EP1631706A1 - Agent augmentant la dilatation destine a la production de fils synthetiques a partir de matrices polymeriques formant des fibres et filables a chaud - Google Patents

Agent augmentant la dilatation destine a la production de fils synthetiques a partir de matrices polymeriques formant des fibres et filables a chaud

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Publication number
EP1631706A1
EP1631706A1 EP04725925A EP04725925A EP1631706A1 EP 1631706 A1 EP1631706 A1 EP 1631706A1 EP 04725925 A EP04725925 A EP 04725925A EP 04725925 A EP04725925 A EP 04725925A EP 1631706 A1 EP1631706 A1 EP 1631706A1
Authority
EP
European Patent Office
Prior art keywords
weight
elongation
melt
polymer
polyester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04725925A
Other languages
German (de)
English (en)
Inventor
Alexander Klein
Helmut Schwind
Michael Wicker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1631706A1 publication Critical patent/EP1631706A1/fr
Withdrawn legal-status Critical Current

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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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
    • 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
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters

Definitions

  • the present invention relates to an elongation enhancer, which is amorphous and thermoplastically processable, from free-radically polymerized, vinyl monomers for the production of synthetic threads from a melt-spinnable fiber-forming matrix polymer which is incompatible with the elongation enhancer.
  • the invention further relates to plastic granules containing the elongation enhancer and a method for its production.
  • the invention further relates to a method for producing synthetic threads in a melt spinning process from a polymer mixture of a melt-spinnable, fiber-forming matrix polymer and an elongation-increasing agent and the further use of the synthetic threads.
  • the spinning of polymer mixtures into synthetic threads is already known.
  • the aim is to obtain a higher elongation at break in the spinning thread at a certain spinning speed than without modification by additional polymer. This should allow a higher draw ratio for the production of the end yarn, which should result in a higher productivity of the spinning unit.
  • the producer or process provider must consider the entire production chain and cannot stop at increasing the production of a sub-step (e.g. the spinning mill).
  • the subsequent processes must not be impaired.
  • it is a main aim of this invention not to reduce the processing conditions in the subsequent steps, preferably to improve them, and this despite the increased spinning speed.
  • EP 0 047 464 B (Teijin), DE 197 07 447 (Zimmer), DE 199 37 727 (Zimmer), DE 199 37 728 (Zimmer) and WO 99/07 927 (Degussa ) disclosed.
  • EP 0 047 464 B relates to an undrawn polyester yarn, the addition of 0.2-10% by weight of a polymer of the type - (- CH 2 - CR ⁇ R 2 -) n -, such as poly (4-methyl-1 -pentene) or polymethyl methacrylate, an improved productivity is obtained by increasing the elongation at break of the filament at speeds between 2500 - 8000 m / min and correspondingly higher draw ratios.
  • a fine and uniform dispersion of the additive polymer is necessary Mix, whereby the particle diameter must be ⁇ 1 ⁇ m to avoid fibril formation.
  • the decisive factor for the effect is the interaction of three properties - the chemical additive structure, which hardly allows the additive molecules to stretch, the low mobility and the compatibility of polyester and additive. The measures serve to increase productivity. Requirements for stretch texturing are not disclosed. The reworking of the technical teaching within the framework of WO 99/07927 resulted in a high use of additives and, in connection with this, an impairment of the quality and further processability.
  • WO99 / 47735 (TEIJIN LTD.) Discloses that the additives used in EP 0 047 464 B lead to a change in the friction behavior of the threads and that it is not at all possible to achieve a satisfactory package build-up when winding the threads. According to WO99 / 47735 a satisfactory winding behavior of threads based on polymer blends can only be achieved by using additives with a thermal deformation temperature in the range of 105 to 130 ° C, ie considerably above that of polyester, and choosing specific spinning measures to achieve a radial distribution of the Additive inclusions in the thread cross section are set, in which the additive inclusions in the outer region of the thread are reduced.
  • the publication DE 199 37 727 discloses the production of polyester staple fibers from a polymer mixture which contains 0.1 to 2.0% by weight of an incompatible, amorphous, polymeric additive which has a glass transition temperature in the range of 90 up to 170 ° C.
  • 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 HMLS threads made of polyester, polymeric additive and optionally additives with a spinning take-off speed of 2500 to 4000 m / min.
  • the polymeric additive should have a glass transition temperature in the range from 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 mixtures based on polyester with a take-off speed v of at least 2500 m / min, a second, amorphous, thermoplastically processable copolymer having a glass transition temperature of more than 100 ° C. being added to the polyester.
  • the ratio of the melt viscosity of the copolymer to the melt viscosity of the polyester is 1: 1 to 10: 1.
  • At least 0.05% by weight of copolymer is added to the polyester and the maximum amount M of the copolymer added to the polyester depends on the take-off speed v and is
  • ZIMMER AG discloses specific extrusion and mixing conditions, as well as restrictions with regard to the residence time of the additives in the spinning system, which have a practicable quality and yield, i. H. ensure a practical thread break rate.
  • DE 101 15 203 A1 describes a method for producing synthetic threads from a mixture based on fiber-forming polymers.
  • the process is characterized in that an additive polymer is used which can be obtained by multiple initiation.
  • the multiple initiation causes a reduction in the residual monomer content in the polymer and, in particular, a further reduction in the thread break events during the production of the synthetic threads.
  • the thermal stabilization of radically polymerized methacrylate polymers by means of the addition of 2-mercaptoethylalkylene carboxylate compounds or by means of alkyl-3-mercapropropionate compounds as molecular weight regulators in the polymerization is known in principle (see, for example, EP-A 0 178 115).
  • expansion aids and processes are desired which permit the production of granules based on polyester and expansion aids which can be spun as a raw material in extruder spinning mills at high spinning speeds, dispensing with a dosage of the expansion aids in the spinning mill itself.
  • the melt mixture is then for a certain time at high temperatures in the polycondensation reactor and z. B. held in direct spinners in the melt distribution lines until the actual melt spinning process begins. This leads to a considerable thermal load on the elongation enhancer. It can e.g. B. Residence times of approx. 30 min at melt temperatures around 290 ° C occur.
  • the inventors have found that practically all of the prior art elongation enhancers thermally decompose under these conditions, which can be followed by the formation of monomeric components from the polymeric elongation enhancers.
  • the proportion of monomers formed by thermal decomposition is usually considerably higher than the comparatively low residual monomer proportion from the polymerization of the elongation enhancer itself.
  • the so-called residual monomer content already present in the polymer, which originates from the polymerization, is comparatively small compared to the content of monomers that can subsequently form due to thermal decomposition and is negligible for the present consideration, especially if the residual monomer content is caused by multiple initiation during the Additive manufacturing was reduced accordingly.
  • Elongation enhancer which is amorphous and thermoplastically processable, from radically polymerized, vinyl monomers for the production of synthetic threads from a Elongation-increasing agents incompatible, melt-spinnable fiber-forming matrix polymers, characterized in that the elongation-increasing agent is thermally stabilized by adding an antioxidant substance, so that after a thermal load at 290 ° C. under argon for 30 minutes it has a total content of not more than 6% by weight. % has decomposition products detectable with the gas chromatographic head-space method.
  • Gas chromatographic head-space analysis is a method for the determination of vaporizable constituents in liquids and solids (including monomers in thermoplastics; determination of the annealing time from the time of introducing the sample bottle in the metal block thermostats preheated to 290 ° C; sample amount approx. 30 mg in one 22 ml headspace sample bottles).
  • the detectable decomposition products that arise during thermal stress are predominantly monomers regressed by depolymerization, e.g. B. methyl methacrylate or styrene. As a rule, the proportion of non-monomeric decomposition products is negligible.
  • thermally stabilized polymer or copolymer therefore fulfills the condition mentioned above. Without thermal stabilization, the monomer content is usually well above the upper limit mentioned, e.g. B. in the range of 10 wt .-% or above.
  • a suitable thermal stabilization of the elongation enhancer can e.g. B. can be achieved by adding an antioxidant and / or by containing a copolymerized d- to C ⁇ 2 -, preferably C - to C ⁇ -, alkyl acrylate and / or in that it is in the presence of a molecular weight regulator which is an alkyl 3- is mercaptopropionate, where alkyl is linear or for branched Ci - C ⁇ s hydrocarbon groups, was polymerized.
  • a polymer or copolymer is thermally stabilized in the sense of the invention if it is e.g. B. contains one of the measures mentioned or was produced in the manner mentioned, so that it meets the test conditions specified as claimed.
  • the stretching agent may contain an antioxidant in an amount of 0.05 to 5% by weight.
  • the antioxidative substance can be selected from the class of the sterically hindered phenols and / or the divalent thio compounds and / or the trivalent phosphorus compounds and / or the sterically hindered piperidine derivatives.
  • the antioxidant substance octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferred.
