US3111369A - Elastic polyurethane filamentary material and method of making same - Google Patents

Elastic polyurethane filamentary material and method of making same Download PDF

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US3111369A
US3111369A US182001A US18200162A US3111369A US 3111369 A US3111369 A US 3111369A US 182001 A US182001 A US 182001A US 18200162 A US18200162 A US 18200162A US 3111369 A US3111369 A US 3111369A
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Prior art keywords
thread
water
bath
diamine
setting
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US182001A
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Robert A Gregg
Charles V Tallman
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Uniroyal Inc
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United States Rubber Co
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Priority to NL280681D priority Critical patent/NL280681A/xx
Application filed by United States Rubber Co filed Critical United States Rubber Co
Priority to US182001A priority patent/US3111369A/en
Priority to ES277839A priority patent/ES277839A1/es
Priority to GB20974/62A priority patent/GB950797A/en
Priority to SE653362A priority patent/SE220554C1/sv
Priority to FR901060A priority patent/FR1341504A/fr
Priority to BE619866A priority patent/BE619866A/fr
Priority to CH821562A priority patent/CH414934A/fr
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • 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
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/77—Processes of molding urethanes

Definitions

  • the invention is based upon the discovery that superior coagulation of a polyurethane thread in an aqueous aliphatic diamine bath can be obtained by having an additional organic solvent, selected from the group consisting of monoalcohols, glycols, and mixtures thereof, present in the bath.
  • the thread is subsequently cured by the action of water, preferably with prior washing of the ghiglad immediately upon removal from the coagulating
  • the invention is an improvement upon the polyurethane thread and method of making same disclosed in US. patents of Kohrn et al., 2,953,839, September 27, 1960, and 3,009,762, November 21, 1961.
  • a polyurethane thread or filament from a polyurethane prepolymer, which is a reaction product of a hydroxy-terminated polyester or polyether or the like with an organic diisocyanate.
  • a polyurethane prepolymer is extruded into an aqueous solution of an aliphatic primary diamine to coagulate the thread, that is, to cause a rapid setting or gelling of the surface of the thread.
  • cure of the thread is completed by the action of water.
  • thread made in this manner trends to be flattened in cross-section rather than round. It also tends to be non-uniform in cross-section, i.e., it may have thin spots, and this gives rise to breakage and other undesirable effects in subsequent processing.
  • FIG. 1 is a diagrammatic elevational view representing one method of carrying out the invention
  • FIG. 2 is a similar fragmentary view of a modification of the invention.
  • FIG. 3 is a sectional elevational view representing one step in the invention.
  • FIG. 4 is an enlarged cross-sectional view of a thread made in accordance with the invention.
  • the aqueous aliphatic primary diamine setting bath additionally contains from 5 to 90% by weight of an organic solvent, selected from the group consisting of monoalcohols, glyools, and mixtures thereof, which causes extremely rapid coagulation, and by careful subsequent handling it is possible to obtain substantially round, essentially regularly shaped thread, by the action of water (in the form of liquid or vapor).
  • an organic solvent selected from the group consisting of monoalcohols, glyools, and mixtures thereof, which causes extremely rapid coagulation, and by careful subsequent handling it is possible to obtain substantially round, essentially regularly shaped thread, by the action of water (in the form of liquid or vapor).
  • the solvents which may be added to the aqueous diamine setting bath for this purpose are monoalcohols, glycols, and mixtures thereof, having up to carbon atoms, which, by physical and/or chemical action, lead to the rapid formation of a much tighter gel structure (i.e., a network of alkylene-diureido linkages) than is possible in a plain water-diamine bath. While it is not desired to limit the invention to any particular theory of operation, it appears possible that the ability to obtain a round thread of uniform cross-section in the present process is directly related to the influence of the added 3 ,111,369 Patented Nov. 19, 1963 ice organic solvent in the gelling or setting step.
  • the alcohols particularly aliphatic and heterocyclic alcohols, and especially monoaloohols having from 1 to 8 carbon atoms, such as the alkanols. These are especially effective in enhancing the gelling action of the aqueous diamine bath.
  • Preferred alkanols are those having 1-4 carbon atoms, and especially the 3 and 4 carbon atom alkanols.
  • secondary alkanols may be used, such as isopropanol or isobutanol, as Well as tertiary alkanols such as tertiary butyl alcohol or tertiary amyl alcohol. Tertiary butyl alcohol is most preferred.
