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US3078138A - Shrinkproofing wool with polyamides - Google Patents

Shrinkproofing wool with polyamides Download PDF

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Publication number
US3078138A
US3078138A US98718A US9871861A US3078138A US 3078138 A US3078138 A US 3078138A US 98718 A US98718 A US 98718A US 9871861 A US9871861 A US 9871861A US 3078138 A US3078138 A US 3078138A
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United States
Prior art keywords
wool
component
solution
diamine
chloride
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US98718A
Inventor
Lowell A Miller
Robert E Whitfield
William L Wasley
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Individual
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Individual
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Priority to BE629488D priority Critical patent/BE629488A/xx
Priority to BE602620D priority patent/BE602620A/xx
Application filed by Individual filed Critical Individual
Priority to US98718A priority patent/US3078138A/en
Priority to GB13127/61A priority patent/GB913370A/en
Priority to FR858833A priority patent/FR1289709A/en
Priority to DE1961L0038742 priority patent/DE1297575B/en
Priority to US198653A priority patent/US3429650A/en
Application granted granted Critical
Publication of US3078138A publication Critical patent/US3078138A/en
Priority to GB7837/63A priority patent/GB994497A/en
Priority to FR927493A priority patent/FR83662E/en
Priority to DE19631444087 priority patent/DE1444087A1/en
Priority to CH528763A priority patent/CH403705A/en
Priority to FR995576A priority patent/FR87014E/en
Priority to FR9189A priority patent/FR87668E/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/006—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with wool-protecting agents; with anti-moth agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • D06M15/507—Polyesters
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06M15/59—Polyamides; Polyimides
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/18—Grafting textile fibers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/917—Wool or silk

Definitions

  • a principal object of this invention is the provision of new methods for shrinkproofing wool. Another object of the invention is the provision of the novel products so produced. Further objects and advantages of the invention will be obvious from the following description wherein parts and percentages are by weight unless otherwise specified.
  • the shrinkage properties of wool can be improved by applying to the wool fibers a high molecular weight polyamide such as polyhexamethylene adipamide or similar polyamide of the nylon type.
  • a high molecular weight polyamide such as polyhexamethylene adipamide or similar polyamide of the nylon type.
  • the selected polyamide is first converted into soluble form, for example, by forming an N-methylolderivative thereof.
  • the N-methylol derivative is applied to the wool and the treated wool is then immersed in hydrochloric acid whereby the N-methylol polyamide is converted to the unsubstituted polyamide.
  • a primary disadvantage of this known process is that it is cumbersome and inefficient because it requires procurement of a preformed polyamide, conversion of this to a soluble form, and final reconversion to an insoluble form. Particular trouble is encountered in the last step where extended contact with acid is required to insolubilize the coating of N-methylol polyamide. Unless this acid treatment is complete, the polyamide will remain
  • a pre-formed polyamide is not used but a polyamide (or other condensation polymer) is formed in situ on the wool fibers.
  • a polyamide or other condensation polymer
  • the wool is first impregnated with an aqueous solution of a diarnine and then impregnated with a solution of a diacid chloride in a water-immiscible solvent such as carbon tetrachloride.
  • each fibrous element is coated with a two-phase system, for example, an inner layer of diarnine in water and an outer layer of diacid chloride in water-immiscible solvent. Under these conditions the diamine and diacid chloride react almost instantaneously at the interface be'twcenthe phases, producing in situ on the fibers a high molecular weight, resinous polyamide whichcoats the fibers and renders them shrinkproof.
  • a two-phase system for example, an inner layer of diarnine in water and an outer layer of diacid chloride in water-immiscible solvent.
  • condensation polymers such as polyurethanes, polyureas, polyesters, polycarbonates, or various interpolymers "thereof can be formed in situ on wool fibers.
  • the polymer formed is insoluble so that the shrinkproofing effect is durable; it is retained even after repeated washings with soap and water or detergent and waterformulations.
  • a feature of the invention is that the high molecular weight resinous polymers are formed in many cases at ordinary (room) temperature, which is in sharp contrast to the much higher temperatures required in the conventional melt condensations used in preparing polyamides, polyurethanes, etc.
  • room temperature which is in sharp contrast to the much higher temperatures required in the conventional melt condensations used in preparing polyamides, polyurethanes, etc.
  • temperatures of over 200 C. are customarily employed.
  • the treatment in accordance with the invention renders the treated wool essentially shrinkproof so that garments produced from the treated wool may be laundered in conventional soap and water or detergent and water formulations with negligible shrinking or felting.
  • the treated wool or garments prepared therefrom are in the easy-care category in that after washing and tumble drying, they are quite free from wrinkles so that they require only a minor amount of pressing.
  • An important .ppint to be stressed is that the shrinkproofing effect is secured without damage to the hand of the fabric. That is, the treated fabric retains its normal hand so that it is useful for all the conventional applications in fabricating garments as is untreated wool.
  • the treatment does not cause any degradation of the wool so that there is no significant loss of tensile strength, abrasion resistance, resiliency, elasticity, etc.
  • the polymer since the polymer is formed in situ on the fibers-in contrast to systems wherein polymers arespread en masse over the face of a fabric-'there is substantially no loss of porosity of the fabric.
  • the treated wool may be dyed with conventional wool dyes to obtain brilliant, level dyeings.
  • the invention is applicable to wool in any physical form, for example, bulk fibers, slivers, rovings, yarns, felts, woven textiles, knitted textiles, or even completed garments or garment parts.
  • a remarkable feature :of the invention is that the polymers fiormed on the wool fibers are not merely physical coatings; they are chemically bonded to the wool, that is, the added polymer .is grafted onto the wool.
  • the fact that a chemical bonding is achieved rather than a mere physical adhesion has been demonstrated by experiments wherein it was attempted to dissolve the grafted polymer with solvents which are capable of dissolving the polymers in bulk.
  • wool cloth was serially impregnated with (1) an aqueous solution of hexamethylene diamine and (2) a solution of sebacoyl chloride in carbon tetrachloride.
  • the treated wool was rinsed in water and dried in air. It was foundthat the wool had a polyamide resin uptake of 4.4% and showed an area shrinkage of 1% on being subjected to a very severe washing test. Samples of this treated wool were subjected to these tests:
  • both benzyl alcohol and 98% formic acid are good solvents for fiberforming polyamides such as polyhexamethylene sebacamide and had the polyamide on the wool been merely a coating, the extraction would have resulted in a weight loss and a marked increase in the percentage of shrink-
  • the mechanism by whice the graft polymerization occurs is believed to involve a reaction of functional groups on one or the other of the complementary agents with the free amino or hydroxy groups present in the wool molecule, these reactions giving rise to such linkages as amide, ester, urea, urethane, carbonate, etc. which chemically unite the wool with the polymer.
  • graft polyamides can be postulated by the following idealized formulas:
  • W represents the polypeptide chain of the wool, containing prior to the reaction, free amino (NH or free hydroxy (-OH) groups.
  • R and R are bivalent organic radicals (representing in this case the residues of the diamine and diacid chloride, respectively), and n represents the number of polyamide repeating units.
  • the invention encompasses the grafting of other types of polymers besides polyamides onto the wool molecule.
  • Typical polymers which may be applied in accordance with the invention are polyurethanes, polyureas, polyesters, polycarbonates, and interpolymers wherein the recurring units contain two or more different units of the classes of amide, urethane, urea, ester, and carbonate.
  • the grafting of typical examples of these different types of polymers onto wool are shown in the formulas below, again following an idealized plan:
  • non-0x0 is used in the usual sense of excluding aldehyde and ketone configurations.
  • the non-0x0 carbonyl group may occur in various types of combinations, illustrative examples of which are given below.
  • Component A is first made of the appropriate complementary agentsherein termed Component A and Component B-required to form the desired polymer on the wool fibers.
  • Component A may be a diamine, a diol, or a mixture of a diamine and a diol.
  • Component B may be, for example, a diacid chloride, at bischloroformate, a diisocyanate, or mixtures of these classes of compounds. Since Components A and B may be selected to form any desired type of condensation polymer, these components may be aptly termed as complementary organic condensation polymer-forming intermediates. They may further be appropriately designated as fast-reacting or direct-acting because they form the resinous polymers rapidly and directly on contact without requiring any after-treatments, such as treatment with curing agents, oven cures, etc.
  • Components A and B are formed into separate solutions for application to the wool to be treated.
  • An essential consideration in the preferred modification of the invention is that the solvents used in the respective solutions of Components A and B be substantially mutually immiscible so that a liquid-liquid interface will be set up between the two solutions on the wool fibers.
  • Component A is dissolved in water and Component B is dissolved in benzene, carbon tetrachloride, toluene, xylene, ethylene dichloride, chloroform, hexane, octane, petroleum ether or other volatile petroleum distillate, or any other inert water-immiscible solvent.
  • the two solutions are then applied to the wool serially, that is, the wool is treated first with one solution then with the other.
  • the order of applying the solutions is not critical. Generally, the solution of Component A is applied first and the solution of Component B is applied next; however, the reverse order gives good results and it is within the ambit of the invention to apply the solutions in either sequence.
  • the solutions may be applied to the wool in any desired way as long as they are applied serially.
  • a preferred method involves immersing the wool in one solution, removing excess liquid as by use of squeeze rolls, immersing the wool with the second solution, again removing excess liquid, rinsing the treated fabric in water and then drying it.
  • Conventional apparatus consisting of tanks, padding rolls, squeeze rolls and the like are generally used in applying the respective solutions.
  • the amount of each solution applied to the textile may be varied by altering the residence time in the solutions, the pressure exerted by the squeeze rolls and by varying the concentration of the active materials in the respective solutions.
  • the wool after its immersion in the first solution may be subjected to drying conditions such as a current of warm air to concentrate the solution carried by the Wool.
  • a critical factor in the preferred form of the invention is that the complementary-agents-Component A and Component B-are serially applied to the textile dispersed in solvents which are substantially mutually immiscible.
  • the nature of the solvents is of no consequence as long as they are essentially inert and possess the above-stated property of substantial immiscibility.
  • volatile solvents are preferred as they may be removed from the treated textile by evaporation.
  • non-volatile solvents can be used, in which case they may be removed from the product by extraction with suitable volatile solvents therefor or Washed out with soap and water or detergent and water formulations.
  • the ingredients of Component A are soluble in water and may thus be applied to the textile in aqueous solution.
  • the solvent for Component B may be any inert, essentially water-immiscible organic solvent.
  • Typical illustrative examplies thereof are benzene, toluene, xylene, carbon tetrachloride, ethylene dichloride, chloro form, hexane, octane, petroleum ether or other volatile petroleum fraction. It is, however, not essential that Component A be employed in aqueous solution.
  • a system of two essentially immiscible organic solvents Component A being dispersed in one solvent and Component B in the other.
  • Component A may be dispersed in Z-bromoethyl acetate and Component B dispersed in benzene.
  • Another example involves using formamide, dimethylformamide, or diethylformamide as the solvent for Component A and using nhexyl ether as the solvent for Component B.
  • a further example involves a system of adiponitrile as the solvent for Component A and ethyl ether as the solvent for Component B.
  • Examples of other pairs of solvents which are substantially immiscible with one another and which may be used for preparing the solutions of the respective reactants are 2-bromoethyl acetate and n-hexyl ether, ethylene glycol diacetate and n-hexyl ether, adiponitrile and n-butyl ether, adiponitrile and carbon tetrachloride, benzonitrile and formarnide, n-butyl ether and formarnide, di-N-propyl aniline and formamide, isoamyl sulphide and formamide, benzene and formamide, butyl acetate and formamide, benzene and nitromethane, n-butyl ether and nitromethane, carbon tetrachloride and formamide, dimethyl aniline and formamide, ethyl benzoate and formamide.
  • the solvents therefor may contain hydroxy groups. Because amine, alcoholate, and phenolate groups are so much more reactive than hydroxy groups, there will be little if any interference by reaction of the hydroxy groups of the solvent with the active agents of Component B, particularly if the solutions of the reactants are at ordinary temperatures.
  • solvent pairs of the following types may be employed: Diethylene glycol rnonomethyl ether and nhexyl ether, diethylene glycol monoethyl ether and n-hexyl ether, 2-ethylhexanol and adiponitrile, isoamyl alcohol and adiponitrile, glycerol and acetone, capryl alcohol and formamide, ethylene glycol and benzonitrile, diacetone alcohol and di-N-propylaniline, Z-ethylhexanol and formamide, triethylene glycol and benzyl ether.
  • the concentration of active materials (Component A and Component B) in the respective solutions is not critical and may be varied widely. Generally, it is preferred that each of the pair of solutions contains about from 1 to 20% of the respective active component.
  • enough of the respective solutions are applied to the wool to give a polymer deposit on the fibers of about 1 to 10%. Such amounts provide a substantial degree of shrinkproofing with no significant reduction in hand of the wool. Greater amounts of polymer may be deposited on the fibers if desired but tend to change the nature hand of the wool. Also, thicker deposits are likely to contain substantial amounts of non-grafted polymer.
  • the relative amounts of Component A and Component B applied to the wool may be varied as desired for individual circumstances. Generally, it is preferred to apply the components in equimolar proportions, that is, the amounts are so selected that there are the same number of functional groups provided by Component A as provided by the functional groups or" Component B.
  • reaction promoters or catalysts it is often desirable to add reaction promoters or catalysts to either of the solutions of Component A or B in order to enhance reaction between the active agents.
  • a diamine or a-diol
  • a diacid chloride or a bischloroformate it is desirable to add to either of the solutions a sufficient amount of alkaline material to take up the HCl formed in the reaction.
  • a tertiary amine such as pyridine, dirnethyl aniline, or quinoline or an alkalimetal hydroxide, or, more preferably, an alkaline material with buffering capacity such as sodium carbonate, sodium bicarbonate, trisodium phosphate, borax, etc.
  • Component A includes a diamine and Component B includes a diacid chloride or bischloroformate
  • the reaction of Components A and B may also be catalyzed by addition of such agents as tributyl tin chloride, stannous tartrate, ferric chloride, titanium tetrachloride, boron trifluoride-diethyl ether complex, or tin salts of fat acids such as tin laurate, myristate, etc.
  • Such catalysts are particularly useful to promote reaction between (1) diols and (2) diisocyanates, diacid chlorides, and bischloroformates.
  • one of the solutions of the reactants contains water as the solvent
  • a surface-atcive agent to aid in dispersing the reactant and to assist in penetration of the solution into the textile.
  • a surface-atcive agent such agents as sodium alkyl (C -C sulphates, the sodium alkane (cg-C13) sulphonates, the sodium alkyl (C -C benzene sulphonates, esters of sulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps, typically sodium salts of fat acids.
  • Emulsifying agents of the non-ionic type are suitable, for example, the reaction products of ethylene oxide with fatty acids, with polyhydric alcohols, with partial esters of fatty acids and polyhydric alcohols or with alkyl phenols, etc.
  • Typical of such agents are a polyoxyethylene stearate containing about 20 oxyethylene groups per mole, a polyoxyethylene ether of sor-bitan monolaurate containing about 16 oxyethylene groups per mole, a distearate of polyoxyethylene ether of sorbitol containing about 40 oxyethylene groups per mole, iso-octyl phenyl ether of polyethylene glycol, etc.
  • a supplementary solvent may be added to the primary solvent (water) in quantity sufficient to disperse the active reactant.
  • acetone or other inert volatile solvent, particularly one that is at least partially miscible with water.
  • the treatment of the wool with the solutions of the complementary agents is carried out at room temperature as at such temperature the polymerization takes place very rapidly, that is, in a matter of a minute or less. If, however, a higher rate of polymerization is desiredas in continuous operation on long lengths of cloth--the second solution may be kept hot, for example, at a temperature up to around 150 C. Also, where the agents used include a diol as such (in contrast to the alkali salt thereof) it is preferable to heat the second solution as the polymerization rates with the diols are generally unsatisfactory at room temperature.
  • the solutions of Components A and B--the complementary condensation polymer-forming intermediates are serially applied to the wool in the form of mutually-immiscible solutions to provide a liquid-liquid interface between the solutions as they are serially laid onto the fibers.
  • a system which utilizes a solid-liquid interface.
  • Such a system is established in the following way: The wool is first impregnated with a solution of one of the complementary agents-for example, Component A-dispersed in an inert volatile sol vent. The Wool is then subjected to drying as by subjecting it to a current of hot air.
  • the wool fibers which are now covered with a deposit of the first component in a solid state are then impregnated with the complementary agent-Component B, in this case, dispersed in an inert, preferably volatile solvent.
  • the fibers are layered with a superposed system of solid component A and a solution of Component B. Under these conditions polymerization takes place rapidly forming the polymer in situ on the fibers and grafted thereto.
  • Component A may be applied in water solution and Component B in a watermiscible solvent such as dioxane or acetone.
  • a typical example of practicing this modification involves immersing the wool in an aqueous solution of a diamine and an Hcl'acceptor, removing the wool from the solution, squeezing it through rolls to remove excess liquid, subjecting it to a draft of hot air until the wool is dry to the touch (about 10-20% moisture in the impregnated wool) and then immersing the wool in a solution of a diacid chloride dissolved in an inert, volatile solvent.
  • the wool is then removed from this second bath, squeezed through rollers to remove excess water, rinsed, and dried in air. though this system is operative, it is not a preferred technique because the polymerization at the solid-liquid interface is slower and less uniform in degree of polymerization and the degree of shrinkproofing afforded to the wool per unit weight of polymer formed on the fibers is less than with the system of mutuallyimmiscible solutions.
  • Component A may be a diamine, a diol, or a mixture of a diamine and a diol
  • Component B may be a diacid chloride, 21 bischloroformate, a diisocyanate, or a mix ture of two or more of these classes of compounds.
  • Typical examples of compounds which can be employed as Component A in a practice of the invention are described below.
  • the diamine one may employ any of the aromatic, aliphatic, or heterocyclic compounds containing two primary or secondary amine groups, preferably separated by at least two carbon atoms.
  • the diamines may be substituted if desired with various non-interfering (nonfunctional) substituents such as ether radicals, thioether radicals, tertiary amino groups, sulphone groups, fluorine atoms, etc.
  • Typical compounds in this category are listed below merely by way of illustration and not by way of limitation. Ethylene diamine, trimethylene diamine.
  • tetramethylene diamine hexamethylene diamine, octarnethylene diamine, decamethylene diamine, N,N'-dimethyl-1,3-propanediamine, 1,2-diamino 2 methylpropane, 2,7-diamine-2,o-dimethyloctane, N,N'-dimethyl-1,6- hexanediamine, 1,4-diarnino cyclohexane, 1,4-bis(aminomethyl) cyclohexane, 2,2-diaminodiethyl ether, 2,2'-diaminodiethyl sulphide, bis(4--aminocyclohexyl) methane, N,N dimethyl 2,2,3,3,4,4 hexafluoropentane-1,5-diamine, ortho-, meta-, or para-phenylene diamine, benzidine, xylylene diamine, m-toluylene diamine, ortho-
  • the diol one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two hydroxy groups, preferably separated by at least two carbon atoms.
  • the diols may be substituted if desired with various non-interfering (non-functional) substituents such as ether groups, sulphone groups, tertiary amine groups, thioether groups, fluorine atoms, etc.
  • Typical compounds which may be used are listed below merely by Way of illustration and not limitation: Ethylene glycol, diethylene glycol, 2,2-dimethyl propane-1,3-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol, decane- 1,10-diol, dodecane-1,12-diol, butane-1,2-diol, hexane-1,2- diol, l-O-methyl glycerol, Z-O-methyl glycerol, cyclohexane-1,4-diol, hydroquinone, resorcinol, catechol, bis
  • aliphatic diols for example, those of the type:
  • n has a value from 2 to 12.
