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Home , Halogenated ether

Patented Aug. 19, 1941 2,253,102

UNITED STATES PATENT OFFICE 2,253,102 METHOD OF REDUCING SHRNKAGE OF WOO, Joseph Frederic Walker, Lewiston, N.Y., assignor to E. I. du Pont de Nemours & Company, Wil mington, Del, a corporation of Delaware No Drawing. Application October 19, 1939, Serial No. 300,281 Claims. (C. 8-128) This invention relates to the improvement of These objects are accomplished by the foll Wool and other keratinous textile fibers, and more lowing invention wherein a keratin-containing particularly to reduction of the shrinking tendency animal fiber, e. g., Wool, is subjected to the action of Such fibers. of an alpha-halogenated wherein the radi A number of keratinous (see Lloyd and Shore, 5 cals attached to the ether contain each Chemistry of the Proteins, 1938, page 88) textile not more than six carbon . fibers, of which wool is the most important, are The shrinking tendency of wool can be re characterized by their tendency to felt When sub duced or completely eliminated by treating the jected to mechanical working. This felting Wool With alpha-halogenated in which tendency is essential in the finishing of Some 10 the or are attached to an ali Woolen goods to give a dense surface and in the phatic carbon or carbon atoms and in manufacture of felts for hats, paper machine which each organic radical separated from the blankets, and the like. However, since it causes remainder of the molecule by ether oxygen con shrinking during laundering, it is a serious dis tains not more than six carbon atoms. More advantage in many wool applications. Consider than One halogen atom may be attached to either able attention has therefore been given to reduc or both of the carbon atoms linked by the ether ing or eliminating shrinkage due to felting. For OXygen atom and the compound may contain some applications, including knit goods, baby more than one alpha-halogen ether grouping. clothing, underwear, and Socks, it is desirable to Halomethyl ethers, e. g., chloromethyl ethers, have the material as completely shrinkproof aS that is, compounds of the structure ROCH2Cl, is possible. For overcoats, suits, dresses, blankets, may be readily prepared by reacting the corre jackets, and other articles which are laundered Sponding of the formula. ROH with less frequently, the shrinking tendency of the formaldehyde and halide, e. g., hydro wool need be only partially and not completely gen chloride. Dichloromethyl ether, eliminated to be satisfactory in practice. 2 5 Methods previously proposed for reducing the CICH2OCH2Cl shrinking tendency of Wool include treatment Which has proven particularly valuable in the With halogens, hypohalites, sulfuryl chloride and practice of this invention and is therefore par the like. However, chlorination procedures re ticularly preferred, may be prepared by the re Sult in damage to the Wool which is manifested 30 action of formaldehyde with hydrochloric acid in decreased strength, increased harshness, a in the presence of concentrated sulfuric acid. slimy feel when wet, discoloration, and loss of 2,3-dichlorodioxan, which is also particularly the natural Water repellency of the Wool. An Suited to the practice of the invention and there other disadvantage of is that "tail fore particularly preferred, exemplifies the many ing" effects occur, due to the rapid reaction of halogenated ethers which may readily be pre the halogen with the Wool first entering the bath, pared by the reaction of free halogen with the which exhausts the reagents before all of the corresponding ether. All of these methods are fabric is treated. Well known to the art. The use of sulfuryl chloride does not discolor The treatment with halogenated ethers may and weaken the wool to the same extent as does 40 conveniently be carried out as follows: The wool, halogenation, but the wool so treated is some after preconditioning at a suitable humidity, is What harsh and has lost its natural water re immersed in a vessel containing a solution of the pellency. halogenated ether. The solvent used should, of This invention has as an object the improve course, be an inert solvent, i. e., one which does ment of the physical characteristics of kerat not itself readily react with the halogenated inous textile fibers. A further object is the ether under the conditions of the treatment. treatment of Wool and similar keratin-contain such as , , naphtha, ing fibers to reduce their tendency to felt on me and chlorinated hydrocarbons such as trichloro chanical Working. A still further object is re and carbon tetrachloride, are suitable. duction of the tendency of wool to shrink on Ethers, including dioxan and 1,2-dimethoxy laundering. Another object is the preparation ethane, are also useful as solvents. Particularly of keratin-containing fibers of reduced tendency good results are obtained when ketones such as to shrink on laundering, which retain their nat methyl ethyl ketone and methyl amyl ketone are ural Water repellency, resiliency when wet, and employed as the solvents. The concentration of softness. Other objects will appear hereinafter. 55 the halogenated ether in the solution, the dura