  • monoalcohols that may be used include those containing ether linkages or cyclic structures such as Ethyl Oarbitol which has the structure nocmcn ocn cmocmcn,
  • omort 4-methoxy-4-methyl pentanol-Z which has the structure OIl:tC-CHCH(OII)CH C H; and methoxy triglycol which has the structure CH OCH CH OCH CH OCH CH OH
  • monoalcohols such as those described above are used along with glycols (having up to 10 carbon atoms for example), as the organic solvent additive to the aqueous diamine setting bath.
  • the alkylene glycols and alkylene ether glycols especially those having from 2 to 8 carbon atoms, such as ethylene glycol, propylene glycol, diethylene glycol, tricthylene glycol, 2-methyl-2,4-pentanediol and the like.
  • these glycols may be used by themselves as the organic solvent additive to the aqueous diamine setting bath, it is preferred to use them along with one or more of the monoalcohols as described above.
  • Unsaturated alcohols may be employed, whether ethylenically unsaturated as in the case of allyl alcohol, or acetylenically unsaturated as in the case of methyl butynol:
  • unsaturated glycols are included.
  • the last four named materials are solids, but for purposes of the invention they may be regarded as solvents because when dissolved in the bath (with the aid of other more soluble alcohols if necessary), they appear to exert a solubilizing effect, or carrying effect on the diarnine with respect to the polyurethane prepolymer.
  • tertiary glycols when employed in admixture with primary or secondary alcohols, are of special value in that they appear to aid in reducing any tendency for such primary or secondary alcohols to interfere with, or block, the cure with water.
  • solvent additives employed in the invention are not reactive with the aliphatic diamine in the setting bath, under the conditions of use. Furthermore, they are employed as solutions in setting bath, being either sufiiciently water soluble of themselves for this purpose, or sufliciently water soluble in admixture in various combinations.
  • the organic alcoholic solvent additive that is, the monoalcohol, the mixture of monoalcohol with glycol, or the glycol, preferably constitutes from 20 to 70% by weight of the setting bath.
  • polyurethane prepolymer that are used in the present invention
  • polyurethane prepolymer is typically a liquid derived from a polymer of molecular weight from 300 to 5000 having terminal hydroxyl groups.
  • polymer may be a chain extended polyester made from a glycol, preferably a mixture of ethylene and propylene glycols, and a saturated organic dicarboxylic acid, preferably adipic acid.
  • the glycol contains from 4 to 20 carbon atoms
  • the acid contains from 4 to 20 carbon atoms.
  • An excess of the glycol over the acid is used in preparing the polyester, so that the resulting polyester contains terminal hydroxyl groups.
  • Such an amount of glycol is used as to give a polyester having a hydroxyl number of 22 to 225, and preferably 36 to 75, and a low acid value less than 6 and preferably less than 1.
  • the molecular weight of the polyester usually ranges from 500 to 5,000 and preferably from 1500 to 3000. In general the most suitable polyesters are chiefly linear in type with melting point levels of C. or lower.
  • polyesters for use in preparing the prepolymer are polyethylene adipate, polyethylene adipatephthalate, polyneopentyl sebacate, etc.
  • tri-alcohols such as trimethylolpropane or trimethylolethane may be included in the preparation of the glycol-dicarboxylic acid polyester, and such modified forms of polyester are included within the term polyester as used herein.
  • polyesters just described there may be used (for reaction with the polyisocyanate) one or more members of the class of elastomer-yielding polyethers.
  • polyethers are typically anhydrous chainextended polyethers possessing ether linkages (O-) separated by hydrocarbon chains either alkyl or aryl in nature.
  • the ether should also contain terminal groups reactive to isocyanate, such as alcoholic hydroxyl groups.
  • the polyethers used are chiefly linear in type with melting point levels of 90 C. or lower.
  • the molecular weight may range from 500 to 5,000 (i.e., hydroxyl number of about 225 to 22), but is preferably within the range of 750 to 3,500 (i.e., hydroxyl number of about to 32).
  • Preferred polyethers may be represented by the formula H(OR),,OH where R is a lower (2-6 carbon atoms) alkylene group and n is an integer such that the molecular weight falls within the range specified.
  • examples of polyethers used are polyethylene glycol, polypropylene glycol, polypropylenc-ethylene glycol, and polytetramethylene glycol.
  • Mixtures of polyesters and polyethers may be used as well as polyesters derived from polyethers [e.g. poly(diethylene glycol adipate), poly(tri ethylene glycol adipate)
  • polyesters or polyethers suitable for forming prepolymers useful in the invention are the polyesters and polyethers mentioned in US.
