1 to about 100, preferably from about 5 to about 40.

(IV) (CH CH=CHCH which is derived from polybutadiene, wherein the average degree of polymerization, u is between about 6 and about 100.

which is one kind of linear polyester radical, where n is 2 to 6, and the average value of v is between about 3 and about 80.

which is another kind of linear polyester radical, where nis2to 6, qis3 to5,andris2to 35.

where a is 1 to 4; x and y independently are 1 to and L is a divalent alicyclic radical of 3 to 20 carbon atoms, C to C alkylene, or C to C alkylene having the chain interrupted by one to ten groups in which R is H or alkyl having 1 to 5 carbon atoms.

In the general formula: I is derived from a polyol J(-OH) having a molecular weight between about 500 and about 5,500.

For instance, suitable divalent radicals of the type rep resented for Formula VII are provided by condensation products of the alkoxylate type which can be formed from any of the following starting compounds HOLOH,v

which are given by way of example, by

(A) Ethoxylation with approximately 10, to moleparts of ethylene oxide,

In carrying out the present invention, the wool-containing textile material which may be in any suitable form such as fiber, yarn or fabric may be treated with the polyfunctional compounds defind by Formula I, generally by impregnation with a solution thereof.

The solvent vehicle may be aqueous or non-aqueous. The treating mixture of solvent and polyfunctional compound may be in the form of a solution, suspension, emulsion or the like. The textile material may be sprayed, padded, immersed, dipped, brushed or similarly contacted with the polyfunctional compound, thereafter dried and cured. Exposure to elevated temperature may be used to insolubilize the polyfunctional compound. Alternatively, the textile, after being contacted with the polyfunctional compound may be permitted to stand for a brief period so as to achieve insolubilization.

If desired, the treated wool-containing textile material may thereafter be washed to remove residual soluble chemicals which may interfere or adversely affect the properties of the final product. Excellent dimensional stability is imparted to woolen textiles treated in the aforementioned manner. When laundered by conventional procedures commonly used for cotton or hydrophobic fibers, the woolen textile materials treated in accordance with the present invention as well as garments made from such woolen textile materials do not exhibit noticeable felting, fuzzy appearance, shrinkage or other undesirable properties which would deleteriously affect the final quality of the garment.

The present invention constitutes a considerable advance over what has gone heretofore inasmuch as the treatment with the selected polyfunctional compounds does not deleteriously alter the color, hand or other aesthetic properties of the woolen textile and, moreover, does not substantially adversely impair the tensile strength, tear strength, abrasion resistance and other important properties of the textile material.

In accordance with a further preferred aspect of the present invention, textile materials containing wool are treated with the aziridine compounds represented by the Formula I supra in combination with the coreactants as defined hereinafter to achieve even greater enhancement of the dimensional stability and other desirable properties of the textile products. Suitable co-reactants are polybasic acids and polyamine compounds particularly saturated aliphatic dicarboxylic acids containing from 2 to 12 carbon atoms and polyalkylenepolyamines containing, for example, from 4 to 20 carbon atoms and 2 to 5 nitrogen atoms. Representative examples of acids include succinic acid, adipic acid, sebacic acid, citric acid, tartaric acid, polyacrylic acid, and the like. Examples of polyamines include diethylenetriamine, tetraethylenepentamine, hydroxyethylethylenediamine, polyethyleneimines of wide molecular weight range, 1,3-diaminopropane, 1,6-diaminohexane, and the like.

In general, it has been observed that the coreactants will accelerate insolubilization of the polyfunctional compound in or on wool and will drive the polymerization reaction to completion in a shorter period of time. In addition, it has been observed that in certain respects the resulting properties of the textile are superior to that treated with the polyfunctional compound alone. It is, however,

to be noted that the invention does not require the presence of co-reactants in order to achieve satisfactory dimensional stability or other desirable properties in the wool-containing textile.

The treating mixture containing the polyfunctional compounds as defined by the structural Formula I and a vehicle therefor may take the form of a solution in organic solvents orwater when feasible. The compounds may also be applied from aqueous emulsion which can be rapidly prepared by suitable choice of solvents and emulsifying agents. Because of their stability at room temperature over relatively long periods of time, solutions and emulsions of the treating agents of the present invention may normally be stored without special precautions being necessary.

According to a further more detailed aspect of the present invention, the wool-containing textile material may be treated with the above-defined polyfunctional compounds, either before or after dyeing because the treatment with aziridines does not alter or deleteriously affect the dyeing properties of the woolen textiles. No adverse effects on the rate and evenness of the dyeing have been observed, even if the treatment with the polyfunctional compound is carried out before the dyeing operation. Moreover, there is no change of shade or adverse effect on color-fastness if the treatment with the polyfunctional compound is applied to the textile after the dyeing operation. This aspect of the invention is particularly important from a commercial standpoint inasmuch as it allows a wider range of operating conditions and greater flexibility in carrying out the modification of the woolen textile product.

When carrying out the process of the invention utilizing arizidinyl compounds in combination with selected coreactants as defined above, the treatment may be carried out in a single step or in several separate steps. Because of their nature, it is possible to use the polyfunctional compounds as defined herein in a single step in conjunction with other functional finishes such as water and stain repellents, soil release agents and the like. The latter include the acrylics and their salts as well as the fluorocarbons. The ease of formulation and application of the polyfunctional compounds makes them particularly suitable for use in combination with other finishes to impart permanent creasing properties to woolen fabrics.

No special precautions need be taken when carrying out the process of the present invention inasmuch as the insolubilization reaction of the polyfunctional compound on the wool textile can take place at moderate temperatures. It is therefore possible to obtain the desired insolubilization reaction even by tumble-drying procedures which are especially desirable when the objective is the stabilization of manufactured woven or knitted garments which cannot be conveniently processed in curing ovens at elevated temperature. Thus, the present invention provides a commercially feasible means for applying shrinkproofing finishes to manufactured garments in a convenient or simple method without requiring the use of complex equipment and procedures.

Applicable to Wool textile materials in any form or shape, the present invention may be used to impart dimensional stability and other desired properties to wool fibers, Woolen and worsted yarn, woven or knitted fabrics and (B) Propoxylation with approximately 8 to 95 moleparts of propylene oxide, or

(C) Alkoxylation with a proportionate mole ratio of higher or mixed alkylene oxides.

alkyl having 1 to 5 carbon atoms, and L is CH2CH2N(R)CH2CH2.

When trivalent, the residue J is the radical remaining upon removal of 3 hydroxyls from a polyol higher in degree than a diol. Examples of the residue J in the trivalent form are represented by the indivdual compounds embraced within the following collective Formula VIII:

(VIII) H(CuH2a-)x 0 MO(C nHZnO-) H H(0CuH2o )Z after removal of the 3 terminal hydrogen atoms, wherein the value of a is 1 to 4, while x, y, and 2, each ranging from 1 to about 100, denote mole-parts of one or more kinds of alkylene oxide C H O condensed with a trihy- O M at 6 dric starting compound, (HO) M, M being -a trivalent organic radical. For instance, a suitable trivalent radical of the type represented by Formula VIII is derived from glycerol condensed with approximately mole-parts of propylene oxide. In that case (referring to Formula VIII) M is the radical and a is 3, while the sum of x, y, and z is 50. Other aliphatic starting compounds of the type (HO) M which may be alkylated (as by CH CH O, C H O, and C H O) are, for example, Z-methyl 1,2,3-propanetriol, butanetriols, hexanetriols, 2-alkyl-2-(hydroxymethyl)-l,3-propanedio1s (especially wherein the alkyl group has 3 or less carbon atoms), triethanolamine, and 2-dimethylamino)-2-(hydroxymethyl)-1,3 propanediol.

The m-valent residue J of the formulae is also provided by the condensation products which are alkylene oxide derivatives of many starting compounds other than those specifically named, whether the prealkoxylated compound is of the dihydric type HO-L-OH or of the trihydric type (HO) M. Further examples of suitable starting compounds conforming to the types of HOL-OH and (HO) M will be found in British Pat. No. 919,861.

Typical of the methods whereby the aziridinyl compounds may be rnade is the procedure shown in Example XXVI which describes the reaction of a polyol and an isocyanate and the subsequent reaction with the alkylenimine.

Illustrative of the above compounds are:

garments. In general, for optimum effects to be realized, the fabric customarily contains appreciable proportion of wool fiber, generally 30% or more, 60 to 100% being the preferred range.

It will be apparent from the foregoing that the wool present in the textile can be by itself or present in a blend or admixture with other natural fibers such as cotton or with synthetic fibers such as polyamides, polyesters, polyolefins and acrylic fibers. The examples which appear hereinafter generally show the reaction condition suitable for obtaining satisfactory results. It will be noted, however, that the optimum conditions for processing any given fiber blend or mixture will be determined by many factors such as concentration of reagent, time of impregnation, temperature, atmospheric conditions, configuration, as well as other parameters. Conditions within the ranges discussed hereinafter will generally give satisfactory results on the textile materials indicated although these ranges are not to be construed as limiting the invention in any way.