  • the antioxidative substance can be selected from the following compounds: - 2,6-di-tert-butyl-4-methylphenol
  • antioxidants or stabilizers can be added to stabilize the polymer even better.
  • Suitable organic phosphites can be any aliphatic, aromatic or aliphatic-aromatic phosphites and thiophosphites, such as:
  • Hindered piperidine derivatives can be, for example: - Poly [[6 - [(1, 1, 3,3-tetramethylbutyl) amino] -5-triazine-2,4-diyl] - [(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene- [2,2,6,6-tetramethyl-4-piperidyl) imino]]
  • Suitable thioesters can be, for example
  • the antioxidative substance can advantageously be added to the monomer mixture before or during the polymerization without impeding it (see, for example, EP-A 254 348). This has the advantage that the manufacturing process for the thermally stabilized elongation enhancer is simplified.
  • the production of the polymer in the presence of the antioxidant ensures a homogeneous distribution of the antioxidant in the entire polymer before the subsequent further processing by means of a melt process, and thus largely prevents thermal damage to the polymer during further processing and assembly.
  • Another advantage of the process of adding antioxidants already during the polymerization is the significantly lower costs for producing a homogeneously, thermally stabilized polymer without an additional packaging step.
  • a suitable thermal stabilization of the elongation enhancer can e.g. B. can be achieved by a C - to -C 2 alkyl acrylate is contained in an amount of 1.5 to 15 wt .-% as a thermally stabilizing comonomer based on the total weight of the elongation enhancer.
  • N-Butyl acrylate is particularly preferably present as a thermally stabilizing comonomer.
  • the elongation enhancer can be polymerized from monomers of the general formula I
  • R 1 and R 2 independently of one another, identically or differently, denote a substituent which consists of the optional atoms C, H, O, S, P and halogen atoms, the sum of the molecular weights of R 1 and R 2 being at least 40 and at most 400 daltons is.
  • the elongation enhancer can be a thermally stabilized polymethyl methacrylate.
  • X a C 1 to C 12 , preferably a C 4 to C ⁇ alkyl acrylate, which is different from A.
  • the elongation enhancer can be a thermally stabilized copolymer of methyl methacrylate and n-butyl acrylate.
  • the elongation enhancer can be a thermally stabilized copolymer of methyl methacrylate, styrene, and n-butyl acrylate.
  • the elongation enhancer can be a thermally stabilized copolymer of at least three of the following monomer units:
  • the elongation enhancer can preferably consist of 60 to 94% by weight of E, 0 to 20% by weight of F, 6 to 30% by weight of G and 0 to 20% by weight of H, the sum of E, F, G and H together give 100% by weight.
  • Component H is an optional component.
  • 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.
  • Component H can u. a. can be used to modify the properties of the copolymer as desired, e.g., by increasing or improving the flow properties when the copolymer is heated to the melting temperature, or to reduce residual color in the copolymer, or by using a polyfunctional monomer to do so 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 MA and MMA, which do not copolymerize per se, but copolymerize without problems when a third component such as styrene is added.
  • the monomers suitable for this purpose include vinyl esters, esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid which differ from 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 ether, dienes, such as 1, 3-butadiene and divinylbenzene.
  • the color reduction of the copolymer can For example, particularly preferably by using an electron-rich monomer, such as a vinyl ether, vinyl acetate, styrene or ⁇ -methylstryrene.
  • Aromatic vinyl monomers such as styrene or ⁇ -methylstyrene, are particularly preferred among the compounds of component H.
  • the elongation enhancer can be a thermally stabilized terpolymer of methyl methacrylate, styrene and N-cyclohexylmaleimide.
  • the elongation enhancer can be a copolymer of at least four of the following monomer units:
  • F 0 to 50% by weight of monomers selected from the group consisting of styrene and C 3 -3 -alkyl-substituted styrenes, with
  • G 0 to 50% by weight of monomers selected from the group of compounds consisting of compounds of the formula II, III and IV where R 3 , R 4 and R 5 are each an H atom or a C 15 alkyl group or a Cs - ⁇ - cycloalkyl group or a C 6 - 4 aryl group, with optionally
  • H 0 to 50% by weight of one or more ethylenically unsaturated monomers copolymerizable with E and / or with F and / or G from the group consisting of ⁇ -methylstyrene, vinyl acetate, acrylic acid esters, methacrylic acid esters which differ from E, acrylonitrile , Acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, halogen-substituted styrenes, vinyl ethers, isopropenyl ether and dienes,
  • X 1.5 to 15% by weight of a Ci to C 12 -, preferably a C 4 to C ⁇ -, alkyl acrylate other than E.
  • Component H is an optional component. Although the advantages to be achieved according to the invention can already be achieved by copolymers which have 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. 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.
  • Component H can u. a. can be used to modify the properties of the copolymer as desired, e.g., by increasing or improving the flow properties when the copolymer is heated to the melting temperature, or to reduce residual color in the copolymer, or by using a polyfunctional monomer to do so 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 MA and MMA, which do not copolymerize per se, but copolymerize without problems when a third component such as styrene is added.
  • Suitable monomers for this purpose include u. a. Vinyl esters, esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid which differ from 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 ether, dienes such as 1, 3-butadiene and divinylbenzene.
  • the color reduction of the copolymer can, for example, particularly preferably be achieved by using an electron-rich monomer, such as, for example, a vinyl ether, vinyl acetate, styrene or ⁇ -methylstryrene.
  • Aromatic vinyl monomers such as styrene or ⁇ -methylstyrene, are particularly preferred among the compounds of component H.
  • the elongation enhancer can in particular be a copolymer of methyl methacrylate, N-cyclohexylmaleimide and n-butyl acrylate.
  • the elongation enhancer can further be a copolymer of methyl methacrylate, styrene, N-cyclohexylmaleimide and n-butyl acrylate.
  • the process should enable the production of polyester-based POYs with elongation at break values in the range from 90% to 165%, high uniformity with regard to the filament characteristics and a low degree of crystallization.
  • Another object of the present invention was to provide a method for spinning synthetic threads that can be carried out on a large scale and inexpensively, including in existing plants. Furthermore, it should be possible to wind the threads even when the feeler roller drive is less than 0.3% higher than the winding mandrel drive of the winder, or even with winders without a separately controlled feeler roller with good bobbin buildup at speeds above 3800 m / min. Through the Possibility of slippage between thread and feeler roller, which can occur in the event of large cant, is avoided and a high uniformity of dyeing of the threads is ensured in further processing. In particular, the method according to the invention should enable the production of POYs with the highest possible withdrawal speeds, preferably> 2500 m / min.
  • the POYs obtainable according to the invention should enable further processing in a drawing or drawing texturing process, preferably at high processing speeds, with a small number of thread breaks.
  • the elongation-increasing agent is preferably produced by multiple initiation in accordance with DE 101 15 203 A1, as a result of which a low residual monomer content already results from the preparation. This is possible by simultaneous initiation with different initiators or by successive multiple initiations.
  • Plastic pellets are preferably produced by multiple initiation in accordance with DE 101 15 203 A1, as a result of which a low residual monomer content already results from the preparation. This is possible by simultaneous initiation with different initiators or by successive multiple initiations.
  • a plastic granulate comprising or consisting essentially of the elongation enhancer and a melt-spinnable fiber-forming matrix polymer.
  • the fiber-forming matrix polymer can be a polyester, a polylactic acid, a polyamide or polypropylene.
  • the melt-spinnable, thread-forming polyester is a polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate or polybutylene terephthalate, wherein the polyester can optionally contain up to 15 mol% of a copolymer and / or up to 0.5% by weight of a polyfunctional branching component.
  • the granules are at a temperature which is higher, preferably at least 10 ° C, higher than the glass transition temperature of the
  • Elongation-increasing agent is reduced to less than 0.3% by weight, based on the proportion by weight of the elongation-increasing agent in the granules.
  • the granules are preferably thermally conditioned for at least 4 hours under vacuum, dry air or an inert gas atmosphere. This can expediently take place in the course of drying the matrix material, in particular the polyester. Furthermore, this conditioning is possible in the course of the solid-phase condensation of the matrix polymer, which does not significantly impair its reaction rate in the presence of the elongation enhancer. Because of the high temperatures that occur there, this process variant particularly requires the use of the thermally stable elongation-increasing agents according to the invention.
  • the content of the elongation-increasing agent in the granulate can be higher than the content required for spinning, e.g. B. 5 - 30 wt .-%. This makes it possible to add additives using conventional master batch dosing devices.
  • additives can particularly preferably already during the compounding of a master batch which contains additional ingredients, such as, for. B. pigments, optical brighteners or flame retardants.
  • the invention is a process for producing the plastic granulate, in which the melted expansion aid is preferably transported through a degassing zone before or after it is mixed into the melt of the matrix polymer, in which the melt is preferably degassed by applying a vacuum before the granulation takes place.
  • plastic granules which, based on the proportion by weight of the elongation-increasing agent, contain less than 0.8, preferably less than 0.6% by weight of monomer from its thermal decomposition.
