A preparation method and application of amino acid-modified polyester fiber

Abstract

The present invention discloses a preparation method and application of amino acid-modified polyester fibers, and relates to the technical field of textile materials. The present invention discloses a preparation method of amino acid-modified polyester fibers, comprising the following steps: electrostatic spinning and drying of amino acid-modified polyester to obtain amino acid-modified polyester fibers; the preparation method of amino acid-modified polyester comprises the following steps: ionizing lysine to obtain liquid component one; carboxylating graphene oxide to obtain modified graphene; esterifying the hydroxyl group of hydroxyl-terminated polyester with 1,2,4,5-benzenetetracarboxylic dianhydride to obtain modified polyester; using modified graphene and modified polyester as raw materials, and using ionized lysine in liquid component one as a crosslinking agent to prepare amino acid-modified polyester. The amino acid-modified polyester fibers prepared in the present application have excellent hygroscopic heat generation performance and excellent water resistance.

Description

Technical Field

[0001] The invention relates to the technical field of textile materials, and in particular to a preparation method and application of amino acid-modified polyester fibers. Background Art

[0002] For winter clothing, the ability to keep warm is one of the important indicators to test its comfort. The traditional method of keeping warm is to prevent heat convection, control heat conduction and reduce heat radiation, such as by accumulating thick fabrics or cotton wool for warmth, or coating the fabric with metal coating for warmth. However, traditional warm clothing is too bulky, and as people's requirements for clothing increase, it gradually cannot meet people's needs. With the development of science and the improvement of people's quality of life, clothing fabrics are gradually developing towards functional diversification, such as heat generation. Heating fiber is a heat-generating thermal fiber that actively generates heat. At present, it has achieved diversified development, mainly including the following: light-energy heating fiber, phase change material, hygroscopic heating fiber, chemical exothermic material and electric heating material. Among them, hygroscopic heating fiber can generate heat autonomously after absorbing water, that is, the corresponding fabric can absorb moisture (trace water) emitted by the human body and generate a certain amount of heat, accelerate the temperature balance between the skin and clothing, and adjust and alleviate the temperature difference between the two. Hygroscopic heating fabrics have great market prospects.

[0003] Polyester is the commercial name of polyethylene terephthalate fiber. Polyester is obtained by polycondensation of terephthalic acid and ethylene glycol. It is the most industrialized and used synthetic fiber on the market. Compared with other natural or chemical fibers, polyester has stronger light resistance and wear resistance, higher elasticity and strength, and is therefore widely used in the field of clothing. However, polyester has a weak moisture absorption capacity. In addition to two terminal hydroxyl groups, the tightly arranged molecular structure has no other hydrophilic or polar groups, and has poor hygroscopicity. Under the conditions of relative temperature of 20°C and relative humidity of 65%, the moisture regain of polyester fiber is only 0.4% (cotton fiber 7-8%, polyamide fiber 4%, polyacrylonitrile fiber 1-2%). Even at 100% relative humidity, its moisture regain is only 0.6-0.8%, which is a typical hydrophobic material. Therefore, when people sweat, the sweat on the body surface is not easy to be guided to the outside of the fabric through the polyester fabric, which will make the wearer feel stuffy and uncomfortable. Underwear needs to have good hydrophilicity and moisture permeability in order to absorb moisture and generate heat. Summary of the invention

[0004] The purpose of the present invention is to provide a preparation method and application of amino acid-modified polyester fibers to solve the following technical problems: Existing polyethylene terephthalate fibers are typical hydrophobic materials with poor hygroscopicity and cannot achieve the effect of absorbing moisture and generating heat as underwear.

[0005] The object of the present invention can be achieved by the following technical scheme: a method for preparing amino acid-modified polyester fibers, comprising the following steps: electrospinning the amino acid-modified polyester and then drying it to obtain the amino acid-modified polyester fibers; the method for preparing the amino acid-modified polyester comprises the following steps:

[0006] A1: Add hydroxyl-terminated polyester, 1,2,4,5-benzenetetracarboxylic dianhydride and N,N-dimethylformamide into reactor A, control the temperature to 80-90°C, keep the temperature for 1-3 hours under stirring, and remove the solvent by rotary evaporation to obtain modified polyester;

[0007] A2: Add modified polyester, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and deionized water into reactor B and disperse them evenly. Control the temperature at 0-5°C and keep the reaction warm for 9-12 hours. Add lysine-modified graphene and control the temperature at 0-5°C. Keep the reaction warm for 9-12 hours. Perform dialysis to remove impurities and obtain amino acid-modified polyester.