  • the polyester or polyether is, an indicated, reacted with an aromatic diisocyanate, such as p.p-diphenyln1ethane diisocyanate or toluene diisocyanate, using a considerable molar excess, commonly from a 20% to a 250% and preferably from a 50% to a l50% molar excess, of the aromatic diisocyanate over that amount which would be required to react with all of the alcoholic hydroxyl groups furnished by the polyester.
  • aromatic diisocyanate such as p.p-diphenyln1ethane diisocyanate or toluene diisocyanate
  • the reaction is frequently effected by mixing the polyester and the aromatic diisocyanate under anhydrous conditions either at room temperature, or at a moderately elevated temperature, e.g., 70l50 C., to form a soluble (in methyl ethyl ketone), uncured, liquid prepolymer which is an essentially linear polyurethane having terminal isocyanate groups.
  • aromatic diisocyanates that may be mentioned, by way of non-limiting examples, are such materials as mand p-phenylene diisocyanate, toluene diisocyanate, p,p'-diphenyl diisocyanate and 1,5-naphthalene diisocyanate, and in this category w include the aromatic-aliphatic diisocyanates such as p,p'-diphenylmethane diisocyanate.
  • aromatic diisocyanates suitable for reaction with polyesters or the like to yield polyurethane prepolymers capable of being cured to the elastomeric state are disclosed in the prior art (such as the patents referred to previously), and it is desired to emphasize that the invention embraces the use of any and all such aromatic diisocyanates.
  • the setting bath into which such prepolymer is extruded to form the thread is an aqueous aliphatic diamine bath, modified in accordance with the invention by addition of a monoalcohol, a mixture of monoalcohol with a glycol, or, less preferably, a glycol itself.
  • the solution used as the setting bath may contain, for example, from 0.5 to 20% by weight of the diamine, to 90% by weight of the organic solvent, and 5 to 90% by weight of water, along with small percentages of any desired accessory ingredients, such as wetting agents. It may be employed at ordinary ambient temperatures, or heated to an elevated temperature (e.g., 100 F., up to, for example, 200 F.).
  • the setting bath is operated at a temperature of from 110 to 160 F., depending on the thickness of the extruded filament.
  • a temperature of from 110 to 160 F. depending on the thickness of the extruded filament.
  • setting bath temperatures of about 110- 120 F. are most suitable.
  • temperatures of about 140160 F. are most suitable.
  • the amines most suitable for this purpose are diprimary diamines that may be represented by the general formula NH -ANH where A is a divalent organic radical in which the terminal atoms are carbon, and which is preferably devoid of groups reactive with isocyanate, that is, the two primary amino groups are preferably the sole groups in the molecule that will react with the isocyanate groups of the polyester-diisocyanate, to provide the desired curing action.
  • the two primary amino groups are linked by a divalent aliphatic hydrocarbon radical, as in ethylene diamine, hexamethylenediamine, 1,4-diamino-cyclohexane, etc.
  • the connecting radical between the two essential primary amino groups need not be purely a hydrocarbon, but may contain other atoms in addition to carbon and hydrogen, as in 3,3-diaminodipropyl ether, and diaminodibutyl sulfide.
  • the amine should be at least slightly soluble in water.
  • a wetting agent there is included in the setting bath a small amount (typically about /2%, although the amount is not critical) of a wetting agent. This is frequently found to be useful in insuring complete and uniform setting of the entire surface of the extruded filament.
  • any known Wetting agents of the non-ionic or anionic type are suitable for this purpose (such as those disclosed, for example, in Sisley and Wood Encyclopedia of Surface Active Agents), and among the more effective wetting agents there may be mentioned the sodium salts of products obtained by sulfation of higher fatty alcohols (e.g., sodium oleyl sulfate).
  • one method of practicing the invention involves forcing a liquid polyurethane prepolymer of the kind described in the form of a round stream from a nozzle suspended just above the surface of a setting bath 11 comprising an aqueous aliphatic diamine containing the organic solvent additive (monoaleohol, glycol, or mixture thereof) in accordance with the invention.
  • an organic solvent additive selected from the group consisting of monoalcohols, glycols, and mixtures thereof in accordance with the invention.
  • the nozzle 14 may be immersed below the surface of the setting bath 15.
  • the action of the setting bath is such that the round stream of liquid prepolymer is substantially immediately gelled or set upon contacting the bath, forming a round thread or filament 17 (FIG. 1) which is passed under a fixed guide bar 18 located in proximity to the nozzle.
  • the thread passes through the bath for a distance, which may be as little as only about an inch or may be indefinitely longer, usually at a speed of, for example, from 50 to 500 feet per minute and then over the upper portion of a driven spinning roll 20 located just outside of the setting bath.
