EP2449155A1

EP2449155A1 - Polyamide fibers comprising stainable particles and method for the production thereof

Info

Publication number: EP2449155A1
Application number: EP10727413A
Authority: EP
Inventors: Stefan Schwiegk; Christof Kujat; Axel Wilms; Alexander Traut; Norbert Wagner
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2009-06-30
Filing date: 2010-06-24
Publication date: 2012-05-09
Also published as: WO2011000772A1; JP5800807B2; CN102471938B; US20120108710A1; CN102471938A; KR20120048576A; US9080259B2; JP2012531537A; KR101723700B1

Abstract

The novel polyamide fibers comprising stainable particles contain 80 to 99.95% by weight polyamide, 0.05 to 20% by weight stainable particles, and 0 to 19.95% by weight additives, wherein the sum of the weight percentages is 100%.

Description

Description: The present invention relates to novel polyamide fibers with dyeable particles and to processes for their preparation.

The production of fiber polyamide by polycondensation of amide-forming monomers is known in principle (Matthies, Kunststoff-Handbuch, Volume 3/4: Polyamides, Section 2.2.1). The concentrations of the end groups (amino end groups, carboxylene groups) have significant effects on the properties of a polymer.

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).

Furthermore, the average molecular weight achievable in the polycondensation and the stability of the melt during the processing in terms of average molecular weight are strongly dependent on the concentration and type of end groups (Matthies, Kunststoff-Handbuch, Volume 3/4: Polyamides, Section 2.2.1 ).

To control the end group concentrations are usually used amide-forming chain regulators and preferably carboxylic acids or amines (Matthies, Kunststoff- Handbuch, Volume 3/4: polyamides, Section 2.2.1), which 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.

It is an object of the present invention to adjust the properties of dyeing and condensation independently, ie to develop new and improved polyamide fibers and processes for their preparation. Accordingly, new polyamide fibers with dyeable particles and processes for their preparation have been found.

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.

For example, 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, e.g. in US Pat. Nos. 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 are preferred. Examples of these are 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. As dicarboxylic acids alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used. Adipic acid, azelaic acid, sebacic acid, dodecanedioic acid (= decanedicarboxylic acid) and terephthalic and / or isophthalic acid may be mentioned as acids here. 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. Further suitable polyamides are obtainable from ω-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.

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.

Also, 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. Furthermore, such 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.

The following non-exhaustive list contains the mentioned, as well as other polyamides A according to the invention and the monomers contained:

AB-polymers:

PA 6 ε-caprolactam

PA 7 ethanolactam

PA 8 capryllactam

PA 9 9-aminopelargonic acid

PA 1 1 1 1 -aminoundecanoic acid

PA 12 laurolactam

AA / BB-polymers:

PA 46 tetramethylenediamine, adipic acid

PA 66 hexamethylenediamine, adipic acid

PA 69 hexamethylenediamine, azelaic 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 MXD6 m-xylylenediamine, adipic 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 PACM 12 diaminodicyclohexylmethane, laurolactam

PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane

PA 12 / MACMI laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid

PA 12 / MACMT laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid

PA PDA-T phenylenediamine, terephthalic acid

These 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 Munich 1992 (keyword "polyamides" and following), and Saechtling, plastic paperback, 27th edition, Carl Hanser-Verlag München1998, pages 465-478. Preferably, 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.

Preferably, 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. The common methods 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. By postcondensation of 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. If necessary, 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.

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 .

Furthermore, mixed oxides such as BaTiO ₃ or any mixed oxides of the abovementioned metal oxides in any desired composition can also be used. The use of 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.

More simple silanes could be:

from the halide

(3-bromopropyl) trimethoxysilane)

from the epoxy

e.g. (3-glycidoxypropyl) tιϊmethoxysilan

from the acrylate, or methacrylate

e.g. Methacryloxypropyl tris (methoxy) silane

R = Me, Et, .... sterically hindered aminosilanes (commercial):

(RO) -Si ^' ^• _NO . R '= -Me, -Et, -EtOH Furthermore, the surface modification of the particles with 2 or more different reagents is possible. The above-mentioned silanes can be combined in any desired mixing ratios or used in combination with one or more other silanes.

