EP0579979A2 - Procédé pour la fabrication de solutions de filage d'élasthane, ayant une viscosité stabilisée et une faible teneur en gel - Google Patents

Procédé pour la fabrication de solutions de filage d'élasthane, ayant une viscosité stabilisée et une faible teneur en gel Download PDF

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Publication number
EP0579979A2
EP0579979A2 EP93110270A EP93110270A EP0579979A2 EP 0579979 A2 EP0579979 A2 EP 0579979A2 EP 93110270 A EP93110270 A EP 93110270A EP 93110270 A EP93110270 A EP 93110270A EP 0579979 A2 EP0579979 A2 EP 0579979A2
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Prior art keywords
nozzle
mixing
reactor
viscosity
stage
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German (de)
English (en)
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EP0579979A3 (fr
EP0579979B1 (fr
Inventor
Bernd Dipl.-Ing. Klinksiek
Rolf-Volker Dr. Meyer
Beatrix Dr. Frauendorf
Klaus Dr. Rall
Wolfgang Dipl.-Ing. Bäcker
Hans-Joachim Dr. Wollweber
Helmut Dr. Ohse
Wolfram Dr. Wagner
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Bayer AG
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Bayer AG
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
    • B01F25/3124—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characterised by the place of introduction of the main flow
    • B01F25/31243—Eductor or eductor-type venturi, i.e. the main flow being injected through the venturi with high speed in the form of a jet
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
    • B01F25/3121—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof with additional mixing means other than injector mixers, e.g. screens, baffles or rotating elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/312—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof
    • B01F25/3124—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characterised by the place of introduction of the main flow
    • B01F25/31242—Injector mixers in conduits or tubes through which the main component flows with Venturi elements; Details thereof characterised by the place of introduction of the main flow the main flow being injected in the central area of the venturi, creating an aspiration in the circumferential part of the conduit
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/45—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/45—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
    • B01F25/452—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
    • B01F25/4521—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through orifices in elements, e.g. flat plates or cylinders, which obstruct the whole diameter of the tube
    • B01F25/45211—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through orifices in elements, e.g. flat plates or cylinders, which obstruct the whole diameter of the tube the elements being cylinders or cones which obstruct the whole diameter of the tube, the flow changing from axial in radial and again in axial

