EP1287192A1 - Verfahren zur herstellung von synthetischen fäden aus einer auf faserbildenden polymeren basierenden schmelze-mischung - Google Patents
Verfahren zur herstellung von synthetischen fäden aus einer auf faserbildenden polymeren basierenden schmelze-mischungInfo
- Publication number
- EP1287192A1 EP1287192A1 EP01936385A EP01936385A EP1287192A1 EP 1287192 A1 EP1287192 A1 EP 1287192A1 EP 01936385 A EP01936385 A EP 01936385A EP 01936385 A EP01936385 A EP 01936385A EP 1287192 A1 EP1287192 A1 EP 1287192A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- polymer
- additive
- fiber
- forming matrix
- 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.)
- Granted
Links
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/06—Feeding liquid to the spinning head
- D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
Definitions
- the present invention relates to a method for producing synthetic threads from a mixture based on fiber-forming polymers.
- the threads can be used on the one hand as continuous threads or can be further processed into staple fibers.
- 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 higher productivity of the spinning unit.
- the producer or process provider must take the entire production chain into account and cannot stop at increasing the production of a sub-step (e.g. the spinning mill).
- the subsequent processes must not be impaired.
- Polymer blends called very high elongations at break, also for high spinning speeds, which markedly reduce the degree of orientation. It is known that such spun threads are not stable in storage and cannot be applied and processed in stretch texturing processes at high speeds. Elongation at break ⁇ 70% given at high spinning speeds in turn indicate a considerable degree of crystallization, which reduces the achievable strengths in the texturing process.
- EP 0 047464 B relates to an undrawn polyester yarn, the addition of 0.2-10% by weight of a polymer of the type - ( ⁇ CH 2 - CR 1 R 2 -) n -, such as poly (4-methyl- l-pentene) or polymethyl methacrylate, 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 by mixing is necessary, and 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 additive consumption and associated impairment of quality and processability.
- 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 at 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.
- the polyester at least 0.05% by weight of copolymer is added and the maximum amount M of the copolymer added to the polyester depends on the withdrawal speed v and is
- the elongation-increasing agents used are usually granulated before they are metered into the polyester in order to increase the flowability of the additive polymer.
- the granulated additive polymer can also be dosed only relatively poorly and unevenly.
- Uniformity of the synthetic threads e.g. dyeing behavior.
- the application requires processes for melt spinning polymer mixtures which enable the use of non-granulated elongation-increasing agents.
- the elongation-increasing means should be able to be metered in uniformly and continuously.
- 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 which can be carried out on an industrial scale and at low cost.
- 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 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.
- Due to the high uniformity of the synthetic thread obtainable by the process it is possible in a simple manner to set a good bobbin structure, which enables the synthetic thread to be dyed and processed evenly and almost without errors.
- 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 successful 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 then melted.
- synthetic threads refer to all types of threads which can be obtained by spinning thermoplastically processable mixtures of synthetic polymers. They include 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, smooth 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). In a particularly preferred embodiment of the present invention, the matrix Polymer polyethylene terephthalate, polytrimethylene terephthalate or polybutylene terephthalate, in particular polyethylene terephthalate.
- PET polyethylene terephthalate
- PTMT polyethylene naphthalate
- PBT polybutylene terephthalate
- the matrix Polymer polyethylene terephthalate, polytrimethylene terephthalate or polybutylene terephthalate, in particular polyethylene terephthalate.
- Homopolymers are preferred according to the invention.
- copolymers preferably polyester copolymers, 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.
- conventional comonomers such as, for. 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 which are customary for thermoplastic molding compositions and which contribute to improving the polymer properties.
- additives include: antistatic agents, antioxidants, flame retardants, lubricants, dyes, light stabilizers, polymerization catalysts and assistants, adhesion promoters, matting agents and / or organic phosphites.
- additives are used in the usual amount, preferably in amounts of up to 10% by weight, preferably ⁇ 1% by weight, based on 100% by weight of the polymer mixture.
- a polyester may also contain a small proportion (maximum 0.5% by weight) of branching components, 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 must Glass transition temperature (determined by DSC with 10 ° C / min heating rate) of more than 100 ° C and can be 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. That is, 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.
- a ratio of the melt viscosities between 1.7: 1 and 6.5: 1 is particularly preferred Under these conditions, the average particle size of the additive polymer is 140-350 nm.