  • a single-screw extruder in particular with at least one vacuum degassing zone, or particularly preferably a twin-screw extruder, in particular with at least one vacuum degassing zone, is preferably used to melt the expansion aid.
  • the additive is metered either by gravimetrically controlled loading of the extruder with the expansion aid or volumetrically by means of a melt metering pump, provided that the extruder is alone with the Strain aids is applied.
  • twin-screw extruders and high throughputs a relined operation of the extruder is preferred. If a single-screw extruder is used to melt non-granulated elongation enhancer, the extruder barrel is preferably provided with grooves in the feed area.
  • Mixing into the matrix material can take place in the extruder itself and / or subsequently by means of static mixers. Gentle mixing is particularly preferred exclusively by means of static mixing.
  • the number of mixing elements is preferably selected so that there is a pressure drop of less than 80 bar, particularly preferably from 5 to 50 bar, when the melt passes through the mixing section.
  • the elongation enhancer according to the invention can be used as an additive in the production of synthetic threads from a melt-spinnable, fiber-forming matrix polymer which is a polyester, a polylactic acid, a polyamide or polypropylene.
  • the melt-spinnable, thread-forming polyester can be a polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate or polybutylene terephthalate, wherein the polyester can optionally contain up to 15 mol% of a copolymer and / or up to 0.5% by weight of a polyfunctional branching component.
  • a process for the production of synthetic threads in a melt spinning process from a polymer mixture of a melt-spinnable, fiber-forming matrix polymer and an elongation-increasing agent is characterized in that at least one elongation-increasing agent according to the invention is added to the fiber-forming matrix polymer in an amount of 0.05 to 5 wt .-%, based on the total weight of fiber-forming matrix polymer with this elongation enhancer.
  • the additive polymer can be added and mixed with the matrix polymer in a manner known per se. It is described, for example, in WO 99/07 927, or DE 199 35 145 or DE 100 22 889, the disclosure of which is hereby expressly incorporated by reference.
  • the improved thermal stability of the new additive polymers advantageously allows the following methods of addition to be used on an industrial scale, without excessive formation of monomers from their thermal decomposition:
  • the matrix polymer and the elongation enhancer can be introduced as raw material in the form of a granulate for the production of the synthetic threads in the production process.
  • the elongation-increasing agent can be added to a melt-spinnable, fiber-forming polyester during the production of the polyester in the final stage of the polycondensation plant.
  • the addition of the elongation enhancer to a melt-spinnable, fiber-forming polyester can take place after the discharge of the polyester melt from the final stage of the polycondensation plant during the transport of the polyester melt for direct spinning, the elongation enhancer being melted by means of a side-stream extruder and the melted elongation-increasing agent preferably being transported through an elongation degassing zone.
  • the melt is degassed by applying a vacuum before the degassed melt is metered into the stream of the polyester melt by means of a gear metering pump and mixed with it by means of a static mixing section.
  • a single-screw extruder in particular with at least one vacuum degassing zone, or particularly preferably a twin-screw extruder, in particular with at least one vacuum degassing zone, is preferably used to melt the expansion aid.
  • the additive is metered either by gravimetrically controlled loading of the extruder with the expansion aid or volumetrically by means of a melt metering pump.
  • twin-screw extruders and high throughputs a relined operation of the extruder is preferred.
  • the extruder barrel is preferably provided with grooves in the feed area.
  • the mixing into the matrix material is then carried out using static mixers.
  • the number of mixing elements is preferably chosen so that there is a pressure drop of less than 80, particularly preferably from 5 to 50 bar when the melt passes through the mixing section.
  • a spinning take-off speed of at least 2500 m / min is preferred.
  • the fiber-forming matrix polymer can in particular be a thermoplastically processable polyester, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate or polybutylene terephthalate, the polyester optionally containing up to 15 mol% of a copolymer and / or up to 0.5% by weight of a polyfunctional branching component can.
  • a thermoplastically processable polyester such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate or polybutylene terephthalate
  • the polyester optionally containing up to 15 mol% of a copolymer and / or up to 0.5% by weight of a polyfunctional branching component can.
  • Synthetic threads are obtainable by the process described.
  • Synthetic threads comprise, contain, or consist essentially of a polymer mixture of polyester and the elongation enhancer, the threads containing less than 40 ppm of monomer from the thermal decomposition of the elongation enhancer.
  • the synthetic threads can be used or further processed in a drawing or drawing texturing process.
  • the synthetic threads can be used for the production of staple fibers or further processed.
  • the synthetic threads can be used for the production of nonwovens or further processed.
  • the synthetic threads can be used or processed for the production of technical yarns.
  • the method according to the invention has a number of further advantages. These include:
  • the method according to the invention can be carried out in a simple manner, on an industrial scale and inexpensively.
  • the method allows spinning and winding at high take-off speeds.
  • the method according to the invention is particularly suitable for the production of polyester-based POYs with elongation at break values in the range from 90% to 165%, a high uniformity with regard to the filament characteristics and a low degree of crystallization.
  • the synthetic threads obtainable by the process can be processed in a simple manner, on an industrial scale and inexpensively.
  • the POYs according to the invention can be stretched or stretch-textured at high speeds and with a small number of thread breaks.
  • the method of the present invention relates to the production of synthetic threads from a melt mixture based on fiber-forming matrix polymers.
  • the spinning can be carried out both by a direct spinning process, in which the elongation-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 elongation-increasing agent is metered in as a solid to the matrix polymer and subsequently melted. Further details on the methods mentioned can be found in the prior art, for example in 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 expressly incorporated by reference.
  • synthetic threads refer to all types of threads which can be obtained by spinning thermoplastically processable mixtures of synthetic polymers. They include inter alia staple fibers (staple fibers), textile filaments such as plain yarns, POYs, FOYs, and technical filaments.
  • the method according to the invention is used to produce 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 polyester. Mixtures of different polymers are also conceivable. Polyesters are preferred in the context of the present invention, 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, in particular polyethylene terephthalate.
  • Homopolymers are preferred according to the invention. But there are also copolymers, preferably polyester copolymers with a proportion up to about 15 mol% of conventional comonomers, such as. B. diethylene glycol, triethylene glycol, 1, 4-cyclohexanedimethanol, polyethylene glycol, isophthalic acid and / or adipic acid, in question.
  • the polymers according to the invention can contain, as further constituents, additives such as are customary for thermoplastic molding compositions and contribute to improving the polymer properties. Examples include: antistatic agents, antioxidants, flame retardants, lubricants, dyes, light stabilizers, polymerization catalysts and assistants, adhesion promoters, matting agents and / or organic phosphites. These 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, that is to say z.
  • branching components that is to say z.
  • 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% by weight, the additive polymer having to be amorphous and largely insoluble in the matrix polymer.
  • the two polymers are essentially incompatible with one another and form two phases that can be distinguished microscopically.
  • the additive polymer should preferably have a glass transition temperature (determined by DSC with a heating rate of 10 ° C./min) of more than 90 ° C., in particular more than 100 ° C., and should be capable of being processed thermoplastically.
  • the melt viscosity of the additive polymer should be chosen so that the ratio of its melt viscosity extrapolated to the measuring time zero, measured at an oscillation rate of 2.4 Hz and a temperature that is equal to Melting temperature of the matrix polymer plus 34.0 ° C (for polyethylene terephthalate 290 ° C) relative to that of the matrix polymer, measured under the same conditions, is between 1: 1 and 10: 1.
  • 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 under the above-mentioned conditions is preferably between 1.4: 1 and 8: 1.
  • the average particle size of the additive polymer is 140-350 nm after extrusion from the spinneret.
  • the flow activation energy of the additive polymer is higher than that of the matrix polymer, in the case of polyester higher than 80 kJ / mol, in order to allow the fibril structure of the additive to solidify before the matrix material solidifies during thread formation.
  • the use of such additive polymers which have a thermal deformation temperature (ASTM D-648) of 70 to 104 ° C., preferably less than 105 °, is particularly advantageous for the production of polyester threads C.
  • 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 amounts of less than 1.5% are sufficient, at take-off speeds above 3500 and up to 6000 m / min and more, often even less than 1.0%, which is a considerable cost advantage.
  • the additive polymer is mixed with the matrix polymer in a manner known per se. It is described, for example, in WO 99/07 927, or DE 199 35 145 or DE 100 22 889, the disclosure of which is hereby expressly incorporated by reference.
  • the polymer mixture is spun at temperatures, depending on the matrix polymer, in the range from 220 to 320 ° C.
  • elongation enhancers to be used according to the invention are known per se. They can be prepared in bulk, solution, suspension or emulsion polymerization. Helpful hints can be found with regard to substance polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Information on solution polymerization can be found there on page 1156ff. The suspension polymerization technique is described there on page 1149ff, while the emulsion polymerization is described and explained there on page 1150ff.