  • Another preferred category of aliphatic compounds are the polyethylene glycols, i.e.:
  • a preferred category of aromatic diols are the bisphenols, that is, compounds of the type D no W it wherein RC-R represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R represents hydrogen or a lower alkyl radical.
  • especially preferred compounds are 2,2-bis(parahydroxyphenyl) propane, often designated as bisphenol-A; 2,2- bis(3-methyl-4-hydroxypheny1) propane; 2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and brominated derivatives of bisphenol A, such as 2,2-bis(4-hydroxy-dibromophenyl) propane.
  • the diols are employed as such or in the form of their alkali-metal salts, that is, as alcoholates or phenolates, depending on whether the diols are aliphatic or aromatic.
  • the alkali-metal derivatives are preferred as they will react with the active agents of Component B at room temperature. With the diols, as such, temperatures above room temperature are generally required to promote reaction with their complements in Component B. In such case proper temperature for the reaction can be achieved by holding the second solution into which the textile is immersed ,at about 50 to 150 C. It is obvious that the solvent selected for the second solution will need to be one which has a boiling point above the temperature selected, or, in the alternative, a pressurized system can be used to maintain the solvent in the liquid phase.
  • the diacid chloride one may employ any of the aliphatic aromatic, or heterocyclic compounds containing two carbonylchloride (-COCl) group, preferably separated by at least two carbon atoms.
  • the diac i'd chlorides may be substituted if desired with non-interfering (nonfunctional) substitutents such as ether groups, thioether groups, sulphone groups, etc.
  • the sulphur analogues of these compounds may be used and are included within the spirit of the invention.
  • compounds containing two --COC1 groups one may use compounds containing one -CSCl and one -COC1 group or compounds containing two "CSCl groups.
  • the diacid "chlorides are preferred as they are reactive and relatively inexpensive, the corresponding bromides and iodines may be used as the diacid chloride, it is generally preferred to use the aliphatic compounds containing two carbonylchloride groups in alpha, omega position, particularly those ofthe type:
  • n has a value from 2 to 12.
  • Another preferred category includes the compounds of the formula ClCO-ACOC1 (where A is the benzene or cyclohexane radical), especially para-substituted compounds such as terephthalyl and hexahydroterephthalyl chlorides.
  • the bischloroformate one may use any of the aliphatic, aromatic, or heterocyclic compounds containing two chloroformate groups preferably separated by at least two carbon atoms.
  • the bischloroformates may be substituted if desired with nonphone groups, ether groups, thioether groups, etc.
  • Ethylene glycol bischloroformate diethylene glycol bischloroformate, 2,2-dimethyl propane 1,3-diol bischloroformate, propane-1,3-diol bischloroformate, butane-1,4- diol bischloroformate, hexane-1J6-diol bischloroformate, octane-1,8-diol bischloroformate de'cane-LlO-dio1 bischloroformate, butane-1,2-diol 'bischloroforrnate, hexanel,2-diol bischloroforrnate, 2-methoxyglycerol 1,3 bischloroformate, glycerol-1,2-bischloroformate,
  • aliphatic bischloroformates for example, those of the type:
  • n has a value from-2to 12.
  • Another preferred 11 category of compounds are the bis-chloroformates derived from polyethylene glycols, e.g.,
  • R R R r Q it 01-60 it oo-o1 wherein R-CR represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R is hydrogen or a low alkyl radical.
  • the sulphur analogues of the hischloroformates may be used and such are included within the spirit of the invention.
  • the compounds containing two groups one may use any of the compounds containing the sulphur analogues of these groups, for example, the compounds containing two groups of the formula X-("JCl wherein one X is sulphur and the other is oxygen or wherein both Xs are sulphur.
  • the bichloroformates are preferred because they are reactive and relatively inexpensive, it is not essential that they contain chlorine and one may use the corresponding bisbromoformates or bisiodoformates.
  • diisocyanate one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two isocyanate (NCO) groups, preferably separated by at least two carbon atoms.
  • the diisocyanates may be substituted if desired with non-interfering (nonfunctional) substituents such as ether groups, thioether groups, sulphone groups, etc.
  • Ethylene diisocyanate Ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, cyclohexylene diisocyanate, bis- (2-isocyanatoethyl) ether, bis (2-isocyanatoethyl) ether of ethylene glycol, o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-L6-diisocyanate, 3,3'-bitolylene-4,4-diisocyanate, i.e.,
  • biphenylene diisocyanate 3,3-dimethoxy-biphenylene- 4,4'-diisocyanate, naphthalene diisocyanates, polymethyl polyphenyl isocyanates, etc.
  • the .sulphur analogues of these compounds may be used and such are included within the spirit of the invention.
  • Another point to be made is that it is within the spirit of the invention to utilize the derivatives which yield the same products with compounds containing active hydrogen as do the isocyanates.
  • n has a value from 2 to 12.
  • Other preferred compounds are the toluene diisocyanates, xylylene diisocyanates, and diphenylmethane-4,4'-diisocyanate which may also be termed methylene-bis(p-phenylisocyanate).
  • Polysulphonamides-f0rmed by conjoint use 0) a diamine and a disulphonyl chloride A typical example in this category involves applying to the wool an aqueous solution of a diamine, followed by applying to the wool a disulphouyl chloride dissolved in benzene, toluene, or other inert, essentially water-immiscible solvent.
  • any of the diamines above described may be used in conjunction with such disulphouyl chlorides as benzene-1,3-disulphonyl chloride, biphenyl-4,4'-disuiphonyl chloride, toluene disulphouyl chlorides or aliphatic compounds such as those of the formula wherein n has a value from 2 to 12.
  • Related polymers can be formed by applying these disulphouyl chlorides (as Component B) in conjunction with such compounds as urea, guanidine, thiourea, biuret, dithiobiuret, or the like as Component A.
  • a disulphouyl chloride in inert essentially Water-immiscible solvent.
  • a variant of this procedure is to use the corresponding dithiol in place of the diol, thus to form a polythiolsulphonate.
  • diacid chlorides An alternative to the diacid chlorides is the use of mixed anhydrides of the corresponding dicarboxylic acids with monobasic acids such as trifluoroncetic acid, clihutylphosphoric acid, or the like.
  • Such mixed anhydrides may be employed, for example, as Component B in conjunction with a diamine, diol, or dithiol as Component A to 13 form polyamides, polyesters, or polythiolesters, respectively.
  • Another plan involves the use of urea, thiourea, biuret, dithiobiuret, guanidine, or the like (as Component A) in conjunction with diacid chlorides as Component B to form polyureas, polythioureas, etc.
  • Component A is a diamine and Component B is a diacid chloride.
  • B-y such selection of the complementary agents, polyamides are deposited on the wool fibers and grafted thereto.
  • prepolymer containing internal amide units and terminal amine groups can be prepared, for example, by reacting in known manner a molar excess of diamine with a diacid chloride. The prepolymer would then be used as Component A while for Component B one would use a diacid chloride. A typical example of procedure in this area would be to use as Component A a prepolymer of the type.
  • Component B a diacid chloride (C1CORCOCl) thus to produce a polyamide containing repeating units of the type 0 o 0 -HN-RNH "J-R'iNH-RNH- n"-ti- (In these formulas, R, R, and R represent bivalent organic radicals.)
  • Z is oxygen; R and R represent bivalent hydrocarbon radicals or bivalent hydrocarbon radicals interrupted by internal ether (-O--) linkages; and x is hydrogen.
  • the reactants are so chosen that R and R represent bivalent hydrocarbon radicals containing at least two carbon atoms.
  • Standard shrinkage tests were conducted in the following way: The wool samples were milled at 1700 r.p.m. for 2. minutes at 40-42 C. in an Accelerotor with 0.5% sodium oleate solution, using a liquorto-wool ratio of 50 to 1. After this washing operation the samples were measured to 'determine their area and. the shrinkage was calculated from the original area. With this washing method, samples of control (untreated) wool gave an area shrinkage of 45%.
  • the Accelerotor is described in the American Dyestuff Reporter, vol. 45, p. 685, Sept. 10, 1956.
  • Example 1 A solution was prepared containing 8.8 grams of hexamethylene diamine and 0.2 gram of a commercial wetting agent, the isooctylphenyl ether of polyethylene glycol, per 100 ml. water. 7
  • a sample of wool cloth was immersed in solution A for seconds, run through squeeze rolls to remove excess liquid, immersed for 90 seconds in solution B, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air at room temperature.
  • the treated wool had a polyamide resin uptake of 8.3% and on Washing exhibited an area shrinkage of 3%.
  • Example 1-A A sample of the treated wool prepared as described above in Example 1, run 3, and a sample of the untreated wool (control) were subjected to a series of tests to compare the properties of the two materials. The results are tabulated below.
  • Example 2 W001 cloth was treated as described in Example 1 with variation in sequence of applying the two solutions and residence time in these solutions.
  • solution A was as in Example 1;
  • solution B still contained 2 ml. of scbacoyl chloride in 100 ml. solvent but the nature of the solvent was varied as indicated below.
  • the conditions used and results obtained are tabulated as follows:
  • Example 3 A series of solutions were prepared containing varying amounts of hexamethylene diamine in water. A minor proportion-about 0.1%of the isooctylphcnyl other of polyethylene glycol was also added to each.
  • Wool cloth was treated with the solutions in the following manner.
  • the cloth was immersed in one solution (A or B) for 15 seconds, squeezed to remove excess liquid, immersed for 15 seconds in the next solution (B or A), squeezed to remove excess liquid, rinsed in water, and dried in air.
  • Example 4 A series of solutions were prepared containing either hexaniethylcne diaminc or metaxylylenc diamine dissolved in water. A minor pcrcentageabout 0.1 %--of the isooctylphcnyl ether of polyethylene glycol was also added to each solution.
  • Wool cloth was treated with the solutions in the following manner: "he cloth was immersed in one solution (A or B) for a predetermined time, squeezed to remove excess liquid, immersed for a predetermined time in the next solution (B or A), squeezed to remove excess liquid, and dried in air.
  • diemine 9 ride 2 mL/lOO mlJlOD ml. ml. carbon water. tetrachloride. 5 Mctarylylene Sermcoyl ehlo- 15 1.4 20. 3
  • diaznine 4.5 ride 1 inL/IOO BIL/100 ml. ml. carbon water. tetrachloride. 6 Terephthaloyl Met-axylylene 00 2. 2 19.0
  • Component A is a diamine and Component B is a bischloroiormate.
  • prepolymer containing internal urethane units and terminal amino groups can be prepared, for example, in known manner by reacting a molar excess of diaminc with a bischloroformate.
  • the prcpolyrncr would then be used as Component A while for Component B one would use a bischloroforrnatc.
  • a typical example of procedure in this area would be to use as Component A a prepolymcr of the type HzNRNH- ORO-lNII-RNHJ and to use as Component B a bischloroformate (ClCDGFJOOCCl) thus to produce a polymer containing repeating units of the type R and R" represent bivalent orgroups.
  • Component B a prepolymer used as Component B in conjunction with a diamine as Component 'A would yield a polyurethane similar to that shown above.
  • 'Z is oxygen; R and R-'represent bivalent hydrocarbon radicals or bivalent hydrocarbon radicals interrupted by internal ether (-O-) linkages andx is hydrogen.
  • the reactants are so chosen that R and R represents bivalent hydrocarbon radicals containing at least two carbon atoms.
  • Component A Xylylene diamines or aliphatic alpha
  • ethylene glycol bischloroforrnate diethylene glycol bischloroformate, or hexane-1,6-di'ol bis'chloroformate.
  • A' solution was: prepared containing glycol bischloroformate in benzene.
  • Example 6 The procedure of Example 5 was repeated using as solution A 3% ethylene glycol bischloroformate in benzene and as solution B, a 4l% solution of hexamethylene diamine water. I The following results were obtained:
  • Example 7 The process of ExampleS was repeated using assolution A 4%"heXamethylene'diamine in water and as solution B, a 3% solution of ethylene glycol bischloroformate in carbon tetrachloride. The following results were obtained:
  • Example 8 The process of Example 5 was repeated using as solution A- 4% hexamethylene diamine in water and'as solution B; a 3% solution ofdiethylene glycol bisc'hloroforn'rate in carbon tetrachloride. "The following results were obtained:
  • Polyurethane 1 resin depos- Area shrinkitetl on wool, age, percent percent a Polyurethane resin depos- Area shrinkited on wool, wage, percent percent 1 None (control). 7
  • Example 10 The process of Example was repeated using as solution A 2% metaxylylene diamine in water and as solution B, a 3% solution of diethylene glycol bischloroformate 1 None (control).
  • Example 1 I A series of solutions were prepared containing 4% hexamethylene diamine (or 4% metaxylylene diamine), 4% Na CO and 0.1% of a commercial wetting agent, the isooctylphenyl ether of polyethylene glycol, in water.
  • Wool cloth was treated with the solutions in the following manner: The cloth was immersed in solution A for a predetermined time, squeezed to remove excess liquid, immersed for a predetermined time in solution B, squeezed to remove excess liquid, rinsed in water, and dried in air.
  • the polyureas deposited onto the wool and grafted thereto will contain repeating units of the type Z z -NR-N NH-R'-NH lwhere R and R represent bivalent organic radicals; Z represents oxygen or sulphur; and the xs taken separately represent two hydrogen atoms or two monovalent organic radicals, or, taken together they represent a single divalent organic radical linking the two nitrogen atoms to which these are attached.
  • Z represents oxygen
  • R and R represent bivalent hydrocarbon radicals or bivalent hydrocarbon radicals interrupted by internal ether (--0-) linkages
  • x is by- Time of Resin up- I immersion take on Area Run First treating solution Second treating solution in each wool, shrinkage,
  • Component A is a diamine and Component B is a diisocy-anate.
  • Component B is a diisocy-anate.
  • a prepolymer containing internal urea units and terminal amino groups can be prepared, for example, in known manner by reacting a molar excess of diamine with a diisocyanate. The prepolymer would then be used as Component A while for Component B one would use a diisocyanate.
  • the reactants are so chosen that R and R represent bivalent hydrocarbon radicals containing at least two carbon atoms.
  • Example 13 I The process of Example 12 was repeated using as solution A 4% hexamethylene diamine in water and as solution B a 3% solution of methylene-bis(p-phenylisocyahate) in carbon tetrachloride. The time of immersion of the cloth in each solution was 60 seconds. 7 p
  • the treated wool had a polyurea resin uptake of.2.4% and on washing exhibited an area shrinkage of 8.8%
  • Component A- is a diol and Component B is a diacid chloride.
  • polyesters are deposited on the Wool fibers and grafted thereto.
  • prepolymers can be prepared, for example, in known HO-R'O ,-R' -OROH and to use as Component B a diacid chloride (ClCORfCOCl) thus to produce a polyester containing repeating units of the type H (In these formulas R, R, and R" represent bivalent organic radicals.)
  • Z is oxygen
  • R and R represent bivalent hydrocarbon radicals or bivalent 'hydrocarbon radicals interrupted'by internal ether (O--) linkages;
  • the reactants are s'o chosen that R and R represent bivalent hydrocarbon rad icals containing at least two carbon atoms.
  • Embodiment 4 of the invention is further dem'on strated by the following illustrative examples.
  • a solution was prepared containing 3% .terephthalyl chloride in methylchloroform.
  • I a v A sarnpieof wool cloth was immersed in solution .A for seconds, run through squeeze rollersito remove excess liquid, immersed for60 seconds in solution B, run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
  • the treated wool had a polyester resin uptake of 1% and .onwashing exhibited an area shrinkage of 21.7%.
  • Example 16 The procedure of Example 15 was repeated-using'as solution B 3% sebacyl chloride in carbon tetrachloride. Two runs were made, in one case holdingthe wool 30 seconds in each solution, in the other holding the wool 60 seconds in each solution. The results are tabulated be low:
  • Component A is a diol and Component B is a bischloroformate.
  • prepolymer containing internal carbonate units and terminal hydroxy groups can be prepared, for example, in known manner by reacting a molar excess of diol with a hischloroformate. The prepolymer would then be used as Component A while for Component B one would use a bischloroformate.
  • Component A a prepolymer of the type O H0R-o( ioR'-0i 0-R-0H and to use as Component B a bischloroformate (ClCOOR"COOC1) thus to produce a polycarbonate containing repeating units of the type it OROiiOR'0iiO-ROi JO-R"0C (In these formulas, R, R, and R represent organic radicals.)
  • Example 20 A sample of wool cloth was immersed for 60 seconds in a 6% solution of the sodium salt of 2,2-bis(3-methyl- 4-hydroxyphenyl) propane in water. The cloth was run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 5 parts by Volume of the bischloroformate of hexane-1,6-diol dissolved in parts by volume of a petroleum solvent containing 96% aromatics, 1% parafiins, and 3% naphthenes, specific gravity 0.87, boiling range 314-352 F. The cloth was run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
  • the treated wool had a polycarbonate resin uptake of 4.2% and on washing exhibited an area shrinkage of 20%.
  • Example 21 The procedure of Example 20 was repeated with the exception that the second treatment solution contained 5 parts by volume of the bischloroformate of 2,2-dimethyl-propanediol-l,3 in 100 parts by volume of the petroleum solvent.
  • the treated wool had a polycarbonate resin uptake of 3.6% and on washing exhibited an area shrinkage of 23.5%.
  • Example 22 A sample of wool cloth was immersed for 60 seconds in a 6% solution of the sodium salt of 2,2-bis(3-isopropyl- 4-hydroxyphenyl) propane in water. The cloth was run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 5 parts by volume of the bischloroformate of 2,2-dimethyl-propanediol-1,3 in 100 parts by volume of the petroleum solvent described in Example 20. The cloth was run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
  • Example 23 I A sample of wool cloth was'immersed for 60 seconds 'in a 6% solution of the sodium salt of 2,2-bis(4-hy'droxyphenyl) propanein water. The cl-othwas run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 5 parts by volume of squeeze rolls to remove excess liquid,'rinsed with water,
  • the in-terpoly ners produced inaccordance with these embodiments contain in their recurring structural elements at least two different units selected from the category of amideyurethane, ,ure'a, .esten and carbonate units, these units being linked togetherthrough carbon atoms.
  • the types of different unitsin the interpolyrner I are determined by the reactants applied to the wool fabric.
  • adiarninea diacid chloride, and bischloroformate are applied to the fabric whereby the interpolymer fonned contains both amide and urethane groups, hence is referred to as a copoly (amide-urethane).
  • 'Th formation of this interpolymer may be illustrated as follows: v y
  • interpolyrner contains the amide j 1 v I T if (CNH) and urethane (NI-I--( JO-) V units linked through the bivalent radical R. These units are underlined in the above formula of the interpolymer.
  • the inter-polymers need not contain, only two differentu its, they may contain more than two different units,,.as for, example ⁇ terpoly (amide-.urethaneaurea), te rpoly (arnide-urea-ester), terpoly (amide-urethane-,car'- bona te), or other. combination of thevaforcsaid amide, urethane, urea, .ester,,,and carbonate units.
  • interpolymers produced'in accordance -wtih the invention may-be described as interp'olyrners wherein the: recurring, structures contain at least two different units of the category amide, urethane, urea, ester, and carbonate, thesevunits beingv linked. through carbon atoms;
  • interpolymers can thus be designated by the formulae i t wherein X, X, X", X, X" representthe'diiferent units (amide, urethane urea, ester, or'carb'onate and Q represents the divalent'radicals 'linking'the units together.
