US3331887A - Novel polyurethane elastic filaments and yarns and process for producing the same - Google Patents

Novel polyurethane elastic filaments and yarns and process for producing the same Download PDF

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Publication number
US3331887A
US3331887A US359769A US35976964A US3331887A US 3331887 A US3331887 A US 3331887A US 359769 A US359769 A US 359769A US 35976964 A US35976964 A US 35976964A US 3331887 A US3331887 A US 3331887A
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polymer
diisocyanate
dimethyl
yarns
solution
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Wakasa Ryoichi
Suzuki Isamu
Iwashita Hidemaro
Omura Jukichi
Iwasa Toshio
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
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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

Definitions

  • polymers (1) and (2) are disadvantageous in that they exhibit low resistance to bleaching and low light fastness and the polymer (3) is disadvantageous in its low resistance to heat and mechanical properties.
  • the present polymers have repeating structural units represented by the formula:
  • this invention relates to novel polyurethane elastic filaments and yarns consisting of repeating structural units represented by the formula 0 o o o 0 ll 1! II H H wherein R is a bivalent organic radical such as 1,3-phenylene, 1,4-phenylene, 2,4-tolylene, 2,6-tolylene, 4,4-biphenylene, 2,2-dimethyl-4,4-biphenylene, 3,3'-dimethyl-4,4-
  • R and R represent respectively a bivalent organic residue and A represents a bivalent polymer residue, said filaments and yarns having improved characteristics in mechanical properties such as elastic recovery, light fastness and chemical properties.
  • polyurethanes have been produced in steadily increasing quantities and grades in recent years and because of their unique properties in elasticity, polyurethanes are useful in wide variety of applications in the form of yarns.
  • polyurethane filaments and yarns made by combining the conventionally known prepolymers with the compounds having bifunctional active hydrogen atoms have not been satisfactory in elastic recovery, strength, resistance to solvents.
  • An object of this invention is to provide elastic polyurethane filaments and yarns having an improved elastic recovery, strength and resistance to solvents, in comparison with conventional yarns made by combining conventional prepolymers with compounds having bifunctional active hydrogen atoms even without further subjecting the resultant yarn to a cross linking treatment.
  • Another object of this invention is to provide other polyurethane elastic filament yarns which can be obtained by subjecting the foregoing filaments and yarns to a cross-linking step, having additional advantageous properties such as insolubility in hot dirnethyl formamide and hot dimethyl sulfoxide, higher light fastness, increase in elastic recovery, tensile strength and tensile elongation.
  • R is a bivalent organic radical such as ethylene, propylene, iso-propylene and n-butylene radicals;
  • A is a bivalent polymer residue such as polyester residue, polyether residue and poly(oxyalkylene-carboxyalkylene) residue.
  • the raw materials employed in the present invention have respective features toward the properties of the elastic fibers produced from the raw materials. Typical examples therewith will be described as follows.
  • Aromatic aminoalcohol is insufficient in its reactivity and besides the elastic fiber resulting from the use thereof is defective in that the fiber is stained by sunlight.
  • Aminoalcohols containing a substituent group even in an aliphatic aminoalcohol is liable to make the intermolecular force of the elastic fiber therefrom lower; thereby causing deformation by an external force.
  • Dimethylol urea-Formalin improves resistance to solvents and chemicals, tensile strength and modulus, but since the cross-linking condition is considerably drastic, the fiber surface becomes hard and the fiber becomes brittle.
  • Paraformaldehyde-Formalin cross-linking is effected in mild condition; accordingly various mechanical and.
  • diol polymers are polyester glycol, polyether glycol and poly(oxyalkylene-carboxyalkylene) glycol.
  • Diol polymers having side chains such as polypropylene glycol decrease tensile strength and increase stress relaxa tion in stretching of the elastic fiber therefrom.
  • Diol polymers not having side chains improve mechanical properties such as tensile strength and stress relaxation of the fiber.
  • diol polymers come to have a molecular weight above about 1500, permanent set at low temperature becomes greater.
  • Diols of the polyester type have a weakness in chemical properties, especially in resistance to acid and base, but dialsof the polyether type and lactone polyester type improve these properties.
  • Diols having ether linkages and ester linkages in the main chain such as poly-oxyalkylene-carboxyalkylene) glycol are liable to improve the permanent set at low temperature when compared with those having either ether linkages or ester linkages in the main chain. 7
  • the present polyurethane filaments and yarns are produced in accordance with the following procedures:
  • the process of this invention consists of four steps.