  • Bead polymers whose particle size is in a particularly favorable range are particularly preferred in the context of the invention.
  • the additive polymers to be used according to the invention for example by mixing into the melt of the fiber polymers, are particularly preferably in the form of particles having an average diameter of 0.1 to 1.0 mm. However, larger or smaller pearls can also be used.
  • polymer blends of polyethylene terephthalate for textile applications such as POYs with an intrinsic viscosity of about 0.55 to 0.75 dl / g, and elongation enhancers with viscosity numbers in the range from 70 to 130 cm 3 / g are preferred.
  • an elongation enhancer which can be obtained by multiple initiation. This has the advantage that an elongation-increasing agent with a comparatively low residual monomer content is obtained.
  • the presence of residual monomers Incomplete polymerization can be just as harmful as the additional monomers that result from the decomposition of the elongation enhancer due to thermal stress. If the residual monomer content is low, this contributes to a lower total content of monomers in the elongation enhancer.
  • multiple initiation includes both a single or multiple post-initiation of radical polymerization, i. H. the one or more additions 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.
  • Graduated 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 preferably used, each having a half-life of one hour in temperature ranges that are at least 10 ° C apart.
  • a single compound can be used as the 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 with a half-life Ti of one hour in the range from 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.
  • Further initiators l n which can optionally be used, preferably have decomposition temperatures T n between Ti and T 2 .
  • the amount of the initiator mixture to be used can be varied within relatively wide limits; the polymerization time can thus be controlled, and the polymerization temperature can also be influenced by the amount of initiators used.
  • the quantitative data 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 part by weight per 100 parts by weight of monomers, advantageously 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; the weight ratio of the individual initiators to one another is preferably 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 tests.
  • Suitable initiators which can be used according to the invention include the initiators which are customary per se and 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, and 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.
  • Initiator mixtures whose components are selected from the following initiators have proven particularly useful:
  • Peroxidic initiators are very particularly preferred according to the invention.
  • One way to thermally stabilize the elongation enhancer is to carry out the polymerization in the presence of an EV molecular weight regulator which is an alkyS-3-mercapto-propionate, where alkyl is methyl, ethyl, n-butyl, 2-ethylhexyl and n-octadecyl, in usual amounts, e.g. B. 0.2 to 2 wt .-% based on the polymerization batch. This surprising effect is not understood.
  • an EV molecular weight regulator which is an alkyS-3-mercapto-propionate, where alkyl is methyl, ethyl, n-butyl, 2-ethylhexyl and n-octadecyl, in usual amounts, e.g. B. 0.2 to 2 wt .-% based on the polymerization batch.
  • the polymerization can be carried out largely or over wide ranges under isothermal conditions.
  • the polymerization takes place in at least two steps.
  • a first step polymerization is first carried out at a lower temperature, preferably at a temperature between 60 and 85 ° C.
  • the polymerization is continued at a higher temperature, preferably at a temperature between 85 and 120 ° C.
  • the elongation-increasing agent preferably has a residual monomer content of less than 0.62% by weight, suitably less than 0.47% by weight, preferably less than 0.42% by weight, in each case based on the total weight of the additive polymer.
  • the residual monomer content of the elongation-increasing agent is less than 0.37% by weight, preferably less than 0.30% by weight, suitably less than 0.25% by weight, in particular less than 0.20% by weight. %, in each case based on the total weight of the elongation-increasing agent.
  • the residual monomer content in the elongation enhancer denotes the amount of monomer that remains in the polymer after the polymerization and polymer isolation.
  • it is usually in the range from 0.65% by weight 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 from the prior art. For example, it can be reduced by degassing the polymer melt, preferably in the extruder directly before spinning. flow aids
  • pouring aids refer to all auxiliaries which are added in small quantities to pulverulent or granulated, in particular hygroscopic, substances in order to prevent them from clumping or caking and thus to ensure permanent free flow.
  • polymers and / or copolymers are therefore particularly preferred as flow aids.
  • the polymers and / or copolymers mentioned below have proven to be particularly useful:
  • the flow aid can be a polymer which is obtained by polymerizing monomers of the general formula (I):
  • R 1 and R 2 are substituents consisting of the optional atoms C, H, O, S, P and halogen atoms and the sum of the molecular weights of R 1 and R 2 is at least 40.
  • the trickle aid can be a copolymer which contains the following monomer units:
  • the trickle aid can be a copolymer which contains the following monomer units:
  • R 3 , R 4 and R 5 are each an H atom or a C 1 -C 8 alkyl radical or a C 6-14 aryl radical or a C 5 -1 2 cycloalkyl radical,
  • the copolymer consisting of 15 to 95% by weight of C and 2 to 80% by weight of D, preferably of 50 to 90% by weight of C and 10 to 50% by weight of D and particularly preferably of 70 to 85% by weight C and 15 to 30 wt .-% D, the sum of C and D together making 100 wt .-%.
  • the trickle aid can be a copolymer which contains the following monomer units:
  • G one or more monomers of the formula II, IM or IV
  • R 3 are each an H atom or a C- ⁇ -1 5 - 14 aryl radical, - an alkyl group or Cs-i ⁇ cycloalkyl or a C 6
  • H one or more ethylenically unsaturated monomers copolymerizable with E and / or with F and / or G from the group consisting of ⁇ -methylstyrene, vinyl acetate, acrylic acid esters, methacrylic acid esters other than E, acrylonitrile, acrylamide, methacrylamide, vinyl chloride , Vinylidene chloride, halogen-substituted styrenes, vinyl ether, isopropenyl ethers and dienes,
  • the copolymer consists of 30 to 99% by weight of E, 0 to 50% by weight of F, 0 to 50% by weight of G and 0 to 50% by weight of H, preferably 45 to 97% by weight of E , 0 to 30% by weight of F, 3 to 40% by weight of G and 0 to 30% by weight of H and particularly preferably from 60 to 94% by weight of E, 0 to 20% by weight of F, 6 up to 30 wt .-% G and 0 to 20 wt .-% H, the sum of E, F, G and H together making 100 wt .-%.
  • Component H is an optional component. Although the advantages to be achieved according to the invention can already be achieved by copolymers which have 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.
  • 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.
  • Component H can be used, inter alia, to modify the properties of the copolymer in a desired manner, for example by increasing or improving the Flow properties when the copolymer is heated to the melting temperature, or to reduce residual color in the copolymer or by using a polyfunctional monomer 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 MA and MMA, which do not copolymerize per se, but copolymerize without problems when a third component such as styrene is added.
  • Suitable monomers for this purpose include u. a. Vinyl esters, esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid which differ from 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 ether, dienes such as 1, 3-butadiene and divinylbenzene.
  • the color reduction of the copolymer can, for example, particularly preferably be achieved by using an electron-rich monomer, such as, for example, a vinyl ether, vinyl acetate, styrene or ⁇ -methylstryrene.
  • Aromatic vinyl monomers such as styrene or ⁇ -methylstyrene, are particularly preferred among the compounds of component H.
  • the production of the pouring aids mentioned is known per se. They can be prepared in bulk, solution, suspension or emulsion polymerization. Helpful hints can be found with regard to substance polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Information on solution polymerization can be found there on page 1156ff. The suspension polymerization technique is described there on page 1149ff, while the emulsion polymerization is carried out and explained there on page 1150ff. The polymers may still need to be ground.
  • Free-flowing aids are preferred whose particle size is in a particularly favorable range. Particularly preferably, they are in the form of particles with an average diameter of 0.01 to 100 ⁇ m. However, pouring aids with larger or smaller particle sizes can also be used.
  • the imidized types of copolymers can be prepared from the monomers using a monomeric imide or by subsequent complete or, preferably, partial imidization of a copolymer containing the corresponding maleic acid derivative.
  • These flow aids are obtained, for example, by completely or preferably partially reacting 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 still have to be ground.
  • pouring aids have proven particularly useful, which have a largely identical chemical composition to the additive polymer used.
  • the trickle aid and the additive polymer used advantageously have at least 50% by weight, advantageously at least 60% by weight, preferably at least 70% by weight, in particular at least 80% by weight, in each case based on the total weight the Trickle aid or the additive polymer used, the same repeating units.
  • the repeating units characterize the repeating units in the polymer which are derived from the monomers originally used.
  • the pouring aid and the elongation enhancer used are at least 90% by weight, preferably at least 95% by weight, in particular at least 97% by weight, in each case based on the total weight of the pouring aid or additive polymer used, which have the same repeating 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 weight average molecular weight similar to that of the additive polymer used.
  • the weight average molecular weight of the flow aid preferably deviates from that of the elongation-increasing agent used by less than 50%, suitably by less than 30%, in particular by less than 20%.
  • the preferred concentration range of the flow aid in the additive polymer is 0.05 to 5.0% by weight, preferably 0.05 to 1.0% by weight, in each case based on the total weight of 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% by weight is preferred.