- the amount of the additive polymer to be added to the matrix polymer is between 0.05% by weight and 5% by weight, based on the total weight of the polymer mixture. For many applications, for example for the production of POYs, addition quantities 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 100 22 889, the disclosure of which is hereby explicitly incorporated by reference.
- the polymer mixture is spun at temperatures, depending on the matrix polymer, in the range from 220 to 320 ° C.
- additive polymers to be added to the fiber-forming polymer in the context of the invention can have a different chemical composition.
- Additive polymers which are particularly suitable according to the invention include the polymers and / or copolymers mentioned below:
- R 'and R z are substituents consisting of the optional atoms C, H, O, S, P and halogen atoms and the sum of the
- R 1 and R 2 Molecular weight of R 1 and R 2 is at least 40.
- Cycloalkyl radical or a C 6 . 14 aryl radical, B styrene or C 1-4 alkyl-substituted styrenes,
- R 3 , R 4 and R 5 are each an H atom or a .js alkyl radical or a C 6 . 14 aryl radical or a C 5 .
- R 3 , R 4 and R 5 are each an H atom or a .js alkyl radical or a C 6 . 14 aryl radical or a C 5 .
- 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 .-%.
- F styrene or C ⁇ _ 3 -alkyl-substituted styrenes
- R 3 , R 4 and R 5 are each an H atom or a C ⁇ . 15 alkyl radical or a C 5 . 12 -cycloalkyl radical or a C 6 . 14 aryl radical,
- 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,
- G and 0 to 50% by weight H preferably composed of 45 to 97% by weight E, 0 to 30% by weight F, 3 to 40% by weight G and 0 to 30% by weight % H and particularly preferably from 60 to 94% by weight E, 0 to 20% by weight F, 6 to 30% by weight G and 0 to 20% by weight of H, the sum of E, F, G and H totaling 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. therefore be used to modify the properties of the copolymer as desired, for example by increasing or improving the flow properties when the copolymer is heated to the melting temperature, or to reduce a residual color in the
- Copolymer or by using a polyfunctional monomer to introduce some degree of crosslinking into the copolymer in this way.
- 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,
- 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 methylstyrene.
- Aromatic vinyl monomers such as styrene or ⁇ -methylstyrene are particularly preferred among the compounds of component H.
- the preparation of the additive polymers to be used according to the invention is known per se. They can be prepared in bulk, solution, suspension or emulsion polymerization. Helpful hints can be found with regard to substance polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Hints for 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 by, for example, 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.
- copolymers according to the invention are commercially available or can be prepared by a process familiar to the person skilled in the art.
- additive polymers with viscosity numbers in the range from 70 to 130 cm 3 / g are preferred for polymers of type 1, 2, 3 or 4.
- an additive polymer is added, which can be obtained by multiple initiation.
- multiple initiation encompasses both one or more subsequent initiations of a radical polymerization, ie one or more additions of initiator at later reaction times, and also radical polymerization in the presence of a mixture comprising at least two initiators with graded half-lives
- graduated half-life means that the at least two initiators each have different half-lives or have the same half-life at a specific temperature, but in different temperature ranges used, each of which has a half-life of one hour in temperature ranges which are at least 10 ° C.
- a single compound can be used as the initiator in each of the 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 Tj 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 Range 85 to 100 ° C having.
- Further initiators I-_ which can optionally be used, preferably have decomposition temperatures T n between Tj 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 are used for the 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. These include in particular azo compounds such as 2,2'-azobisisobutyionitrile and 2,2'-azobis (2,4-dimethylvaleronitrile). Initiator mixtures whose components are selected from the following initiators have proven particularly useful:
- Dibenzoyl peroxide T (1 hour) 91 ° C, tert.
- Amylperoxy-2-ethylhexanoate T (1 hour) 91 ° C, tert.
- Butyl ⁇ eroxy-2-ethylhexanoate T (1 hour) 92 ° C, tert.
- Butyl peroxy isobutyrate T (1 hour) 96 ° C.
- Peroxidic initiators are very particularly preferred according to the invention.
- 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 less than 85 ° C.
- a second step the polymerization is continued at a higher temperature, preferably at a temperature between 85 and 120 ° C.
- the additive polymer 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 additive polymer 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.