  • the reactants are chosen so that Q represents bivalent hydrocarbon 'radicals containing at least two carbon atoms.
  • Q represents bivalent hydrocarbon 'radicals containing at least two carbon atoms.
  • the "interpolymers containing two differentunitsand among these the ones which provide particularly good shrink-proofing effects with low levels of interpolyme-r deposits are those of the types Carbonate:
  • Component A may be a diamine, a diol, or a mixture of a diamine and a diol.
  • Component B may be a diacid chloride, a bischloroformate, a diisocyanate, or mixtures of these classes of compounds.
  • Components A and B must include reagents of at least three classes. For example, if Component A includes both a diamine and a diol then Component B may rep resent any one of the classes of diacid chlorides, bischloroformates, or diisocyanates. A typical example in this area would be to use a mixture of a diamine and a diol as Component A and a diacid chloride as Component B, whereby the resin eventually formed would he a copoly (amide-ester).
  • Component A is a diamine (or a diol) then Component B would need to include at least two reagents of ditferent class, for instance, a diacid chloride and a bischloroformate, a diacid chloride and a diisocyanate, or other combinations of any two or more of the group diacid chlorides, bischloroformates, and diisocyanates.
  • a typical example in this area would be to use a diamine as Component A and a mixture of diacid chloride and diisocyanate as Component B, whereby the resin eventually formed would be a copoly (amide'urea).
  • the guiding factors involved in the selection of materials for Components A and B to produce a desired interpolymer will be evident to those skilled in the art from the above general description and the detailed information set forth hereinafter.
  • these agents are applied to wool in the same manner as employed for the polymers previously described.
  • EMBODIMENT 6 EMBODIllIENT 6.COMPONENT A: DIAMINE Component B 1 l'nterpolymer formed Diacid chloride and bischloroformate- Dist-id chloride and diisocyanate."
  • Copoly (urethane-urea). Terpoly (amldeurethane-urea).
  • Component B include at least two of the classes of bifunctional compounds.
  • Component B may be a mixture of diacid chloride and bischloroformate or a mixture of diacid chloride and diisocyanate or a mixture of bischloroformate and diisocyanate or a mixture of diacid chloride, bischloroformate and diisocyanate.
  • the relative amounts of these reactants of difierent class may be varied depending on the character of the interpolymer to be produced.
  • the proportion of amide to urethane groups in the interpolymer may be increased by increasing the proportion of diacid chloride used in the mixture.
  • the resulting interpolymer will contain substantially equal number of amide and urethane units.
  • the use of equimolar mixtures is by no means critical and one may use any mixture containing 10 to (molar basis) of the reagent of one class and the remainder (90 to 10%) of the reagents of the other classes.
  • prepolymer containing internal amide (or urethane or urea) units and terminal amino groups.
  • prepolymers can be prepared, for example, by reacting in known manner a molar excess of diamine with a diacid chloride, bischloroformate, or diisocyanate.
  • the prepolymer would then be used as Component A while for Component B one would use any one of the reagents (diacid chloride, bischloroformate or diisocyanate) which was not used in preparing the prepolymer.
  • the following alternatives are among those possible.
  • COMPONENT A PREPOLYMER CONTAINING INTERNAL AMIDE UNITS AND TERMINAL AMINO GROUP-3
  • Component B Inter-polymer formed Bischloroformate Copoly (amide-urethane).
  • COMPONENT A PREPOLYMER CONTAINING INTERNAL URETHANE UNITS AND TERMINAL AMINO GROUPS
  • Component B Interpolymer formed Diacid chloride.- Copoly (urethane-amide).
  • Dusocyanate-- Copoly (urethane-urea).
  • COMPONENT A PREPOLYMER CONTAINING INTERNAL UREA UNITS AND TERMINAL AMINO GROUPS Component B Interpolymer formed Diacid chloride Copoly (urea-amide) Bischloroformate Copoly (urea-urethane).
  • a typical example of procedure in this area would be to use as Component A a prepolymer of the type thus to produce an interpolymer containing amide and urethane units of the type
  • a typical exampleof procedurein this area would be to use as Component A a prepolyme-r of the type HzN-R-NH- 0 RO (.7-'-NH-RNH2 and to use as Component 3 a diacid chloride (ClCOR'-'COCI) I thus to produce an interpolymer containing amide and urethane units of the type s w v I natural ste a -etumn nmtniut
  • This principle of using prepolymers could be in other ways as well. Forfexamplega li ol could be canor bischloroformate) to produce alprepolymer con ain.
  • Component B a compound containing internal carbonate units and terminal'is'ocyanate groups, havingthe'formula 0 a ooR-Noo
  • This compound used in conjunction with H R--NH as Component A v would yield a copoly (carbonate-urea) containing recurring units of theftype
  • Component B a compound containing internal carbonate units j and terminal carbonyl chloride groups, having the formula 0' o "-"o g nu- I '01- R-OOO -R-OG.O- -R O -..Cl, thi compound used, in c njnnct iolIIWith N
  • the petroleum solvent referred to in the examples was a commercial hydrocarbon mixture having the following characteristics: 96% aromatics, parafiins, 3% naphthenes; specific gravity 0.87; boiling range 314-362 F.
  • the commercial wetting agentreferred to in the examples was the isooctylphenyl ether of polyethylene glycol.
  • the toluene diiso'cyanatereferred to in Examples 29 and 30 was toluene 2,4-diisocyanate.
  • Component B Diacidchlorideand vbischloroformate.
  • a sample of wool cloth was immersed for 30 seconds in a solution containing 4g. hexan 1ethylene diamine and ,8; g; Na CQ per ,100 ml. water and50.1%l of a commeni t Wet n a e Th sl t .w r m d from ibis o 1 u;tion, run through squeeze rolls to removeexcess liquid, then immersed for 30 secondsinza solution containinglj ml. sebacyl chloride and 1.5 ml.
  • the jcloth was: removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
  • Example 26 Co p 0-ly (Amide-Urethane) Component A: Mixture of diamines.
  • I I I l Component B Diacid chloride and bischloroformate. A sample ofwool cloth was immersed for 30 seconds in 'asolu'tion containing 2 g. hexamethylene diamine. and
  • the cloth-" was removed from this solution, runthro'u'gh squeeze rolls; to remove and dried in air.
  • Component B Diacid chloride and diisocyanate.
  • a sample of wool cloth was immersed for 30 seconds in a solution containing 4 g. hexamethylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 g. methylene bis (pphenylisocyanate) per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
  • Component B Diacid chloride and diisocyanate.
  • a sample of wool cloth was immersed for 30 seconds in a solution containing 4 g. metaxylylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 g. methylene bis (p-phenylisocyanate) per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
  • Component B Diacid chloride and diisocyanate.
  • a sample of wool cloth was immersed for 30 seconds in a solution containing 4 g. hexamethylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 m1. toluene diisocyanate per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
  • Component B Bischloroformate and diisocyanate.
  • a sample of wool cloth was immersed for 30 seconds in a solution containing 4 ml. meta-xylylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent.
  • the cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 g. methylene bis (p-phenylisocyanate) and 1.5 ml. hexane-1,6-diol bischloroformate per 100 ml. benzene.
  • the cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
  • Iuterpolymer resin Area shrinkdeposlted age, percent on wool, percent EMBODIMENT 7 EMBODIMENT 7.-COMPONENT A: DIOL Component B Inter-polymer formed Copoly (ester-carbonate).
  • Embodiment 7 of the present invention is attained by using as Component B a mixture of diacide chloride and bischloroformate or a mixture of diacid chloride and diisocyanate or a mixture of bischloroformate and diisocyanate or a mixture of diacid chloride, bischloroformate, and diisocyanate. It is evident that with regard to Component B of this embodiment, the same considerations are applicable as in Embodiment 6 described above.
  • prepolymer containing internal ester (or carbonate or urethane) units and terminal hydroxy groups.
  • Such prepolymers can be prepared for example, by reacting in known manner a molar excess of diol with a diacid chloride, bischloroformate, or diisocyanate.
  • the prepolymer would then be used as Component A while for Component B one would use any one of the reagents (diacid chloride, bischloroformate, or diisocyanate) which was not used in preparing the prepolymer.
  • the following alternatives are among those possible.
  • COMPONENT A PREPOLYMER CONTAINING INTERNAL ESTER UNITS AND TERMINAL HYDROXY GROUPS Component B Interpolymer formed Bischloroformate Gopoly (ester-carbonate). Diisocyanate Cop-01y (ester-urethane).
  • COMPONENT A PREPOLYMER CONTAINING INTERNAL OARBONATE UNITS AND TERMINAL HY- DROXY GROUPS Component B Interpolymer formed Oopoly (carbonate-ester). Oopoly (carbonate-urethane).
  • Diacid chloride Diisocyanate COMPONENT AzPBEPOLYMER CONTAINING INTERNAL URETHANE UNITS AND TERMINAL IIY- DROXY GROUPS.
  • Component B Inter-polymer formed Diacid chloride Bischloroformate Copoly (urethaneester). Copoly (urethane-carbonate)
  • Component A a prepolymer of the type:
  • Embodiment 7 of the invention is further dem onstrated by the following illustrative examples.
  • the commercial wetting agent referred to in the examples was the isooctylphenyl ether of polyethylene glycol.
  • the petroleum solvent referred to in the examples was a commercial hydrocarbon mixture having the following characteristics. 96% aromatics, 3% naphthene-s, 1% para ffins; specific gravity 0.87; boiling range 314-362" F.
  • Component B Diacid chloride and bischloroformate.
  • a sample of wool cloth was immersed for 60 seconds in a solution containing 10 g. of 2,2-bis (4-hydroxy-dibromophenyl) propane per 100 ml. of water, with addition of suttficient sodium hydroxide to dissolve the hisphenol, and 0.1% of a commercial wetting agent.
  • the cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 ml. -hexane-1,6.-diol bischloroformate per 10.0 ml. petroleum solvent.
  • the cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
  • 'Component B Diacid chloride and bischloroformate.
  • EMBODIMENT S.COMPONENT A DIAMINE AND DIOL Component B Interpolyrncr formed Diacid chloride. Copoly (amide-ester). Bischlorofonnate- Copoly (urethane-carbonate). Drisocyanate Copoly (uren'urcthanc Diacid chloride and bischloroformate. Diacid chloride and diisoeyanatm- Tet-rspoly (amide-urethane-cstercarlonate) 'letrapcly (amide-uzctlianc-urca) ester).
  • Component A for practice of Embodiment 8 of the invention, one may use any of the diamines and diols set forth above.
  • the relative amounts of diamine and diol which comprise Component A may be varied depending on the character of the interpolymer to be produced. For example, in a system using a diacid chloride as Component B, the proportion of amide to ester units in the interpolymer may be increased by increasing the ratio of diamine to diol in Component A.
  • the diamine and diol in equirnolar proportions, thus to provide an interpolymer having any equal proportion of difierent units.
  • the resulting interpolymer will contain substantially an equal ratio of carbonate and urethane units.
  • the use of equimolar proportions is by no means critical and one can use as Component A any mixture containing to 90% (molar basis) of diamine and the remainder (90 to 10%) diol.
  • Component B With regard to Component B, one may use a diacid chloride, bischloroformate, diisocyanate, or mixtures of these.
  • the types of interpolymer resulting from different values chosen for Component B are exemplified in the initial paragraph of the description of this embodiment of the invention.
  • Component A a single compound containing terminal hydroxy and amino groups, for example, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 6-aminohexanol, S-aminooctanol, o-aminophenol, m-aminophenol, p-aminophenol, para (4-aminopheny1) phenol, etc.
  • Component B various interpolymers may be formed on the Wool.
  • COMPONENT A COMPOUND CONTAINING TERMINAL AMINO AND TERMINAL HYDROXY GROUPS
  • the commercial wetting agent referred to in the examples was the isooctylphenyl ether of polyethylene glycol.
  • the petroleum solvent referred to in the examples was a commercial hydrocarbon mixture having the following characteristics: 96% aromatics, 3% naphthenes, 1% paralfins; specific gravity 0.87; boiling range 314-362 F.
  • a solution was prepared containing 2 g. hexamethylene diamine, 5 g. 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 1.5 g. NaOH and 4.0 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent.
  • a sample of wool cloth was immersed for 60 seconds in the solution, then removed, run through squeeze rolls to remove excess liquid and immersed for 60 seconds in a second solution containing 3 ml. sebacyl chloride per 100 ml. benzene. The cloth was removed from the second solution, run through squeeze rolls to remove excess liquid, rinsed in water and dried in air.
  • Component A Diamine and diol.
  • Component B Bischloroformate.
  • a sample of wool cloth was immersed for 60 seconds in a solution containing 2 g. hexamethylene diamine, 5 g. 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1.5 g. NaOH and 4 g. Na 'CO per 100 ml. water and 0.1% of a commercial wetting agent.
  • the cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 3 ml. hexane-1,6-diol bischloroformate per 100 ml. benzene.
  • the cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
  • Interpolyrner resin Area shrinkdepositcd age, percent 021 wool, percent EXAA4PLE 3 7 .C0p0ly (Carbonate- Urethane) solvent. The cloth was removed from the second solunon, run through squeeze rolls to remove excess liquid, rinsed in water and dried in air.
  • the present invention finds its greatest field of utility in the shrinkproofing of wool and is peculiarly adapted for such use because of a combination of important factory-including the advantages that a high degree of shrink resistance is imparted with a minor amount of polymer, that the shrinkproofing treatment does not significantly impair the hand of the wool, that the treatment does not impair other desirable fiber characteristics such as tensile strength, elasticity, porosity, etc., that the polymer is grafted to the wool molecules so that the shrinkproofing efiect is exceedingly durable and is retained even after long Wear and repeated launderingit is evident that the invention may be extended to other areas.
  • the principles of the invention may be extended to forming polymers in situ on other substrates besides Wool, particularly substrates of a fibrous structure.
  • Typical examples of such materials are animal hides, leather; animal hair; cotton; hemp; jute; ramie; fiax; Wood; paper; synthetic cellulosic fibers such as viscose, cellulose acetate, cellulose acetate-butyrate; casein fibers; polyvinyl alcohol-protein fibers; alginic fibers; glass fibers; asbestos; and organic non-cellulosic fibers such as poly (ethylene glycol terephthalate), polyacryonitrile, polyethylene, polyvinyl chloride, polyvinylidene chloride, etc.
  • Such applications of the teachings of the invention may be for the purposes of obtaining functional or decorative effects such as sizing, finishing, increasing gloss or transparency, increasing water-repellancy, increasing adhesionor bonding-characteristics of the substrates with rubber, polyester resins, etc. It is not claimed that in such extensions of our teachings shrinkp-roofing would be attained nor that graft polymers would be produced. However, it might be expected that graft polymers would be formed with proteinous substrates such as animal hair, animal hides, and the like.
  • polyesters are the subject of Serial No. 101,599, filed April 7, 1961; polycarbonates are the subject of Serial No. 102,323, filed April 11, 1961; and interpolymers are the subject of Serial No. 109,229 filed May 10, 1961.
  • a process for shrinkproofing wool without significant impairment of its hand which comprises serially impregnating wool with two solutions, one solution containing a diamine dispersed in Water, the other solution containing a diacid chloride dispersed in an inert, volatile, essentially water-immiscible solvent, the said diamine and diacid chloride reacting to form in situ on the Wool fibers .a resinous polyamide.
  • n has a value from 6 to 10.
  • a process for shrinkproofing wool without significant impairment of its hand which comprises serially impregnating wool with two solutions, one containing a diamine in a first solvent, the other containing a diacid chloride in a second solvent, said first and second solvents being substantially mutually immiscible, the said diamine and diacid chloride reacting to form in situ on the Wool fibers a resinous polyamide.
  • a modified wool fiber which exhibits improved shrinkage properties as compared with the unmodified wool fiber comprising wool fiber having a polyamide formed in situ thereon and chemically bonded to the Wool.
  • a modified wool fiber which exhibits improved shrinkage properties as compared with the unmodified wool fiber comprising Wool fiber having a polyamide of a diamine and a dicarboxylic acid formed in situ thereon and chemically bonded to the Wool.
  • polyamide contains recurring structural groups of the formula wherein n has a value from 4 to 10 and m has a value from 6 to 10.
  • a process for treating a fibrous material which comprises serially depositing on said fibrous material in superposed phases in interfacial relationship a pair of complementary, direct-acting, organic, polyamide-forming intermediates, at least one of said phases being liquid, the said intermediates directly reacting under said conditions to form a polyamide in situ on said material.
  • a process for treating a fibrous material which comprises serially applying to said fibrous material a pair of complementary, direct-acting, organic, polyamideforming intermediates in separate liquid phases of limited mutual solubility.
  • a process for treating a fibrous material which comprises serially distributing on the surface of the fibrous elements of said material a pair of complementary, direct-acting, organic, polyamide-forming intermediates in superposed phases of limited mutual solubility, at least one of said phases being liquid, the said intermediates reacting under such conditions to form a polyamide in situ on said fibrous elements.
  • a process for treating wool which comprises serially distributing on the surface of the wool fibers a pair of complementary, direct-acting, organic, polyamideforming intermediates in superposed liquid phases of limited mutual solubility, said intermediates reacting rapidly under said conditions to form a polyamide in situ on said fibrous elements and grafted thereto.
  • a process for treating a fibrous material which comprises serially impregnating a fibrous material with two solutions, one solution containing one member of a pair of complementary, direct-acting, organic, polyamideforming intermediates in a first solvent, the other solution containing the complementary member of said pair of complementary, direct-acting, organic, pol /amideforming intermediates in a second solvent, the first and second solvents being substantially mutually immiscible, the said pair of intermediates reacting rapidly under said conditions to form in situ on the fibers a resinous polyamide.

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Description

United States Patent SHRINKPROOFIN G WOOL WITH POLYAMIDES Lowell A. Miller and Robert E. Whitfield, Walnut Creek,
and William L. Wasley, Berkeley, Calif., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Mar. 27, 1961, Ser. No. 98,718
16 Claims. (Cl. 8-128) (Granted under Title 35, U.S. Code (1952), sec. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.
A principal object of this invention is the provision of new methods for shrinkproofing wool. Another object of the invention is the provision of the novel products so produced. Further objects and advantages of the invention will be obvious from the following description wherein parts and percentages are by weight unless otherwise specified.
In the prior art it is suggested that the shrinkage properties of wool can be improved by applying to the wool fibers a high molecular weight polyamide such as polyhexamethylene adipamide or similar polyamide of the nylon type. This is accomplished in the following mannet: The selected polyamide is first converted into soluble form, for example, by forming an N-methylolderivative thereof. The N-methylol derivative is applied to the wool and the treated wool is then immersed in hydrochloric acid whereby the N-methylol polyamide is converted to the unsubstituted polyamide. A primary disadvantage of this known process is that it is cumbersome and inefficient because it requires procurement of a preformed polyamide, conversion of this to a soluble form, and final reconversion to an insoluble form. Particular trouble is encountered in the last step where extended contact with acid is required to insolubilize the coating of N-methylol polyamide. Unless this acid treatment is complete, the polyamide will remain soluble and be removed from the textile when it is washed.