Definitions

  • the invention relates to a process for the preparation of spinning solutions of segmented polyurethaneurea elastomers which are surprisingly stable in their solution viscosity in highly polar solvents such as dimethylformamide (DMF) or dimethylacetamide (DMAC), without or with reduced pasting tendency and without or with very low gel content , characterized by the use of a multi-stage nozzle reactor device for performing the method.
  • highly polar solvents such as dimethylformamide (DMF) or dimethylacetamide (DMAC)
  • the subject of the invention is also a multi-stage nozzle reactor without mechanically moving parts as a device, which allows the reaction components to be mixed very quickly and intensively, e.g. to continuously produce segmented polyurethane urea elastomers as homogeneous solutions in highly polar solvents.
  • Another subject of the invention are those obtainable by the method and by means of this device Elastane spinning solutions or elastane fibers obtainable therefrom.
  • Elastane fibers are threads that consist of at least 85% by weight segmented polyurethane (urea).
  • elastane fibers are usually produced by first end-capping a long-chain diol (macrodiol) with an aromatic diisocyanate, so that a macrodiisocyanate (NCO prepolymer) is obtained.
  • NCO prepolymer is then reacted in a second step with a chain extender, which usually consists of a (cyclo) aliphatic diamine, in solution to give a high molecular weight polyurethane urea.
  • chain extender usually consists of a (cyclo) aliphatic diamine
  • the hard segments then act in the solid due to their crystallinity as fixed points of the network and are therefore decisive for the strength and the softening range of the shaped bodies produced from the polymer.
  • the soft segments on the other hand, whose glass transition temperature should be below the service temperature, are decisive for the elasticity of the elastomers (B. v. Falkai, Synthesefaser, Verlag Chemie, 1981, p. 179 to 187).
  • the chain extension is usually carried out batchwise in such a way that the chain extender (an aliphatic diamine, preferably ethylenediamine) and possibly in a stirred kettle at reduced temperature a chain terminator, a secondary monoamine, such as, for example, diethylamine in a polar solvent (DMF or DMAC), (and preferably mixed with carbon dioxide).
  • the NCO prepolymer is then added to this suspension of the diamine carbamate, which is now preferably obtained by adding CO2 and reduced in its reactivity, and an elastomer solution with a defined elastomer solids content is formed with stirring.
  • a disadvantage of this type of production is that the desired viscosity of the elastane solutions is often not in the intended range, which is necessary for further processing and then has to be adjusted to the desired viscosity by subsequent dosing, for example of aliphatic diisocyanates.
  • Another disadvantage is the pasting of parts of the solution and / or the presence of gel particles if not mixed sufficiently. Such elastane solutions can then not be practically processed further.
  • discontinuously prepared solutions obviously contain more branched polyurethane ureas which, at a given concentration, have higher viscosities than more linear polyurethane ureas because of a lack of mixing intensity.
  • spinning should be made from elastane spinning solutions with high solids concentrations ⁇ 30% if possible.
  • high solids concentrations there are particular problems with regard to a limited solubility of the polymers, especially in the case of long storage times of the spinning solutions, which manifests itself in pasting or an increase in viscosity.
  • the increasing insolubility often means that the elastane solution can no longer be processed or spun. The cause of these phenomena can be of different types.
  • the solubility decreases with increasing molecular weight, so that pasting must be expected. For this reason, the polyaddition is frequently allowed to proceed to a defined viscosity in a batchwise procedure and / or a monofunctional chain terminator such as dibutylamine, octylamine, butanone oxime (Houben Weyl Volume E 20 / Part 2, p. 1642), but preferably diethylamine (Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 10, p. 612). This also gives a narrower molecular weight distribution.
  • a monofunctional chain terminator such as dibutylamine, octylamine, butanone oxime (Houben Weyl Volume E 20 / Part 2, p. 1642), but preferably diethylamine (Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 10, p. 612). This also gives a narrower molecular weight distribution.