  • the first step is the preparation of a prepolymer.
  • the prepolymer is prepared by reacting a linear bifunctional hydroxyl-terminated polymer having a melting point below about 50 C. and a molecular weight between 800 and 2500 with an organic diisocyanate in a ratio of isocyanate radical to hydroxyl. radical of 1.0 -2.0:1.0, preferably 1.3-2.0:1.0.
  • one mole of a linear hydroxy-terminated polymer (hereinafter referred to as a diol polymer) is reacted with two moles of 4,4'-diphenylrnethane diisocyaare regularly arranged.
  • the crystalline part has 4 urethane linkages and 2 urea linkages .and the urethane linkage is separated from a urea linkage-by ethylene radical.
  • the usual condition i.e. a temperature of 60150 C. for 1 to 2 hours, preferably C;
  • a glycol, polyether glycol, and poly(oxyalkylene-carboxyalkylene) glycol are effectively used.
  • known catalysts e.g. tertiary amines, such as triethylene amine; or organo-metallic compounds such as dibutyl tin-dilaurate may be used.
  • the second step consists of dissolving the prepolymer obtained in the first step in an organic solvent to produce a homogeneous solution and reacting the resulting prepolymer solution with an aminoalcohol in amounts equivalent to the isocyanate in the prepolymer to produce a macrodiol of a low molecular hydroxyl-termin'ated polymer.
  • This step is the essential part of the present invention which is considered to be a necessary condition for constituting an invention.
  • an organic solvent for the prepolymer in the second step dioxane, acetone, methyl ethylketone, benzene, toluene, dimethyl formamide, dimethyl acetamide, and dimethyl sulfoxide areused singly or as a mixture.
  • an aminoalcohol ethanolamine, propanolamine, isopropanolamine and n-butanol'amine, are effectively used.
  • the amount of the arninoalcohol is preferably equal to the isocyanate radicals in the above mentioned prepolymer.
  • the amount is excessive, unreacted aminoalcohol remains. And when it is insuflicient, the free isocyanate radicals still remaining after the reaction with amino radicals is completed is allowed to react gradually with hydroxy radicals. In either case, the following step of chain extending which uses a diisocyanate as connecting agent does not proceed smoothly and the quality of the resulting polymer shows deterioration.
  • an aminoalcohol is used in this invention.
  • a diamine is used instead of this, both terminals are occupied by amino radicals, the crystalline part of polymers connected by the diisocyanate contains 4 urea linkages and the quality of polymers generally shows deterioration when the cross-linking reaction is applied to it, probably due to an increase of cross linking points. In most of these cases a decrease of elongation is inevitable and it is difiicult to obtain reproducible elastic filaments and yarns.
  • none of such defects are recognized and it is easy to obtain high quality filaments and yarns with reproducibility.
  • the description on the second step continues as follows.
  • the prepolymer obtained in the first step is cooled to about room temperature, and brought to a homogeneous solution by the addition of dehydrated, purified dirnethylformamide. Dropping this solution into a dimethyl formamide solution of aminoalcohol, the amount of which is equivalent to the isocyanate radicals, a macrodiol solution can be obtained. If the above solution is introduced into a large amount of ethanol, stirred with cooling at a very low temperature, a white solid substance begins to be separated gradually. After filtration, washing with a small amount of ethanol and drying at a reduced pressure, a macrodiol is separated.
  • This substance is a stable compound whose terminal hydroxy radicals can be determined quantitatively by the acetylation method and which shows a definite melting point.
  • 300 g. of dimethyl formaldehyde solution of a macrodiol obtained in Example 1 (which will be later given) is dropped into 2.5 l. of 95 percent ethanol at room temperature with stirring. Further vigorous stirring is continued for 30 minutes. Subsequently this solution is cooled to C. by use of ice water-salt mixture. The separated white substance is filtered, washed with a small amount of cold ethanol several times and dried at a reduced pressure until it does not show any further decrease of weight.
  • the resulting macrodiol has a melting point between 38 C. and 39 C.
  • the average molecular weight determined by the acetylation method is 2,450 (the theoretical molecular weight is 2,320).
  • the OH number is 45.85 and the acid number is 0.
  • the macrodiol obtained in the second step is transferred to the third step.