In accordance with this invention, a pre-formed polyamide is not used but a polyamide (or other condensation polymer) is formed in situ on the wool fibers. This is accomplished by serially applying to the wool the complementary agents required to form the desired polymer, these agents-in the preferred modification of the invention--being dissolved in mutually-immiscible solvents. Thus in a typical embodiment of the invention the wool is first impregnated with an aqueous solution of a diarnine and then impregnated with a solution of a diacid chloride in a water-immiscible solvent such as carbon tetrachloride. Generally, the solutions are applied in the order given above, however, the reverse order gives good results and it is within the ambit of the invention to apply the solutions in either sequence. By serial application of these solutions to the fabric, each fibrous element is coated with a two-phase system, for example, an inner layer of diarnine in water and an outer layer of diacid chloride in water-immiscible solvent. Under these conditions the diamine and diacid chloride react almost instantaneously at the interface be'twcenthe phases, producing in situ on the fibers a high molecular weight, resinous polyamide whichcoats the fibers and renders them shrinkproof. By suitable selection of the complementary reactants other condensation polymers such as polyurethanes, polyureas, polyesters, polycarbonates, or various interpolymers "thereof can be formed in situ on wool fibers. The polymer formed is insoluble so that the shrinkproofing effect is durable; it is retained even after repeated washings with soap and water or detergent and waterformulations.
3,078,138 Patented Feb. 19, 1963 A feature of the invention is that the high molecular weight resinous polymers are formed in many cases at ordinary (room) temperature, which is in sharp contrast to the much higher temperatures required in the conventional melt condensations used in preparing polyamides, polyurethanes, etc. For example, in the usual preparation of polyamides by melt procedures, temperatures of over 200 C. are customarily employed.
As noted above, the treatment in accordance with the invention renders the treated wool essentially shrinkproof so that garments produced from the treated wool may be laundered in conventional soap and water or detergent and water formulations with negligible shrinking or felting. Further, the treated wool or garments prepared therefrom are in the easy-care category in that after washing and tumble drying, they are quite free from wrinkles so that they require only a minor amount of pressing. An important .ppint to be stressed is that the shrinkproofing effect is secured without damage to the hand of the fabric. That is, the treated fabric retains its normal hand so that it is useful for all the conventional applications in fabricating garments as is untreated wool. Other items to be mentioned are that the treatment does not cause any degradation of the wool so that there is no significant loss of tensile strength, abrasion resistance, resiliency, elasticity, etc. Moreover, since the polymer is formed in situ on the fibers-in contrast to systems wherein polymers arespread en masse over the face of a fabric-'there is substantially no loss of porosity of the fabric. A further item is that the treated wool may be dyed with conventional wool dyes to obtain brilliant, level dyeings.
.A particular feature of the invention and one that emphasizes its simplicity is that no heat-curing step is required. Following application of the two solutions, the textile merely needs to be rinsed or washed. Then, after drying, it is ready for use or sale.
The invention is applicable to wool in any physical form, for example, bulk fibers, slivers, rovings, yarns, felts, woven textiles, knitted textiles, or even completed garments or garment parts.
A remarkable feature :of the invention is that the polymers fiormed on the wool fibers are not merely physical coatings; they are chemically bonded to the wool, that is, the added polymer .is grafted onto the wool. The fact that a chemical bonding is achieved rather than a mere physical adhesion has been demonstrated by experiments wherein it was attempted to dissolve the grafted polymer with solvents which are capable of dissolving the polymers in bulk. Thus, wool cloth was serially impregnated with (1) an aqueous solution of hexamethylene diamine and (2) a solution of sebacoyl chloride in carbon tetrachloride. The treated wool was rinsed in water and dried in air. It was foundthat the wool had a polyamide resin uptake of 4.4% and showed an area shrinkage of 1% on being subjected to a very severe washing test. Samples of this treated wool were subjected to these tests:
(a) A-sample of the treated wool was extracted for 6 hours with benzyl alcoholv at.910 .C.
(b) Another sample of the treated wool was extracted with formic acid (98% first for 2 hours at 70 C., then at 35 C. for 22 hours.
(c) The extracted wool samples were treated to evaporate the solvents and weighed to determine the possible loss of resin. Also, the extracted samples were again subjected tothe same severe washing test to determine their shrinkage. It was found 'that'there was no measurable decrease in weight, indicating no loss of polyamide by the'wool and, moreover, the area shrinkage was still 1% or .less, further-.indicating-that there was no loss of polyamide. It may be noted that both benzyl alcohol and 98% formic acid are good solvents for fiberforming polyamides such as polyhexamethylene sebacamide and had the polyamide on the wool been merely a coating, the extraction would have resulted in a weight loss and a marked increase in the percentage of shrink- The mechanism by whice the graft polymerization occurs is believed to involve a reaction of functional groups on one or the other of the complementary agents with the free amino or hydroxy groups present in the wool molecule, these reactions giving rise to such linkages as amide, ester, urea, urethane, carbonate, etc. which chemically unite the wool with the polymer. Thus the case of graft polyamides can be postulated by the following idealized formulas:
CRONH-R-N]I W o L J In the above and succeeding formulas, W represents the polypeptide chain of the wool, containing prior to the reaction, free amino (NH or free hydroxy (-OH) groups. R and R are bivalent organic radicals (representing in this case the residues of the diamine and diacid chloride, respectively), and n represents the number of polyamide repeating units.
The above formulas are obviously simplified and idealized as the polyamide chains may be attached at both their ends to a single wool molecule or they may crosslink together different wool molecules through amide or ester linkages. The important point from a practical and realistic view is that chemical bonding of the polyamide to the wool has been demonstrated and the theoretical nature of the mechanism of bonding is not of real concern to the invention.
The invention encompasses the grafting of other types of polymers besides polyamides onto the wool molecule. Typical polymers which may be applied in accordance with the invention are polyurethanes, polyureas, polyesters, polycarbonates, and interpolymers wherein the recurring units contain two or more different units of the classes of amide, urethane, urea, ester, and carbonate. The grafting of typical examples of these different types of polymers onto wool are shown in the formulas below, again following an idealized plan:
Polyurethane grafted to wool through urethane or carbonate linkage:
L Jr.
Polyurea grafted to wool through urea or urethane linkage:
Polycarbonate grafted to wool through urethane or carbonate linkage:
Copoly (amide-urethane) grafted to wool through amide or ester linkage:
wherein Z is oxygen or sulphur. The term non-0x0 is used in the usual sense of excluding aldehyde and ketone configurations. The non-0x0 carbonyl group may occur in various types of combinations, illustrative examples of which are given below.
Amide:
Z JLI L Urethane:
z L Urea:
2 ---NH-- i k-NH- Ester:
Z Carbonate:
z z-- z (Z being sulphur or oxygen).
GENERAL CONSIDERATIONS In the practice of the invention, selection is first made of the appropriate complementary agentsherein termed Component A and Component B-required to form the desired polymer on the wool fibers. The interrelationship between the nature of the agents to be used as Components A and B and the type of polymer produced is explained in detail below in connection with the various modifications of the invention. However, it is apropos to mention at this point that in general, Component A may be a diamine, a diol, or a mixture of a diamine and a diol.
Dependant on the materials selected for Component A, Component B may be, for example, a diacid chloride, at bischloroformate, a diisocyanate, or mixtures of these classes of compounds. Since Components A and B may be selected to form any desired type of condensation polymer, these components may be aptly termed as complementary organic condensation polymer-forming intermediates. They may further be appropriately designated as fast-reacting or direct-acting because they form the resinous polymers rapidly and directly on contact without requiring any after-treatments, such as treatment with curing agents, oven cures, etc.
Having selected the desired Components A and B, these are formed into separate solutions for application to the wool to be treated. An essential consideration in the preferred modification of the invention is that the solvents used in the respective solutions of Components A and B be substantially mutually immiscible so that a liquid-liquid interface will be set up between the two solutions on the wool fibers. Thus, for example, Component A is dissolved in water and Component B is dissolved in benzene, carbon tetrachloride, toluene, xylene, ethylene dichloride, chloroform, hexane, octane, petroleum ether or other volatile petroleum distillate, or any other inert water-immiscible solvent. The two solutions are then applied to the wool serially, that is, the wool is treated first with one solution then with the other. The order of applying the solutions is not critical. Generally, the solution of Component A is applied first and the solution of Component B is applied next; however, the reverse order gives good results and it is within the ambit of the invention to apply the solutions in either sequence.
The solutions may be applied to the wool in any desired way as long as they are applied serially. A preferred method involves immersing the wool in one solution, removing excess liquid as by use of squeeze rolls, immersing the wool with the second solution, again removing excess liquid, rinsing the treated fabric in water and then drying it. Conventional apparatus consisting of tanks, padding rolls, squeeze rolls and the like are generally used in applying the respective solutions. The amount of each solution applied to the textile may be varied by altering the residence time in the solutions, the pressure exerted by the squeeze rolls and by varying the concentration of the active materials in the respective solutions. To decrease carry-over of the solvent from the first treating solution to the second solution, the wool after its immersion in the first solution may be subjected to drying conditions such as a current of warm air to concentrate the solution carried by the Wool.
As noted above, a critical factor in the preferred form of the invention is that the complementary-agents-Component A and Component B-are serially applied to the textile dispersed in solvents which are substantially mutually immiscible. The nature of the solvents is of no consequence as long as they are essentially inert and possess the above-stated property of substantial immiscibility. Usually volatile solvents are preferred as they may be removed from the treated textile by evaporation. However, non-volatile solvents can be used, in which case they may be removed from the product by extraction with suitable volatile solvents therefor or Washed out with soap and water or detergent and water formulations. In many cases the ingredients of Component A are soluble in water and may thus be applied to the textile in aqueous solution. In such case the solvent for Component B may be any inert, essentially water-immiscible organic solvent. Typical illustrative examplies thereof are benzene, toluene, xylene, carbon tetrachloride, ethylene dichloride, chloro form, hexane, octane, petroleum ether or other volatile petroleum fraction. It is, however, not essential that Component A be employed in aqueous solution. Thus, one may utilize a system of two essentially immiscible organic solvents, Component A being dispersed in one solvent and Component B in the other. As an example,
Component A may be dispersed in Z-bromoethyl acetate and Component B dispersed in benzene. Another example involves using formamide, dimethylformamide, or diethylformamide as the solvent for Component A and using nhexyl ether as the solvent for Component B. A further example involves a system of adiponitrile as the solvent for Component A and ethyl ether as the solvent for Component B. Examples of other pairs of solvents which are substantially immiscible with one another and which may be used for preparing the solutions of the respective reactants are 2-bromoethyl acetate and n-hexyl ether, ethylene glycol diacetate and n-hexyl ether, adiponitrile and n-butyl ether, adiponitrile and carbon tetrachloride, benzonitrile and formarnide, n-butyl ether and formarnide, di-N-propyl aniline and formamide, isoamyl sulphide and formamide, benzene and formamide, butyl acetate and formamide, benzene and nitromethane, n-butyl ether and nitromethane, carbon tetrachloride and formamide, dimethyl aniline and formamide, ethyl benzoate and formamide.
In cases where Component A is a diamine and/ or a diol in the form of its alkali-metal salt, the solvents therefor may contain hydroxy groups. Because amine, alcoholate, and phenolate groups are so much more reactive than hydroxy groups, there will be little if any interference by reaction of the hydroxy groups of the solvent with the active agents of Component B, particularly if the solutions of the reactants are at ordinary temperatures. In such event, then, solvent pairs of the following types may be employed: Diethylene glycol rnonomethyl ether and nhexyl ether, diethylene glycol monoethyl ether and n-hexyl ether, 2-ethylhexanol and adiponitrile, isoamyl alcohol and adiponitrile, glycerol and acetone, capryl alcohol and formamide, ethylene glycol and benzonitrile, diacetone alcohol and di-N-propylaniline, Z-ethylhexanol and formamide, triethylene glycol and benzyl ether.
The concentration of active materials (Component A and Component B) in the respective solutions is not critical and may be varied widely. Generally, it is preferred that each of the pair of solutions contains about from 1 to 20% of the respective active component. In applying the process of the invention, enough of the respective solutions are applied to the wool to give a polymer deposit on the fibers of about 1 to 10%. Such amounts provide a substantial degree of shrinkproofing with no significant reduction in hand of the wool. Greater amounts of polymer may be deposited on the fibers if desired but tend to change the nature hand of the wool. Also, thicker deposits are likely to contain substantial amounts of non-grafted polymer. The relative amounts of Component A and Component B applied to the wool may be varied as desired for individual circumstances. Generally, it is preferred to apply the components in equimolar proportions, that is, the amounts are so selected that there are the same number of functional groups provided by Component A as provided by the functional groups or" Component B.
It is often desirable to add reaction promoters or catalysts to either of the solutions of Component A or B in order to enhance reaction between the active agents. For example, in cases where the system involves reaction between a diamine (or a-diol) and a diacid chloride or a bischloroformate it is desirable to add to either of the solutions a sufficient amount of alkaline material to take up the HCl formed in the reaction. For such purpose one may use a tertiary amine such as pyridine, dirnethyl aniline, or quinoline or an alkalimetal hydroxide, or, more preferably, an alkaline material with buffering capacity such as sodium carbonate, sodium bicarbonate, trisodium phosphate, borax, etc. Another plan which may be used in instances where Component A includes a diamine and Component B includes a diacid chloride or bischloroformate, involves supplying the diamine in excess so that it will act both as a reagent and as an -HClacceptor. The reaction of Components A and B may also be catalyzed by addition of such agents as tributyl tin chloride, stannous tartrate, ferric chloride, titanium tetrachloride, boron trifluoride-diethyl ether complex, or tin salts of fat acids such as tin laurate, myristate, etc. Such catalysts are particularly useful to promote reaction between (1) diols and (2) diisocyanates, diacid chlorides, and bischloroformates.
Where one of the solutions of the reactants contains water as the solvent, it is often desirable to incorporate a minor proportion of a surface-atcive agent to aid in dispersing the reactant and to assist in penetration of the solution into the textile. For this purpose one may use such agents as sodium alkyl (C -C sulphates, the sodium alkane (cg-C13) sulphonates, the sodium alkyl (C -C benzene sulphonates, esters of sulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps, typically sodium salts of fat acids. Emulsifying agents of the non-ionic type are suitable, for example, the reaction products of ethylene oxide with fatty acids, with polyhydric alcohols, with partial esters of fatty acids and polyhydric alcohols or with alkyl phenols, etc. Typical of such agents are a polyoxyethylene stearate containing about 20 oxyethylene groups per mole, a polyoxyethylene ether of sor-bitan monolaurate containing about 16 oxyethylene groups per mole, a distearate of polyoxyethylene ether of sorbitol containing about 40 oxyethylene groups per mole, iso-octyl phenyl ether of polyethylene glycol, etc. Generally, only a small proportion of surface-active agent is used, on the order of 0.05 to 0.5%, based on the weight of the solution. In addition to, or in place of the surface-active agent, a supplementary solvent may be added to the primary solvent (water) in quantity sufficient to disperse the active reactant. For such purpose one may employ acetone, or other inert volatile solvent, particularly one that is at least partially miscible with water. It is evident that the solutions of Components A and B need not necessarily be true solutions; they may be colloidal solutions, emulsions, or suspensions, all these being considered as solutions for the purposes of the present invention.
Ordinarily, the treatment of the wool with the solutions of the complementary agents is carried out at room temperature as at such temperature the polymerization takes place very rapidly, that is, in a matter of a minute or less. If, however, a higher rate of polymerization is desiredas in continuous operation on long lengths of cloth--the second solution may be kept hot, for example, at a temperature up to around 150 C. Also, where the agents used include a diol as such (in contrast to the alkali salt thereof) it is preferable to heat the second solution as the polymerization rates with the diols are generally unsatisfactory at room temperature.
As has been explained above, in the preferred modification of the invention the solutions of Components A and B--the complementary condensation polymer-forming intermediatesare serially applied to the wool in the form of mutually-immiscible solutions to provide a liquid-liquid interface between the solutions as they are serially laid onto the fibers. In a less preferred modification of the invention, a system is used which utilizes a solid-liquid interface. Such a system is established in the following way: The wool is first impregnated with a solution of one of the complementary agents-for example, Component A-dispersed in an inert volatile sol vent. The Wool is then subjected to drying as by subjecting it to a current of hot air. The wool fibers which are now covered with a deposit of the first component in a solid state, are then impregnated with the complementary agent-Component B, in this case, dispersed in an inert, preferably volatile solvent. In this way the fibers are layered with a superposed system of solid component A and a solution of Component B. Under these conditions polymerization takes place rapidly forming the polymer in situ on the fibers and grafted thereto. In
this system it is not essential that the respective solvents be immiscible. Thus, for example, Component A may be applied in water solution and Component B in a watermiscible solvent such as dioxane or acetone. A typical example of practicing this modification involves immersing the wool in an aqueous solution of a diamine and an Hcl'acceptor, removing the wool from the solution, squeezing it through rolls to remove excess liquid, subjecting it to a draft of hot air until the wool is dry to the touch (about 10-20% moisture in the impregnated wool) and then immersing the wool in a solution of a diacid chloride dissolved in an inert, volatile solvent. The wool is then removed from this second bath, squeezed through rollers to remove excess water, rinsed, and dried in air. though this system is operative, it is not a preferred technique because the polymerization at the solid-liquid interface is slower and less uniform in degree of polymerization and the degree of shrinkproofing afforded to the wool per unit weight of polymer formed on the fibers is less than with the system of mutuallyimmiscible solutions.
COMPONENTS A AND B As noted briefly above, the selection of Components A and B depends on the type of polymer desired to be formed on the wool fiber and grafted thereto. In general, Component A may be a diamine, a diol, or a mixture of a diamine and a diol; Component B may be a diacid chloride, 21 bischloroformate, a diisocyanate, or a mix ture of two or more of these classes of compounds. Typical examples of compounds which can be employed as Component A in a practice of the invention are described below.
As the diamine one may employ any of the aromatic, aliphatic, or heterocyclic compounds containing two primary or secondary amine groups, preferably separated by at least two carbon atoms. The diamines may be substituted if desired with various non-interfering (nonfunctional) substituents such as ether radicals, thioether radicals, tertiary amino groups, sulphone groups, fluorine atoms, etc. Typical compounds in this category are listed below merely by way of illustration and not by way of limitation. Ethylene diamine, trimethylene diamine. tetramethylene diamine, hexamethylene diamine, octarnethylene diamine, decamethylene diamine, N,N'-dimethyl-1,3-propanediamine, 1,2-diamino 2 methylpropane, 2,7-diamine-2,o-dimethyloctane, N,N'-dimethyl-1,6- hexanediamine, 1,4-diarnino cyclohexane, 1,4-bis(aminomethyl) cyclohexane, 2,2-diaminodiethyl ether, 2,2'-diaminodiethyl sulphide, bis(4--aminocyclohexyl) methane, N,N dimethyl 2,2,3,3,4,4 hexafluoropentane-1,5-diamine, ortho-, meta-, or para-phenylene diamine, benzidine, xylylene diamine, m-toluylene diamine, ortho-tolidine, piperazine, and the like. If desired, mixtures of different diamines may be used. It is generally preferred to use aliphatic alpha, omega diamines, particularly of the type wherein n has a value of 2 to 12, preferably 6 to 10.