- Residual monomer content of the additive polymer 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 additive polymer.
- the residual monomer content in the additive polymer denotes the amount of monomer that remains in the additive 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, by degassing the polymer melt, preferably in
- Extruder can be lowered just before spinning.
- polymerization parameters it is also possible to obtain polymers with a reduced residual monomer content.
- pouring aids refer to all auxiliaries which are added in small amounts to powdered or granulated, in particular hygroscopic substances, in order to clump them or To prevent 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:
- Atoms are C, H, O, S, P and halogen atoms and the sum of the
- Molecular weight of R 1 and R 2 is at least 40.
- R is an H atom or a CH 3 group and R' is a C ⁇ s alkyl radical or a C 5 . 12 - (I ⁇ Cloalkylrest or a C 6 " 14 aryl residue, as well as styrene and C ⁇ - alkyl-substituted styrenes.
- B styrene or C 1-4 alkyl-substituted styrenes
- R 3 , R 4 and R 5 are each an H atom or a Cns alkyl radical or a C 6 . ⁇ 4 aryl radical or a C 5 .
- R 3 , R 4 and R 5 are each an H atom or a Cns alkyl radical or a C 6 . ⁇ 4 aryl radical or a C 5 .
- R ' is a C L ⁇ alkyl radical or a C 5 _
- G one or more monomers of formula II, Irish or TV
- R 3 are each an H atom or a C j .i s alkyl radical or a C. 5 12 cycloalkyl or a C 6 . 14 aryl radical,
- 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, acyl nitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, halogen-substituted styrenes, vinyl ethers, isopropenyl ether and dienes,
- the copolymer consists of 30 to 99% by weight E, 0 to 50% by weight F, 0 to 50% by weight G and 0 to 50% by weight H, preferably 45 to 97% by weight 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 u. a. can be used to modify the properties of the copolymer as desired, 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 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 MSA and MMA, which do not copolymerize per se, but copolymerize easily 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 rank 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 ⁇ -methylstiyrene.
- Aromatic vinyl monomers such as styrene or ⁇ -methylstyrene are particularly preferred among the compounds of component H.
- pouring aids are preferred according to the invention, the particle size of which is in a particularly favorable range. They are particularly preferably in the form of particles with an average diameter of 0.01 to less than 100 microns. However, pouring aids with larger or smaller particle sizes can also be used.
- the imidized types 3 and 4 of copolymers can be prepared from the monomers using a monomeric imide or by subsequent complete or, preferably, partial imidization of the corresponding one
- Copolymer containing maleic acid derivative 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.
- ammonia or a primary alkyl or arylamine for example aniline (Encyclopedia of Polymer Science and Engineering Vol. 16 [1989], Wiley-Verlag, page 78)
- pouring aids have proven particularly useful which have a largely identical chemical composition to the additive polymer used.
- the flow 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 have the same repeat units.
- the repeating units characterize the repeating units in the polymer which are derived from the monomers originally used.
- results which are particularly advantageous according to the invention can be achieved if the pouring aid and the additive polymer 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 the additive polymer used, which have the same repeating units.
- the polymer composition of the pouring aid and that of the additive polymer used are completely identical in terms of the repeating units.
- Use flow aid that 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 additive polymer 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, based in each case 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.
- concentration of the flow aid required for the flow-promoting effect increases. If the pouring aid concentration is too low, the flow-promoting effect is incomplete, while if the pouring aid concentration is too high, no further improvement in the flow behavior is achieved, but instead a strong, technically undesirable dust formation occurs due to the excess, finely divided pouring aid powder.
- the trickle aid is expediently by a
- Emulsion polymerization process prepared 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 elongation-increasing agent to be used according to the invention is not granulated.
- granulating refers to the production of so-called pellets (granules) of the same type
- the polymer to be granulated is usually melted in a single or twin screw extrader and fed to a pelletizing machine.
- the crushing can be carried out both by cold pelletization and by hot pelletization.
- Cold pelletizing is done through the granulating nozzle Strands, strips or thin foils are produced, which are solidified after solidification using 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 game) and WO 99 / 07 927 (POYs).
- the disclosure content of these writings is therefore explicitly referred to. Since the method according to the invention for the production of POYs has proven to be particularly useful, a particularly preferred embodiment of the method according to the invention for the production of POYs is described below. The transfer of the teaching according to the invention to processes for producing other synthetic threads is immediately obvious to the person skilled in the art.