  • the peripheral speed of the spinning roll exceeds the linear speed of emergence of the prepolymer from the nozzle (usually 2 to 8 times the speed of emergence, preferably 2 to 4 times), with the result that the thread is drawn or stretched out and maintained under slight tension as it passes through the setting bath.
  • the frictional engagement and surface tension forces between the thread and the upper surface of the spinning roll enable the roll to produce a draw or controlled elongation upon the thread. Control of this action is assisted by the guide bar 18 which produces a kind of snubbing action.
  • the thread Since the thread is still quite weak at this point, that is, it is simply set or gelled by the action of the diamine without actually being cured" to a condition of high tensile strength, care must be taken not to break the thread or to exert so much tension that the soft, round thread would tend to become distorted or flattened out as it passes over the spinning roll.
  • the lower portion of the spinning roll is immersed in a bath of wash water 2 1, with the result that the residue of the setting bath carried by the thread is washed away by the action of the continually changing film of wash water carried up from the wash bath on the surface of the spinning roll.
  • the thread next passes under an additional wash roll 22 partially immersed in a second wash bath 23.
  • the additional wash roll is driven at the same speed as the spinning roll or at a slightly lower speed.
  • the wash water may of course be changed continuously or intermittently for efficient washing.
  • the turbulence of the wash water on and in contact with the surfaces of the rolls insures effective and rapid washing of traces of the setting bath from the thread.
  • the setting bath contains n-propanol or the like as the additive and if the thread is not washed thoroughly and appreciable time elapses between setting and final cure, it is found that the thread is not susceptible of final cure by the action of water, presumably because the n-propanol has had sufiicient opportunity to react with the free isocyanate groups of the prepolymer, thereby rendering the polymer incapable of further cure.
  • the cure of the thread may be carried out batchwise or continuously, the latter representing a particularly preferred practice of the invention because of its economy, speed, and the uniformly high quality obtainable in the product of the continuous process.
  • the thread is taken up on reels which are subsequently subjected to the action of Water (as a liquid, or in the form of Water vapor or steam)-preferably under pressure to forestall any tendency to develop voids in the thread as a result of generation of carbon dioxide which accompanies the water cure of a polyurethane.
  • the thread is conveyed continuously through a water bath or humid atmosphere, for example on a conveyor belt passing under water in a long tank or passing through a chamber in which a suitable atmosphere is maintained, or the thread may be conveyed by suitable thread advancing reels (partially or completely immersed in the liquid curing bath and/or surrounded by a curing atmosphere containing steam or water vapor and/or subjected to gentle sprays of water) which serve to store and advance the thread While it undergoes cure, typically as a single strand, either at atmospheric or super atmospheric pressure.
  • Such continuous cure may be carried out while passing the thread through one or more baths containing water, or through steam or other humid atmosphere, or through sprays containing water, successively or alternately in any desired order.
  • the washed thread passes over a roll 25, the lower portion of which rotates in a bath 26 of weakly acidic material such as up to 15% aqueous acetic acid or other water soluble fatty acid which serves to neutralize any diamine remaining in the thread (in accordance with U.S. Patent 3,009,765 issued to Slovin on November 21, 1961).
  • the bath 26 also suitably contains a conventional textile lubricant (e.g. of silicone oil textile lubricant whether in emulsion or water-soluble form) and a wetting agent (e.g. /2 of any suitable conventional wetting agent such as a nonionic wetting agent).
  • the purpose of neutralizing the diamine is to prevent too much of the cure of the thread from being accomplished by diamine (i.e., to prevent too many of the available isocyanate groups from being consumed by the diamine, leaving little or no isocyanate groups for subsequent reaction with water), since a predominately diamine-cured polyurethane thread would have inferior physical properties compared to the highly elastomeric, strong (high tensile strength) thread of the invention in which the final cure is effected by reaction with water.
  • the thread 17 is then wound up into a package on a drum 29.
  • the drum 29 is rotated at a speed no greater than or slightly lower than the speed of the spinning roll 20.
  • the peripheral speed of the spinning roll may typically be 1.00 to 1.20 times the take-up speed of the package.
  • the batchwise cure may be effected by immersing a plurality of packages or drums 30 (FIG. 3) bearing the thread under water 31 contained in an autoclave 32 maintained under pressure at an elevated temperature for a suitable period of time. Frequently such batchwise curing may be carried out at temperatures within the range of from 80 F. to 250 F. for a period of time of from A to 24 hours, at pressures ranging from to 250 pounds per square inch gauge.
  • the final cure may if desired be accomplished partly in the autoclave, and then completed in the open atmosphere at ambient temperatures (sufficient moisture being present in the thread and/or available from the atmosphere), or in an oven with a heated and/or humidified atmosphere.