As the diol one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two hydroxy groups, preferably separated by at least two carbon atoms. The diols may be substituted if desired with various non-interfering (non-functional) substituents such as ether groups, sulphone groups, tertiary amine groups, thioether groups, fluorine atoms, etc. Typical compounds which may be used are listed below merely by Way of illustration and not limitation: Ethylene glycol, diethylene glycol, 2,2-dimethyl propane-1,3-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol, decane- 1,10-diol, dodecane-1,12-diol, butane-1,2-diol, hexane-1,2- diol, l-O-methyl glycerol, Z-O-methyl glycerol, cyclohexane-1,4-diol, hydroquinone, resorcinol, catechol, bis
(parahydroxyphenyl) methane, 1,2-bis'(par'ahydroxyphenyl) ethane, 2,2-bis(parahydroxyphenyl) propane, 2,2-bis(parahydroxyphenyl) butane, 4,4-dihydroxyb'enzophenone, naphthalene-1,5 diol, biphenyl-4,4'-diol, 2,2- bis(3-methyl-4-hydroxyphenyl) propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-dibrornophenyl) propane, etc. If desired, mixtures of different diols may be used. It is also within the purview of the invention, though less preferred, to use the compounds containing more than two hydroxy groups as for example, glycerol, diglycerol, hexanetriol, pentaerythritol, etc. Moreover, it is within the spirit of the invention to utilize the sulphur analogues of the diols. Thus, for example, instead of using the compounds containing two hydroxy groups one can use the analogues containing either (a) two -SH groups or (b) one -SH group and one O-H group.
Among the preferred compounds are the aliphatic diols, for example, those of the type:
wherein n has a value from 2 to 12. Another preferred category of aliphatic compounds are the polyethylene glycols, i.e.:
wherein n has a value from zero to 10. A preferred category of aromatic diols are the bisphenols, that is, compounds of the type D no W it wherein RC-R represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R represents hydrogen or a lower alkyl radical. In this category especially preferred compounds are 2,2-bis(parahydroxyphenyl) propane, often designated as bisphenol-A; 2,2- bis(3-methyl-4-hydroxypheny1) propane; 2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and brominated derivatives of bisphenol A, such as 2,2-bis(4-hydroxy-dibromophenyl) propane.
The diols are employed as such or in the form of their alkali-metal salts, that is, as alcoholates or phenolates, depending on whether the diols are aliphatic or aromatic. The alkali-metal derivatives are preferred as they will react with the active agents of Component B at room temperature. With the diols, as such, temperatures above room temperature are generally required to promote reaction with their complements in Component B. In such case proper temperature for the reaction can be achieved by holding the second solution into which the textile is immersed ,at about 50 to 150 C. It is obvious that the solvent selected for the second solution will need to be one which has a boiling point above the temperature selected, or, in the alternative, a pressurized system can be used to maintain the solvent in the liquid phase.
In the modification of the invention wherein water is used as the solvent for Component A (a diol in this case) and Component B is dispersed in a water-immiscible, inert solvent, it is preferred to use aromatic diols in their salt (phenolate) form. This affords several distinct advantages. Thus the alkali-metal phenolates are quite soluble in water, they are relatively stable in aqueous solution (in contrast to the alcoholates), and they will react at room temperature with diacid chlorides, bischloroformates, or diisocyanates so that no heating is required.
Typical examples of compounds which can be employed as Component B in a practice of the invention are described below.
As the diacid chloride one may employ any of the aliphatic aromatic, or heterocyclic compounds containing two carbonylchloride (-COCl) group, preferably separated by at least two carbon atoms. the diac i'd chlorides may be substituted if desired with non-interfering (nonfunctional) substitutents such as ether groups, thioether groups, sulphone groups, etc. Tyical examples of compounds in this category are listed below merely by way of illustration and not limitation: 'Oxalyl chloride, maleyl chloride, fumaryl chloride, malonyl chloride, succinyl ClCOCH -'CH="CH-'CH COCI diglycollic acid chloride, i.e., O'(CH -COCl) higher :hornologues of this compound as O(CH -CH COCl) 'dithiodiglycollic acid chloride, diphenylolpropan'e-diacetic chloride, i.e., (CH C(C H ,OCH COCD and the like. If desired, mixtures of different diacid chloride may be used. It is also evident that the sulphur analogues of these compounds may be used and are included within the spirit of the invention. Thus, instead of using compounds containing two --COC1 groups one may use compounds containing one -CSCl and one -COC1 group or compounds containing two "CSCl groups. Moreover, although the diacid "chlorides are preferred as they are reactive and relatively inexpensive, the corresponding bromides and iodines may be used As the diacid chloride, it is generally preferred to use the aliphatic compounds containing two carbonylchloride groups in alpha, omega position, particularly those ofthe type:
ClCO' CH CO Cl wherein n has a value from 2 to 12. Another preferred category "includes the compounds of the formula ClCO-ACOC1 (where A is the benzene or cyclohexane radical), especially para-substituted compounds such as terephthalyl and hexahydroterephthalyl chlorides.
As the bischloroformate one may use any of the aliphatic, aromatic, or heterocyclic compounds containing two chloroformate groups preferably separated by at least two carbon atoms. The bischloroformates may be substituted if desired with nonphone groups, ether groups, thioether groups, etc. interfering (non-'fuctional) substituent-s such as sul- Typical examples of compounds in this category are listed below merely by way of illustration and not limitation: Ethylene glycol bischloroformate, diethylene glycol bischloroformate, 2,2-dimethyl propane 1,3-diol bischloroformate, propane-1,3-diol bischloroformate, butane-1,4- diol bischloroformate, hexane-1J6-diol bischloroformate, octane-1,8-diol bischloroformate de'cane-LlO-dio1 bischloroformate, butane-1,2-diol 'bischloroforrnate, hexanel,2-diol bischloroforrnate, 2-methoxyglycerol 1,3 bischloroformate, glycerol-1,2-bischloroformate, glycerol-l, 3-bischloroformate, diglycerol bischloro formate, hexanetriol bischloroformate, pentaeryt hritol bischloroformate, cyclohexane-lA-diol bischlo'roformate, hydroquinone bischloroformate, resorcinol bischloroformate, catechol bischloroformate, bischloroformate of 2,2-bis (parahydroxyphenyl) propane, bischlor'oformate of 2,2-bis (parahydroxyphenyl) butane, "bischloroformate of 4,4'-dihydroxybenzophenone, bischloroformate of 1,2-bis(parahydroxyphenyl) ethane, naphthalene- 1,5-diol bischloroformate, biphenyl-4,4'-diol bischloroformate, etc. If desired, mixtures of diiferentbischloroformates may be used.
Among the preferred compounds are the aliphatic bischloroformates, for example, those of the type:
wherein n has a value from-2to 12. Another preferred 11 category of compounds are the bis-chloroformates derived from polyethylene glycols, e.g.,
ClC O-CH:-CH:-[O oHl-oHi ]n-o Ora-crn-o'b-m wherein n has a value from zero to 10. A useful category of aromatic bischloroformates are the bisphenol chloroformates, that is, compounds of the type:
R R R r Q it 01-60 it oo-o1 wherein R-CR represents an aliphatic hydrocarbon group containing 1 to 12 carbon atoms and R is hydrogen or a low alkyl radical.
It is also evident that the sulphur analogues of the hischloroformates may be used and such are included within the spirit of the invention. Thus, instead of using the compounds containing two groups one may use any of the compounds containing the sulphur analogues of these groups, for example, the compounds containing two groups of the formula X-("JCl wherein one X is sulphur and the other is oxygen or wherein both Xs are sulphur. Moreover, although the bichloroformates are preferred because they are reactive and relatively inexpensive, it is not essential that they contain chlorine and one may use the corresponding bisbromoformates or bisiodoformates.
As the diisocyanate one may employ any of the aliphatic, aromatic, or heterocyclic compounds containing two isocyanate (NCO) groups, preferably separated by at least two carbon atoms. The diisocyanates may be substituted if desired with non-interfering (nonfunctional) substituents such as ether groups, thioether groups, sulphone groups, etc. Typiial examples of compounds in this catagory are listed below merely by way of illustration and not limitation: Ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, cyclohexylene diisocyanate, bis- (2-isocyanatoethyl) ether, bis (2-isocyanatoethyl) ether of ethylene glycol, o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-L6-diisocyanate, 3,3'-bitolylene-4,4-diisocyanate, i.e.,
CH; GB:
diphenyl ether-4,4'-disocyanate, i.e.,
3, 5, 5-bixylylene-4,4-diisocyanate, i.e.,
l R (R is-CH diphenylmethane-4,4'-diisocyanate, i.e.,
biphenylene diisocyanate, 3,3-dimethoxy-biphenylene- 4,4'-diisocyanate, naphthalene diisocyanates, polymethyl polyphenyl isocyanates, etc. It is also evident that the .sulphur analogues of these compounds may be used and such are included within the spirit of the invention. Thus for example, instead of using the compounds containing two --NCO groups one may use their analogues containing either two -NCS groups or one NCO group and one NCS group. Another point to be made is that it is within the spirit of the invention to utilize the derivatives which yield the same products with compounds containing active hydrogen as do the isocyanates. Particular reference is made to the biscarbamyl chlorides which may be used in place of the diisocyanates. Thus one may use any of the above-designated compounds which contain carbamyl chloride groups I N-d-o1) or their sulphur analogues in place of the isocyanate groups.
Among the preferred compounds are the aliphatic dnsocyanates, for example, those of the type wherein n has a value from 2 to 12. Other preferred compounds are the toluene diisocyanates, xylylene diisocyanates, and diphenylmethane-4,4'-diisocyanate which may also be termed methylene-bis(p-phenylisocyanate).
There has been set forth above a comprehensive disclosure of the preferred types of complementary agents, that is, diamines, diols, diacid chlorides, bischloroformates, diisocyanates, and their equivalents. Although it is preferred to use these agents for optimum results, they are by no means the only compounds which may be used. The invention in its broadest aspect includes the application of many other types of complementary agents which have the ability to form condensation polymers when applied to Wool by the disclosed procedures. V arious examples are thus set forth of other types of compounds which may be used.
Polysulphonamides-f0rmed by conjoint use 0) a diamine and a disulphonyl chloride.A typical example in this category involves applying to the wool an aqueous solution of a diamine, followed by applying to the wool a disulphouyl chloride dissolved in benzene, toluene, or other inert, essentially water-immiscible solvent. Any of the diamines above described may be used in conjunction with such disulphouyl chlorides as benzene-1,3-disulphonyl chloride, biphenyl-4,4'-disuiphonyl chloride, toluene disulphouyl chlorides or aliphatic compounds such as those of the formula wherein n has a value from 2 to 12. Related polymers can be formed by applying these disulphouyl chlorides (as Component B) in conjunction with such compounds as urea, guanidine, thiourea, biuret, dithiobiuret, or the like as Component A.
Polysulphonates-formed by the conjoint use of a dial and a disulphouyl chloride-In a typical example in this area, an aqueous solution of a diol-preferably in the form of its alkali-metal saltis first applied to the Wool, followed by application of a disulphouyl chloride in inert, essentially Water-immiscible solvent. For this purpose one may use any of the diols and disulphouyl chlorides exemplified above. A variant of this procedure is to use the corresponding dithiol in place of the diol, thus to form a polythiolsulphonate.
An alternative to the diacid chlorides is the use of mixed anhydrides of the corresponding dicarboxylic acids with monobasic acids such as trifluoroncetic acid, clihutylphosphoric acid, or the like. Such mixed anhydrides may be employed, for example, as Component B in conjunction with a diamine, diol, or dithiol as Component A to 13 form polyamides, polyesters, or polythiolesters, respectively.
Another plan involves the use of urea, thiourea, biuret, dithiobiuret, guanidine, or the like (as Component A) in conjunction with diacid chlorides as Component B to form polyureas, polythioureas, etc.
Having now described the types of compounds which may be used as Components A and B, we will next explain how these compounds may be selected in various combinations to form the preferred types of polymers in situ on wool fibers and grafted thereto.
EMBODIMENT 1 In this preferred embodiment of the invention, Component A is a diamine and Component B is a diacid chloride. B-y such selection of the complementary agents, polyamides are deposited on the wool fibers and grafted thereto.
Particularly desirable features of this embodiment 1 of the invention are that a high degree of shrinkproofing is attained with a low level of polymer formed on the fiber. Moreover, the process is especially simple because the serial treatments may be carried out at ordinary (room) temperature, the polyamide being formed virtually instantaneously under such conditions.
Numerous variations of the basic procedure of this embodiment will suggest themselves to those skilled in the art in the application of Embodiment l of the invention, without departing from the fundamentals of the invention. Some of these variations are explained below.
If desired, one may prepare a prepolymer containing internal amide units and terminal amine groups. Such prepolymers can be prepared, for example, by reacting in known manner a molar excess of diamine with a diacid chloride. The prepolymer would then be used as Component A while for Component B one would use a diacid chloride. A typical example of procedure in this area would be to use as Component A a prepolymer of the type.
and to use as Component B a diacid chloride (C1CORCOCl) thus to produce a polyamide containing repeating units of the type 0 o 0 -HN-RNH "J-R'iNH-RNH- n"-ti- (In these formulas, R, R, and R represent bivalent organic radicals.)
In the alternative, one may prepare a prepolymer containing internal amide groups and terminal carbonylchloride (-COCl) groups. Such a prepolymer used as Component B in conjunction with a diamine as Component A, would yield a polyamide similar to that shown above.
It is evident from the foregoing description that there is a very wide choice available in the selection of the complementary agents (diamine and diacid chloride) so that generically the pol-yamides deposited on the wool and grafted thereto will contain repeating units of the type wherein R represents a bivalent organic radical; Z represents an oxygen or sulphur atom; R represents a bivalent organic radical or a bond linking the two carbonyl groups; and the two xs taken separately represent two hydrogen atoms or two monovalent organic radicals, or taken together the xs represent a single bivalent organic radical linking the two nitrogen atoms to which they are attached. In the preferred modifications of the invention, Z is oxygen; R and R represent bivalent hydrocarbon radicals or bivalent hydrocarbon radicals interrupted by internal ether (-O--) linkages; and x is hydrogen. In the especially preferred modifications of the invention, the reactants are so chosen that R and R represent bivalent hydrocarbon radicals containing at least two carbon atoms.
Coming under special consideration, particularly because of the exceptionally high shrink resistance obtained with a very small percentage of polyamide, are the use (as Component A) of aliphatic alpha, omega diamines, particularly of the type wherein n has a value from 6 to 10 and the conjoint use (as Component B) of the aliphatic compounds containing two carbonylchloride groups in alpha, omega positions, particularly those of the type wherein n has a value from 4 to 10. Typical examples are the conjoint use of (A) hexamethylene diamine with (B) s'ebacyl chloride or adipyl chloride. p
This Embodiment l of the invention is further demonstrat'ed by the following illustrative examples. I
Standard shrinkage tests.The tests for shrinkage referred to below were conducted in the following way: The wool samples were milled at 1700 r.p.m. for 2. minutes at 40-42 C. in an Accelerotor with 0.5% sodium oleate solution, using a liquorto-wool ratio of 50 to 1. After this washing operation the samples were measured to 'determine their area and. the shrinkage was calculated from the original area. With this washing method, samples of control (untreated) wool gave an area shrinkage of 45%. The Accelerotor is described in the American Dyestuff Reporter, vol. 45, p. 685, Sept. 10, 1956.
Example 1 A. A solution Was prepared containing 8.8 grams of hexamethylene diamine and 0.2 gram of a commercial wetting agent, the isooctylphenyl ether of polyethylene glycol, per 100 ml. water. 7
B. A solution was prepared containing 2 ml. sebacoyl chloride per 100 ml. carbon tetrachloride.
A sample of wool cloth was immersed in solution A for seconds, run through squeeze rolls to remove excess liquid, immersed for 90 seconds in solution B, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air at room temperature. The treated wool had a polyamide resin uptake of 8.3% and on Washing exhibited an area shrinkage of 3%.
The procedure as described immediately above was repeated with variation as to sequence of application of the two solutions and time of residence ineach. The conditions used and the results of these experiments and the first are tabulated below.
TABLE I Order of Residence Resin up- Area Run applying time in each take by shrinka e,
solutions solution, wool. percent seconds percent Example 1-A A sample of the treated wool prepared as described above in Example 1, run 3, and a sample of the untreated wool (control) were subjected to a series of tests to compare the properties of the two materials. The results are tabulated below.
acra ae l Cantilever procedure, AS'lM D-l388-55T.
1 ASTM test method D-l295-53T.
3 ASTM method 13-39-40, 1-inch wide strip.
Sample immersed in 4 M IiOl for 1 hour at 65 C, then weight-loss determined as measure of acid solubility.
5 Sample immersed in 0.1 M NaOI-l for 1 hour at 65 C, then weightloss determined as measure of alkali solubility.
Sample immersed in 2% pcrecetie acid for 24 hours at 25 0, then treated with 0.3% ammonia for 2% hours at 25 C. The weight-loss is then determined as a measure of peracetic acid-N33 solubility.
Example 2 W001 cloth was treated as described in Example 1 with variation in sequence of applying the two solutions and residence time in these solutions. In this case, solution A was as in Example 1; solution B still contained 2 ml. of scbacoyl chloride in 100 ml. solvent but the nature of the solvent was varied as indicated below. The conditions used and results obtained are tabulated as follows:
TABLE II Solvent in Order of Residence Resin Area Run sebacoyl applying time in each uptake shrinkage,
chloride solutions solution, by wool. percent solution seconds percent Example 3 A. A series of solutions were prepared containing varying amounts of hexamethylene diamine in water. A minor proportion-about 0.1%of the isooctylphcnyl other of polyethylene glycol was also added to each.
B. Another series of solutions were prepared containing varying amounts of adipoyl chloride in various solvents.
Wool cloth was treated with the solutions in the following manner. The cloth was immersed in one solution (A or B) for 15 seconds, squeezed to remove excess liquid, immersed for 15 seconds in the next solution (B or A), squeezed to remove excess liquid, rinsed in water, and dried in air.
The conditions employed and the results obtained are tabulated below.
TABLE III First treating solution, Second treating solu- Resin Area Run concentration of active tion, concentration of uptake shrinkingredient, and active in redient, and on wool, t solvent used solvent used (pcr- (percent) ccn t) l-. Hexamethylenc di- Adipoyl chloride, 2 4. 9 8. 8
amine, 8.8 gJlOO ml. mlJlOO ml. carbon water. tetrachloride. 2 .do Adipoyl chloride 2 5.7 4.9
rnl./l00 ml. toluene. 3... Bore-methylene di- Adipoyl chloride, 1 3.6 12. 6
amine, 4.4 g./l00 ml. ml./l00 ml. carbon water. tetrachloride. 4-.--. Adipoyl chloride, 1 Hexemethylene di 2. 5 18.2
mL/lGO ml. carbon amine, 4.4 g./l00 nil. tetrachloride. water. 5--- Hexairethylene di- Adipoyl chloride, 4 7.3 2.0
amine, 17.6 gJlOO nil/10G ml. carbon ml. Water. tetrachloride. =6"..- Adipoyl chloride. 4 Hoxamct-hylene di- 4. 8 2.0
mlJlOO ml. carbon amine, 17.6 gJlOO tetrachloride. ml. water.
16 Example 4 A. A series of solutions were prepared containing either hexaniethylcne diaminc or metaxylylenc diamine dissolved in water. A minor pcrcentageabout 0.1 %--of the isooctylphcnyl ether of polyethylene glycol was also added to each solution.
B. Another series of solutions was prepared containing terephthaloyl chloride or scbacoyl chloride dissolved in carbon tetrachloride or methylene chloride.
Wool cloth was treated with the solutions in the following manner: "he cloth was immersed in one solution (A or B) for a predetermined time, squeezed to remove excess liquid, immersed for a predetermined time in the next solution (B or A), squeezed to remove excess liquid, and dried in air.