  • the rapid mixing of two or more reactive liquids is a conventional technique in polyurethane chemistry for carrying out polyaddition reactions of NCO precursors with water, aliphatic diols or aromatic diamines. All process operations such as dosing, mixing and Filling of moldings must be completed before the chemical reaction (pot life) begins.
  • the central operation is the mixing of specified amounts of liquid. This includes mixing in batch with mechanical stirrers or in a pass through rotor / stator dispersing machines and spiked mixers (see Plastics Manual, Volume 7, Carl Hauser Verlag 1977). In addition, mixing with high-pressure mixers is common in PU technology (see H. Proksa, plastic consultant 3/1988; high-pressure mixing, pioneer of modern PU technology), whereby two reaction components are sprayed against each other under high pressure via nozzles in a small mixing chamber and through the intensive Turbulence are mixed (see DE-A 2 344 135 and DE-A 1 157 386). The reaction times of such polyurethane reactions are at least in the range of seconds.
  • EP-A 399 266 describes a process for the production of highly concentrated, finely divided dispersions from the melt of high-melting organic compounds, but no reaction mixtures, by using a melt to form a pre-suspension in a colder liquid phase at a temperature below the crystallization temperature metered in and this pre-emulsion finely dispersed in a downstream homogenizing nozzle.
  • dispersing equipment i.a. specified an emulsifying device with a mixing nozzle and a downstream homogenizing nozzle.
  • the object of the invention was therefore to implement a cost-reducing and also environmentally compatible manufacturing process (use of less solvent and improvement in economy by rapid spinning) for highly concentrated spinning solutions, preferably elastane solutions with improved flow properties (improvement in spinning ability due to a lower solution viscosity while maintaining the necessary molecular weights) and one improved viscosity constancy with long storage times of spinning solutions without loss of the thermal and elastic behavior of the end products obtained therefrom as well as a gel-free form of spinning solutions with increased linearity of the polymer.
  • the invention relates to a continuously operated process for the production of highly concentrated elastane spinning solutions with improved flow properties and high viscosity constancy with a long service life while maintaining the usual thermal and elastic property level of the elastane fibers obtainable from these solutions, preferably obtainable from appropriately produced segmented polyurethane ureas with certain monoamines and / or Monoisocyanates as chain terminators.
  • highly concentrated elastane spinning solutions based on polyurethane ureas with a solids content of up to 40% by weight can be prepared without problems, which have excellent solubility and constant viscosity, even when a higher proportion of hard segments is set, e.g. due to a higher proportion of diisocyanate, and surprisingly also a reduction in the viscosity of the elastane spinning solution at the same concentration of the polymer.
  • homogeneous, highly concentrated, outstandingly viscosity-stable spinning solutions preferably consist both of polyester or polyether diols and, in particular, of mixtures of polyester and polyether diols, with excellent flow properties and therefore better spinnability can be produced by the process if the mixing and homogenizing device according to the invention (multi-stage nozzle reactor) is used continuously in the chain extension stage (polyaddition). Because of the very rapid mixing during the course of the reaction, the use of, for example, carbon dioxide as a reaction inhibitor can then be dispensed with.
  • the multi-stage nozzle reactor device enables very reactive components to be mixed with one another more quickly than the reaction is taking place (for example ⁇ 10 ms) (FIG. 2).
  • the well-known arrangement (see Fig. 1b) is unsuitable, however, because the mixing of the components proceeds too slowly. (The residence time of the reaction mixture is> 100 ms).
  • the material nozzle (21) and the mixing nozzle (22) must be very closely coupled to each other to guarantee a quick, optimal mixing and the reduction of backmixing.