  • the continuous cure is carried out at atmospheric pressure, ordinarily at elevated temperature (e.g., 100 F. to 212 F.).
  • the period of hold-up of thread in the curing zone should be sufficient to effect at least partial cure, and for this purpose hold-up times of about one minute to minutes or more are ordinarily employed.
  • the cure water particularly in the initial stages of the cure, may contain surfactants or catalysts. At the final stages the water may contain lubricants and may serve to flush the thread clean of acid etc., and the cured thread finally may be wound up on a drum.
  • the thread packages thus obtained may be stored at room. temperature to advance the cure further if necessary, by the action of residual water in the thread, over a period of time (e. g., 1-2 days). If desired such storage can be shortened to as little as a few minutes or a period of hours by carrying it out in a humid atmosphere at an elevated temperature (e.g.140 R).
  • a quantity of weakly acidic material e.g., about 0.1 to 10% by weight of an organic carboxylic acid, such as benzoic acid, acetic acid or other water-soluble carboxylic acids.
  • an organic carboxylic acid such as benzoic acid, acetic acid or other water-soluble carboxylic acids.
  • this has a remarkable catalytic effect on the cure, enabling the cure to be carried out more rapidly and thoroughly, to provide a cured product having excellent physical properties, in a short time.
  • the optimum quantity of acetic acid for this purpose is about 4 or 5%, the accelerating effect falling off at lower or higher concentrations.
  • catalysts may be used in the cure water, such as for example 1 to 4% by weight of 1,2-dimethylimidazole or other imidazole, or other tertiary amines such as tetram-ethyl-1,3-butanediamine; tetramethylethylenediamine; N,N,N',N',N" pentamethyldiethylenediamine or 4-methylpyridine.
  • 1,2-dimethylimidazole or other imidazole or other tertiary amines such as tetram-ethyl-1,3-butanediamine; tetramethylethylenediamine; N,N,N',N',N" pentamethyldiethylenediamine or 4-methylpyridine.
  • the cured thread may finally be dried to a predetermined moisture content (usually between /2 and 2%) and rewound if necessary on commercial spools.
  • the cured thread 49 (FIG. 4) produced as described is remarkable for its uniformity as compared to thread similarly produced by initial setting in a plain water-diamine bath that does not contain the organic solvent additive in accordance with the invention.
  • the present thread shows improved retention of tensile strength in hot alkaline solution as compared to previous thread. It also shows a lower rate of strength loss in hot chlorine bleach solutions. We do not know whether this improvement in resistance to degradation is due to a change in the nature of the surface or merely to greater uniformity of the thread.
  • the roundness of the thread may be characterized by measuring its axial ratio which is defined as the ratio of the maximum cross-sectional diameter to the minimum cross-sectional diameter. Thread having an axial ratio of 1.5 or less is considered as being substantially round.
  • the thread 49 is cured successively with diamine and with water, it may be represented as having an outer shell or skin 50- at the surface wherein much of the combined curative is the diamine and an inner core or center 51 wherein much of the combined curative is water, but it will be understood that there is not necessarily any line of demarcation between these zones, and the respective cures by diamine and water are diffusion-controlled phenomena which probably take place to some extent throughout the whole cross-section of the thread.
  • EXAMPLE I A polyester having a molecular weight of 2100 and an acid value of 0.7 was prepared by condensing a 70/30 mixture of ethylene glycol and 1,2-propylene glycol with adipic acid, the glycol being used in slight molar excess to insure hydroxyl terminal groups. Ten percent of titanium dioxide was dispersed into the polyester, for
  • the prepolymer was extruded as described in US. Patent 2,953,839 at the rate of 2 cc. per minute into a coagulating bath containing 2 parts of ethylene diamine, 0.5 part of a nonionic wetting agent (e.g., methylphenolethylene oxide condensation product, Triton X-100), 62.5 parts of water and 35 parts of n-propanol, maintained at 90 F.
  • a nonionic wetting agent e.g., methylphenolethylene oxide condensation product, Triton X-100
  • the diameter of the nozzle opening was 0.02 inch.
  • the surface of the extruded round stream of liquid set to a solid condition immediately as it entered the setting bath.
  • the thread was immediately washed thoroughly with water to remove the n-propanol, and then with 10% aqueous acetic acid to neutralize any diamine remaining in the thread, by passing around wash rolls, at a speed of 290 feet per minute.
  • the thread was wound on a drum at a speed of 280 feet per minute and immersed in water at 150 F. under a pressure of 50 p.s.i. for two hours to cure the thread by the action of water on the polymer.
