US3376264A - Process for producing stabilized polyurethane fibers - Google Patents

Process for producing stabilized polyurethane fibers Download PDF

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Publication number
US3376264A
US3376264A US457171A US45717165A US3376264A US 3376264 A US3376264 A US 3376264A US 457171 A US457171 A US 457171A US 45717165 A US45717165 A US 45717165A US 3376264 A US3376264 A US 3376264A
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Prior art keywords
diisocyanate
polyester
water
fibers
spinning
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US457171A
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English (en)
Inventor
Wieden Horst
Brenschede Wilhelm
Lenz Hans
Rellensmann Wolfgang
Nischk Gunther
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Bayer AG
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Bayer AG
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Classifications

    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • 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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/906—Fiber or elastomer prepared from an isocyanate reactant

Definitions

  • ABSTRACT OF THE DISCLOSURE Stabilized polyurethane fibers are produced by (A) reacting in a solvent which will dissolve polyacrylonitrile (1) an NCO prepolymer prepared from a linear polyester containing terminal hydroxyl groups and an arcmatic diisocyanate with (2) Water and (3) a bifunctional chain extending agent containing tertiary nitrogen compounds and (B) spinning the solution into an elastic fiber having improved dyeability with acidic dyes.
  • This invention relates to spandex fibers and to a method of preparing the same. More particularly, it relates to a method of preparing spandex fibers capable of being dyed with acidic dyes.
  • This copending application discloses and claims a process for preparing spandex fibers by reacting a dihydroxy polyester having an hydroxyl number of 35 to 110 and preferably from 40 to 70 with an excess of from about 115 to about 300% of an aromatic diisocyanate in the melt at a temperature less than 120 C. and then reacting this product with from about 80 to about 120% of water based on the free NCO groups at a temperature of from about to 50 C. and preferably '18 to 40 C. in a polyacrylonitrile solvent.
  • This solution is then degassed and spun into fibers by either the wet or dry spinning method.
  • Such fibers exhibit good textile technological properties such as high tensile strength, low set and a high elasticity modulus. However, they cannot be satisfactorily dyed using anionic (acidic) dyes. Further, dyeing of these spandex fibers in mixtures with other wellknown synthetic fibers cannot be accomplished in the known one-bath procedure.
  • spandex fibers capable of being dyed by acidic dyes. It is also an object of this invention to provide a method of preparing spandex fibers capable of being dyed with acidic dyes. It is still another object of this invention to provide spandex fibers having good textile technological properties which are capable of being dyed by acidic dyes.
  • the invention thus contemplates preparing a spinning solution of a polyurethane polymer in a polyacrylonitrile solvent by reacting a dihydric polyester having an hydroxyl number of about 35 to about with an excess of from about to about 300% of an aromatic diisocyana-te based on the hydroxyl groups present, at a temperature of from about 10 to about 50 C. with from about 80% to about based on the free NCO groups remaining of water, this reaction being conducted in a polyacrylonitrile solvent, and during the preparation of the spinning solution, reacting a compound having the formulas set forth above in an amount of from about 1 to about 40% based on the excess of diisocyanate.
  • T represents a straight carbon atoms in the chain, for example, ethylene, propylene, butylene, amylene, hexylene, heptylene, octylene, Z-methyl propylene, 2-ethyl propylene, 3-cyclohexyl butylene, 4-propyl butylene, 3-methyl butylene, l-ethyl propylene, 6-cyclopentyl octylene, Z-methyl ethylene and the like;
  • R represents an alkyl or cycloalkyl radical such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl and various positional isomers thereof, such as, for example, l-methylbutyl, Z-methylbutyl, 3-methylbutyl, 1,1dimethylpropyl, 1,2-d
