[1]3 @ 0 , 8 0 , 2 8 1 United States Patelit Office Pat'e,,ited Mar. 5, 1963 HYDROX%Z.CONTAINING HEMI-ACETA@LS, THEIR PREPARATION AND USE Rudolph F. Fischer, Oakland, and Curtis W. Smth7 Beri,e- 5 ley, CqJ!f., assignors to Shell. Oil Compar-,y, N4--,v York, N.Y., a corporation of Dclawz,,ie No Drawing. Filed Jan. 22, 1960, Ser. No. 3,993 14 Claims. (Cl. 167-49.5) This invention relates to a new class of acetals and 10 to their preparation. More particularly, the invention relates to new hydroxy-containing hemi-acetals, to their preparation from formaldehyde and a d;ssimilar aldehyde, and to their utilization, particularly for the trealment of textiles. 15 Specifically, the invention provides new and particularly I hydroxy-containing hemi-acetals which surprisil et i @,@l@sy act in many cases like aldehydes but do not pcssess the disadvantages of aldehydes, such as strong odor and high toxicity. T'he new products comprise 20 organic compounds possessin-, at least one and preferably two or more hemi-acetal 0- -U- IU ii-0- U LL2 0- 25 I groups and at least one and preferably a plurality of alcoholic Off groups. As a special embodiment, the invention provides new 30 hydroxy-containing hemi-acetals of the formula ORI I RI R10[(CH20).-(CH2RCHO wherein R is an alkylene radical, x is an integer,of I to 5, 25 y is an integer of 1 to 5 and n is an iriteger of at least 2, and preferably 2 or 3. At least one of the Rl's is bydrogen and the others may be hydro.-en or alkyl groups, or in some cases, two of the -OR,'s may be removed and the remaining radicals joined together through an oxy,-en 40 atom to form say a carbonyl group or a cyclic ring, The invention further provides a process for preparing the above-described n--w hydroxy-containing hemi-acetals which comprises reacting formaldehyde with a dissimilar aldehyde, such as, for example, acrolein, in at least a 1: 1 45 mol ratio in the presence of an OH-containing material and in an acidic medium. It is an object of the invention to provide a new class of acetals. It is a further object to provide new hydroxycontaining hemi-acetals and a method for their prepara- 50 tion. It is a further object to provide new hydroxy-containing hemi-acetals which have properties -,vhich make them particularly useful and valuable in industry. It is a furthe@- object to provide new hydroxy-containing hemiacetals which react in many cases like aldehydes, but are 55 free of the deleterious effects of aldehydes such as stron.- odor and high toxicity. It is a ftirther object to provide new hydroxy-containing hemi-acetals prepared from acrolein which possess the trifunctionality of acrolein but do not possess the disadvantages of acrolein, such as stro@ig 60 odor. It is a further object to provide new liquid nonvolatile hemi-acetals that are particularly effective for trea-ting fibrous material. It is a further object to provide new hydroxy-containing hemi-acetals that are particularly effective as wet strength agents for paper. It is a further 65 object to provide new hydroxy-containing hemi-acetals that are useful for the preparation of non-woven fabrics. It is a further object to provide iiew hydroxy-containing hemi-acetals that are good cross-linkin.- agents for hydroxy-containing materials as starch. It is a further ob- TO ject to provide new hemi-acetals that can be condensed with phenois to form new phenolic materials. It is a 2 further object to provide new hydroxy-containing hemiac@tals that can be used to insolubilize casein and other albuminous materials. It is a further object to provide new liquid hemi-acetals from formaldehyde and acrolein v@hich react with amines to form useful resinous materials. T'hese and other objects of the invention will be apparent from the following detailed description thereof. It has now been discovered that these and other objects of the invention can be accomplished by the new hydroxycontaining hemi-acetals which possess at least one and preferably two or more hemi-acetal 0- I I I -C-C-CH-0-CH20- I groups and at least one and preferably a plurality of alcoholic OT-4 groups. It has been found that the abovedescribed new hydroxy-containing hemi-acetals possess many valuable properties which make them