  • the concentration of the flow aid required for the flow-promoting effect increases. If the trickle aid is too low, the flow-promoting effect is incomplete, while if the flow aid is too high, no further improvement in flow behavior is achieved, but instead a strong, technically undesirable dust formation occurs due to the excess, fine-particle flow aid powder.
  • the trickle aid is expediently produced by an emulsion polymerization process and isolated by spray drying.
  • Spray drying can be carried out in a manner known per se. Exemplary descriptions of spray drying can be found in DE 332 067 or Ullmann's Encyclopedia of Industrial Chemistry, 5th edition (1988), B 2, pages 4-23.
  • spray unit single-substance nozzle, two-substance nozzle or atomizer disc
  • particles with an average grain diameter of 20 to 300 ⁇ m are obtained.
  • the mixing of the elongation enhancer and the flow aid to produce a uniform (homogeneous) elongation enhancer can be carried out in a manner known per se. Further details are described, for example, in Ullmanns Encyclopedia of Industrial Chemistry, 5th edition (1988) and in Römpps Chemie Lexikon (CD) - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995.
  • the pouring aid after the preparation by emulsion polymerization can also be applied directly to the elongation-increasing agent in the form of the aqueous dispersion and dried together with it.
  • the additive polymer which is preferably dried using a fluidized bed dryer, and the spray-dried pouring aid using a fluidized bed dryer.
  • a fluidized bed dryer Details on the fluidized bed process can also be found in the specialist literature, for example, Ullmann's Encyclopedia of Technical Chemistry, 5th edition (1988) and Römpps Chemistry Lexicon (CD) - Version 1.0, Stuttgart New York: Georg Thieme Verlag 1995.
  • the elongation enhancer to be used according to the invention can optionally be granulated.
  • granulating 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-screw or twin-screw extruder, preferably fed with reline, preferably degassed, and fed to a pelletizing machine.
  • the crushing can be carried out both by cold pelletization and by hot pelletization.
  • cold pelletizing strands, strips or thin foils are produced through the pelletizing nozzle, which are chopped up after solidification by means of rotating knives.
  • hot pelletizing the plasticized polymer is pressed through the nozzle and the emerging strand is comminuted by means of a rotating knife, which is usually attached to the nozzle plate. After pelletizing, the melt is usually cooled with either air or water.
  • the synthetic threads are produced from the polymer mixtures according to the invention by melt spinning using spinning devices known per se, as described, for example, in documents DE 199 37 727 (staple fibers), DE 199 37 728 and DE 199 37 729 (technical yarns) and WO 99 / 07 927 (POYs). The disclosure content of these writings is therefore explicitly referred to.
  • the melt spinning of POYs is preferably carried out at spinning take-off speeds of at least 2500 m / min.
  • the filter package according to the known prior art is equipped with filter devices and / or loose filter media (e.g. steel sand).
  • the molten polymer mixture is pressed through the holes in the nozzle plate in the nozzle package.
  • the melt threads are cooled below their softening temperature by means of cooling air, so that sticking or upsetting on the following thread guide member is avoided.
  • the formation of the cooling zone is not critical, provided that a homogeneous air flow that evenly penetrates the filament bundle is guaranteed.
  • An air quiet zone for delaying the cooling can be provided directly below the nozzle plate.
  • the cooling air can be supplied from a climate system by transverse or radial blowing or can be removed from the surroundings by self-suction using a cooling pipe.
  • the filaments are bundled and spinning oil is applied to them.
  • oiling stones are used, to which the spinning oil is fed as an emulsion from metering pumps.
  • the prepared thread advantageously runs through an entangling device (interlacing device) to improve the thread closure.
  • Handling and safety devices can also be attached before the thread reaches the winding unit and is wound there into packages on cylindrical bobbins.
  • the peripheral speed of the thread package is regulated automatically and is equal to the winding speed.
  • the take-up speed of the thread can be 0.2-2.5% higher than the winding speed due to its traversing movement.
  • after preparation or before driven godets are used for the winding.
  • the peripheral speed of the first godet system is referred to as the take-off speed. Additional godets can be used to stretch or relax.
  • the incompatibility of the two polymers has the effect that the elongation-increasing agent immediately after the polymer mixture emerges from the spinneret predominantly forms radially symmetrical elongated particles in the matrix polymer in the direction of the thread.
  • the length / diameter ratio is preferably> 2.
  • the diameter (d) was determined perpendicularly and the length parallel to the direction of the thread. The best conditions were found when the mean particle diameter (arithmetic mean) dso ⁇ 400 nm and the proportion of particles> 1000 nm in a sample cross-section was below 1%.
  • a flow activation energy of the copolymers of at least 80 kJ / mol, ie a flow activation energy higher than that of the polymer matrix, is required for the effectiveness of the additives according to this invention. Only under this condition is it possible for the additive fibrils to solidify in front of the polyester matrix and to absorb a significant proportion of the spinning tension present. This makes it possible to achieve the desired increase in capacity of the spinning system.
  • the preferred embodiment of the method according to the invention described above is in the same way for the rapid spinning of POY threads with a POY (single) filament titer of> 3 dtex to 20 dtex or above, as well as POY filament titles ⁇ 3 dtex per filament , particularly suitable microfilaments with 0.2 to 2.0 dtex per filament.
  • the thread breakage rate is higher than that known from the prior art Process significantly reduced.
  • the thread break rate is less than 0.75 breaks per ton of polymer mixture, advantageously less than 0.5 breaks per ton of polymer mixture, preferably less than 0.4 Fractions per ton of polymer blend.
  • the synthetic threads obtainable by the process according to the invention can be used directly in the present form or can be further processed in a manner known per se. In a particularly preferred embodiment of the present invention, they are used for the production of staple fibers. Further details on the production of staple fibers can be found in the prior art, for example in the document DE 199 37 727 and the documents cited therein.
  • POYs produced by the method according to the invention are stretched or stretch-textured.
  • the following is important for the further processing of the spun thread in the stretch texturing process at high speeds:
  • Spinning threads according to this invention as roving for stretch texturing - usually referred to as POY - are preferably particularly preferred at take-off speeds> 2500 m / min, preferably> 3500 m / min > 4000 m / min.
  • These yarns must have a physical structure that is characterized by a specific degree of orientation and low crystallization. The parameters elongation at break, birefringence, degree of crystallization and cooking 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 Tensile strength at least 17 cN / tex.
  • the elongation at break of the polymer filaments is preferably between 85 and 160%.
  • the conditions are particularly favorable when the elongation at break of the polymer filaments 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 stretching or stretch texturing process. A lower number of thread breaks can also be observed during further processing.
  • the stretch texturing takes place at different speeds depending on the filament title type, with speeds> 750 m / min, preferably> 900 m / min, being used for normal titer filaments> 2 dtex per filament (final titer). For microfilaments and fine titers (final titers) ⁇ 2 dtex per filament, speeds between 400 and 750 m / min are preferred.
  • the method can advantageously be applied to these titers and in particular microfilaments between 0.15 and 1.10 dtex (final titer) per filament.
  • the draw ratios to be used for the specified spun threads are between 1.35 and 2.2, with draw ratios in the upper region and vice versa preferably being used for a lower degree of orientation.
  • the stretching ratio is influenced by fluctuations in tension (surging) as a function of the working speed. Drawing ratios according to the formula:
  • the ratio of the melt viscosity of the copolymer to the melt viscosity of the matrix polymer can preferably be 1: 1 to 10: 1.
  • the amount of the copolymer added to the matrix polymer may e.g. B. at least 0.05 wt .-% (based on the polyester) and a maximum of M, where M is given by the formula m
  • An elongation-increasing agent is preferably added to the matrix polymer in an amount of at least 0.05% by weight, the elongation-increasing agent having to be amorphous and largely insoluble in the matrix polymer.
  • the two polymers are essentially incompatible with one another and form two phases that can be distinguished microscopically. Furthermore, it is favorable if the elongation-increasing agent has a glass transition temperature (determined by DSC with a heating rate of 10 ° C./min) of more than 90 ° C. and can be processed thermoplastically.
  • the melt viscosity of the elongation enhancer can be chosen so that the ratio of its melt viscosity extrapolated to the measuring time zero, measured at an oscillation rate of 2.4 Hz and a temperature which is equal to the melting temperature of the polyester plus 34.0 ° C (for polyethylene terephthalate 290 ° C) relative to that of the polyester, measured under the same conditions, is between 1: 1 and 10: 1.
  • the melt viscosity of the elongation enhancer is at least equal to or preferably higher than that of the polyester.
  • the particularly preferred viscosity ratio for the use of polymer blends for the production of synthetic filament yarns lies above the range which is indicated in the literature as being favorable for the blending of two polymers.
  • the viscosity ratio increases drastically in the area of the thread formation after the polymer mixture emerges from the spinneret.
