EP2449155A1 - Fibres de polyamide à particules pouvant être colorées et procédé de fabrication associé - Google Patents

Fibres de polyamide à particules pouvant être colorées et procédé de fabrication associé

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Publication number
EP2449155A1
EP2449155A1 EP10727413A EP10727413A EP2449155A1 EP 2449155 A1 EP2449155 A1 EP 2449155A1 EP 10727413 A EP10727413 A EP 10727413A EP 10727413 A EP10727413 A EP 10727413A EP 2449155 A1 EP2449155 A1 EP 2449155A1
Authority
EP
European Patent Office
Prior art keywords
acid
particles
weight
polyamide
polyamides
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Withdrawn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
EP10727413A
Other languages
German (de)
English (en)
Inventor
Stefan Schwiegk
Christof Kujat
Axel Wilms
Alexander Traut
Norbert Wagner
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP10727413A priority Critical patent/EP2449155A1/fr
Publication of EP2449155A1 publication Critical patent/EP2449155A1/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Withdrawn legal-status Critical Current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
    • D01F6/58—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
    • 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
    • D01F1/06—Dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2503/00—Domestic or personal
    • D10B2503/04—Floor or wall coverings; Carpets

Definitions

  • the present invention relates to novel polyamide fibers with dyeable particles and to processes for their preparation.
  • the concentration of amino groups is for later staining of the polyamide, e.g. in fiber application, of crucial importance (McGregor, Textile Chemist and Colorist 9, 98, (1977), Peters, J. of the Society of Dyers and Colourists 61, 95 (1945), Nylon Fiber: A Study of the Mechanism of the Dyeing Process with Acid Dyes).
  • the stability of the melt with respect to constancy of the amino end group concentration also depends essentially on the concentration and type of end groups (Matthies, Kunststoff-Handbuch, Volume 3/4: Polyamides, Section 2.2.1).
  • amide-forming chain regulators and preferably carboxylic acids or amines are usually added together with the monomeric feedstocks in the polycondensation, with reacting to the end groups of the chains, usually to amides, so that the end groups are bound so that they are available neither for condensation nor for later staining.
  • This approach has the disadvantage that the staining property and the condensation ability of the polymer are coupled to each other and can not be optimized independently.
  • the new polyamide fibers with dyeable particles contain 80 to 99.95% by weight of polyamide, 0.05 to 20% by weight of dyeable particles and 0 to 19.95% by weight of additives, the sum of the percentages by weight being 100% results.
  • Suitable polyamides A generally have a viscosity number VZ of 50 to 300, preferably 100 to 200 and particularly preferably 120-160 ml / g, determined in accordance with ISO 307 EN on a 0.5% strength by weight solution of the polyamide in 96 wt .-% sulfuric acid at 25 ° C.
  • suitable polyamides having aliphatic partially crystalline or partially aromatic and amorphous structure of any kind and their blends including polyether amides such as polyether block amides.
  • Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000 are preferred.
  • polyamides which are derived from lactams with 7 to 13 ring members such as polycaprolactam, polycapryllactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines.
  • dicarboxylic acids alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used.
  • Suitable diamines are, in particular, alkanediamines having 6 to 12, in particular 6 to 8, carbon atoms and also m-xylylenediamine, di (4-aminophenyl) methane, di (4-aminocyclohexyl) methane, di (4-amono-3 methylcyclohexyl) methane, isophoronediamine, 1,5-diamino-2-methylpentane, 2,2-di- (4-aminophenyl) -propane or 2,2-di (4-aminocyclohexyl) propane.
  • Preferred polyamides are polyhexamethylene adipamide (PA 66) and polyhexamethylene sebacamide (PA 610), polycaprolactam (PA 6) and polylaurolactam (PA 12). Also preferred are copolyamides PA 6/66, in particular with a proportion of 5 to 95 wt .-% of caprolactam units, and copolyamides PA 6/12, in particular with 5 to 95 wt .-% Laurinlactam units. PA 6, PA 66 and Copolyamide 6/66 are particularly preferred; PA 6 is most preferred.