particularly useful and valuable in industry. It has been found, for example, that these new materials surprisingly react like aldehydes in many cases but do not have the disadvantages of aldehydes, such as strong odor and high toxicity. The new materials have been found to beparticularly outstanding for treating fibrous material as they impart improved properties thereto. Textile fabrics treated with the new materials have greatly improved crease resistap-ce in both wet and dry state. Furthermore, this improvement is accomplished by the -ase of only very small amounts of the new hydroxy-containing hemi-acetals and without causing a loss of other desired properties, such as hand, strength and ffie IP,-,e. Further advantage is also found in the fact that the treated fabric is non-chlorine retentive and can be subjected to bleaching and application of heat without discoloration. The new hemi-acetals are also of particular value in the treatment of other fibrous materials, such as paper, leather and the like. They are particularly effective as wet strength agents for sulfite and Kraft paper aiid as tanning agents for cowhide, calfskin, goatskin and the like. They are also useful in the preparation of nonwoven fabrics from synthetic and natural materials. The hemi-acetals of the present invention are also useful as insolubilizing agents for starch, such as cereal, corn, rice, wheat, root, pot-@to, tapio-.a and the like, starches and as insolubilizing agents for casein and other albuminous materials. They are also of value as cross-linkiig agents for hydroxy-containing materials, such as cellulose derivatives, cellulose etliers and esters as ethyl and methyl cellulose, cellulose acetate and propionate, and cross-linking agents for hydroxy-containing polymers as polyvinyl alcobol, bydrolyzed copulymers of vinyl acetate and alpha-olefins, polyalyl alcohois and the like. The new hemi-acetals may also be used to produce resinous materials by reaction with polyhydric alcohols sur-h as pentacrythri@lol, di- and polypentaerythritols, and then reacting the resulting prodilct with polyisocyanates, such as, for example, toluene diisocyanate, durene diisocyanate, benzene diisocyanate and the like. The new hemi-acetals also find use in the pr-@paration of r@ew phenolic derivatives by condensation with pbenols. '-',ljch mat@-rials may be subsequently reacted with epichlorohydrin iii the pres-@nce of caustic to form new epoxy resins. The hemi-ac-,tals of the present invention may be used for the treatment of wood, as tissue fixing agents as embalm-n- fluids a-.qd agents for ii-se in medical pa-thological vvork and as intermediates for the preparation of fungicides and nsecticides and as intermediates for the predaration of oil-soluble derivatives for use in lubricatin-g and fuel oil compositions. The new hydroxy-containing hemi-acetals of the present invention comprisethose organic compounds possess-
[2]3,060,P@81 3 ing at least 6ne and preferably tivo or iiiore hemi-acetal 0- ic- icir-OCR20- I eou@s and b@t least one, and preferably a plurality of alcoholic OH groups. The main chain containing the above-noted group or groups may be @ open-chain or cyclic aiid may-coiit,@in substantially aliphatic or cycloaliphatic carbon; zitoriis @hd or- okygen atOMs. -The length of the molecule will d-.pefid on the m t '- selected. a erial The preferred hydrcixy-cbntainihg hemi-acetals of the p'tesent ihvention include those of the@ formula ORL RI OE (CIT20) @(dH2R @HO),]-Ri wjierein R is an alkylene radical, x is an integer of 1 to 5, y is an integer of 1- to 5 and n is an integer of at least 2, and-preferably 2 or 3. At least one RI is hydrogen and the- 6th&rs are hydrogen or @lkyl or in sojhe cases' two of th6 -,OR I @@s may be removed And@ the romaining radical s jbined together thrbugh an oxygen ;@tom to fotm say a carbon@l grotip or a cyclic ring. Exaiii@les of the now - hemi'-acetals inelude, among othdrs@ 'OH Oll RO (Cltib)2CH20IT26HO'( @C]120)'2CH2CH2'6H OH 'o H O.U HO CH20 CH2CH2@.HO CH20 CI[2c]12@R Oil OH R IIO CU20 bR@CR2c)HO Cla2O C:ff2Ct[lc@O Oil @OH I 116CHiOCI12CH2CHOClr2CH2' HOH OR OH ;I 1: HO(C)H20)SCH2CI12CHO(CH20)3CH2L;.U3U'.UV@U 0 H IEEG(013@20)@2CH2CI12CII@.