  • the diameter of the thread was 0.0065 inch. Its physical properties were:
  • the thread was round for all practical purposes, and substantially uniform in thickness and cross-section all along its length. It could be covered with textile material and otherwise processed and fabricated without difficulty and without formation of defects.
  • the example was repeated except that the n-propanol was not washed off the thread immediately.
  • the thread could not be cured properly with water, presumably because the n-propanol reacted with the available isocyanate groups, thus blocking" the cure.
  • Example II was repeated as far as and including the step of washing the thread with dilute acetic acid to neutralize the diamine.
  • the thread was then led continuously onto a moving supporting surface as a single filament and conveyed on such surface without delay through a tank of boiling water. Four minutes were required for the thus-supported thread to traverse the tank, during which time the cure with water became essentially completed.
  • the cross-section of the resulting cured thread was perfectly round (axial ratio, 1.00). It
  • Example III Example I was repeated, except that the diameter of the nozzle opening was 0.03 inch, the rate of delivery of the prepolymer was 5 cc. per minute, and the speed of the spinning roll was 170 feet per minute. Speed of the wash rolls was 165 feet per minute and speed of the takeup drum was 160 feet per minute. Cure was as in Example I. Thread properties were:
  • Example III was repeated, except that the thread was cured continuously at the boil as a single filament rather than as a wound package. Thread properties were:
  • EXAMPLE V In this example the prepolymer was made from a polyether, rather than a polyester. One mole of polypropylene glycol (molecular weight about 2000) was heated 1 hour at C. with about two moles of p,p'-diphenylmethane diisocyanate. Thread was made from this prepolymer as in Example I. Thread properties were:
  • Example VI In this example the prepolymer used in Example V was again employed, but the curing procedure of Example IV was employed (i.e. continuous cure of single filament in water at a temperature of 210 F.). Thread properties were:
  • the prepolymer was of a white color and had a Brookfield viscosity of 8250 poises at 100 F.
  • This prepolymer was extruded as in Example I into a setting bath containing 55 parts of n-propanol, 36.5 parts of water, 8 parts of ethylene diamine and 0.5 part of wetting agent. Washing and curing were carried out as in Example I. Thread properties were:
  • Bath was 77 parts of ethylene glycol, 22 pants of water and 1 part of ethylene diamine, maintained at 140 F.
  • Cured thread properties were: Tensile, 1000 p.s.i.; elongation, 670%; set, 9%; axial ratio, 1.28.
  • Bath was 45 parts of methanol, 54 pants of water and 1 part of ethylene diamine; temperature 130 F. Properties were: Tensile, 8800 p.s.i.; elongation, 745%; crosssection was round.
  • Bath was 90 parts of isopropanol, 9 parts of water and 1 part of ethylene diamine at 130 F.
  • Tensile 5500 p.s.i.; round cross-section.
  • Bath was 90 pants of n-butanol, 9 parts of water and 1 part of ethylene diamine at 110 F.
  • Tensile 6800 p.s.i.; elongation, 690%; round cross-section.
  • Bath was 88 parts iso-butanol, 11 parts water, 1 part ethylene diamine at 130 F.
  • Bath was 76 parts methoxy triglycol, 23.5 pants water, 0.5 part ethylene diamine at 130 F.
  • Tensile 6100 p.s.i.; 675% elongation; round crosssection.
  • Bath was 40 parts methoxy triglycol, 16 parts n-propanol, 43 parts water with 1 part ethylene diamine at 130 F.
  • Tensile 5900 p.s.i.; 567% elongation; round crosssection.
  • Bath was 41 parts diothylene glycol, 16 parts n-propanol, 42 parts in water, 1 part ethylene diamine at 130 F.
  • Tensile 7600 p.s.i.; elongation, 685%; axial ratio 1.2.
  • Bath was 80 parts triethylene glycol, parts n-propanol, 14 parts water, 1 part ethylene diamine at 130 F.
  • Tensile 5300 p.s.i.; elongation, 670%; round cross-section.
  • Bath was 20 parts tetrahydropyran-2-methanol, 79.5 parts water, 0.5 part ethylene diamine at 130 F.
  • Bath was 50 parts Ethyl Carbitol, 49.5 parts water, 0.5 part ethylene diamine at 130 F.
  • Bath was 50 parts tetrahydrofurfuryl alcohol, 49.5 parts water, 0.5 part ethylene diamine at 120 F.
  • Example IX The prepolymer of Example I was extruded into a bath containing 50 parts n-propanol, and 50 parts water at 120 F. in essentially the same manner as Example I.