2 2,253,102 tion of the treatment, and the amount of solu Eacample II tion used in proportion to the amount of wool to be treated, may be varied considerably. After Wool flannel which has been conditioned in a treatment, the wool is removed from the solu chamber maintained at 100 F. and 86% relative tion, freed from excess liquid by any convenient humidity is treated at 140° F. for an hour with a method such as centrifuging or squeezing, and 4% Solution by volume of dichloromethyl ether dried. A final washing with water, soap solition, in Stoddard solvent. The wool is freed from the or a weak solution of ammonia may follow. " excess solution as in Example: Elie treated It has been found that impregnation of the Wool is completely shrinkproof, as determined by textile material with an amide such as urea be. lo the laundering test, and retains the natural re fore treatment yields particularly soft and:white. ... siliency, soft feel, and Water resistance of the un wool. A weight of urea equivalent to 2-6% of treated wool. the weight of the fibers may be used. Eacample in determining the shrinkproofness of the . Woolfiannel is soaked in a 4% solution of urea treated wool, it has been found convenient to 5. in Water and then wrung until it-contains only use a uniform testing procedure, referred to he re v . . . . . its own weight of the solution. The fabric is then inafter as the laundering test. In this test: conditioned overflight in a chamber maintained small sample of Wool fabric treated with an at 90 F. and 86% relative humidity, and then alphahalogenated ether and a similar sample of. immersed for one hour at 140 F. in 5 parts by untreated fabric are measured to determine their 20 Weight of a 3.8% solution of dichloromethyl ether respective areas and then each is passed a defi in Stoddard solvent. The product is completely nite number of times (usually 150) through a shrinkproof and retains the natural resilien 3. rubber-roll wringer, dipping after - each pass in water resistance of the untreated woes to a solution containing 0.25% of a detergent, particularly e.g., "Ivory Soap' or sulfated oley and 0.1% sodium carbonate at 25° C. Other dilute 25 . . . . . alkaline soap solutions can be used in this test. Wool fannel which has been condit After laundering, the samples are dried and chamber maintained at 110°F and 80% relative again measured. The area losses sustained by humidity is treated at 210°F. for 2 minutes with the samples are then determined and the per 30 75 parts by weight of a 2% solution by volune cent shrinkproofness is calculated from the fol of dichloromethyl ether' in Stoddard solvent lowing formula: : ...... (A. S. T. M. vol. 38, part 1, 1938). The excess treating solution is removed from the sample and 100X (Area, loss of untreated fabric the wool is rinsed inwater. The shrinking tend area. OSS of treated fabric) ency of the treated wool is reduced 33 per cent, (Area loss of untreated fabric) as determined by the laundering test. Per cent shrinkproofness, i. e., per cent, re ...... Eacample, W ...... duction of tendency to shrink. 3: The percent shrinkproofness given in the follow Woolflannel which has been conditioned at ing examples was determined by this method. 40 110F. in an atmosphere of 80% relative humid The laundering test is also a convenient method ity is treated at 140 of following the shrinkproofing treatment since parts by weight of a 2. a small sample may be taken from the textile ethyleneglycol bis-chloronet material which is immersed in the alpha-hal ogenated ether solution at the end of a period judged to be suitable for obtaining the desired effect and tested in the above manner to deter mine the per cent shrinkproofness. If the ma teria has not yet been treated to the desired: de gree, the process may be continued until another test indicates that the desired degree of shrink proofness has been achieved. . . . . The more detailed practice of the invention is illustrated by the following examples, wherein by volume of trimethylene glycol bis-chloromethyl parts are given by Weight. There are of course 5 5 ether in Stoddard solvent. The shrinking tend many forms of the invention other than these ency of the treated wool is reduced 33 percent: specific embodimentS. ... is ...... Ecample VII.

