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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
  • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
• • 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
• • 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
  • Y10S528/903—Polymerizing or processing an isocyanate under substantially anhydrous conditions
• • 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

• R1 LR where R and R are lower alkyl and R is an alkylene ing, by providing spinning solutions for the preparation radical of 2 to 6 carbon atoms.
• the solutions are spun of spandex fibers by reacting in a polar solvent for polyby the wet or dry spinning method to prepare filaments.
• This invention relates to the preparation of polyure- R thane spinning solutions and to rubbery elastic filaments J and fibers from segmented polyurethane-polyurea elastomers which are resistant to gel formation when dissolved 0 in polyacrylonitrile solvents.
• the elastic filaments and fibers based on polyurethanes, which prepolymer is prepared by reacting a substantially linear filaments and fibers have a large number of uses in the 40 polyester having terminal hydroxyl groups and a molecutextile industry in which they are either spun singly or lar weight of from about 1600 to about 2600 with 4,4-diare ensheathed by other filaments wound or spun around phenylmethane diisocyanate in a ratio of NCO to OH them. They are mainly used in the production of corsets, of from about 1.5/1 to about 1.95/1.
• the highly viscous sportswear, elastic stockings and in the manufacture of spinning solutions are subsequently formed into elastic elastic bands for use in underwear and stockings.
• the filaments by the wet or dry spinning process.
• the diamino compounds used in admixture with ethylhigh molecular weight segmented polymers containing in ene diamine and represented by the formula above may the molecule, urethane and urea groups, which polymers also be represented by the formulae may be prepared by the isocyanate polyaddition process R from polyesters or polyethers containing hydroxyl groups, l l
• the prepolymers are extruded by a process known as chemical spinning, through spin- R2 ning nozzles into a coagulating bath which contains crossh re R 1 War 1k 1 Such a meth l eth 1 l linking agents.
• R4 is an alkylene radical of 2 to 6 carbon atoms sirable to prepare solutions of high molecular weight seg- Such as ethylene, P py y n myl n 0f xylmented polyurethane-polyurea adducts in suitable solv- 6116, bonded to the Carbon atom term diat t W0 ents and to work up these solutions into filaments and a omatic rings to form a cycloaliphatic radical. fibers by the wet or dry spinning process.
• polyesters conbe used Such f pl 2,2-bis-(4-amin0phenyl) taining hydroxyl groups and diisocyanates may be reacted propane, l,1-bis-(4-aminophenyl)-cyclohexan together at elevated temperatures to produce NCO-conaminophenyl)-diethylmethane, bis-(4 aminophenyl)- taining prepolymers and then to react these in polyacryloethyl, isopropyl methane, bis-(4-am1nophenyl)-tert1ary nitrile solvents at temperatures below 20 C.
• the filaments obtainable from these bis-(4-aminophenyl)-cyclopropane, 1,1 bis-(4 aminosolutions by spinning have good physical and elastic propphenyl)-cyclobutane, 1,l-b1s-(4-am1nophenyl)-cyclopen 3 tane, 1, l-bis- (4-aminophenyl) -cyclohexane, aminophenyl)-cycloheptane and the like.
• a substantially linear polyester containing hydroxyl groups and having an average molecular Weight of from about 16 to about 2600, preferably from about 1700 to about 2100 is reacted in the melt or in inert solvents such as methylene dichloride, tetrahydrofuran, dioxan, benzene or chlorobenzene, and if desired mixed with low molecular weight diols containing one or more tertiary nitrogen atoms, with diphenyl methane- 4,4'-diisocyanate at temperatures below 130 C.
• the ratio of NCO to OH groups in the components used in the reaction should be from about 1.5 :1 to about 1.95:1 in order that prepolymers containing free NCO groups will be produced.
• the linear polyesters containing terminal hydroxyl groups are prepared by condensation of dicarboxylic acids and diols at elevated temperatures.
• the acid numbers are generally below 8, preferably 0 to 3.
• the melting point of the polyester is preferably below about 60 C. because otherwise the elastic properties of the end products will be impaired, especially at low temperatures, and the tendency of the polymers to gel in solution will also be adversely affected.
• Any suitable dicar-boxylic acids may be used in the preparation of the polyesters such as, for example, succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, thiodibutyric acid, sulphonyl dibutyric acid and the like.
• Any suitable diol may be used, such as for, example, ethylene glycol, diethylene glycol, propane-1,2-diol, butane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, hexahydrop-xylylene glycol, 2,2-dirnethylpropane-1,3-diol, 2,2-diethy1-propane-1,3-diol, the hydroxyalkylation products of the above glycols and the like. Polyesters of lactones, e.g. s-caprolactone, may also be used as starting materials.
