EP0579979B1 - 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
EP0579979B1
EP0579979B1 EP93110270A EP93110270A EP0579979B1 EP 0579979 B1 EP0579979 B1 EP 0579979B1 EP 93110270 A EP93110270 A EP 93110270A EP 93110270 A EP93110270 A EP 93110270A EP 0579979 B1 EP0579979 B1 EP 0579979B1
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EP
European Patent Office
Prior art keywords
nozzle
mixing
reactor
viscosity
process according
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EP93110270A
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German (de)
English (en)
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EP0579979A2 (fr
EP0579979A3 (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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    • 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
    • B01F25/3124—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
    • 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 method for producing of surprisingly stable in their solution viscosity Spinning solutions of segmented polyurethane urea elastomers in highly polar solvents such as dimethylformamide (DMF) or dimethylacetamide (DMAC) without or with reduced tendency to paste and without or with a very low gel content, characterized by the Use of a multi-stage nozzle reactor device to carry out the procedure.
  • 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 by very fast and intense Mixing of the reaction components allowed, e.g. segmented polyurethane urea elastomers as homogeneous solutions in highly polar solvents continuously to manufacture.
  • Another subject of the invention are those according to the method and obtainable by means of this device Elastane spinning solutions or elastane fibers obtainable therefrom.
  • Elastane fibers are understood to mean threads that are too at least 85% by weight of segmented polyurethane (urea) consist.
  • elastane fibers are commonly used made by first making a long chain Diol (macrodiol) terminated with an aromatic diisocyanate is capped so that you get a macro diisocyanate (NCO prepolymer).
  • the NCO prepolymer is then in a second step with a chain extender, which usually consists of a (cyclo) aliphatic Diamine is made up in solution to a high molecular weight Implemented polyurethane urea.
  • chain extender usually consists of a (cyclo) aliphatic Diamine is made up in solution to a high molecular weight Implemented polyurethane urea.
  • Hard or soft segments from high-melting crystalline and low-melting amorphous segments (Hard or soft segments).
  • the hard segments then act in the solid due to their crystallinity as fixed points of the network and are therefore decisive for the firmness and the softening range of the the molded article produced by the polymer.
  • the soft segments however, whose glass transition temperature is below the temperature of use should be for the elasticity of the elastomers (B. v. Falkai, synthetic fibers, Verlag Chemie, 1981, pp. 179 to 187).
  • the chain extension is usually carried out batchwise in such a way that the chain extender (an aliphatic diamine, preferably ethylene diamine) and possibly a chain terminator, a secondary monoamine, such as diethylamine in a polar solvent (DMF or DMAC) are placed in a stirred kettle ( 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 CO 2 and has a reduced 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 cannot then be practically processed further.
  • discontinuously produced solutions obviously contain more branched polyurethane ureas because of a lack of mixing intensity, which, at a given concentration, have higher viscosities than more linear polyurethane ureas.
  • the solubility decreases with increasing molecular weight, so that pasting must be expected. Therefore one often leaves the polyaddition at discontinuous Work up to a specified viscosity and / or uses 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). So you get at the same time 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). So you get at the same time a narrower molecular weight distribution.
  • the central operation is the mixing of specified amounts of liquid. This includes mixing in batch with mechanical Stirrers or as they pass through rotor / stator dispersing machines and prick mixers (see plastic manual, Volume 7, Carl Hauser Verlag 1977). Furthermore is mixing with high pressure mixers in PU technology usual (see H. Proksa, plastic consultant 3/1988; High pressure mixing, pioneer of modern PU technology), being two reaction components under high pressure over Nozzles jetted together in a small mixing chamber and are mixed by the intense turbulence (see DE-A-2 344 135 and DE-A-1 157 386). The response times such polyurethane reactions are at least in the second range.
  • EP-A-399 266 describes a process for the production from highly concentrated, finely divided dispersions the melt of high-melting organic compounds, however no reaction mixtures, described, by using a melt to form a pre-suspension into a colder liquid phase at a temperature below metered the crystallization temperature and this pre-emulsion in a downstream homogenizing nozzle finely dispersed.
  • a disperser i.a. an emulsifying device with a mixing nozzle and specified a downstream homogenizing nozzle.
  • Such dispersing devices are in their mixing times still too slow, and are only suitable if the response time is more than 0.1 seconds.