  • a particularly narrow particle size distribution of the additive in the polyester matrix is achieved and by combining the viscosity ratio with a flow activation energy of significantly more than that of the polyester (PET about 60 kJ / mol), i.e. H. of more than 80 kJ / mol, preferably more than 100 kJ / mol, the required fibril structure of the additive is obtained in the filament.
  • the glass transition temperature which is high compared to polyester, ensures that this fibril structure is quickly consolidated in the spun thread.
  • the maximum particle sizes of the additive polymer are about 1000 nm immediately after emerging from the spinneret, while the average particle size is 400 nm or less.
  • the ratio of the melt viscosity of the elongation-increasing agent to that of the matrix polymer is preferably between 1.4: 1 and 8: 1.
  • a ratio of the melt viscosities between 1.7: 1 and 6.5: 1 is particularly preferred average particle size of the additive polymer z. B. 220 - 350 nm.
  • the amount of the copolymer to be added to the polyester is usually at least 0.05% by weight. For many applications, addition quantities of less than 1.5% are sufficient, with withdrawal speeds above 3500 and up to 6000 m / min and more, often even less than 1.0%, which is a considerable cost advantage.
  • the upper limit of the elongation-increasing agent to be added for take-off speeds of more than 2900 m / min can be defined by a size M * where
  • the amount of elongation-increasing agent to be added to the matrix polymer is preferably at least equal to a size N, but preferably at least 0.05% by weight, where
  • the minimum quantity would be between 0.057 and 0.57% by weight. If the above-mentioned preferred viscosity ratio of additive polymer to polyester is observed, the amount of the elongation-increasing agent to be added would correspond to that of the matrix.
  • the amount of elongation enhancer to be added in this preferred case can thus be between 0.07% and 1.39% by weight at spinning speeds of 3900 to 6000 m / min.
  • these formulas can also be used for spinning speeds of over 6000 m / min up to about 12000 m / min.
  • the matrix polymer is the matrix polymer
  • Preferred fiber-forming matrix polymers are thermoplastically processable polyesters, such as polyethylene terephthalate (PET), polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate. Usually these are homopolymers. However, there are also copolymers of these polyesters with a proportion of up to about 15 mol% of conventional comonomers, such as, for. B. diethylene glycol, triethylene glycol, 1, 4-cyclohexanedimethanol, polyethylene glycol, isophthalic acid and / or adipic acid in question.
  • PET polyethylene terephthalate
  • PET polyethylene naphthalate
  • polypropylene terephthalate polypropylene terephthalate
  • polybutylene terephthalate polybutylene terephthalate
  • copolymers of these polyesters with a proportion of up to about 15 mol% of conventional comonomers, such as, for. B. diethylene glycol, tri
  • the polymers can contain additives such as catalysts, stabilizers, optical brighteners and matting agents.
  • the polyester can also contain a small proportion (maximum 0.5% by weight) of branching components.
  • the elongation-increasing agent can be mixed with the matrix polymer by adding it as a solid to the matrix polymer chips in the extruder inlet with a chip mixer or gravimetric metering, or alternatively by melting the additive polymer, metering by means of a gear pump and feeding it into the melt stream of the matrix polymer.
  • a homogeneous distribution can then be produced by mixing in the extruder and / or by means of static or dynamic mixers.
  • a specific particle distribution is set by the specific choice of mixer and the duration of the mixing process before the melt mixture is passed on through product distribution lines to the individual spinning stations and spinnerets.
  • Mixers with a shear rate of 16 to 128 sec “1 and a residence time in the mixer of at least 8 sec have proven successful.
  • the product of the shear rate (s " 1 ) and the 0.8th power of the residence time (in sec) is 250 to 2500 , preferably 300 to 600.
  • the shear rate is defined by the shear rate in the empty tube (s "1 ) times the mixer factor, the mixer factor being a characteristic parameter of the mixer type. For Sulzer SMX types, for example, this factor is about 7-8.
  • the shear rate ⁇ in the empty tube is calculated according to
  • V2 inner volume of the empty pipe (cm 3 )
  • Both the mixing of the two components and the subsequent spinning of the polymer mixture generally take place at temperatures, depending on the matrix polymer, in the range from 220 to 320 ° C.
  • the production of synthetic filaments from the matrix polymer and the elongation enhancer by rapid spinning at take-off speeds> 2500 m / min is preferably carried out using spinning devices known per se.
  • the filter package according to the known prior art is equipped with filter devices and / or loose filter media (e.g. steel sand).
  • the molten polymer mixture is pressed through the holes in the nozzle plate in the nozzle package.
  • the melt threads are cooled below their softening temperature by means of cooling air, so that sticking or upsetting on the following thread guide member is avoided.
  • the formation of the cooling zone is not critical, provided that a homogeneous air flow that evenly penetrates the filament bundle is guaranteed.
  • An air quiet zone for delaying the cooling can be provided directly below the nozzle plate.
  • the cooling air can be supplied from a climate system by transverse or radial blowing or can be removed from the surroundings by self-suction using a cooling pipe.
  • the filaments are bundled and spinning oil is applied to them.
  • oiling stones are used, to which the spinning oil is fed as an emulsion from metering pumps.
  • the prepared thread advantageously runs through an entangling device (interlacing device) to improve the thread closure.
  • Handling and safety devices can also be attached before the thread reaches the winding unit and is wound there into packages on cylindrical bobbins.
  • the peripheral speed of the thread package is regulated automatically and is equal to the winding speed.
  • the take-up speed of the thread can be 0.2-2.5% higher than the winding speed due to its traversing movement.
  • 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. Additional godets can be used to stretch or relax.
  • the incompatibility of the two polymers causes the additive polymer to form spheroidal or elongated particles in the matrix polymer immediately after the polymer mixture emerges from the spinneret.
  • the length / diameter ratio is preferably> 2. The best conditions were obtained when the mean particle size (arithmetic mean) was dso ⁇ 400 nm and the proportion of particles> 1000 nm in a sample cross section was below 1%.
  • a certain flow activation energy of preferably at least 80 kJ / mol that is, a higher flow activation energy than that of the matrix polymer, is generally required for the effectiveness of the elongation-increasing agents.
  • the additive fibrils solidify in front of the polyester matrix and absorb a significant proportion of the applied spinning tension. As a result, it is advantageously possible to achieve the desired increase in capacity of the spinning system.
  • the spun thread structure is essentially formed in the draft zone below the spinneret.
  • the length of the draft zone is varied by the thread draw-off speed.
  • Typical values for roving at conventional take-off speeds of at least 2500 m / min are at lengths of about 300 mm, preferably for POY at> 250 mm to ⁇ 700 mm.
  • the warpage zone is extended compared to conventional spinning. The sudden twisting (necking) of the filaments observed at high speeds is suppressed.
  • the change in the thread speed along the draft path takes on a value which corresponds to that of the conventional POY produced at 3200 m / min.
  • the method according to the invention is in the same way for the rapid spinning of POY threads with a POY (single) filament titer from> 3 dtex to 20 dtex and more, as well as POY filament titles ⁇ 3 dtex, particularly suitable for microfilaments with 0.2 to 2.0 dtex per filament.
  • the stretch texturing process can take place at high speeds.
  • Synthetic threads according to this invention as roving for stretch texturing - usually referred to as POY - are produced at take-off speeds> 2500 m / min, preferably> 3500 m / min, particularly preferably> 4000 m / min.
  • These yarns are said to have a physical structure that has a specific degree of orientation and low crystallization.
  • the parameters elongation at break, birefringence, degree of crystallization and cooking shrinkage have proven useful for characterizing these properties.
  • a suitable polymer mixture can e.g. B. have an elongation at break of the PET filaments (POY) of at least 85% and a maximum of 180%.
  • the boiling shrinkage is preferably 32-69%, the birefringence is usually between 0.030 and 0.075, the crystallinity is preferably less than 20% and the tensile strength is advantageously at least 17 cN / tex.
  • PET polyethylene terephthalate
  • the stretch texturing can be carried out at different speeds depending on the filament title type, with> 2 dtex per filament (final titer) and speeds> 750 m / min, preferably> 900 m / min, usually being used for normal titer filaments.
  • speeds> 750 m / min preferably> 900 m / min, usually being used for normal titer filaments.
  • speeds between 400 and 750 m / min are preferred.
  • the method can advantageously be applied to these titers and in particular microfilaments between 0.15 and 1.10 dtex (final titer) per filament.
  • the draw ratios to be used for the specified spun threads are preferably between 1.35 and 2.2, with draw ratios in the upper region and vice versa preferably being used for a lower degree of orientation.
  • the stretching ratio is influenced by fluctuations in tension (surging) as a function of the working speed. Drawing ratios according to the formula:
  • high-boiling decomposition products In addition to the outgassing of volatile decomposition products (monomers), the formation of high-boiling decomposition products is a problem in the industrial use of the expansion aids.
  • the high-boiling decomposition products can impair the yields in the spinning mill due to increased thread breaks and a deteriorated winding behavior.