The hindered piperidine derivative is preferably an aminopolyalkylpiperidine. Exemplary hindered piperidine derivatives include:

4-amino-2,2 ', 6,6'-tetramethylpiperidine;

4- (aminoalkyl) -2,2 ', 6,6'-tetramethylpiperidine;

4- (aminoaryl) -2,2 ', 6,6'-tetramethylpiperidine;

4- (aminoaryl / alkyl) -2,2 ', 6,6'-tetramethylpiperidine;

3-amino-2,2 ', 6,6'-tetramethylpiperidine;

3- (aminoalkyl) -2,2 ', 6,6'-tetramethylpiperidine;

3- (aminoaryl) -2,2 ', 6,6'-tetramethylpiperidine;

3- (aminoaryl / alkyl) -2,2 ', 6,6'-tetramethylpiperidine;

2,2 ', 6,6'-tetramethyl-4-piperidinecarboxylic acid;

2,2 ', 6,6'-tetramethyl-4-piperidine alkylcarboxylic acid;

2,2 ', 6,6'-tetramethyl-4-piperidinearylcarboxylic acid;

2,2 ', 6,6'-tetramethyl-4-piperidine alkyl / arylcarboxylic acid;

2,2 ', 6,6'-tetramethyl-3-piperidinecarboxylic acid;

2,2 ', 6,6'-tetramethyl-3-piperidine alkylcarboxylic acid;

2,2 ', 6,6'-tetramethyl-3-piperidinearylcarboxylic acid;

2,2 ', 6,6'-tetramethyl-3-piperidine alkyl / arylcarboxylic acid;

4-amino-1, 2,2 ', 6,6'-pentamethylpiperidines;

4- (aminoalkyl) -1,2,2 ', 6,6'-pentamethylpiperidines;

4- (aminoaryl) -1,2,2 ', 6,6'-pentamethylpiperidines;

4- (aminoaryl / alkyl) -1, 2,2 ', 6,6'-pentamethylpiperidines;

3-amino-1, 2,2 ', 6,6'-pentamethylpiperidines;

3- (aminoalkyl) -1,2,2 ', 6,6'-pentamethylpiperidines;

3- (aminoaryl) -1,2,2 ', 6,6'-pentamethylpiperidines;

3- (aminoaryl / alkyl) -1,2,2 ', 6,6'-pentamethylpiperidines;

1, 2,2 ', 6,6'-pentamethyl-4-piperidinecarboxylic acid;

1, 2,2 ', 6,6'-pentamethyl-4-piperidine alkylcarboxylic acid;

1, 2,2 ', 6,6'-pentamethyl-4-piperidinearylcarboxylic acid;

1, 2,2 ', 6,6'-pentamethyl-4-piperidine alkyl / arylcarboxylic acid;

1, 2,2 ', 6,6'-pentamethyl-3-piperidinecarboxylic acid;

1, 2,2 ', 6,6'-pentamethyl-3-piperidine alkylcarboxylic acid;

1, 2,2 ', 6,6'-pentamethyl-3-piperidinearylcarboxylic acid; and

1, 2,2 ', 6,6'-pentamethyl-3-piperidine alkyl / arylcarboxylic acid. Most preferred, 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).

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. Thus, 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. The polymerization of

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. In principle, compound (I) and starting monomers can be separated or fed as a mixture to the reactor. Preferably, the compound (I) is added according to a predetermined amount / time program.

In a preferred embodiment of the invention, 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 cyclohexyldiamine, and mixtures of such acids and mixtures of such amines. In this case, 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. If dicarboxylic acids are used as chain regulators, 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.

In another preferred embodiment, 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. By using a compound (I) (also as a chain regulator component), 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). Subsequently, 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 polymerization series and the characterization of the polymers obtained are described in detail below.

PA polymerization in an unstirred autoclave Preparation of the polymers

3 mixtures in an autoclave run polymerized together (3 glass adjustment containers) a.) 50 g CPL + 10 g H ₂ O.

b.) 50 g CPL + 10 g H ₂ O + particles for 15 mmol TAD (quantity see table) c.) 50 g CPL + 10 g H ₂ O + particles for 30 mmol TAD (amount see table) Samples in the autoclave, the starting materials were mixed heated to about 55 ° C, giving a clear, homogeneous solution.