  • FIG. 3 shows the flow diagram of the process according to the invention essentially for the continuous polyurethane urea chain extension from NCO prepolymer solution and (cyclo) aliphatic diamines.
  • the two material flows are e.g. NCO prepolymer solution (B) and aliphatic diamine solution (A) are metered in continuously from metering containers 3 and 4 by means of metering pumps 5 and 6.
  • the mixture preparation of the amine solution (chain extender, chain terminator and solvent) and the NCO prepolymer solution (NCO prepolymer and solvent) can be weighed into the templates or can be produced continuously using metering pumps.
  • the multi-stage nozzle reactor (see FIG. 2) consists of a series connection of different nozzles, namely the material nozzle 1, the mixing nozzle 2 and the homogenizing nozzle 7 with the bores 8 and, in a preferred embodiment, the displacement body 9.
  • the material nozzle and the mixing nozzle are connected in direct succession, so that the residence time until complete mixing of the amine stream (A) with the prepolymer stream (B) is completed in a time ⁇ 10 ms, preferably 0.1 to 5 ms.
  • Both nozzles 1 and 2 are designed so that there is an injector effect and backmixing into the area 10 between the two nozzles is avoided.
  • the homogenizing nozzle 7 with the bores 8 adjoins the injector part and homogenizes the already reacting reaction mixture again intensively. So that the mixing takes place with the lowest possible viscosity, the volume between the mixing and homogenizing nozzle is minimized by a displacer 9.
  • the reaction solution enters the intermediate buffer vessel 11 (FIG. 3), which has the task of hydraulically decoupling the nozzle reactor with its upstream metering pumps from the downstream piping system with the discharge pumps 12 and 13. This prevents back pulses on the metering pumps 5 and 6, which can cause fluctuations in the microdosing range. Direct introduction into a spinning kettle would also be possible.
  • the course of the reaction can be measured by direct pressure measurement in the nozzle reactor e.g. be tracked between the mixing nozzle 2 and the homogenizing nozzle 8.
  • the degree of polymerization of the polymer solutions can be monitored via the viscosity measuring devices 14 and 15. Since the reaction in the intermediate buffer vessel 11 may not yet have been completed and the use of the viscosity as a control variable for controlling the recipe is therefore difficult, the buffer vessel 11 is preferably provided with a pump-around circuit and this is particularly preferably provided with a heat exchanger 16. So-called KSM heat exchangers (the heating or cooling coil is shaped like a static mixer in a tube) are particularly suitable as heat exchangers 16. A complete conversion is achieved in this area by heating to about 50 to 60 ° C., so that the viscosity constant 14 can be achieved by regulating the metering pumps 5 and 6 with the viscosity measurement value 14.
  • KSM heat exchangers the heating or cooling coil is shaped like a static mixer in a tube
  • Further possible intervention parameters for controlling the viscosity are the continuous or gravimetric weighing of the amine kettle via the ratio of chain extender to chain terminator or through the amount of the excess amine selected via the NCO end group content.
  • the pressure can be tracked at various points in the device via pressure measuring devices 17.
  • the advantages of the method lie in the achievement of high throughputs in the nozzle reactor with uniform product quality (eg with regard to molecular weight distribution) and product concentration, since each volume part of the reaction solution with exactly the same shear and concentration conditions mixed and thus brought to reaction and there is practically no possibility of side reactions (eg crosslinking reactions).
  • the segmented polyurethane urea elastomers constructed according to the invention provide clear, gel-free, stable spinning solutions which can be processed very well by conventional wet and, in particular, dry spinning processes, even at high solids concentration (e.g. 30 to 40% by weight).
  • the preferably highly concentrated spinning solutions produced according to the invention have excellent viscosity stability both at 25 ° C. and at 50 ° C. with storage times (for example also at high concentrations) of up to at least 5 days and longer.
