US3552911A - Continuous uniform grafting process for keratin fibers - Google Patents

Continuous uniform grafting process for keratin fibers Download PDF

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US3552911A
US3552911A US640155A US3552911DA US3552911A US 3552911 A US3552911 A US 3552911A US 640155 A US640155 A US 640155A US 3552911D A US3552911D A US 3552911DA US 3552911 A US3552911 A US 3552911A
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substrate
catalyst solution
fibers
monomer
catalyst
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Emile E Habib
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Deering Milliken Research Corp
Milliken Research Corp
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    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • 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
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/06—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of animal origin, e.g. wool or silk

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  • EMILE E. HABIB ATTORNEY Jan. 5, 1971 I E. E. HABIB "3,552,911 CONTINUOUS UNIFORM'GRAFTING PROCESS FOR jKERATIN FIBERS v Filed May 22. '19s? 2' Sheets-Shet z INVENTOR.
  • This invention relates to a continuous process for uniformly grafting a substrate containing protein fiber, and more preferably, to a continuous grafting method Wherein the graft occurs within the fibers.
  • a continuous process for uniformly grafting a substrate containing keratin fibers with at least one ethylenically unsaturated compound (hereinafter often referred to as the monomer) is obtained by the process comprising conveying said substrate through a path of travel wherein the substrate is progressively (a) contacted with at least one ethylenically unsaturated compound,
  • the continuous process of this invention may be utilized to deposit polymer either within the fibers or partially within the fibers and partially on the fibers of the substrate.
  • a surface coating is desirable and/ or will not affect the aesthetic properties of the substrate.
  • surface coatings which serve as lubricants, oil or water repellants, or as soil releasing agents, and which do not seriously affect the hand and other properties of the substrate may be desirable.
  • surface coatings often facilitate differential surface dyeing. When such coatings are applied to loose fibers which must be processed into yarns and fabrics, however, the presence of significant amounts of surface polymer should be avoided unless the surface polymer exhibits lubricating properties and does not cause processing problems in the mill such as lapping.
  • the process of this invention provides a method for grafting loose fibers with at least one ethylenically unsaturated compound without forming significant amounts of polymer on the surface of the substrate.
  • FIG. 1 is a fragmentary view of an untreated wool fiber magnified 1800 times.
  • FIG. 2 is a fragmentary view of a wool fiber treated in accordance with this invention magnified 1800 times.
  • FIG. 3 is a fragmentary view of the polymer portion, magnified 665 times, obtained by digestion and removal of the wool portion of a grafted fiber similar to the fiber illustrated in FIG. 2.
  • FIG. 4 is a side view of a preferred apparatus for carrying out the continuous process of this invention.
  • FIG. 5 is an enlarged transverse sectional view of the reaction vessel and baffle in position as the substrate is conveyed through the vessel.
  • the process of this invention provides for the conveyance of the substrate through successive liquid processing baths with control of tension at any given stage or zone of the process, eespecially during the critical entry to and passage through the reaction vessel, preferably without disturbance of the substrate.
  • the process also provides a continuous method for treating substrates in the absence of conditions which tend to impair, damage, or rearrange the fibers or the associated monomer coating thereon such as those which arise from excessive or non-uniform tension and agitation.
  • the process of the invention provides for a more effective action of the liquid solutions on the substrate thereby permitting a greater possible rate of travel of the subtrate through the reaction vessel resulting in greater productive capacity and reduced cost.
  • the grafted keratin fibers obtained will contain generally less than two percent of surface polymer and often less than one percent.
  • FIGS. 4 and 5 a preferred apparatus is shown in FIGS. 4 and 5 comprising a monomer application tank 20 and a rectangular reaction vessel 35 suitably arranged and interconnected so that the substrate to be treated in accordance with the process of the invention is continuously conveyed through the monomer application tank 20, through reaction vessel 35, squeezed of any excess catalyst solution by the action of ,squeeze rolls 58 and 59, and thereafter dried in oven 75.
  • a preferred apparatus is shown in FIGS. 4 and 5 comprising a monomer application tank 20 and a rectangular reaction vessel 35 suitably arranged and interconnected so that the substrate to be treated in accordance with the process of the invention is continuously conveyed through the monomer application tank 20, through reaction vessel 35, squeezed of any excess catalyst solution by the action of ,squeeze rolls 58 and 59, and thereafter dried in oven 75.
  • the substrate may be subjected to washing and/ or neutralization operations prior to drying in oven 75.
  • the monomer application tank 20 contains an immersion roll 22 which is located within the monomer which is continuously maintained at monomer level 21. Also located within monomer tank 20 but above the monomer level 21 is a pair of mating squeeze rolls 24 and 25.
  • the lower squeeze roll 24 is suitably supported and driven by driving means (not shown).
