EP1287192B1 - Procede de fabrication de fils synthetiques a partir d'un melange fondu a base de polymeres fibrogenes - Google Patents

Procede de fabrication de fils synthetiques a partir d'un melange fondu a base de polymeres fibrogenes Download PDF

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Publication number
EP1287192B1
EP1287192B1 EP01936385A EP01936385A EP1287192B1 EP 1287192 B1 EP1287192 B1 EP 1287192B1 EP 01936385 A EP01936385 A EP 01936385A EP 01936385 A EP01936385 A EP 01936385A EP 1287192 B1 EP1287192 B1 EP 1287192B1
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EP
European Patent Office
Prior art keywords
polymer
additive
weight
fibre
und
Prior art date
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EP01936385A
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German (de)
English (en)
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EP1287192A1 (fr
Inventor
Helmut Schwind
Werner Ude
Wolfgang Janas
Alexander Klein
Bernd Kretschmann
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Roehm GmbH Darmstadt
LL Plant Engineering AG
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ZiAG Plant Engineering GmbH
Roehm GmbH Darmstadt
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Priority claimed from DE10022889A external-priority patent/DE10022889B4/de
Priority claimed from DE2001115203 external-priority patent/DE10115203A1/de
Application filed by ZiAG Plant Engineering GmbH, Roehm GmbH Darmstadt filed Critical ZiAG Plant Engineering GmbH
Publication of EP1287192A1 publication Critical patent/EP1287192A1/fr
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Classifications

    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the present invention relates to a process for producing synthetic filaments from a fiber-forming polymer-based mixture.
  • the threads can on the one hand be used as continuous threads or else processed into staple fibers.
  • the spinning of polymer blends into synthetic filaments is already known.
  • the aim is to obtain a higher elongation at break in the filament at a certain spinning speed than without modification by additional polymer.
  • a higher draw ratio for the production of the final yarn should be possible, which should cause a higher productivity of the spinning unit.
  • the production increase aims to improve the profitability of the manufacturing process. This is being sidelined to some extent by production hurdles and more expensive high speed equipment. Significantly of influence are the additional costs for the additive polymer, so that there is even a zero point for the economy, depending on the amount added.
  • the availability of additive polymers also plays an important role in the market. For these reasons, a large number of the additives described in the literature are ruled out for large-scale implementation.
  • the producer or procurer must take into account the entire production chain and can not stop increasing the production of a partial step (eg spinning).
  • the follow-up processes must not be impaired.
  • EP 0 047 464 B relates to an undrawn polyester yarn, wherein by addition of 0.2-10% by weight of a polymer of the type - (- CH 2 -CR 1 R 2 -) n -, such as poly (4-methyl 1-pentene) or polymethyl methacrylate, improved productivity is achieved by increasing the elongation at break of the spun yarn at speeds between 2500-8000 m / min and correspondingly higher draw ratios.
  • the document DE 199 37 727 discloses the production of polyester staple fibers from a polymer blend containing 0.1 to 2.0% by weight of an incompatible, amorphous, polymeric additive having a glass transition temperature in the range of 90 up to 170 ° C has.
  • the ratio of the melt viscosity of the polymeric additive to the melt viscosity of the polyester component should be 1: 1 to 10: 1.
  • DE 199 37 728 (Zimmer) relates to a process for the production of polyester HMLS filaments, polymeric additive and optionally additives having a spinning take-off speed of 2500 to 4000 m / min.
  • the polymeric additive should have a glass transition temperature in the range of 90 to 170 ° C and the ratio of the melt viscosity of the polymeric additive to the melt viscosity of the polyester component should be 1: 1 to 7: 1.
  • WO 99/07 927 relates to the production of POYs by spinning polymer blends based on polyester at a take-off speed v of at least 2500 m / min, wherein the polyester, a second, amorphous, melt-processable copolymer having a glass transition temperature of more than 100 ° C is added.
  • the ratio of the melt viscosity of the copolymer to the melt viscosity of the polyester is 1: 1 to 10: 1.
  • the elongation-enhancing agents used are usually granulated before being added to the polyester in order to increase the flowability of the additive polymer.
  • the granulated additive polymer can only be metered relatively poorly and unevenly. This leads to a deterioration of the yarn characteristics, in particular the uniformity of the synthetic threads (eg staining behavior).
  • the application since the granulation step of the strain enhancer is time consuming and costly, the application requires methods of melt spinning polymer blends which permit the use of non-granulated stretch enhancers.
  • the strain-increasing agents should be uniformly and continuously metered.
  • the process should allow the production of polyester-based POYs having elongation at break values in the range of 90% -165%, high uniformity in filament characteristics and a low degree of crystallization.
  • Another object of the present invention was to provide a method for spinning synthetic threads, which is industrially and inexpensively feasible.
  • the inventive method should allow the production of POYs with the highest possible take-off speeds, preferably ⁇ 2500 m / min.
  • the synthetic threads should be able to be further processed in a simple manner.
  • the POYs obtainable according to the invention should allow further processing in a draw or draw texturing process, preferably at high processing speeds, with a small number of yarn breaks.