(H2@ko (CH2'0)@ 2CH2CH2CH2CHOH OH OH 1 110(CH20)3 112CIICHO(CH,-0)2CH2CHCHOH @H3 @Ha an'd@ cyclic hemi-acetals stch as CH2 IrC-011 CIE[2 CH' CH2 @112 CH2@ H6-OTT 0 0 and ClEI2 I 0 c Hs CH2 @112 \0/ \0/ and @CH2 CH2 0 HOCH20-@H iilc-Clr2CH@OCH20H 0 Especially preferred are those having the formula 0 RI I Rio[ @cH20) wh6toin t is 1 'to 3, y is I to 3, n is at least 2 and prefq@ably 2 or 3, R is an alkylene group cointaining I to 3 i@arbon at&m-q,- aiid Ri is hydtogeii or alkyl. 4 The new products of th-@ invention are prepared by reacting fornialdehyde with a dissimilar aldehyde uilder acidic conditions. Preferred aldehydes to be reacted with formaldehyde include the aliphatic polyaldehydes, such as glutaraldehyde, hydroxyadipaldehyde, succinaldehyde and the like, and those aldehydes having attached to or involving a carbon atom alpha or beta to the 0 group a fu@-ictional as OH, -NHR (wherein R ig an alkyl radical), -NH2 or cH or an aliphatic carbon-to-carbon upsaturated linkage, Examples of these include, among others, 2-hydroxypropionaldehyde,, 3-hydroxypropionalde15 hyde, 2-hydro7@ybutyraldehyde, 3-hydroxybLityraldehyde, 3- mercaptopropionaldehyde, 3-aminopentanal, 2-mercaptohexanal, 2- aminododecanal, 3-hydroxycyclohexan I al, acrole:n, methacroleiii, crotonaldehyde, alphaphenylacrolein@ alpha-cyclohexylacrolein, 2-pentenal, 3- hexenal, 2- 20 decenal 2-cyclohexenal and 2-hydroxy-3-mercaptotetradecanal. Pr.eferred members o'l, the above group of aldehydes include the alphahydroxy-substituted aliphatic and cycloaliphati-- monoaldehydes, the alphaamino substituted all25 phatic and cycloaliphatic monoald@hydes, the alpharnercapto substiti-ited aliphatic and cycloaliphatic monoaldehydes, the alp ha,beta-ethylenically unsaturated aliphatic and cycloaliphatic m(inoaldehydes, the beta-hydroxysubstituted aliphatic and cyc!6a@liphatic monoalde30 hydes, the beta-amiro substituted aliphatic and cycloali@hatic monoaldehydes, the alpha-merc@apto substitute'd: aliphatic and cycloaliphatic monoaldehydes, and the beta, g,,Lrima-ethylenically unsaturated aliphatic ahd cycloaliphatic monoaldehydes, the total nur@iber of carbon @toms 35 in each case not exceeding 14. Also prefcrred are the above-iioted substituted alkanals, cycloalkanals and alker@als and cycloalkenals containing up to 12 carbon atoms. The preferred members may be exemplified by the followilig forinulae 40 I'@ x p c C -C=O x 45 R-C=CR R II I @ I RC= -C-C=O 60 i@iherein at least one and preferably 1 to 2 X's is or are an OT.1, SI-I or NH2 or alkyl substituted amino group, a@d the other X's not @o occupied is. (or are) A an R. R is a 65 rperiber of the group consis' ing of hydrogen atom and hydrocarbon radicals, and preferably aliphatic and cycloaliphat@:c hydrocarbon radicals containing up to 12 carbon atoms. Coming under special consideration are the ethyleni60 cally unsaturated aldehydes, particularly because 6f the outstandiig properties of the resulting products in the treatnient of textile fabrics. These incllude, among others, the alpha,b@ta-ethylenically unsaturated monoaldehydes and the beta--amma-ethylenically unsaturated monoaldeC)5 hydes, such as acrolein, methacrolein, crotonaldehyde, alpha-ey@lohexylacrolein and the like. Formaldeliyde may be employed in any of its forms in making the new products. This includes, for example, formalin, para-formadlehyde, trioxane and methylal. 70 The an-lount of the dissimilar aldehyde and the formaldehyde to be empioyed will vary within certain limits, The dissimilar aidehyde and formaldehyde may, for ekampl@e, be combined in mol ratios varying from say 8 @ I to l@8. Pqrticularly outstanding results are obtained when 75 the aldehyde and formaldehyde are combined in mbl