  • the object of the invention was therefore to implement a cost-reducing and also environmentally friendly manufacturing process (Use less solvent and Improvement of economy through fast spinning) for highly concentrated elastane spinning solutions with improved flow properties (Improved spinnability through a lower Solution viscosity while maintaining the necessary molecular weights) and an improved viscosity constancy long storage times of spinning solutions without loss in thermal and elastic behavior of the resulting End products 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 Maintaining the usual level of thermal and elastic properties the one available from these solutions Elastane fibers preferably available from accordingly produced segmented polyurethane ureas with certain monoamines and / or monoisocyanates as chain terminators.
  • the method of the invention can easily highly concentrated elastane spinning solutions based on Polyurethane ureas with a solids content of up to 40 wt .-% are produced, which is excellent Solubility and constant viscosity, even when adjusted a higher proportion of hard segments e.g. by a higher proportion of diisocyanate, and surprisingly also a reduction in the viscosity of the elastane spinning solution have at the same concentration of the polymer.
  • the invention relates to a continuous process for the production of highly concentrated elastane spinning solutions with improved flow properties and high viscosity constancy from fast reacting polyaddition components, characterized in that the reaction components from the Batch containers in a multi-stage nozzle reactor consisting of a Mixing chamber with a fabric nozzle, a mixing nozzle and a homogenizing nozzle, which are connected in direct succession, are continuously metered in the first stage of the multi-stage nozzle reactor, the reaction components in the mixing nozzle of the reactor can be mixed with each other in up to 10 ms reacting mixture in a second stage, in a homogenizing nozzle is homogenized and then in a downstream reactor is reacted.
  • Fig. 1a shows a section through a nozzle reactor with short residence times of the reaction mixture in the area of the mixing chamber (not according to the invention).
  • 1b shows a section through a known nozzle reactor with a long one Residence time of the reaction mixture (>> 100 ms) in the area of the mixing chamber.
  • Fig. 2 shows schematically a section through an inventive Multi-stage nozzle reactor.
  • FIG. 3 shows a diagram of the overall method according to the invention for Production of spinning solutions.
  • the multi-stage nozzle reactor device makes it possible to mix reactive components faster than the reaction expires (e.g. ⁇ 10 ms) (Fig. 2).
  • the well-known arrangement (see Fig. 1b) is unsuitable because of the mixing the components run too slowly. (The dwell time the reaction mixture here is > 100 ms).
  • the fabric nozzle (21) and the mixing nozzle (22) must be very be closely linked to one another for fast, optimal Mixing and reducing backmixing to guarantee.
  • FIG. 3 shows the flow diagram of the method according to the invention essentially for continuous polyurethane urea chain extension from NCO prepolymer solution and (cyclo) aliphatic diamines.
  • the two material flows e.g. NCO prepolymer solution (B) and aliphatic Diamine solution (A) using metering pumps 5 and 6 from the Batch containers 3 and 4 metered in continuously.
  • the Mixture preparation of the amine solution (chain extender, chain terminator and solvent) and the NCO prepolymer solution (NCO prepolymer and solvent) can weighed into the templates or using dosing pumps be produced continuously.
  • the multi-stage nozzle reactor (see e.g. Fig. 2) exists from a series connection of different nozzles namely the fabric nozzle 1, the mixing nozzle 2 and the homogenizing nozzle 7 with the holes 8 and in a preferred Execution of the displacer 9.
  • Fabric nozzle and Mixing nozzle are connected in direct succession, so that the residence time until complete mixing the amine stream (A) with the prepolymer stream (B) in a time of ⁇ 10 ms, preferably 0.1 to 5 ms is.
  • Both nozzles 1 and 2 are designed that there is an injector effect and backmixing avoided in the area 10 between the two nozzles becomes.
  • the homogenizing nozzle is connected to the injector part 7 with the holes 8, which is already reacting Reaction mixture homogenized again intensively.
  • the volume between the mixing and homogenizing nozzle minimized by a displacer 9.
  • One of the possible constructive embodiments shows 2.
  • the course of the reaction can be measured by direct pressure measurement in the nozzle reactor e.g. between mixing nozzle 2 and homogenizing nozzle 8 are tracked.
  • the degree of polymerization of the polymer solutions can be about the viscosity measuring devices 14 and 15 are tracked.
  • the buffer boiler 11 preferably with a pumping circuit and this particularly preferably provided with a heat exchanger 16.
