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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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
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• 0
  • BE BE629488D patent/BE629488A/xx unknown
  • BE BE602620D patent/BE602620A/xx unknown
• 1961
  • 1961-03-27 US US98718A patent/US3078138A/en not_active Expired - Lifetime
  • 1961-04-12 GB GB13127/61A patent/GB913370A/en not_active Expired
• 1962
  • 1962-05-29 US US198653A patent/US3429650A/en not_active Expired - Lifetime
• 1963
  • 1963-02-27 GB GB7837/63A patent/GB994497A/en not_active Expired
  • 1963-03-25 DE DE19631444087 patent/DE1444087A1/de active Pending
  • 1963-04-26 CH CH528763A patent/CH403705A/fr unknown

Patent Citations (9)