[3]3)080,281 5 ra-@os varylr@g from 4:1 to 1:4 and more preferably in n-lol ratios varying from 1: 1 to 1: 2. The reaction between t@-e above-described aldehyde reactants is accompl-ished in an acidic medium. It is preferred to have the reaction medium at a pH between 5 .5 to 6, and still more preferably between .5 to 3. When expressed on a normality basis, it is preferred to use reaction media hav-lng a normality of .05 N to 1 NT. r The acidi , meditini can be obtained by the addition of a variety of acidic or acid forniin.- materials, such as, for 1( exar.iple, stiltliric acid, oxal@@c acid, alkane sulfonic acids, phosphoric acid, amine phosphates, acid metallic halides, such as zinc chloride, ma.-nesium chloride, stannic chloride, alumin,,ini chloride, zinc nitrate, acid clays, etc. The concentration of the acids employed and amount 15 added will depend on th.- particular ingredient se'@ected and the acidity desired. It is oenerally preferred to utilize moderately strong acids, such as sulj'uric acid in concentratio@-is rangin.- from about 20% to 98% by weight. When the product is to be used for cloth treatm, ent, it is 20 sow.-.times preferred to ii-se the acid actin.- saits such as ma.-nesiu@-n chloride and zinc nitrate as the catalyst. in tl,is case the material can be retained in the material and used as a catalyst for the subseqtient reaction with the cloth. 25 The reaction is conducted in the presence of liquid medium containin.- OH .-roups such as water and aliphatic, cycloaliphatl'c and heterocyclic alcohols. The us.- of water is particularly desi@-able as the reaction prodiict may then be used directly in the reaction medium for the treat- 30 ment of textiles as noted hereinafter. If desired other diluents, such as ethanol, isobutanol, tetrahydrofuran, ond the like and mixtures thereof may also be employed. Temperatures employed may vary over a wide range. As the reaction is exothermic cooling should generally be 35 employed to keep the temperature within the des:ired range. Preferred temperatiires range from about O' C. to 80' C., and more preferably temperatures range from 10' C. to 50' C. Superatmospheric, atmospheric or subatmospheric pressures may be used as desired. 40 Dependin.- on method of preparation, the products may be used as such or may be subjected to further processing. If the products have been prepared in a suitable medilm, stich as water, avd with catalysts, such as magnesitim 1- 1, chloride or zinc nitrate, the prodtict -may be used directly @0 in applications, sil-ch as cloth treating, leather treating and pap-@r treatipg. If strong acids haie been used that may be detritnental or riot satisfactory for furthcr - applications, the reaction medium r@lay be neutralized with basic materials before further Litilization. r)o Further processing steps may also be employed to favor the production of the cyclic materials over the linear products. Thus, by use of ether extraction foilowed by azeotropi-, removal of the water with benzene until substantially all water has been removed, it is p6ssible to greatly 55 increase the format-ion of the cyclic hemi-acetal structures as shown above. Products prep-ared by the above-noted techn;ques also may possess srnall an-iounts of other materials wliieh for most kioplications will not b-- harmful and in -@nany cases 60 add to the effectiveness of the utilization. Thus, there may be small amounts of ma:terials havi-@i,,, a strlieure similar to thos-. sliovai Pbove wh@,reii x is 0 or n is 1. For exarriple, when x is 0, coir@poliids coiiing i,-nder t@he 65 above-described formula iiiay have the structure 0 IT, R 0 CH2'R H\ OTT 1\ 70 and when n is 1, they wiH have the structure OH 110 (OR20).CH2p. @HOIEE 75 The cow@pounds may also have a cycte strlcture such as CH2 CE2 0 I-[o-6H HCI -OLT2CH20H 0 and OH CH2 0 @H2 @H2 \0/ If not desired, these,compounds may be rerqoved by suitable means, sucli as extraction, distillation land the like. For cloth treatrier@t, there is no need to remove such n-iaterials as flieir presence gives adnantages. The iiew hydroxy-terminated hewi-acetals produced by the above process will gencra'ily be substantially colorless fluid licilids. Their molecular we-"ghts will vary froii-i labout 1-50 to 250. The products are lion-acid a,,ld iionalkali stabl-- and deco imdose on application of heat. BIcatise of Lhese characteristics, it is preferred to rnain@ta,.n tne material in solution as formed. As noted above, small amoiints of other types of acetals, and partir_ularly t'@iose of loaer molecular weight, will generally be formed -a-long wi-th the desired hydroxy-terminated hemiacetals. i-t h-ps been fourid for ir@ost applications, and particularly for t@e use in treatment of fibrous rnaterials, @Lhat these additional impurities have no effect on the Litility of the na7,v products' The new products ma3i be used for a variety of iniportant applications. As noted, they may be used in the preparation of aqueo@,is surface coating composiitons or impregiiating coiipositions or may be cross-linked to forq-i c,@istings a.