  • So-called heat exchangers 16 come in particular KSM heat exchanger (the heating or cooling coil is in a tube shaped like a static mixer). By heating to about 50 to 60 ° C in this Area achieved a complete implementation, so that with the viscosity measured value 14 through the viscosity constancy Regulation of the metering pumps 5 and 6 can be achieved.
  • Viscosity Other possible intervention parameters for controlling the Viscosity are continuous or gravimetric Weighing of the amine boiler via the ratio of chain extender to chain terminators or by the amount of selected amine excess over the NCO end group content.
  • the pressure can be at various points on the device be tracked via pressure gauges 17.
  • the advantages of the method lie in the achievement high throughputs in the nozzle reactor with uniform Product quality (e.g. regarding molecular weight distribution) and product concentration since each volume of reaction solution with exactly the same shear and concentration conditions mixed and thus for reaction was brought and practically no way to Side reactions (e.g. cross-linking reactions) exist.
  • the segmented polyurethane urea elastomers constructed according to the invention deliver clear, gel-free stable Spinning solutions that according to usual wet and special after the dry spinning process even with high solids concentration (e.g. 30 to 40% by weight) very well processed can be.
  • the inventive preferably have highly concentrated spinning solutions excellent viscosity stability both at 25 ° C as well as at 50 ° C with storage times (e.g. also at high Concentrations) up to at least 5 days and longer.
  • Spinning solutions have a lower viscosity given solid concentration as such elastomer solutions, those after discontinuous polyaddition processes getting produced. It is believed that a linear polymer structure is achieved, which is not only on productivity, but also on a better one Spinning behavior of the elastane solutions.
  • Nozzle reactor as a mixing and homogenizing device, preferably with a downstream buffer tank, Pump circulation and heat exchanger, enables the invention Manufacturing process accordingly using advantages such as improved solubility, reduced viscosity, Viscosity constancy also with longer storage time and elevated temperature as well as improved Quality constancy, the production of Elastomer threads without sacrificing thermal and mechanical property profile of the elastane threads.
  • the invention also relates to threads or fibers, prepared from the spinning solutions according to the invention.
  • the elastane solutions according to the invention can also be used for Manufacture of films, foils, tubes or coatings be used.
  • the production of the polyurethane urea elastomers according to the invention can according to known process steps respectively.
  • the synthesis has proven particularly successful according to the NCO prepolymer process, the first Process step a higher molecular weight diol a) in the solvent or in the melt with diisocyanate c), if appropriate in the presence of low molecular weight diols b) an NCO prepolymer is reacted so that the NCO prepolymer Contains NCO end groups in a certain amount.
  • high-molecular dihydroxy compounds a) are especially polyester diols and polyether diols. These diols generally have molecular weights from 1,000 to 8,000, preferably 1,500 to 4,000.
  • polyester diols e.g. Aliphatic dicarboxylic acid polyester
  • dicarboxylic acids both several Diols as well as several dicarboxylic acids or hydroxycarboxylic acids can contain.
  • Mixed adipic acid esters are particularly suitable from adipic acid, 1,6-hexanediol and neopentyl glycol, Adipic acid, 1,4-butanediol and neopentyl glycol or adipic acid, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol.
  • polyether diols Particularly suitable as long-chain polyether diols Polytetramethylene oxide diols or their copolyethers with others ether-forming compounds such as ethylene oxide or Propylene oxide. Mixtures of the above can also be used Connections are used.
  • 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 connections of this Substance classes.
  • aromatic diisocyanates c) Diisocyanates are used. You will if necessary in combination (with smaller proportions) of (Cyclo) aliphatic diisocyanates, but optionally the (cyclo) aliphatic diisocyanates are used alone. You get particularly useful results with 4,4'-diphenylmethane diisocyanate or corresponding isomer mixtures with minor amounts of 2,4'- and / or 2,2'-isomers, and with toluene diisocyanate (TDI). Of course it is possible to use mixtures of aromatic To use diisocyanates.
  • aliphatic diisocyanates are suitable, in particular 1,6-hexamethylene diisocyanate, 1,8-octamethylene diisocyanate, 2/3-methylhexamethylene diisocyanate-1,6 or 2,4-diisocyanato-1-methyl-cyclohexane as well as the 4,4'-dicyclohexylmethane, 4,4'-dicyclohexylalkylidene, 4,4-dicyclohexyl ether diisocyanate or isophorone diisocyanate in their various stereoisomers or stereoisomer mixtures.