- 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 melted 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 thickening occurs the following thread guide is avoided.
- the formation of the cooling zone is not critical, provided that a homogeneous air flow that penetrates the filament bundle is guaranteed.
- An air quiet zone can be provided directly below the nozzle plate to delay cooling.
- the cooling air can be supplied from a climate system by transverse or radial blowing or can be removed from the environment by self-suction using a cooling pipe.
- the filaments are bundled and spinning oil is applied to them.
- oil stones are used, to which the spinning oil is fed as an emulsion from metering pumps.
- the prepared thread advantageously runs through a
- Entangling device to improve the thread closure.
- Handling and safety devices can also be attached before the thread arrives at 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 pulling-off 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 compatibility of the two polymers has the effect that the additive polymer immediately after the polymer mixture has emerged 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 running. The best conditions were found when the average particle diameter (arithmetic mean) d 50 ⁇ 400 nm, and the proportion of particles> 1000 nm in a sample cross-section was less than 1%.
- Flow activation energy of the copolymers of at least 80 kJ / mol, ie a higher flow activation energy than that of the polymer matrix is advantageous. Under this condition, it is possible for the additive fibrils to solidify in front of the polyester matrix and to absorb a significant proportion of the applied spinning tension. The desired increase in capacity of the spinning system can thus be achieved in a simple manner.
- 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 filament titer of> 3 dtex to 20 dtex and more, as well as POY filament titles ⁇ 3 dtex, in particular microfilaments with 0, Suitable from 2 to 2.0 dtex.
- the thread break rate is significantly reduced compared to the methods known from the prior art due to the additive polymer added, which can be obtained by multiple initiation.
- the thread breakage 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 breaks 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 pocketing texturing process at high speeds: spinning threads according to this invention as roving for the stretch texturing - usually as
- POY - are preferably at take-off speeds> 2500 m / min, preferably> 3500 m / min, particularly preferably> 4000 m / min. These games must have a physical structure that is characterized by a specific degree of orientation and low crystallization. The parameters of elongation at break, birefringence, degree of crystallization and boiling point 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%.
- the boiling point is 32-69%
- the birefringence is between 0.030 and 0.075
- the crystallinity is less than 20%
- the tensile strength is 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. It can also with the
- 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
- the hiding conditions to be used for the specified spun threads are between 1.35 and 2.2, with preference being given for a lower degree of orientation
- Stretching ratios in the upper area and vice versa are caused by fluctuations in tension (Surging) depending on the working speed. Stretching ratios according to the formula are therefore particularly preferred:
- the residual monomer content of methyl methacrylate and styrene was measured using gas chromatographic headspace analysis, a method for determining evaporable components in liquids and solids (including monomers in thermoplastics).
- the residual monomer content of N-cyclohexylmaleimide was determined by gas chromatography on a solution of the polymer in dichloromethane.
- the mean grain diameter of the spray-dried trickle aid was determined by laser diffraction spectroscopy with a Mastersizer Microplus from Malvem (measuring range: 0.05 - 555 ⁇ m).
- the mean grain diameter of the staple fiber additive beads was determined via a sieve analysis with an Alpme air steel sieve machine (type A 200 LS).
- the intrinsic viscosity was determined on a solution of 0.5 g polyester in 100 ml of a mixture of phenol and 1,2-dichlorobenzene (3: 2 parts by weight) at 25 ° C.
- 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 in the Ubbelohde viscometer with hanging ball level, Schott type no. 53203 and capillary 0c according to DIN -Norm 51562 were averaged at 25 ° C. Chlorofoim was used as the solvent.
- VZ - 1 to) c
- the melting temperature determined in this way corresponds to the typical processing or spinning temperature of the respective polymer.
- the amount of sample was chosen so that the rheometer gap was completely filled.
- the measurement was carried out in oscillation with the frequency 2.4 Hz (corresponding to a cut-off rate of 15 sec "1 ) and a deformation amplitude of 0.3, and the amount of the complex viscosity was determined as a function of the measuring time.
- the initial viscosity was then determined by linear regression converted to zero measurement time.