[0008] As a further solution of the present invention: the specific steps of electrospinning are: voltage 15-25 kV, 15-25 cm from the spinneret to the collecting screen, flow rate 0.5-0.8 mL / h, and tin foil as the collecting screen.

[0009] As a further embodiment of the present invention, the addition ratio of the terminal hydroxyl polyester, 1,2,4,5-benzenetetracarboxylic dianhydride and N,N-dimethylformamide in A1 is 10 g: 1-2 g: 50-200 mL.

[0010] As a further embodiment of the present invention: the addition ratio of the modified polyester, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, lysine-modified graphene, and deionized water in A2 is 10 g: 1-2 g: 5-6 g: 0.5-1 g: 500-2000 mL.

[0011] As a further solution of the present invention: the preparation method of lysine-modified graphene comprises the following steps:

[0012] S1: Add lysine and deionized water into a reaction bottle and disperse them evenly, add sodium hydroxide, and stir evenly to obtain liquid component 1;

[0013] S2: adding graphene oxide, deionized water, hydrazine hydrate solution and ammonia water into reactor C, controlling the temperature at 90-100° C., keeping the temperature under stirring for 1-3 hours, filtering and drying, neutralizing in hydrochloric acid solution, washing with water until neutral, and drying to obtain modified graphene;

[0014] S3: Add the modified graphene and liquid component 1 into the reaction kettle D, control the temperature to 80-90° C., keep the temperature for reaction for 1-3 hours, filter, wash with water, and dry to obtain lysine-modified graphene.

[0015] As a further solution of the present invention: the addition ratio of lysine, deionized water and sodium hydroxide in S1 is 10 g: 200-600 mL: 2-5 g.

[0016] As a further solution of the present invention: the hydrazine hydrate solution in S2 is a 35-80wt% hydrazine hydrate solution, and the ammonia water is a 25-28wt% ammonia water; the addition ratio of graphene oxide, deionized water, hydrazine hydrate solution, and ammonia water is 10g: 100-200mL: 0.2-0.5mL: 2-5mL.

[0017] As a further solution of the present invention: the addition ratio of modified graphene and liquid component 1 in S3 is 10g:200-600mL.

[0018] As a further solution of the present invention: application of the polyester fiber prepared by any of the preparation methods described above in textile materials.

[0019] As a further solution of the present invention: the textile material is obtained by blending amino acid-modified polyester fibers and cotton fibers.

[0020] The beneficial effects of the present invention are as follows: the present invention uses graphene oxide prepared by the Hummers method as a raw material, uses ammonia water and hydrazine hydrate as reducing agents to reduce the graphene oxide, and uses a hydrochloric acid solution for neutralization treatment to convert hydroxyl groups and epoxy groups on the surface of the graphene into carboxyl groups, thereby obtaining modified graphene containing carboxyl groups on the surface; lysine is ionized, and the obtained liquid component one contains ionized lysine; the present invention uses 1,2,4,5-benzenetetracarboxylic acid dianhydride to carry out esterification reaction with terminal hydroxyl polyester to obtain modified polyester, and the terminal group of the modified polyester prepared by the present invention is a carboxyl group; finally, the present invention uses N-hydroxysuccinimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride as activators and catalysts to activate the carboxyl group of the modified polyester, and uses ionized lysine as a cross-linking agent to carry out an amide bonding reaction to cross-link the modified graphene and the modified polyester to obtain an amino acid-modified polyester.