For most purposes, the polyfunctional compounds employed in this invention are used in amount sufficient to keep shrinkage below 6% based upon the original dimensions of the substrate. Generally, between about 0.5 and 10% by weight add-on based upon the weight of the dry substrate is sufficient to keep shrinkage below the desired level. This add-on is referred to as a modifying amount of polyfunctional composition throughout this application. For example, in a typical embodiment where a 100% wool substrate is treated, add-on amounts of about 2% to about 5% based on the weight of the wool treated are preferred, although amounts outside these ranges may be used.

In accordance with the aspect of this invention relating to the combination of the aziridine compound and coreactant, when the co-reactant is used, the amount thereof employed should be sufficient to provide approximately 0.5 to about 2.0 reactive groups of the co-reactant which is in the form of amino groups or carboxyl groups for each aziridinyl group of the aziridinyl compound defined by Formula I. In other words, approximately 0.5 to about 2.0 equivalents of the co-reactant, polyamine or polycarboxylic acid, should be present for each aziridinyl equivalent present. It has been determined that the coreactant may be added to the treating solution which contains the aziridinyl compound of Formula I or can be applied in a separate step either before or after application of the aziridinyl compound. Properties and characteristics may vary somewhat depending upon the sequence of reaction; however, it has been observed that generally the order of reactants can be varied with equally satisfactory results.

As mentioned above, the aziridinyl compound can be applied to the Wool-containing textile material in any convenient manner. Generally, the aziridinyl compound is dissolved at the desired concentration in an anhydrous organic solvent such as a hydrocarbon including toluene, xylene, petroleum fractions and similar materials, halogenated solvent such as carbon tetrachloride and perchloroethylene or any other convenient inert solvent in which the aziridinyl compound is soluble and which in itself will not adversely affect the woolen textile material or deleteriously interfere with the insolubilization of the aziridinyl compound or interfere with the functioning of the co-reactant if any is used.

The aziridinyl compound may be applied to the woolen textile substrate in the form of a self-emulsifiable concentrate which is diluted with water to the desired concentration prior to using same. In any event, the coreactant polyamine or polycarboxylic acid may be added to the treating solution or emulsion containing the aziridinyl compound or the co-reactant may be applied in a separate step from a solution prepared from the same solvent as that used in connection with the aziridine compound, or a different organic solvent or water. When the co-reactant is applied in a separate step either before or after the treatment with the aziridinyl compound, the solvent as that used in connection with the aziridine commaterial may be miscible or immiscible with the solvent system from which the aziridinyl compound is applied. It has been observed that the pH of the treating solution may be varied within a considerable range. Generally, very high and very low pH ranges should be avoided since degradation of the wool can occur under extreme conditions. A pH range in general of 3.0 to about 9.0 is suitable with the range of 4.0 to 8.0 being preferred for most applications.

Methods of application of the polyfunctional compounds to the woolen textile not being critical, the treating solution can be applied by any suitable means including padding, spraying, dipping or the like. Excess solution is generally removed by wringing, squeezing, centrifuging or spinning. Thereafter, the woolen textile material is dried at a temperature ranging from ambient temperature to about 100 C., the range of 50 C. to 70 C. being particularly convenient. It is to be noted that the drying step is not essential to the overall efiiciency of the process. After drying, the treated textile is cured by allowing it to stand at ambient temperature for several hours or preferably by heating for a few minutes at 110 C. to about 170 C. to complete the insolubilization reaction. The time required for the curing step varies with the particular reagent and the concentrations employed. It will be noted that the curing duration will be dependent upon the temperature, the higher temperatures requiring less curing time. Curing cycles of 3 to 15 minutes at 120 C. to 150 C. have been found to give excellent results in the majority of situations. The above ranges are indicative of suitable reaction conditions and are by no means considered limiting of the present invention.

Although the textile may be used without further treatment, it is generally preferred to wash the textile after the curing step with suitable detergent solutions, solvent scours or by any other desirable means in order to remove residual soluble unreacted chemicals. .The .textile material can thereafter be dyed by conventional pro-. cedures or subjected to other conventional chemical or mechanical finishing operations such as shearing, topping with softeners and other textile treatments designed to impart specific properties or behavior characteristics.

The following examples are illustrative of the process of the invention. Parts are by weight unless otherwise specified. The methods used in obtaining the test data given in the examples are as follows:

Shrinkage.-Measurement after laundering according to the following procedure: Samples ca. 18 X 18 inches with 10 x 10-inch markings laundered in an automatic home-type agitator washing machine at 41 C., using a 5-lb. load, detergent (Fab or Tide) and 15 minutes suds time. Washed samples were rinsed, extracted in the washer for the full cycle, dried flat on a horizontal screen and flat-bed pressed for 5 seconds at -150 C. and conditioned for a minimum of 12 hours at 63 to 67% RH. and 20-22 C. The samples were then measured for shrinkage in the warp and filling directions.'Results reported in percent. The number of laundering-drying cyclesis indicated by 5L or 10L, respectively.

Flex abrasion resistance.ASTM-Dl-61T. (Stoll Flex Abrader, lb. head, 2 lbs. toggle). Results reported in cycles to break.

Stifiness-Cantilever procedure. ASTM-D-l388-55T. Results reported in milligram-centimeters.

Reflectance.-ASTME9755. Photovolt Search 6104, using the green tristumulus filter.

Oil repellency.-Minnesota Mining and Manufacturing Bulletin on Fluorochemical, Appendix A, pages 1-2.

610 and Measured after laundering (same washing procedure asfor Shrinkage) and after dry cleaning (Minnesota Mining and Manufacturing Test Method for laboratory dry cleaning procedure, 1.0. page 4).

1 l Tensile strength.ASTM D 1682 9T, one-inch ravelled strip method. Reported in pounds.

F uzziness rating.-The hairy appearance was expressed by the following numerical scale after brushing the fabric for minutes on a testing machine:

( 1) Severe fuzzing (2) Considerable fuzzing (3) Moderate fuzzing (4) Slight fuzzing (5) No (or negligible) fuzzing Fuzzing caused by laundering was rated after machine washing at 105 F. and tumble drying (12 such cycles in Example XXII, 10 in Example XXIII).

Flat frosting rating.Variation in appearance of colored fabric caused by concentrated localized abrasive wear. (Flexing is not used in fiat frosting.) The AATCC Gray Scale for Evaluating Changes in Color was used in applying the following rating scale to the descriptive meanings:

(1) Severe change (2) Considerable change (3) Moderate change (4) Slight change (5) No (or negligible) change 12 polymer has three of the following groups per molecule attached to a polypropylene ether glycol backbone:

-o oo-rrn-Q-om i CH 3 I1IHCON/ a. The full structure is believed to be:

wherein x+y+z=50.

The solution contained 4% ITP-63A and Wasapplied to the sample by using a laboratory padder and setting the rolls of the padder at such a pressure as to obtain a wet pickup of about 110%.

The fabric sample so treated was framed at the original dimensions and dried at 65 C., then cured for 5 minutes at 135 C. in a forced-draft oven. The cured fabric was rinsed in toluene, dioxane, and finally in water. The sample was then again framed to the original dimensions and dried. The test results obtained were as follows:

Percent shrinkage after 5L 10L Flex Wash-and-wear rating. AATCC88A-l964T, Test IICl.

Colorfastness to wash.AATCC-6 l1962.

Colorfastness to light.AATCC16A-1964.

Colorfastness to cr0cking.AAT CC8-196l.

Colorfastness t0 perspirati0n.AATCC15-1962.

Abbreviations in tables..When used individually, F means filling direction, and W means warp direction. OWB: On the Weight of the bath. OWF: On the Weight of the fabric. WPU: Wet pickup. OWB times WPU/ 100% :OWF.

Isocyanate content-As in a fraction of an equivalent per 100 grams: Determined by a modification of the dibutylamine procedure of W. Siefken, Liebigs Annalen der Chemie, vol. 562, page 100 (1949).

EXAMPLE I Dimensional stabilization of woolen fabric by treatment with a propylene imine-terminaied polymer of polypropylene ether glycol A sample of plain weave 100% Woolen fabric, in the ready-to-dye state, was treated with a liquid, trifunctional, propylene imine-terminated polymer of polypropylene ether glycol (Interchemical Corp. ITP-63A) having an average molecular weight of about 3700. This product may be made by the condensation reaction of mole parts of bound propylene oxide With 1 mole of glycerol. The resulting propoxylate may then be treated with toluene diisocyanate and is then condensed with propylene imine. The resulting product contains 3 aziridinyl radicals per mole, an imine content of 0.65-0.67 meq./gram polymer and a viscosity of about 890 poises and is hereafter referred to as ITP63A. This material is dissolved in a 4:1

benzenedimethylformamide solvent mixture. The ITP-63A Dimensional stabilization of wool fabricv by treatment with the imine-terminated polymer of Example I and a polyamine Samples of plain weave woolen fabric in the ready-to-dye state were treated with mixtures of TIP-63A and polyamines by padding from a 4:1 benzene-DMF solution. The equivalent ratio of the imine.-terminated polymer to the amine co-reactant was 1:1, with the weight ratio as specified below. Thesteps of thetreatment Were as described in Example 1, except that the wet pickup was about I In the pad solution Percent Total j Percent Percent reag. Percent Amine amine PIP-63A OWF W.G.