• polyesters prepared in this way are highly reactive one may deactivate them using small quantities of dioxane/SO adduct, benzoyl chloride or traces of hydrogen chloride before the subsequent reaction with diphenyl methane-4,4-diisocyanate.
• any suitable low molecular weight diols containing one or more tertiary nitrogen atoms may, if desired, be mixed in with the polyester, such as, for example, the bishydroxyalkylation products of primary and disecondary amines with ethylene oxide, propylene oxide and butylene oxide, and have a molecular weight of less than 500 such as, for example, N-methyLdiethanolamine, N-butyI-diethanolamine, N-cyclohexyl-diethanolamine, N,N-di-(/8- hydroxyethyl) N,N-diethyl-hexahydro-p-phenylene diamine, N,N-di-(fi-hydroxyethyl)-N,N-di-methyl-ethylene diamine, bis-jS-hydroxyethylpiperazine and the like.
• the polyester such as, for example, the bishydroxyalkylation products of primary and disecondary amines with ethylene oxide, propylene oxide and but
• tertiary nitrogen atoms particularly preferred are compounds such as l lmethyldiisopropanolamine and N,N di (ii-hydroxypropyl)-N,N-dimethyl-ethylene diamine, although low molecular Weight basic polyethers containing tertiary nitrogen atoms, which polyethers are obtainable by condensation of the above mentioned compounds in the presence of phosphorus acid, may also be mixed with the polyester.
• the quantity of diols containing one or more tertiary nitrogen atoms should always be so calculated that the tertiary nitrogen atoms-content based on the finished elastomer substance, does not exceed 200 millequivalents/ kg. but in most cases only 80 to 150 millequivalents of tertiary nitrogen are present per kilogram of elastomer substance.
• the NCO-containing prepolymers obtained in the melt are introduced slowly, with stirring, at temperatures 'below about 35 C., and preferably below about 25 C. into a solution of ethylene diamine and the additional diamine in a polyacrylonitrile solvent.
• the quantity of solvent used is usually so calculated that the polyurethane-polyurea solution has the desired final concentration after termination of the chain lengthening reaction.
• the solids content of the final elastomer solution may amount to 18 to 30% by Weight.
• the polyacrylonitrile solvents used such as N,-N-dimethylformamide, N,N-dimethyl-acetamide and N-methylpyrrolidone, must be free from constituents Which are capable of reacting with diisocyanates although these solvents may contain the small quantities of water usually present in the commercial products.
• the molar ratio of the chain lengthening mixture of ethylene diamine and additional diamine employed may be varied between 50:50 and :15 but is preferably between 75 :25 and 80:20. However, the molar ratio of chain lengthening mixture is partly predetermined by the ratio of NCO to OH groups used in the preparation of the NCO-containing prepolymer. In general, if the NCO content of the prepolymer is relatively low, the proportion of additional diamine used in the chain lengthening mixture will also be low, whereas conversely a higher NCO content in the prepolymer will necessitate a higher proportion of additional diamine when preparing non-yellowing polyurethane-polyurea solutions.
• the quantity of diamine mixture used in the chain lengthening reaction amounts to to mols percent, depending on the NCOzOI-I ratio and the desired final viscosity of the prepolymer, the given percentage being based on the free NCO group-content of the prepolymer.
• the prepolymer melt can be dissolved in part of the polyacrylonitrile solvent and the solution rapidly cooled to about 25 C. to about 30 C. This solution is then added to the solution of chain lengthening mixture described before. If, however, the prepolymer was prepared in one of the above mentioned inert solvents, it is generally advisable to remove the solvent by distillation before the chain lengthening reaction takes place although the process is in no way impaired by the presence of these inert solvents provided they do not amount to more than 20% by weight of the total quantity of solvent.
• polyurethane-polyurea polymers which may be obtainable in solution under the given conditions are of special importance for working up on an industrial scale owing to their good solubility, and the resistance of their solutions to gel formation and to degradation at room temperature or slightly elevated temperature.
• the elastic filaments or fibers are produced by known spinning techniques either dry, i.e., by spinning the elastomer solution into air or inert gases at elevated temperature or Wet, i.e. injecting the elastomer solution into coagulating baths and winding the resulting filaments, and surface treating the filaments so formed with talc or oily dressing to prevent their sticking together on the spool.
• the spun filaments have excellent physical properties such as high elongation on tearing and strength, low permanent elongation and high E-modulus.