  • polyamides are obtainable from ⁇ -aminoalkyl nitriles such as amino capronitrile (PA 6) and adiponitrile with hexamethylene diamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and EP-A 922065 described.
  • PA 6 amino capronitrile
  • PA 66 adiponitrile with hexamethylene diamine
  • polyamide 46 Also contemplated are polyamides, e.g. are obtainable by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide 46). Manufacturing processes for polyamides of this structure are known e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
  • polyamides which are obtainable by copolymerization of two or more of the aforementioned monomers, or mixtures of several polyamides are suitable, wherein the mixing ratio is arbitrary.
  • partially aromatic copolyamides as PA 6 / 6T and PA 66 / 6T have proven to be particularly advantageous, the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).
  • the preparation of partially aromatic copolyamides with a low triamine content can be carried out according to the methods described in EP-A 129 195 and 129 196.
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid
  • PA 610 hexamethylenediamine, sebacic acid
  • PA 612 hexamethylenediamine, decanedicarboxylic acid
  • PA 613 hexamethylenediamine, undecanedicarboxylic acid
  • PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid
  • PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid
  • PA 6T hexamethylenediamine, terephthalic acid
  • PA 61 hexamethylenediamine, isophthalic acid
  • PA 6-3-T trimethylhexamethylenediamine, terephthalic acid
  • PA 6 / 6T (see PA 6 and PA 6T)
  • PA 6/66 (see PA 6 and PA 66)
  • PA 6/12 see PA 6 and PA 12
  • PA 66/6/610 see PA 66, PA 6 and PA 610)
  • PA 6I / 6T see PA 6I and PA 6T
  • PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
  • PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane
  • PA PDA-T phenylenediamine, terephthalic acid
  • polyamides A and their preparation are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 19, pp. 39-54, Verlag Chemie, Weinheim 1980; Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21, pp. 179-206, VCH Verlag, Weinheim 1992; Stoeckhert, Kunststofflexikon, 8th edition, pp. 425-428, Carl Hanser Verlag Kunststoff 1992 (keyword “polyamides” and following), and Saechtling, plastic paperback, 27th edition, Carl Hanser-Verlag Ober1998, pages 465-478.
  • the polyamides are prepared in the usual way by hydrolytic or activated, anionic polymerization of the monomers in discontinuous or continuous apparatuses, e.g. Autoclaves or VK pipes, manufactured.
  • the residual content of monomers and / or oligomers may optionally be obtained by vacuum distillation of the polyamide melt or by extraction of the granules recovered from the polyamide melt, e.g. with hot water, to be removed.
  • the hydrolytic polymerization in an autoclave or one to three-stage VK tubes with subsequent extraction of the residual monomers with water in the range 95 to 130 0 C and drying in the shaft dryer with ISb or tumble dryer under vacuum are known to those skilled in the art and described in their principles in the relevant literature, eg. In the mentioned Ullmanns Encyclopedia or in Kirk-Othmer, Ecyclopedia of Chemical Technology, John Wiley and Sons, New York 2004.
  • the polyamide granules in the solid state at temperatures of 1 to 100 0 C, preferably 5 to 50 ° C, below the melting point of the polyamide, the relative viscosity can be raised to the desired final value.
  • the polyamide can be dried before processing to form the molding composition of the invention to a residual moisture of, for example, 0.001 to 0.2 wt .-%.
  • the novel dyeable particles contain one or more inorganic oxides having an average particle size (particle diameter) of 0.1 to 900 nm, preferably 1 to 500 nm, particularly preferably 3 to 250 nm, in particular 5 to 100 nm and adhering to the particles, chemically bonded substances which impart special properties to the particle and the polymer containing the particle, for example piperidine derivatives, to control the dyeability of the polymer and to stabilize the polymer against degradation by UV light or thermal oxidation.