  • the third step consists of reacting the macrodiol with an organic diisocyanate.
  • the macrodiol can be used either by taking out and dissolving in a suitable solvent such as dimethyl formamide or the like or as it is Without taking out.
  • a suitable solvent such as dimethyl formamide or the like or as it is Without taking out.
  • an organic diisocyanate is added in an amount equivalent to the macrodiol in the solution or in a slight excess, and after suificient stirring in the absence of a catalyst or in the presence of a known catalyst which accelerates the reaction between the NCO radical and the 0H radical, e.g. such as trimethylene diamine, dibutyl tin dilaurate, polymerization is carried out at a suitable temperature with or without stirring.
  • the organic diisocyanate added at this time is the same as the one used in the preparation of the prepolymer in the first step or not.
  • the diisocyanate used in preparing the prepolymer can be aromatic or aliphatic, but it is preferable that the organic diisocyanate used in the third step be aromatic.
  • aromatic diisocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6- tolylene diisocyanate, 4,4'-biphenylene diisocyanate, 2,2- dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethyl- 4,4'-diphenylmethane diisocy-anate, 1,5-naphthylene diisocyanate and 1,8-naphthylene diisocyanate are effectively used.
  • trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate can be effectively used.
  • the amount of organic diisocyanate to be added is cont-rolled so as to be in a ratio of hydroxy radical of macrodiol to isocyanate radical of the organic diisocyanate ranging of from 1.00 to 1.04.
  • this ratio is smaller than 1, a high molecular weight polymer cannot be obtained.
  • gelatination occurs and deteriorates the quality of the resulting elastic yarns.
  • the fourth step consists of spinning the polymer solution obtained in the third step to yield polyurethane yarns, and if required, the resulting yarns are subjected to a cross linking step.
  • Yarns and filaments of this invention are prepared by either wet or dry spinning. In the spinning the following conditions are employed.
  • Orifice of spinneret its dimension is freely variable
  • Spinning velocity 5-60 m./min., especially 20-30 rn./min.
  • Coagulation bath DMF aq. solution, water, methanol, aq. Na CO solution, etc., bath temperature 40-60 C., spinning depth 3-5 m.
  • Bath temperature 50-70 C., especially 4060 C.
  • Orifice of spinneret dimension 0.08 mm.0.2 mm.
  • Polymer cone. of spinning solution 25-35%.
  • the cross linking method of the resulting yarns there are wet heating method and dry heating method.
  • a cross linking agent aldehydes such as formaldehyde acetaldehyde, and dimethylol compounds such as dimethylol urea, dimethylol propylene urea, are used.
  • an acidic catalyst such as hydrochloric acid, ammonium chloride, magnesium chloride, zinc nitrate, or the like are effectively used.
  • the cross linking reaction is carried out at a condition of the cross linking agent concentration being 5 to 40 percent (especially preferable when it is more than 10 percent) and the temperature being 50 to 100 C. for 1 to 10 minutes.
  • L represents the initial length of an elastic fi-ber
  • AL represents LL
  • L represents a length of the fiber obtained by loading, to the fiber having the initial length L a weight by which the fiber is drawn up vto length of 3 in a draw rate of 100% per minute, and setting the loading fiber for 30 minutes at the 3 state and thereafter removing the load and allowing to stand the unloaded fiber at the unloading state for 30 minutes, provided these procedures are carried out at 20 C.
  • Example 1 340 g. of polyvalerolactone having an average molecular Weight of 1,700, and whose terminal groups are fixed by propylene oxide; and 100 g. of 4,4- diphenylrnethane diisocyanate are reacted at 95 C. for 120 minutes under a nitrogen atmosphere with stirring. The reaction is completed when the concentration of diisocyanate reaches-1.175 mm./ g. After cooling the reaction mixture to room temperature, 600 g. of purified dimethylformarnide are added thereto, and stirred at a temperature between 28 and 30 C. to produce a homogenous solution.
  • Yarn thus obtained is washed with cold water for one hour, and dried at 30 C. for hours- Resulting yarn possesses the following properties.