Wool flannel which has been wool flannel which has been conditioned over night in a chamber maintained at 100 F. and 86% relative humidity is immersed at 40 F. for one hour in a 2% solution, by volume of dichloro lutionmethylpropane by volume in of Stoddard 1,3-bis-chlorometho solvent, "The treated methyl ether in the solvent having 65 wool is about 65 percent shrinkproof and re. a typical boiling point range from 300-400° F, tains the lofty handle and natural water repel which is known to the trade as Stoddard solvent. tre 'e .. Five parts by weight of solution are used per part lency of the un of wool. The sample is then freed from excess solution by wringing, rinsed and dried. The 70 product is 75% shrinkproof, as determined by the laundering test and has a very desirable soft humidity is treated for one hour at 14 feel. The treated wool is wetted only with diff 7.5 parts by weight of 5.4% solution by culty, resembling in this respect the untreated of n-butyl chloromethyl ether in Stoddard isol WOOl. 75 vent. The shrinking "tendency of the treated ES 2,253,102 Eacample C Wool is reduced 52 per cent, The flannel has an Wool (5 parts) conditioned at about 8% relative extremely soft feel. humidity was treated with a solution of 1 part Eacample IX of dichloromethyl ether and 0.6 part of hexameth. Wool flannel which has been conditioned in a 5 ylenimine in 27 parts of Stoddard solvent at 60° C. chamber maintained at 80° F, and 80% relative for one hour. The shrinkage reduction was only humidity is treated for one hour at 140 F. With 5.5%. 5 parts by weight of a 2% solution by volume of Any keratin-containing animal fiber, e.g., Wool, 2,3-dichlorodioxan in Stoddard solvent. The alpaca, vicuna, angora rabbit hair, goat hair, and shrinking tendency of the treated Wool is reduced 10 camel hair may be reduced in shrinking tendency 60 per cent. The fiannel retains the natural Wa according to this invention. The material which ter repellency and soft feel of the untreated Wool. is to be processed may be a fabric, or may be in Eacamplex another form, for example, in the form of fibers. yarn, or threads. Wool flannel which has been conditioned over 15 The treatment may take place either before or night in a chamber maintained at 92 F. and after dyeing, or, if a suitable solvent is used, it 86% relative humidity is treated for one hour at may take place in the dyeing bath. Other finish 140 F. with 6 parts by weight of a 3% solution ing treatments can be applied before or after the by volume of the bis-bromomethyl ether of ethyl shrinkproofing treatment. The duration and the ene glycol in Stoddard solvent. The excess Solu 20 temperature of the treatment are mutually inter tion is removed from the sample which is then dependent. Thus, it is possible to vary the ten rinsed first in dilute ammonia solution and then perature Within Wide limits and obtain a satis in Water. The treated Wool retains the Water re factory product. At the same time, the duration pellency and softness of the untreated WOol and of the treatment may be correspondingly reg is about 89 per cent shrinkproof. ulated. In general, it is preferred to treat the While normal, air-dried wool, which contains wool at 130-150 F. for one to two hours. HoW about 6% moisture, for example, Wool Which has ever, if the temperature is raised to 210" F. a been stored at 77 F. at a relative humidity of period of two minutes is sufficient to obtain a good about 15%, may be used, and Some effect is ob effect. Treatment at room temperature or below tained even with bone-dry Wool, it is preferred, 30 requires such extended treatment to obtain satis in order to obtain more pronounced effects, to factory effects that it is not ordinarily practiced. treat wool which contains about 12 to 28% mois Treatment at temperatures above 210° F. is or ture, for example, wool which has been condi dinarily of no particular further advantage. tioned at 50-100% relative humidity at 77-100° The reagent may be applied either in the liquid F., because more complete removal of the shrink phase, when the compound is a liquid under the ing tendency is thereby obtained. The effect can conditions of the treatment, or the wool may be thus be varied by controlling the moisture con treated with the vapor of the compould at nor tent of the wool to be treated. The conditioning mal or reduced pressures, either pure or admixel treatment may be varied somewhat with the dif with non-reactive gas. In general, it has been ferent types of wool to get the best results. It is, 40 found preferable to apply the halogenated ethers of course, possible to otbain the same percentage from an inert solvent, i.e., diluent. From a com Of moisture in the Wool under