  • the basic aqueous coagulating agent was varied.
  • Coagulating agent was 1 part of 1,3-diaminopropane. Tensile, 5900 p.s.i.; elongation, 675%; axial ratio 1.12.
  • Coagulating agent was 2 pants of 1,6-hexanediamine. Tensile, 6200 p.s.i.; elongation, 690%; round cross-section.
  • compositions Aqueous Setting Baths (Parts) Tertiary Ethylene Glycol Butyl Water Diainine Alcohol lti Methyl Carbitol" 12 7t). 5 1 ,32 14 Butyl Carbitol"-.. 15 lit). 5 1';' 16 methoxytriglycoL.. 12 70. 5 1 ⁇ ; 14 Z-nmthyl-Z,4-pcntanc-diol 12 7t). .5 1 20 Butyl Carbitol" 1 u 60.5 1% 28 2-1ncthyl-2A'pcntunu-diol 70. 5 11+;
  • glycols with tertiary monoalcohols represent a highly preferred form of the invention.
  • the improved round, uniform thread of the invention is characterized by the ability to be covered with a textile material without undesirable build-up of twist with consequent kinks and similar irregularities. Breaks during the covering and finishing operations are minimized.
  • the thread of the invention feeds evenly through knitting and twisting equipment without requiring excessive lubrication.
  • a method of making a filamentary material comprising the steps of providing a liquid polyurethane prepolymer having terminal isocyanate groups, extruding a stream of said liquid prepolymer into an aqueous aliphatic diprimary diamine bath to effect an initial setting of the extruded material, and thereafter curing the extruded material by the action of water, the improvement comprising providing in the setting bath from 5 to by weight of an organic solvent selected from the group consisting of monoalcohols having from 1 to 8 carbon atoms, glycols having from 2 to 10 carbon atoms, and mixtures thereof.
  • a method of making a filamentary material comprising in combination the steps of providing a liquid polyurethane prepolymer having terminal isocyanate groups, extruding a stream of said liquid, passing said extruded stream into a setting solution comprising water, an aliphatic diprimary diamine and a mixture, in amount of from 20 to 70% by weight of the setting solution, of a monoalcohol having from 1 to 8 carbon atoms with a glycol having from 2 to 10 carbon atoms, to effect an initial setting of the extruded stream in the form of a filament, and thereafter curing the filament by the action of water.
  • a method of making a filamentary material comprising the steps of providing a liquid polyurethane prepolymer having terminal isccyanaite groups, extruding a stream of said liquid into a setting bath comprising water, an aliphatic diprimary diamine and an organic additive, in amount of from 20 to 70% by weight of the bath, selected from the group consisting of monoalcohols having from 1 to 8 carbon atoms, glycols having from 2 to 10 carbon atoms, and mixtures thereof, to effect an initial setting of the extruded stream in the form of a filament, passing the filament over a spinning roll rotating at a peripheral speed 2 to 8 times the speed of extrusion of the filament to eflect a spinning thereof at a definite spinning speed, immediately washing the filament to remove any residue of the setting bath liquid therefrom, winding the filament up into a package at a definite winding speed, the
  • said spinning speed being 1.00 to 1.2 times the said winding speed, and thereafter curing the filament with water.
  • a method of making a filamentary material comprising the steps of providing a liquid polyurethane prepolymer having terminal isocyanate groups, extruding a stream of said liquid into a setting bath comprising water, an aliphatic diprimary diamine and an organic additive, in amount of from 20 to 70% by weight of the bath, selected from the group consisting of monoalcohols having from 1 to 8 carbon atoms, glycols having from 2 to 10 carbon atoms, and mixtures thereof, to effect an initial setting of the extruded stream in the form of a filament, passing the filament over a spinning roll rotating at a peripheral speed 2 to 8 times the speed of extrusion of the filament to effect a spinning thereof, immediately washing the filament to remove any residue of the setting bath liquid therefrom, and immediately thereafter curing, the filament by passing it continuously through a curing zone wherein it is contacted with water,
  • An improved polyurethane thread characterized by uniformity of size and shape along its length, made by the method of claim 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Artificial Filaments (AREA)
US182001A 1961-07-13 1962-03-23 Elastic polyurethane filamentary material and method of making same Expired - Lifetime US3111369A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL280681D NL280681A (enrdf_load_stackoverflow) 1961-07-13
US182001A US3111369A (en) 1961-07-13 1962-03-23 Elastic polyurethane filamentary material and method of making same
ES277839A ES277839A1 (es) 1961-07-13 1962-05-30 Procedimiento de obtención de un material filamentoso
GB20974/62A GB950797A (en) 1961-07-13 1962-05-31 Methods of making polyurethane filamentary material
SE653362A SE220554C1 (enrdf_load_stackoverflow) 1961-07-13 1962-06-12
FR901060A FR1341504A (fr) 1961-07-13 1962-06-18 Procédé de fabrication de fibres ou de fils élastiques, en polyuréthanes, de forme et de grosseur uniformes
BE619866A BE619866A (fr) 1961-07-13 1962-07-06 Procédé de fabrication de fibres ou de fils élastiques, en polyuréthanes, de forme et de grosseur uniformes.