The autoclave has about 2I internal volume. In the autoclave, three open-topped jars of about 100 ml each are placed in each run containing the reaction mixtures (50 g each per sample).

After nitrogen purging and closing the autoclave, this is heated to 280 ⁰ C outside temperature (about 270 ⁰ C internal temperature). After reaching about 0.5 bar internal pressure, the reactor was briefly depressurized to remove the isopropanol contained. After further heating for about 1 h at 270 ⁰ C internal temperature, a pressure of about 14 bar. This pressure and the temperature were kept constant for 1 h. Then the pressure is reduced to ambient pressure over 1 h (at a further 270 ° internal temperature). Subsequently, it is postcondensed over 1, 5h at 20l / h nitrogen flow stream without pressure. Then another 3 bar of nitrogen is pressed in and the heating is switched off so that the boiler cools down to ambient temperature (about 20 ° C) for about 5 hours. The polymer samples are removed and the polymer is ground to coarse grains.

Basic chemical data

( ^* 2) Mixture No. 341 18/36 Result:

The addition of particles greatly increases the number of amino end groups.

According to microscopic examination of thin sections of the polymerization products, the nanoparticles are uniformly distributed and do not form agglomerates.

PA polymerization in 10 liter stirred tank

4 batches were successively polymerized in the stirred tank under approximately identical conditions. a.) unregulated standard PA6 (4000 g CPL + 400 g H ₂ O)

b.) PA6 with about 17 mmol / kg PA6 TAD (as described under a., but in addition with

17 mmol / kg TAD)

c.) 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) d.) PA6 with the same particles Amount as in c), but without functionalization of the 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.

After filling the starting materials into the vessel, it was purged several times with nitrogen, then sealed and heated to 280 ^° C. outside temperature (approx.

270 ^° C internal temperature) (after reaching about 0.5 bar internal pressure, the reactor was briefly depressurized, to remove the isopropanol contained) (at 280 ⁰ C then sets a pressure of about 14 bar). The reaction is continued at about 270 ^° C. internal temperature and about 14 bar pressure. Then the pressure over about 1 h to ambient pressure is relaxed at a further approximately 270 ⁰ C internal temperature. Subsequently, 70-80 min (see table) at 20l / h nitrogen flow flushing depressurized nachkondensiert. Finally, by applying an overpressure nitrogen, the polymer is expelled from the reactor in the form of a strand and granulated and dried. Granular data

Result: Due to the particle additive the number of amino end groups is greatly increased.

According to microscopic examination of thin sections of the polymerization products, the functionalized nanoparticles are uniformly distributed and do not form an agglomerate rate. In contrast, the same nanoparticles without functionalization in the polymer form numerous, large agglomerates (agglomerate size: about 100-300 nm).

Example fiber spinning

The dried granules (water content <0.06%) were spun into fibers on a conventional spinning plant. For this purpose, 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.

Spinning the samples / 012- / 013 on the piston spinning machine

ILOY + cold drawing, 10017 dtex

Result:

The samples with the functionalized particles could easily be processed into threads.

The physical base yarn properties of the two materials (thread strength, thread elongation) were approximately equal for the two materials. Incidentally, the fibers with particles show no abnormalities compared to standard PA fibers in mechanical properties. In the case of the relative staining depth, 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.

According to microscopic examination of thin sections of the fibers, the nanoparticles are evenly distributed in the fibers and do not form agglomerates. PA polymerization in 1 liter stirred tank

(Production of samples with increased particle content, about 3% and about 6% solids content, production conditions analogous to the previous stirred tank experiments in 101-stirred tank, see above) Granular data

( ^* 1) Particulate TAD mixture used: No. 34429/1 1, 67.1 g and 134.2 g, respectively

Even relatively high particle concentrations (2.6% and 5.2% solids content) can be incorporated into PA6.

According to microscopic examination of thin sections of the fibers, 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:

Production of polyamide fibers with dyeable particles:

It is possible to add 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.