-)-d pottings and the like. The pi-o'ucts ar-, particularly useful, howeve:,-, for the treatment ol. fibrous materials, such as textile fabrics, yarns, threads, cords, paper, leather and the like to irnprove many of their deqired properties or in glazing or embossing ol-eratio-iis. In these applica'ions, the prodticts rnay be used in the un-,xtract--d form (as shown in Llie work-ing examples) or in the extracted forril. T@icy are preferably eniployed iii an aqi,-eous rriedium and in combination w@qh acidic curing agents. However, other media sucn as solvents or mixtures oj' waler and solvents may be used as well as other types of culring agents. Suitable solvents includ,-, among others, ethyl alcohol, butyl alcohol, isopropyl alcohol, acetone, dioxane, diacetone alcohbl, esters, ethers, and ether esters of glycol and glycerol, ethylerie dichlo.-ide, benzene, toluene and the like aiid mixtures ttiereof. In some cases, it may be desirable to eniploy tne new products -in an aqueo-,is emulsion or suspension. Su-table emulsifyir,.g agents include th.- ionic and non-ionic a.,Cnts, si-ich as, for exariiple, monooleate o'L soeoitan polyoxyethylene, thetrioleat-. of sarbitan polyoxyethylene, sorbitan tristernte, sorbitan nionolaurate, polyoxyetliylene ethers of alkylphenols, carboxymethyleellulose, starch, guni arabic, aryl and alkylated aryl sulfonates, such as cetyl sulfonate, oleyl sulfonate, sull.onated mineral oils, and @Lhe like, a-@id i-nixtures thereof. The eiiulsifyi.'Ig agents are generally employed in amounts varying from ,0.1% to 10% by weight and more preferably from 1% to 5 % by weight. The amount of the produot employed in the aqueous mediun-i for treatment of the fibrous materials riay vary over a considerable range depending chiefly on the amount of product to be deposited on the fibrous n-iaterial and this in t@@irn will depend on the number of applications and the pick-q-D allowed per application. When the solution is applied but once, with a 90% to 100% pick-up by
[4]7 weight of the fabric in the dry state, a concentration ranging from about .5 % to 25 % by weigh@t will ordinarily suffice. Preferred concentratio-@is range from about 1.5% to 4%, and particularly 2%. If less than 80% pick-iip is permitted, the co-neentration may, in some cases, @o as high as 30% to 50%. The curiilg agent employed may be any acidic catalytic material, sueh as organic and inorganic acids, such as, for example, oxalic acid, lactic acid, suceinic acid, acetic acid, maleic acid, phosphoric ac@id, boric acid, sulfonic acid, perchloric acid, persulfuric acid, p-l'olueiiesulfonic acid, sulfuric acid, and metal salts, such as zinc fluoborate, copper fluoroborate, z:inc persi-ilf ate, cuoric arseiiite, cupric chlorate, cupric chromate, cupric dichromate, cupric fluosilicate, cupric nitrate, zinc nitrate, cupric sulfate, cobaltic. clilorostannate, cobaltous fluoborate, cobaltous ffuosfficate, cobaltous sulfite, chromic Qulfate, i:@hronlic nitrate, lead borate, lead chlorate, lead phosphate, bariurpchlorate, barium phosphate, ma.-nesium fluosilicale, magnesium dichloridt, magn-@sium perchlorate, maa-.iesiurn nitrate, magnesiimfl@,ioborate, magntsium sulfate, m-anganese sulfate, manganese fluoliorate, eadmiu,.,n arsenate,, cadmium borate, cadmium perchlorate, cadmium phosphate, aluminum arsenate, alumini-im chlorate, al@uminum nitra@te, aluminimi -fluoborate, nickel phosphate, nickel selenate, nick-el sulfate, silver sulfa'ce, silver.nitrate, silver thiosulfate, stannie fluoborate, strontium chlorate, titanilim stilfate, vanadium sulfa,e, zinc chlorate, zi@-ic fltiosilicate, zinc permanganate, zinc phosphate, zinc sulfate, zirconium sulfat--, aluminum phosphate, alliminum sulfate, vanadium nitrate, vanadium sulfate, vanadium fluoborate, vanadium selen,ate, bismuth phosphate, ferric phosphate, ferric pyrophosphate, ferric sul'Late, f--rrous sulfite, ferrous perchlorate, mercuric