  • the upper squeeze roll 25, generally felt or rubbercovered, is suitably supported and constructed so that it turns with the lower roll and may be adapted to exert and adjustable downward force upon squeeze roll 24. Squeeze rolls 24 and 25 are therefore arranged to move and squeeze the substrate interposed therebetween providing a method for controlling the amount of monomer on the substrate prior to entry into reaction vessel 35.
  • Reaction vessel 35 contains an enclosed rectangular jacket 38 running the length of the tank and beneath the inner bottom surface 37 of the tank for continuously circulating a fluid heating medium whereby the catalyst solution located within vessel is maintained at a preselected temperature.
  • Serpentine coils 40 are located within enclosed jacket 38 and in contact with the heating medium, said coils being connected at one end through supply line 68 to main catalyst supply tank 72 and auxiliary tank 73 by way of heat exchanger 69, pump 70, and control valves 71 and 76.
  • the exit end of serpentine coils 44 is located below the liquid surface near the entrance of the substrate into reaction vessel 35 to provide a constant supply of fresh catalyst at the point of entry of the substrate.
  • Baffie 50 is adjustably mounted above reaction vessel 35 and adapted to be moved up and down between the vertical sides 36 of tank 35 and into the catalyst solution. Means are provided for adjusting the position of baffle 50 and thereby the width of slot between the lower horizontal surface 51 of baffle and the inner upper surface 37 of vessel 35.
  • this control is provided by a plurality of pulleys 80, a roll 81 and wires 82 and 83, said wires being attached to the bafile and responding to the turning of roll 81, as indicated, to either raise or lower the bafile.
  • Roll 81 is provided with means (not shown) for locking in position thereby maintaining the bafile at any desired level within vessel 35.
  • the position of bafile 50 within vessel 35 may be controlled by adjusting a series of screws 84 which are mounted on the top of the vertical sides 36 of vessel 35.
  • the reaction vessel 35 is equipped with a continuous conveyor 55 which is of the endless belt type.
  • Suitable parallel cylindrical guides and driving rolls 56 support and guide the conveyor belt, and upon rotation move conveyor belt 55 in continuous counter-clockwise travel from the right-hand end of the wow of FIG. 4 toward the left-hand end of reaction vessel 35, between squeeze rolls 58 and 59 and then back to the right hand side of the reaction vessel by way of cylindrical guide rolls 56 supported beneath the reaction vessel. Travel of the upper level of the conveyor through the reaction vessel toward the left side of FIG. 4 is referred to herein as forward travel.
  • Some or all of the driving rolls 56 may be connected to a source of power (not shown).
  • Bafile 50 also is equipped with a continuous conveyor belt 54 which is supported and driven by a plurality of parallel cylindrical guide and driving rolls 56 along a clockwise path above and below the bafile as indicated in FIG. 4. That is, upon rotation of the driving rolls, the conveyor belt 54 moves around the baffle in clockwise manner, the lower level of the belt, i.e., the portion of the belt below the bafile and within reaction vessel 35, travelling from the right-hand end to the left-hand end of the reaction vessel between squeeze rolls 58 and 59 and then back over the top of the baffle to the right-hand end of the reaction vessel.
  • the continuous conveyor belt 54 of bafile 50 is aligned with the continuous conveyor belt 55 of the reaction vessel 35 and adapted to move with and in the same direction as belt 55 and thereby engage and carry the substrate between the belts and through reaction vessel 35.
  • the path of travel through reaction vessel 35 is preferably horizontal with a slight upward trend (approximately 10 to 20 degrees) near the end of the tank to allow for gradual removal of the substrate from the reaction vessel without substantial disturbance of the substrate.
  • Cylindrical roll 58 serves a dual function as guide roll and as one of a pair of squeeze rolls when the bafile is lowered into position and pressure is exerted by squeeze roll 58 against squeeze roll 59 of reaction vessel 35.
  • Suitable adjustment mechanism (not shown) is provided for adjusting the squeezing pressure exerted by the roll.
  • the pressure exerted on the substrate by mating squeeze rolls 58 and 59 compresses the substrate thereby extracting catalyst solution entrained in the substrate.
  • Trough 77 is located beneath squeeze rolls 58 and 59 to collect
  • a suitable conveyor 74 conveys the treated substrate from squeeze rolls 58 and 59 and delivers the substrate continuously into drying unit 75 and thereafter to further processing.
  • the substrate may be further purified after the action of squeeze rolls 58 and 59 and prior to drying by continuously washing and neutralizing the substrate.
  • the conveyor belts are constructed of a flexible permeable material such as woven wire screens, open mesh polyester filament fabrics, or solid sheets of flexible materials perforated with a plurality of openingsto permit the passage of liquid therethrough.
  • the permeability of the belt to liquids and air must be substantial in order to permit entrained air to escape and to allow the catalyst solution to completely and uniformly wet-out the substrate,
  • the permeable flexible material of the conveyor belts must be non-reactive to the catalyst solution to any degree that would reduce the efficiency of the catalyst or cause undue degradation of the belts.