  • Example 3--26 g. of valerolactone having an average molecular weight of. 1300 and 10 g. of 4,4'diphenylmethane diisocyanate are introduced into a 300 cc. threeneck flask equipped with a stirrer and a nitrogen inlet pipe, and is heated at a temperature between 98 C. for
  • Example 2 In order to make it readily spinnable, it is diluted with dimethyl formamide until the viscosity becomes 2- 30,000 op. and subjected to spinning as in Example 2. The yarn thus spun is washed with water and subjected to a cross linking treatment as in Example 1 except that Formalin and ammonium chloride in Example 1 are replaced by dimethylol ethylene urea and magnesium chloride respectively. The yarn obtained exhibits the following properties.
  • 1,6-hexamethylene diisocya-nate are made into a pro-- polymer by using the same apparatus and the same method as in Example 2, cooled to 60 C., added to g. of dimethylformamide, and after being stirred for 2 hours at a temperature of 30 C., the remaining isocyanate radical is analysed quantitatively. Then a dimethyl sulfoxide solution of the resulting prepolymer is added to 50 cc. of dimethyl sulfoxide containing 1.22 g. of ethanolamine over 30 minutes with stirring. 1.21 g. of 4,4-di.-
  • Example 5.38.7 g. of caprolactone-ethylene oxide copolymer having OH number of 107 and containing 20 mole percent of ethylene oxide and 12.90 g. of 4,4- diphenylmethane diisocyanate are added to 150 g. of dehydrated and purified dimethylformamide and stirred at 31 C.- -0.5 C. for 4 hours in a nitrogen atmosphere. Then the resultant solution is added to 47 g. of dimethylformamide containing 1.55 g. of ethanolamine while sufiiciently stirring and after 30 minutes 3.31 g. of 4,4- diphenylmethane diisocayanate are added thereto. The solution thus obtained is stirred at 31 C.i0.5 C. for 4 hours and is left in a constant temperature room of 35 C. for 32 hours and subsequently spun in the same procedure as in Example 2. Yarn dried at 110 C. for one hour exhibits the following properties.
  • a polyurethane elastic yarn having a creep recovery above 90% and an intrinsic viscosity between 0.8 and 1.2 'when measured in dimethyl formamide and consisting of a polymer having solely the repeating structural units of the formula o 0 o 0 H H I! II II 10 polymer residue having a molecular weight between 800 and 2500 and a melting point below about 50 C.
  • a method for producing polyurethane elastic yarn comprising reacting a linear bifunctional hydroxyl-terminated polymer having a molecular Weight between 800 and 2500 and a melting point below about 50 C. with an organic diisocyanate, the molar ratio of the isocyanate radical to the hydroxyl radical being 1.02.0: 1.0 to produce an isocyanate-terminated prepolymer, adding at least one organic solvent to said isocyanateterminated prepolymer to prepare a prepolymer solution, reacting the prepolymer in solution with an aminoalcohol in a molar amount equivalent to the isocyanate radical of said prepolymer to produce a low molecular 15' weight hydroxyl-terminated polymer, reacting said low molecular weight hydroxyl-terminated polymer with an organic diisocyanate, the molar ratio of the isocyanate radical to the hydroxyl radical in said low molecular weight hydroxyl-terminated polymer being 1.001.04: 1.00
  • a method for producing polyurethane elastic yarn having a creep recovery above 90% and a cross linked structure comprising reacting a linear bifunct-ional hydroxyl-terminated polymer having a molecular Weight between 800 and 2500 and a melting point below about 50 C.
  • R is a bivalent organic radical selected from the group consisting of 1,3-phenylene, 1,4-phenylene, 2,4- tolylene, 2,6-tolylene, 4,4'-biphenylene, 2,2-dimethyl-4,4'- biphenylene, 3,3 dimethyl 4,4 biphenylene, 4,4'-diphenylmethane, 3,3'-dimethyl-4,4-diphenylmethane, 1,5- naphthylene, 1,8-naphthylene, trimethylene, tetramethylene, pentamethylene and hexamethylene radicals; R is a bivalent organic radical selected from the group consisting of ethylene, propylene, iso-propylene and n-butylene radicals; A is a bivalent polymer residue selected from the group consisting of polyester residue, poly(ethylene)-propylene and n-butylene radicals;
  • a cross linking agent selected from the group consisting of formaldehyde, acetaldehyde, and dimethylol ureas and an acidic catalyst.
  • linear bifunctional hydroxyl-terminated polymer is selected from the group consisting of polyester glycol, polyether glycol and poly(oxyalkylene-carboxalkylene) glycol.
