Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/487—Aziridinylphosphines; Aziridinylphosphine-oxides or sulfides; Carbonylaziridinyl or carbonylbisaziridinyl compounds; Sulfonylaziridinyl or sulfonylbisaziridinyl compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
  • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
  • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D203/16—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms
  • C07D203/20—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with acylated ring nitrogen atoms by carbonic acid, or by sulfur or nitrogen analogues thereof, e.g. carbamates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/61—Polyamines polyimines

Definitions

• 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.
• 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.
• a proteinaceous textile substrate such as wool and its blends is treated with a solution of polyfunctional composition represented by the structural formula:
• A is selected from the group consisting of 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
• 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,
• 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.
• a more restricted group of compositions included within the above broad group cornprise the preferred compositions of this invention.
• 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,
• Q is methylphenylene
• 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.
• 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.
• the pickup varies between about 50% to about 300%.
• 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.
• 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.
• 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.
• residue I can be (a) divalent, (b) trivalent, or (c) tetravalent.
• 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.
• I is derived from a polyol J(-OH) having a molecular weight between about 500 and about 5,500.
• 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
• 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.
• 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.
• 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.
• 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.
• polyamines examples include diethylenetriamine, tetraethylenepentamine, hydroxyethylethylenediamine, polyethyleneimines of wide molecular weight range, 1,3-diaminopropane, 1,6-diaminohexane, and the like.
• 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.
• 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.
• 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.
• 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.
• 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
• alkyl having 1 to 5 carbon atoms, and L is CH2CH2N(R)CH2CH2.
• 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:
• 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.
• Example XXVI 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.
• the fabric customarily contains appreciable proportion of wool fiber, generally 30% or more, 60 to 100% being the preferred range.
• 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.
• 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.
• 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.
• approximately 0.5 to about 2.0 equivalents of the co-reactant, polyamine or polycarboxylic acid should be present for each aziridinyl equivalent present.
• 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.
• the aziridinyl compound can be applied to the Wool-containing textile material in any convenient manner.
• 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.
• 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 deleter
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• F uzziness rating The hairy appearance was expressed by the following numerical scale after brushing the fabric for minutes on a testing machine:
• No (or negligible) change 12 polymer has three of the following groups per molecule attached to a polypropylene ether glycol backbone:
• 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%.
• 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
• 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
• 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.
• 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:
• 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 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
• Example II 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.
• 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.
• Example VIII 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.
• 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.
• 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.
• 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.
• Example XI 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.
• Example XIII 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.
• Example XI 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.
• Example XI 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 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.
• TEPA tetraethylenepentamine F rating
• TEPA tetraethylenepentamine
• TEPA tetraethylenepentamine
• a co-reactant was used, viz., tetraethylenepentarnine (TEPA).
• TEPA tetraethylenepentarnine
• ITP-63A the imine-terminated polymer described in Example I
• 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).
• the concentration of ITP-63A in the'thick emulsion was 40%.
• an approximately 3.9% dispersion of ITP-63A was made by blending pounds of said thick emulsion and gallons (approximately 830 pounds) of water.
• ITP-63A 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.
• 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.)
• reaction mixture rise to 25 C. during 1 hour.
• the reaction mixture was stored at approximately 5 C. for several days.
• 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.
• the first stage of the process consisted of convertrng was 0.40 equivalent (theoretically 0.393 equivalent).
• Example XXVI 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
• 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.
• 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.
• 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.
• 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:
• 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 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,
• 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,
• 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
• 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.
• A is selected from the group consisting of 10.
• n is an integer ranging from 2 to 8.
• v is an integer ranging from 3 to 4
• n is an integer ranging from 2 to 8.
• v is an integer ranging from 2 to 6
• n is an integer ranging from 4 to 8.
• 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.
• n is an integer of from 2 to 6
• v is an integer of from 3 to 80.
• u is an integer of from about 6 to 100.
• v is an integer of from about 3 to 80
• n is an integer of from 2 to 6.
• x is an integer of from about 1 to 100.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=27413553

Family Applications (1)

Country Status (4)

Cited By (4)

Citations (4)

Family Cites Families (3)

• 0
  • CH CH1199066D patent/CH1199066D/xx unknown
• 1966
  • 1966-08-16 GB GB36564/66A patent/GB1109946A/en not_active Expired
  • 1966-08-18 DE DE1619169A patent/DE1619169C2/de not_active Expired
• 1968
  • 1968-11-08 US US774508A patent/US3523750A/en not_active Expired - Lifetime

Patent Citations (4)

Also Published As

Similar Documents