Sample:

B Tetraethylene 0.11 3.49 4.42 4.0

pentamine. C Dietl ylenetri- 0.10 3.50 4.24 5 5 amine. D 1,3-diamin0pro- 0.11 3. 4 9 4. 28 6.1

pane. E 1,6-diaminohexane- 0.16 3. 44 4. 31 t 6.2

The properties of the treated samples were as follows:

' Percent shrinkagc- ,7

10L Stifii a ness' W, --Flex abn, Rcflcc-t W F mg.cm. eycles llli tance 13 EXAMPLE I11 Dimensional stabilization of woolen fabric with a propylene imine-terminated polymer employed in Example I and a polycarboxylic acid 14 (4% toluene, 0.4% Triton X-100 nonionic surface active agent, 95.6% water) at room temperature for 5 minutes, then washed in water at 100 (F. for minutes, rinsed in cold water and dried on frames.

The properties of the treated samples were as follows:

Percent shrinkage Percent 5L 10L polymer Percent Stifiness, Flex. abr. Fabric OWF W.G. W F W F mg.cm. res., cycles Plain weave, woolen RTD* 3. 7 3. 1 2. 5 2. 5 2. 5 3. 0 136 600 Untreated RTD 19. 0 17. 5 28. 5 26. 0 103 475 Twill weave, woolen RTD. 3. 6 2. 7 1. 5 2. 0 1. 5 2. 0 203 775 Untreate 20. 0 18. 5 27. 5 26. 0 164 575 Twill weave, woolen dyed green 3. 6 2. 9 5. 0 5. 5 6. 5 6. 5 171 400 Untreated dyed 23. 5 20. 0 30.0 25. 5 105 525 Twill weave, worsted. 3. 2 2. 5 3. 5 3. 5 176 3, 400 Untreated RTD 33. 5 30.0 165 4,190

"RTD Ready-to-Dye.

Example II was repeated, but polycarboxylic acids were EXAMPLE V used as co-reactants in the treating solution in place of the amino co-reactants.

In the pad solution Percent Polyear- Percent poiytotal boxylic carboxylic Percent reag. Percent acid acid ITP-63A OWF W.G.

The properties of the treated samples were as follows:

Percent shrinkage Dimensional stabilization of woolen fabrics of various weaves using the polymer employed in Example I Samples of plain .weave and twill weave woolen fabric Dimensionally stabilizing and imparting oil repellency to woolen fabrics Samples of dyed plain weave 100% woolen and twill weave worsted fabric were treated with a mixture of ITP- 63A aqueous emulsion (preparation of the emulsion is described in Example IV) and of a fluorochemical emulsion, Scotchgard FC-208 (product of Minnesota Mining & Manufacturing Co.), which is a nonionic latex of a' modified fluorinated acrylic polymer of the type polyperfluoroalkyl acrylate using a laboratory padder and setting the rolls at such a pressure as to give 90116% wet pickup. The fabric samples so treated were framed and dried at 150 F., then cured at 320 F. for 5 minutes in a forced-draft oven. The cured fabric samples were washed and dried in the manner described in Example IV. The properties of the treated samples were as follows:

TREATMENT Percent Scotch- TESTIN G Percent shrinkage Oil Repellency 1L 5L Stifi- Flex abr.

ness W, res, W 2 Dry W F W F mg.-cm. cycles Orig. 1L 5L 1 D .C. cleanings and of twill weave worsted fabric were treated with an Generally, the above mentioned fluorochemical finishes aqueous emulsion of ITP63A.

The emulsion was. prepared by mixing 120 parts of a 50% xylene solution of ITP-63A with 10 parts of the nonioni'c surface active agent, t-octylphenylnona(ethyleneoxy)ethanol (Triton X-100, a product of Rohm & Haas 'C0.), dissolved in 20 parts of water with stirring. The emulsion obtained in this manner was diluted with water to the desired concentration. The fabric samples were treated with the diluted emulsion using a laboratory padder, setting the rolls at such a pressure to give 80- 100% wet pickup.

The fabric samples so treated were framed to the original dimension and dried at 150 F., then cured for 5 minutes at 300 F. in a forceddraft oven. The cured fabare believed to be made from monomers having the basic formula R CH OCOCH=CH where R can vary from C F to C F for example.

EXAMPLE VI Hydroextraction of dimensionally stabilized woolen fabric ric samples were rinsed in an aqueous toluene emulsion ner described in Example 1V.

15 The properties of the treated samples were as follows: is a linear polyester (molecular weight of approximately 2100, made from a diol and a dibasic acid of the type Percent shrinkage shown in Formula IV) containing the following' imine Drying 1L 5L group attached to the backbone: Percent'I'lP in the Percent Time in H bath IT ,OWF minutes W F W F 5 OCO NH CH3 g 3-; 33 ;-g 3-; g; 3-2, 1 118 22 2 2 8 2 3 2 at 1.8

8.5 5.0 14.5 12.5 (JHZ 1 A 5:4:1 DMF-toluene-acetone solution was used to pre- EXAMPLE VII pare the treating solution used for the application. The Dyeing of woolen fabrics dimensionally stabilized with 21 22 2 fig i 223 23 f if fl zg i i gg aqueous emulsion of polymers employed in Example y g lndicated below. IV

The treatment was earned out in the manner described Samples of twill weave 100% woolen fabric in readyin Example I. i to-dye state were treated with an aqueous ITP-63A emulsion (percent polymer OWE: 4%) according to the pro- Percent Percent cedure described in Example IV. After the shrinkproofing Total pad Percent- Reag. Percent treatment, the samples were dyed with 0.75% and 3.0% Amine solution ITP-43 OWF W0. Du Pont Anthraquinone Blue SWF (C.I. No. 62055, C.I., Sample. I v Acid Blue acid dye and also with 0.75% capracyl Tetraethylene- 0.11 3.7 4.0 6.3 Red 15B (Color Index name C.I. Acid Red 178) pref Q15 metallrzed dyestuff. In each case, untreated wool sarn :1 pm ples were dyed in the same dye bath with the treated 25 :p noprosamples. Testing of the samples before and after dyefi q 0.16 ing gave the following results: N H Percent shrinkage 5L 10L Res. to 81:15- Tensile flex abr., ness, Color W F W F str., W W cycles ing.'crn

Sample: A-l, treated RID 3.0 3.5 20 900 231 11-2 untreated RID 22.5 22.5 27.0 25.0 20 775 142 Light Red 2.5 3.0 2.5 3.0 20 450 240 ..do 15.5 18.5 18.5 22.5 17 400 110 Dark Red... 2.0 2.5 2.0 2.5 10 415 231 do.. 18.0 10.0 22.5 23.5 17 325 167 Light 131115.... 1.5 1.0 1.5 1.5 21 575 218 ..do 15.5 17.5 20.0 23.5 20 575 147 Dark Blue 2.0 0.5 2.0 1.0 22 775 160 E2, untreated .do 16.0 17.5 10.5 22.5 20 800 231 The depth of shade and the brightness of color ob- The physical properties of the treated samples were as tained in dyeing the shrinkproofed and the untreated samfollows: 3 ples were fully comparable and the treated samples dyed as evenly as the untreated. 5

The colorfastness of the dyed samples shown in the preceding table were as follows: In each case the 1 samples were dyed after shrinkproofing and the 2 samples were dyed in the untreated state.

NOTE .-S Satisfactory; U Unsatisfactory.

EXAMPLE VIII Dimensional stabilization of Woolen fabric with another type of imine-terminated polymer and a polyamine Samples of twill weave 100% woolen fabric in the ready-to-dye state were treated with mixtures of an imineterminated polymer marketed by the Interchemical Corp. under the trade name of ITP-43 and having an average molecular weight of about 2600, and an aziridinyl content of about 0.65 meq./g., and with the polyamines shown in the table as co-reactants. The ITP-43 polymer Percent Shrinkage-5L Flex Abr. Stirr- Res., ness-W, W V E Cycles rug-em.

XA L 1 Dimensional stabilization of woolen fabrics with the imine-terminated polymer of Example VIII and a polycarboxylic acid Example VIII was repeated :but, in place of the polyamines,'polycarboxylic .acids wereused as co-react'ants with ITP-43.