  • particle diameter particle size of 0.1 to 900 nm, preferably 1 to 500 nm, particularly preferably 3 to 250 nm, in particular 5 to 100 nm and adhering to the particles, chemically bonded substances which impart special properties to the particle and the polymer containing the particle, for example piperidine derivatives, to control the dyeability of the polymer and to stabilize the polymer against degradation by UV light or thermal oxidation.
  • Suitable inorganic oxides are SiO 2 , ZnO, Al 2 O 3 , AlOOH, TiO 2 , ZrO 2 , CeO 2 , Fe 2 O 3 , Fe 3 O 4 , In 2 O 3 , SnO 2 , MgO, preferably SiO 2 , ZnO, Al 2 O 3 , TiO 2 , ZrO 2 , particularly preferably SiO 2 .
  • mixed oxides such as BaTiO 3 or any mixed oxides of the abovementioned metal oxides in any desired composition can also be used.
  • core-shell particles such as SiO 2 / ZnO or SiO 2 / TiO 2 is also possible.
  • Suitable additives for functionalizing the particle surface are all compounds which give the particle and / or the polymer a special functionality (dyeability, UV protection, stabilization against heat / air exposure, flame retardancy, etc.) and those via a reactive group can be chemically attached to the surface.
  • Particularly suitable for attachment to the surface are those reactive groups which can react with the OH groups on the surfaces of the inorganic oxides, e.g. Alkoxy silanes, silanols, silyl halides, carboxylic acids, phosphates, phosphonates, amines, etc. preferably alkoxy silanes, phosphates and phosphonates particularly preferably alkoxy silanes.
  • the hindered piperidine derivative is preferably an aminopolyalkylpiperidine.
  • exemplary hindered piperidine derivatives include:
  • the hindered piperidine derivative is 4-amino-2,2 ', 6,6'-tetramethylpiperidine or 4-amino-1, 2,2', 6,6'-pentamethylpiperidine.
  • the dyeable particles can be combined with conventional chain regulators in polymer manufacture (e.g., with mono- and di-carboxylic acids such as acetic acid, propionic acid or adipic acid, and mono- and dialkylamines such as hexamethylenediamine and benzylamine).
  • chain regulators e.g., with mono- and di-carboxylic acids such as acetic acid, propionic acid or adipic acid, and mono- and dialkylamines such as hexamethylenediamine and benzylamine).
  • the polymerization can be carried out according to the conventional conditions for the polyamide polycondensation (see above), from the corresponding monomers and by mixing the functionalized particle into the monomer or into the polymerizing reaction mixture.
  • the polymerization or polycondensation of the starting monomers in the presence of the compound (I) is preferably carried out by the usual methods.
  • the polymerization of caprolactam in the presence of a compound (I) for example, according to the in DE-A 14 95 198, DE-A 25 58 480, DE-A 44 13 177, Polymerization Process, Interscience, New York, 1977, P. 424-467 and Handbook of Technical Polymer Chemistry, VCH Verlagsgesellschaft, Weinheim, 1993, pp. 546-554, both of which are continuous or batch processes.
  • AH salt in the presence of a compound (I) can be prepared by the usual batch process (see: Polymerization Processes, Interscience, New York, 1977, pp. 424-467, especially 444-446) or by a continuous process, e.g. according to EP-A 129 196, carried out.
  • compound (I) and starting monomers can be separated or fed as a mixture to the reactor.
  • the compound (I) is added according to a predetermined amount / time program.
  • the compound (I) is combined with at least one of the conventional chain regulators.
  • Suitable chain regulators are, for example, aliphatic and aromatic monocarboxylic acids such as acetic acid, propionic acid and benzoic acid, aliphatic and aromatic dicarboxylic acids such as C 4 -C 10 -alkanedicarboxylic acids, preferably sebacic acid and dodecanedioic acid, in particular adipic acid and azelaic acid, aliphatic C 1 -C 8 -cycloalkanedicarboxylic acids, in particular cyclohexane 1,4-dicarboxylic acid, aromatic dicarboxylic acids such as benzene and naphthalenedicarboxylic acids, preferably isophthalic acid, 2,6-naphthalenedicarboxylic acid, in particular terephthalic acid, monofunctional amines and difunctional amines, preferably hexamethylenediamine or cycl
  • the chain regulator combination and the amounts used are selected, inter alia, according to the desired polymer properties, such as viscosity or end group content.