  • organic diisocyana-te is selected from the group consisting of 1,3-
  • R is a bivalent organic radical selected from the group consisting of 1,3-phenylene, 1,4-phenylene, 2,4- tolylene, 2,6-tolylene, 4,4'-biphenylene, 2,2'-dimethyl- 4,4'-biphenylene, 3,3'-dimethyl-4,4'-biphenylene, 4,4'-diphenylmethane, 3,3-dimethyl-4,4'-diphenylmethane, 1,5- naphthylene, 1,8-naphthylene, trimethylene, tetramethylene, pentamethylene and hexamethylene radicals;
  • R is a bivalent organic radical selected from the group consisting of ethylene, propylene, iso-propylene and n-butylene radicals;
  • A is a bivalent polymer residue selected from the group consisting of polyester, polyether and poly (oxyalkylene-carboxyalkylene) residues, said bivalent 75 phenylene diisocyan
  • aminoalcohol is selected from the group consisting of ethanolamine, propanolamine, iso-propanolamine, and n-butanolamine.
  • organic solvent is selected from the group consisting of dioxane, acetone, methylethyl ketone, benzene, toluene, dirnethyl torma-mide, diethyl acetamide and dimethyl sulfoxide.
  • linear b'itunctional hydroXyl-terminated polymer is selected from the group consisting of polyester glycol, polyether glycol and poly(oxyalkylene-carboxyalkylene) glycol.
  • organic diisocyanate is selected from the group consisting of 1,3- phenylene diisocyan-ate, 1,4-phenylene diisocyanate, 2,4- tolylene diisocyanate, 2,6-tolylene di-isocyanate, 4,4-biphenylene diisocyanate, 2,2'-dirnethyl-4,4-biphenylene d iisocyanate, 3,3-dimethyl-4,4-diphenylmethane diisocyan ate, 1,5-naphthylene diisocyan-ate, 1,8-naphthylene di-' isocyanarte, trimethylene diisocyan-ate, tetramethylene diisocyanate,pentarnethylene diisocyanate and hexamethylene diisocyanate.
  • aminoalcohol is selected from the group consisting of ethanolarnine, propanolamine, iso-propanol'amine and n-butanolamine.
  • organic solvent is selected from the group consisting of dioxane, acetone, methylethyl ketone, benzene, toluene, dimethyl formamide, ,diethyl a-cetamide and dimethyl sulfoxide.

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyurethanes Or Polyureas (AREA)
US359769A 1963-04-20 1964-04-14 Novel polyurethane elastic filaments and yarns and process for producing the same Expired - Lifetime US3331887A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467626A (en) * 1964-11-02 1969-09-16 Teijin Ltd Process for preparing a highly elastic linear polymer and an elastic article produced therefrom from isocyanate terminated prepolymers reacted with an aminohydrazide
US4102847A (en) * 1975-09-03 1978-07-25 Basf Aktiengesellschaft Baking finishes of low solvent content

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087912A (en) * 1957-09-13 1963-04-30 Bayer Ag Process for the production of crosslinked plastics of high molecular weight
US3148173A (en) * 1959-01-26 1964-09-08 Wyandotte Chemicals Corp Polyurethane-ureas containing urealinked nu-(2-hydroxypropyl) alkylene diamines
US3149998A (en) * 1962-08-01 1964-09-22 Du Pont Color stabilized articles and process for preparing same
US3184426A (en) * 1959-04-17 1965-05-18 Bayer Ag Polyurethane elastic fibers and a method of producing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3087912A (en) * 1957-09-13 1963-04-30 Bayer Ag Process for the production of crosslinked plastics of high molecular weight
US3148173A (en) * 1959-01-26 1964-09-08 Wyandotte Chemicals Corp Polyurethane-ureas containing urealinked nu-(2-hydroxypropyl) alkylene diamines
US3184426A (en) * 1959-04-17 1965-05-18 Bayer Ag Polyurethane elastic fibers and a method of producing the same
US3149998A (en) * 1962-08-01 1964-09-22 Du Pont Color stabilized articles and process for preparing same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467626A (en) * 1964-11-02 1969-09-16 Teijin Ltd Process for preparing a highly elastic linear polymer and an elastic article produced therefrom from isocyanate terminated prepolymers reacted with an aminohydrazide
US4102847A (en) * 1975-09-03 1978-07-25 Basf Aktiengesellschaft Baking finishes of low solvent content

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GB1054215A (enrdf_load_stackoverflow)

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