  • high-boiling decomposition products can deposit on parts of the system and lead to impairments there. Such deposits can build up on the metal surfaces in the spinning system and must be removed there. Such deposits can form on the spinneret bores and contribute to thin threads and thread breaks. This affects the spinning safety and the quality of the threads.
  • the high-boiling decomposition products reduce filter service life, nozzle service life and nozzle wiping cycles and thus the yield of the spinning mill. It was therefore seen as a task to reduce the formation of high-boiling decomposition products or to avoid them altogether.
  • an elongation enhancer which is amorphous and thermoplastically processable, from radically polymerized, vinyl monomers for the production of synthetic threads from a melt-spinnable fiber-forming matrix polymer which is incompatible with the elongation enhancer and not more than 0.05% by weight.
  • the stretching agent can be thermally stabilized by adding an antioxidant substance, so that it additionally - as already described - after thermal exposure at 290 ° C. under argon for 30 minutes has a total content of not more than 6% by weight with the gas chromatography Head space method detectable Has decomposition products.
  • the presence or amount of high boiling decomposition products in the elongation enhancer can e.g. B. be determined by gas chromatography.
  • Residues from lubricant additives in the elongation enhancer which are not more than 0.05, preferably not more than 0.03, particularly preferably not more than 0.01% by weight, can be achieved by adding the addition in the manufacture of the elongation enhancer completely dispensed with lubricants or add them in concentrations not higher than 0.02% by weight.
  • Residues from secondary initiator products in the elongation enhancer which are not more than 0.06, preferably not more than 0.04,% by weight can be achieved by reducing initiators used in the manufacture of the elongation enhancer as far as possible, or almost completely, by means of additional purification steps.
  • a suitable additional purification step can e.g. B. vacuum degassing of the melt in the extruder, optionally using entraining agents, such as e.g. Water or monomer (e.g. methyl methacrylate).
  • Additional purification steps can e.g. B. the coagulation of the polymer, optionally with precipitation aids and / or additional washing steps, dewatering the polymer melt in a twin-screw extruder with degassing and dewatering zones or the like.
  • elongation enhancers to be used according to the invention additive polymers
  • additive polymers can be prepared in bulk, solution, suspension or emulsion polymerization. Helpful hints can be found with regard to substance polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Information on solution polymerization can be found there on page 1156ff.
  • the suspension polymerization technique is described there on page 1149ff, while the emulsion polymerization is described and explained there on page 1150ff.
  • Bead polymers whose particle size is in a particularly favorable range are particularly preferred in the context of the invention.
  • the additive polymers to be used according to the invention are particularly preferably in the form of particles having an average diameter of 0.1 to 1.0 mm. However, larger or smaller beads or granules can also be used.
  • the additive polymer has a residual monomer content of less than or equal to 0.45% by weight, advantageously less than or equal to 0.35% by weight, preferably less than or equal to 0.25% by weight, in each case based on the total weight of the additive polymer.
  • the residual monomer content of the additive polymer is in the range from greater than or equal to 0.05% by weight to less than or equal to 0.25% by weight, in each case based on the total weight of the additive polymer.
  • the residual monomer content in the elongation enhancer denotes the amount of monomer which remains in the additive polymer after the polymerization and polymer isolation.
  • polymers produced by radical polymerization it is usually in the range from 0.4% by weight 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 from the prior art. For example, it can be reduced by degassing the polymer melt, preferably in the extruder directly before spinning.
  • the additive polymers are obtained by a radical polymerization using several initiators with different half-lives (see, for example, DE 101 15 203 A1).
  • trickling aids to the additive polymer (see, for example, DE 102 10 018 A1).
  • the dried polymer beads are then mixed with 0.1 part by weight of a spray-dried MMA / styrene Emulsion polymers added and mixed for about 5 minutes in a fluidized bed dryer (according to detailed description in DE 10210018).
  • a mixture of 93.5 parts by weight of methyl methacrylate, 6.5 parts by weight of styrene, 0.035 parts by weight of tert-butyl peroxy-2-ethylhexanoate and 0.075 part by weight of methyl 3-mercaptopropionate is continuously used in an amount of 3385 g / h fed into a stirred reactor kept at 150 ° C. with a volume of 2.4 l. In the steady state, the reaction mixture has a polymer content of about 45.5% by weight.
  • a single-screw extruder with a screw diameter of 20 mm and a length of 25 D is used, which is operated in the temperature range from 240 - 250 ° C and at decreasing pressures from 1 to 0.01 bar (vacuum).
  • the monomer vapors are drawn off, condensed and recycled to produce the starting reaction mixture.
  • the polymer melt is extruded into round strands approximately 2 mm thick, which are passed through a water bath and, after cooling to below the softening temperature, are broken down into granules.
  • a mixture of 94.5 parts by weight of methyl methacrylate, 5.5 parts by weight of methyl acrylate, 0.03 part by weight of tert-butylperoxy-2-ethylhexanoate and 0.093 part by weight of methyl 3-mercaptopropionate is continuously used in an amount of 3390 g / h fed into a stirred reactor kept at 150 ° C. with a volume of 2.4 l. In the steady state, the reaction mixture has a polymer content of about 44% by weight.
  • reaction mixture corresponding to the feed is continuously removed and a solution of 50.75 parts by weight of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate in 650 parts by weight of this polymer syrup Methyl methacrylate metered in in an amount of 116 g / h.
  • a static mixer of the SMX type from Sulzer Chemtech
  • the mixture is heated to 180 ° C. in a heat exchanger and then fed to a degassing extruder.
  • a single-screw extruder with a screw diameter of 20 mm and a length of 25 D is used, which is operated in the temperature range from 240 - 250 ° C and at decreasing pressures from 1 to 0.01 bar (vacuum).
  • the monomer vapors are drawn off, condensed and recycled to produce the starting reaction mixture.
  • the Polymer melt is extruded into round strands approximately 2 mm thick, which are passed through a water bath and, after cooling below the softening temperature, are broken down into granules.
  • the thermal resistance is determined as follows
  • the open sample tubes are introduced into a glove box, rendered inert with argon and encapsulated in the glove box with a combination of a PTFE-clad silicone disc, spring washer and aluminum crimp cap.
  • the encapsulated sample glasses are removed from the glove box and annealed in a metal block thermostat with holes in the dimensions of the sample glasses at 290 ° C (temperature control using a calibrated thermocouple) for 10, 20 or 30 min (annealing time measured from the time of introducing the sample bottle in the metal block thermostats preheated to 290 C C).
  • the sample should stand still for about 10 minutes so that the solution can drain from the lid or septum.
  • the sample glass is then encapsulated with a fresh septum.
  • the sample glasses are placed in the autosampler of a headspace sampler and examined using the principle of static headspace technology using vapor chamber gas chromatography. The solvent DMF is flushed back using the backflush technique. Headspace settings:
  • Polyethylene glycol e.g. HP-INNOWax (manufacturer: Fa.
  • the evaluation of the monomer components formed is carried out via an external calibration.
  • the results of the tempering tests are summarized in Tables 3 and: The only information given is the methyl methacrylate (MMA) or the styrene content, the proportion of other monomers (butyl acrylate or methyl acrylate) was negligible ( ⁇ 0.08% by weight) ).
  • Comparison B Commercial copolymer of 99% by weight methyl methacrylate and 1% by weight butyl acrylate with a viscosity number of about 75 cm 3 / g
  • n. nct est mmt
  • the residual monomer content was measured using gas chromatographic headspace analysis, a method for determining evaporable components in liquids and solids (including monomers in thermoplastics).
  • the mean grain diameter of the staple fiber additive beads was determined via a sieve analysis with an Alpine air jet sieving machine (type A 200 LS).
  • the viscosity number VZ (also Staudinger function) is the concentration-related relative viscosity change of a 0.5% Solution of the copolymer in chloroform based on the solvent, whereby the throughput times were determined in an Ubbelohde viscometer with a suspended ball level, Schott type no. 53203 and capillary 0c according to DIN standard 51562 at 25 ° C. Chloroform was used as the solvent.
  • VZ (- t - 1 ⁇ • - ⁇ o c
  • c concentration in g / 100 ccm
  • PET granulate
  • Type TPE 50-5 from Karl Fischer Industrieanlagen GmbH, Berlin, under the following technological conditions:
  • the moisture was determined several times during the drying by means of a moisture meter, type Aquatrac from Brabender. The moisture content determined was 10-30 ppm.
  • Expansion aids Drying was carried out in a discontinuously operated dry air dryer
  • the determined moisture values were 50-100 ppm.
  • the melt mixture thus prepared was granulated in a water bath using a strand pelletizer.
  • a masterbatch granulate with an additive content of 10% by weight is obtained.
  • the ready-to-use compound was produced by mixing the masterbatch granulate from 4.1 Predrying the raw materials
  • the PET was dried under the same conditions as described above.