  • open mesh wire screens are useful in the process, open mesh polyester filament belts are preferred because of their resistance to degradation and their better flexibility.
  • a multiplicity of slivers 11 are withdrawn from sliver cans and pass through porcelain eye guides 12 and U-shape guides 13 into constricting throat or trumpet member 14 whereby the slivers form a matt-like structure of fibers approximately 11 inches wide.
  • the matt passes down into monomer application tank and under immersion roller 22 situated so that at least a portion of the roller is below monomer level 21 and thereafter passes upwardly and between squeeze rolls 24 and 25 where pressures range from about 500 to about 2000 pounds per linear inch at the nip of the rolls.
  • the pressure exerted by pressure rollers 24 and 25 on substrate 11 determines the amount of monomer which remains on the substrate as the substrate passes out of application tank 20 and into reaction vessel 35. Hence, when higher amounts of monomer on the substrate are desired, less pressure is applied, and, conversely, lower amounts of monomer remain on the substrate when higher pressures are applied.
  • the monomer solution wet pickup should not exceed 60% by weight based on the keratin content of the substrate. Optimum results are obtained when the wet pickup is below 40% by weight.
  • upper squeeze roll 25 should be either a felt covered or rubber covered stainless steel roll. Rubber covered rolls cannot be used in instances where the monomer is soluble in rubber.
  • the excess monomer solution which is extracted by squeeze rolls 24 and 25 is allowed to return to the monomer solution at the bottom of tank 20, Vegetable and other foreign matter which may accumulate in the monomer solution as a result of such reuse is removed by subjecting the monomer to continuous straining or by constructing a sump into monomer application tank 20 and periodically removing solid matter that settles into the sump.
  • the substrate After passing between squeeze rolls 24 and 25, the substrate exits from monomer application tank 20 through constricting throat or trumpet member 15 and is inserted between endless belts 54 and 55 which are adapted as indicated above to move together and to engage and carry the substrate between the belts and through reaction vessel 35.
  • the width of the slot 45 is adjusted as desired to control the ratio of catalyst solutions to substrate.
  • Belt 54 travels continuously on upper surface of slot 45, and engages the upper side of the substrate during passage of the substrate through the reaction vessel.
  • Lower belt 55 engages the under side of the substrate and supports it during its passage through the vessel. In this manner the substrate is firmly engaged between the two belts and conveyed through slot 45 while constrained in this position to minimize movement and interaction between the substrate and the catalyst solution.
  • the belts carrying the substrate move downwardly (preferably vertically) into the reaction vessel containing the catalyst solution and with a minimum of tension on the substrate in order to allow the substrate to be wet by the catalyst solution.
  • the substrate feeds into the mouth formed by the presence of guide rolls 45 and 52 (adjustable) on either side of the belts and the pressure exerted on the substrate at this point by the belts is adjusted to grasp and carry the substrate through the catalyst solution.
  • the almost vertical entry of the substrate into the catalyst solution has been found to minimize air entrainment.
  • the use of permeable belts having sufficient porosity to allow the catalyst solution to enter the sandwiched substrate also promotes and facilitates the removal of air without disrupting the arrangement of the substrate between the belts.
  • the substrate after having been wetted with the catalyst and freed of entrained air, is conveyed through the reaction vessel and maintained at a temperature within the range of from about 50 to about 100 C. for a period of time sufllcient to effect grafting of the monomer into the keratin fibers of the substrate but insufficient to effect the formation and deposition of significant amounts of polymers on the surface of the substrate or in the catalyst solution.
  • the speed of the belts is adjusted to maintain the substrate within the solution for the desired time. Generally, the substrate is maintained within the catalyst solution for up to about 30 minutes. The time of contact will depend on the monomer, and the temperature, strength and nature of the catalyst solution.
  • the substrate When lower temperatures are utilized, the substrate may be maintained in contact with the solution for longer periods of time without forming significant amounts of polymer on the surface of the fibers of the substrate or the catalyst solution. At higher temperatures, the contact time may be proportionately reduced. In a preferred embodiment, the substrate is maintained in contact with the catalyst solution for a. period of from about 8 to about 1'2. minutes, said catalyst solution being within the temperature range of from about 65 to about C.
  • the substrate which is coated with the ethylenically unsaturated compound be conveyed through the catalyst solution in a manner which discourages significant amounts of agitation or movement of the catalyst solution relative to the substrate.
  • Such disturbances should be avoided if the ethylenically unsaturated compound is to be maintained within the fibers and significant amounts of polymer in the catalyst solution and on the surface of the fibers are to be avoided.
  • the process of this invention when the process of this invention is repeated with the exception that themonomer coated substrate is conveyed through the catalyst solution under conditions which increase the movement of the cataly solution in the vicinity of the substrate, the amount of monomer in the catalyst solution is increased, and the conversion of monomer to polymer within the fiber is significantly reduced, indicating that the movement of the catalyst solution washes or extracts monomer from the surface of the substrate prior to effecting grafting of the monomer within the fibers.