The conditions and the results are tabulated below TABLE IV Time of First treating Second treating immer- Resin Area solution. 00113621- solution, conccnsion in uptake shrinkliun tration of active tration of active each on wool, one, ingredient, and ingredient, and solu- (per- (pur solvent used solvent used Lion, ccntl cent) seconds 1 Terephthaloyl Hexamethylenc co 1. G i). 0
chloride 2.5 diamine 17.6 ml. cargJlOO inl non tetrawater. chloride 2 ..d0 do .l 1. 5 4.0 3 -.dodo 3;] 0. ii 7.9 4 Metax'ylylene Sehscoyl chlo- 60 4. 5 15.4
diemine 9 ride 2 mL/lOO mlJlOD ml. ml. carbon water. tetrachloride. 5 Mctarylylene Sermcoyl ehlo- 15 1.4 20. 3
diaznine 4.5 ride 1 inL/IOO BIL/100 ml. ml. carbon water. tetrachloride. 6 Terephthaloyl Met-axylylene 00 2. 2 19.0
chloride diuinino 8 g./ g./lo0 ml. 100 cc. waiter. methylene chloride. Control. 45
EMBODIMENT 2 In this embodiment of the invention, Component A is a diamine and Component B is a bischloroiormate. By such selection of the complementary agents, polyurethanes are deposited on the Wool fibers and grafted thereto.
Particularly desirable features of this Embodiment 2 of the invention are that a high degree of shrinkproofing is attained with a low level of polymer formed on the fiber. vioreover, the process is especially simple because the serial treatments may be carried out at ordinary (room) temperature, the polyurethane being formed virtually instantaneously under such conditions.
Numerous variations of the basic procedure of this embodiment will suggest themselves to those skilled in the art in the application of Embodiment 2 of the invention without departing from the fundamentals of the invention. Some of these variations are explained below.
If desired, one may prepare a prepolymer containing internal urethane units and terminal amino groups. Such prepolymcrs can be prepared, for example, in known manner by reacting a molar excess of diaminc with a bischloroformate. The prcpolyrncr would then be used as Component A while for Component B one would use a bischloroforrnatc. A typical example of procedure in this area would be to use as Component A a prepolymcr of the type HzNRNH- ORO-lNII-RNHJ and to use as Component B a bischloroformate (ClCDGFJOOCCl) thus to produce a polymer containing repeating units of the type R and R" represent bivalent orgroups. Such a prepolymer used as Component B in conjunction with a diamine as Component 'A would yield a polyurethane similar to that shown above.
-It is evident from the foregoing description that there is a very wide choice available in: the selection'of the complementary agents (diamine and bischlorofor'mat'e) so that generically the polyurethanes deposited "on the Wool and grafted thereto will contain repeating units of the type z N II R-N --ZR-ZC I l v t wherein R and R are bivalent organic radicals; Z represents an oxygen or sulphur atom;-and the xs taken separately represent two hydrogen atoms or" two monovalent organic radicals, or, takentogether the xs' represent a single bivalent organic radical which links the two gen atoms to which they are attached. I
in the preferred modifications of the invention, 'Z is oxygen; R and R-'represent bivalent hydrocarbon radicals or bivalent hydrocarbon radicals interrupted by internal ether (-O-) linkages andx is hydrogen. In the especially preferred modifications of'the invention, the reactants are so chosen that R and R represents bivalent hydrocarbon radicals containing at least two carbon atoms. Coming under special condition particularly because of the exceptionally high shrink resistance imparted with a very small proportion of polyurethane, are the use of the following materials as thecomplementary agents.
Component A: Xylylene diamines or aliphatic alpha,
ethylene glycol bischloroforrnate, diethylene glycol bischloroformate, or hexane-1,6-di'ol bis'chloroformate.
This Embodiment 2 of, the invention isfurtherdemo-nstrated by the followingillustrative examples;
The tests for shrinkage referred to in the examples were conducted as described above in the paragraphentitled Standard Shrinkage Test. The control (untreated) wool used in these examples had an area shrinkage of 47 I Example 5 A. A solution was prepared containing 2% ofmetaxylylene diamine in water.
B. A' solution was: prepared containing glycol bischloroformate in benzene.
A sample of wool cloth wasimmersed in solution A for 30 seconds, run through squeeze rolls to remove'excess liquid, immersed for 30'secondsin solution B,.run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air at room temperature; The treated wool had a polyurethane resin uptake of 1.6% and on washing exhibited an area shrinkage of 107%. These 3% ofethylene nitrois results are tabulated below, together with the shrinkage of the untreated wool sample;
Polyurethane resin deposited on Wool, percent Area shrinkage, percent 1 None (control).
Example 6 The procedure of Example 5 was repeated using as solution A 3% ethylene glycol bischloroformate in benzene and as solution B, a 4l% solution of hexamethylene diamine water. I The following results were obtained:
Polyurethane resin dep0s-' ited on wool,
-Area shrinkage, percent percent 1 None (control).
Example 7 The process of ExampleS was repeated using assolution A 4%"heXamethylene'diamine in water and as solution B, a 3% solution of ethylene glycol bischloroformate in carbon tetrachloride. The following results were obtained:
Polyurethane resin depos- Area shrinkited on wool, age, percent I percent None (control) I Example 8 The process of Example 5 was repeated using as solution A- 4% hexamethylene diamine in water and'as solution B; a 3% solution ofdiethylene glycol bisc'hloroforn'rate in carbon tetrachloride. "The following results were obtained:
Polyurethane 1 resin depos- Area shrinkitetl on wool, age, percent percent a Polyurethane resin depos- Area shrinkited on wool, wage, percent percent 1 None (control). 7
Example 10 The process of Example was repeated using as solution A 2% metaxylylene diamine in water and as solution B, a 3% solution of diethylene glycol bischloroformate 1 None (control).
Example 1 I A. A series of solutions were prepared containing 4% hexamethylene diamine (or 4% metaxylylene diamine), 4% Na CO and 0.1% of a commercial wetting agent, the isooctylphenyl ether of polyethylene glycol, in water.
B. Another series of solutions were prepared containing 3% 1,6-hexanediol bischloroformate in benzene or carbon tetrachloride.
Wool cloth was treated with the solutions in the following manner: The cloth was immersed in solution A for a predetermined time, squeezed to remove excess liquid, immersed for a predetermined time in solution B, squeezed to remove excess liquid, rinsed in water, and dried in air.
The conditions used and the results obtained are tabulated below:
(OCN- "-NCO) the type 0 0 -NH-R-NHd-NH-R'-NH-d-NH-R-NH- -NH-R NH-d- (In these formulas, R, R, and R" represent bivalent organic radicals.)
In the alterantive, one may prepare a prepolymer containing internal urea units and terminal isocyanate groups. Such a prepolymer used as Component B in conjunction with a diamine as Component A would yield a polyurea similar to that shown above.
It is evident from the above description that there is a very Wide choice available in the selection of the complementary agents so that generically the polyureas deposited onto the wool and grafted thereto will contain repeating units of the type Z z -NR-N NH-R'-NH lwhere R and R represent bivalent organic radicals; Z represents oxygen or sulphur; and the xs taken separately represent two hydrogen atoms or two monovalent organic radicals, or, taken together they represent a single divalent organic radical linking the two nitrogen atoms to which these are attached. In the preferred modifications of the invention, Z represents oxygen; R and R represent bivalent hydrocarbon radicals or bivalent hydrocarbon radicals interrupted by internal ether (--0-) linkages; and x is by- Time of Resin up- I immersion take on Area Run First treating solution Second treating solution in each wool, shrinkage,
solution, percent percent sec.
1 4% hexamethylene diamine, 4'7 3% 1,6-hexanediol bischlorotormate 0 5.4 0
NazCOa, 0.1% of the isooctylphenyl in benzene. c of polyethylene glycol inwater. 2 do do 2.4 0 3 do 3% li-giexanediol bischlorotormato 30 4.6 1
111 l. 4 4% metnxylyleuedlamiue,4% NazCOz, 3% 1,6-hexanediol bischlorotormate 30 4.4 3.0
0.1% of the isooetylphenyl ether of polyethylene glycol in water. in benzene. 5 (control)--- 47. 0
EMBODIMENT 3 In this embodiment of the invention, Component A is a diamine and Component B is a diisocy-anate. By such selection of the complementary agents, polyureas are deposited on the wool fibers and grafted thereto.
Particularly desirable features of this Embodiment 3 of the invention are that a high degree of shrinkproofing is attained with a low level of polymer formed on the fiber. Moreover, the process is especially simple because the serial treatments are carried out at ordinary (room) temperature, the polyurea being formed virtually instantaneously under such conditions.
Numerous variations of the basic procedure of this embodiment will suggest themselves to those skilled in the art in the application of Embodiment 3 of the invention without departing from the fundamentals of the invention. Some of these variations are explained below.
If desired, one may prepare a prepolymer containing internal urea units and terminal amino groups. Such prepolymers can he prepared, for example, in known manner by reacting a molar excess of diamine with a diisocyanate. The prepolymer would then be used as Component A while for Component B one would use a diisocyanate. A typical example of procedure in this area would be to use as Component A a prepolymer of the type 0 0 H=N--R-NHd-NH-W-NH-d-NH-R-NH, and to use as Component B a diisocyanate drogen. In the especially preferred modifications of the invention, the reactants are so chosen that R and R represent bivalent hydrocarbon radicals containing at least two carbon atoms.
Coming under special consideration, particularly because of the exceptionally high shrink resistance obtained with very small percentages of polyurea, are the use (as Component A) of xylylene diamines or aliphatic alpha, omega diamine-s, particularly those of the type Example 12 A. A solution was prepared containing 4% of hem-- methylene diamine in water.
B. A solution was prepared containing 3% methylenebis(p-phenylisocyanate) in benzene.
A sample of wool cloth was immersed in solution A for a polyurea resin uptake of 1.7% and on washing inthe Accelerotor, exhibited an area shrinkage of 9.8%.
Example 13 I The process of Example 12 was repeated using as solution A 4% hexamethylene diamine in water and as solution B a 3% solution of methylene-bis(p-phenylisocyahate) in carbon tetrachloride. The time of immersion of the cloth in each solution was 60 seconds. 7 p
The treated wool had a polyurea resin uptake of.2.4% and on washing exhibited an area shrinkage of 8.8%
Example 14 v The conditions and the results are tabulated below. N
First treating Second treating Resin Area solution, concen- 1 solution eoncenuptake shrink- Run tration of active tration of active on 1 aga ingredient and ingredient and wool, percent solvent used solvent used percent 1 3% methylene 4% hexarnethy- 2. 2 5. 9
bis(p-phenyllone diamine in isocyanate) in water.
4. 2 4% metaxylylene 3% toluene di- 5. 4 7. 9
diamino in isocyanate in water. ben ene. 3 4% metaxylylene 3% toluene 1i- 5. 20.0
. diamine in lsccyanate in ,r
I water. 4. 4 (control). 47.0
EMBODIMENT 4 In this embodiment of the invention, Component A-is a diol and Component B is a diacid chloride. By such selec tion of the complementary agents, polyesters are deposited on the Wool fibers and grafted thereto.
Numerous variations in the basic procedure of this embodiment will suggest themselves tothose skilled in the art in the application of the invention without departing from the fundamentals of the invention. Some of these variations are explained below.
If desired, one may preparea prepoiymer. containing internal ester units and terminal hydroxy groups. .Such
prepolymers can be prepared, for example, in known HO-R'O ,-R' -OROH and to use as Component B a diacid chloride (ClCORfCOCl) thus to produce a polyester containing repeating units of the type H (In these formulas R, R, and R" represent bivalent organic radicals.)
In the alternative, one may'prepare a prepolymer containing internal esterunits and terminal carbonylchloride groups. Such a prepolymer used as Component B in conjunction with a diol as Component A would yield a polyester similar to that shown above.
It is evident from the above description that there is a very wide choice available in the selection of the complementary agents so thatgenerically the polyesters deposited onto the wool andtgrafted thereto will contain repeating units of the type where R representsa bivalent organic radical; Z represents an oxygen or sulphur atom; and Rf represents'a bivalent organic radical or a bond linking the two carbonyl groups. ln'jthepreferred modifications of the invention, Z is oxygen, R and R represent bivalent hydrocarbon radicals or bivalent 'hydrocarbon radicals interrupted'by internal ether (O--) linkages; "In the especially p're i e'rred modifications of the invention, the reactantsare s'o chosen that R and R represent bivalent hydrocarbon rad icals containing at least two carbon atoms.
This Embodiment 4 of the invention is further dem'on strated by the following illustrative examples.
The tests'for shrinkage referred to in Examples 15 to 18 were conducted as described above in the paragraph entitled Standard Shrinkage Test; The control (untreat-' ed) wool used in the experiments had an area shrinkage Example .15
- A. A solution was preparedcoutaining 4% of the so dium salt of 2,2-bis(parahydroxyphenyl) propane, and 0.1% of a commercialwetting agent, the isooctylphenyl ether ofpolyethylene glycol, in Water. I, L A. I
B. A solution was prepared containing 3% .terephthalyl chloride in methylchloroform. I a v A sarnpieof wool cloth was immersed in solution .A for seconds, run through squeeze rollersito remove excess liquid, immersed for60 seconds in solution B, run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
The treated wool had a polyester resin uptake of 1% and .onwashing exhibited an area shrinkage of 21.7%.
Example 16 The procedure of Example 15 was repeated-using'as solution B 3% sebacyl chloride in carbon tetrachloride. Two runs were made, in one case holdingthe wool 30 seconds in each solution, in the other holding the wool 60 seconds in each solution. The results are tabulated be low:
, Residence, Polyester Area Run time in each resin dep0sshrinkage,
'- solution, see. ited onwool, percent;
A y, percent 1. so i I 1.9 22:6 2 y 60 as 20.8
- Example 17 23 The following results were obtained:
Polyester Area resin deposshrinkage, ited on wool, percent percent Example 18 (l) A sample of wool cloth was immersed for 30 seconds in a solution of 3% sebacyl chloride in carbon tetrachloride. The cloth was run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 5% of the potassium salt of ethylene glycol (KOCH CH OK) in isopropyl alcohol. The cloth was run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
(2) A sample of wool cloth was immersed for 120 secends in a solution containing 5% of the potassium salt of ethylene glycol in isopropyl alcohol. The cloth was run through squeeze rolls to remove excess liquid, then immersed for 120 seconds in a solution of 3% terephthalyl chloride in carbon tetrachloride. The cloth was run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
The results are tabulated below:
Polyester resin Area Run deposited on shrinka e,
Wool, percent percent Example 19 {tree shrinkage, percent Sample Example 15 Examrlc 16, run 1 Example 16. run 2 Example 17 Example 18, run 1 Example 18, run 2 Untreated contr EMBODIMENT In this embodiment of the invention, Component A is a diol and Component B is a bischloroformate. By such selection of the complementary agents, polycarbonates are deposited onto the wool fibers and grafted thereto.
Numerous variations in the basic procedure of this embodiment will suggest themselves to those skilled in the art in the application of the invention without dcparting from the fundamentals of the inventions. Some of these variations are explained below.
If desired, one may prepare a prepolymer containing internal carbonate units and terminal hydroxy groups. Such prepolymers can be prepared, for example, in known manner by reacting a molar excess of diol with a hischloroformate. The prepolymer would then be used as Component A while for Component B one would use a bischloroformate. A typical example in this area would he to use as Component A a prepolymer of the type O H0R-o( ioR'-0i 0-R-0H and to use as Component B a bischloroformate (ClCOOR"COOC1) thus to produce a polycarbonate containing repeating units of the type it OROiiOR'0iiO-ROi JO-R"0C (In these formulas, R, R, and R represent organic radicals.)
In the alternative, one may prepare a prepolymer containing internal carbonate units and terminal OCOCl groups. Such a prepolymer used as Component B in conjunction with a diol as Component A would yield a polycarbonate similar to that shown above.
It is evident from the above description that there is a very wide choice available in the selection of the complementary agents so that generically the polycarbonates deposited onto the wool and grafted thereto will contain repeating units of the type -ZRZ-( 2--Z--R-Z-i 3- wherein Z represents an oxygen or sulphur atom; R and R represent bivalent organic radicals. In the preferred modifications of the invention, Z is oxygen; R and R represent bivalent hydrocarbon radicals or bivalent hydrocarbon radicals interrupted by internal ether (O-) linkages. In the especially preferred modifications of the invention the reactants are so chosen that R and R represent bivalent hydrocarbon radicals containing at least two carbon atoms.
This Embodiment 5 of the invention is further demonstrated by the following illustrative examples.
The tests for shrinkage referred to in the examples were conducted as described above in the paragraph entitled Standard Shrinkage Test. The control (untreated) wool used in the experiment had an area shrinkage of 47%.
Example 20 A sample of wool cloth was immersed for 60 seconds in a 6% solution of the sodium salt of 2,2-bis(3-methyl- 4-hydroxyphenyl) propane in water. The cloth was run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 5 parts by Volume of the bischloroformate of hexane-1,6-diol dissolved in parts by volume of a petroleum solvent containing 96% aromatics, 1% parafiins, and 3% naphthenes, specific gravity 0.87, boiling range 314-352 F. The cloth was run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
The treated wool had a polycarbonate resin uptake of 4.2% and on washing exhibited an area shrinkage of 20%.
Example 21 The procedure of Example 20 was repeated with the exception that the second treatment solution contained 5 parts by volume of the bischloroformate of 2,2-dimethyl-propanediol-l,3 in 100 parts by volume of the petroleum solvent.
The treated wool had a polycarbonate resin uptake of 3.6% and on washing exhibited an area shrinkage of 23.5%.
Example 22 A sample of wool cloth was immersed for 60 seconds in a 6% solution of the sodium salt of 2,2-bis(3-isopropyl- 4-hydroxyphenyl) propane in water. The cloth was run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 5 parts by volume of the bischloroformate of 2,2-dimethyl-propanediol-1,3 in 100 parts by volume of the petroleum solvent described in Example 20. The cloth was run through squeeze rolls to remove excess liquid, rinsed with water, and dried in air.
'and dried in air.
. Example 23 I A sample of wool cloth Was'immersed for 60 seconds 'in a 6% solution of the sodium salt of 2,2-bis(4-hy'droxyphenyl) propanein water. The cl-othwas run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 5 parts by volume of squeeze rolls to remove excess liquid,'rinsed with water,
The treated wool hadfla' polycarbonate'r'esin uptake of 1.3% and on washing exhibitedan area shrinkage INTERPOLYMERS: 1
In accordance with fErnbodirnents 6, .and tl,
polymers are formed in situ on wool fibers and grafted thereto. The in-terpoly ners produced inaccordance with these embodiments contain in their recurring structural elements at least two different units selected from the category of amideyurethane, ,ure'a, .esten and carbonate units, these units being linked togetherthrough carbon atoms. The types of different unitsin the interpolyrner I are determined by the reactants applied to the wool fabric.
In a typical example of the invention, adiarninea diacid chloride, and bischloroformate are applied to the fabric whereby the interpolymer fonned contains both amide and urethane groups, hence is referred to as a copoly (amide-urethane). 'Th formation of this interpolymer may be illustrated as follows: v y
ll. ll Diacid chloride ClC-RG-Cl Bischlorofor'mate ClC-O--R +C'-G1 Oopoly (amideurethan'e) l 1 0 -NH-RNH-il-R- NHRNH+t .lO-R O and 4HC1 (In the above, and following formulae R, R, andfR" represent bivalent organic radicals.)
It will be observed that the above interpolyrner contains the amide j 1 v I T if (CNH) and urethane (NI-I--( JO-) V units linked through the bivalent radical R. These units are underlined in the above formula of the interpolymer.