  • the spinning solutions produced in accordance with the invention have a lower viscosity at a given solids concentration than those elastomer solutions which are produced by discontinuous polyaddition processes. It is believed that a linear polymer structure is achieved, which affects not only productivity, but also better spinning behavior of the elastane solutions.
  • the manufacturing method according to the invention accordingly makes use of the advantages such as solubility improvement, viscosity reduction, and viscosity constancy Longer storage time and elevated temperature as well as improved quality consistency, the production of elastomer threads without loss in the thermal and mechanical property profile of the elastane threads.
  • the invention also relates to threads or fibers produced from the spinning solutions according to the invention.
  • the elastane solutions according to the invention can also be used for the production of films, foils, tubes or coatings.
  • the polyurethane urea elastomers according to the invention can be produced by process steps known per se.
  • the synthesis according to the NCO prepolymer method has proven particularly useful, with a higher molecular weight diol a) in the solvent or in the melt being reacted with diisocyanate c), optionally in the presence of low molecular weight diols b), to give an NCO prepolymer that the NCO prepolymer contains NCO end groups in a certain amount.
  • Polyester diols and polyether diols are particularly suitable as long-chain, higher molecular weight dihydroxy compounds a) (also called macrodiols). These diols generally have molecular weights of 1,000 to 8,000, preferably 1,500 to 4,000.
  • Suitable polyester diols are, for example, dicarboxylic acid polyesters of aliphatic dicarboxylic acids which contain both several diols and also several dicarboxylic acids or hydroxycarboxylic acids can contain.
  • Mixed adipic acid esters of adipic acid, 1,6-hexanediol and neopentylglycol, adipic acid, 1,4-butanediol and neopentylglycol or adipic acid, 1,4-butanediol, neopentylglycol and 1,6-hexanediol are particularly suitable.
  • Particularly suitable long-chain polyether diols are polytetramethylene oxide diols or their copolyethers with other ether-forming compounds such as ethylene oxide or propylene oxide. Mixtures of the compounds mentioned can also be used.
  • diols e.g. Dihydroxylactone esters or dihydroxypolycarbonates as known from the prior art
  • diols e.g. Dihydroxylactone esters or dihydroxypolycarbonates as known from the prior art
  • Low molecular weight diols b) are e.g. Ethylene glycol, 1,2-butanediol, 1,4-butanediol, 1,4- and / or 1,3-cyclohexanedimethanol, N, N-bis ( ⁇ -hydroxypropyl) methylamine, N, N'-bis- ( ⁇ -hydroxyethyl) -piperazine, N, N-dimethyl-N ', N'-hydroxyethyl-hydrazine and other compounds of these classes.
  • aromatic diisocyanates can be used as diisocyanates c). They are optionally used in combination (with smaller proportions) of (cyclo) aliphatic diisocyanates, but optionally also the (cyclo) aliphatic diisocyanates alone. Particularly useful results are obtained with 4,4'-diphenylmethane diisocyanate or corresponding isomer mixtures with minor amounts of 2,4 'and / or 2,2'-isomers, and with toluenediisocyanate (TDI). It is of course possible to use mixtures of aromatic diisocyanates.
  • the following (cyclo) aliphatic diisocyanates are also suitable as mixture components or individual components, in particular 1,6-hexamethylene diisocyanate, 1,8-octamethylene diisocyanate, 2/3-methylhexamethylene diisocyanate-1,6 or 2,4-diisocyanato-1-methylcyclohexane as well as the 4,4'-dicyclohexylmethane, 4,4'-dicyclohexylalkylidene, 4,4-dicyclohexyl ether diisocyanates or isophorone diisocyanate in their various stereoisomers or stereoisomer mixtures.
  • the macrodiols are reacted in the melt or in a solvent with excess molar amounts of diisocyanates c) via the diols (a + b) so that the reaction product contains isocyanate end groups.
  • the OH / NCO ratios are chosen between 1: 1.4 to 1: 4.0, preferably 1: 1.6 to 1: 3.8, so that NCO prepolymers with an NCO content of 1.4 to about 4.5 wt .-%, preferably 1.8 to 4.0 wt .-% NCO arise.
  • the OH / NCO ratio must be chosen within the ratio specified here so that the NCO content of the NCO prepolymer falls within the range measured here.
  • Suitable catalysts for the NCO prepolymer production are: Lewis acid catalysts such as tin salts or e.g. Organotin compounds such as organotin carboxylates or halides, dibutyltin dilaurate, inorganic salts of organic acids, e.g.