- the polymer sample was first melted at 310 ° C. for 1 min and immediately quenched to room temperature. The melting temperature was then determined by DSC measurement (differential scanning calorimetry) at a heating rate of 10 ° C./min. Pretreatment and measurement were carried out under nitrogen blanketing.
- the titer was averaged in a known manner with a precision weight and a weighing device.
- the pretension was expediently 0.05 cN / dtex for pre-oriented filaments (POYs) and 0.2 cN / dtex for textured yarn (DTY).
- the tensile strength and the elongation at break were determined in a Statimat measuring device under the following conditions; the clamping length was 200 mm for POY or 500 mm for DTY, the measuring speed was 2000 mm / min for POY or 1500 mm / min for DTY, the pretension was 0.05 cN / dtex for POY or 0.2 cN / dtex for DTY.
- the tensile strength was determined by dividing the values for the maximum tear load by the titer and the elongation at break was evaluated at maximum load. Comparative example
- Polyethylene terephthalate chips with a water content of less than 35 ppm, an intrinsic viscosity of 0.64 dl / g and a melt viscosity (at 290 ° C.) of 250 Pas were passed into the feed of an extruder.
- a downpipe was arranged perpendicular to the direction of conveyance of the extruder screw and centrally to the extruder feed, through which the additive dried to a residual moisture of ⁇ 0.1% by weight was metered into the polyester chips using a gravimetric metering system in the feed area above the extruder screw.
- a bead polymer based on MMA / StyiOl / N-cyclohexylmaleimide prepared in suspension was used as an additive. This was a partial polymer composed of 89.2% by weight of methyl methacrylate, 8.8% by weight of styrene and 2% by weight of N-cyclohexylmaleimide, the terpolymer having a viscosity number VZ of approximately 101 cm 3 / g and a Melt viscosity (at 290 ° C) of about 1400 Pas.
- the MMA / StyiOl / N-cyclohexylmaleimide additive with VZ 101 cmVg was obtained as follows:
- a mixture of 525 kg of completely deionized water, 0.071 kg of KHSO 4 and 13 kg of a 13% aqueous solution of a polyacrylic acid was heated to 40 ° C. in a 1000 l polymerization vessel with a heating / cooling jacket equipped with a stirrer, reflux condenser and thermometer.
- the dried polymer beads are then mixed with 0.1 part by weight of a spray-dried MMA / styrene emulsion polymer and mixed in the fluidized bed dryer for about 5 minutes.
- the MMA / styrene emulsion polymer which acts as an antistatic agent or flow aid, was obtained as follows:
- the polymer dispersion obtained was then spray-dried in a spray tower from Niro, equipped with an atomizing disc rotating at 15,000 rpm.
- the air supplied had a temperature of 180 to 190 ° C; the emerging air had a temperature of 75 to 80 ° C.
- the VZ of the spray-dried MMA / styrene copolymer was 97 cm 3 / g.
- the spray-dried MMA / styrene copolymer, as already described above, was mixed in a concentration of 0.1% by weight with the MMA / styrene / N-cyclohexylmaleimide in a fluidized bed dryer at room temperature for 5 minutes.
- the additive was added in a concentration of 0.77% by weight, based on the total amount of the polymer mixture of polyester and additive, which was removed by the spinning system fed by the extruder.
- the total amount of polymer mixture removed was defined by the number of spinning pumps operated in the spinning system described below and by the throughput of the respective spinning pump. When all the spinning pumps were in operation, a total of 304.5 kg / h of polymer mixture was removed from the spinning system and the additive was gravimetrically metered into the extruder feed at a rate of 2.34 kg / h.
- the wave movement of the extruder screw premixed the additive beads with the polyester chips.
- the polyester chips and the additive beads were melted and mixed together in the extruder, an LTM-24D / E8 spinning extruder from Baimag AG, Remscheidt / DE.
- This first polymer mixture was discharged at a temperature of 290 ° C. with a pressure of 180 bar, conveyed through the melt line as a melt flow of 304.5 kg / h and subjected to filtration with a 20 ⁇ m filter candle.
- the filtered first polymer mixture was fed to a static mixer of the SMX type from Sulzer AG with an inner diameter of 52.5 mm and a length of 525 mm, where it was homogenized and dispersed to form a second polymer mixture.
- This second polymer mixture was distributed via product line to twelve spinning positions, each containing six spin packs, the average residence time of the second polymer mixture from the exit from the static mixer to the entry into the spin pack being five minutes.