  • the compounds having the generic formula set forth are added in an amount based on the excess of diisocyanate present of from about 1 to about 40% and preferably from about 5 to about 30%
  • Specific compounds within the formula represented include N-methyldiethanol amine, N-cyclohexyl-diethanol amine, N('yamino propyl)N,N'-dirnethyl ethylene diamine, N(yamino propyl)N-methyl ethanol amine, N,N'-di(flhydroxy ethyl)N,N-diethyl hexahydro-p-phenylene diamine, N,N-di(' -amino propyl)N,N'-dimethyl ethylene diamine and the like.
  • piperazine derivatives such as, for example, N,N'-bis(hydroxyalkyl)- piperazine, N,N"bis(amino alkyl) piperazine, N-(hydroxalkyl)piperazine and N-(amino alkyl) piperazine and particularly, N,N-bis(B-hydroxy ethyl)piperazine, N,N'- bis ('y-amino propyl)piperazine, N-(B-hydroxyethyD-piperazine and N-(fi-amino ethyl) piperazine and the like.
  • the piperazine compounds are preferred because in addition to improving the dye baths of the spun fibers, they also improve the ultraviolet stability of the fibers.
  • the highly viscous solutions obtained according to the present invention having a substantially linear molecular structure, do not cross-link on standing even for a long period.
  • these solutions do not show any degradation phenomena, either at room temperature or at higher temperature, since as a result of their linear molecular structure, no allophanate or biuret groups form in the solvent. After complete degasification in vacuo, they can be spun by the Wet or the dry spinning processes.
  • Any linear polyesters containing terminal hydroxyl groups having an hydroxyl number of from about 35 to about 110, preferably from about 40 to about 70 and an acid number below about and preferably between 0 and 3, can be used in accordance with this invention such as, for example, those prepared by reacting a lactone with a suitable initiator such as those disclosed in US. Patents 2,890,208, 2,933,478 and 2,990,379 and those prepared by reacting a dicarboxylic acid with a dihydric alcohol.
  • Any suitable dicarboxylic acid may be used in the preparation of the hydroxyl polyester such as, for example, adipic acid, succinic acid, sebacic acid, suberic acid, oxalic acid, methyl adipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, thiodipropionic acid, thodibutyric acid, sulfonyl-dibutyric acid, maleic acid, fumaric acid, citraconic acid, itaconic acid and the like.
  • adipic acid succinic acid, sebacic acid, suberic acid, oxalic acid, methyl adipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, thiodipropionic acid, thodibutyric acid, sulfonyl
  • any suitable dihydric alcohol may be used in the reaction with the dicarboxylic acid to form a polyester such as, for ex ample, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, amylene glycol, hexanediol, hexahydroxylene, glycol, bis(hydroxymethylcyclohexane) and the like.
  • the hydroxyl polyester may contain urethane groups, urea groups, amide groups, chalkogen groups and the like.
  • the hydroxyl terminated polyester includes, in addition to hydroxyl terminated polyesters, also hydroxyl terminated polyester amides, polyester urethanes, polyetheresters and the like.
  • Any suitable polyester amide may be used such as, for example, the reaction product of a diamine or an amino alcohol with any of the compositions set forth for preparing polyesters.
  • Any suitable amine may be used such as, for example, ethylene diamine, propylene diamine, tolylene diamine and the like.
  • Any suitable amino alcohol such as, for example, fl-hydroxy ethyl-amine and the like may be used.
  • Any suitable polyester urethane may be used such as, for example, the reaction of any of the above-mentioned polyesters or polyester amides with a deficiency of an organic polyisocyanate to produce a compound having terminal hydroxyl groups. Any of the polyisocyanates set forth hereinafter may be used to prepare such compounds.
  • Any suitable polyetherester may be used such as, for example, the reaction product of an ether glycol and a polycarboxylic acid such as those mentioned above, with relation to the preparation of polyesters.