• EXAMPLE 1 About 250 parts of a polyester of adipic acid, hexane- 1,6-diol and 2,2-dimethylpropane-l,3-diol (proportion by weight of diols 65/35; OH number 55.5; acid number 0.8) are dehydrated for about one hour at about 120 C. and under a pressure of about 12 mm. Hg and are then reacted with about 50 parts of diphenylmethane-4,4'-diisocyanate at from about 90 to about 95 C. for about one hour. The melt of the polyesterdiisocyanate adduct is dissolved in about 400 parts of N,N-dimethylforrnamide and cooled to 20 to 25 C. within about minutes.
• This solution is introduced in the course of about 5 minutes at to C., with stirring, into a solution of about 3.8 parts of ethylene diamine, about 3.6 parts of 2,2-bis-(4'-aminophenyl)-propane and about 432 parts of N,N-dimethylformamide, the viscosity of the solution increasing rapidly during this operation.
• the spinning solution which contains about 27% of solids has a viscosity of about 390 poises at 20 C. It is spun by the wet spinning process under the spinning conditions described hereinafter to yield filaments having the following properties:
• About 250 parts of the dehydrated polyester described in Example 1 are reacted at 90 to 100 C. in about 130 parts of anhydrous chlorobenzene with about 50 parts of diphenylmethane-4,4-diisocyanate in the course of about one hour.
• the solution of the polyester-diisocyanate adduct is then cooled to about C. and introduced at 15 to 20 C. into a solution of about 3.6 parts of ethylene diamine, about 3.4 parts of 2,2-bis-(4-aminophenyD-propane and about 702 parts of N,N-dimetbylformamide.
• the spinning solution produced is a accompanied by a rapid rise in viscosity to about 300 poises at 20 C., and the solution having a solids content of about 27%, is spun by the wet spinning process described hereinafter to form filaments having the following properties:
• Elongation at break percent 650 Permanent elongation do 18 E-modulus mg./de n 62 EXAMPLE 3 About 3 parts of a 36% SO /dioxan solution are added to about 250 parts of the polyester described in Example 1 and this reaction mixture is stirred for about 4 hours at about 100 C. and then allowed to stand for about one hour at about 100 C. and then freed from dioxane and traces of water by keeping it at about 100 C. under a pressure of about 12 mm. Hg for about one hour.
• N-methyl-diisopropanolarnine About 5 parts are stirred into the polyester melt, and an NCO-containing prepolymer is obtained by further reaction with about 63.6 parts of diphenylrnethane-4,4'-diisocyanate at about 80 to about 85 C. for one hour.
• This prepolymer is dissolved within about 10 minutes in about 400 parts of N,N-dimethylformamide (H O content 0.01%) and is at the same time cooled to about 25 C.
• the prepolymer solution is introduced at about 16 to about 22 C. with stirring, in the course of about 25 minutes into a mixture of about 4.95 parts of ethylene diamine, about 7.28 parts of 1,1-bis-(4-aminophenyl)- cyclohexane, about 8.3 parts of titanium dioxide and about 517 parts of N,N-dimethylformamide. Viscosity of the solution is 237 poises/20 C.
• the solids content of the solution is 27% by weight.
• the elastomer contains 100 millequivalents of tertiary nitrogen per kilgram.
• the spinning solution is worked up into filaments under the conditions of the wet spinning process described hereinafter, the following filament properties being obtained.
• About 250 parts of the polyester described in Example 1 are deactivated in a manner analogous to that described in Example 3 and dehydrated.
• About 5 parts of N-methyldiisopropanolamine are then stirred in and an NCO- containing prepolymer is obtained by reaction with about 71.5 parts of diphenylmethane-4,4-diisocyanate at about to about C. for about one hour.
• the prepolymer is dissolved within about 15 minutes in about 400 parts of N,N-dimethylformamide (H O content of 0.01%) and is at the same time cooled to about 25 C.
• NCO-containing solution a stirred mixture of about 6.28 parts of ethylene diamine, about 9.3 parts of 1,1 bis-(4-aminophenyl)- cyclohexane, about 8.6 parts of titanium dioxide and about 548 parts of N,N-dimethylformamide at about 20 to about 27 C.
• About one part of hexamethylene-1,6 diisocyanate dissolved in about 5 parts of N,N-dimethylformarnide is then stirred in, After about four hours, the viscosity is about 340 poises/20 C.
• the proportion of elastorner compound in the spinning solution is 27% by weight and the amount of tertiary nitrogen is 97 millequivalents/ kg. of solid.