Percent.- Pereent Polycar- Polycarbox- Total boxylic ylie acid in the Percent reag. Percent acid pad bath ITP-43 OWE W.G

17 EXAMPLE X Dimensional stabilization of a dyed wool fabric A 100-yd. length of 100% woolen fabric of -60-inch width, twill weave, dyed bright red, was treated by padng with an aqueous emulsion containing 8% of the ITP-63A imine-terminated polymer. The wet pickup was 60%. The fabric was dried on a frame, cured for 6 minutes at 275 F., thoroughly washed at 110 F. in a nonionic detergent solution, dried and sheared to enhance its appearance. The properties of the red fabric before and after the shrinkproofing treatment described are tabulated below:

Before After treatment treatment Count (W x F) 36 x 32 37 x 33 Percent shrinkage in relaxation (W x F). 5. x 4. 3 2. O x 2. Total after 1L .5 x 7. 5 2.0 x 2. 5 Total after 5L 22 0x170 2.5x2.8 Total alter L. 25 0 x 19. 5 3. 0 x 3.0 Tensile strength, W lbs 19 21 Tear strength, W lbs 2. 8 2. 7 Flex abr. res., cycles... 490 550 Stiffness, mg.cn 132 134 Weight (oz./sq. yd.) 7. 29 7. 48 Colorfastness:

To light:

20 hrs 5 5 40 hrs 4/5 4/5 To wash 4/5 4/5 To croeking' Dry- 5 5 T et 7 i. 3 5

o perspna ion:

cid 3 4 Alkali 3 4 EXAMPLE XI Preparation of a polyfunctional compound having 1) a polyester chain as its backbone and (2) terminal l-aziridinyl radicals Isocyanate-terminated polyester, wherein v=34 and n is about 6.

l-aziridinyl-terminated polyester.

The isocyanate-terminated polyester used as the starting material had an isocyanate content of 9.5% and was obtained under the registered trademark of lsofoam L-128 from Isocyanate Products, Inc., Wilmington, Del.

A l-liter 3-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with 100 grams (0.23 equivalent based on isosolved in grams of methylene chloride. Ethylem'mine 10.7 grams, 0.25 equivalent), dissolved in 100 ml. of methylene chloride, was added dropwise to the stirred solution in the flask at 25 to 28 C. The addition was completed in 1 hour, and the reaction solution remained homogeneous. Stirring was continued for 5 hours longer. Then solvent and unreacted ethylenimine were distilled off in vacuo, leaving behind the addition product, ethylenimine-terminated polyester, as a waxy solid.

The product was analyzed for aziridinyl content by a procedure modified after that of Allan and Seaman, Anal. Chem., vol. 27, page 540 (1955). It was found to have an aziridinyl content of 1.73 milliequivalents per gram, as compared with 2.06 millieq./g. theoretically possible. The conversion, based on aziridinyl activity, was 84%. The product was very soluble in toluene and in N,N- dimethylformamide.

EXAMPLE XII Preparation of a polyfunctional compound having 1) a polyester chain as its backbone and (2) terminal Z-methyl-l-aziridinyl radicals Isocyanate-terminated polyester as in Example XI Propylenimine-terminated polyester A l-liter 3-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with 14.2 grams (0.26 equivalent) of propylenimine dissolved in 50 ml. of methylene chloride. Isocyanate-terminated polyester (100 grams, 0.23 equivalent) dissolved in ml. of methylene chloride was added dropwise to the stirred solution at 25 to 28 C. (The isocyanate-terminated polyester was of the same composition as that used as starting material in Example XI, but both the order of addition and the alkylenimine were different from those of Example XI.) The addition was completed in 1 hour, and the reaction solution remained homogeneous. Stirring was continued for 5 hours longer. Then solvent and unreacted propylenimine were distilled off in vacuo, leaving behind the addition product, propylenimine-terminated polyester, as a waxy solid.

Using the analytical method cited in Example XI, the product "was found to have 1.60 milliequivalents of aziridinyl nitrogen per gram. Based on that, the extent of conversion was'80%. This product was very soluble in cyanate content) of isocyanate-terminated polyester dis- 75 toluene and in N,N-dimethylformamide.

19 EXAMPLE XIII HO(--CHzCH=CHCHz-)..OH Hydroxyl-terminated polybutadlene (u =60;l:5)

HaC

Isocyanate-terminated polybutadiene (VI) Second stage:

First-A 500-ml. flask equipped as in Example XIII was charged with 85.3 grams of the hydroxyl-terminated polybutadiene dissolved in 50 grams of methylene chloride. Toluene diisocyanate (18.5 grams, 0.16 mole of NCO l-Aziridinyl-terminated polybutadiene The hydroxyl-terminated polybutadiene used as the starting material had a hydroxyl content of 0.80 milliequivalent per gram, an iodine number of 395, and an average molecular weight of 325 0:25 0. The polymer was supplied under the trade name Poly B-D Liquid Resin R-lSM by Sinclair Petrochemicals, Inc. Prior to use, the resin was kept in vacuo in a slowly rotating flask for several hours to strip off moisture.

The first stage of the process consisted of converting the hydroxyl-terminated polybutadiene into isocyanateterminated polybutadiene. A 2-liter 3-neck flask equipped with a stirrer, a thermometer, a gas inlet tube, and a dropping funnel was charged with 200 grams of the hydroxyl-terminated polybutadiene dissolved in 200 grams of methylene chloride. Toluene diisocyanate (43.6 grams, 0.25 mole of 2,4 and 2,6 isomers in the ratio of 80/20) was added while a stream of nitrogen was passed into the solution and the temperature was maintained at 20 C. After the addition, the solution was stirred at -28 C. for 8 hours.

Next, the second stage of adding terminal l-aziridinyl radicals was carried out. Ethylenimine (12.9 grams, 0.30 mole), dissolved in 100 grams of methylene chloride, was added dropwise to the stirred solution. The addition was completed in 2.5 hours, during which time the temperature of the reaction was maintained at 25 C. The solution was stirred for 4 hours longer. Then solvent and unreacted ethylenimine were distilled off in vacuo. The product (223 grams) which remained was a lightbrown viscous liquid.

Using the analytical method cited in Example XI, the product was found to have 1.00 milliequivalent of aziridinyl per gram, as compared with 0.97 millieq./g. expected. The product, ethylenimine-terminated polybutadiene, was very soluble in toluene, benzene, tetrahydrofuran, and carbon tetrachloride.

EXAMPLE XIV Preparation of a polyfunctional compound having (1) A polybutadiene chain as its backbone and (2) Terminal 2-methyl-1-aziridinyl radicals H H H C-CH; H3CC\ (H) /C-CHa joined as in um i Example x111 CH2 H2O CH2 Propylenimine-terminated polybutadiene 2,4 and 2,6 isomers in the ratio of 80/20) was added slowly while a stream of nitrogen was passed into the solution and the temperature was maintained at 20 C. After the addition, the solution was stirred at 25 to 28 C. for 16 hours.

Second.Propyleniminc (6.70 grams, 0.18 mole), dissolved in 50 grams of methylene chloride, was added dropwise to the stirred solution during a 3-hour period. The solution was stirred for 4 hours longer. Then solvent and unreacted propylenimine were distilled off in yacuo. The product which remained was a light-brown 'iquid.

Using the analytical method cited in Example XI, the product was found to have 0.90 milliequivalent of aziridinyl nitrogen per gram, as compared with 0.97 millleqJg. theoretically possible. The product, propylenimine-terminated polybutadiene was very soluble in toluene.

EXAMPLE XV Enhancement of surface characteristics of :30 rayon-wool fabric by imine-terminated polymer Plain-weave fabric woven from a 70:30 blend of highmodulus high-tenacity rayon and Wool was treated with the propylenimine-terminated polymer identified in Example I so that the reagent applied was 4%, based on the weight of the fabric. The fabric specimen so treated was framed at the original dimensions and dried at 150 F. (in approximately 10 minutes), then cured for 6 minutes at 275 F. The cured fabric was scoured to remove unreacted reagent by using an emulsion for mulated from 4 parts of toluene, 0.4 part of Triton X-100 (emulsifying agent identified in Example IV), and 95.6 parts of water. Then the fabric specimen was again framed to the original dimensions and dried. The following results, along with those on an untreated fabric sample used as the control, clearly show that the treatment enhanced surface characteristics, and even improved the strength somewhat.

22 framed at the original dimensions and dried at 150 F.

Flex abras.

Shrinkage, percent Curing ten niq (time= 5 mins.)