  • the catalyst solution in contact with conveyor belts 54 and 55 and substrate 11 is carried along with the substrate to the end of the reaction vessel and removed.
  • Fresh catalyst solution is continuously added to the reaction vessel near the point of entry of the substrate and below the surface of the catalyst solution at the entrance to the reaction vessel to inhibit dissolving air into the catalyst and to minimize agitation of the catalyst solution within vessel 35.
  • the apparatus is designed to provide a supply of fresh, unused catalyst solution at the entrance to slot 45 of reaction vessel 35, the used solution being carried along with the substrate and discarded at the exit end of the apparatus.
  • the width of slot 45 should be sufiiciently narrow to enable all or substantially all of the catalyst solution to be carried along with the moving substrate and belts and discarded.
  • the slot may be desgined with a slight downgrade so that the catalyst solution will flow naturally from the entrance to the exit, and thereby limit or eliminate the possibility of an occasional accumulation of monomer in the slot for a period of time where such monomer may react to form polymer deposits on the fiber surface.
  • the sandwiched substrate is remove-d from the slot of the reaction vessel and subjected to a squeezing action by squeeze rolls 58 and 59 immediately after emerging from reaction vessel 35.
  • the substrate is then removed from the co-acting conveyor belts and conveyed into heated oven 75 to be dried.
  • the substrate may be washed in water prior to entering heated oven 75.
  • the substrate may be further treated with an aqueous or alcoholic alkaline solution capable of neutralizing the acid within the substrate. The desirability of these added treatments will be determined by the nature of any additional processing such as, for example, dyeing which may be acid sensitive.
  • the mechanism by which the substrate is coated within monomer application tank 20 may be varied so long as the mechanism chosen does not disturb excessively the orientation of the fibers within the substrate, and the amount and uniformity of application of monomer to the substrate can be controlled. It is also possible to design an apparatus to provide for a series of continuous or co-acting endless belts so that the substrate is conveyed through each step of the process between said co-acting belts.
  • the substrate may be conveyed through the entire process between one continuous pair of co-acting belts, although this latter method is not recommended since the monomer can be carried by the belt and, unless removed, will either contaminate the catalyst solution or render the belt impermeable to the liquid catalyst solution.
  • the substrate treated in accordance with this invention may be in the form of a fabric or yarn although the process is particularly useful for treating keratin fibers in a substantially loose mass such as top, roving, sliver, mats and the like.
  • the mats can have parallel or random directional distribution of fibers.
  • loose fibers as utilized herein includes fibers having a configurational degree of freedom usually found prior to processing into yarns or fabrics either woven, non-woven, or knitted.
  • the loose fibers for example, wool top
  • the loose fibers may be given a slight twist to increase the strength of the top sufficiently to enable the top to be treated in the con tinuous manner described. It is preferable that loose fibers are conveyed into the catalyst solutionin a parallel or substantially parallel configuration since such orientation facilitates wetting of the fibers with the catalyst solution and releasing of entrained air.
  • the monomer is applied preferably in solution so that small amounts of monomer are deposited on the fabric. Alternatively, the monomer may be applied by spraying or by padding on small amounts of monomer to each side of the fabric with a transfer roll.
  • the monomers useful in the process of this invention are preferably ethylenically unsaturated compounds, that is, compounds containing the group
  • ethylenically unsaturated compounds include vinyl halides and esters such as vinyl chloride, vinyl bromide, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate; vinyl ethers such as methyl vinyl esther, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; vinyl ketones such as ethyl vinyl ketone and methyl vinyl ketone; vinyl aromatic compounds such as styrene, p-bromo styrene and pentachloro styrene; vinyl naphthalenes, such as 4- chloro-l-vinyl naphthalene and 6-chloro-2-naphthalene; nitriles such as acrylonitrile and methacrylonitrile; and
  • acrylic u-alkyl acrylic and u-halo acrylic esters of saturated monohydric alcohols such as the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, octyl, decyl, dodecyl, and pentadecyl esters of acrylic, methacrylic, ethacrylic, chloroacrylic, itaconic, maleic, crotonic, and fumaric acids; these latter acids and the anhydrides thereof; the phenyl, benzyl, and phenethyl esters of the aforementioned esters; acrylamides and substituted acrylamides such as N-(p-anisyl) methacrylamide, N-phenyl methacrylamide, N-ethyl methacrylamide, N- methyl methacrylamide, N-(p-tolyl) methacrylamide, N,N-dimethyl acrylamide, N,N-
  • Mixtures of the above ethylenically unsaturated compounds may also be used in the process of this invention.
  • examples of such mixtures include styrene/butylacrylate (/15), styrene/dichlorostyrene (SO/20), methyl methacrylate/ethyl acrylate 80/ 20), butyl methyacrylate/ ethyl methacrylate (60/40 and 30/70), butyl methacrylate/lauryl methacrylate (80/20), and methyl meth acrylate/methyl acrylate (70/30).