  • Tin octoate, tin stearate, tin acetate, lead octoate, plug-in catalysts such as organotin alcoholates, ⁇ -dicarbonyl compounds, oxides, mercaptides, sulfides, organoamine tin compounds, phosphine tin compounds: Lewis base catalysts such as tertiary amines, phosphines and pyridines are also suitable as catalysts are known in principle in the prior art of polyurethane production. Dibutyltin dilaurate (Desmorapid® Z / Bayer AG) or diazobicyclooctane (DABCO®) are preferably used. In most cases, the use of catalysts is dispensed with, but often small amounts of deactivators are used compared to alkali acids.
  • DABCO® diazobicyclooctane
  • chlorobenzene, N-methylpyrrolidone, dimethyl sulfoxide and especially the highly polar amide solvents dimethylformamide and dimethylacetamide, which are mostly used as spinning solvents, are particularly suitable for this.
  • the desired urea groups are introduced into the macromolecules by a chain extension reaction of the NCO prepolymers with diamines.
  • the NCO prepolymers synthesized in the NCO prepolymer stage (also Macrodiisocyanates)) are reacted in highly polar solvents with chain extenders f), preferably aliphatic diamines and chain terminators / blocking agents (secondary monoamines) g) in accordance with the process according to the invention with the aid of the multistage mixing and homogenizing device according to the invention.
  • Straight-chain or branched diamines are preferably used as diamines f), e.g. 1,2-propylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,3-diamino-cyclohexane or also 1,3-diamino-2,2-dimethylpropane; however, ethylenediamine is preferably used as the sole or predominant chain extender.
  • cycloaliphatic diamines can also be used as co-chain extenders, e.g. 1,3-diamino-cyclohexane.
  • Secondary amines such as piperazine, N-methylethylenediamine or N, N'-dimethylethylenediamine can also be used as codiamines, but this is less preferred.
  • the chain extension reaction is preferably carried out in solution using highly polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone, but preferably dimethylformamide or in particular dimethylacetamide.
  • the viscosity of the elastomer solution necessary for the preferred dry spinning process is in general Range from 10 to 350 Pa.s at 50 ° C and a shear rate of 23s ⁇ 1, the concentration of the spinning solution can be between 18 and 34 wt .-%.
  • the elastomer solutions prepared by the process according to the invention can have solids concentrations of up to 40% and more, the viscosity of the elastomer solution being in the range from 100 to 250 Pa.s at 50 ° C. (shear rate 23 s ⁇ 1).
  • the solutions prepared according to the invention have a viscosity stability of at least ⁇ 20% over at least 5 days, preferably at least 7 days, and are significantly cheaper than the batch process.
  • the desired molecular weight can be easily set.
  • the usual additives i) used for a wide variety of purposes can also be added in effective amounts to the elastomer solutions prepared according to the invention.
  • Ca or magnesium carbonates can contain.
  • Such zinc oxides with alkaline earth oxides or carbonates as additives can provide excellent chlorine resistance of both ether and polyester elastomer threads against chlorinated water (detergents / swimming pools / bleaches) without having to meet high purity requirements, e.g. in the zinc oxide or trace sulfur content.
  • the elastomer solutions obtained by the process according to the invention can be spun into elastomer threads according to the processes specified, but can also be processed into film coatings or similar flat structures. This can be done by drying or by coagulation.
  • the elastomer solutions according to the invention show an unusual combination of excellent solubility and constant viscosity, even at high temperature and long storage times.
  • the tenacity was determined based on DIN 53 815 (cN / dtex).
  • the maximum tensile force elongation (in%) was also carried out in accordance with DIN 53 815.
  • the module at 100% or 300% elongation for the first time was determined in cN / dtex at an elongation rate of 4 x 10 ⁇ 3 meters per second.
  • the residual elongation was determined after five expansions to 300% and after a recovery time of 60 seconds.
  • the measurement of heat distortion temperature (HDT), hot tear time (HRZ) or hot water voltage drop (HWSA) takes place according to methods described in man-made fibers / textile industry, January 1978, issue 1/78, 28.180. Vintage are described on pages 44 to 49. Corresponding information can also be found in DE-OS 25 42 500 (1975).