  • the chain regulators are preferably used in an amount of from 0.06 to 0.6 mol%, preferably 0.1 to 0.5 mol%, each based on 1 mol of acid amide group of the polyamide, a.
  • the polymerization or polycondensation is carried out by the process according to the invention in the presence of at least one pigment.
  • Preferred pigments are titanium dioxide, wherein titanium dioxide is preferably in the anatase modification, or coloring compounds of inorganic or organic nature.
  • the pigments are preferably added in an amount of 0 to 5 parts by weight, in particular 0.02 to 2 parts by weight, in each case based on 100 parts by weight of polyamide.
  • the pigments may be fed to the reactor with the starting materials or separately therefrom.
  • the properties of the polymer are significantly improved over a polymer which contains only pigment and no compound (I) or only pigment and one of the 2,2,6,6 mentioned above - contains tetramethylpiperidine derivatives.
  • the polyamides of the invention can be advantageously used for the production of threads, fibers, films, fabrics and moldings. Threads which are obtained from polyamides, in particular polycaprolactam, by rapid spinning at take-off speeds of at least 4000 m / min are particularly advantageous.
  • the threads, fibers, films, sheets and moldings obtained using the polyamides according to the invention can be used in many ways, for example as textile clothing or carpet fibers. Examples of PA polymerization with functionalized particles
  • the particle-monomer mixtures were mixed with additional CPL and adjusted to the target concentration of particle-bound TAD and amino end groups (AEG).
  • the target concentration of particle-bound TAD was in most cases 15-20 mmol / kg-PA (corresponding to approximately 1.5% to 2% SiO 2 particle content); in some cases, higher concentrations of about 30 and 60 mmol / kg were set (corresponding to about 3% and 6% SiO 2 particle content).
  • the isopropanol contained was distilled off, added water for the CPL ring opening and the polymerization at 15 bar pressure, 260 0 C melt temperature and 2h melt residence time.
  • the autoclave has about 2I internal volume.
  • three open-topped jars of about 100 ml each are placed in each run containing the reaction mixtures (50 g each per sample).
  • the nanoparticles are uniformly distributed and do not form agglomerates.
  • PA6 with about 17 mmol / kg PA6 TAD (as described under a., but in addition with
  • PA6 with about 15 mmol / kg-PA6 particle-bound TAD (batch as in a., but in addition with 15 mmol / kg TAD, which is bound to SiC "2 particles)
  • the boiler is a 10-liter pressure-resistant double-shell metal boiler with built-in stirrer and heater and a bottom drain valve. Before using the samples in the stirred tank, the starting materials were mixed heated to about 55 ° C and thereby gave a clear, homogeneous solution.
  • the functionalized nanoparticles are uniformly distributed and do not form an agglomerate rate.
  • the same nanoparticles without functionalization in the polymer form numerous, large agglomerates (agglomerate size: about 100-300 nm).
  • the dried granules (water content ⁇ 0.06%) were spun into fibers on a conventional spinning plant.
  • the polymer granules were introduced into the heatable cylinder of the spinning plant and heated to about 230-240 0 C. With a piston, the melt was then pressed through a spinneret (7-hole Spinneret, nozzle capillary diameter 0.25 mm).
  • the melted filaments were cooled by blowing with blown air, wet by passing through a preparation thread guide with liquid spin finish and then passed through unheated godets (one monogalette and two duo godets) and finally wound up. Due to different relative speeds of the godets, the thread was stretched with a hiding ratio of 1: 2.5.
  • the conditions are summarized in the following table.
  • the samples with the functionalized particles could easily be processed into threads.
  • the physical base yarn properties of the two materials were approximately equal for the two materials.
  • the fibers with particles show no abnormalities compared to standard PA fibers in mechanical properties.