  • amorphous additive polymer which is incompatible with the fiber-forming matrix polymer in a process for producing synthetic filaments from a melt-based matrix polymer-based melt mixture, which process comprises adding to the fiber-forming matrix polymer at least is added in an amount of 0.05 to 5 wt .-%, based on the total weight of fiber-forming matrix polymer and with this incompatible additive polymer, wherein the additive polymer is obtainable by multiple initiation, it succeeds not without Another foreseeable way to provide a process for the production of synthetic filaments from a fiber-forming matrix polymer-based mixture, which enables the production of synthetic filaments with a lower yarn breakage rate in a simple manner. In particular, granulation of the strain-increasing agent is no longer necessary for the process according to the invention.
  • the process of the present invention relates to the production of synthetic filaments from a melt-forming matrix polymer-based melt mixture.
  • the spinning can be carried out both by a direct spinning process in which the strain-increasing agent in the form of a melt is metered into the melt of the matrix polymer, and by an extruder spinning process in which the strain-increasing agent is metered as a solid to the matrix polymer and subsequently melted. Further details of the above-mentioned methods can be found in the prior art, for example in the publications EP 0 047 464 B, WO 99/07 927, DE 100 49 617 and DE 100 22 889, the disclosure of which is hereby incorporated by reference.
  • synthetic filaments denote all types of filaments obtainable by spinning thermoplastically processable mixtures of synthetic polymers. They include inter alia staple fibers (spun fibers), textile filaments such as plain yarns, POYs, FOYs, and engineering filaments.
  • the process according to the invention is used for the production of staple fibers, plain yarns, POYs, FOYs or technical filaments. It has proven to be particularly suitable for the production of POYs.
  • Suitable fiber-forming matrix polymers according to the invention are thermoplastically processable polymers, preferably polyamides, such as polyamide-6 and polyamide-6,6, and polyesters. Also mixtures of different polymers are conceivable.
  • polyesters are preferred, in particular polyethylene terephthalate (PET), polyethylene naphthalate, polytrimethylene terephthalate (PTMT) and polybutylene terephthalate (PBT).
  • the matrix polymer is Polyethylene terephthalate, polytrimethylene terephthalate or polybutylene terephthalate, especially polyethylene terephthalate.
  • Homopolymers are preferred according to the invention. But there are also copolymers, preferably polyester copolymers with a proportion of up to about 15 mol% of conventional comonomers, such as.
  • diethylene glycol triethylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, isophthalic acid and / or adipic acid, in question.
  • the polymers according to the invention may contain, as further constituents, additives which are customary for thermoplastic molding compositions and which contribute to improving the polymer properties.
  • additives which are customary for thermoplastic molding compositions and which contribute to improving the polymer properties. Examples which may be mentioned as such are: antistatic agents, antioxidants, flame retardants, lubricants, dyes, light stabilizers, polymerization catalysts and auxiliaries, adhesion promoters, matting agents and / or organic phosphites.
  • additives are used in the usual amount, preferably in amounts of up to 10% by weight, preferably ⁇ 1% by weight, based on 100% by weight of the polymer mixture.
  • a polyester may also contain a small proportion (maximum 0.5% by weight) of branching components, ie, for example.
  • branching components ie, for example.
  • polyfunctional acids such as trimellitic acid, pyromellitic acid, or tri- to hexavalent alcohols, such as trimethylolpropane, pentaerythritol, dipentaerythritol, glycerol, or corresponding hydroxy acids.
  • an additive polymer is added to the matrix polymer in an amount of at least 0.05 wt .-%, wherein the additive polymer must be amorphous and substantially insoluble in the matrix polymer.
  • the two polymers are incompatible with each other and form two phases that can be distinguished microscopically.
  • the additive polymer must have a
  • the melt viscosity of the additive polymer should be selected such that the ratio of its melt viscosity extrapolated to zero measurement time, measured at an oscillation rate of 2.4 Hz and a temperature equal to the melting temperature of the matrix polymer plus 34.0 ° C is (for polyethylene terephthalate 290 ° C) relative to that of the matrix polymer, measured under the same conditions, between 1: 1 and 10: 1. Ie. the melt viscosity of the additive polymer is at least equal to or preferably higher than that of the matrix polymer.
  • the ratio of the melt viscosity of the copolymer to that of the matrix polymer is preferably between 1.4: 1 and 8: 1 under the above-mentioned conditions.
  • a ratio of the melt viscosities of between 1.7: 1 and 6.5: 1 is particularly preferred In these conditions, the average particle size of the additive polymer is 140-350 nm.
  • the amount of the additive polymer to be added to the matrix polymer is between 0.05% by weight and 5% by weight, based on the total weight of the polymer mixture. For many applications, for example for the production of POYs, addition levels of less than 1.5%, at take-off speeds over 3500 and up to 6000 m / min and more, often even less than 1.0% are sufficient, which is a significant cost advantage.
  • the mixing of the additive polymer with the matrix polymer is carried out in a manner known per se. It is described, for example, in WO 99/07 927 or DE 100 22 889, the disclosure of which is hereby incorporated by reference.
  • the spinning of the polymer mixture takes place at temperatures, depending on the matrix polymer, in the range of 220 to 320 ° C.
  • Component H is an optional component. Although the advantages to be achieved according to the invention can already be achieved by copolymers comprising components from groups E to G, the advantages to be achieved according to the invention also occur if further monomers from group H are involved in the construction of the copolymer to be used according to the invention
  • the component H is preferably selected so that it has no adverse effect on the properties of the copolymer to be used according to the invention.
  • the component H can u. a. Therefore, it can be used to desirably modify the properties of the copolymer, for example by increasing or improving the flow properties when the copolymer is heated to the melting temperature, or reducing a residual color in the copolymer or by using a polyfunctional monomer, in this way and to introduce some degree of crosslinking into the copolymer.