  • the spinning was carried out after the dry spinning process according to the examples under the following conditions: Shaft temperature 200 ° C Air temperature 220 ° C Air volume 40 m3 / h jet 12 holes, diameter 0.3 mm Spin head temperature 80 ° C Air swirl nozzle 0.6 bar Deduction of godets 1, 2, 3 325/340/340 m / min
  • Example 1 NCO prepolymer solution for Examples 3, 4, 5, 7 and 8)
  • the solution was spun using the dry spinning process using a 12-hole nozzle with 0.3 mm diameter holes.
  • the textile data are shown in Table 1 and the long-term viscosity behavior is summarized in Table 2.
  • Example 4 (comparison to Example 7)
  • Example 5 (comparison to Example 8)
  • Example 6 (comparison to Example 9)
  • the diameter of the fabric nozzle 1 and the mixing nozzle 2 was 0.5 mm and 0.75 mm, respectively.
  • the diameter of the holes in the homogenizing nozzle is 0.75 mm.
  • the NCO prepolymer solution was fed to the nozzle reactor with an admission pressure of 25 bar and a mass flow of 45 kg / h and the amine solution with an admission pressure of 28 bar and a mass flow of 15 kg / h by means of the metering pumps 5 and 6.
  • the residence time in the mixing zone was approximately 0.5 to 5 ms.
  • the reaction solution then reached the after-reaction part, in which it was heated to 50 ° C. with the heat exchanger 16 for the after-reaction.
  • the gear pump 12 moved the mass flow at 90 kg / h and conveyed 30 kg / h into the heat exchanger and 60 kg / h from the after-reaction part.
  • the finished, clear, homogeneous and gel-free elastomer solution is then conveyed out of the device with the discharge pump 13.
  • the elastomer solution has an elastomer solids content of 30% by weight and a solution viscosity of only 56 Pa.s / 50 ° C. The inherent viscosity was 1.13 dl / g. Additives as in Example 3 were added to this elastomer solution.
  • the polymer solution was spun analogously by the dry spinning process (data on fibers are shown in Table 1 and the long-term viscosity behavior in Table 2).
  • Examples 8 and 9 were carried out according to example 7 in the device described there under the same reaction conditions.
  • Table 3 shows the composition of the starting components and the viscosity and the inherent viscosity of the elastomer solutions obtained.
  • Example 3 additives were added to the elastomer solutions obtained. They were spun using the dry spinning method analogous to this example. Table 1 summarizes the textile data and Table 2 summarizes the long-term viscosity behavior. It should be particularly pointed out that according to the invention Process receives elastane threads with increased elasticity, which is of particular advantage for a number of application areas. Table 2 Service life behavior of the elastomer solutions from Examples 3, 4, 5, 7, 8 at 25 ° C example Solution viscosities [Pa.s (50 ° C; in Example 3: 20 ° C)] 1.
  • the diameter of the fabric nozzle 23 was 0.4 mm and the mixing nozzle 24 had two holes with a diameter of 0.6 mm.
  • the NCO prepolymer was first fed at a primary pressure of 30 bar and a mass flow of 45 kg / h and the amine solution at a primary pressure of 35 bar and a mass flow of 15 kg / h.
  • the residence time in the mixing zone was approximately 100 ms. After a short driving time, uncontrolled pressure fluctuations of up to> 40 bar occurred, which were associated with a swelling of the escaping reaction solution, so that the experiment had to be stopped.
  • the diameter of the fabric nozzle 21 was 0.4 mm and the mixing nozzle 22 had a bore of 0.6 mm in diameter.
  • the NCO prepolymer was first fed at a pre-pressure of 20 bar and a mass flow of 45 kg / h and the amine solution with a pre-pressure of 25 bar and a mass flow of 15 kg / h.
  • the residence time in the mixing zone was about 5 ms.
  • the spinning solution obtained from this contained microgels which resulted in repeated fiber tears when the spider solution was subsequently spun dry.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP93110270A 1992-07-10 1993-06-28 Procédé pour la fabrication de solutions de filage d'élasthane, ayant une viscosité stabilisée et une faible teneur en gel Expired - Lifetime EP0579979B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4222772 1992-07-10
DE4222772A DE4222772A1 (de) 1992-07-10 1992-07-10 Verfahren zur Herstellung von viskositätsstabilen, gelarmen hochkonzentrierten Elastan-Spinnlösungen