different Sets of mercial standpoint, it is often preferable to use a, relative humidity-temperature conditions. Al low concentration of the reagent in the solvent, though the Wool to be treated may contain 6 to e.g., below 10%. It is particularly preferred to 28% moisture or more, it is particularly preferred 45 use a concentration of 2-5%. Among the Sol to employ wool which contains about 17-24% vents which are suited for the application of the moisture. reagent are hydrocarbons or hydrocarbon mix AS indicated in the above examples, the wool is tures such as hexane, octane, xylene, , treated with the alpha-halogenated ether per se, benzine, and naphtha; chlorinated hydrocarbons i. e., the ether as such and not in combination. 50 Such as carbon tetrachloride, , Treatment of wool with the alpha-halogenated and perchloroethylene; ethers, including dioxan; ethers in combination with other materials reac ketones, and other inert solvents. The solvent tive therewith, e. g., tertiary bases, does not at may be recovered after each treatment, or Series tain the results of this invention as is further dis of treatments, for example by distillation, or it closed in Examples A, B, and C below. For this 55 may be reused after replenishing the active agent. reason, applicant describes his treating agent as From a commercial standpoint, dichlorodi an alpha-halogenated ether wherein the radicals methyl ether and dichlorodioxan are preferred, bounded by ether oxygen atoms are each of not but any other alphahalogenated ether, including more than six carbon atoms and this ether is used thioethers, wherein any organic radical separated per se, i. e., as such and not in combination with 60 from the rest of the molecule by ether oxygen or any material reactive therewith to any substan thioether sulfur, i. e., each carbon chain attached tial extent. to the ether oxygen or thioether sulfur contains Eacample A not more than six carbon atoms may be employed Wool (5.5 parts) conditioned at 78% relative to accomplish the object of this invention. There humidity was treated with a solution of 1.5 parts 65 is no limitation on other groups present in the of the bis-pyridinium salt of dichloromethyl ether compound except that none should be present, in 35 parts of water at 60° C. for one hour. The Which Would react with the halogenated ether, reduction in shrinkage was only 8%. Such as an amino group. For example, the com Eacample B pounds may contain one or more aromatic nuclei 70 which may also contain halogen substitutes. Wool (5.5 parts) conditioned at 78% relative Aryl halogens are not necessary in increasing humidity was treated with a solution of 1.3 parts of the pyridinium salt of n-butyl chloromethyl the resistance of the wool to shrinkage. Ethers ether in 53 parts of water at 60° C. for one hour. in which the halogen atom is substituted on a The reduction in shrinkage was 8%. 75 Saturated carbon atom are much preferred over

4. 2,258,102 ethers in which the halogen atom is substituted on an unsaturated carbon atom, Oxygen ethers Thus when flannel is treated for 5.5 hours at are preferred to thiocthers because of lower cost 77 F, and at a pH of greater than 9 with 18 and freedom fl'on l'esidual odor. parts by weight of a 10% solution of formalde hyde in water, then rinsed in water, the shrink Thus, there may be used in the processes of thc ing tendency of the wool is not reduced. present invention any alpha-halogenated ether, When fifty parts by weight of a solution con including thioether, wherein any organic radical taining 5 grams per liter of a suspension of 4 separated from the rest of the molecule by ether grams of a 40% aqueous formaldehyde solution oxygen or thioether sulfur, i.e., each carbon chain With 10 grams of 50% lactic acid and 7.5 grams attached to the ether oxygen or thioether sulfur O of "Monopol' oil was applied to wool at 120° F. contains not more than six carbon atoms, includ for 15 minutes and the wool then rinsed in ing the following reagents which are illustrative water, there was actually a slight increase in of compounds useful in practicing this invention: the shrinking tendency of the treated wool, Chlorodimethyl ether------ClCHOCH3 Sym.-dichlorodimethyl ether------ClCHOCH2Cl Unsym.