  • Any suitable ether glycol may be used such as, for example, diethylene glycol, triethylene glycol, 1,4-phenylene'bis-hydroxy ethyl ether, 2,2-diphenylpropane-4,4-bis-hydroxy ethyl ether and the like. It is desirable to use those polyesters of which the acids and glycols contain a relatively large number of carbon atoms, particularly in order to obtain water-repellent filaments or fibers. It is preferred to use scarcely lengthened and carry free isocyanate groups. It
  • polyester-diisocyanate adducts By this increase in the quantity of diisocyanate, it is possible to vary considerably the ratio between soft and hard molecule segments and thus also the elongation at break,
  • aromatic diisocyanates such as, for example, p-phenylene diisocyanate, 1,5-napthylene diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3
  • dimethyl-4,4-diphenylmethane diisocyanate 4,4'-diisocyanatostilbene, 4,4'-diisocyanatodibenzyl and, mixtures of 2,4- and 2,6-toluylene diisocyanate, diphenyl-4,4-diisocyanate and the like. It is. preferred to use symmetrical aromatic diisocyanates and 4,4-diphenylmethane diisocyanate.
  • the isocyanate-modified polyesters with free isocyanate groups as thus prepared are then dissolved in that quantity of polyacrylonitrile solvent which is necessary for the required final concentration and caused to react at 10 to 50, advantageously at 18 to 40, with to of water, based on the free isocyanate groups which are present.
  • the deficiency is notto fall below 20% based on the equivalent quantity.
  • Any suitable solvent that will dissolve polyacrylonitrile may be used such as, for example, dimethylformamide, dimethylacetamide, dimethylsulphoxide, dimethoxy dimethyl acetamide and the like. They must be free from constituents which are capable of reacting with diisocyanates although they can-contain the usual technical quantity of water and this quantity must then be taken into account as part of the total quantity of water.
  • the isocyanate-modified polyester When carrying out the reaction, it is not necessary for the isocyanate-modified polyester to be initially dissolved in the quantity of solvent necessary for the required final condensation and then reacted with the water; the isocyanate-modified polyester can be first of all dis-.
  • the water necessary for the furtherreaction possibly already dissolved in more solvent, is added, dilution being effected during the reaction to the required final concentration.
  • the water in that quantity of solvent which is necessary for the required final concentration is added immediately to the isocyanate-modified polyester.
  • Reaction is allowed to take place for several hours, for example, between 4 and 48 hexamethylene diisocyanate, the reaction products of three mols each of the two aforesaid isocyanates with one mol each of water and one mol of a triol, hexahydrop-phenylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate and 3,3-dimethyl-4,4-dicyclohexylmethane diisocyanate and the like.
  • the spinnable solutions prepared as described have an excellent stability at room temperature or slightly raised temperature. No break-down of the solutions has been observed, even on relatively long storage.
  • the solutions are spun to form elastic filaments or fibers, either dry, i.e., at high temperature in air or inert gases, or wet, i.e., high tensile strength, low permanent elongation and high E-modulus.
  • An additional advantage is that the separate capillaries can be easily separated again after coagulation, so that such fibers can readily be used as staple fibers.
  • the compounds of the generic formula can be added at any step during the preparation.
  • the compounds can be added to the polyacrylonitrile solutions maintained at to 50 C. and preferably at 10 to C. Subsequently, to this addition, the desired amount of water can be added. It is not absolutely necessary, however, that the isocyanate modified polyester be dissolved in the polyacrylonitrile solvent in the final concentration and then reacted with the basic compound and water. It is also within the scope of the invention to dissolve the modified polyester in a small amount of solvent and then add the basic compound and water which may be dissolved in a further quantity of solvent. This solution can then be diluted during reaction until the desired end concentration is reached.
  • the compound in accordance with the formula set forth and the water are added directly in the total amount to reach the final concentration to the modified polyester.
