CN108893986B - Method for thermo-sensitive modification of wool fabric through HRP (horse radish peroxidase) catalysis thiol-ene click reaction - Google Patents
Method for thermo-sensitive modification of wool fabric through HRP (horse radish peroxidase) catalysis thiol-ene click reaction Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
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Abstract
The invention discloses a method for carrying out temperature-sensitive modification on wool fabrics by using HRP (horse radish peroxidase) to catalyze a mercapto-alkene click reaction, belonging to the technical field of application of dyeing and finishing of wool fabrics in the wool spinning industry. According to the invention, by utilizing the temperature-sensitive characteristic of PNIPAm, the terminal group of the synthesized PNIPAm is firstly connected with vinyl, and then the PNIPAm is grafted to the surface of the wool fabric by utilizing the catalytic characteristic of HRP enzyme through a reaction mechanism of mercapto-alkene click chemistry, so that the intelligent finishing is carried out on the wool fabric. The wool fabric treated by the method not only presents different hydrophilicity and hydrophobicity at different temperatures, but also improves the strength of the wool fabric to a certain extent, and plays a role in strong repair. Compared with the traditional chemical process, the HRP enzyme catalyzed reaction is less in pollution and more environment-friendly, and the PNIPAm is finished on the fabric in a covalent bond mode, so that the functionality is more durable, which is also an outstanding advantage of the method compared with other processes.
Description
Technical Field
The invention relates to a method for carrying out temperature-sensitive modification on wool fabrics by HRP (horse radish peroxidase) catalyzed mercapto-alkene click reaction, belonging to the technical field of application of dyeing and finishing of wool fabrics in the wool spinning industry.
Background
With the improvement of living standard and the development of science and technology, the application field of textiles such as wool fibers and the like is continuously expanded, and the requirements of human beings on the functions, the attractiveness and the like of the textiles are higher and higher, such as comfort, air permeability, antibacterial property, radiation resistance, health care and the like. The method of utilizing chemical, physical, biological and nano technologies to endow the fabric with multifunctionality is a research hotspot of the current textile technology, and the intelligent wool fiber fabric is also a part of the future market demand.
The intelligent wool textile is a wool textile which is comprehensively developed through multiple disciplines such as textile, electronics, chemistry, biology, medicine and the like and has high intelligence, can simulate a life system based on a bionics concept, and has double functions of perception and reaction. The intelligent wool textile can not only sense the change of external environment and internal state, but also realize various special functions such as self-detection, self-diagnosis, self-adjustment and self-repair. Currently, many intelligent woollen textiles have been used in the market, such as: intelligent temperature-adjusting wool textiles, shape-memory wool textiles, intelligent waterproof moisture-permeable wool textiles, intelligent color-changing wool textiles and electronic information intelligent textiles. The wool textiles have the intelligent characteristic which is not possessed by common textiles, but the production cost is high, the serviceability is low, and the energy conservation and the environmental protection are not enough.
An intelligent polymer material is a polymer material which can sense the change of the surrounding environment and respond accordingly. The external environmental changes may be physical changes, chemical changes, and stimulation of biological signals, such as temperature, pressure, acidity, acoustic waves, solvents, electric fields, magnetic fields, etc. When the external environment is stimulated, properties of the intelligent polymer material, such as phase, shape, volume, surface area, optics, mechanics and the like, are mutated. An intelligent high polymer material with responsiveness to temperature stimulation belongs to a temperature-sensitive high polymer material, and poly N-isopropyl acrylamide PNIPAAm is a typical temperature-sensitive high polymer material. The linear PNIPAAm is a temperature-sensitive polymer with a low critical solution temperature LCST (about 32 ℃) in water, and a molecular chain contains a hydrophilic group (amide group) and a hydrophobic group (isopropyl group). When the temperature is lower than LCST, amide groups in the PNIPAAm chain and water form hydrogen bond action, a macromolecular chain is stretched, and the PNIPAAm is dissolved in the aqueous solution; when the temperature is increased to LCST, the hydrophobic skeleton and the nonpolar isopropyl group in the PNIPAAm chain begin to aggregate, the molecular chain shrinks in a curling way, and precipitation is generated.