-dichlorodimethyl ether------. Cl2CHOCH3 Chloromethyl butyl ether------CCHOC4H9 Bromodimethyl ether------BrCH2OCH3 Iododimethyl ether------ICH2OCH TrinnethyleneEthylene glycol glycolbis-chloromethyl bis-chloromethyl ether--ClCH2OCH2CH2OCHCl ether ------ClCH2OCH2CH2CH2OCHC) Dibromodiethoxymethane ------C2H5OCBr2OCH5 Alpha, alpha'-dichlorodiethyl ether----CH3-CHCl-O-CHCl-CH3 Alpha,Ethylene alpha'-dichlorodiethyl glycol bis (alpha-chloroamyl) sulfide----CH3-CHCl-S-CHCl-CH Beta-phenoxyethylether ------alpha-chloroethyl C4H9CHC-O-CH2CH2-O-CHCICH Beta-phenoxyethylether ------chloromethylether--Cohe-O-CH2CH2-O-CH2Cl ------C6H6-O-CH2CH2-O-CHCCH Halogenated cycloaliphatic ethers, including 2,3- dichlorodioxan, may be used. When flannel is treated for one hour at 1220 The ethers may also be defined as of the F. With 11.5 parts by weight of a 0.33% sus formula: R-X-R, wherein X is a member of pension of paraformaldehyde in Stoddard sol the 6th group of the periodic table having an 35 vent, then rinsed in water, the shrinking tend atomic weight not greater than approximately ency of the wool is not altered. 32,06 (1935 Table), R and R' are the non-hy An important advantage of this invention is droxy residues or portions of alcohols and have that it yields a superior product which is neither a chain of carbon atoms not longer than six harshened by the treatment nor made readily atoms and at least one of the radicals contains 40 Susceptible to wetting. The advantages of a halogen on the carbon attached to the ether Softer feel and lofty handle are readily apparent oxygen or thioether sulfur, i. e., on the alpha in applications of the treated wool to the manu carbon. For convenience the term "ether' in facture of clothing, in particular baby clothing, the claims includes both oxyethers and thio where the comfort of the wearer is of prime in ethers. portance. The fact that the wetting character Although fluoro-, bromo-, and iodo-ethers istics of the wool are unchanged by the treat may be used, the chloroethers are preferred be ment is also of extreme importance. Natural cause they are less expensive, are more stable Wool, after cleaning, degreasing, and Scouring in storage, and are outstanding in the quality of is markedly resistant to wetting. When wetted the products which they produce. by prolonged contact with moisture, it has the Combinations of halogenated ethers may be property of taking up considerable water with used to reduce the shrinking tendency of the out acquiring a soaked, scroopy, feel. wool. The advantages of this characteristic are It has not been possible to advance a theory of obvious in the case of outer garments such as reaction adequate to explain the shrinkproofing SWeaters, suits and overcoats. However, the effect of the halogenated ethers. The shrink advantage is also marked in the case of clothes proofing is accomplished without destroying the to be worn next to the body as in the case of natural soft feel and water repellency of the underwear, Socks, and baby clothing. The chief Wool. This shows that the treatment must have advantage of wool for these uses is that due to a radically different effect on the wool from that 80 its free air spaces, it has a high insulating value of inorganic halogen compounds Su?h as Sulfuryl and also retains the moisture given off by the chloride, , or hypochlorites, organic or body next to the skin thus retarding evaporation in organic, as these reagents cause Wool to be and cooling of the body surfaces. When wool is come harsh and to wet readily. damaged, as in previous shrinkproofing treat Although some of the agents of this inven ments, it takes up body moisture readily, filling tion can be prepared from formaldehyde and up the free air Spaces, and also transfers mois hydrochioric acid, the effect is not due to pos ture away from the skin, thus pernitting more sible hydrolysis to formaldehyde, as is shown by rapid evaporation by air currents. In this Way the fact that wool treated with formaldehyde the warmth-retaining characteristics of wool are itself is not reduced in its tendency to shrink on 70 partly lost. These disadvantages are overcome laundering, and by the fact that many of the by the processes of the present invention where agents, including 2,3-dichlorodioxan, an espe by the shrinking tendency of the wool is reduced cially effective agent, do not yield formaldehyde without destroying the natural resistance to on hydrolysis. Wetting, So that the natural insulating value 75 of the Wool is also retained. It should be pointed 2,253,102 S out, however, that the processes of the present 5. Process for reducing the tendency of wool to invention do not render the wool water-proof or Shrink which comprises treating said wool with more resistant to wetting than the natural, un an alpha-chlorinated oxyether wherein the radi treated product. The uses for which wool of re cals attached to the ether oxygen contain each duced shrinking tendency produced according to 5 not more than six carbon atoms, said ether being the present invention is particularly suited in employed as such. clude knitted goods, such as socks, sweaters, and 6. Process for reducing the