All samples were cured for 5 minutes. The cured fabric was rinsed in toluene, then in p-dioxane and finally in water containing 0.4% Triton X-l (identified in Example IV). The samples were again framed to the origiand rayon was treated with the propylenrmme-terminated nal dimensions and dried. Excellent dimensional stabilizapolymer identified in Example I so that the reagent ap- Total add-0n, percent on ight of fabric 3,523,750 21 EXAMPLE XVI Control imparted on shrinkage and fuzziness to 50:50

tion was achieved, as borne out by the following results:

Percentages on wt. of bath Wet pickup, we

Reagent TEPA percent wool-rayon fabric by imine-terminated polymer Plain-weave fabric woven from a 50:50 blend of wool 5055555505550 0 LLLLZL&LZZ4 W 000000000000 5 5 55 5 4 om25 4 &2

Shrinkage, percent Curing F. 5L (time= 5 mins.) W F EXAMPLE XVIII and redrying were those of Example XV. The following Dimensional Stablhzatlon of Woolen fabric by treatment results, and those of the untreated fabric sample used as the control, show much more satisfactory control of shrinkage and of fuzziness for the treated specimen.

Total add-on, percent on tem weight on fabric with propylenimine-terminated polybutadiene (A) Pad bath solventzToluene dimethylformamide (1:1).Samples of plain-weave woolen fabric in the ready-to-dye state were treated with solutions of various concentrations of the reagent prepared in Example XIV, namely propylenimine-terminated polybutadiene. In the Fumness treatment of some of the samples, tetraethylenepentamine F rating (TEPA) was used as a co-reactant.

4 The procedure followed that of Example XVII. 2 Results tabulated below show that this i-mine-terminated polymer also provided excellent control of shrinkage.

Percentages on weight of bath Wet pickup, Reagent 'IEPA percent Shrinkage, percent (Tumble dried at 105 F.)

plied was 3.5% based on the weight of the fabric. Conditions of framing, drying, curing, scourmg, reframmg,

Treated specimen. Untreated control.

555000050 LLLLZZLLZ 3 0550550 5 ZLLomZLZLH 005555050 LLLOJLLLL5 ght ratio of toluene-dimethyl- Flex abras.

B) Pad bath solventzToluene dimethylformamide (5 :1).--The procedure described under part A was followed,'except that a 5:1 wei formamide was used instead of the 1:1 ratio, and lower concentrations of the reagent were used to establish its ng efficiency. As before, shrinkage control was impressive, as shown by the following results.

Total Curing Shrinkage, percent Percentages on add-on, temp,

wt. of bath Wet percent on F. 5L

pickup, weight of (time= Reagent TEPA percent fabric fimins.) W

EXAMPLE XVII Dimensional stabilization of woolen fabric by treatment with ethylenimine-ter-minated polybutadiene Samples of plain-weave woolen fabric in the readyto-dye state were treated with solutions of various conshrinkproofi centrations of the reagent prepared in Example XIII Sample:

EXAMPLE XIX Dimensional stabilization of woolen fabric by treatment with ethylenimine-terminated polyester Samples of plain-weave woolen fabric in the ready-todye state were treated with solutions of various concenof a laboratory padder. After padding, the fabric was trations of the reagent prepared in Example XI, namely,

namely, ethylenimine terminated polybutadiene. Concentrations and other details were shown in the accompanying table. In preparing certain of the samples, tetraethylenepentamine (TEPA) was also used in the pad bath. The solvent was toluene-dimethylformamide (1:1). Solutions were applied to the fabric samples by means 23 ethylenimine-terminated polyester. In the treatment of some of the samples, a co-reactant was used, viz., tetraethylenepentamine (TEPA). The procedure followed that of Example XVII. Excellent shrinkage control resulted, as the following data show.

24 EXAMPLE XXII Improvement of dyed acrylic-wool blends by imineterminated polymer, particularly with respect to control of fuzziness and resistance to abrasion Each of three 30-yard lengths of colored fabrics repre- Total Shrinkage, percent Percentages on add on, Curing weight of bath Wet percent on temp., F L L ckup, weight of (t e= Reagent TE PA percent fabric 5 mins.) W F W F 5.0 None 133 6. 6 275 1.0 1. 5 1. 5 2. 5 5. 0 None 133 6. 6 325 0. 5 2. 0 1. 0 2. 0 5. 0 0. 5 133 6. 6 275 1. 5 3. 0 2. 0 3. 0 5. 0 0.5 131 6. 5 325 1. 0 2.0 1. 5 3.0 3.0 None 132 4. 0 275 1. 5 3. 0 2.0 3. 5 3. 0 None 130 4. 0 325 1. 0 3. 0 1. 5 3. 5 3. 0 0.5 134 4.0 275 1. 0 3. 0 2. 5 4. 0 3. 0 0. 5 13. 0 3. 9 325 1. 5 2. 5 2. 0 4. 0 23. 5 22. 5 30. 0 29. 0

EXAMPLE XX sentmg various acryl1c-wool blends identified 1n the ac- Dimensional stabilization of woolen fabric by treatment with propylenimine-terminated polyester Samples of plain weave woolen fabric in the ready-todye state were treated with solutions of various concentrations of the reagent prepared in Example XH, namely, propylenimine-terminated polyester. In the treatment of some of the samples, a co-reactant was used, viz., tetraethylenepentarnine (TEPA). The procedure followed that of Example XVII. The following results show that superior shrinkage control was obtained:

companying table was padded with a dispersion formulated as follows: First, ITP-63A (the imine-terminated polymer described in Example I) was dissolved in an equal weight of xylene, and a thick emulsion was prepared by mixing parts of that solution with 20 parts of a 2:1 blend of water and Triton X-100 (identified in Example IV). Hence, the concentration of ITP-63A in the'thick emulsion was 40%. Next, an approximately 3.9% dispersion of ITP-63A was made by blending pounds of said thick emulsion and gallons (approximately 830 pounds) of water.

Total Curing} Shrinkage, percent Flex abras. Percentages en add-on, temp., 1 (15 lb. 1: Stifiness, wt. of bath Wet percent on F. 5L 10L 211).), mg.-em., pickup, weight of (time: No L, No L Reagent TEPA percent fabric 5 mins.) W F W F (warp) (warp) 3. 0 114 3.4 275 1. 5 1.0 3. 0 1.5 850 505 2. 0 115 2. 3 275 3. 5 0. 5 5. 5 2. 5 900 370 1. 0 1. 2 275 7. 0 3. 5 12. 5 7. 5 725 160 3.0 111 3. 3 275 2. 0 0. 5 3.0 0. 5 1, 050 625 2. 0 110 2. 2 275 1. 5 None 3. 0 1. 5 900 355 F 1. 0 111 1. l 275 4. 5 0. 5 6.5 3. 5 825 210 Untreated control 27 25 32 31 850 100 EXAMPLE XXI Dimensional stabilization of woolen garments in the readyto-wear condition by shrinkproofing agents applied as perchloroethylene solutions Wet pickup around 50%, the pad pressure being 16 tons and the speed 25 yards per minute. For the combined step of drying-curing, conditions were 300 F. for 4.83 minutes. Next, the lengths were scoured at 100 F. for 15 minutes in a dispersion formulated from 4 parts of toluene, 0.4 part of a nonionic dispersant, nonylphenylpoly(ethyleneoxy)ethanol (Triton N-l00, a product of Rohm & Haas (10.), and 95.6 parts of water. Then the lengths of fabric were rinsed until no foam was evident. The goods were dried and given dry finishing by shearing off the fuzz and semidecating (pressing by steaming between pieces of fabric). Results on the treated acrylic- Tumble Time of Solids, drying Percent of shrinkhydro- Wet percent (curing) Sweater proofer in perchloroextraction, plekup, on weight time, Other conditions applied prior to measurspeermen ethylene seconds percent of fabric minutes ing process shrinkage W 10% of ITP-63A 7 154 15.4 60 15-min. wash in toluene water 4:96 at 105 F., then tumble-dried. X 10% of ITP-63A 8 103 10. 3 60 Same as for W. Y 10% of ITP-63A 5 234 23. 4 60 1 wash at F.; then tumble-dried.