Enzymes are generally highly specific for the substrates they act upon, but horseradish peroxidase (HRP) catalyzes a variety of oxidation reactions. HRP enzymes can catalyze the oxidation of electron rich peroxides and aromatic compounds such as phenol and aniline derivatives to produce aromatic polymers, and thiols to produce thioacyl or disulfide compounds.
Disclosure of Invention
The invention aims to endow wool with a temperature-sensitive characteristic, and provides a method for carrying out temperature-sensitive intelligent modification on wool fabric based on HRP enzyme catalyzed mercapto-alkene click reaction.
The invention relates to a method for carrying out temperature-sensitive intelligent modification on wool fabric based on HRP enzyme catalyzed mercapto-alkene click reaction, which is characterized in that HRP enzyme can catalyze mercapto-alkene click chemical reaction, and a temperature-sensitive polymer poly N-isopropyl acrylamide (PNIPAM) is grafted to the surface of the wool fabric in a covalent cross-linking manner, so that wool obtains temperature-sensitive characteristics.
The method comprises the following steps:
(1) the synthesis process of the temperature-sensitive polymer comprises the following steps: synthesizing poly N-isopropyl acrylamide (PNIPAm) by taking N- (isopropyl acrylamide) (NIPAAm) as a monomer, trithiocarbonate (CAT) as a chain transfer agent, N-Dimethylformamide (DMF) as a solvent and Ammonium Persulfate (APS) or Azobisisobutyronitrile (AIBN) as an initiator;
(2) processing temperature-sensitive polymer terminal olefin;
(3) wool fabric reduction pretreatment: degreasing, washing and drying the wool fabric, then treating the wool fabric by using a reducing agent and then cleaning the wool fabric;
(4) grafting process of temperature-sensitive polymer: adding the temperature-sensitive polymer obtained in the step (2) into a container, completely dissolving the temperature-sensitive polymer by using acetic acid/sodium acetate buffer solution, and then putting the wool fabric pretreated in the step (3) into the container, wherein the molar ratio of the mercapto content in the wool fabric to the vinyl content in the temperature-sensitive polymer is 1: (1-5), adding horseradish peroxidase and H2O2And catalyzing the grafting reaction under the protection of inert gas.
Specifically, the method comprises the following steps:
(1) the synthesis process of the temperature-sensitive polymer comprises the following steps: adding Trithiocarbonate (CAT) and a monomer N- (isopropyl acrylamide) (NIPAAm) into a 50mL three-neck flask, adding 20mL of a solvent N, N-Dimethylformamide (DMF) to ensure that the concentration of the NIPAAm in the solution is 5-20% (w/v), and adding N2Stirring for 30min under the atmosphere; adding Ammonium Persulfate (APS) or Azobisisobutyronitrile (AIBN), N22-4 h in the atmosphere; CAT: AIBN/APS: the molar ratio of NIPAAm is 1: 0.1: (50-100); after the reaction is finished, precipitating with ethyl ether for three times, and drying in vacuum;
(2) temperature-sensitive polymer end group olefin treatment process: dissolving the temperature-sensitive polymer obtained in the step (1) in 20mL of N, N-Dimethylformamide (DMF) to ensure that the concentration of the solution is 5-20% (w/v), adding ethanolamine and a small amount of reducing agent after the polymer is completely dissolved, stirring the reaction mixture at room temperature for 1-2 h, then adding 2-hydroxyethyl acrylate into the reaction mixture, and stirring the mixture at room temperature for 8-16 h, wherein the temperature-sensitive polymer: ethanolamine: reducing agent: the mol ratio of acrylic acid-2-hydroxyethyl ester is 1: 2: 2: (1-5), finally, dialyzing the solution in water by using a dialysis membrane (MWCO 3500g/mol), and freeze-drying;