  • a significantly greater staining depth is obtained with the particle-additized fibers than with the comparative product prepared with an equivalent amount of TAD, but here the TAD was not bound to particles before the polycondensation but with the polycondensation mixture as free TAD had been added to the starting materials.
  • the nanoparticles are evenly distributed in the fibers and do not form agglomerates.
  • PA polymerization in 1 liter stirred tank
  • the nanoparticles are evenly distributed in the fibers and do not form agglomerates.
  • the process according to the invention can be carried out as follows:
  • the new dyeable particles to the monomer and at a temperature of 10 to 200 ° C., preferably from 20 to 180 ° C., more preferably from 25 to 100 ° C. and a pressure of from 0.01 to 10 bar, preferably from 0 , 1 to 5 bar, more preferably from 1 to 1, 5 bar polymerize in the presence of catalysts.
  • a 4-aminopiperidine derivative can be obtained with a surface-active compound (eg alkoxy-silanes, silanols, carboxylic acids, phosphates, phosphonates) which additionally contains an electrophilic group (eg isocyanate, epoxide, halide, electron-poor double bond, etc.). ) has at a temperature of 0 to 300 ° C, preferably from 10 to 160 ° C, more preferably from 15 to 80 ° C and a pressure of 0.2 to 100 bar, preferably from 0.7 to 5 bar, more preferably from 0.9 to 1, 1 bar implement.
  • a surface-active compound eg alkoxy-silanes, silanols, carboxylic acids, phosphates, phosphonates
  • an electrophilic group eg isocyanate, epoxide, halide, electron-poor double bond, etc.
  • the reaction can be carried out in the presence of a solvent A.
  • the amount of solvent can be varied within wide limits and is generally 0.1: 1 to 1000: 1, preferably 0.5: 1 to 100: 1, especially 1: 1 to 50: 1 based on the 4-aminopiperidine derivative.
  • the reaction can be carried out essentially in the absence of a solvent, ie at 0.09: 1 to 0.0001: 1, preferably 0.05: 1 to 0.001: 1, based on the 4-aminopiperidine derivative or in the absence of a solvent.
  • the 4-aminopiperidine derivative is not a solvent for the purposes of this invention.
  • solvents A are ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-chloro-2-propanol, cyclopentanol, cyclohexanol, 1, 4- Dioxane, tetrahydrofuran, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-ethoxyethanol, 2-methyl-2-propanol, 2-methoxyethanol, dimethylformamide, acetonitrile, acetone, methyl ethyl ketone, dichloromethane, chloroform, dimethyl sulfoxide, Toluene, xylene, nitrobenzene, chlorobenzene, pyridine, diethyl ether, tert-butyl methyl ether, hexane, heptane, petroleum ether, cyclohexane, N-methyl-2-pyrrolidon
  • the resulting product and / or other surface-active compounds can with one or more oxides at a temperature of 0 to 300 0 C, preferably from 10 to 160 0 C, particularly preferably from 20 to 85 ° C and a pressure of 0.2 to 100 bar, preferably from 0.7 to 5 bar, more preferably from 0.9 to 1, 1 bar are reacted.
  • aqueous metal oxide dispersions are used, more preferably aqueous silica dispersions.
  • the content of silica, calculated as SiO 2 is from 10 to 60% by weight, preferably from 20 to 55, particularly preferably from 25 to 40% by weight. It is also possible to use silica sols with a lower content, but the excess water content must then be removed by distillation in a later step.
  • the resulting acidified solution may be mixed with 0 to 10 times, preferably 0.2 to ⁇ times, more preferably 0.4 to 3 times, and most preferably 0.5 to 2 times the amount of water ( based on the amount of silica sol used) and 0.1 to 20 times, preferably 0.3 to 10 times, more preferably 0.5 to ⁇ fachen and most preferably 1 to 3 times the amount (based on the amount of used silica sol) is added to at least one organic solvent B.
  • a preferred embodiment is to add no additional water.
  • the organic solvent is selected according to the following criteria: Under the mixing conditions, it should have both sufficient miscibility with water and miscibility with the caprolactam.