Publications (3)

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EP0579979A2 true EP0579979A2 (fr) 1994-01-26
EP0579979A3 EP0579979A3 (fr) 1994-11-30
EP0579979B1 EP0579979B1 (fr) 1999-03-24

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Country Status (4)

Country Link
US (1) US5302660A (fr)
EP (1) EP0579979B1 (fr)
DE (2) DE4222772A1 (fr)
ES (1) ES2128368T3 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643159A1 (fr) * 1993-09-10 1995-03-15 Bayer Ag Procédé pour la fabrication de fibres d'élastane contenant une combinaison de polyméthylsiloxane et polyméthylsiloxane éthoxylé
WO1998039373A1 (fr) * 1997-03-05 1998-09-11 Du Pont-Toray Company, Ltd. Solutions stables de polyurethanne-uree
WO2000020669A1 (fr) * 1998-10-02 2000-04-13 E.I. Du Pont De Nemours And Company Preparation de fibres de polyurethanne uree
US6225435B1 (en) 1997-03-05 2001-05-01 Dupont Toray Co. Ltd. Stable polyurethaneurea solutions

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DE4446339C1 (de) * 1994-12-23 1996-05-02 Bayer Faser Gmbh Verfahren zur Einstellung der Viskosität von hochkonzentrierten Elastanlösungen für das Trockenspinnen oder Naßspinnen von Elastanfasern und nach dem Verfahren erhältliche Elastanspinnlösung
DE19504316C1 (de) * 1995-02-10 1996-08-01 Bayer Faser Gmbh Verfahren zur Herstellung von mehrfädigen, naßgesponnenen Elastanfäden
US7293228B1 (en) * 1997-01-31 2007-11-06 Timebase Pty Limited Maltweb multi-axis viewing interface and higher level scoping
AUPO489297A0 (en) * 1997-01-31 1997-02-27 Aunty Abha's Electronic Publishing Pty Ltd A system for electronic publishing
DE19805104A1 (de) 1998-02-09 1999-08-12 Bayer Ag Beschichtungsmittel für Fasern
DE19829164A1 (de) 1998-06-30 2000-03-30 Bayer Faser Gmbh Elastanfäden und Verfahren zu ihrer Herstellung
DE19907830A1 (de) 1999-02-24 2000-08-31 Bayer Ag Verfahren und Vorrichtung zur Herstellung von Elastanfäden aus Recyclingmaterial
US6433218B1 (en) * 1999-11-30 2002-08-13 Bayer Corporation Stable isocyanate formulations
US20030041305A1 (en) * 2001-07-18 2003-02-27 Christoph Schnelle Resilient data links
US7363310B2 (en) * 2001-09-04 2008-04-22 Timebase Pty Limited Mapping of data from XML to SQL
US7281206B2 (en) * 2001-11-16 2007-10-09 Timebase Pty Limited Maintenance of a markup language document in a database
AU2003259972A1 (en) 2002-08-20 2004-03-11 Roof Matrix, Inc. Non-toxic hydrophobic elastomeric polymer chemistry system for wood preservation
FR3031099B1 (fr) * 2014-12-24 2019-08-30 Veolia Water Solutions & Technologies Support Buse optimisee d'injection d'eau pressurisee contenant un gaz dissous.
KR101956332B1 (ko) * 2017-07-27 2019-03-08 주식회사 나노텍세라믹스 폴리우레탄우레아 탄성섬유 제조용 첨가제 슬러리
IT202000016327A1 (it) * 2020-07-06 2022-01-06 Omitaly Srl Dispositivo generatore di micro e nano bolle

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UST864005I4 (en) * 1968-11-20 1969-07-15 Method and apparatus for continuously producing spinnino dopes of spandex polymers
EP0399266A2 (fr) * 1989-05-20 1990-11-28 Bayer Ag Préparaton de dispersiones sphérique par cristallisation d'émulsiones

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US4526907A (en) * 1983-05-07 1985-07-02 Basf Aktiengesellschaft Process and device for the preparation of a reaction mixture of at least two components for the production of foams

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
UST864005I4 (en) * 1968-11-20 1969-07-15 Method and apparatus for continuously producing spinnino dopes of spandex polymers
EP0399266A2 (fr) * 1989-05-20 1990-11-28 Bayer Ag Préparaton de dispersiones sphérique par cristallisation d'émulsiones

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643159A1 (fr) * 1993-09-10 1995-03-15 Bayer Ag Procédé pour la fabrication de fibres d'élastane contenant une combinaison de polyméthylsiloxane et polyméthylsiloxane éthoxylé
US6123885A (en) * 1993-09-10 2000-09-26 Bayer Aktiengesellschaft Process for the production of elastane fibers by inclusion of a combination of PDMS and ethoxylated PDMS in the spinning solution
US6284371B1 (en) 1993-09-10 2001-09-04 Bayer Aktiengesellschaft Yarn formed of eastane fibers produced by the dry spinning or wet spinning of spinning solutions which include polydimethylsiloxane and ethoxylated polydimethylsiloxane
US6171537B1 (en) 1995-10-16 2001-01-09 E.I. Du Pont De Nemours And Company Preparation of poly (urethaneurea) fibers
WO1998039373A1 (fr) * 1997-03-05 1998-09-11 Du Pont-Toray Company, Ltd. Solutions stables de polyurethanne-uree
US6225435B1 (en) 1997-03-05 2001-05-01 Dupont Toray Co. Ltd. Stable polyurethaneurea solutions
WO2000020669A1 (fr) * 1998-10-02 2000-04-13 E.I. Du Pont De Nemours And Company Preparation de fibres de polyurethanne uree

Also Published As

Publication number Publication date
DE59309471D1 (de) 1999-04-29
EP0579979A3 (fr) 1994-11-30
DE4222772A1 (de) 1994-01-13
US5302660A (en) 1994-04-12
EP0579979B1 (fr) 1999-03-24
ES2128368T3 (es) 1999-05-16

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