  • H can also be chosen so that a copolymerization of components E to G at all possible or supported, as in the case of MSA and MMA, which do not copolymerize per se, but copolymerize readily with the addition of a third component such as styrene.
  • Suitable monomers for this purpose include vinyl esters, esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid other than methyl methacrylate, for example butyl methacrylate and ethylhexyl methacrylate, acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, styrene, ⁇ - Methylstyrene and the various halogen-substituted Styrenes, vinyl and isopropenyl ethers, dienes such as 1,3-butadiene and divinylbenzene.
  • the color reduction of the copolymer can be achieved, for example, particularly preferably by using an electron-rich monomer, for example a vinyl ether, vinyl acetate, styrene or ⁇ -methylstyrene.
  • aromatic vinyl monomers such as styrene or ⁇ -methylstyrene.
  • the preparation of the additive polymers to be used according to the invention is known per se. They can be prepared in bulk, solution, suspension or emulsion polymerization. Helpful hints can be found regarding the bulk polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Information on solution polymerization can be found on page 1156ff. The suspension polymerization technique is also described on page 1149ff, while the emulsion polymerization is carried out and explained there on page 1150ff.
  • bead polymers whose particle size is in a particularly favorable range.
  • the additive polymers to be used according to the invention by, for example, mixing into the melt of the fiber polymers are present in the form of particles having an average diameter of 0.1 to 1.0 mm.
  • larger or smaller beads can also be used.
  • copolymers according to the invention are commercially available or can be prepared by a process familiar to the person skilled in the art.
  • additive polymers having viscosity numbers in the range from 70 to 130 cm 3 / g.
  • an additive polymer is added, which is obtainable by multiple initiation.
  • multiple initiation encompasses both a single or multiple re-initiation of free-radical polymerization, i. H. the single or multiple re-addition of initiator at later reaction times, as well as the radical polymerization in the presence of a mixture comprising at least two initiators with graded half-lives, which is particularly preferred in the context of the present invention.
  • Graded half-life means in the context of the present invention that the at least two initiators each have different half-lives at a certain temperature or have the same half-life, but in different temperature ranges.
  • initiators are used, each having a half-life of one hour in temperature ranges which are at least 10 ° C apart.
  • a single compound can be used as the initiator as an initiator from the individual temperature ranges, but it is also possible to use two or more initiators with the corresponding half-lives from the corresponding temperature ranges.
  • an initiator mixture which has an initiator I, with a half-life T 1 of one hour in the range 70 to 85 ° C. and a further initiator I 2 with a half-life T 2 of one hour in the range 85 to 100 ° C having.
  • Further initiators I n which can be used if appropriate, preferably have decomposition temperatures T n between T 1 and T 2 .
  • the amount of initiator mixture to be used can be varied within relatively wide limits; It can thus be controlled, the polymerization, and the polymerization temperature can be influenced by the amount of initiators used.
  • the quantities used according to the invention are given in parts by weight of initiator per 100 parts by weight of monomers. It is advantageous to use a total amount of initiator mixture of about 0.05 to 1.0 parts by weight per 100 parts by weight of monomers, suitably 0.05 to 0.5 parts by weight, in particular 0.15 to 0.4 parts by weight per 100 parts by weight of monomers.
  • the weight ratio of the individual initiators to one another in the initiator mixture can likewise be varied within relatively wide limits; Preferably, the weight ratio of the individual initiators to one another is in the range from 1: 1 to 1:10, preferably 1: 1 to 1: 4. Suitable amounts and mixing ratios can be determined on the basis of simple preliminary experiments.
  • Suitable initiators which can be used according to the invention include the per se conventional initiators which are used for radical formation in free-radically initiated polymerizations. These include compounds such as organic peroxides such as dicumyl peroxide, diacyl peroxides such as dilauroyl peroxide, peroxydicarbonates such as diisopropyl peroxydicarbonate, peresters such as tert. Butyl peroxy-2-ethylhexanoate and the like. Other types of compounds which can form radicals are also suitable in the context of the present invention. These include in particular azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis- (2,4-dimethylvaleronitrile).
  • the polymerization can be carried out largely or over a wide range under isothermal conditions.
  • the polymerization takes place in at least two steps. In a first step, initially at a lower temperature, preferably at a temperature between 60 and less than 85 ° C, polymerized. In a second step, the polymerization is continued at a higher temperature, preferably at a temperature between 85 and 120 ° C.
  • the additive polymer has a residual monomer content of less than 0.62 wt .-%, advantageously less than 0.47 wt .-%, preferably less than 0.42 wt .-%, each based on the total weight of the additive polymer on.
  • the residual monomer content of the additive polymer is less than 0.37 wt .-%, preferably less than 0.30 wt .-%, advantageously less than 0.25 wt .-%, in particular less than 0.20 wt .-%, each based on the total weight of the additive polymer.
  • the residual monomer content in the additive polymer denotes the amount of monomer which remains in the additive polymer after polymerization and polymer isolation.
  • it is in the range of 0.65% to 1.0% by weight, based on the total weight of the polymer.
  • Methods for reducing the residual monomer content of a polymer are known in the art. For example, it can be lowered by degassing the polymer melt, preferably in the extruder directly before spinning.
  • such flow aids have proved to be of limited suitability, since they are disadvantageous for the spinning process.