  • the reaction is permitted to run for several hours, e.g., between 3 and 24 hours at a temperature of 10 to 50 C. and preferably from about 18 to 40 C.
  • the solution Prior to spinning, it is preferred that the solution be degassed under vacuum and that the solids-content of this solution in the time of spinning is from about 10 to about 35%.
  • these compounds can also be added within the limits stated to the reaction of the polyester within the aromatic diisocyanate in the melt.
  • the polymers of the fibers formed from the spinning solutions are substantially free of cross-links. These solutions exhibit excellent stability at room temperature or even slightly higher temperatures and do not degrade after long storage periods.
  • Example 1 About 250 parts of a polyester having an hydroxyl number of 56 and prepared from adipic acid, 1,6-hexanediol and neopentyl glycol in a mol ratio of 10:6.6:3.5 are heated to a temperature of about 75 C. and clear melt results. To this melt, with stirring, is added about 71.9 parts of 4,4-diphenylmethane diisocyanate and maintained at a temperature of about 75 to about C. for about 45 minutes.
  • the solids content of the solution is about 27% (c) To the polyester-diisocyanate adduct and free diisocyanate melt is added with agitation, about 1.25 parts of N,N-bis(fi-hydroxyethyl)piperazine and about 2.55 parts of water and about 863 parts of dimethyl formamide at a reaction temperature of about 50 C. After 5 to 6 hours, the solution has the desired spinning viscosity. An additional 0.8 part of water is added to the spinning solution which is allowed to cool to room temperature. The solids content of the solution is about 27%.
  • Example 3 The fibers thus obtained can be dyed with acidic dyes
  • To about 250 parts of the polyester of Example 1 and the quantities of N,N-bis(l3-hydroxyethyl)piperazine set forth in Table 2 in the molten state at about 75 C. are added under intensive agitation about 71.9 parts of 4,4- diphenylmethane diisocyanate.
  • the reaction is permitted to proceed for about 45 minutes at a temperature of about 75 -80 C. and then the quantities of dimethyl formamide set forth in Table 2 are added.
  • the dimethyl formamide has incorporated therein the quantities of Water also set forth in the table.
  • the quantities of dirnethyl formarnide given are calculated to yield a solids content of 27%.
  • the reaction temperature is maintained at about 50 C.
  • the solution has reached the desired spinning viscosity.
  • the reaction is stopped by stirring therein an amount of water calculated to be about 12 to in excess of the free isocyanate present in the polyisocyanate reaction melt. This amount of water is indicated in the last column of the table.
  • the solution is then cooled to room temperature.
  • the elastomeric spinning solutions are degassed in vacuum and filtered. These solutions have the desired spinning viscosity for producing endless multi-fillers, elastomeric fibers having a titer between about 40 and 2000 denier.
  • the solutions are spun through a multi-hole nozzle into a heated channel having substantially no turbulence near the nozzle and which is blown with heated air or inert gas.
  • the solvent containing air is sucked away from the channel ending.
  • the fiber leaving the channel is wound on a spool with a velocity of 200-1000 rn./rnin.
  • the temperature of the channel and the blown air or inert gas is set such that the spun fibers have a final solvent content of less than one percent.
  • the solution is spun through a multi-hole nozzle into an aqueous precipitation bath having a length of from about 10 to 20 meters and maintained at a temperature of from about 20 to about 70 C.
  • the aqueous bath contains alone or in combination with other synthetic filaments capable of being dyed with the same type dyes to produce final products suitable for weaving certain fabrics having stretched properties such as, for example, swimming apparel and the like.
  • T-Z II-ZT.L (T-Z) H
  • Z is selected from the group consisting of- NHand-O-
  • T is an alkylene radical having from 2 to 8 carbon atoms in the chain
  • n is a cardinal number of from 0 to 1
  • L is a member selected from the group consisting of wherein R is a radical selected from the group consisting of alkyl and cycloalkyl and A is a radical selected from 3.