  • alkyl acrylates are utilized as the ethylenically unsaturated compounds in the process of this invention, and alkyl acrylates having from about 1 to about 12 carbon atoms in the alkyl group are particularly preferred.
  • the ethylenically unsaturated compound may be applied to the substrate as monomer or dissolved in a solvent although 100% monomer is preferred.
  • solvents which have been found useful include: hydrocarbons such as toluene, xylene, benzene and cyclohexane;
  • esters such as n-amyl acetate; ketones such as methyl isobutyl ketone and ethyl butyl ketone; and amides such as N,N-dimethyl acetamide.
  • monomer solvents which are not soluble in the catalyst solution. In this way, contamination of the catalyst solution by solvent and monomer is minimized.
  • the solvent may be removed from the substrate prior to entering the reaction vessel or may be carried through to the end of the process and removed in the drying oven. However, if the monomer solvent is soluble in the aqueous catalyst solution, it is preferably removed from the top prior to entering the catalyst solution.
  • the catalysts which have been found useful in the process of this invention include azo catalysts such as azobisisobutyronitrile and free radical catalysts such as ammonium peroxydisulfate.
  • the catalyst system most generally used is a redox catalyst system composed of a reducing agent and an oxidizing agent. The interaction of the reducing agent and the oxidizing agent provides free radicals which effect grafting of the monomer into the keratin fibers of the substrate.
  • the reducing agent may be an iron compound, such as the ferrous salts including the sulfates, acetates, phosphates, ethylenediamine tetraacetates and the'like; metallic formaldehyde sulfoxylates, such as zinc formaldehyde sulfoxylate; alkali-metal sulfoxylates, such as sodium formaldehyde sulfoxylate; alkali-metal sulfites, such as sodium and potassium bisulfite, sulfite, metabisulfite or hydrosulfite; mercaptan acids, such as thioglycollic acid and its water-soluble salts, such as sodium, potassium or ammonium thioglycollate; mercaptans, such as hydrogen sulfide and sodium or potassium hydrosulfide; alkyl mercaptans, such as butyl or ethyl mercaptans and mercaptan glycols, such as beta
  • a salt of hydrazine may be used as the reducing agent, the acid moiety of the salt being derived from any acid such as hydrochloric, hydrobromic, sulfuric, sulfurous, phosphoric, benzoic, acetic and the like.
  • Suitable oxidizing agents initiators for use in the redox catalyst system include inorganic peroxides, e.g. hydrogen peroxide, barium peroxide, magnesium peroxide, etc., and the various organic peroxy catalysts, illustrative examples of which are the dialkyl peroxides, e.g., diethyl peroxide, dipropyl peroxide, dilauryl peroxide, dioleyl peroxide, distearyl peroxide di-(tert-butyl) peroxide and di-(tert-amyl) peroxide, such peroxides often being designated as ethyl, propyl, lauryl, oleyl, stearyl, tert-butyl, tertamyl peroxides; the alkyl hydrogen peroxides, e.g., tertbutyl hydrogen peroxide (tert-butyl hydroperoxide), etc.; symmetrical diacyl peroxides
  • organic peroxide initiators that can be employed are the following: tetralin hydroperoxide, tert-butyl diperphthalate, cumene hydroperoxide, tertbutyl perbenzoate, 2,4-dichlorobenzoyl peroxide, urea peroxide, caprylyl peroxide, p-chlorobenzoyl peroxide, 2,2-
  • oxidizing agents particularly the salts of inorganic peracids
  • ferric salts can be used as oxidizing agents and form a redox catalyst system with hydrogen peroxide, in which case the peroxide functions as a reducing agent.
  • the polymerization catalyst generally is dissolved in water and the substrate is conveyed through the catalyst solution maintained at a temperature of from about 50 to about 100 C. A temperature in excess of about 90 C., generally is not preferred when a redox catalyst system is used since some of the components may degrade at these elevated temperatures.
  • the water used to prepare the catalyst solution should be filtered through carbon to remove organic material, and in some instances, depending upon impurities in the water, deionized to remove interfering metals such as lead which, in very small amounts, poison the catalyst.
  • the substrate remains in contact with the catalyst solution for a period of up to 30 minutes depending upon such conditions as the temperature and the pH of the catalyst solution. Shorter reaction times are desirable where higher reaction temperatures are em ployed. Conversely, where the temperature of the catalyst solution is maintained at a temperature of from 50 to 60 C., the rate of polymerization is slower and the reaction time greater. Preferably, a reaction temperature of from about 65 to about C. for a period of from about 8 to 12 minutes is utilized.
  • Redox catalyst systems appear to perform better when the catalyst solution is maintained highly acidic. For example, a catalyst solution comprising ferric nitrate, hydrogen peroxide, and sulfuric acid provides maximum conversion at a pH of less than about 1.7.