  • they can be deposited in the spinning device and thus lead to blockages of the lines and nozzles and thus to malfunction.
  • Component H is an optional component. Although the advantages to be achieved according to the invention can already be achieved by copolymers comprising components from groups E to G, the advantages to be achieved according to the invention also occur if further monomers from group H are involved in the construction of the copolymer to be used according to the invention.
  • the component H is preferably selected so that it has no adverse effect on the properties of the copolymer to be used according to the invention.
  • the component H can u. a. Therefore, it can be used to desirably modify the properties of the copolymer, for example by increasing or improving the flow properties when the copolymer is heated to the melting temperature, or reducing a residual color in the copolymer or by using a polyfunctional monomer, in this way and to introduce some degree of crosslinking into the copolymer.
  • H can also be chosen so that a copolymerization of components E to G is possible or supported in the first place, as in the case of MSA and MMA, which do not copolymerize per se, but copolymerize readily with the addition of a third component such as styrene.
  • Suitable for this purpose are u. a. Vinyl esters, esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid other than methyl methacrylate, for example butyl methacrylate and ethylhexyl methacrylate, acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, styrene, ⁇ -methylstyrene and the various halosubstituted styrenes, vinyl and isopropenyl ethers, dienes such as 1,3-butadiene and divinylbenzene.
  • the color reduction of the copolymer can be achieved, for example, particularly preferably by using an electron-rich monomer, for example a vinyl ether, vinyl acetate, styrene or ⁇ -methylstyrene.
  • aromatic vinyl monomers such as styrene or ⁇ -methylstyrene.
  • Riesel birthdayiana The preparation of said Riesel birthdayn is known per se. They can be prepared in bulk, solution, suspension or emulsion polymerization. Helpful hints can be found regarding the bulk polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Information on solution polymerization can be found on page 1156ff. The suspension polymerization technique is also described on page 1149ff, while the emulsion polymerization is carried out and explained there on page 1150ff. Optionally, the polymers must still be ground.
  • flow aids whose particle size is in a particularly favorable range.
  • Particularly preferred are in the form of particles with a mean diameter of 0.01 to less than 100 microns ago.
  • Rieselbaumn be used with larger or smaller particle sizes.
  • the imidized copolymer types 3 and 4 can be prepared both from the monomers using a monomeric imide and by subsequent complete or preferably partial imidization of a copolymer containing the corresponding maleic acid derivative.
  • These free-flowing aids are obtained, for example, by complete or preferably partial reaction of the corresponding copolymer in the melt phase with ammonia or a primary alkyl- or arylamine, for example aniline (Encyclopedia of Polymer Science and Engineering Vol. 16 [1989], Wiley-Verlag, page 78). , The resulting copolymers may need to be ground.
  • copolymers according to the invention and, if present, their non-imidized starting copolymers are commercially available or can be prepared by a process familiar to the person skilled in the art.
  • flow aids which have a largely identical chemical composition to the additive polymer used have proven particularly useful.
  • the flow aid and the additive polymer used to at least 50 wt .-%, advantageously at least 60 wt .-%, preferably at least 70 wt.%, In particular at least 80 wt .-%, each based on the total weight of Riesel Anlagen or the additive polymer used, the same repeat units.
  • the repeating units characterize the repeating units derived from the monomers originally used in the polymer.
  • the flow aid and the additive polymer used to at least 90 wt .-%, preferably at least 95 wt .-%, in particular at least 97 wt .-%, each based on the total weight of the flow aid or of the additive polymer used which have the same repeat units.
  • the polymer composition of the flow aid and that of the additive polymer used are completely identical with respect to the repeating units.
  • a flow aid which has a similar weight average molecular weight as the additive polymer used.
  • the weight-average molecular weight preferably deviates from the flow aid by less than 50%, advantageously by less than 30%, in particular by less than 20%, from that of the additive polymer used.
  • the preferred concentration range of the flow aid in the additive polymer is 0.05 to 5.0 wt .-%, preferably 0.05 to 1.0 wt .-%, each based on the total weight of the additive polymer and flow aid, and depends on the surface and thus on the average diameter of the additive polymers.
  • a concentration of the flow aid of 0.05 to 0.3 wt .-% is preferred.
  • the concentration of the flow aid required for the flow-promoting effect increases. At too low a concentration of the flow aid the flow-promoting effect is incomplete, while at too high concentrations of Riesel Garssel no further improvement of the flow behavior is achieved, but it enters a strong, technically undesirable dust formation by the excess, finely divided Riesel faux powder.
  • the trickle aid is prepared by an emulsion polymerization process and isolated by spray drying.
  • the spray drying can be done in a known per se. Exemplary descriptions of the spray drying can be found in DE 332 067 or Ullmanns Enzyklopadie der ischen Chemie, 5th edition (1988), B 2, page 4-23.
  • the spray unit single-fluid nozzle, two-fluid nozzle or atomizer disk
  • particles with an average particle diameter of 20 to 300 ⁇ m are obtained.
  • the mixing of the additive polymer and the flow-through aid for the production of a homogeneous (as far as possible) strain-increasing agent can be carried out in a manner known per se. Further details are described, for example, in Ullmanns Enzyklopadie der ischen Chemie, 5th edition (1988) and in Rompps Chemie Lexikon (CD) - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995.
  • the strain-increasing agent to be used according to the invention is not granulated in contrast to the prior art.