  • the masterbatch required for the compound production was crystallized and dried under the following conditions using the continuously operating Karl Fischer drying system: Dry air temperature: 105 ° C dew point dry air: ⁇ -40 ° C residence time in the dryer: 8 h moisture content: ⁇ 50ppm test procedure
  • test was carried out using a co-rotating ZSK40 twin-screw extruder from the Cooperi Werner & Pfleiderer company in accordance with the following processing conditions (Table 6).
  • the melt mixture thus prepared was granulated in a water bath using a strand pelletizer.
  • a ready-to-use polyethylene terephthalate additive compound with 0.42% by weight additive content is obtained in granular form. 5.
  • Polyester chips (commercially available polyethylene terephthalate granules, intrinsic viscosity IV 0.67 dl / g, approx. 0.3% by weight TiO 2 ), which by means of
  • Vacuum tumble dryer according to the following program
  • Polyester chips dosed into the extruder feed are Polyester chips dosed into the extruder feed.
  • the spinneret package contained, in
  • Capillary bores with 0.25 mm and a capillary length of 0.50 mm.
  • the mean residence time of the polymer melt from the exit from the extruder to the exit from the spinneret plate was approximately 7.5 min.
  • the melt threads emerging from the nozzle plate were in one perforated tube cooled by self-sucked ambient air. At a distance of 1800 mm from the nozzle plate, the cooled threads were bundled using a slit-shaped preparation stone and with an emulsion of 92% water and 8% spin preparation (e.g. Lurol PT L220 from Goulston Technologies, INC. Monroe / USA) with a preparation pad of 0.35%.
  • spin preparation e.g. Lurol PT L220 from Goulston Technologies, INC. Monroe / USA
  • the filament sheet was then swirled with an air nozzle (Heberlein PolyJet SP ECO 25-E-H132 / CN) at an air pressure of 2.5 bar and in a winding unit from Barmag AG, Remscheid / DE, type CW8, with a winding speed of 4500 m / min at a thread tension of 25 to 27 g with a titer of approx. 145 dtex.
  • an air nozzle Heberlein PolyJet SP ECO 25-E-H132 / CN
  • Example 17 (comparison), a strong tendency to form unwanted tension threads (strippers) was observed.
  • the methyl methacrylate content in the wound-up POY thread would be about 30 to 40% less in all trials than in the undrawn vault, since methyl methacrylate still evaporates from the thread during the cooling process.
  • the methyl methacrylate content is also significantly reduced in the finished thread compared to the comparative example.
  • the undesirable methyl methacrylate emission is reduced overall. This effect is all the more important in large-scale plants in which the melt mixture has to travel much longer.
  • the masterbatch described in point 4.1 (premix of 10% additive according to synthesis example 6 and 90% PET), which had previously been dried for 6 hours in a tumble dryer at 160 ° C., was gravimetrically at a concentration of 6.0 % By weight (based on the total amount of polymer) metered into the polyester chips in the feed of the extruder.
  • an MMA content of less than 10 ppm in the masterbatch was determined, i. H. there has been a very effective depletion of the initial MMA content under the drying conditions described. Apparently there was no degradation of the additive. If drying were carried out below the glass point of the additive polymer, i.e. below approx.
  • the polymer throughput per spin pack was 59 g / min and the
  • Example 19 the additive according to Example 6 was added as a solid in a concentration of 0.42% by weight.
  • Example 20 the additive according to Example 6, which was already contained in the modified polyethylene terephthalate chips in a concentration of 0.42% by weight, was used under otherwise identical conditions, so that no addition step was necessary. In comparison to Example 19, the further increased coefficient of friction of the threads was remarkable.
  • the use of Modified polyethylene terephthalate chips according to the invention enable the use of the additive spinning process even in conventional extruder spinning mills which do not have additive-specific mixing and metering units.
  • the intrinsic viscosity was determined on a solution of 0.2 g PET and 40 ml mixture of 1, 2-dichlorobenzene: phenol (1: 1 parts) at 25 ° C.
  • MMA contents in mixtures of PET and expansion aids were determined by gas chromatography using headspace GC after extraction (approx. 3 g sample, 3 days at room temperature in 20 ml dimethylformamide).
  • thermally stabilized expansion aids form deposits to a lesser extent, especially if they were made without the addition of lubricants (stearic and palmitic acid).
  • the polymer was dissolved in dichloromethane, which contained myristic acid as an internal standard in a known amount, and precipitated with n-hexane. After filtration, the dissolving and precipitation process was repeated on the filtration residue in order to largely exclude the inclusion of analytes in the precipitated polymer.
  • the filtered polymer was washed out several times with a little n-hexane.
  • the precipitation filtrate was on Rotary evaporator evaporated to dryness and taken up with a defined amount of dichloromethane.

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Abstract

L'invention concerne un agent augmentant la dilatation qui est amorphe et transformable par voie thermoplastique et est composé de monomères vinyliques radicalement polymérisés destinés à la production de fils synthétiques à partir d'une matrice polymérique formant des fibres et filable à chaud, incompatible avec l'agent augmentation la dilatation. L'invention est caractérisée en ce que l'agent augmentant la dilatation peut être thermiquement stabilisé par l'addition d'une substance antioxydante de telle façon qu'il ait, après avoir été soumis à une contrainte thermique de 290 °C en présence d'argon pendant 30 minutes, une teneur totale en monomères de maximum 6 % en poids. L'invention concerne également des granulés de plastique, contenant l'agent augmentant la dilatation et son procédé de production. L'invention concerne également un procédé de production de fils synthétiques selon un procédé de filature à chaud à partir d'un mélange constitué d'une matrice polymérique formant de fibres et filable à chaud et d'un agent augmentant la dilatation et l'utilisation ultérieure des fils synthétiques.
EP04725925A 2003-04-30 2004-04-06 Agent augmentant la dilatation destine a la production de fils synthetiques a partir de matrices polymeriques formant des fibres et filables a chaud Withdrawn EP1631706A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10319761A DE10319761A1 (de) 2003-04-30 2003-04-30 Dehnungserhöhungsmittel für die Herstellung von synthetischen Fäden aus schmelzspinnbaren faserbildenden Matrix-Polymeren
PCT/EP2004/003645 WO2004097083A1 (fr) 2003-04-30 2004-04-06 Agent augmentant la dilatation destine a la production de fils synthetiques a partir de matrices polymeriques formant des fibres et filables a chaud

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CN (1) CN1780942A (fr)
BR (1) BRPI0409858A (fr)
DE (1) DE10319761A1 (fr)
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EP2025494A1 (fr) * 2007-08-10 2009-02-18 Motech GmbH Technology & Systems Procédé et dispositif de fabrication d'une bande d'emballage
DE102008040152A1 (de) 2008-07-03 2010-01-07 Evonik Röhm Gmbh Rheologiemodifier
KR101062422B1 (ko) 2009-06-30 2011-09-06 코오롱글로텍주식회사 높은 연신성에 의한 고강도 폴리프로필렌 단섬유 및 이의 제조방법, 이로 만들어진 부직포
US9982940B2 (en) 2012-08-09 2018-05-29 Patheon Austria Gmbh & Co Kg Process for drying polymeric materials
US10000637B2 (en) * 2013-06-06 2018-06-19 Basf Se Composition and process for making fine denier polyamide fiber
CN104569248A (zh) * 2014-12-08 2015-04-29 江苏泰洁检测技术有限公司 一种工作场所丙烯酸酯类中丙烯酸甲酯浓度测定方法
WO2021035122A1 (fr) * 2019-08-22 2021-02-25 Penn Color, Inc. Fibre délustrée
WO2021262977A1 (fr) * 2020-06-26 2021-12-30 Jabil Inc. Articles obtenus par fusion-soufflage améliorés et leur procédés de formation
CN113186654B (zh) * 2021-04-26 2023-05-02 杭州科百特科技有限公司 一种聚酯熔喷无纺布及其制备方法

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US4661571A (en) * 1984-10-02 1987-04-28 Sumitomo Chemical Company, Limited Process for the production of heat resistant methacrylic resin
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DE19937729A1 (de) * 1999-08-10 2001-02-15 Lurgi Zimmer Ag Hochfeste Polyesterfäden und Verfahren zu deren Herstellung
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US6667003B2 (en) * 2000-05-25 2003-12-23 Zimmer A.G. Method for the manufacture of synthetic fibers from a melt mixture based on fiber forming polymers
JP3661600B2 (ja) * 2000-07-27 2005-06-15 住友化学株式会社 メタクリル酸メチル系樹脂組成物およびその成形体
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KR20060008944A (ko) 2006-01-27
US20070149697A1 (en) 2007-06-28
DE10319761A1 (de) 2004-11-18
BRPI0409858A (pt) 2006-05-16
TW200508435A (en) 2005-03-01
WO2004097083A1 (fr) 2004-11-11
CN1780942A (zh) 2006-05-31
JP2006524756A (ja) 2006-11-02

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