(3) wool fabric reduction pretreatment: extracting and degreasing a wool fabric with acetone at 76 ℃, washing with water, drying in a drying box at 50 ℃, treating with a reducing agent at a bath ratio of 1:50 for 1-10 h, at a reaction temperature of 0-60 ℃ and with the use amount of 0-5% o.w.f, and fully cleaning a treated sample;
(4) grafting process of temperature-sensitive polymer: the temperature-sensitive polymer in the step (2) is buffered and dissolved by 0.2mol/L acetic acid/sodium acetateAdjusting the pH value to be 4-6, enabling the NIPAAm concentration in the solution to be 5-20% (w/v), after completely dissolving, putting the wool fabric pretreated in the step (3) into a flask, wherein the molar ratio of the mercapto content in the wool fabric to the vinyl content in the temperature-sensitive polymer is 1: 1-5, adding a certain volume of 1mg/mL horseradish peroxidase (HRP) enzyme stock solution to ensure that the added total enzyme activity is 4-20U, and introducing 30min N into an ice/water bath2Injection of H by micro-syringe2O2(2-4. mu. mol) and immersed in an oil bath at 30 ℃. In N2And continuing the reaction for 1-5 hours under protection.
In one embodiment of the invention, the whole experimental operation is protected by nitrogen.
In one embodiment of the present invention, the reducing agent in step (1) comprises sodium dithionate, sodium thiosulfate and sodium sulfite.
In one embodiment of the present invention, the reducing agent in step (3) comprises L-cysteine, sodium sulfite, mercaptoethanol.
In one embodiment of the invention, the method is to synthesize the poly-PNIPAM to obtain the temperature-sensitive polymer, and then to perform olefin alkylation on the terminal group of the temperature-sensitive polymer and then to graft the polymer on the surface of the wool fabric.
In one embodiment of the invention, the method utilizes a mechanism that HRP (horse radish peroxidase) catalyzes a mercapto-alkene click chemical reaction to graft the synthesized temperature-sensitive polymer with the double bond at the end group to the surface of the wool fabric.
In one embodiment of the invention, the method finally obtains an intelligent wool textile with temperature-sensitive characteristics.
The invention has the advantages and effects that:
(1) the invention uses HRP enzyme to catalyze the mercapto-alkene click chemical reaction to graft the temperature-sensitive polymer to the surface of wool, and has less dosage than chemical reagents, higher efficiency and mild conditions.
(2) The invention utilizes the film-forming property of PNIPAM to solve the problem that strength is reduced by etching the surface of wool with a reducing agent and endow wool fabric with temperature-sensitive property.
(3) According to the invention, a sulfydryl clicking method is adopted to graft PNIPAM to the surface of wool in a disulfide bond mode, so that PNIPAM is stably grafted to the surface of wool in a covalent crosslinking mode, and the intelligent characteristic of the PNIPAM is prolonged.
Detailed Description
Moisture regain: an indication of the degree of moisture absorption of the textile material. Expressed as the weight of moisture contained in the material as a percentage of the weight of the dry material.
o.w.f: i.e., On weight the fabric, concentration units, ratio of dye to weight of fabric.
Thiol-ene click: the process of collision between mercapto and alkene groups like mouse click to form carbon-sulfur bond.
Warp (weft) direction breaking strength: the maximum tension in the warp (weft) direction of the fabric at which it is stretch broken during a tensile test conducted under specified conditions.
Contact angle: the tangent to the gas-liquid interface at the intersection of the gas, liquid and solid phases, the angle theta between the liquid-side and the solid-liquid boundary, is a measure of the degree of wetting.
Wetting time: the time for the water drops on the cloth surface to disappear.
The present invention will be described in detail below.
Example 1: the wool fabric selected in this example was all-wool gabardine.