CH821562A CH414934A (fr) 1961-07-13 1962-07-09 Procédé de fabrication de fibres ou de fils élastiques en polyuréthanes

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Application Number Priority Date Filing Date Title
US12361761A 1961-07-13 1961-07-13
US182001A US3111369A (en) 1961-07-13 1962-03-23 Elastic polyurethane filamentary material and method of making same

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US (1) US3111369A (enrdf_load_stackoverflow)
BE (1) BE619866A (enrdf_load_stackoverflow)
CH (1) CH414934A (enrdf_load_stackoverflow)
ES (1) ES277839A1 (enrdf_load_stackoverflow)
GB (1) GB950797A (enrdf_load_stackoverflow)
NL (1) NL280681A (enrdf_load_stackoverflow)
SE (1) SE220554C1 (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3198863A (en) * 1963-05-02 1965-08-03 Thiokol Chemical Corp Process of curing urethane threads utilizing slow and fast curing agents
US3387071A (en) * 1964-05-05 1968-06-04 Globe Mfg Company Fibers
US3482010A (en) * 1963-09-30 1969-12-02 Kuraray Co Process for the production of polyurethane elastic fiber having less adhesivity
US3494994A (en) * 1966-10-11 1970-02-10 Kuraray Co Method of producing polyurethane elastomer staple fibre
WO1994017012A1 (en) * 1993-01-27 1994-08-04 University Of Cincinnati Porous ceramic and porous ceramic composite structure
US6245876B1 (en) * 1997-02-27 2001-06-12 Asahi Kasei Kogyo Kabushiki Kaisha Continuous molded article for polyurethaneurea and production method thereof
US20040006964A1 (en) * 2002-07-10 2004-01-15 Claudio Sironi Wet spinning process of an elastomeric polymer thread
US20230272558A1 (en) * 2020-09-11 2023-08-31 Asahi Kasei Kabushiki Kaisha Polyurethane Elastic Fiber, Gather Member Containing Same, and Sanitary Material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009762A (en) * 1958-08-21 1961-11-21 Us Rubber Co Method of making polyurethane filamentary material
US3009765A (en) * 1959-02-20 1961-11-21 Us Rubber Co Method of making polyurethane filamentary material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009762A (en) * 1958-08-21 1961-11-21 Us Rubber Co Method of making polyurethane filamentary material
US3009765A (en) * 1959-02-20 1961-11-21 Us Rubber Co Method of making polyurethane filamentary material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3198863A (en) * 1963-05-02 1965-08-03 Thiokol Chemical Corp Process of curing urethane threads utilizing slow and fast curing agents
US3482010A (en) * 1963-09-30 1969-12-02 Kuraray Co Process for the production of polyurethane elastic fiber having less adhesivity
US3387071A (en) * 1964-05-05 1968-06-04 Globe Mfg Company Fibers
US3494994A (en) * 1966-10-11 1970-02-10 Kuraray Co Method of producing polyurethane elastomer staple fibre
WO1994017012A1 (en) * 1993-01-27 1994-08-04 University Of Cincinnati Porous ceramic and porous ceramic composite structure
US6245876B1 (en) * 1997-02-27 2001-06-12 Asahi Kasei Kogyo Kabushiki Kaisha Continuous molded article for polyurethaneurea and production method thereof
US20040006964A1 (en) * 2002-07-10 2004-01-15 Claudio Sironi Wet spinning process of an elastomeric polymer thread
US20230272558A1 (en) * 2020-09-11 2023-08-31 Asahi Kasei Kabushiki Kaisha Polyurethane Elastic Fiber, Gather Member Containing Same, and Sanitary Material

Also Published As

Publication number Publication date
BE619866A (fr) 1962-11-05
GB950797A (en) 1964-02-26
NL280681A (enrdf_load_stackoverflow)
ES277839A1 (es) 1963-01-16
SE220554C1 (enrdf_load_stackoverflow) 1968-05-14
CH414934A (fr) 1966-06-15

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