arsenate, mercuric chromate, mercuric sulfate, mercurous chlorate,. mercurous fluoborate, nickel fluoborate, nickel arsenate and the like, and mixt Lires thereof. Particularly preferred curing agents -are the organic and inorganic of the group consisting of organic mono- and dicarboxylic acids containing up to 10 carbon atoms, inorganic acids containing at least one element of the group consisting of halogen atoms, oxygen, sulfur, nitrogen and phosphorous, and metal salts of metals having an ator-qic weight -between 10 and 240,, and acids of the formula Ha[(X),,,(Z),] wherein X is a non-metal having an atomic weight above 2, Z is an element which tends to gain from l to 2 electrons in its outer orbit, w is an integer, y is an integer @gkeater than 11 and a equals the valency of the radical (X)W(Z)Y. The amount of the curing agent to be utilized will vary over a wide range depending upon the condensation product selected, the method of cure, etc. Generally, amount used will vary from about .1% to 15% based on the weight of the condensation product. The metal salts and BF3 complexes are preferably employed in amounts varyin.@ from about .1% to 8% and the organic acids and inorganic acids are preferably employed in amounts varyin@ from .1% to 10% by weight of the condensation product. The solution employed to treat the fibro@us material may also contain plasticizers to improve their flexibility, though these should not be present in such proportions as. to render the finished materials soft or sticky at temperature and humidities to which they would be exposed, It is found, howcver, that the substances employed in the present invention yield products which are sufficiently flexible for most purposes without the use of plasticizers. Among plasticizers that may be used according to the present invention may be mentioned organic and inorganic derivatives of phenols, for example, diphenylol propane and,triphenyl and.tricresyl phosphates, sulphonamides, sulphonsioso,281,- 8 jand glycol phthalates, diethyl tartarate, derivatives of poly-! hydric alcohols, for example, mono-, di- and triacetin, and, products obtained by condensing polyhydric alcohols, with themselves or with aldehydes or ketones. The-compositions may also contain natural resins, e.g., shellac, rosin and other natural resins and synthetic or semi-syntheti'@ resins, e.g., ester gum, polyhydroxy-polybasic alkyd resins, phenolaldehyde and urea-aldehyde resins. The new products may also be used in combination lo with polyepoxides, such as,, for example,. glycidyl ethers of polyhydric alcohols or phenols. T6xtile softening agents, and particularly those of thecationic-type as stearam I idoethyl diethyl methyl quaternary ammonium methyl sulphate, trimethyl ammonium methyl 15 sulphate of monostearylmetaphenylenediarnine, s-di@ 1-(2paln-iitaniidoethyl) urea niono I acetate, palmityl amine hy@ drochloride, and the like, and. mixtures thereof; may -alsobe added in varying amounts to improve the feel of the -treated fabrics.@ Other examples of suitable materials, in7 20 clude polyethylenes, acrylics, silicones and the like.@ The application of the solution containing the product to the fibrous material may be eflected in any suita-ble manner, the method selected depending, upon the results@ desired. If it is desired to apply the solution only to one, 25 surface of the material, as, for example, when it is desired to,treat the back only of @a fabric having@a face of artifici al or natural silk and a cotton back, the application may be. effected by spraying as a liquid or,gas or by-means, of rollers, or the composition may be spread@upon the surface 30 by means of a doctor blade. When, hdwever, it is de@-ired: to coat both surfaces, of the material, or ff the material is to be thoroughly impregnated with it, the material may be simply dipped in the solution or run through con-. ventional-type padding rollers. The solutions may also 0'5 be applied locally to the material, for example, by means of printing rollers or by stencilling. The amount of the product to be deposited on the fibrous material varies over a wide range depending upon the property or properties to be imparted -and the use of 40 the finished material. If treated @material is a fabric that is@to have a soft feel, such as that,intended for use for dresses, shirts, etc@, the amount of condensation product deposited will generally vary from 1% to 20% by weight 45 of the fabric. If stiffer materials are required such as for shoe fabrics,@draperies, etc. still higher.amounts of resins, such as of the order of 25% to 50% by wei.