- Each spin pack contained a round die with 34 holes 0.25 mm in diameter and twice the length of the die.
- the spin pack contained a spin filter pack above the nozzle plate, consisting of a steel sand pack 30 mm high and a grain size of 0.5 to 0.85 mm, as well as a mesh fabric of 40 ⁇ m and a steel fleece filter of 20 ⁇ m pore diameter.
- the diameter of the spin filter package was 85 mm.
- the residence time of the melt in the filter pack was approximately 1.5 minutes.
- the heating of the spin pack was set to 290 ° C.
- the surface of the spinneret was 30 mm above the boundary of the heating box.
- a nozzle pressure of 150 bar was established during the throughput of the melt mixture.
- the average residence time of the polymer mixture of polyester and additive melt from the extruder exit to the exit from the spin packs was about ten minutes.
- the molten filaments extraded from the nozzle holes were cooled by blowing air flowing horizontally to the thread run at a speed of 0.55 m / s and a temperature of 18 ° C and bundled at a distance of 1250 mm from the nozzle plate in an oiling stone to the thread and with spin preparation coated.
- the breakage rate during the operation of the spinning system averaged 0.75 breaks per ton of polymer mixture.
- the POYs obtained were stretch-textured with a texturing machine of type FK6 from Barmag AG / Germany at a speed of 900 min.
- the draw ratio was selected as 1.77 and the heater temperatures 1 and 2 as 210 and 170 ° C.
- the textured yarn had a denier of 74 den, a tensile strength of 4.5 g / den, an elongation at break of 18.3% and was characterized by a good dyeing uniformity.
- the spinning system described in the comparative example was used again with the same throughputs and spinning conditions.
- an additive consisting of 89.2% by weight of methyl methacrylate, 8.8% by weight of styrene and 2% by weight of N-cyclohexylmaleimide was also used, the terpolymer having a viscosity number VZ of about 101 cm 3 / g had.
- an MMA / styrene / N-cyclohexylmaleimide additive was used, which was obtained by multiple initiation as follows:
- the polymer beads were filtered off, washed thoroughly with demineralized water and dried in a fluidized bed dryer at 80.degree.
- the dried polymer beads were then mixed with 0.1 part by weight of a spray-dried MMA / styrene emulsion polymer, the synthesis of which is described above in the comparative example, and mixed for about five minutes in a fluidized bed dryer.
- the additive from the example according to the invention thus had a comparable pearl size and treatment with MMA / styrene emulsion polymer in a fluidized bed. Dryer has a significantly lower residual monomer content compared to the additive from the comparative example.
- the additive was added in an amount of 0.77% by weight, based on the total amount of the polymer mixture fed to the spinning system, and the polymer mixture was spun analogously to the comparative example.
- POY threads were again produced during a production period of seven days, characterized by a titer of 126 den, an elongation at break of 117% and a tensile strength of 2.4 g / den.
- the broke rate during operation of the spinning system averaged 0.35 breaks per ton of polymer mixture passed through.
- the POYs were stretch-textured analogously to the comparative example at a speed of ⁇ 900 m / min.
- the breakage rate averaged 18 breaks per ton of textured yarn.