Other illustrative examples of interpolymers which can be produced on wool fibers in accordance with the invention are given below. The units in pointare underlined.
Copoly (amide-urea):
Copoly (amide-ester):
Copoly (urethaneurea):
the bischloroformate of hexane-l,'6-diol dissolved in 100 10 'parts by'volume ofbenzene. The cloth Was'run through Copoly (carbonate-urethane):
Copoly (ester-carbonate) of U ,79 fQ t1 fQ r --Q% 2* :2
.Otherpossi ble combinations willibe obvious towthose skilled-g in the art," from the above exemplifications. Moreover, the inter-polymers need not contain, only two differentu its, they may contain more than two different units,,.as for, example} terpoly (amide-.urethaneaurea), te rpoly (arnide-urea-ester), terpoly (amide-urethane-,car'- bona te), or other. combination of thevaforcsaid amide, urethane, urea, .ester,,,and carbonate units. ,1 v Generically; the interpolymers produced'in accordance -wtih the invention may-be described as interp'olyrners wherein the: recurring, structures contain at least two different units of the category amide, urethane, urea, ester, and carbonate, thesevunits beingv linked. through carbon atoms; These interpolymers can thus be designated by the formulae i t wherein X, X, X", X, X" representthe'diiferent units (amide, urethane urea, ester, or'carb'onate and Q represents the divalent'radicals 'linking'the units together. It will be evident from the following descriptionthat the values of Q ,(as well as the values 'of X',"X etc.) will depend'on the nature of the reactants chosen fo r jfori nin-g the inter-polymers. As "disclosed below, these reactants may be chosen from a wideivariety of categories so that generically -Q" represents a bivalent organic radical. More specifically, and preferably, the reactants re chosen so that Q're'prese'nt's a bivalent'hydrocarbon radical o'r'a' bivalent hydrocarbon radical interrupted by internal ether ('O') linkages. In an especially referred modification of the invention, the reactants are chosen so that Q represents bivalent hydrocarbon 'radicals containing at least two carbon atoms. Generally, excellent results are obtained with the "interpolymers containing two differentunitsand among these the ones which provide particularly good shrink-proofing effects with low levels of interpolyme-r deposits are those of the types Carbonate:
wherein Z is oxygen or sulphur.
In the practice of this aspect of invention, selection is first made of the appropriate complementary agents herein termed Component A and Component Brequired to produce the desired interpolymer. The interrelationship between the nature of the agents to be used as Components A and B and the type of interpolymer produced are explained in detail below in connection with the different modifications of the invention. However, it is apropos to mention at this point that in general, Component A may be a diamine, a diol, or a mixture of a diamine and a diol. Dependent on the materials selected for Component A, Component B may be a diacid chloride, a bischloroformate, a diisocyanate, or mixtures of these classes of compounds. Since the aim in every case is to produce an interpolymer, the selection of materials must include this proviso: Taken together, Components A and B must include reagents of at least three classes. For example, if Component A includes both a diamine and a diol then Component B may rep resent any one of the classes of diacid chlorides, bischloroformates, or diisocyanates. A typical example in this area would be to use a mixture of a diamine and a diol as Component A and a diacid chloride as Component B, whereby the resin eventually formed would he a copoly (amide-ester). If, however, Component A is a diamine (or a diol) then Component B would need to include at least two reagents of ditferent class, for instance, a diacid chloride and a bischloroformate, a diacid chloride and a diisocyanate, or other combinations of any two or more of the group diacid chlorides, bischloroformates, and diisocyanates. A typical example in this area would be to use a diamine as Component A and a mixture of diacid chloride and diisocyanate as Component B, whereby the resin eventually formed would be a copoly (amide'urea). The guiding factors involved in the selection of materials for Components A and B to produce a desired interpolymer will be evident to those skilled in the art from the above general description and the detailed information set forth hereinafter.
Having selected Components A and B, these agents are applied to wool in the same manner as employed for the polymers previously described.
EMBODIMENT 6 EMBODIllIENT 6.COMPONENT A: DIAMINE Component B 1 l'nterpolymer formed Diacid chloride and bischloroformate- Dist-id chloride and diisocyanate..."
Bischloroformute and diisocyanate.-.
Diacid chloride. bischloroformate.
and diisocyanate.
Copoly (amide-urethane). Copoly (amide-urea).
Copoly (urethane-urea). Terpoly (amldeurethane-urea).
As noted hereinabove, in this Embodiment 6 of the invention, it is necessary that Component B include at least two of the classes of bifunctional compounds. Thus Component B may be a mixture of diacid chloride and bischloroformate or a mixture of diacid chloride and diisocyanate or a mixture of bischloroformate and diisocyanate or a mixture of diacid chloride, bischloroformate and diisocyanate. The relative amounts of these reactants of difierent class may be varied depending on the character of the interpolymer to be produced. For example, in using a mixture of diacid chloride and bischloroformate as Component B, the proportion of amide to urethane groups in the interpolymer may be increased by increasing the proportion of diacid chloride used in the mixture. In many cases it is preferred to employ the reagents in equimolar proportions, thus to provide an interpolymer having an equal number of different units. For example, by using an equimolar mixture of a diacid chloride and a bischloroformate as Component B, the resulting interpolymer will contain substantially equal number of amide and urethane units. However, the use of equimolar mixtures is by no means critical and one may use any mixture containing 10 to (molar basis) of the reagent of one class and the remainder (90 to 10%) of the reagents of the other classes.
Numerous variations in procedure will suggest themselves to those skilled in the art in the application of Embodiment 6 of this invention, without departing from the fundamentals of the invention. Some of these variations are explained below.
If desired, one may prepare a prepolymer containing internal amide (or urethane or urea) units and terminal amino groups. Such prepolymers can be prepared, for example, by reacting in known manner a molar excess of diamine with a diacid chloride, bischloroformate, or diisocyanate. The prepolymer would then be used as Component A while for Component B one would use any one of the reagents (diacid chloride, bischloroformate or diisocyanate) which was not used in preparing the prepolymer. Thus, taking into account the variation in the internal units of the polymer, the following alternatives are among those possible.
COMPONENT A: PREPOLYMER CONTAINING INTERNAL AMIDE UNITS AND TERMINAL AMINO GROUP-3 Component B Inter-polymer formed Bischloroformate Copoly (amide-urethane). Dusocyanate Copo1y(aznidc-urea).
COMPONENT A: PREPOLYMER CONTAINING INTERNAL URETHANE UNITS AND TERMINAL AMINO GROUPS Component B Interpolymer formed Diacid chloride.- Copoly (urethane-amide). Dusocyanate-- Copoly (urethane-urea).
COMPONENT A: PREPOLYMER CONTAINING INTERNAL UREA UNITS AND TERMINAL AMINO GROUPS Component B Interpolymer formed Diacid chloride Copoly (urea-amide) Bischloroformate Copoly (urea-urethane).
A typical example of procedure in this area would be to use as Component A a prepolymer of the type thus to produce an interpolymer containing amide and urethane units of the type A typical exampleof procedurein this area would be to use as Component A a prepolyme-r of the type HzN-R-NH- 0 RO (.7-'-NH-RNH2 and to use as Component 3 a diacid chloride (ClCOR'-'COCI) I thus to produce an interpolymer containing amide and urethane units of the type s w v I natural ste a -etumn nmtniut This principle of using prepolymers could be in other ways as well. Forfexamplega li ol could be canor bischloroformate) to produce alprepolymer con ain.
ing internal ester or carbonate) funitls] terminal and 'tis QmN -R' HQ as Component A one could depositon'the wool fibers acopoly (ester-urea) containingrecurringunits of. the type Another example ofthis system'is'touse as Component B- a compound containing internal carbonate units and terminal'is'ocyanate groups, havingthe'formula 0 a ooR-Noo This compound used in conjunction with H R--NH as Component A vwould yield a copoly (carbonate-urea) containing recurring units of theftype A further example of this system is to employ as Component B a compound containing internal carbonate units j and terminal carbonyl chloride groups, having the formula 0' o "-"o g nu- I '01- R-OOO -R-OG.O- -R O -..Cl, thi compound used, in c njnnct iolIIWith N -R 'L NH as Component AWill 'yield a copoly (carbonate-amide) containing recurring units of the type This Embodiment 6 of the invention is further demonstrated byLthe followingillustrative,examples The shrinkage tests referred to in the'example's were carried outas described above in the-paragraph entitled de'rise d: inknown' manner with an'excessjofdia cid chloride Standard Shrinkage Test. The control (untreated) wool used in these experiments had an area shrinkage of 47%.
The petroleum solvent referred to in the examples was a commercial hydrocarbon mixture having the following characteristics: 96% aromatics, parafiins, 3% naphthenes; specific gravity 0.87; boiling range 314-362 F.
The commercial wetting agentreferred to in the examples was the isooctylphenyl ether of polyethylene glycol.
The toluene diiso'cyanatereferred to in Examples 29 and 30 was toluene 2,4-diisocyanate. I
Example 24.C0p0ly (Amide-Urethane) Component A; Diarnine. y I Component B: Diacidchlorideand vbischloroformate. A sample of wool cloth was immersed for 30 seconds in a solution containing 4g. hexan 1ethylene diamine and ,8; g; Na CQ per ,100 ml. water and50.1%l of a commeni t Wet n a e Th sl t .w r m d from ibis o 1 u;tion, run through squeeze rolls to removeexcess liquid, then immersed for 30 secondsinza solution containinglj ml. sebacyl chloride and 1.5 ml. hexane-1,6- diol 'bischlo1'oormate per. 100 ml, petroleum, solvent. The jcloth was: removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Interpqlymer resin Area shiiukdeposited age,-perc,cnt
on wool, percent ina solution containing 4 g. hexamethylene diarnine and 8. g.- N CO per 100. mlrwater and 0.1% of-a commercial etting-agent. The cloth was removedifrom this solution, runthrough squeeze rolls to remove'excess liquid, then'immersed fo'r30 seconds ina solution containing 1.5 ml. sebacyl chlorideand 1.5 ml. diethyleneglycol v-bischloroformate per IOOmIwbenZene; The cloth 'was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, .and dried in air. I s
The following results were obtained:
Interpolymer I resin Area shrink- I deposited agapercent on wool,
percent Example 26.- Co p 0-ly (Amide-Urethane) Component A: Mixture of diamines. I I I l Component B: Diacid chloride and bischloroformate. A sample ofwool cloth was immersed for 30 seconds in 'asolu'tion containing 2 g. hexamethylene diamine. and
2' mlf meta-xylylene dia'mine per 100 Water and 0.1%
of a commercial wetting agent. f The cloth was'removed from this solution, run'through squeeze rolls toremov'e excess liquid, then immersed for 30 seconds in a'solution 'containi'nglj mlfsebacyl'chloride and 1.5 ml. hexanel,6-diol bischlorof-ormate per 100 mi. petroleum solvent.
The cloth-"was removed from this solution, runthro'u'gh squeeze rolls; to remove and dried in air.
excess liquid," rinsed water,
The following results were obtained:
Interpolymer resin Area shrinkdeposited age, percent on wool, percent Example 27.-Copoly (Amide-Urea) Component A: Diamine.
Component B: Diacid chloride and diisocyanate.
A sample of wool cloth was immersed for 30 seconds in a solution containing 4 g. hexamethylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 g. methylene bis (pphenylisocyanate) per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Interpolymer resin Area shrinkdeposited age, percent on wool, percent Example 28.Cpoly (Amide-Urea) Component A: Diamine.
Component B: Diacid chloride and diisocyanate.
A sample of wool cloth was immersed for 30 seconds in a solution containing 4 g. metaxylylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 g. methylene bis (p-phenylisocyanate) per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Interpolymer resin Area shrinkdeposited age, percent on wool, percent Example 29.Cop0ly (Amide-Urea) Component A: Diamine.
Component B: Diacid chloride and diisocyanate.
A sample of wool cloth was immersed for 30 seconds in a solution containing 4 g. hexamethylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 m1. toluene diisocyanate per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Interpolymer resin deposited on wool, percent Area shrlnkage, percent Example 30.--C0p0ly (Urethane-Urea) Component A: Diamine. Component B: Bischloroformate and diisocyanate. A sample of wool cloth was immersed 'for 30 seconds in a solution containing 4 g. hexamethylene diamine and 8 g. Na CO per ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 ml. toluene diisocyanate and 1.5 ml. hexane- 1,6-diol bischloroformate per 100 ml. benzene. The cloth was'removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Interpolymer resin Area shrinkdeposltcd age, percent on wool percent Example 31.C0p0ly (Urethane-Urea) Component A: Diamine.
Component B: Bischloroformate and diisocyanate.
A sample of wool cloth was immersed for 30 seconds in a solution containing 4 ml. meta-xylylene diamine and 8 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 30 seconds in a solution containing 1.5 g. methylene bis (p-phenylisocyanate) and 1.5 ml. hexane-1,6-diol bischloroformate per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Iuterpolymer resin Area shrinkdeposlted age, percent on wool, percent EMBODIMENT 7 EMBODIMENT 7.-COMPONENT A: DIOL Component B Inter-polymer formed Copoly (ester-carbonate).
Copoly (ester-urethane). Copoly (carbonate-urethane). Terpoly (ester-carbonate'urethane) Diacid chloride and bischloroformate Diacid chloride and diisocyanate Bisehloroformate and diisocyanate- Diacid chloride. blschloroiormate.
and diisocyanate As noted above, the objects of Embodiment 7 of the present invention are attained by using as Component B a mixture of diacide chloride and bischloroformate or a mixture of diacid chloride and diisocyanate or a mixture of bischloroformate and diisocyanate or a mixture of diacid chloride, bischloroformate, and diisocyanate. It is evident that with regard to Component B of this embodiment, the same considerations are applicable as in Embodiment 6 described above.
That is, all the information set forth above in describing the compounds suitable for use as Component B of Embodiment 6, the proportions of these compounds, the conditions of reaction, etc., is equally applicable in the present embodiment.
Numerous variations in procedure will suggest themwives to those skilled in the art in the application of Embodiment 7 of this invention without departing from the fundamentals of the invention as described herein. Some of these variations are explained below.
If desired, one may prepare a prepolymer containing internal ester (or carbonate or urethane) units and terminal hydroxy groups. Such prepolymers can be prepared for example, by reacting in known manner a molar excess of diol with a diacid chloride, bischloroformate, or diisocyanate. The prepolymer would then be used as Component A while for Component B one would use any one of the reagents (diacid chloride, bischloroformate, or diisocyanate) which was not used in preparing the prepolymer. Thus, taking into account the variation in the internal units of the prepolymer, the following alternatives are among those possible.
COMPONENT A: PREPOLYMER CONTAINING INTERNAL ESTER UNITS AND TERMINAL HYDROXY GROUPS Component B Interpolymer formed Bischloroformate Gopoly (ester-carbonate). Diisocyanate Cop-01y (ester-urethane).
COMPONENT A: PREPOLYMER CONTAINING INTERNAL OARBONATE UNITS AND TERMINAL HY- DROXY GROUPS Component B Interpolymer formed Oopoly (carbonate-ester). Oopoly (carbonate-urethane).
Diacid chloride. Diisocyanate COMPONENT AzPBEPOLYMER CONTAINING INTERNAL URETHANE UNITS AND TERMINAL IIY- DROXY GROUPS.
Component B Inter-polymer formed Diacid chloride Bischloroformate Copoly (urethaneester). Copoly (urethane-carbonate) A typical example of this procedure in this area would be to use as Component A a prepolymer of the type:
and to use as Component B, a bischloroformate (CIOCOR"OCOC1) o I! -o.-o1
groups and/ or terminal ll ---0 Gr-Ql groups. This prepolymer used as Component B in conjunction with a diol as CompDnfint A would yield an interpolymer containing both ester and carbonate units.
This Embodiment 7 of the invention is further dem onstrated by the following illustrative examples.
The shrinkage tests referred to in the example were carried out as described above in the paragraph entitled Standard Shrinkage Test. The control (untreated) wool used in these experiments had an area shrinkage of 47%.
The commercial wetting agent referred to in the examples was the isooctylphenyl ether of polyethylene glycol.
The petroleum solvent referred to in the examples was a commercial hydrocarbon mixture having the following characteristics. 96% aromatics, 3% naphthene-s, 1% para ffins; specific gravity 0.87; boiling range 314-362" F.
Example 3Z.C0p0ly (Ester-Carbonate) Component A: Diol.
Component B: Diacid chloride and bischloroformate.
A sample of wool cloth was immersed for 60 seconds in a solution containing 10 g. of 2,2-bis (4-hydroxy-dibromophenyl) propane per 100 ml. of water, with addition of suttficient sodium hydroxide to dissolve the hisphenol, and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 1.5 ml. sebacyl chloride and 1.5 ml. -hexane-1,6.-diol bischloroformate per 10.0 ml. petroleum solvent. The cloth Was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Interpolymer resin Area shrinkdeposited age, percent on Wool, percent 7' Example 33.-C0p0ly (Ester-Carbonate) Component A: Diol.
'Component B: Diacid chloride and bischloroformate.
A sample of wool cloth was immersed for 60 seconds in a solution containing 5 g. of 2,2-bis (3-methy1-4-hydroxyphenyl) propane per 100 ml. of water, with addition of sufficient sodium hydroxide to dissolve the bis- Interpolymer I resin Area shrinkdeposited age, percent on wool,
percent 35 EMBODIMENT s EMBODIMENT S.COMPONENT A: DIAMINE AND DIOL Component B Interpolyrncr formed Diacid chloride. Copoly (amide-ester). Bischlorofonnate- Copoly (urethane-carbonate). Drisocyanate Copoly (uren'urcthanc Diacid chloride and bischloroformate. Diacid chloride and diisoeyanatm- Tet-rspoly (amide-urethane-cstercarlonate) 'letrapcly (amide-uzctlianc-urca) ester).
In formulating Component A for practice of Embodiment 8 of the invention, one may use any of the diamines and diols set forth above. The relative amounts of diamine and diol which comprise Component A may be varied depending on the character of the interpolymer to be produced. For example, in a system using a diacid chloride as Component B, the proportion of amide to ester units in the interpolymer may be increased by increasing the ratio of diamine to diol in Component A.
In many cases it is preferred to employ the diamine and diol in equirnolar proportions, thus to provide an interpolymer having any equal proportion of difierent units. For example, by using an equimolar mixture of diamine and diol as Component A and a bischloroformate as Component B, the resulting interpolymer will contain substantially an equal ratio of carbonate and urethane units. However, the use of equimolar proportions is by no means critical and one can use as Component A any mixture containing to 90% (molar basis) of diamine and the remainder (90 to 10%) diol.
With regard to Component B, one may use a diacid chloride, bischloroformate, diisocyanate, or mixtures of these. The types of interpolymer resulting from different values chosen for Component B are exemplified in the initial paragraph of the description of this embodiment of the invention.
Numerous variations in procedure will suggest themselves to those skilled in the art in the application of Embodiment 8 of this invention, without departing from the fundamentals of the invention as taught herein. Some of these variations are explained below.
Ifi desired, one may use as Component A, a single compound containing terminal hydroxy and amino groups, for example, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 6-aminohexanol, S-aminooctanol, o-aminophenol, m-aminophenol, p-aminophenol, para (4-aminopheny1) phenol, etc. Then, by suitable selection of Component B, various interpolymers may be formed on the Wool. Some of the possible alternatives in this system are given below.