  • the OH / NCO ratios are between 1: 1.4 to 1: 4.0, preferably 1: 1.6 to 1: 3.8, selected, so that NCO prepolymers with an NCO content of 1.4 to about 4.5% by weight, preferably 1.8 to 4.0% by weight, of NCO, arise.
  • the OH / NCO ratio must be dependent of the molecular weight of the macrodiol within the ratio specified here are chosen so that the NCO content of the NCO prepolymer in the here measured Area falls.
  • Lewis acid catalysts such as tin salts or e.g. Organotin compounds such as organotin carboxylates or halides, dibutyltin dilaurate, inorganic Organic acid salts, 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: furthermore are Lewis base catalysts such as tertiary amines, phosphines, pyridines as catalysts suitable, as in the prior art of Polyurethane production are known in principle.
  • Lewis base catalysts such as tertiary amines, phosphines, pyridines as catalysts suitable, as in the prior art of Polyurethane production are known in principle.
  • dibutyltin dilaurate (Desmorapid® Z / Bayer AG) or diazobicyclooctane (DABCO®).
  • DABCO® diazobicyclooctane
  • chlorobenzene are particularly suitable for this, N-methylpyrrolidone, dimethyl sulfoxide and especially most of them also used as spinning solvents Amide solvent dimethylformamide and dimethylacetamide.
  • NCO prepolymer stage synthesized NCO prepolymers also Macro diisocyanates are called
  • highly polar solvents with chain extenders f preferably aliphatic diamines and chain terminators / Blocking agents (secondary monoamines) g
  • Diamines used e.g. 1,2-propylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,3-diamino-cyclohexane or also 1,3-diamino-2,2-dimethylpropane; prefers however, ethylenediamine is the sole or predominant Chain extender used.
  • Cycloaliphatic diamines can also be used in proportions ⁇ 50 mol-X are used as co-chain extenders, e.g. 1,3-diamino-cyclohexane.
  • Secondary amines such as piperazine, N-methylethylenediamine can also be used or N, N'-dimethylethylenediamine as codiamines be used, 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 especially dimethylacetamide.
  • the viscosity of the elastomer solution required for the preferred dry spinning process is generally in the range from 10 to 350 Pa.s at 50 ° C. and a shear rate of 23 s -1 , the concentration of the spinning solution being between 18 and 34% by weight.
  • the elastomer solutions produced 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 - if necessary up to heated to approx. 120 ° C - spinning solutions with viscosities of at least 30 Pa.s at 50 ° C through nozzles in one to about 150 to 250 ° C heated, about 4 to 8 m long spinning shaft, in the air heated to about 150 to 350 ° C or blowing in inert gases such as nitrogen or steam will be spun.
  • the solutions prepared according to the invention have one Viscosity stability of at least ⁇ 20% over at least 5 days, preferably at least 7 days compared to the discontinuous process cheaper.
  • the elastomer solutions produced according to the invention can also the usual ones for various purposes Additives i) are added in effective amounts.
  • Additives i) are added in effective amounts.
  • Such zinc oxides with alkaline earth oxides or Carbonates as additives can have excellent chlorine resistance of ether as well as polyester elastomer threads against chlorine water (detergents / swimming pools / bleach) can be achieved without a high Purity requirement, e.g. in zinc oxide or trace sulfur content, should adhere to.
  • the elastomer solutions obtained by the process according to the invention can according to the specified procedures Spun elastomer threads, but also for film coatings or similar fabrics will. This can be done by drying or by coagulation happen.
  • the elastomer solutions according to the invention show an unusual one 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% initial elongation 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 1178, 28.180. Vintage are described on pages 44 to 49. Corresponding information can also be found in DE-A-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 m 3 / 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 method via a 12-hole nozzle with holes from 0.3 mm diameter each.
  • the textile data are in table 1 and the long-term viscosity behavior is in table 2 summarized.
  • 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.
  • the NCO prepolymer solution was the nozzle reactor with a form of 25 bar and a mass flow of 45 kg / h and the Amine solution with a pre-pressure of 28 bar and a mass flow of 15 kg / h using the metering pumps 5 and 6 fed.
  • the residence time in the mixing zone was approx. 0.5 to 5 ms. Then the reaction solution got into the Post-reaction part, in which they for post-reaction 50 ° C was heated with the heat exchanger 16.