  • the miscibility with water under the reaction conditions should be at least 20% by weight (based on the final water-solvent mixture), preferably at least at least 50 wt .-% and particularly preferably at least 80 wt .-% amount. If miscibility is too low, there is a risk that the modified silica sol forms a gel or flocculates larger nanoparticle aggregates. Furthermore, the solvent B should have a boiling point of less than 80 0 C in a pressure range of atmospheric pressure to 50 hPa, so it is easily separable by distillation.
  • the solvent B forms an azeotrope or heteroazeotrope with water under the conditions of the distillation, so that the distillate forms an aqueous and an organic phase after the distillation.
  • solvents B are ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-chloro-2-propanol, cyclopentanol, cyclohexanol, 1, 4- Dioxane, tetrahydrofuran, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-ethoxyethanol, 2-methyl-2-propanol, 2-methoxyethanol, dimethylformamide, acetonitrile and acetone.
  • the sol is concentrated by distillation until the residual water content is less than 30%, preferably less than 20%, particularly preferably less than 10%.
  • the distillation of water and the organic solvent B is carried out under normal or reduced pressure, preferably at 10 hPa to normal pressure, particularly preferably at 20 hPa to normal pressure, very particularly preferably at 50 hPa to normal pressure and in particular at 100 hPa to normal pressure ,
  • the temperature at which the distillation takes place depends on the boiling point of water and / or organic solvent B at the respective pressure.
  • the resulting sol is subsequently diluted with caprolactam and solvent B.
  • a sol with a higher residual water content can also be used so that the previous distillation can be dispensed with.
  • water and solvent B are distilled off to the extent that the content of functionalized silica particles is from 0.1 to 80% by weight, preferably from 1 to 60 and particularly preferably from 5 to 50% by weight.
  • the residual content of water in the finished product should be less than 10 wt .-%, preferably less than 5, more preferably less than 2, most preferably less than 1, in particular less than 0.5 and especially less than 0.3 wt. -% be.
  • the residual content of solvent (L) in the finished product should be less than 40 wt .-%, preferably less than 20, more preferably less than 10, most preferably less than 3, especially less than 2 and especially less than 1 wt. -%.
  • polyamide fibers with dyeable particles according to the invention can be dyed or dyed by means of methods known per se with dyes or mixtures thereof. Examples
  • the particle size was determined using the Zetasizer Nano S device from Malvern. Since the particle size was determined by DLS (dynamic light scattering) and reflects the hydrodynamic radius, the actual particle size is below the measured values.

Abstract

L’invention concerne de nouvelles fibres de polyamide à particules pouvant être colorées et contenant de 80 à 99,95 % en poids de polyamide, de 0,05 à 20 % en poids de particules pouvant être colorées et de 0 à 19,95 % en poids d’additifs, la somme des pourcentages en poids étant de 100 %.
EP10727413A 2009-06-30 2010-06-24 Fibres de polyamide à particules pouvant être colorées et procédé de fabrication associé Withdrawn EP2449155A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10727413A EP2449155A1 (fr) 2009-06-30 2010-06-24 Fibres de polyamide à particules pouvant être colorées et procédé de fabrication associé

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09164087 2009-06-30
PCT/EP2010/058993 WO2011000772A1 (fr) 2009-06-30 2010-06-24 Fibres de polyamide à particules pouvant être colorées et procédé de fabrication associé
EP10727413A EP2449155A1 (fr) 2009-06-30 2010-06-24 Fibres de polyamide à particules pouvant être colorées et procédé de fabrication associé

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KR20120048576A (ko) 2012-05-15
CN102471938B (zh) 2014-08-13
US9080259B2 (en) 2015-07-14
US20120108710A1 (en) 2012-05-03
JP5800807B2 (ja) 2015-10-28
CN102471938A (zh) 2012-05-23
JP2012531537A (ja) 2012-12-10
KR101723700B1 (ko) 2017-04-18
WO2011000772A1 (fr) 2011-01-06

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