  • a supplementary swelling agent for the keratin fibers is added to the catalyst solution.
  • swelling agents include mineral acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid, formic acid, and trichloroacetic acid; lithium salts such as lithium chloride and lithium bromide; amides such as formamide, acetamide and N,N'-dimethyl formamide; and other swelling agents such as urea and thiourea.
  • wetting agents also serves to enhance the penetration of the reactants into the keratin fibers.
  • surface active agents which are useful as wetting agents in the catalyst solution include long-chain alkyl sodium sulfates or sulphonates, sodium alkyl benzene sulphonates, organic ammonium salts such as Arquad 16-50, a hexadecyl trimethyl ammonium chloride, and non-ionic surface active agents such as mannitol laurate, sorbitol laurate, and ethylene oxide reaction products of fatty acids, fatty alcohols, polyhydric alcohols and aromatic alcohols such as surfonic N-95, a non-ionic wetting agent obtained by condensing nonyl phenol With ethylene oxide in the molar ratio of 129.5.
  • One of the advantages of the process and apparatus of this invention is the ability to carry out the desired grafting reaction in a continuous manner without using large amounts of catalyst solution.
  • the weight ratio of catalyst solution to substrate is controlled easily in the apparatus described previously by varying the position of baffle 50 and thereby regulating the width of the slot through which the conveyor and substrate pass.
  • the weight ratio of catalyst solution to substrate is generally less than 20: 1. In some instances, however, higher weight ratios may be utilized. The desirability of using higher ratios depends on the cost of the catalyst and the rate of polymerization of the monomer in the catalyst solution.
  • the reactivity of the monomer in the catalyst solution is low (e.g., lauryl methacrylate in a redox solution)
  • the presence of monomer in the solution can be tolerated for longer periods and the solution need not be discarded continuously or as often.
  • higher weight ratios are feasible.
  • catalyst solutions containing the more reactive monomers cannot remain in Contact with the substrate, for any appreciable length of time, since the polymers formed in solution will be deposited on the substrate and equipment. Although high weight ratios can be used in such situations, they are not economical because the solution must be discarded either continuously or after using for a shorter period of time.
  • this invention provides a method for a successful continuous grafting operation with extremely low ratios of less than :1. Preferably, ratios of about 5:1 or less are utilized. The use of such low Weight ratios not only simplifies apparatus requirements, but also provides an economical process without the necessity of reclaiming the used catalyst solution.
  • the process of this invention has been described generally as a grafting process since the monomer, catalyst system, and reaction conditions are those generally used in grafting reactions. Furthermore, the product of the process behaves like a grafted product or one in which the polymer is attached by strong covalent bonds. Evidence for such a conclusion is supplied by the failure of solvent to extract significant amounts of the polymers from the treated substrates obtained in the preferred embodiment.
  • the process is believed to be a grafting process, the invention is not to be limited thereto since polymers deposited within the fibers may or may not be reacted with the wool.
  • EXAMPLE 1 W001 top consisting of sixteen slivers of about 500 grains per yard each of 64s grade wool and containing about 11% moisture is fed into monomer application tank of the continuous grafting apparatus described in FIGS. 4 and 5.
  • the monomer utilized in this example is butyl methacrylate.
  • the amount of butyl methacrylate on the wool top after passing through squeeze rolls (felt covered) and 24 at a pad pressure about 800 pounds per linear inch at the nip is about 33%.
  • the butyl methacrylate coated top is then fed into the reaction vessel between open mesh polyester filament belts 54 and 55.
  • the catalyst solution utilized in this example is prepared by dissolving 22 parts of reagent grade ferric nitrate nonahydrate, 78 parts of hydrogen peroxide (commercial grade containing 50% water), 800 parts of concentrated sulfuric acid, and parts of surfonic N-95 in about 99,000 parts of deionized water.
  • the catalyst solution is pumped into reaction vessel 35 at a flow rate of about 4.5 to 5.3 pounds per minute to keep an approximate constant level of catalyst, and the temperature of the solution is maintained at approximately 72 73 C.
  • the position of the baffie within the curing tank is adjusted to provide a slot width of about of an inch. In this manner, the weight ratio of catalyst solution to Wool top is about 5:1 as the top travels through the slot 45 at a rate 12 of 26.8 inches per minute for a reaction time of 10 min utes.
  • the top After emerging from the slot, the top is passed through squeeze rolls 58 and 59, washed twice with cold water, and dried on a Fleissner drier at 65 C. at the rate of two yards per minute. Measurement of the increase in weight due to the polymer graft indicates essentially con version.
  • Example 2 The procedure of Example 1 is repeated except that the conveyor belts travel through reaction vessel 35 at the rate of 33.5 inches per minute thereby reducing the reaction time to 8 minutes. A 94% yield of the polymer Within the fibers is obtained, and less than 2% of surface polymer is detected.