• the solution is worked up by the wet spinning process described hereinafter, filaments having the following properties being obtained:
• EXAMPLE 5 About 2 parts of a 39 percent SO /dioxane solution are added to about 250 parts of the polyester described in Example 1 and the reaction mixture is stirred for about 2 hours at about C. and then freed from dioxane and traces of Water by heating for about one hours at about 100 C. under a pressure of 12 mm. Hg.
• NCO-containing prepolymer obtained by reaction of this solution with about 56.25 parts of diphenylmethane- 4,4'-diisocyanate for about one hour at about 85 to about 90 C., and this prepolymer is then dissolved in about 400 parts of N,N-dimethylformamide (H O content 0.02 percent) and cooled to about .25 C. within about 15 minutes.
• Elongation at break percent 440 Permanent elongation do 19 E-modulus mg./den-- 145 EXAMPLE 6
• About 3750 parts of the dehydrated polyester described in Example 1 are reacted for about one hour at about 82 to about 87 C., with stirring, with about 844 parts of diphenylmethane-4,4'-diisocyanate, the product then being dissolved in about 6000 part of N,N-dimethylformamide and cooled to about C. in about 25 minutes.
• This NCO-containing prepolymer solution is introduced at 20 to 25 C.
• the resulting spinning solution has a viscosity of 620 poises/ 20 C. at a solids content of 27 percent.
• the spinning solution is then worked up by the dry spinning process described hereinafter to form filaments which have the following properties:
• About 3750 parts of the dehydrated polyester described in Example 1 are reacted for about one hour at 80 to 85 C. with stirring, with about 750 parts of diphenylmethane-4,4'-diisocyanate and product obtained is dissolved in about 6000 parts of N,N-dimethylformamide and cooled to about 25 C. in about 20 minutes. This NCO-containing prepolymer solution is introduced at 18 to 24 C.
• solutions mentioned hereinabove may be spun either wet or dry.
• the emerging filaments are drawn off at a rate of 5 to meters per minute, at a draught of 0.5 to 5. After a drying at about C., the filaments are wound.
• the physical properties given in the examples are determined by known methods.
• the permanent elongation is determined after stretching the filament 3 times by 300 percent of its initial length, and after a recovery time of 30 s conds.
• the modulus is determined at an elongation of the filament to 300 percent of its initial length.
• EXAMPLE 8 About 21,000 parts of a mixed polyester of hexane 1,6-diol, 2,2-dimethylpropane-1,3-diol and adipic acid (molar ratio of diols /35, OH number 63.9, acid number 1.45) are dehydrated in vacuo at about 120 C. for about one hour, mixed at about C. with about 445 parts of N-methyldiisopropanolamine and about 6300 parts of diphenylmethane-4,4'-diisOcyanate and heated to about C. for about 50 minutes with stirring.
• NCO-containing prepolymer melt 50 obtained About 23,800 parts of the NCO-containing prepolymer melt 50 obtained are introduced with intensive stirring into a cold solution of about 480 parts of ethylene diamine and about 600 parts of 2,2-bis-(4-aminophenyl)-propane in about 70,000 parts of N,N-dimethylformamide which contains in addition about 1035 parts of titanium dioxide (rutile) dispersed therein.
• a spinning solution having a solids content of 27 percent and a viscosity of 610 poises/20 C. is obtained.
• a portion of the solution is briefly heated to 90 C and immediately thereafter spun dry from a 48 aperture spinneret at a shaft temperature of about 200 C.
• a dressing agent for reducing adhesion is applied to them.
• the filaments are wound at a rate of 300 meters per minute.
• a spinning solution for the preparation of polyurethane fibers prepared by the process which comprises reacting in a polar solvent for polyacrylonitrile an NCO-terminated prepolymer with a mixture of ethylene diamine and a diamine having the formula wherein R and R are lower alkyl, and R is an alkylene radical containing 2 to 6 carbon atoms joined to the methylene carbon atom to form a cycloaliphatic radical, said prepolymer being prepared by the process which comprises reacting one mol of a substantially linear polyester having terminal hydroxyl groups and a molecular weight of from about 1600 to about 2600 with about 1.5 to about 1.95 of 4,4-diphenylmethane diisocyanate.
• the spinning solution of claim 1 wherein the prepolymer is prepared from an hydroxyl polyester, 4,4-diphenylmethane diisocyanate and a glycol containing tertiary nitrogen atoms and having a molecular weight less than 500.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Artificial Filaments (AREA)
• Polyurethanes Or Polyureas (AREA)

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Citations (4)

• 1951
  • 1951-01-28 DE DE19511669412 patent/DE1669412A1/de active Granted
• 1967
  • 1967-06-21 US US647591A patent/US3485800A/en not_active Expired - Lifetime

Patent Citations (4)

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