  • Granulation in this context refers to the production of so-called pellets (granules) of the same shape and size.
  • the polymer to be granulated is usually melted in a single or twin-screw extruder and fed to a pelletizer. The crushing can be done both by cold pelletization and by hot pelletization. Cold pelletizing takes place through the granulating nozzle Strands, strips or thin films produced, which are comminuted after solidification by means of rotating knives. In hot pelletizing, the plasticized polymer is forced through the die and the outgoing strand is comminuted by a rotating knife, which is usually mounted on the die plate. The cooling of the melt takes place after pelletizing usually either with air or water.
  • the melt spinning of POYs is preferably carried out at spinning take-off speeds of at least 2500 m / min.
  • the filter pack according to the prior art with filter devices and / or loose filter media (eg., Steel sand) equipped.
  • the molten polymer mixture is pressed after the shear and filtration treatment in the nozzle package through the holes of the nozzle plate.
  • the melt filaments are cooled by means of cooling air below its softening temperature, so that sticking or upsetting at the following thread guide is avoided.
  • the formation of the cooling zone is not critical, provided that a homogeneous, the filament bundle uniformly penetrating air flow is ensured.
  • a Heilruhezone to delay the cooling can be provided directly below the nozzle plate.
  • the cooling air can be supplied by transverse or radial blowing from an air conditioning system or removed by means of a cooling tube from the environment by self-priming.
  • the filaments are bundled and treated with spin oil.
  • oilers are used, to which the spinning oil is fed as an emulsion of metering pumps.
  • the prepared thread advantageously passes through an Entangling Surprise (Verschling Surprise) to improve the thread closing.
  • handling and security organs may be appropriate before the thread passes to the winding unit and is wound there on cylindrical bobbin to packages.
  • the peripheral speed of the thread package is automatically controlled and is equal to the winding speed. Due to its traversing movement, the withdrawal speed of the thread can be 0.2 - 2.5% higher than the winding speed.
  • driven godets can be used after preparation or before winding.
  • the peripheral speed of the first godet system is referred to as the take-off speed.
  • Other godets can be used for stretching or relaxing.
  • the incompatibility of the two polymers causes the additive polymer immediately after the exit of the polymer mixture from the spinneret predominantly forms radially symmetric elongated particles in the matrix polymer in the yarn running direction.
  • the length / diameter ratio is> 2.
  • the diameter (d) was determined perpendicularly and the length parallel to the thread running direction. Best conditions were obtained when the mean particle diameter (arithmetic mean) d 50 ⁇ 400 nm, and the proportion of particles> 1000 nm in a sample cross section was less than 1%.
  • a flow activation energy of the copolymers of at least 80 kJ / mol, ie a higher flow activation energy than that of the polymer matrix is advantageous. Under this condition, it is possible that the additive fibrils solidify in front of the polyester matrix and absorb a significant proportion of the applied spinning tension. Thus, the desired capacity increase of the spinning plant can be achieved in a simple way.
  • the above-described preferred embodiment of the method according to the invention is in the same way for the fast spinning of POY filaments having a POY filament titre of> 3 dtex to 20 dtex and more, as well as of POY filament titres ⁇ 3 dtex, in particular microfilaments with 0, 2 to 2.0 dtex suitable.
  • the yarn breakage rate is markedly reduced compared with the processes known from the prior art.
  • the yarn break rate is less than 0.75 fractions per ton of polymer blend, suitably less than 0.5 fractions per ton of polymer blend, preferably less than 0.4 fractions per mole Ton of polymer blend.
  • the synthetic threads obtainable by the process according to the invention can be used directly in the present form or further processed in a manner known per se. In a particularly preferred embodiment of the present invention, they are used to make staple fibers. In this case, further details for the production of staple fibers of the prior art, for example, the document DE 199 37 727 and the cited in her writings are taken.
  • POYs produced by the process according to the invention are stretched or draw texturized.
  • the following is important for the further processing of the spun yarn in the draw-texturing process at high speeds:
  • Spun yarns according to this invention as roving for draw texturing - usually referred to as POY - are preferably at take-off speeds ⁇ 2500 m / min, preferably> 3500 m / min, particularly preferably> 4000 m / min.
  • These yarns must have a physical structure characterized by a specific degree of orientation and low crystallization. The characteristics of elongation at break, birefringence, degree of crystallization and boiling shrinkage have proven useful for its characterization.
  • the polyester-based polymer mixture according to the invention is characterized by an elongation at break of the polymer filaments (POY) of at least 85% and at most 180%.
  • POY polymer filaments
  • the boiling shrinkage is 32-69%
  • the birefringence is between 0.030 and 0.075
  • the crystallinity is less than 20%
  • the tear strength is at least 17 cN / tex.
  • the elongation at break of the polymer filaments is preferably between 85 and 160%. Particularly favorable conditions exist when the elongation at break of the polymer spun yarns is between 109 and 146%, the tensile strength at the same time is at least 22 cN / tex and the Uster value is at most 0.7%.
  • the synthetic POYs obtainable in this way are particularly suitable for further processing in a draw or draw texturing process. In this case, a lower number of yarn breaks can be observed during further processing.
  • Draw texturing is carried out at different speeds, depending on the type of filament titre, with speeds of 2 dtex per filament (final titre) of speeds ⁇ 750 m / min, preferably ⁇ 900 m / min, being used for normal titre filaments.