-ht may be deposited. If the material is paper and the property to be imparted is wet strength, the,amount of material deposited may vary from about .1% to 15% by weight. In deter50 mining the amount of condensation product deposited, it should, of course, be remembered that the presence of the condensation product in a few @instances causes a slight decrease in tear strength of the material and the amount deposited should be balanced between the desired proper55 -ties. and the desired tear strength If the desired amount of the product deposited is not obtained in one application, the solution can be applied @again or -as many times as desired in order to brin the 9 amount of the condensation product up to the desired 60 level. After the desired amount of solution has been applied the treated material is preferably dried for a short perio@ to remove some or all of the dispersing liquid, such as water, alcohol, and the like., This is generally accom65 plished by exposing the wet material to hot g-as at temper-7 atures ranging from 50' C. to 80' C. The period of drying will depend largely on the aniount of pick-up permitted during the application of the solution, and the concentra70 tion of the condensation product. In most instances, drying periods of from 5 to 30 minutes should be sufficient. The dried material is then exposed to relatively high temperatures to accelerate the cure. Temperatures used for this purpose generally range from 100' C. to 200' C., -arylides,.. alkyl Phthalates,@ for example - diqthyl @ phtha ate 7,5 and more preferably from 10,0' C. to 150' C. At these
[5]preferred temperature ranges the cure can -.enerally be accomplished in from 3 to 10 minutes. Exposures of less than 3 minutes, e.g., I minute, may probably be used in continuous, commercial processing. After curing, it is desirable in most cases to wash the 5 treated material to remove any, soluble - materials. A perborate wash is particularly desirable. The above-described procass may be utilized for the treat@nent of any fibrous material. This inciiides textile material, such as woven fabrics, n-on-woven fabrics, threads, 10 yarn, cord, and string, paper, leather, films and th.- like. These inaterials may be prepared fro@n natural or synthetic materials, such as cotton, linen, natural silk and artificial silk, such as silk obtained from cellulose acetate or other organic esters or ethers of cellu'.ose, rayons, jute, hemp, 15 animal fibers, such as wool, hair, and the like as well as synthp-tic m-,terials which includes, among others, those prepared from acryloiiitrile (Orlon-100% acrylonitrile polymer), vinylidene cyanide polymers, p@olyam,"des (nyIon-super polyan-tide), polyester-polyamides, cellulose 20 esters and ethers, and polymers prepared from corn pro*@ein and formaldehyde (Zein). As in the above-noted addition polymers, this i-neludes the ho@nopolymers as well as copolymers atid -terpolymers, such as, for example, Acrilan (85% -acrylonitrile and 15% vinyl acetate), 25 Dynel (60% vinyl chloride and 40% acrylonitrile) and Saran (85% vinylidene chloride and 15% vinyl chloride). Other synthetic fibers includ-@ those prepared from polyethylenes and polypropylenes, poylurethanes (Perluran), mineral fibers (Fiberglas) and Alginic materials 30 and as Alginate rayorl-. The p-,tpers employed in the process of the invention include those prepared froin wood, cotton, linen, hemp, jlite, mulb.-rry, straw, bamboo, cane fibers or mixtures thereof, by any of the known processes such as the sulfate 35 process, soda pro--ess and sulfite process. The lealher employed is preferably cowliide, calfskin or other hides commonly employed in the preparation of leather goods. ,ss or may 40 The iqbrous materials trea+ed may be colotli, be dyed, printed or otherwise colored to the desired shade. It is also possible to first subject the colorless material to the proc--ss of ti-ic invention and then apply -the desired dye, pi.