Laundering shrinkage, percent, after 10L and Process shrinkage, percent tumble drying I Back Bottom Sleeve Back Bottom Sleeve Sweater speeunen Band length wldth length Chest Band length width length Chest 12. 7 10. 6 None 5. 6 None None 2. 4 +0. 8 2. 4 None. 10. 7 9. 9 (l0 5. 6 None None 2. 4 None 2. 4 Do. 5.7 4.3 2.3 +0.7 1.4 2.3 +3.5 Do.

wool blends as well as'those on untreated controls are tabulated below. The values show a consistent improvement in fuzziness rating in comparison with the corresponding untreated control specimen, both prior to laundering and after .12 launderings. Wash-and-wear ratings were not adversely affected. Resistance to flex abrasion and flat frosting remain either unchanged or were improved by the treatment.

utes. The procedures of scouring, drying, shearing, and semidecating were similar to those of Example XXII. As to properties, crease retention and wash-and-wear rat ings (on pressed specimens) were improved over those of similar fabrics processed in a conventional way. Other values on the treated polyester-wool blends, along with control data, are tabulated below, and show the substantial improvement brought about by the imine-terminated Flat frosting Resistance to flex Fuzziness Wash-and-wear rating (2.5-lb., abrasion, cycles (l-lb. rating rating 1,200 cycles) head, 4-lb. toggle) No L Composition of dyed fabric No L 12 L 1 L 12 L No L Web Rupture 55% acrylic/45% wool 5 4 4. 5 3. 5 5 525 800 55% acrylic/45% wool, untreated controL. 3 3 4. 5 3. 5 5 500 800 65% acrylic/30% wool/5% rayon 3-4 3 4. 3 3. 4 225 525 65% acrylic/30% wool/% rayon, untreated eontrol- 1 1 4. 5 3. 5 3 150 300 70% acrylic/30% wool 4 3-4 3. 5 3. 5 5 375 575 70% acrylic/30% wool, untreated control 2 2 3. 5 3. 5 5 275 475 EXAMPLE XX-III polymer on each polyester-wool blend.

Control of fuzz and abrasion of dyed polyester-wool blends by imine-terminated polymer Each of four 60-yard lengths of colored fabrics of two different polyester-wool blends identified in the accompanying table was padded with a dispersion formulated as follows. An approximately 5.4% dispersion of ITP-63A was made by blending 130 pounds of the thick emulsion (40% ITP- 63A) recorded in Example XXII and 100 gallons (approximately 830 pounds) of water. Wet pickup was approximately 50%, the pad pressure being 12 tons. Speed was 25 yards per minute. For the combined step of drying-curing, conditions were 300 F. for 4.5 min- EXAMPLE XXIV Each of eight lengths of fabrics of four kinds of blends of synthetic fibers with wool as identified in the accompanying table was padded with a solution formulated as follows.

An approximately 5.5% dispersion of ITP-63A was made by blending 113 pounds of the thick emulsion ITP63A) recorded in Example XXII and 85 gallons (approximately 705 pounds) of water. Pad pressure was 12 tons, and speed was 15 yards per minute. For the com- Re i t t flex ij gfiffg 40 blned step of drying-curing, conditions were 275 F. for ggg g 3 ig f 7.5 minutes. The procedures of scouring, drying, shearg ing, and semidecating for the acrylic-wool blends were Co pos t on of dyed fabrws No L 10 L Web Rupture similar to those of Example XXII, but the polyester-wool 55% polyester/% W001, 6m oL/Sq, blends were singed before semidecating. Singeing means Y H 650 285 45 burning off the free projecting fibers from the surface of 55% polyester/45% wool, 6.90 0z./sq. h 1

yd,,unt eated comm; 2 34 525 125 t e 0 0th, leaving it smooth and bare. Upon evaluation, D Y 1 4 H 375 185 it was found that crease retention and wash-and-wear 55%, b'dfitiii kfii bbi,i'if/if. ratings (on pressed specimens) were improved over 10$"..ii3idli32iiiii' 8265755" 2 3 150 those of similar fabrics processed in a conventional mand ihi '1 4 5 1, 050 275 ner. Other data on the treated blends of synthetic fibers 707 olyester/307 wool 6.82 oz.lsq.

e r: untreated o H 3 650 135 and wool, dyed as Well as undyed, together with control 70% polyester/30% wool, 5 500 175 data, are tabulated below. Definite lmprovement was efyd 70% polyester/30% wool, 4.57 oz./sq. fected by the imine terminated polymer on each wool yd., untreated control 3 4 425 110 containing blend. (Control samples were dyed but otherwise untreated.)

Laundering shrinkage, percent (10-inch markings machine wash, Resistance to 105 F. tumble dry, low

flex abrasion setting) cycles (1 lb X et 4-lb.) No L, 5L 10L Yardage pickup, web --1- Composition of fabric State treated percent W F W F 557 polyester/457 wool. Dyed 35 52 650 1.0 1.0 1.0 1.5 Control Untreated 525 1.5 3.0 1.5 a. 5 Undye 35 51 775 1.5 o. 5 1.5 0.5 70% polyester/30% w0ol.. "I, Dyed 35 50 875 0. 5 1. 0 0. 5 1. 5 Contr0l Untreated 775 0. 5 2. 0 0. 5 1 3. 5 Undyed.- 50 1,050 0.5 None 0.5 None 55% acrylic/45% wool Dyed 50 56 650 1. 5 1. 5 2. 5 8.0 Control..- Untreated 525 2. 5 3. 5 2. 5 4. 0 Undyed--. 50 55 725 1.0 2.0 1. 5 2.5 acrylic/30% wool Dyed 50 57 575 1. 5 0. 5 1. 5 1. 0 ControL-.. Untreated 425 2. 5 2.5 2. 5 2.5 Undyed.-. 5o 50 500 1.5 1.0 1.5 1.5

27 EXAMPLE XXV Preparation of a polyfunctional compound having (1) a polyester chain as its backbone, and (2) terminal 2-(1- aziridinyl)ethoxy groups Isocyanate-terminated polyester, wherein v=3 to 4 and n=about 6 -i5 C. 4-methyl-m-phenylene diisocyanate (35.4 grams, 0.203 mole) dissolved in 50 grams of dichloro- Starting materials and the procedure were similar to methane was added. The temperature was allowed to those of Example XI except as follows: The weight of dichloromethane was 330 grams instead of 100 grams. Instead of ethylenimine, (l-aziridine)ethanol (20.7 grams, 0.238 mole) was added dropwise to the stirred solution at 20 to C. The addition was completed within 1 hour. The reaction solution remained homogeneous. One-half hour after termination of the addition, the infrared absorption band was devoid of the isocyanate band (4.3 to 4.5 microns). Analysis revealed an aziridinyl content of 0.15 equivalent per 100 grams of solid (calculated, 0.197 eq./100 g.). The solution was miscible with dimethylformarnide.

EXAMPLE XXVI Preparation of a polyfunctional compound having (1) a polytetramethyleneoxy chain as its backbone, and (2) terminal 2-(1-aziridinyl)ethoxy groups First stage:

NCO

On the average, x=about 26 in Example XXVI, and about 13 in Examples XXVII and XXV-III OCN NCO ICTIT, an isocyanate-terminated intermediate having a backbone derived from a polytetramethyleneoxy chain Second stage:

rise to 25 C. during 1 hour. The reaction mixture was stored at approximately 5 C. for several days.

Next, the second stage of adding terminal 2-(-aziridinyl)ethoxy radicals was carried out. (1-aziridine)ethanol (17.4 grams, 0.20 mole) was added dropwise to 19/20 of the original solution obtained from the first stage. The stirred solution contained 0.19 equivalent of N=C=O [determined by a modification of the dibutylamine procedure of W. Siefken, Liebigs Annalen der Chemie, vol. 562, page 100 (1949)]. The addition was completed in 0.5 hour, during which time the reaction temperature was kept at 26- -2 C. The solution was stirred for 2 hours longer, after which time the infrared spectrum was devoid of the isocyanate band at 4.3 to 4.5 microns. The solu-' tion had an aziridinyl content of 0.076 equivalent per 100 grams of solid (0.084 eq./100 g., calculated). The solution was micible with dimethylformamide.

EXAMPLE XXVII A preparation similar to Example XXVI, but of lower molecular weight The chemical equations of Example XXVI applied, except that x, the degree of polymerization, was about 13 on the average. The polytetramethylene ether glycol used in Example XXVII had an average molecular weight of approximately 1020.

In the first stage, 200 grams (0.393 equivalent of hydroxyl) of polytetramethylene ether glycol and 68.4 grams (0.393 mole) of 4-methyl-m-phenylene diisocyanate were allowed to interact under conditions similar to those of Example XXVI. Two days later, the isocyanate content 2-(l-aziridinyl)ethoxy-terminated polytetramethyleneoxy chain I The polytetramethylene ether glycol used as the starting material had an average molecular weight of approximately 1980. The polymer was marketed under the trade name Polymeg by Quaker Oats Co. 0

The first stage of the process consisted of convertrng was 0.40 equivalent (theoretically 0.393 equivalent).

In the second stage, 93% 0f the isocyanate-terminated intermediate was allowed to react with 34.8 grams (0.4 mole) of (1-aziridine)ethanol in a manner similar to that described in Example XXVI. The aziridinyl content of the product was 0.13 equivalent per grams of solid (0.14 eq./100 g., calculated).