  • speeds of 2 dtex per filament (final titre) of speeds ⁇ 750 m / min, preferably ⁇ 900 m / min, being used for normal titre filaments.
  • speeds between 400 and 750 m / min are preferred.
  • the process can be advantageously applied to these titers and in particular microfilaments between 0.15 and 1.10 dtex (final titer) per filament.
  • the residual monomer content of methyl methacrylate and styrene was measured by gas chromatographic headspace analysis, a method for determining volatiles in liquids and solids (including monomers in thermoplastics).
  • the residual monomer content of N-cyclohexylmaleimide was determined by gas chromatography on a solution of the polymer in dichloromethane.
  • the mean grain diameter in the spray-dried flow aid was determined by laser diffraction spectroscopy using a Mastersizer Microplus from Malvem (measuring range: 0.05-555 ⁇ m).
  • the mean grain diameter of the spun-fiber additive beads was determined by a sieve analysis with an Alpine air-jet screening machine (type A 200 LS).
  • the measuring temperature was 290 ° C for polyethylene terephthalate and additive polymers, which are added to polyethylene terephthalate, or was equal to the melting temperature (method hereafter) of the affected polymer plus 34.0 ° C.
  • the thus determined measuring temperature corresponds to the typical processing or spinning temperature of the respective polymer.
  • the amount of sample was chosen so that the rheometer gap was completely filled.
  • the measurement was carried out in oscillation with the frequency 2.4 Hz (corresponding to a shear rate of 15 sec -1 ) and a deformation amplitude of 0.3, and determines the amount of the complex viscosity as a function of the measuring time. Thereafter, the initial viscosity was converted to the zero measurement time by linear regression.
  • the polymer sample was first melted at 310 ° C for 1 min and then immediately quenched to room temperature. Subsequently, the melting temperature was determined by DSC measurement (differential scanning calorimetry) at a heating rate of 10 ° C / min. Pretreatment and measurement were done under nitrogen fogging.
  • the titer was determined in a known manner with a precision tare and a weighing device.
  • the bias was suitably 0.05 cN / dtex for the oriented filaments (POYs) and 0.2 cN / dtex for the textured yarn (DTY).
  • Tear strength and elongation at break were determined in a Statimat meter under the following conditions; the clamping length was 200 mm for POY and 500 mm for DTY, the measuring speed was 2000 mm / min for POY and 1500 mm / min for DTY, the pretension was 0.05 cN / dtex for POY and 0.2 cN / dtex for DTY. By dividing the values for the maximum tearing load by the titer, the tear strength was determined, and the elongation at break was evaluated at maximum load.
  • Polyethylene terephthalate chips having a water content of less than 35 ppm, an intrinsic viscosity of 0.64 dl / g and a melt viscosity (at 290 ° C) of 250 Pas were fed into the intake of an extruder. Placed perpendicular to the conveying direction of the extruder screw and centric to Extrudereinzug was a downpipe through which the dried to a residual moisture content of ⁇ 0.1% by weight additive was added by means of a gravimetric dosing in the catchment area above the extruder screw to the polyester chips.
  • the additive used was a bead polymer prepared in suspension based on MMA / styrene / N-cyclohexylmaleimide. This was a terpolymer of 89.2 wt .-% of methyl methacrylate, 8.8 wt .-% of styrene and 2 wt .-% N-cyclohexylmaleimide, wherein the terpolymer has a viscosity number VZ of about 101 cm 3 / g and a Melt viscosity (at 290 ° C) of about 1400 Pas.
  • the MMA / styrene / N-cyclohexylmaleimide additive with VZ 101 cm 3 / g was obtained as follows:
  • the dried polymer beads are mixed with 0.1 part by weight of a spray-dried MMA / styrene emulsion polymer and mixed for about 5 minutes in a fluidized bed dryer.
  • the MMA / styrene emulsion polymer acting as antistatic agent or flow aid was obtained as follows:
  • the resulting polymer dispersion was spray-dried in a spray tower from Niro, equipped with a spinner disk rotating at 15,000 rpm.
  • the supplied air had a temperature of 180 to 190 ° C; the exiting air had a temperature of 75 to 80 ° C.
  • the VZ of the spray-dried MMA / styrene copolymer was 97 cm 3 / g.
  • the spray-dried MMA / styrene copolymer was mixed at a concentration of 0.1% by weight with the MMA / styrene / N-cyclohexylmaleimide in a fluid bed dryer at room temperature for 5 minutes as described above.
  • the additive was added at a level of 0.77 weight percent, based on the total amount of the polyester / additive polymer blend removed by the extruder-fed spinning system.
  • the total amount of polymer blend removed was defined by the number of spinning pumps operated in the spinning system described below and by the throughput of the respective spin pump. When all the spinning pumps were in operation, a total of 304.5 kg / h of polymer mixture was removed from the spinning system and the additive was gravimetrically metered into the extruder feed at a rate of 2.34 kg / h.
  • the filtered first polymer mixture was fed to a SMX type static mixer from Sulzer AG with an internal diameter of 52.5 mm and a length of 525 mm, where it was homogenized and dispersed to give a second polymer mixture.
  • This second polymer blend was distributed by product line to twelve spinning positions per position containing six tow packages, with the mean residence time of the second polymer blend from the static mixer exit to the spin pack entering five minutes.
  • Each spin pack contained a round die with 34 holes of 0.25 mm diameter and twice the diameter.