  • the gear pump 12 moved the mass flow at 90 kg / h and promoted 30 kg / h in the heat exchanger and 60 kg / h from the Post-reaction part. Then the finished, clear, homogeneous and gel-free elastomer solution with the discharge pump 13 promoted from the device.
  • 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. In this elastomer solution additives were added as in Example 3.
  • the polymer solution was analogous using the dry spinning process spun (data of the fibers are in Tab. 1 and the long-term viscosity behavior shown in Tab. 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 8 Example 9 Template container 3: NCO prepolymer with the prepolymer concentration from example 1 45.75% from example 2 28.86% Template container 3 : 45.9 parts 72.8 parts Template container 4 : 15.3 parts 24.3 parts Composition template Container 4: - ethylenediamine 394.8 parts 325.8 parts - diethylamine 24.6 parts 20.3 parts - dimethylacetamide 14,880.0 parts 23,910.8 parts
  • the elastomer solution obtained had the following characteristics: - solids content 35% 22% - viscosity 70 Pa.s / 50 ° C 90 Pa.s / 20 ° C - inherent viscosity (see measurement instructions) 1.01 dl / g 1.32 dl / g
  • 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 elastane threads with increased extensibility are obtained by the process according to the invention, which is of particular advantage for a number of application areas.
  • 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 Mixing nozzle 24 had two holes with a diameter of 0.6 mm.
  • the NCO prepolymer was first pre-printed of 30 bar and a mass flow of 45 kg / h and the amine solution with a pre-pressure of 35 bar and a Mass flow of 15 kg / h supplied.
  • the dwell time in the mixing zone was approximately 100 ms. After a short drive there were uncontrolled pressure fluctuations up to> 40 bar on that with a swelling of the emerging reaction solution were connected so that the experiment was terminated had to become.
  • the diameter of the fabric nozzle 21 was 0.4 mm and Mixing nozzle 22 had a bore of 0.6 mm in diameter.
  • the NCO prepolymer was initially printed on a 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 fed from 15 kg / h.
  • the residence time in the Mixing zone was about 5 ms.
  • the spinning solution obtained from this contained microgels during the subsequent dry spinning of the spider solution repeated fiber tears.

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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)

Claims (15)

  1. Procédé en continu, pour la préparation de solutions de filage d'élasthane de concentration élevée avec des propriétés de fluidité améliorées et une constance de viscosité supérieure à partir de composants de polyaddition réagissant rapidement, caractérisé en ce que les composants réactionnels sont dosés en continu à partir d'un récipient de chargement dans un réacteur à buses à plusieurs étapes, constitué d'une chambre de mélange (10) avec une buse pour composant (1), une buse de mélange (2) et une buse d'homogénéisation (7), qui sont placées directement l'une derrière l'autre, dans la première étape du réacteur à buses à plusieurs étapes les composants réactionnels étant mélangés les uns avec les autres dans la buse de mélange (2) du réacteur pendant jusqu'à 10 ms, le mélange réagissant dans une deuxième étape étant homogénéisé dans une buse d'homogénéisation (7) et finalement cesse de réagir dans un réacteur placé en aval.
  2. Procédé selon la revendication 1, caractérisé en ce que les composants réactionnels sont des prépolymères NCO et des diamines cycloaliphatiques ou aliphatiques et en ce que les diamines sont amenées dans la buse de mélange (2) par la buse de composant (1).
  3. Procédé selon la revendication 2, caractérisé en ce que les prépolymères NCO sont préparés à partir de a) des polyester- ou polyéther-diols ou des mélanges de polyester-et polyéther-diols avec une masse moélculaire de 1 000 à 8 000, des diisocyanates c) et éventuellement des diols de masse moléculaire faible b).
  4. Procédé selon la revendication 1 et 2, caractérisé en ce qu'on utilise comme diamine l'éthylènediamine.
  5. Procédé selon les revendications 1 à 4, caractérisé en ce que la solution réactionnelle est amenée directement derrière le réacteur à buses dans un conteneur tampon intermédiaire (11).
  6. Procédé selon la revendication 5, caractérisé en ce que sur le conteneur tampon intermédiaire (11) est placé un circuit de pompage avec un échangeur de chaleur (16).
  7. Procédé selon la revendication 6, caractérisé en ce que la viscosité est maintenue constante dans le circuit de pompage du fait que la viscosité dans le circuit de pompage est mesurée et est utilisée comme grandeur de contrôle pour le dosage des composants réactionnels.