- the textured yarn has the same titer and tear strength as the textured yarn from the comparative example and an elongation at break of 18.6% with the same good dyeing uniformity.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Paper (AREA)
Description
Claims
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10022889A DE10022889B4 (de) | 2000-05-25 | 2000-05-25 | Verfahren zum Herstellen von synthetischen Fäden aus einer Polymermischung auf Polyesterbasis |
DE10022889 | 2000-05-25 | ||
DE10115203 | 2001-03-27 | ||
DE2001115203 DE10115203A1 (de) | 2001-03-27 | 2001-03-27 | Verfahren zur Herstellung von synthetischen Fäden aus einer auf faserbildenden Polymeren basierenden Schmelze-Mischung |
PCT/EP2001/005851 WO2001090454A1 (de) | 2000-05-25 | 2001-05-22 | Verfahren zur herstellung von synthetischen fäden aus einer auf faserbildenden polymeren basierenden schmelze-mischung |
Publications (2)
Publication Number | Publication Date |
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EP1287192A1 true EP1287192A1 (de) | 2003-03-05 |
EP1287192B1 EP1287192B1 (de) | 2006-01-25 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01936385A Expired - Lifetime EP1287192B1 (de) | 2000-05-25 | 2001-05-22 | Verfahren zur herstellung von synthetischen fäden aus einer auf faserbildenden polymeren basierenden schmelze-mischung |
Country Status (15)
Country | Link |
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US (2) | US6667003B2 (de) |
EP (1) | EP1287192B1 (de) |
JP (1) | JP2003534464A (de) |
KR (1) | KR20030011845A (de) |
CN (1) | CN1226474C (de) |
AT (1) | ATE316590T1 (de) |
AU (2) | AU2001262309B2 (de) |
BR (1) | BR0111003A (de) |
CA (1) | CA2407438A1 (de) |
DE (1) | DE50108799D1 (de) |
HK (1) | HK1053676A1 (de) |
MX (1) | MXPA02009470A (de) |
PL (1) | PL358970A1 (de) |
TW (1) | TW548356B (de) |
WO (1) | WO2001090454A1 (de) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
KR100601304B1 (ko) * | 2000-10-16 | 2006-07-13 | 주식회사 코오롱 | 제사성 및 염색성이 우수한 폴리에스테르 섬유 |
DE10063286A1 (de) * | 2000-12-19 | 2002-06-20 | Zimmer Ag | Verfahren zum Spinnen und Aufspulen von PET-Filamenten |
US6923925B2 (en) * | 2002-06-27 | 2005-08-02 | E. I. Du Pont De Nemours And Company | Process of making poly (trimethylene dicarboxylate) fibers |
US6921803B2 (en) * | 2002-07-11 | 2005-07-26 | E.I. Du Pont De Nemours And Company | Poly(trimethylene terephthalate) fibers, their manufacture and use |
US6967057B2 (en) * | 2002-12-19 | 2005-11-22 | E.I. Du Pont De Nemours And Company | Poly(trimethylene dicarboxylate) fibers, their manufacture and use |
DE10319761A1 (de) * | 2003-04-30 | 2004-11-18 | Röhm GmbH & Co. KG | Dehnungserhöhungsmittel für die Herstellung von synthetischen Fäden aus schmelzspinnbaren faserbildenden Matrix-Polymeren |
DE102004038531A1 (de) * | 2003-08-19 | 2005-03-17 | Kuraray Specialities Europe Gmbh | Polyvinylacetal-haltiges Granulat, Verfahren zu seiner Herstellung sowie seine Verwendung |
US20050147784A1 (en) * | 2004-01-06 | 2005-07-07 | Chang Jing C. | Process for preparing poly(trimethylene terephthalate) fiber |
FR2919878A1 (fr) * | 2007-08-08 | 2009-02-13 | Rhodia Poliamida E Especialidades Ltda | Procede de filage pour la production de fils synthetiques a filaments continus |
DE102016102494A1 (de) | 2016-02-12 | 2017-08-17 | Poromembrane Gmbh | Filamentherstellvorrichtung |
KR102183241B1 (ko) * | 2019-03-29 | 2020-11-26 | 주식회사 휴비스 | 제사성이 우수한 재생 폴리에스테르 섬유 및 이의 제조방법 |
CN111139563A (zh) * | 2019-12-24 | 2020-05-12 | 常州欣战江特种纤维有限公司 | 一种室内家居装饰用异收缩有色aty纤维的生产方法 |
CN111719189A (zh) * | 2020-06-23 | 2020-09-29 | 陈志祥 | 一种极细旦单板环吹5d或7d的poy纺丝线设备 |
CN114351268B (zh) * | 2022-01-06 | 2023-02-28 | 浙江昊能科技有限公司 | 一种阻燃抗熔滴涤锦复合纤维的制备方法 |