  • the spin pack contained above the nozzle plate, a spin filter package consisting of a steel sand packing of 30 mm height and a grain size of 0.5 to 0.85 mm, and a mesh of 40 microns and a steel fleece filter of 20 microns pore diameter.
  • the diameter of the spin filter pack was 85 mm.
  • the residence time of the melt in the filter pack was about 1.5 minutes.
  • the heating of the spin pack was set to 290 ° C.
  • the surface of the spinneret was 30 mm above the boundary of the heating box.
  • the throughput of the melt mixture resulted in a nozzle pressure of 150 bar.
  • the average residence time of the polymer mixture of polyester and additive melt from the extruder outlet to the exit from the spin packs was about ten minutes.
  • the molten-filaments extruded from the nozzle holes were cooled by means of blowing air flowing horizontally to the yarn path at a speed of 0.55 m / s and a temperature of 18 ° C and bundled at a distance of 1250 mm from the nozzle plate in an oiler stone to the yarn and with spin finish coated.
  • a swirling nozzle which was closed when the thread was running normally, was installed, which impressed the thread with a swirling knot number of 13 knots / m with an air pressure of 4.5 bar.
  • the inlet tension in the inlet of the swirling nozzle was set to 0.16 g / den.
  • six threads of a spinning position were wound in a winder into winding packages, wherein the coil speed of 4985 m / min was selected such that the thread tension before winding was 0.1 g / den.
  • Preoriented (POY) filaments were obtained, characterized by a titer of 126 denier, an elongation at break of 116% and a tear strength of 2.4 g / denier.
  • the breakage rate during operation of the spinning system averaged 0.75 breaks per tonne of polymer blend passed through.
  • the obtained POYs were stretch-texturized with a texturing machine of the type FK6 from Barmag AG / Germany at a speed of 900 m / min.
  • the draw ratio was set at 1.77 and heater temperatures 1 and 2 at 210 and 170 ° C, respectively.
  • the textured yarn had a denier of 74 denier, a tenacity of 4.5 g / den, an elongation at break of 18.3% and was characterized by a good staining uniformity.
  • the additive from the inventive example thus had a comparable bead size and treatment with MMA / styrene emulsion polymer in a fluidized bed dryer a significantly lower residual monomer content compared to the additive of the comparative example.
  • the additive was added in an amount of 0.77% by weight, based on the total amount of the polymer mixture fed to the spinning system, and the polymer mixture was spun analogously to the comparative example.
  • POY yarns were produced during a production period of seven days, characterized by a titer of 126 denier, an elongation at break of 117% and a breaking strength of 2.4 g / den.
  • the breakage rate during operation of the spinning system was on average 0.35 fractions per ton of interspersed polymeimischung.
  • the POYs were stretch-texturized analogously to the comparative example at a speed of 900 m / min.
  • the breakage rate was an average of 18 breaks per ton of textured yarn.
  • the textured yarn has the same titer and the same tear strength as the textured yarn of the comparative example and an elongation at break of 18.6% with uniform dye uniformity.

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Claims (14)

  1. Procédé de fabrication de fils synthétiques à partir d'un mélange fondu à base de polymères de matrice fibrogènes, procédé dans lequel on ajoute au polymère de matrice fibrogène au moins un deuxième polymère additif amorphe qui est incompatible avec le polymère de matrice fibrogène, en une quantité de 0,05 à 5 % en poids par rapport au poids total du polymère de matrice fibrogène et avec ce polymère additif incompatible, le polymère additif présentant une température de transition vitreuse supérieure à 100° C et pouvant être transformé de manière thermoplastique, et le rapport de viscosité de fusion du polymère additif par rapport à la viscosité de fusion du polymère de matrice fibrogène se situe entre 1 :11 et 10 :1, la viscosité de fusion étant extrapolée à un temps de mesure zéro et la mesure étant effectuée à un taux d'oscillation de 2,4 Hz et à une température qui se situe 34° C au-dessus de la température de fusion du polymère de matrice, caractérisé en ce que l'on ajoute un polymère additif qui est obtenu par initialisation multiple.
  2. Procédé selon la revendication 1,
    caractérisé en ce que l'on ajoute au polymère de matrice fibrogène, un polymère additif qui est obtenu par polymérisation radicalaire en présence d'un mélange comprenant au moins deux initiateurs présentant des durées de demi-vie échelonnées.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on ajoute au polymère de matrice fibrogène, un polymère additif présentant une teneur en monomère résiduel inférieure à 0,62 % en poids, par rapport au poids total du polymère additif.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on ajoute au polymère de matrice fibrogène, un polymère additif présentant une teneur en monomère résiduel inférieur à 0,47 % en poids par rapport au poids total du polymère additif.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on utilise comme polymère de matrice fibrogène, un ou plusieurs polyesters.
  6. Procédé selon la revendication 5,
    caractérisé en ce que l'on utilise comme polymère de matrice fibrogène, du polyéthylène-téréphtalate (PET), du polytriméthylène-téréphtalate (PTMT) et/ou du polybutylène-téréphtalate (PBT).
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on utilise comme polymère additif, un ou plusieurs polymères qui sont obtenus par polymérisation du monomère de formule générale I
    Figure imgb0012
    R1 et R2 étant, indépendamment l'un de l'autre, identiques ou différents, un substituant qui est constitué des atomes éventuels C, H, O, S, P et halogènes, la somme des poids moléculaires de R1 et R2 étant au moins de 40 Dalton.
