GB947840A - Elastomeric polyurethane threads - Google Patents

Elastomeric polyurethane threads

Info

Publication number
GB947840A
GB947840A GB1358462A GB1358462A GB947840A GB 947840 A GB947840 A GB 947840A GB 1358462 A GB1358462 A GB 1358462A GB 1358462 A GB1358462 A GB 1358462A GB 947840 A GB947840 A GB 947840A
Authority
GB
United Kingdom
Prior art keywords
diisocyanate
glycol
excess
filament
diamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB1358462A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Globe Manufacturing Co
Original Assignee
Globe Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Globe Manufacturing Co filed Critical Globe Manufacturing Co
Publication of GB947840A publication Critical patent/GB947840A/en
Expired legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

An elastic thread is made from an anhydrous liquid polyurethane prepolymer which is a reaction product of a polymer having terminal alcoholic hydroxyl groups selected from polyesters and polyethers with an excess of an aromatic, aliphatic or cycloaliphatic diisocyanate, by extruding the prepolymer in the form of a filament, passing the filament into a setting bath of 50-97% by weight of an aliphatic amine having two primary amine groups, and 50%-3% by weight of a hydroxyl-containing solvent to effect a setting of the external surface only of the extruded material to a solid state while the interior of the filament remains fluid, and thereafter setting the interior of the filament to a solid, non-porous state under anhydrous conditions at a temperature between 37 DEG C. and the melting point of the polyurethane. In a preferred method, the polymer is an ethylene-propylene adipate, the diisocyanate is tolylene diisocyanate, the aliphatic amine is ethylene diamine, the hydroxyl-containing solvent is water and the interior of the filament is set at 65-205 DEG C., desirably 80-150 DEG C. In general, the curing agent may consist solely of the diisocyanate present in the liquid prepolymer or may consist of the diisocyanate and an organic chain extender having at least two groups reactive with isocyanate groups. Suitable chain extenders, which may be present in a proportion of 0.25%-2% of the prepolymer, include triisopropanolamine, 1,4-butanediol, triethanolamine, Quadrol(tetrakis N,N1-b -hydroxyethyl ethylene diamine) and diethanolamine. The diisocyanate may be present in a molar excess of 20-250% over the polymer, which may be a polyester of a dicarboxylic acid and a glycol or a polyether containing two hydroxyl groups, made by a process in which the polymer-forming reactants include a small amount of a trihydric alcohol, e.g. a polyester may be made from a mixture of ethylene glycol, propylene glycol, adipic acid and a small amount of trimethylol propane or trimethylolethane. Other specified glycols include those with 2-20 carbon atoms, e.g. trimethylene glycol, 1,4-butylene glycol, 1,6-hexanediol; 1,4-butenediol, neopentyl glycol, diethylene glycol, thiodiglycol, and 2,21-dimethyl-1, 3-propylene glycol. Suitable acids include those with 4-20 carbon atoms, e.g. succinic, maleic, dihydromuconic, thiodipropionic, adipic, methyl adipic, glutaric, dimerized linoleic, sebacic, suberic, phthalic, and terephthalic acids. Hydroxycarboxylic acids or their lactones may also be used e.g. caprolactone. Less suitably, natural polyesters may be used e.g. castor oil as well as blown drying oils e.g. blown tung, linseed and soya oils. An excess of the glycol over the acid is used in making the polyesters so that they contain terminal hydroxyl groups. Polyethers containing terminal hydroxyl groups which may be used in place of the polyesters include polyethylene glycol, polypropylene glycol, mixed polyethylene-polypropylene glycol and polytetramethylene glycol. Polyethers may be used in conjunction with polyesters as in for example polydiethylene glycol adipate and polytriethylene glycol adipate. The polyester or polyether is "capped" with an excess of the diisocyanate by mixing the reagents at room or elevated temperatures e.g. 70-150 DEG C. and especially 90-100 DEG C. to form an uncured liquid prepolymer soluble in methyl ethyl ketone, the prepolymer being essentially a linear polyurethane having