(1) The synthesis process of the temperature-sensitive polymer comprises the following steps: trithiocarbonate (CAT) and N- (isopropylacrylamide) (NIPAAm) monomer were added to a 50mL three-necked flask, and 20mL of N, N-dimethylformamide was added to give a solution with a NIPAAm concentration of 10% (w/v), N2Stirring for 30min under atmosphere, adding ammonium persulfate or Azobisisobutyronitrile (AIBN), N2Stirring for 2h under an atmosphere, CAT: AIBN: the molar ratio of NIPAAm is 1: 0.1: 50, after the reaction is finished, precipitating with ethyl ether for three times, and drying in vacuum;
(2) temperature-sensitive polymer end group olefin treatment process: dissolving the temperature-sensitive polymer in the step (1) in DMF (20mL) to enable the concentration of the temperature-sensitive polymer in the solution to be 10% (w/v), adding ethanolamine and a small amount of sodium hydrosulfite, stirring the reaction mixture at room temperature for 1h, then adding 2-hydroxyethyl acrylate into the reaction mixture, stirring the mixture at room temperature for 12h, finally dialyzing the solution in water by using a dialysis membrane (MWCO 3500g/mol), and freeze-drying; temperature-sensitive polymer: ethanolamine: sodium dithionite: the mol ratio of acrylic acid-2-hydroxyethyl ester is 1: 2: 2: (1-5);
(3) wool fabric reduction pretreatment: extracting and degreasing wool fabric with acetone at 76 ℃, washing with water, drying in a drying oven at 50 ℃, treating with L-cysteine at a bath ratio of 1:50 for 2h, at a reaction temperature of 30 ℃, with the dosage of a reducing agent of 2% o.w.f, and fully cleaning a treated sample;
(4) grafting process of temperature-sensitive polymer: dissolving the temperature-sensitive polymer in the step (2) by using 0.2mol/L, pH-4 acetic acid/sodium acetate buffer solution to make the solution concentration be 10% (w/v), after completely dissolving, putting the wool fabric pretreated in the step (3) into a flask, wherein the molar ratio of the mercapto content in the wool fabric to the vinyl content in the temperature-sensitive polymer is 1: 2, adding 1mg/mL horseradish peroxidase (HRP) enzyme stock solution to ensure that the total enzyme activity in the reaction system is 5U, and introducing 30min N in ice/water bath2Injection of H by micro-syringe2O2(2. mu. mol) and immersed in an oil bath at 30 ℃. In N2The reaction was allowed to continue for 1h with protection.
The wool fabrics treated according to the method are respectively subjected to the following performance tests, and the results are shown in table 1:
table 1 example 1 temperature sensitive wool fabric properties
It can be seen from table 1 that the unmodified fabric has a low change in contact angle, moisture regain and wetting time at different temperatures. After temperature-sensitive modification, the contact angle of the fabric at 20 ℃ is obviously reduced to indicate that the hydrophilicity is increased, and the contact angle at 40 ℃ is obviously increased to indicate that the hydrophilicity is reduced. The change of the moisture regain and the wetting time also correspond to the conclusion of the contact angle, which shows that the temperature-sensitive modified fabric shows different hydrophilicity and hydrophobicity at different temperatures.
Example 2: the wool fabric selected in this example was a full-wool serge.