  8. Procédé selon la revendication 7,
    caractérisé en ce que l'on utilise comme polymère additif, du polyméthylméthacrylate et/ou du polystyrène.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on utilise comme polymère additif, un ou plusieurs polymères qui sont obtenus par copolymérisation de
    E = 30 à 99 % en poids de monomères choisis dans le groupe comprenant l'acide acrylique, l'acide méthacrylique et des composés de formule générale CH2 = CR - COOR', R étant un atome d'hydrogène ou un groupe CH3 et R' étant un radical alkyle en C1 à C15 ou un radical cycloalkyle en C5 à C12 ou un radical aryle en C6 à C14, avec éventuellement
    F = 0 à 50 % en poids de monomères choisis dans le groupe comprenant le styrène et les styrènes alkyl-substitués en C1 à C3 avec
    G = 0 à 50 % en poids de monomères choisis dans le groupe des composés constitués des composés de formule I, II et III
    Figure imgb0013
    R3, R4 et R5 étant respectivement un atome d'hydrogène ou un radical alkyle en C1 à C15, ou un radical cyclo-alkyle en C5 à C12 ou un radical aryle en C6 à C14, avec éventuellement
    H = 0 à 50 % en poids d'un ou plusieurs monomères copolymérisables éthyléniquement insaturés avec E et/ou F et/ou G du groupe constitué d'α-méthylstyrène, d'acétate de vinyle, d'esters d'acide acrylique, d'esters d'acide méthacrylique qui sont différents de E, d'acrylonitrile, d'acrylamide, de méthacrylamide, de chlorure de vinyle, de chlorure de vinylidène, de styrols substitués par un halogène, d'éthers de vinyle, d'éthers d'isopropényle et de diènes,
    la somme de E, F, G et H ensemble donnant 100 % en poids des monomères polymérisables.
  10. Procédé selon la revendication 9, caractérisé en ce que l'on utilise comme polymère additif, un terpolymère de méthylméthacrylate, de styrène et de N-cyclohexylmaléinimide.
  11. Fil synthétique obtenu par un procédé selon l'une quelconque des revendications précédentes.
  12. Traitement du fil synthétique selon la revendication 11 dans un processus d'étirement ou de texturage par étirement.
  13. Utilisation du fil synthétique selon la revendication 11, pour fabriquer des fibres discontinues.
  14. Utilisation du fil synthétique selon la revendication 11 comme fil technique.
EP01936385A 2000-05-25 2001-05-22 Procede de fabrication de fils synthetiques a partir d'un melange fondu a base de polymeres fibrogenes Expired - Lifetime EP1287192B1 (fr)

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DE10022889 2000-05-25
DE10022889A DE10022889B4 (de) 2000-05-25 2000-05-25 Verfahren zum Herstellen von synthetischen Fäden aus einer Polymermischung auf Polyesterbasis
DE2001115203 DE10115203A1 (de) 2001-03-27 2001-03-27 Verfahren zur Herstellung von synthetischen Fäden aus einer auf faserbildenden Polymeren basierenden Schmelze-Mischung
DE10115203 2001-03-27
PCT/EP2001/005851 WO2001090454A1 (fr) 2000-05-25 2001-05-22 Procede de fabrication de fils synthetiques a partir d'un melange fondu a base de polymeres fibrogenes

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KR100601304B1 (ko) * 2000-10-16 2006-07-13 주식회사 코오롱 제사성 및 염색성이 우수한 폴리에스테르 섬유
DE10063286A1 (de) * 2000-12-19 2002-06-20 Zimmer Ag Verfahren zum Spinnen und Aufspulen von PET-Filamenten
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US6967057B2 (en) * 2002-12-19 2005-11-22 E.I. Du Pont De Nemours And Company Poly(trimethylene dicarboxylate) fibers, their manufacture and use
DE10319761A1 (de) * 2003-04-30 2004-11-18 Röhm GmbH & Co. KG Dehnungserhöhungsmittel für die Herstellung von synthetischen Fäden aus schmelzspinnbaren faserbildenden Matrix-Polymeren
DE202004012387U1 (de) * 2003-08-19 2004-10-28 Kuraray Specialities Europe Gmbh Polyvinylacetal-haltiges Granulat
US20050147784A1 (en) * 2004-01-06 2005-07-07 Chang Jing C. Process for preparing poly(trimethylene terephthalate) fiber
FR2919878A1 (fr) * 2007-08-08 2009-02-13 Rhodia Poliamida E Especialidades Ltda Procede de filage pour la production de fils synthetiques a filaments continus
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KR102183241B1 (ko) * 2019-03-29 2020-11-26 주식회사 휴비스 제사성이 우수한 재생 폴리에스테르 섬유 및 이의 제조방법
CN111139563A (zh) * 2019-12-24 2020-05-12 常州欣战江特种纤维有限公司 一种室内家居装饰用异收缩有色aty纤维的生产方法
CN111719189A (zh) * 2020-06-23 2020-09-29 陈志祥 一种极细旦单板环吹5d或7d的poy纺丝线设备
CN114351268B (zh) * 2022-01-06 2023-02-28 浙江昊能科技有限公司 一种阻燃抗熔滴涤锦复合纤维的制备方法
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CN115652474A (zh) * 2022-09-28 2023-01-31 清华大学 由酰胺酸共聚物制备酰亚胺共聚物的纤维的方法和由其制备的纤维

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