  • Example 3 The procedure of Example 1 is repeated except that the wool top contains 12.6% water, the catalyst flow rate into the curing tank is 5.6 pounds per minute and the temperature of the catalyst solution is about 7274 C. In this manner,-228 pounds of wool top is treated in about five hours. Monomer conversion is approximately 100%.
  • the treated top is neutralized in a continuous manner by conveying the tops through an aqueous alkaline solution contained in a vessel similar to reaction vessel 35 at the rate of 1.25 yards per minute for a total treatment time of 6.8 minutes.
  • the neutralized samples are then washed twice with water and dried.
  • the average pH of the neutralized wool is found to be 7.0.
  • the neutralized wool top is oiled with an emulsion containing 1.8% of worsted, mineral oil based spinning oil and dried at C.
  • the oiled wool top (containing 1.25% by weight of oil) is then subjected to two gilling operations while maintaining the relative humidity of the atmosphere at about 65%.
  • the product is packaged for shipping and subsequent finishing treatments.
  • results demonstrate (1) the increased fiber diameter obtained as a result of the process of this invention, and (2) the uniformity of the grafting as indicated by the absence of any significant change in the coefiicient of variation of average diameter when the top has been treated in accordance with this invention.
  • FIG. 1 represents an untreated wool fiber whereas FIG. 2 represents a typical fiber from treated wool top as obtained in this example.
  • FIG. 2 represents a typical fiber from treated wool top as obtained in this example.
  • the scales of the fiber of FIG. 2 are expanded and open whereas the scales of the fiber of FIG. '1 are tightly bound to the fiber.
  • Such results, and the absence of significant amounts of surface polymer indicate that as the fiber swells upon entering the catalyst solution, the ethylenically unsaturated compound is absorbed within the fiber, and, upon completion of the grafting reaction, maintains the scales in their expanded position.
  • the scales of the fiber are not coated or filled-in with any surface polymer.
  • EXAMPLE 4 W001 card sliver containing 600 grains per yard (obtained by combining two 300 grain slivers) is treated in accordance with the procedure of Example 1 except that the pad pressure exerted by squeeze rolls 24 and 25 is about 900 pounds per linear inch at the nip, the catalyst solution fiow rate is about 6 pounds per minute, and the temperature of the catalyst solution is maintained between about 72 and 74 C. After drying and conditioning overnight, measurement of the increase in weight due to the polymer add-on indicates essentially 100% monomer conversion.
  • Example 5 The procedure of Example 1 is repeated except that the wool tops are -60s grade consisting of 32 slivers of 250 grains per yard each, the ethylenically unsaturated compound is methyl methacrylate, the Wool top contains 11.4% water, the pad pressure exerted by squeeze rolls 24 and 25 is about 700 pounds per linear inch at the nip, and the catalyst fiow rate is about 5.2 pounds per minute.
  • the treated tops are washed twice in cold water, dried at 50 C., and conditioned for three days. At the end of the conditioning period, the increase in the weight of the top resulting from the above treatment represents essentially 100% conversion of methyl methacrylate to the desired graft polymer.
  • Example 7 The procedure of Example 1 is repeated except that the catalyst solution comprises an aqueous solution containing 0.138% hydrazine sulfate, 0.078% hydrogen peroxide, 0.8% sulfuric acid and 0.03% surfonic N-95, and the catalyst solution is maintained at about 85 C.
  • Example 8 The procedure of Example 1 is repeated except that the catalyst solution is maintained at 70 C. and comprises an aqueous solution containing 0.31% potassium peroxydisulfate, 0.0075% sodium hydrogen sulfite, and 0.8% sulfuric acid, and the contact time is 30 minutes.
  • Example 9 The procedure of Example 8 is repeated except that the catalyst solution is an aqueous solution containing 2% potassium peroxydisulfate and 0.8% sulfuric acid, and the ratio of catalyst solution to wool top is about 20: 1.
  • Example 10 The procedure of Example 1 is repeated except that the catalyst solution is maintained at C. and is an aqueous solution containing 1% ammonium peroxydisulfate and 1% dimethyl formamide, the ratio of catalyst solution to top is 10:1, and the contact time is 12 minutes.
  • EXAMPLE 12 A polyester (Dacron)-wool blend fabric (55:45) is padded with a 50% solution of butyl methacrylate in toluene on both sides of the fabric. The toluene is removed by heating the coated fabric, and the amount of butyl methacrylate remaining on the fabric is found to be about 10%.
  • the catalyst solution utilized in this example is prepared by dissolving 22 parts of reagent grade ferric nitrate nonahydrate, 78 parts of hydrogen peroxide containing 50% water, 800 parts of concentrated sulfuric acid, and 120 parts of surfonic N- in about 99,000 parts of deionized Water.
  • the catalyst solution is pumped into reaction vessel 35 at a flow rate of about 5 pounds per minute, and the temperature of the solution is maintained at about 70 C.