-ment or other coloring material. The materials trep-ted according to the above-described 45 process have many improved prop-,rties. As noted, tlle textile materials have improved resistance to creasing and shrinkin.- as well as bett@-r resista-lice to pilling, fraying and snaggin- and improved dyeability. The paper has t' 50 bet'Ler wet s rength and tear resistance a-s well as better abrasion resistar@ce and improved fold endurance. The leather has improved res@@stance to loss of tanning propertics. The product treated as noted above may be utilized for any of the conventional applications, such as in the man- 55 ufacture of dresses, drapes, upholsteries, shoe fabrics, carpets, coats, shirts, uniforms, shoes, towels, cords, constriietion pap-@r, wrappin.@ paper, containers and the like. The use will, in many cases, determine the amount of condensation product to be applied. Thus, less product 60 will be iitilized when the material is to be used for making soft goods, si,-ch as dress-@s, shirts and the like than where crispness and fullness is desired, such as in making ril-g, drapes, shoe fabrics and 'Lhe like. To illu@strate ti@- manner in which the invention may be 65 carried out, the folloiving examples are given. It is to be understood, however, tnat the examples are for the purpose of illustration and the iiivention is not to be regarded as limited to any of the specific materials or 70 conditions recited therein. The wrinkle recovery values reported in the examples were determined by the Monsanto Wrinkle Recovery Method (reported as sum of average warp and fill measures), and the tear strength values were deterriiined by 75 10 the Trapezoid Method ASTM D-39-49. Ali tesis w6td carried out at 50% relative humidity and 78' F. Example I To a solution of I mol of formaldehyde in 11 parts of 50% sulfur-IC acid was added 1 mol of freshly distilled acrolein. The mixture had a normality of about 0.76. The temperature was allowed to rise to about 35-40' C. The mixture was cooled and held at room temperature for about 12 hours. The mixture was then neutralized with sodium hydroxide and then filtered. Analysis of the resulting product by infrared, molecular weight, functionality and carbon and hydrogen analysis indicates the solution contains a hydroxy-containing hemi-acetals of the fo rinulac OH 0 1-7 1 1 HOUH2 ((-U2U-a2UH U Uii2V UJd2U i2uHOH and OH H HO CH20 CII2CH2CT'O CH20 CH2cH2@=0 Small awounts of each of the following were also present: OH OH I HO CH20 CH2CH2CEEO CH2CH2C]ECOH OH OH HOCH2OH2 I H-OCH2CH2@H-OH The above solution was combined with water to form a solution havin.- 29o solids. 3% of 50% magnesium dichloride aqueous solution was added, and the combined mixture tised to pad cotton fabric as in the preceding example. The impregnated sheet was then dried at 2501 F. for 5 nainutes and cured at 300' F. for 5 minutes. TI-ie f@nished product was washed with sodium perborate aiid r@@'Bsed three times in warm water and framed to dimensions and dried at 250' F. The material had a dry crease recovery of 250 (W+F) and had 76% retention of original strength. The scorch test gave a value of 79% reflectance (81 % before test) as compared to 80% (82% before test) for the control. @.bove paddin.- process is repeated using solution having 4, 5, 6, 8, 9 and 10% solids. Related results are obtained. Example If To a solution of 1 mol of formaldehyde (formalin) in 11 parts of 50% sulfuric acid was added 1 mol of freshly distilled acrolein. The mixture had a normality of about 0.76. The temperature of the mixture was not allowed to rise above 35' C. The mixture was held at the lower temperature for several hours. A saturated solution of sodium su!'Lal,e was then added to neutralize the acid and the mixture extra-,ted with ether. The ether was removed under vacuum followed by azeotropic distillation with b-@nzer@e. The resulting product was a clear fluid liquid. Andysis by infrared, molecular weight, functionality and carbon and hydrogen analysis indicates the liquid contained a mixture of a by&oxy-terminated hemi-acetal of the formula 0 0 CH2 OH ---C,/ \C/ '--- I H2 H2 CH CH OH C112 o I CH2 CH2 \ / 0