[0021] The amino acid-modified polyester prepared in the present application has ionized lysine, in which the negatively charged carboxylate groups increase the interaction between the material and water molecules through electrostatic action, thereby increasing the hydrophilicity of the material. The amino acid-modified polyester prepared in the present application has a large number of strong hydrophilic groups such as carboxyl and amide groups on its surface and inside, which can capture water molecules with high kinetic energy in the air and adsorb and fix them on the surface of the fabric. After binding, the water molecules are transformed from the original dynamic state to the static state, so that their kinetic energy is converted into thermal energy, thereby achieving the effect of generating heat. The modified graphene prepared in the present application is grafted with polyester through molecular chains to give the polyester surface a pore structure, effectively improving the hygroscopic and thermal conductivity of the polyester, further improving the hygroscopic heat generation and heat transfer properties of the polyester fiber, and making the heat energy evenly dispersed on the surface of the fabric. DETAILED DESCRIPTION

[0022] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1

[0024] The preparation method of lysine-modified graphene comprises the following steps:

[0025] S1: Add 10 g of lysine and 500 mL of deionized water into a reaction bottle and disperse them evenly, add 5 g of sodium hydroxide, and stir evenly to obtain liquid component 1;

[0026] S2: 10 g of graphene oxide (prepared by the classic Hummers method), 100 mL of deionized water, 0.2 mL of 35 wt% hydrazine hydrate solution, and 2 mL of 28 wt% ammonia water were added to reactor C, the temperature was controlled at 90 ° C, and the mixture was kept warm for 1 h under stirring. The mixture was filtered and dried, and then neutralized in a 5 vt% hydrochloric acid solution for 10 min, washed with water until neutral, and dried to obtain modified graphene.

[0027] S3: Add 10 g of modified graphene and 500 mL of liquid component 1 into reactor D, control the temperature to 80° C., keep the reaction warm for 1 h, filter, wash with water, and dry to obtain lysine-modified graphene.

[0028] Example 2

[0029] The preparation method of lysine-modified graphene comprises the following steps:

[0030] S1: Add 10 g of lysine and 500 mL of deionized water into a reaction bottle and disperse them evenly, add 5 g of sodium hydroxide, and stir evenly to obtain liquid component 1;

[0031] S2: 10 g of graphene oxide (prepared by the classic Hummers method), 150 mL of deionized water, 0.4 mL of 35 wt% hydrazine hydrate solution, and 4 mL of 28 wt% ammonia water were added to reactor C, the temperature was controlled at 95 °C, the mixture was kept warm for 2 h under stirring, filtered, dried, and then neutralized in a 5 vt% hydrochloric acid solution for 15 min, washed with water until neutral, and dried to obtain modified graphene;

[0032] S3: Add 10 g of modified graphene and 500 mL of liquid component 1 into reactor D, control the temperature to 85° C., keep the reaction warm for 2 h, filter, wash with water, and dry to obtain lysine-modified graphene.

[0033] Example 3

[0034] The preparation method of lysine-modified graphene comprises the following steps:

[0035] S1: Add 10 g of lysine and 500 mL of deionized water into a reaction bottle and disperse them evenly, add 5 g of sodium hydroxide, and stir evenly to obtain liquid component 1;

[0036] S2: 10 g of graphene oxide (prepared by the classic Hummers method), 200 mL of deionized water, 0.5 mL of 35 wt% hydrazine hydrate solution, and 5 mL of 28 wt% ammonia water were added to reactor C, the temperature was controlled at 100 °C, and the mixture was kept warm for 3 h under stirring conditions, filtered, dried, and then placed in a 5 vt% hydrochloric acid solution for neutralization treatment for 20 min, washed with water until neutral, and dried to obtain modified graphene;

[0037] S3: Add 10 g of modified graphene and 500 mL of liquid component 1 into reactor D, control the temperature to 90° C., keep the reaction warm for 3 h, filter, wash with water, and dry to obtain lysine-modified graphene.