  • the fabric travels through slot 45 at a rate of 26.8 inches per minute for a reaction time of 10 minutes. After emerging from the slot the fabric is passed through squeeze rolls 58 and 59, Washed twice with cold water and dried at 65 C.
  • the grafting of ethylenically unsaturated compounds to substrates containing keratin fibers by the process of this invention results in a product wherein the polymer is deposited Within the fibers as opposed to deposition on the surface of the fibers.
  • Treated fibers obtained in this manner are characterized by increased diameter and volume Without any significant loss of the desirable properties of the keratin fibers.
  • the treated fibers have the same utility as the untreated fibers.
  • Fabrics having improved hand are provided by treating fibers in accordance with the process of this invention and thereafter processing the treated fibers into fabrics. Moreover, the absence of significant amounts of surface polymer on the fibers treated in accordance with this invention appreciably improves weaving and finishing efficiency. The shape and crease retention of fabrics prepared from such treated fibers is improved.
  • a continuous process for uniformly grafting a substrate containing keratinous fibers with at least one ethyleni-cally unsaturated compound without forming significant amounts of polymer on the surface of the substrate comprising progressively conveying said substrate through a path of travel wherein (a) the substrate is contacted with at least one ethylenically unsaturated liquid to provide a pickup of up to about 60% by'weight,
  • the substrate is passed into a vessel having an entrance end and an opposite end and containing a pair of endless moving belts of a flexible and permeable material,
  • a continuous process for uniformly grafting a substrate containing keratinous fibers with at least one ethylenically unsaturated compound Without forming significant amounts of polymer on the surface of the substrate comprising progressively conveying said substrate through a path of travel wherein (a) the substrate is contacted with at least one ethylenically unsaturated liquid compound to provide a pickup of up to about 60% by weight,
  • the substrate is passed into a vessel having an entrance end and an opposite end and containing a pair of endless moving belts of a flexible and permeable material,
  • an aqueous acidic acid solution containing a free radical or azo polymerization catalyst is continuously supplied near the entrance end of the vessel to maintain a ratio of catalyst to substrate in the vessel
  • the substrate is transported between the moving belts through the vessel and the catalyst solution in a substantially straight path at a solution temperature of from about 50 to about 100 C. for a period of from about 5 to 30 minutes, the movement of the belts and the substrate causing the transfer of the catalyst solution from the entrance end to the opposite end of the vessel without significant amounts of agitation of the catalyst solution,
  • the substrate is separated from any entrained catalyst and unreacted monomers, and- (g) the substrate is dried.
  • the substrate comprises loose keratinous fibers- 7.
  • the loose keratinous fibers are wool fibers in the form of wool top.
  • ethylenically unsaturated compound is an alkyl acrylate having from about 1 to 12 carbon atoms in the alkyl group.
  • aqueous solution of (c) comprises a solution of ferric nitrate, hydrogen peroxide and sulfuric acid.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US640155A 1967-05-22 1967-05-22 Continuous uniform grafting process for keratin fibers Expired - Lifetime US3552911A (en)

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BE (1) BE715323A (enrdf_load_stackoverflow)
CH (1) CH730768D (enrdf_load_stackoverflow)
DE (1) DE1769416A1 (enrdf_load_stackoverflow)
ES (2) ES354137A1 (enrdf_load_stackoverflow)
FR (1) FR1566928A (enrdf_load_stackoverflow)
GB (1) GB1175795A (enrdf_load_stackoverflow)
LU (1) LU56128A1 (enrdf_load_stackoverflow)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5952409A (en) * 1996-01-31 1999-09-14 3M Innovative Properties Company Compositions and methods for imparting stain resistance and stain resistant articles
US20140094578A1 (en) * 2012-09-28 2014-04-03 Gc Corporation Polymerizable compositions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634022A (en) * 1969-05-29 1972-01-11 Colgate Palmolive Co Form-setting keratin substrates by a chemical treatment involving a vinyl monomer
US3676550A (en) * 1969-05-29 1972-07-11 Colgate Palmolive Co Modification of reduced keratinous substrates with a vinyl monomer

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5952409A (en) * 1996-01-31 1999-09-14 3M Innovative Properties Company Compositions and methods for imparting stain resistance and stain resistant articles
US20140094578A1 (en) * 2012-09-28 2014-04-03 Gc Corporation Polymerizable compositions
KR20140042749A (ko) * 2012-09-28 2014-04-07 가부시키가이샤 지씨 중합성 조성물
US9079994B2 (en) * 2012-09-28 2015-07-14 Gc Corporation Polymerizable compositions

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CH730768D (enrdf_load_stackoverflow)
LU56128A1 (enrdf_load_stackoverflow) 1969-02-10
FR1566928A (enrdf_load_stackoverflow) 1969-05-09
ES367934A1 (es) 1971-04-16
DE1769416A1 (de) 1970-10-08
GB1175795A (en) 1969-12-23

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