COMPONENT A: COMPOUND CONTAINING TERMINAL AMINO AND TERMINAL HYDROXY GROUPS Component B Intcrpolymer formed Diacid chloride Copoly (esteramide). Bischloroformate.-. Copoly (carbonate-urethane). Diisocyanate Copoly (urethane-urea).
The shrinkage tests referred to in the examples were carried out as described above in the paragraph entitled Standard Shrinkage Test. The control (untreated) wool used in these experiments had an area shrinkage of 47%.
The commercial wetting agent referred to in the examples was the isooctylphenyl ether of polyethylene glycol.
The petroleum solvent referred to in the examples was a commercial hydrocarbon mixture having the following characteristics: 96% aromatics, 3% naphthenes, 1% paralfins; specific gravity 0.87; boiling range 314-362 F.
Examples 34 and 36.C0p0ly (Amide-Ester) Component A: Dlamine and diol. Component B: Diacid chloride.
(34) A solution was prepared containing 2 g. hexamethylene diamine, 5 g. 2,2-bis(3-methyl-4-hydroxyphenyl) propane, 1.5 g. NaOH and 4.0 g. Na CO per 100 ml. water and 0.1% of a commercial wetting agent. A sample of wool cloth was immersed for 60 seconds in the solution, then removed, run through squeeze rolls to remove excess liquid and immersed for 60 seconds in a second solution containing 3 ml. sebacyl chloride per 100 ml. benzene. The cloth was removed from the second solution, run through squeeze rolls to remove excess liquid, rinsed in water and dried in air.
(35) Wool cloth was treated as in Ex. 11 above except that the second solution contained 3 g. terephthalyl chloride per 100 ml. benzene.
The results are tabulated below:
Component A: Diamine and diol.
Component B: Bischloroformate.
A sample of wool cloth was immersed for 60 seconds in a solution containing 2 g. hexamethylene diamine, 5 g. 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1.5 g. NaOH and 4 g. Na 'CO per 100 ml. water and 0.1% of a commercial wetting agent. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, then immersed for 60 seconds in a solution containing 3 ml. hexane-1,6-diol bischloroformate per 100 ml. benzene. The cloth was removed from this solution, run through squeeze rolls to remove excess liquid, rinsed in water, and dried in air.
The following results were obtained:
Interpolyrner resin Area shrinkdepositcd age, percent 021 wool, percent EXAA4PLE 3 7 .C0p0ly (Carbonate- Urethane) solvent. The cloth was removed from the second solunon, run through squeeze rolls to remove excess liquid, rinsed in water and dried in air.
The results are tabulated below:
Interpolymer resin Area shrinkdeposited age, percent on wool,
percent This application is a continuation-in-part of our copending applications listed below:
Serial No. 90,604, filed February 10, 1961, entitled Shrinkproofing of Wool with Polyamides (which in turn is a continuation-impart of Serial No. 22,651, filed April 15, 1960);
Shrinkproofing of Wool with Polycarbonates.
The prior applications referred to above (Ser. No. 22,651, Ser. No. 83,848, Ser. No. 85,438, S'er. No. 88,232, Ser. No. 88,233, and Ser. No. 90,604) have been abandoned.
Although the present invention finds its greatest field of utility in the shrinkproofing of wool and is peculiarly adapted for such use because of a combination of important factory-including the advantages that a high degree of shrink resistance is imparted with a minor amount of polymer, that the shrinkproofing treatment does not significantly impair the hand of the wool, that the treatment does not impair other desirable fiber characteristics such as tensile strength, elasticity, porosity, etc., that the polymer is grafted to the wool molecules so that the shrinkproofing efiect is exceedingly durable and is retained even after long Wear and repeated launderingit is evident that the invention may be extended to other areas. Thus the principles of the invention may be extended to forming polymers in situ on other substrates besides Wool, particularly substrates of a fibrous structure. Typical examples of such materials are animal hides, leather; animal hair; cotton; hemp; jute; ramie; fiax; Wood; paper; synthetic cellulosic fibers such as viscose, cellulose acetate, cellulose acetate-butyrate; casein fibers; polyvinyl alcohol-protein fibers; alginic fibers; glass fibers; asbestos; and organic non-cellulosic fibers such as poly (ethylene glycol terephthalate), polyacryonitrile, polyethylene, polyvinyl chloride, polyvinylidene chloride, etc. Such applications of the teachings of the invention may be for the purposes of obtaining functional or decorative effects such as sizing, finishing, increasing gloss or transparency, increasing water-repellancy, increasing adhesionor bonding-characteristics of the substrates with rubber, polyester resins, etc. It is not claimed that in such extensions of our teachings shrinkp-roofing would be attained nor that graft polymers would be produced. However, it might be expected that graft polymers would be formed with proteinous substrates such as animal hair, animal hides, and the like.
Attention is called to the fact that the present application is one of a series of applications filed by us generally concerned with shrinkproofing wool wherein various types of condensation polymers are formed on and grafted to the wool fibers. Condensation polymers broadly and polyamides specifically are the subjects of the present application; polyurethanes are the subject of Serial No. 99,319, filed March 29, 1961; polyureas are the subject of Serial No. 100,476, filed April 3, 1961;
polyesters are the subject of Serial No. 101,599, filed April 7, 1961; polycarbonates are the subject of Serial No. 102,323, filed April 11, 1961; and interpolymers are the subject of Serial No. 109,229 filed May 10, 1961.
Having thus described the invention, what is claimed is:
1. A process for shrinkproofing wool without significant impairment of its hand, which comprises serially impregnating wool with two solutions, one solution containing a diamine dispersed in Water, the other solution containing a diacid chloride dispersed in an inert, volatile, essentially water-immiscible solvent, the said diamine and diacid chloride reacting to form in situ on the Wool fibers .a resinous polyamide.
2. The process of claim 1 wherein the diamine has the formula wherein n has a value from 6 to 10.
3. The process of claim 1 wherein the diacid chloride has the formula wherein n has a value from 4 to 10.
4. The process of claim 1 wherein the diamine is hexamethylene diamine.
5. The process of claim 1 wherein the diacid chloride is adipoyl chloride.
6. The process of claim '1 wherein the diacid chloride is sebacoyl chloride.
7. A process for shrinkproofing wool without significant impairment of its hand, which comprises serially impregnating wool with two solutions, one containing a diamine in a first solvent, the other containing a diacid chloride in a second solvent, said first and second solvents being substantially mutually immiscible, the said diamine and diacid chloride reacting to form in situ on the Wool fibers a resinous polyamide.
8. A modified wool fiber which exhibits improved shrinkage properties as compared with the unmodified wool fiber comprising wool fiber having a polyamide formed in situ thereon and chemically bonded to the Wool.
9. A modified wool fiber which exhibits improved shrinkage properties as compared with the unmodified wool fiber comprising Wool fiber having a polyamide of a diamine and a dicarboxylic acid formed in situ thereon and chemically bonded to the Wool.
10. The product of claim 9 wherein the polyamide contains recurring structural groups of the formula wherein n has a value from 4 to 10 and m has a value from 6 to 10.
11. A process for treating a fibrous material which comprises serially depositing on said fibrous material in superposed phases in interfacial relationship a pair of complementary, direct-acting, organic, polyamide-forming intermediates, at least one of said phases being liquid, the said intermediates directly reacting under said conditions to form a polyamide in situ on said material.
12. A process for treating a fibrous material which comprises serially applying to said fibrous material a pair of complementary, direct-acting, organic, polyamideforming intermediates in separate liquid phases of limited mutual solubility.
13. A process for treating a fibrous material which comprises serially distributing on the surface of the fibrous elements of said material a pair of complementary, direct-acting, organic, polyamide-forming intermediates in superposed phases of limited mutual solubility, at least one of said phases being liquid, the said intermediates reacting under such conditions to form a polyamide in situ on said fibrous elements.
14. A process for treating wool which comprises serially distributing on the surface of the wool fibers a pair of complementary, direct-acting, organic, polyamideforming intermediates in superposed liquid phases of limited mutual solubility, said intermediates reacting rapidly under said conditions to form a polyamide in situ on said fibrous elements and grafted thereto.
15. A process for treating a fibrous material which comprises serially impregnating a fibrous material with two solutions, one solution containing one member of a pair of complementary, direct-acting, organic, polyamideforming intermediates in a first solvent, the other solution containing the complementary member of said pair of complementary, direct-acting, organic, pol /amideforming intermediates in a second solvent, the first and second solvents being substantially mutually immiscible, the said pair of intermediates reacting rapidly under said conditions to form in situ on the fibers a resinous polyamide.
16. The process of claim 15 wherein the members of said pair of complementary, direct-acting, organic, polyamide-forming intermediates are a diamine and a diacid chloride.
References Cited in the file of this patent UNITED STATES PATENTS 2,522,338 Angus et a1 Sept. 12, 1950 2,526,948 Himel Oct. 24, 1950 2,537,064 Kropa et al Jan. 9, 1951 2,565,259 Nyquist et al. Aug. 21, 1951 2,644,773 Hammer et a1. July 7, 1953 2,684,305 Quinlivan July 20, 1954 2,696,448 Hammer et a1 Dec. 7, 1954 2,862,836 Oosterhout Dec. 2, 1958 2,929,737 Tischbein et al. Mar. 22, 1960

Claims (1)

11. A PROCESS FOR TREATING A FIBROUS MATERIAL WHICH COMPRISES SERIALLY DEPOSITING ON SAID FIBROUS MATERIAL IN SUPERPOSED PHASED IN INTERFACIAL RELATIONSHIP A PAIR OF COMPLEMENTARY, DIRECT-ACTING, ORGANIC, POLYAMIDE-FORMIING INTERMEDIATES, AT LEAST ONE OF SAID PHASED BEING LIQUID, THE SAID INTERMEDIATES DIRECTLY REACTING UNDER SAID CONDITIONS TO FORM A POLYAMIDE IN SITU ON SAID MATERIAL.
US98718A 1960-04-15 1961-03-27 Shrinkproofing wool with polyamides Expired - Lifetime US3078138A (en)

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BE629488D BE629488A (en) 1960-04-15
BE602620D BE602620A (en) 1960-04-15
US98718A US3078138A (en) 1960-04-15 1961-03-27 Shrinkproofing wool with polyamides
GB13127/61A GB913370A (en) 1960-04-15 1961-04-12 Shrink proofing of wool
DE1961L0038742 DE1297575B (en) 1960-04-15 1961-04-14 Process for the production of shrink-resistant wool
FR858833A FR1289709A (en) 1960-04-15 1961-04-14 Process for treating wool with polyesters to make it non-shrink
US198653A US3429650A (en) 1960-04-15 1962-05-29 Including finishing agents in at least one of two mutually immiscible solutions containing coreactants and serially applying said solutions to fibrous materials
GB7837/63A GB994497A (en) 1960-04-15 1963-02-27 Process for treating wool with finishing agents
FR927493A FR83662E (en) 1960-04-15 1963-03-11 Process for treating wool with polyesters to make it non-shrink
DE19631444087 DE1444087A1 (en) 1960-04-15 1963-03-25 Process for treating textiles with finishing agents
CH528763A CH403705A (en) 1960-04-15 1963-04-26 Method for fixing a textile improving agent in a woolen textile
FR995576A FR87014E (en) 1960-04-15 1964-11-19 Process for treating wool with polyesters to make it non-shrink
FR9189A FR87668E (en) 1960-04-15 1965-03-15 Process for treating wool with polyesters to make it non-shrink

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US8823261A 1961-02-09 1961-02-09
US9060461A 1961-02-20 1961-02-20
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3243253A (en) * 1963-11-20 1966-03-29 Lowell A Miller Continuous shrinkproofing of wool textiles
US3305391A (en) * 1963-12-12 1967-02-21 Universal Oil Prod Co Treatment of fibrous materials with certain amino compounds and certain polyacid polyhalides
US3372978A (en) * 1964-05-28 1968-03-12 Agriculture Usa Fibrous material carrying a deposit of a cross-linked polymer
US3383162A (en) * 1964-05-28 1968-05-14 Agriculture Usa Treatment of textile materials
US3390949A (en) * 1963-10-18 1968-07-02 Universal Oil Prod Co Interfacial polymerization on wool using a polyacid polyhalide and a combination of polyamines
US3429650A (en) * 1960-04-15 1969-02-25 Us Agriculture Including finishing agents in at least one of two mutually immiscible solutions containing coreactants and serially applying said solutions to fibrous materials
US3466136A (en) * 1964-03-17 1969-09-09 Us Agriculture Shrinkproofing of wool
US3473956A (en) * 1964-05-12 1969-10-21 Ici Ltd Shaped polyamide coated with the same polyamide modified by polyalkylene oxides
US3484272A (en) * 1965-10-09 1969-12-16 Iws Nominee Co Ltd Process for coating a substrate of keratinous fibers with polyamide
US3537808A (en) * 1961-02-17 1970-11-03 Rohm & Haas Method of depositing polymers on fibrous products
US3537880A (en) * 1967-01-31 1970-11-03 Fmc Corp Heat-bondable fibers
US3958933A (en) * 1970-08-13 1976-06-01 Ciba-Geigy Corporation Process for the manufacture of fast dyeings on synthetic hydrophobic textile material
US3999942A (en) * 1974-08-01 1976-12-28 Cassella Farbwerke Mainkur Aktiengesellschaft N-Acyloyl-N-alkyl-alkylenediamines as dye levelers
US4365966A (en) * 1981-09-15 1982-12-28 The United States Of America As Represented By The Secretary Of Agriculture Process for modifying cellulosic fabrics for improved heat transfer printing
US5573553A (en) * 1992-04-24 1996-11-12 Milliken Research Corporation Method for improving the bleach resistance of dyed textile fiber and product made thereby
JP2013136867A (en) * 2013-02-27 2013-07-11 Akira Umehara Method of subjecting animal hair fiber to shrink-resistant treatment by means of hydrophobic treatment
CN113853461A (en) * 2019-07-24 2021-12-28 东亚纺株式会社 Method for manufacturing shrink-proof animal hair fiber

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US7148269B2 (en) * 2002-03-11 2006-12-12 Trustees Of The University Of Pennsylvania Interfacial polymer incorporation of nanotubes
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2522338A (en) * 1945-02-19 1950-09-12 Eavenson & Levering Company Process for shrink-proofing wool and woolen fabrics
US2526948A (en) * 1945-10-23 1950-10-24 Phillips Petroleum Co Process of treating textiles with half-acid amide derivatives
US2537064A (en) * 1946-08-30 1951-01-09 American Cyanamid Co Treatment of organic textile materials and products thereof
US2565259A (en) * 1947-05-17 1951-08-21 American Cyanamid Co Treatment of protein-containing textile materials and products thereof
US2644773A (en) * 1949-03-17 1953-07-07 Montclair Res Corp Control of wool shrinkage by polyamides
US2684305A (en) * 1951-01-09 1954-07-20 Celastic Corp Process of effecting polymerization
US2696448A (en) * 1949-03-17 1954-12-07 Montclair Res Corp Shrinkproofed wool and method for producing same
US2862836A (en) * 1955-03-14 1958-12-02 Texas Co In situ polyamide coating method
US2929737A (en) * 1953-08-13 1960-03-22 Bayer Ag Coated textiles and method of producing the same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB579340A (en) * 1946-10-02 1946-07-31 James Gordon Cook Use of polyester-amide compositions for coating, impregnating, adhesive or like purposes
BE602620A (en) * 1960-04-15

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2522338A (en) * 1945-02-19 1950-09-12 Eavenson & Levering Company Process for shrink-proofing wool and woolen fabrics
US2526948A (en) * 1945-10-23 1950-10-24 Phillips Petroleum Co Process of treating textiles with half-acid amide derivatives
US2537064A (en) * 1946-08-30 1951-01-09 American Cyanamid Co Treatment of organic textile materials and products thereof
US2565259A (en) * 1947-05-17 1951-08-21 American Cyanamid Co Treatment of protein-containing textile materials and products thereof
US2644773A (en) * 1949-03-17 1953-07-07 Montclair Res Corp Control of wool shrinkage by polyamides
US2696448A (en) * 1949-03-17 1954-12-07 Montclair Res Corp Shrinkproofed wool and method for producing same
US2684305A (en) * 1951-01-09 1954-07-20 Celastic Corp Process of effecting polymerization
US2929737A (en) * 1953-08-13 1960-03-22 Bayer Ag Coated textiles and method of producing the same
US2862836A (en) * 1955-03-14 1958-12-02 Texas Co In situ polyamide coating method

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3429650A (en) * 1960-04-15 1969-02-25 Us Agriculture Including finishing agents in at least one of two mutually immiscible solutions containing coreactants and serially applying said solutions to fibrous materials
US3537808A (en) * 1961-02-17 1970-11-03 Rohm & Haas Method of depositing polymers on fibrous products
US3390949A (en) * 1963-10-18 1968-07-02 Universal Oil Prod Co Interfacial polymerization on wool using a polyacid polyhalide and a combination of polyamines
US3243253A (en) * 1963-11-20 1966-03-29 Lowell A Miller Continuous shrinkproofing of wool textiles
US3305391A (en) * 1963-12-12 1967-02-21 Universal Oil Prod Co Treatment of fibrous materials with certain amino compounds and certain polyacid polyhalides
US3466136A (en) * 1964-03-17 1969-09-09 Us Agriculture Shrinkproofing of wool
US3473956A (en) * 1964-05-12 1969-10-21 Ici Ltd Shaped polyamide coated with the same polyamide modified by polyalkylene oxides
US3406005A (en) * 1964-05-28 1968-10-15 Agriculture Usa Fibrous material having a polyamide bound thereto by a polyfunctional fixative
US3385653A (en) * 1964-05-28 1968-05-28 Agriculture Usa Treatment of textile materials
US3433575A (en) * 1964-05-28 1969-03-18 Us Agriculture Polyurethane associated with fibrous substrate through reaction with polyamide
US3440002A (en) * 1964-05-28 1969-04-22 Us Agriculture Fibrous material having a polyalkylene imine bound thereto by a polyfunctional fixative
US3383162A (en) * 1964-05-28 1968-05-14 Agriculture Usa Treatment of textile materials
US3372978A (en) * 1964-05-28 1968-03-12 Agriculture Usa Fibrous material carrying a deposit of a cross-linked polymer
US3484272A (en) * 1965-10-09 1969-12-16 Iws Nominee Co Ltd Process for coating a substrate of keratinous fibers with polyamide
US3537880A (en) * 1967-01-31 1970-11-03 Fmc Corp Heat-bondable fibers
US3958933A (en) * 1970-08-13 1976-06-01 Ciba-Geigy Corporation Process for the manufacture of fast dyeings on synthetic hydrophobic textile material
US3999942A (en) * 1974-08-01 1976-12-28 Cassella Farbwerke Mainkur Aktiengesellschaft N-Acyloyl-N-alkyl-alkylenediamines as dye levelers
US4365966A (en) * 1981-09-15 1982-12-28 The United States Of America As Represented By The Secretary Of Agriculture Process for modifying cellulosic fabrics for improved heat transfer printing
US5573553A (en) * 1992-04-24 1996-11-12 Milliken Research Corporation Method for improving the bleach resistance of dyed textile fiber and product made thereby
JP2013136867A (en) * 2013-02-27 2013-07-11 Akira Umehara Method of subjecting animal hair fiber to shrink-resistant treatment by means of hydrophobic treatment
CN113853461A (en) * 2019-07-24 2021-12-28 东亚纺株式会社 Method for manufacturing shrink-proof animal hair fiber
CN113853461B (en) * 2019-07-24 2024-05-28 东亚纺株式会社 Method for manufacturing shrink-proof animal hair fiber

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