[0038] Example 4

[0039] A method for preparing amino acid-modified polyester fiber comprises the following steps:

[0040] A1: 10 g of hydroxyl-terminated polyester (polyethylene terephthalate, length 38 mm, linear density 1.4 dtex, curl 15.23%, breaking strength 2.5 cN / dtex), 2 g of 1,2,4,5-benzenetetracarboxylic dianhydride, and 1000 mL of N,N-dimethylformamide were added to reactor A, the temperature was controlled at 80°C, the mixture was kept warm for 3 h under stirring, and the solvent was removed by rotary evaporation to obtain a modified polyester;

[0041] A2: 10 g of modified polyester, 2 g of N-hydroxysuccinimide, 6 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and 1000 mL of deionized water were added to reactor B and dispersed evenly. The temperature was controlled at 0° C. and the reaction was kept warm for 12 h. 1 g of lysine-modified graphene prepared in Example 1 was added, the temperature was controlled at 0° C. and the reaction was kept warm for 12 h. The polyester was dialyzed to remove impurities to obtain amino acid-modified polyester.

[0042] A3: The amino acid modified polyester was electrospun and then dried. The specific steps of electrospinning were: voltage 25 kV, 20 cm from the spinneret to the collecting screen, flow rate 0.8 mL / h, and tin foil as the collecting screen to obtain amino acid modified polyester fibers.

[0043] Example 5

[0044] Compared with Example 4, Example 5 is only replaced by an equal amount of lysine-modified graphene prepared in Example 1 added in Example 4 with lysine-modified graphene prepared in Example 2, and its components and preparation method are completely consistent with those of Example 4.

[0045] Example 6

[0046] Compared with Example 4, Example 6 is the same as Example 4, except that the lysine-modified graphene prepared in Example 1 added in Example 4 is replaced by the lysine-modified graphene prepared in Example 3 in equal amount. The components and preparation method are exactly the same as those in Example 4.

[0047] Comparative Example 1

[0048] The preparation method of modified graphene comprises the following steps:

[0049] 10 g of graphene oxide (prepared by the classic Hummers method), 150 mL of deionized water, 0.4 mL of 35 wt% hydrazine hydrate solution, and 4 mL of 28 wt% ammonia water were added to reactor A, the temperature was controlled at 95 °C, and the mixture was kept warm for 2 h under stirring. The mixture was filtered and dried, and then neutralized in a 5 vt% hydrochloric acid solution for 15 min, washed with water until neutral, and dried to obtain modified graphene.

[0050] Comparative Example 2

[0051] The preparation method of lysine-modified graphene comprises the following steps:

[0052] S1: Add 10 g of lysine and 500 mL of deionized water into a reaction bottle, disperse them evenly, and stir them evenly to obtain liquid component 1;

[0053] S2: 10 g of graphene oxide (prepared by the classic Hummers method), 150 mL of deionized water, 0.4 mL of 35 wt% hydrazine hydrate solution, and 4 mL of 28 wt% ammonia water were added to reactor C, the temperature was controlled at 95 °C, the mixture was kept warm for 2 h under stirring, filtered, dried, and then neutralized in a 5 vt% hydrochloric acid solution for 15 min, washed with water until neutral, and dried to obtain modified graphene;

[0054] S3: Add 10 g of modified graphene and 500 mL of liquid component 1 into reactor D, control the temperature to 85° C., keep the reaction warm for 2 h, filter, wash with water, and dry to obtain lysine-modified graphene.

[0055] Comparative Example 3

[0056] Compared with Example 4, Comparative Example 3 is that the lysine-modified graphene prepared in Example 1 added in Example 4 is replaced by an equal amount of the modified graphene prepared in Comparative Example 1, and its components and preparation method are completely consistent with those of Example 4.

[0057] Comparative Example 4

[0058] Compared with Example 4, Comparative Example 4 is that the lysine-modified graphene prepared in Example 1 added in Example 4 is replaced by an equal amount of lysine-modified graphene prepared in Comparative Example 2, and its components and preparation method are completely consistent with those of Example 4.