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  • Chemical & Material Sciences (AREA)
  • 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)
US457171A 1964-01-15 1965-05-19 Process for producing stabilized polyurethane fibers Expired - Lifetime US3376264A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEF41746A DE1235499B (de) 1964-01-15 1964-01-15 Herstellen von Faeden oder Fasern aus Polyurethanen
DEF42967A DE1244335B (de) 1964-01-15 1964-05-23 Verfahren zur Herstellung von gummielastischen Faeden bzw. Fasern

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US739946*A Expired - Lifetime US3536668A (en) 1964-01-15 1968-05-28 Process for the production of polyurethane fibers

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BE (1) BE658363A (d)
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GB (1) GB1072081A (d)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3495929A (en) * 1965-12-01 1970-02-17 Geigy Chem Corp Method for improving the fastness to gas fading of dyed material
US3518045A (en) * 1964-12-10 1970-06-30 Bayer Ag Dyed polyurethane threads
US3522304A (en) * 1967-07-03 1970-07-28 Wyandotte Chemicals Corp Preparation of polyhydroxy diureas
US3666708A (en) * 1969-02-13 1972-05-30 Asahi Chemical Ind Method for preparing stable polyurethane solutions

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1669423C3 (de) * 1967-03-10 1974-07-18 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von elastischen Polyurethanfäden
DE3145991A1 (de) * 1981-11-20 1983-06-01 Beiersdorf Ag, 2000 Hamburg "verwendung von beschleunigern zur polyurethan-haertung und entsprechende polyurethan-klebstoffe"
DE3223398A1 (de) * 1982-06-23 1983-12-29 Bayer Ag, 5090 Leverkusen Polyamine, verfahren zur herstellung von polyaminen und deren verwendung zur herstellung von polyurethanen
DE3534947A1 (de) * 1985-10-01 1987-04-09 Bayer Ag Verfahren zur herstellung von polyaminen, polyamine und deren verwendung zur herstellung von polyurethanen
US5183614A (en) * 1989-01-26 1993-02-02 E. I. Du Pont De Nemours And Company Method for producing x-ray detectable spandex fibers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2755266A (en) * 1951-02-22 1956-07-17 Bayer Ag Solutions of elastomers derived from isocyanate modified polyesters
US3097192A (en) * 1958-01-09 1963-07-09 Du Pont Elastic filaments from polyesterurethane-urea polymers
US3180853A (en) * 1961-04-06 1965-04-27 Du Pont Polyurethane prepolymer chain-extended with an n-lower alkyl amino-bislower alkyl amine
US3248370A (en) * 1961-10-31 1966-04-26 Bayer Ag Polyurethane process utilizing a diisocyanate mixture
US3305533A (en) * 1961-12-30 1967-02-21 Bayer Ag Polyurethane polymers having urethane and semi-carbazide groupings

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2755266A (en) * 1951-02-22 1956-07-17 Bayer Ag Solutions of elastomers derived from isocyanate modified polyesters
US3097192A (en) * 1958-01-09 1963-07-09 Du Pont Elastic filaments from polyesterurethane-urea polymers
US3180853A (en) * 1961-04-06 1965-04-27 Du Pont Polyurethane prepolymer chain-extended with an n-lower alkyl amino-bislower alkyl amine
US3248370A (en) * 1961-10-31 1966-04-26 Bayer Ag Polyurethane process utilizing a diisocyanate mixture
US3305533A (en) * 1961-12-30 1967-02-21 Bayer Ag Polyurethane polymers having urethane and semi-carbazide groupings

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3518045A (en) * 1964-12-10 1970-06-30 Bayer Ag Dyed polyurethane threads
US3495929A (en) * 1965-12-01 1970-02-17 Geigy Chem Corp Method for improving the fastness to gas fading of dyed material
US3522304A (en) * 1967-07-03 1970-07-28 Wyandotte Chemicals Corp Preparation of polyhydroxy diureas
US3666708A (en) * 1969-02-13 1972-05-30 Asahi Chemical Ind Method for preparing stable polyurethane solutions

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Publication number Publication date
BE658363A (d) 1965-04-30
GB1072081A (en) 1967-06-14
DE1244335B (de) 1967-07-13
US3536668A (en) 1970-10-27
DE1235499B (de) 1967-03-02

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