CN115627554B (zh) * | 2022-09-28 | 2024-04-05 | 清华大学 | 制备酰亚胺共聚物的纤维的方法和由其制备的纤维 |
CN115652474A (zh) * | 2022-09-28 | 2023-01-31 | 清华大学 | 由酰胺酸共聚物制备酰亚胺共聚物的纤维的方法和由其制备的纤维 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1172789A (en) * | 1980-09-25 | 1984-08-14 | Hideo Kasahara | POLYMERIC MATERIAL COMPRISING A POLYAMIDE BONDED TO A COPOLYMER CONTAINING AN IMIDE OF AN .alpha.,.beta. UNSATURATED CARBOXYLIC ACID |
US4328329A (en) * | 1980-12-11 | 1982-05-04 | E. I. Du Pont De Nemours And Company | Process for polymerizing methyl methacrylate syrup using a dual initiator system |
US5166238A (en) * | 1986-09-22 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
SK1202000A3 (en) * | 1997-08-05 | 2000-10-09 | Degussa | Process for shaping polymer mixtures into filaments |
DE19917987A1 (de) * | 1999-04-21 | 2000-10-26 | Roehm Gmbh | Verfahren zur Herstellung von blockförmigen Polymethacrylimidschaumstoffen |
DE19937727A1 (de) * | 1999-08-10 | 2001-02-15 | Lurgi Zimmer Ag | Polyester-Stapelfasern und Verfahren zu deren Herstellung |
DE19937729A1 (de) * | 1999-08-10 | 2001-02-15 | Lurgi Zimmer Ag | Hochfeste Polyesterfäden und Verfahren zu deren Herstellung |
DE19937728A1 (de) * | 1999-08-10 | 2001-02-15 | Lurgi Zimmer Ag | HMLS-Fäden aus Polyester und Spinnstreckverfahren zu deren Herstellung |
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 |
DE10022889B4 (de) * | 2000-05-25 | 2007-12-20 | Lurgi Zimmer Gmbh | Verfahren zum Herstellen von synthetischen Fäden aus einer Polymermischung auf Polyesterbasis |
-
2001
- 2001-05-10 US US09/852,515 patent/US6667003B2/en not_active Expired - Fee Related
- 2001-05-22 AU AU2001262309A patent/AU2001262309B2/en not_active Ceased
- 2001-05-22 CN CNB018100465A patent/CN1226474C/zh not_active Expired - Fee Related
- 2001-05-22 MX MXPA02009470A patent/MXPA02009470A/es not_active Application Discontinuation
- 2001-05-22 AT AT01936385T patent/ATE316590T1/de not_active IP Right Cessation
- 2001-05-22 BR BR0111003-9A patent/BR0111003A/pt not_active IP Right Cessation
- 2001-05-22 AU AU6230901A patent/AU6230901A/xx active Pending
- 2001-05-22 KR KR1020027015330A patent/KR20030011845A/ko active IP Right Grant
- 2001-05-22 WO PCT/EP2001/005851 patent/WO2001090454A1/de active IP Right Grant
- 2001-05-22 PL PL01358970A patent/PL358970A1/xx not_active Application Discontinuation
- 2001-05-22 CA CA002407438A patent/CA2407438A1/en not_active Abandoned
- 2001-05-22 EP EP01936385A patent/EP1287192B1/de not_active Expired - Lifetime
- 2001-05-22 DE DE50108799T patent/DE50108799D1/de not_active Expired - Fee Related
- 2001-05-22 JP JP2001586646A patent/JP2003534464A/ja active Pending
- 2001-05-24 TW TW090111870A patent/TW548356B/zh not_active IP Right Cessation
-
2003
- 2003-08-21 HK HK03105988A patent/HK1053676A1/xx not_active IP Right Cessation
- 2003-11-10 US US10/704,862 patent/US20040096655A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
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See references of WO0190454A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR20030011845A (ko) | 2003-02-11 |
CN1430685A (zh) | 2003-07-16 |
TW548356B (en) | 2003-08-21 |
PL358970A1 (en) | 2004-08-23 |
US6667003B2 (en) | 2003-12-23 |
JP2003534464A (ja) | 2003-11-18 |
US20020017735A1 (en) | 2002-02-14 |
DE50108799D1 (de) | 2006-04-13 |
AU6230901A (en) | 2001-12-03 |
ATE316590T1 (de) | 2006-02-15 |
AU2001262309B2 (en) | 2004-11-04 |
CA2407438A1 (en) | 2002-10-23 |
WO2001090454A1 (de) | 2001-11-29 |
MXPA02009470A (es) | 2004-05-14 |
BR0111003A (pt) | 2003-04-15 |
CN1226474C (zh) | 2005-11-09 |
US20040096655A1 (en) | 2004-05-20 |
EP1287192B1 (de) | 2006-01-25 |
HK1053676A1 (en) | 2003-10-31 |
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