[0059] Comparative Example 5

[0060] A method for preparing amino acid-modified polyester fiber comprises the following steps:

[0061] A1: 10 g of hydroxyl-terminated polyester, 2 g of 1,2,4,5-benzenetetracarboxylic anhydride, and 1000 mL of N,N-dimethylformamide were added to reactor A, the temperature was controlled at 80°C, the mixture was kept warm for 3 h under stirring, and the solvent was removed by rotary evaporation to obtain a modified polyester;

[0062] A2: 10 g of modified polyester and 1000 mL of deionized water were added to reactor B and dispersed evenly. The temperature was controlled at 0° C. and the reaction was kept warm for 12 h. 1 g of amino acid-modified graphene prepared in Example 2 was added. The temperature was controlled at 0° C. and the reaction was kept warm for 12 h. The amino acid-modified polyester was removed by dialysis to obtain the amino acid-modified polyester.

[0063] A3: The amino acid modified polyester was electrospun and then dried. The specific steps of electrospinning were: voltage 25 kV, 20 cm from the spinneret to the collecting screen, flow rate 0.8 mL / h, and tin foil as the collecting screen to obtain amino acid modified polyester fibers.

[0064] Performance Testing

[0065] Preparation of textile materials: The amino acid-modified polyester fibers prepared in Examples 4-6 and Comparative Examples 3-5 were blended with viscose and spun into textile materials (33.12 tex, 21 counts), wherein the mass ratio of the polyester fiber to the viscose was 50:50.

[0066] (1) Moisture regain: The moisture regain of the textile materials prepared above was tested according to GB / T 9995-1997 "Determination of moisture content and moisture regain of textile materials", and the test was carried out using the oven drying method. The oven method is to weigh the wet mass of the sample, dry the sample in an oven at (105±2)℃, weigh the dry weight, and calculate the moisture regain using the following formula:

[0067] η=[(m1-m0) / m0]×100%

[0068] In the formula: η is moisture regain, %; m1 is wet mass; m0 is dry mass. The test results are shown in Table 1.

[0069] (2) Wicking height: The wicking height of the textile materials prepared above was tested according to FZ / T 01071-2008 “Test method for capillary effect of textiles”. Each group of specimens was 215 mm × 30 mm, 3 in each of the horizontal and vertical directions. The mass of the pre-tensioned clamp was (3.00 ± 0.15) g. The water temperature was (20 ± 1) °C, the test time was 30 min, the ambient temperature was (20 ± 2) °C, and the relative humidity was (65 ± 2)%; the test results are shown in Table 1.

[0070] (3) Water vapor permeability: The water vapor permeability of the textile material prepared above was tested in accordance with GB / T 12704.1-2009 “Test method for water vapor permeability of textile fabrics Part 1: Moisture absorption method”. A water vapor permeability cup filled with desiccant (anhydrous calcium chloride dried at 160°C for 3h) and sealed with the sample was placed in a sealed environment with a temperature of (38±2)°C, a relative humidity of (90±2)% and a certain circulating airflow of (0.3-0.5) m / s. The water vapor permeability of the sample was calculated based on the change in the mass of the water vapor permeability cup within a specific time. The calculation method is shown in the following formula:

[0071] ε = (Δm-Δm0) / (At)

[0072] Where: T-water vapor permeability, g / m 2 ·24h; Δm-the difference between two consecutive weighings of the same sample, g; Δm0-the mass difference of the blank sample, g; A-the effective test area in the sample test, m 2 , this test is 0.00283m 2 ; t-test time, s; the test results are shown in Table 1;

[0073] (4) Washing resistance: According to the AATCC 135-2003 "Dimensional Changes of Household Fabrics after Washing", at a temperature of 27°C, with a mass ratio of textile material to non-phosphate detergent of 1:1, add water and stir to wash for 12 minutes, then rinse and dry (solid-liquid ratio 1:50), and test the moisture regain again. The test results are shown in Table 1.

[0074]

[0075] It can be seen from Table 1 that the amino acid-modified polyester fiber prepared in the present application has excellent moisture absorption properties and still maintains a good moisture regain after multiple washings.