terminal isocyanate groups. In addition to tolylene diisocyanate, others specified include m- and p-phenylene diisocyanate, p-p1-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, p-p1-diphenyl methane diisocyanate, 3,31-bitolyene-4,41-diisocyanate 2,4-6-tolylene diisocyanate dimer, dianisidine diisocyanate, and 4-chloro-1,3-phenylene diisocyanate. Prior to spinning the polyester or polyether and diisocyanate mixture may be diluted with 0-20% of conventional urethane solvents e.g. acetone, methyl ethyl ketone, dimethyl formamide, dimethyl acetamide, ethylene carbonate, propylene carbonate and dimethyl sulphoxide. Pigments, delusterants, heat stabilisers and ultra-violet absorbents may also be added. Suitable amines for the amine-water bath include, in addition to ethylene diamine, hexamethylene diamine, diethylene triamine, tetraethylene pentamine, 3,31-diaminodipropyl ether, diaminodibutyl sulphide and propylene diamine. The preferred hydroxyl compound is water, but other compounds which may be used include ethylene glycol, 1,4-butanediol, 1,3-butylene glycol, propylene glycol, glycerine, hexanetriol and ethyl alcohol. Desirably the bath is at 90-95 DEG C., but room temperature or temperatures of 35-100 DEG C. may in general be used. The surface of the extruded filament quickly becomes solid, the interior remaining liquid, and further diffusion of the diamine into the core is thus prevented. After spinning, and prior to curing the interior, the thread may be passed first through a water bath to remove unreacted diamine, dried over steam heated rolls and then passed through a talc box to coat the surface of the thread and eliminate the possibility of sticking to itself when taken up on a spool. The threads are then cured e.g. at 65-205 DEG C. for 30 minutes to 30 hours, usually 1-18 hours, preferably at 90-120 DEG C. for 1-2 hours. The excess diisocyanate present in the core reacts internally to complete the cure, so that no curing agent need be present. The cured threads can be stretched up to 400% their original length in conventional manner, the stretched threads being then post-cured at least 65 DEG C., 93 DEG C.-150 DEG C. being preferred, for 30 minutes-30 hours, usually for 1-15 hours. The elastic polyurethane threads so made by the partial interfacial and bulk polymerization process are thought to comprise polyester or polyether segments capped with a molecular excess of diisocyanates and reacted with aliphatic primary diamines, biuret linkages obtained from subsequent reaction of the urea hydrogens with the excess diisocyanate, and allophonate linkages obtained from subsequent reaction of the urethane hydrogens with the excess diisocyanate. The threads show no blistering, and do not discolour upon heat ageing, and are resistant to chlorine bleach. U.S.A. Specifications 2,650,212, 2,755,266, 2,953,839, 2,957,852 and 2,962,470 are referred to.
GB1358462A 1961-05-17 1962-04-09 Elastomeric polyurethane threads Expired GB947840A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11082061A 1961-05-17 1961-05-17

Publications (1)

Publication Number Publication Date
GB947840A true GB947840A (en) 1964-01-29

Family

ID=22335125

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1358462A Expired GB947840A (en) 1961-05-17 1962-04-09 Elastomeric polyurethane threads

Country Status (1)

Country Link
GB (1) GB947840A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415790A (en) * 1964-06-29 1968-12-10 Eastman Kodak Co Removing unreacted diisocyanates from macrodiisocyanates and polymerizing to form segmented polyurethane copolymers
US3496144A (en) * 1965-12-04 1970-02-17 Basf Ag Production of hydrolysis-resistant polyurethane elastomers based on adipic acid; 1,6-hexanediol; 2,2,4-trimethyl-1,3-pentanediol polyesters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3415790A (en) * 1964-06-29 1968-12-10 Eastman Kodak Co Removing unreacted diisocyanates from macrodiisocyanates and polymerizing to form segmented polyurethane copolymers
US3496144A (en) * 1965-12-04 1970-02-17 Basf Ag Production of hydrolysis-resistant polyurethane elastomers based on adipic acid; 1,6-hexanediol; 2,2,4-trimethyl-1,3-pentanediol polyesters

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