Preparation of the dyeable particles: 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.

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.

Examples of suitable 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-pyrrolidone, ethyl acetate. 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.

In a preferred form, 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.

In order to functionalize the surface of the SiO 2 nanoparticles, the resulting acidified solution may be mixed with 0 to 10 times, preferably 0.2 to δ 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 δfachen 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.

If an aqueous metal oxide dispersion is used, 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.

In a preferred embodiment, 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.

Examples of suitable 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.

If the resulting system is present in a solvent mixture of water and solvent B, the sol is concentrated by distillation until the residual water content is less than 30%, preferably less than 20%, particularly preferably less than 10%. For this purpose it may be necessary to add further solvent before distillation or during distillation. 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. In one embodiment, a sol with a higher residual water content can also be used so that the previous distillation can be dispensed with.

As a rule, 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. -%.

The 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.

example 1

Preparation of the 4-aminopiperidine derivative

Preparation of N- (2,2,6,6-tetramethyl-4-piperidinyl) -N '- [3- (triethoxysilyl) propyl] -urea

59.5 g (0.228 mol) of isocyanatopropyltriethoxysilane were initially charged in 50 ml of dichloromethane (abs.) And 35.63 g (0.228 mol) of 4-amino-2,2,6,6-tetramethylpiperidine in 30 ml of dichloromethane at a temperature added dropwise from 20 to 40 ⁰ C and stirred for 18 h. After removal of the solvent i.Vak. 97.62 g of N- (2,2,6,6-tetramethyl-4-piperidinyl) -N '- [3- (triethoxysilyl) propyl] urea were obtained, with residual traces of solvent as a colorless oil. The product was characterized by 1 H-NMR.

Example 2

Preparation of dyeable particles

Preparation of SiC "2 [hereinafter referred to as PSH-SiO 2] linked with N- (2,2,6,6-tetramethyl-4-piperidinyl) -N '- [3- (triethoxysilyl) propyl] urea

In a beaker, 1000 g of a basic silica sol with a SiC "2 solids content of 30 wt .-% and an average particle size of 15 nm (Levasil®200, HCStark GmbH, Leverkusen, Germany) with 100 g of a strongly acidic cationic ion exchanger (Amberjet® 1200 (H), Sigma Aldrich Chemie GmbH, Taufkirchen, Germany), stirred for 30 minutes at room temperature, with a pH of 2.3, and the ion exchanger was subsequently removed by filtration. To 361 g of this aqueous sol containing 30% by weight [108.3 g] of SiO 2 was added 361 ml of isopropanol. After addition of 48.4 g (0.120 mol) of N- (2, 2,6,6-tetramethyl-4-piperidinyl) -N '- [3- (triethoxysilyl) propyl] urea was stirred at RT for 24 hours. After addition of 1800 ml of isopropanol, the sol at 50 ⁰ C under comparable reduced pressure was applied to 390 g of concentrated (residual water content: 3.1%).

Example 3

Transfer of dyeable particles into the polymerization monomer The sol of Example 2 was then added dropwise to a solution of 400 g of caprolactam and 400 g of isopropanol and concentrated at 50 ^° C. under reduced pressure to 675 g. This gave a clear dispersion of a SiO 2 having an average particle size of 68 nm (residual water content 0), which was bonded to N- (2,2,6,6-tetramethyl-4-piperidinyl) -N '- [3- (triethoxysilyl) propyl] urea. 7%).

Example 3a

Stability test of the dispersion obtained according to Example 2 with N- (2, 2,6,6-)

Tetramethyl-4-piperidinyl) -N '- [3- (triethoxysilyl) propyl] urea-bonded SiC "2 The residual solvent from 10 g of the clear dispersion of Example 2 having an average particle size of 68 nm was removed by distillation , 17 g of a solid (about 28 wt .-% functionalized SiC "2 in caprolactam). After heating to 120 ° C., a transparent dispersion is again obtained. The particle size remained constant even after 5 hours at 120 ⁰ C at 68nm.

The result showed that the dispersion was stable under these conditions.

Claims

21

claim

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.