tendency of wool to mufflers; woven goods such as baby clothing, shrink which comprises treating said wool with underwear, Suits, overcoats, sports apparel, and o,0'-dichlorodimethyl ether, said ether being blankets; and the yarns or threads from which O employed as such. these are made. 7. Process for reducing the tendency of Wool to The agents are, in general, readily soluble in shrink which comprises treating said Wool with common Organic solvents so that the wool can 2,3-dichlorodioxan, said ether being employed be given a uniform treatment by easily prepared aS Such. Solutions. The action, in contrast to chlorina 8. Process for reducing the tendency of a ker tion, is slow enough to permit of easy control atinous textile fiber to shrink which comprises by varying the duration and temperature of the treating said keratinous textile fiber containing treatment. Dichloromethyl ether, a preferred from about 12% to about 28% of moisture with agent, is readily prepared from formaldehyde an alpha-halogenated oxyether Wherein the radi and hydrogen choride. cals attached to the ether oxygen contain each The above description and examples are in not more than six carbon atoms, said ether being tended to be illustrative only. Any modifica employed as such. tion of or variation therefrom which conforms 9. Process for reducing the tendency of wool to to the spirit of the invention is intended to be shrink which comprises treating said Wool Con ncluded within the scope of the clams. 2 5 taining from about 12% to about 28% of mois What is claimed is: ture with an alpha-chlorinated oxyether wherein 1. Process for reducing the tendency of a the radicals separated from the remainder of keratinous textile fiber to shrink, which com the molecule by ether oxygen contain each - not prises treating said fiber with an alpha-halo more than six carbon atoms, said ether being em genated ether wherein the organic radicals have 30 ployed as such. each not more than six carbon atoms, said ether 10. Process for reducing the tendency of Wool being employed as such. to shrink which comprises treating said wool 2. Process for reducing the tendency of wool containing from about 17% to about 24% of to shrink which comprises treating said wool moisture with an alpha-chlorinated OXy ether with an alpha-halogenated ether wherein the 35 wherein the radicals, separated from the re organic radicals have each not more than six mainder of the molecule by ether oxygen contain carbon atoms, said ether being employed as such. each not more than six carbon atoms, in 2-5% 3. Process for reducing the tendency of a ker concentration in an inert solvent at 130-150 F. atinous textile fiber to shrink, which comprises for 1-2 hours, said ether being employed as such. treating said fiber with an alpha-halogenated 40 11. Process for reducing the tendency of Wool Oxyether wherein the organic radicals have each to shrink which comprises treating Wool con not more than six carbon atoms, said ether being taining from about 17% to about 24% of mois employed as such. . . . ture with a 2-5%. Solution of a,c-dichloro 4. Process for reducing the tendency of wool dimethyl ether in an inert solvent at 130-150 F. to shrink which comprises treating said wool with 45 for 1-2 hours, said ether being employed as Such. an alpha-halogenated oxyether wherein the or ganic radicals have each not more than six car JOSEPH FREDERIC waLKER. bon atoms, said ether being employed as such.

CERTIFICATE OF CORRECTION. Patent No. 2,253,102. August 19, 19ll. JOSEPH FREDERIC waLKER. t is hereby certified that error appears in the printed specification of the above numbered patent requiri ng correction as follows: Page 3, first column, line ll, for "otbain" read -- obtain--; and second column, line 2, for "8" read --80 -- page 5, first column, line 25, for "ncluded" read --included--; and that the said. Letters. Patent should be read with this correction therein that the same may conform to the record of the case in the Patent office. Signed and sealed this 28th day, of October, A. D. 19ll. .

Henry Van Arsdale, (Seal) Acting Commissioner of Patents. CERTIFICATE OF CORRECTION. Patent No. 2,255,102. . - August 19, 194l. JOSEPH FREDERIC walkER. It is hereby certified that error appears in the printed specification of the above. numbered patent requiring correction as foliows: Page 5, first column, line lyl, for "otbain" read --obtain--; and second column, line 2, for "86" read --80 (-; page 5, first column, line 25, for "ncluded" read --included--; and that the said. Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office Signed and sealed this 28th day of October, A. D. l.9ll.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.