  8. Procédé selon les revendications 1 à 7, caractérisé en ce que le temps de séjour des réactifs dans le réacteur jusqu'à la fin de la buse de mélange (2) s'élève de 0,1 à 5 ms.
  9. Solutions de filage d'élastomère de polyuréthane-urée exemptes de gel pouvant être préparées selon le procédé selon l'une des revendications 1 à 8 avec une viscosité de 10 à 350 Pa.s mesurée à 50 °C et une vitesse de cisaillement de 23 s-1, caractérisées en ce qu'elles présentent une concentration de matière solide > 30 % en poids et une stabilité de viscosité d'au moins +/- 20 % pendant au moins 5 jours de stockage à 50 °C.
  10. Solution de filage selon la revendication 9 préparée par le procédé selon les revendications 1 à 8.
  11. Fibres ou fils, fabriqués à partir de solutions de filage selon les revendications 9 à 10.
  12. Réacteur à buses à plusieurs étapes pour réaliser le procédé selon l'une des revendications 1 à 8, constitué d'une chambre de mélange (10) avec une buse de composé (1), une buse de mélange (2) et une buse d'homogénéisation (7), qui sont placées directement les unes derrière les autres, caractérisé en ce que le temps de séjour des composants réactionnels qui pénètrent dans le réacteur et dont l'un est amené par la buse de composé (1) et les autres réactifs par la buse de mélange (10), jusqu'au mélange complet à la fin de la buse de mélange (2) est ≤ 10 ms et que le mélange en retour dans la chambre de mélange (10) entre la buse de composé (1) et la buse de mélange (2) est évité.
  13. Réacteur à buses à plusieurs étapes selon la revendication 12, caractérisé en ce que la buse de composé (1) et la buse de mélange (2) sont placées l'une derrière l'autre axialement et un corps entraíneur (9) se raccorde sur la buse de mélange (2) devant la buse d'homogénéisation (7), qui conduit les mélanges réactionnels aux trous (8) de la buse d'homogénéisation (7).
  14. Réacteur à buses à plusieurs étapes selon les revendications 12 et 13, caractérisé en ce que le temps de séjour des composés réactionnels dans la chambre de mélange (10) jusqu'à la fin de la buse de mélange (2) est ≤ 10 ms.
  15. Réacteur à buses à plusieurs étapes selon la revendication 14, caractérisé en ce que le temps de séjour des composés réactionnels est de 0,1 à 5 ms.
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
DE4222772A DE4222772A1 (de) 1992-07-10 1992-07-10 Verfahren zur Herstellung von viskositätsstabilen, gelarmen hochkonzentrierten Elastan-Spinnlösungen
DE4222772 1992-07-10

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

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

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DE4330725A1 (de) * 1993-09-10 1995-03-16 Bayer Ag Verfahren zur Herstellung von Elastanfasern durch Einspinnen einer Kombination von PDMS und ethoxyliertem PDMS
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
US6171537B1 (en) * 1995-10-16 2001-01-09 E.I. Du Pont De Nemours And Company Preparation of poly (urethaneurea) fibers
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
US6225435B1 (en) 1997-03-05 2001-05-01 Dupont Toray Co. Ltd. Stable polyurethaneurea solutions
BR9815438A (pt) * 1997-03-05 2001-09-25 Du Pont Toray Co Ltd Solução de viscosidade estável e spandex fiado a seco
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
ATE547218T1 (de) 2002-08-20 2012-03-15 Roof Matrix Inc Nichttoxisches, hydrophobes, elastomeres polymerchemiesystem für die holzkonservierung
US12329185B2 (en) * 2014-10-23 2025-06-17 Formtec, Llc. System and method for creating cavitation and/or flash
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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CA1224310A (fr) * 1983-05-07 1987-07-21 Heino Thiele Methode et dispositif de preparation d'un melange reactif, compris d'au moins deux composantes, pour la production de mousses plastiques
DE3916465A1 (de) * 1989-05-20 1990-11-22 Bayer Ag Herstellung kugelfoermiger dispersionen durch kristallisation von emulsionen

Also Published As

Publication number Publication date
EP0579979A2 (fr) 1994-01-26
US5302660A (en) 1994-04-12
ES2128368T3 (es) 1999-05-16
DE59309471D1 (de) 1999-04-29
EP0579979A3 (fr) 1994-11-30
DE4222772A1 (de) 1994-01-13

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