(1) The synthesis process of the temperature-sensitive polymer comprises the following steps: trithiocarbonate (CAT) and N- (isopropylacrylamide) monomer were added to a 50mL three-necked flask, and 20mL of N, N-dimethylformamide was added to give a NIPAAm concentration of 10% (w/v), N2Stirring for 30min under atmosphere, adding ammonium persulfate or azobisisobutyronitrile, N22h under atmosphere, CAT: AIBN: the molar ratio of NIPAAm is 1: 0.1: 50, after the reaction is finished, precipitating with ethyl ether for three times, and drying in vacuum;
(2) temperature-sensitive polymer end group olefin treatment process: dissolving the temperature-sensitive polymer in the step (1) in DMF (20mL) to ensure that the concentration of the temperature-sensitive polymer in the solution is 10% (w/v), adding ethanolamine and a small amount of sodium hydrosulfite, stirring the reaction mixture at room temperature for 1h, then adding 2-hydroxyethyl acrylate into the reaction mixture, stirring the reaction mixture at room temperature for 12h, finally dialyzing the solution in water by using a dialysis membrane (MWCO 3500g/mol), and freeze-drying; temperature-sensitive polymer: ethanolamine: sodium dithionite: the mol ratio of acrylic acid-2-hydroxyethyl ester is 1: 2: 2: (1-5);
(3) wool fabric reduction pretreatment: extracting and degreasing a wool fabric with acetone at 76 ℃, washing with water, drying with a drying oven at 50 ℃, treating with mercaptoethanol at a bath ratio of 1:50 for 3 hours, at a reaction temperature of 35 ℃, with the use amount of a reducing agent of 2% o.w.f, and fully cleaning a treated sample;
(4) grafting process of temperature-sensitive polymer: dissolving the temperature-sensitive polymer in the step (2) by using 0.2mol/L, pH-4 acetic acid/sodium acetate buffer solution to make the solution concentration be 10% (w/v), after completely dissolving, putting the wool fabric pretreated in the step (3) into a flask, wherein the molar ratio of the mercapto content in the wool fabric to the vinyl content in the temperature-sensitive polymer is 1: 2, adding a certain volume of 1mg/mL horseradish peroxidase (HRP) enzyme stock solution to ensure that the total enzyme activity in the reaction system is 10U, and introducing 30min N into ice/water bath2Injection of H by micro-syringe2O2(2. mu. mol) and immersed in an oil bath at 30 ℃. In thatN2The reaction was allowed to continue for 1.5h with protection.
The wool fabrics treated according to the method are respectively subjected to the following performance tests, and the results are shown in table 2:
table 2 example 2 temperature sensitive wool fabric properties
The temperature-sensitive modified fabric shows different hydrophilicity and hydrophobicity at two temperatures, the contact angle is reduced at 20 ℃, the moisture regain is increased, the wetting time is shortened, the hydrophilicity is increased, and the results are just opposite at 40 ℃ and show stronger hydrophobicity. Because the temperature-sensitive polymer PNIPAm is a high molecular compound, a film can be formed on the surface of wool, the cross-linking of the surface of the wool is increased, and the warp and weft strength of the fabric is increased.
Example 3: the wool fabric selected in this example was all-wool gabardine.
(1) The synthesis process of the temperature-sensitive polymer comprises the following steps: trithiocarbonate and N- (isopropylacrylamide) monomer were added to a 50mL three-necked flask, and 20mL of N, N-dimethylformamide was added to give a solution with a NIPAAm concentration of 10% (w/v), N2Stirring for 30min under atmosphere, adding ammonium persulfate or azobisisobutyronitrile, N22h under atmosphere, CAT: AIBN: the molar ratio of NIPAAm is 1: 0.1: 50. after the reaction is finished, precipitating with ethyl ether for three times, and drying in vacuum;
(2) temperature-sensitive polymer end group olefin treatment process: dissolving the temperature-sensitive polymer in the step (1) in DMF (20mL) to ensure that the concentration of the temperature-sensitive polymer in the solution is 10% (w/v), adding ethanolamine and a small amount of sodium hydrosulfite, stirring the reaction mixture at room temperature for 1h, then adding 2-hydroxyethyl acrylate into the reaction mixture, stirring the reaction mixture at room temperature for 12h, finally dialyzing the solution in water by using a dialysis membrane (MWCO 3500g/mol), and freeze-drying; temperature-sensitive polymer: ethanolamine: sodium dithionite: the mol ratio of acrylic acid-2-hydroxyethyl ester is 1: 2: 2: (1-5);
(3) wool fabric reduction pretreatment: extracting and degreasing wool fabric with acetone at 76 ℃, washing with water, drying with a drying oven at 50 ℃, treating with L-cysteine at a bath ratio of 1:50 for 2h, at a reaction temperature of 30 ℃, with a reducing agent dosage of 2% o.w.f, and fully cleaning a treated sample;
(4) grafting process of temperature-sensitive polymer: dissolving the temperature-sensitive polymer in the step (2) by using 0.2mol/L, pH-4 acetic acid/sodium acetate buffer solution to make the solution concentration be 10% (w/v), after completely dissolving, putting the wool fabric pretreated in the step (3) into a flask, wherein the molar ratio of the mercapto content in the wool fabric to the vinyl content in the temperature-sensitive polymer is 1: 2, adding a certain volume of horseradish peroxidase (HRP) enzyme stock solution to ensure that the total enzyme activity in the reaction system is 20U, and introducing 30min N into ice/water bath2Injection of H by micro-syringe2O2(3. mu. mol) and immersed in an oil bath at 30 ℃. In N2The reaction was allowed to continue for 1.5h with protection.