29 EXAMPLE XXVIII In the second stage, 0.26 equivalent of the isocyanate- A preparation similar to Example XXVII but having terminated intermediate was allowed to react with 11.3

grams (0.26 mole) of ethylenimine in a manner similar to that described in Example XXVI. The aziridinyl content the Chemical equation pp y to the fi Stage, was found to be 0.14 equivalent per 100 grams of solid see Example XXVI, x=about 13 on the average. h i ll 0,14 ,/100

Second stage:

(ICTIT) 2H2NOH2OH2NCH2CH2 terminal 2-(1-aziridinyl)ethylamino groups 0 I'm I'm O=(i3CHzGHzNCH2CHz 0=d-goHioHeNoHioHe 2-(1-aziridinyl)ethylamino terminated polytetramethyl- EXAMPLE XXX eneoxy chain 7 v 7 n A preparation having (1) a complex polyester chain as In the first stage, the isocyanate-terminated intermedi- Its backbone and (2) termmal l'azmdmyl groups ate. (ICTIT) having a backbone derived from a polytetra- First stage:

( 0.164 eq./100 g. calculated.)

HO CHzOHzOH Isoeyanate-terrninated polyester (starting material of EXAMPLE XXV) methyleneoxy chain was prepared in a manner similar to ICTIP, an isocyanate-terminated intermediate having a that of Example XXVII from polytetramethylene ether backbone derived from a complex polyester chain Second stage:

40 The first stage of the process was carried out as fol- 1 col hav-n an avera 5 molecular Wei ht of a roxi lows. A mixture of 6.82 grams of ethylene glycol (0.11 ig g g pp mole) and 75 grams of dichloromethane was added quick- In the Second stage, 031 equivalent of the isocyanate ly to a stirred solutlon at 0 C. consisting of 200 grams terminated intermediate which was 79% of the original 9 dichloromethane and 200 grams ((1446 q v t o amount obtained in the first stage was allowed to react Y of y h nated polyester identlfied with 33.5 grams of 1-(2-aminoethyl)aziridine dissolved 111 Example Stlfrlng Was eontlmled as the reaction i grams f dichloromethane in a manner Similar to mixture was allowed to warm to room temperature. After that described in Example XXVI. The aziridinyl content 2 e the lsoeyanate content e e constant at 0.24 was found to be 0.17 equivalent per 100 grams of solid. equlvalent (calculated, 0-226 q U- For the second stage, a solution of 6.4 grams (0.149 50 mole) of ethylenimine and 50 grams of dichloromethane EXAMPLE XXIX was added dropwise within 1 hour at room temperature Pre aration of a 1 functional compound having (1) a to of -P the product equivalfint r sidue of ethoig la ted glycerol as the central portion of of lsocyanate) ,obtamed m the first Stage- After a its molecule, and (2) terminal l-azidinyl groups of 1 the Infrared .spectrum. was devold ti 1S0- cyanate band. The reaction solution had an azridinyl cont 1 Adduct glycerol and ent of 0 1 equivalent per 100 grams of solid (0.12 eq./

ethylene oxide1z32' 3(OCN )2C6H3*CHS 3HNCHZCH2 100 g., calculated; theoretically 0.103 eq. of the desired approximately, by moles W W product per 100 grams of solids). The desired product has a complex polyester backbone terminated at both ends CHKOCECHQP 60 of the molecule by l-aziridinyl groups.

H(0CHzOHz) 15523132 EXAMPLE XXXI HZ(OCH2OHZ)I H 1! 3 Dimensional stabilization of woolen fabric by treatment with the product of Example )Q(V wherein x+x+z=approximately 32. Samples of 100% woolen fabric in a plain Weave and The ethoxylatedglycerol used as starting material had welghlhg Ounce? Pe q e y Were treated at an average molecular weight of 1495. In the first stage, eefdlngh) the tluantltatlve detalls ill the accompanying 200 grams of the ethoxylated glycerol and grams 70 table With. SOlUtlODS Of the PI'OdllCt Of Example X)(V. (0.402 mole) of 4-rnethyl-m-phenylene diisocyanate were A 38% solution of the product in dichloromethane Was allowed to interact under conditions similar to those of diluted by dimethylformamide to give the percentages Example XXVI. By analysis at the end of the reaction OWB shown in the accompanying table. Solutions were period, the isocyanate content was found to be 0.42 equivapplied by means of a laboratory padder. After padding;

alent (theoretically 0.402 equivalent). the samples were framed at the original dimensions and 31 dried at approximately 50 C. All samples were cured for minutes. The cured fabric was rinsed in dimethylformamide, then in a 0.1% aqueous solution of p- 1,1,3,3 -tetramethylbutyl phenoxynona(ethyleneoxy)etl1- 32 EXAMPLE XXXIII Dimensional stabilization of woolen fabric by treatment with the product of Example XXVII anol again framed to the original dimensions, and dried. 5 The procedure of Example XXXII was repeated using Shrinkproofing evaluation was excellent and durable, as is as the reagent the product of Example XXVII, a lowerevident from the evaluation results in the accompanylng molecular-weight polymer than had been used in Example table. The polymer was reactive because of amine-type XXXII. A 60% solution of the product in dichlorol-aziridinyl groups terminating the chain, the center pormethane was diluted with dimethylformamide to give tion of which was apolyester. the percentages OWB shown in the accompanying table.

Warp flex Shrinkage, percent Product of Example Actual abrasion re- Warp Green XXV, percent Cure weight slstance stlflfilter 5L 10L temp, gain, 0.5 X 2 lb ness, reflect OWB WPU OWF 0 percent cycles mg.crn. ance W F W F Sample:

A-l 5.5 127 7.0 135 4.94 815 1,814 53 1.5 0.5 2.0 0.5 5.5 129 7.1 163 4.38 675 1,241 56 1.5 None 2.0 0.5 2.6 121 3.1 135 2.92 815 651 58 1.5 0.5 2.5 0.5 13-2 2.6 127 3.3 163 2. 74 515 811 55 1.5 None 2.5 0.5 Untreated Control 700 125 62 20.5 16.5 27.5 26.0

EXAMPLE XXXII Dimensional stabilization of woolen fabric by treatment with the product of Example XXVI Samples of the woolen fabric identified in Example Warp flex Green Shrinkage, percent Product of Example Actual abrasion Warp filter XXVIII, percent Cure weight resistance stifireflect- 5L mp., gain, 0.5 x 2 lb., ness, ance,

OWB WPU OWF 0 percent cycles mg.e1n. percent W F 3. 120 4. 1 135 3. 9 1, 100 700 63 2. 5 2. 0 3. 40 116 3. 9 163 3. 9 975 495 63 4. 0 1. 5 1. 119 2. 0 135 3. 2 1, 025 599 64 1. 0 1. 5 1. 70 118 2. 0 163 3. 2 1, 375 499 63 1. 5 1. 5 0. 123 1. 0 135 2. 4 1, 175 320 63 1. 5 2. 0 D-2 0. 35 122 1. 0 163 2. 3 950 328 62 1. 5 2. 0 Untreated control. 815 107 65 22. 5 11. 0

XXXI were treated according to the general procedure of that example with the following variations: The reagent was the product of Example XXVI. A 54% solution of it in dichloromethane Was diluted with dimethylformamide to give the percentages OWB shown in the accompanying table. After padding, samples (18 by 17 inches) were dried at approximately 65 C. Curing was for 5 minutes, and other quantitative details are in the accompanying table. Excellent shrinkproofing resulted from the use of the reactive polymer having a backbone made up of repeating tetramethyleneoxy units, the molecular chain being terminated by amine-type l-aziridinyl groups. Even at low concentration, the reagent was very effective.

EXAMPLE XXXIV Dimensional stabilization of woolen fabric by treatment with the product of Example XXVIII Warp flex Green Shrinkage, percent Product 01 Example Actual abrasion Warp filter XXV III, percent Cure weight resistance stifireflect- 5L emp., gain, 0.5 x 2 1b., ness, ance,

OWB WPU OWF 0 percent cycles mg.-cm. percent W F 3. 3 4. 0 5. 4 1, 510 63 1. 5 1. 5 3. 3 119 3. 9 163 5. 3 915 685 62 1. 0 1. 0 1. 7 120 2. 0 135 2. 6 975 387 64 1. 5 1. 5 1. 7 119 2. 0 163 2. 9 725 429 63 1. 5 1. 5 0. 9 121 1. 1 135 1. 7 750 288 64 4. 0 1. 5 D2 0. 9 118 1. 1 163 1. 7 825 307 64 3. 5 2, 5 Untreated control. 815 107 65 22. 5 11. 0

mg resulted over a good range of concentratlons with It 1s understood that various other modifications will thls reactive polymer. be apparent to and can readlly be made by those skilled v p Warp flex Green Shrinkage, percent Product of Example Actual abrasion Warp filter XXVIII, percent Cure weight resistance stifireflect- 5L temp., gain, 0.5 x 2 1b., ness, ance,

OWB WPU OWF percent cycles ing-cm percent; W F

5.00 118 5.9 135 -7.0 1,475 2,000 63 1.5 0.5 5. 00 117 5. 9 163 6. 8 l, 250 1, 700 62 l. 5 0. 5 3. 33 114 3. 8 135 3. 8 1, 175 1, 300 63 1. 0 0. 5 3. 33 110 3. 8 163 3. 5 1, 025 1, 200 62 1. 5 0. 5 1. 67 111 1. 9 135 2. 1 925 600 62 2. 5 (0. 5) 1. 67 115 1. 9 163 2. 1 850 400 61 2. 5 None 0. 84 114 1. 0 135 1. 4 850 380 64 4. 5 (0. 5) 0.84 117 1.0 163 1.4 775 430 62 4.5 (0. 5) 815 107 65 22. 5 11. 0

' Percentages in parentheses are the opposite of shrinkage. l

EXAMPLE XXXV Dimensional stabilization of woolen fabric by treatment with the product of Example XXIX A procedure similar to that of Example XXXII was followed, using as the product of Example XXIX, a polymer Whose central moiety came from ethoxylated glycerol, and having amide-type l-aziridinyl terminal groups. A 51% solution of the product in dichloromethane was diluted with dimethylformamide to give the percentages OWB shown in the accompanying table. Good results on shrinkproofing are evident.