[0076] (4) Hygroscopic and heat generation performance: The hygroscopic and heat generation performance of the textile materials prepared above was tested according to GB / T 29866-2013 Test method for hygroscopic and heat generation performance of textiles. The samples with a size of 60 mm × 100 mm were sewn into a bag shape with a stitch density of 9 stitches / 2 cm. The opening side of the sample was a thermocouple insertion port. The samples were first dried in an oven at a drying temperature of (105±2)°C to constant weight, and then placed in a sealed desiccator for cooling and drying for 45 min. The samples were then equilibrated in an environment of (20±2)°C and relative humidity of (65±4)% for 1 h before the hygroscopic and heat generation performance test was performed. The test temperature was (20±0.5)°C, the relative humidity was (90±3)%, and the ambient wind speed was 0.2 m / s-0.6 m / s. The test results are shown in Table 2.

[0077]

[0078] It can be seen from Table 2 that the amino acid-modified polyester fiber prepared in the present application has good moisture absorption and heat generation properties.

[0079] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing amino acid-modified polyester fibers, characterized in that: The method comprises the following steps: electrostatically spinning the amino acid-modified polyester and then drying it to obtain the amino acid-modified polyester fiber; The preparation method of the amino acid-modified polyester comprises the following steps: A1: Add hydroxyl-terminated polyester, 1,2,4,5-benzenetetracarboxylic dianhydride and N,N-dimethylformamide into reactor A, control the temperature to 80-90°C, keep the temperature for 1-3 hours under stirring, and remove the solvent by rotary evaporation to obtain modified polyester; A2: Add modified polyester, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and deionized water into reactor B and disperse them evenly. Control the temperature to 0-5°C and keep the temperature for 9-12 hours. Add lysine-modified graphene and control the temperature to 0-5°C. Keep the temperature for 9-12 hours. Dialyze to remove impurities and obtain amino acid-modified polyester. The preparation method of the lysine-modified graphene described in A2 comprises the following steps: S1: Add lysine and deionized water into a reaction bottle and disperse them evenly, add sodium hydroxide, and stir evenly to obtain liquid component 1; S2: adding graphene oxide, deionized water, hydrazine hydrate solution and ammonia water into reactor C, controlling the temperature at 90-100° C., keeping the temperature under stirring for 1-3 hours, filtering and drying, neutralizing in hydrochloric acid solution, washing with water until neutral, and drying to obtain modified graphene; S3: Add the modified graphene and liquid component 1 into the reaction kettle D, control the temperature to 80-90° C., keep the temperature for reaction for 1-3 hours, filter, wash with water, and dry to obtain lysine-modified graphene.

2. The method for preparing amino acid-modified polyester fiber according to claim 1, characterized in that: The specific steps of the electrospinning are: voltage 15-25 kV, 15-25 cm from the spinneret to the collecting screen, flow rate 0.5-0.8 mL / h, and tin foil as the collecting screen.

3. The method for preparing amino acid-modified polyester fiber according to claim 1, characterized in that: The addition ratio of terminal hydroxyl polyester, 1,2,4,5-benzenetetracarboxylic dianhydride and N,N-dimethylformamide in A1 is 10g:1-2g:50-200mL.

4. The method for preparing amino acid-modified polyester fiber according to claim 1, characterized in that: The addition ratio of modified polyester, N-hydroxysuccinimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, lysine-modified graphene, and deionized water in A2 is 10 g: 1-2 g: 5-6 g: 0.5-1 g: 500-2000 mL.

5. The method for preparing amino acid-modified polyester fiber according to claim 1, characterized in that: The addition ratio of lysine, deionized water, and sodium hydroxide in S1 is 10 g: 200-600 mL: 2-5 g.

6. The method for preparing amino acid-modified polyester fiber according to claim 1, characterized in that: The hydrazine hydrate solution in S2 is 35-80wt% hydrazine hydrate solution, and the ammonia water is 25-28wt% ammonia water.

7. The method for preparing amino acid-modified polyester fiber according to claim 6, characterized in that: The addition ratio of graphene oxide, deionized water, hydrazine hydrate solution and ammonia water in S2 is 10 g: 100-200 mL: 0.2-0.5 mL: 2-5 mL.

8. The method for preparing amino acid-modified polyester fiber according to claim 1, characterized in that: The addition ratio of modified graphene and liquid component 1 in S3 is 10 g: 200-600 mL.

9. Use of the polyester fiber obtained by the preparation method according to any one of claims 1 to 8 in textile materials.

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