The wool fabrics treated according to the method are respectively subjected to the following performance tests, and the results are shown in table 3:
example 3 temperature sensitive wool Fabric Properties
Compared with the examples 1 and 2, the enzyme dosage is obviously increased, but the contact angle of the obtained temperature-sensitive fabric is not reduced but slightly increased, which shows that the optimal treatment effect can be achieved when the enzyme dosage is 10-20U. The moisture regain and wetting time also correspond to the contact angle results.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A method for preparing temperature-sensitive wool fabric is characterized in that the end group of poly N-isopropyl acrylamide is subjected to olefination and then grafted to the surface of the wool fabric; the method for performing olefination treatment on the terminal group of the poly N-isopropylacrylamide comprises the following steps: dissolving poly (N-isopropylacrylamide) in N, N-Dimethylformamide (DMF) to ensure that the concentration of the solution is 5-20% w/v, adding ethanolamine and a small amount of reducing agent after the polymer is completely dissolved, stirring the reaction mixture at room temperature for 1-2 h, then adding 2-hydroxyethyl acrylate into the reaction mixture, stirring the mixture at room temperature for 8-16 h, finally dialyzing the solution in water by using a dialysis membrane, and freeze-drying; by utilizing the capability of horseradish peroxidase catalyzing mercapto-alkene click chemistry reaction, the temperature-sensitive polymer alkene alkylated poly-N-isopropyl acrylamide with double bonds at the end group is grafted to the surface of the wool fabric in a covalent crosslinking mode; dissolving a temperature-sensitive polymer with a double bond at an end group by using 0.2mol/L, pH = 4-6 acetic acid/sodium acetate buffer solution to ensure that the concentration of the solution is 5-20% w/v, and after the solution is completely dissolved, putting the pretreated wool fabric into the temperature-sensitive polymer, wherein the molar ratio of the mercapto content in the wool fabric to the vinyl content in the temperature-sensitive polymer is 1: (1-5), adding horseradish peroxidase, introducing inert gas into an ice/water bath, and injecting 2-4 mu mol of H2O2And immersing in an oil bath at 30-35 ℃ to continue the reaction for 1-5 hours under the protection of inert gas.
2. The method of claim 1, wherein the wool fabric is pre-treated by: degreasing, washing and drying the wool fabric, then treating the wool fabric by using a reducing agent and then cleaning the wool fabric.
3. The method of preparing a temperature-sensitive wool fabric according to claim 1 wherein the temperature-sensitive polymer: ethanolamine: reducing agent: the mol ratio of acrylic acid-2-hydroxyethyl ester is 1: 2: 2: (1-5).
4. The method for preparing a temperature-sensitive wool fabric according to claim 2, wherein the wool fabric is extracted and degreased with acetone at 76 ℃, washed with water, dried in a drying oven at 50 ℃, treated with a reducing agent at a bath ratio of 1:50 for 1-10 h at a reaction temperature of 0-60 ℃ and a reducing agent dosage of 0-5% o.w.f, and the treated sample is thoroughly washed.
5. A temperature sensitive wool textile prepared according to any one of claims 1 to 4.
6. A textile prepared by using the temperature-sensitive wool fabric of claim 5.
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