Warp flex Green Shrinkage, percent Product of Example Actual abrasion arp filter XXVIII, percent Cure weight resistance stifireflect- 5L temp., gain, 0.5 x 2 1b., ness, ance,

OWB WPU OWF 0 percent cycles mg.cm. percent W F 129 6. 6 135 7. 8 1, 200 490 62 2. 0 0. 5 124 4. 2 135 6. 0 1, 000 425 62 2. 0 0. 5 121 2. 1 135 3. 5 975 295 63 4. 5 0. 5 D 120 1. 0 135 2. 5 1, 050 260 64 6. 5 None Untreated control- 815 107 65 22. 5 11. 0

EXAMPLE XXXVI Dimensional stabilization using the product of Example XXX A procedure similar to that of Example X)Q(I was followed, using the product of Example XXX, a polymer whose central moiety was mainly a polyester, and whose terminal groups were amide-type l-azinidinyl groups.

teinaceous material a polyfunctional compound of the formula m is in integer of from 2 to 3, A is selected from the group consisting of Az,

The product was diluted wlth dimethylformamlde to and CEHZBAZ give the percentages OWB shown In the accompanylng a is an integer from 1 to 4, table. All samples were cured for 5 minutes at approxi- AZ is mately 163 C. Upon evaluation, good control of shrink- I age was obtained, as is apparent from the accompanying. .60 N

' table.

TABLE T0 EXAMPLE XXXVI I Shrinkage, percent Product of Example XXX, percent Actual Abrasion resls- Warp stifi- 1L 5L weight tance 0.5 x 2 ness, mgr OWB WPU OWF gain% 1b., cycles cm. W F W F Wool fabric sample:

4.4 4.0 875 258 3.5 0.5 4.0 None 2.1 3.2 825 277 3.0 0.5 3.5 0.5 Control untreated 900. 132 10.5 3.0 21.5 12.5

35 wherein R R R are selected from the group consisting of H and alkyl having from 1 to 4 carbon atOrns, J is selected from the group consisting of (g) (C Hawk- 2 a has the meaning given above,

x, y and z independently are integers of from about 1 to 100,

u is an integer of from about 6 to 100,

n is an integer of from 2 to 6,

v is an integer of from about 3 to 80,

q is an integer of from 3 to 5,

r is an integer of from 2 to 35, and

L is a divalent alicyclic radical of 3 to 20 carbon atoms, C to C alkylene, or C to C alkylene having the chain interrupted by one to ten O, -S, or groups in which R is H or alkyl having 1 to 5 carbon atoms,

Q is selected from the group consisting of C H e a(- 3), z e 4 2-, CGH4CGH4 10 6 a said polyfunctional compound being applied from a liquid medium and heating the proteinaceous material having 36 acids of 2 to 12 carbon atoms and polyalkylenepolyamines of 4 to 20 carbon atoms and 2 to 5 nitrogen atoms.

7. A process as claimed in claim 1 wherein Q is 8; The process of claim 6 wherein about 0.5 to about 2.0 equivalents of co-reactant are presentuforeach aziridinyl group present and the pH of the liquid medium ranges between about 30 to about 9.0. i

9. The compound of the structure:

A is selected from the group consisting of 10. The compound of the structure:

polyfunctional compound applied thereto until the desired wherein v is an integer ranging from 3 to 4, and

dimensional stabilization takes place.

2. A process as claimed in claim 1' wherein said proteinaceous material is wool.

3. A process as claimed in claim 1 wherein said polyfunctional material is dissolved in an inert organic solvent.

plied thereto is heated at a temperature of about 100 to 200 C.

6. A process as claimed in claim 1 wherein, in addition to said polyfunctional compound there is applied to said proteinaceous material a coreactant selected from n is an integer ranging from 2 to 8.

11. The compound of the structure:

l r Nfi-OKCH2)40lx(CH2)40%N-@CH3 CH 1? /CH2 O=CgCH2OH2N\ I CH2 CH2 wherein x is an integer ranging from 5 to 40.

12. The compound of the structure:

I onaoomom 0$[JN@CH CH H-(OCH2CHz) o i 2 N-CN H2(OOH2OH2)Z H H o CH2 3 the group consisting of saturated aliphatic dicarboxylic wherein x+y+z=approximately 32.

3,523,750 37 38 13. The compound of the structure: wherein x+y+z=50, and said polyfunctional compound is applied from an aqueous emulsion.

wherein v is an integer ranging from 3 to 4, and n is an integer ranging from 2 to 8.

14. The compound of the structure:

NH CH2 o=o on oomonm oomcmN on, on,

wherein v is an integer ranging from 2 to 6, and n is an integer ranging from 4 to 8.

15. The compound of the structure:

NH /CH2 N CH2 O=(EOCH2CH2N\ O=0CH2CH2N\l CH7 Ha wherein x is an integer ranging from 5 to 40. 18. A process as claimed in claim 6 wherein the poly- 16. A process as claimed in claim 6 wherein said polyfunctional compound is of the structures:

0 0 O O I I (@OK-CHa-MO X-CHzQv--OM-CHz-h-Oy HN- -CH3 HIL- -CH a on, on,

NHG0N\Jj v NHOON H: CH2

functional compound is of the structure: a.

H wherein n is an integer of from 2-to 6; q is an integer CH2(0CsHe)x 0 ON CH; g of from 3 to 5; and r is an integer of from 2 to"35.

Ekwcm)y a 19. A process as claimed in claim 6 wherein the polyfunctional compound is of the structure: Hz(OCaHo)u H H HO:C\ o cm N-i: C-N v I i H,

1120 IIIH t I a H wherein x+y+z=50, the co-reactant is a polyalky lene polyamine, and perchloroethylene is present as an inert organic solvent. wherein u is an integer of from about 6- to 100*. v

17. A process as claimed in claim 6 wherein said poly- 20. A process as claimed in claim ,6 wherein the polyfunctional compound is of the structure: functional compound is of the structure:

H C -CH H (CLHflOCSHI) 0 "N s/ H-(OCaHah O II (I} N\ I H2(OC:H0). 1 OH: 3

on; (I? 0 on; I

N-C (LL-N/ l 112 EN NH OH:

wherein n is an integer of from 2 to 6, and v is an integer of from 3 to 80.

21. A process as claimed in claim 6 wherein the polyfunctional compound is of the structure:

wherein u is an integer of from about 6 to 100.

22. A process as claimed in claim 6 wherein the polyfunctional compound is of the structure:

NH +=o CH2 {i=0 /CH3 OCHzOHzN l OCHzCHzN\l wherein v is an integer of from about 3 to 80, and n is an integer of from 2 to 6.

23. A process as claimed in claim 6 wherein the polyfunctional compound is of the structure: 40 t H H oH3-@N( -o om)401x(ong)io- N-@-ona 0 0 l N /CH2 NH /CH2 O=(L/OCH2CH2N l O=( OCHzCH2N\ H; CH2

wherein x is an integer of from about 1 to 100.

24. A process as claimed in claim 6 wherein the polyfunctional compound is of the structure:

H H CHa-@Nfi-OKCH2)40];(CH2)4OfiN-@CH:1

l 0 0 l IIIH /CH2 IIIH /CH: 0=C-NCH;0H;N O=GNCH2CH2N CHa CH2 wherein x is an integer of from about 1 to 100.

25. A process as claimed in claim 6 wherein the polyfunctional compound is of the structure:

60 H onuoomomn- -ooN-@-om I oil- 0011011 i n on 001 1 013 ll \i 2 Z 2 z 0 H 3 wherein x+y+z=approximately 32.

26. A process as claimed in claim 1 wherein the polyfunctional compound is of the structure:

CH O-C-N N-CO Grimm-o (onnno C-N- CH3 l 1 I H l: II] It I I /CH2 1 HN-(I?N I C Ha