CN110685170A - Wool keratin/waterborne polyurethane composite emulsion coating agent with warm-keeping function and preparation method thereof - Google Patents
Wool keratin/waterborne polyurethane composite emulsion coating agent with warm-keeping function and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/6755—Unsaturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2201/00—Chemical constitution of the fibres, threads or yarns
- D06N2201/04—Vegetal fibres
- D06N2201/042—Cellulose fibres, e.g. cotton
Abstract
The invention relates to a wool keratin/waterborne polyurethane composite emulsion coating agent with a warm-keeping function and a preparation method thereof. The coating agent can be prepared by the following preparation method: taking waste wool as a raw material, and extracting wool keratin from the waste wool; then preparing keratin into O/W type wool keratin emulsion; the aqueous polyurethane emulsion is prepared, and the wool keratin emulsion and the aqueous polyurethane emulsion are compounded and mixed to prepare the wool keratin/aqueous polyurethane composite emulsion coating agent with the warm-keeping function. After the wool keratin/waterborne polyurethane composite emulsion coating agent prepared by the invention is used for coating finishing of cotton fabrics, the heat preservation rate of the cotton fabrics is increased from 24.7% to more than 66%, which indicates that the coating agent has a good heat preservation function. The preparation process is simple, the production process has no pollution to the environment, and the method is favorable for further popularization and application.
Description
Technical Field
The invention belongs to the technical field of coating agents, and particularly relates to a wool keratin/waterborne polyurethane composite emulsion coating agent with a warm-keeping function and a preparation method thereof.
Background
The coating agent is a textile auxiliary agent which is coated on the surface of the textile and can endow the textile with a plurality of characteristics, such as: warm keeping, wind prevention, hydrophobicity, ultraviolet resistance, static resistance and the like. Currently, the coating agents on the market mainly comprise two categories of polyacrylate and polyurethane, and the two categories of coating agents have advantages and disadvantages when used. Along with the improvement of the quality demand of textile and clothing, various novel textile coating agents are continuously researched and produced to meet the market demand.
When sheepskin is used for leather making, a large amount of waste wool remains exist, and in addition, a large amount of waste wool products exist in the garment wool industry. Wool keratin can be extracted from the waste wool remainder, is a natural biopolymer, has excellent heat preservation performance of wool, and has good biodegradability. It follows that wool keratin has great potential in the field of being used in coating agents.
Currently, many new natural materials are widely used in the field of coating agents, such as: chinese patent application No. 200710145401.6 discloses a waterproof moisture-permeable coating agent composition and application thereof, wherein microporous lignin fine powder is added into a polyurethane coating agent. The research on the use of wool keratin for preparing a coating agent is only rarely reported in literature research, and the invention is expected to have a breakthrough in the field.
Disclosure of Invention
The invention aims to provide a wool keratin/waterborne polyurethane composite emulsion coating agent with a warm-keeping function, which is used for solving the defects in the prior art, and after a textile is coated by the coating agent, the textile has a better warm-keeping function.
The invention aims to provide a wool keratin/waterborne polyurethane composite emulsion coating agent with a warm-keeping function, which can be prepared by the following preparation method: taking waste wool as a raw material, and extracting wool keratin from the waste wool; then preparing keratin into O/W type wool keratin emulsion; the aqueous polyurethane emulsion is prepared, and the wool keratin emulsion and the aqueous polyurethane emulsion are compounded and mixed to prepare the wool keratin/aqueous polyurethane composite emulsion coating agent with the warm-keeping function.
The invention also aims to provide a preparation method of the wool keratin/waterborne polyurethane composite emulsion coating agent with the warm-keeping function, which comprises the following steps:
(1) selecting waste wool: the waste clothes made of wool are selected, washed by a clothes washing agent, washed by a large amount of water and dried.
(2) Preparation of wool keratin solution: and (2) dissolving the waste clothes treated in the step (1) in a mixed solution of tricarboxyethylphosphine and urea at the temperature of 60-80 ℃, continuously stirring in the dissolving process, wherein the dissolving time is 4-6 h, filtering, and concentrating to obtain a wool keratin solution, wherein the solid content of the wool keratin solution is 40-60%.
Preferably, the volume-mass ratio of the waste wool (g), the tricarboxyethylphosphine (mL) and the urea (g) is 1: 10-20: 1-2.
(3) Preparation of wool keratin powder: and (3) freeze-drying the wool keratin solution prepared in the step (2) on a freeze dryer to prepare wool keratin powder.
Preferably, the freezing temperature is: -50 to-60 ℃, and the drying time is as follows: 10 to 18 hours.
(4) Preparation of O/W emulsion: adding wool keratin solid into a round-bottom flask, adding N-methylmorpholine, and continuously stirring and completely dissolving the wool keratin solid at 40 ℃ on a constant-temperature electromagnetic stirrer; after the wool keratin is completely dissolved, adding the mixed solution into span 60, and stirring to uniformly mix the mixed solution; adding the mixed solution into saturated sodium dodecyl sulfate aqueous solution, and uniformly stirring by using a magnetic rotor to obtain the O/W type wool keratin emulsion.
Preferably, the solid-to-liquid ratio of wool keratin (g) to N-methylmorpholine (mL) is: 1: 5-10; the dosage ratio of span 60 to N-methylmorpholine is as follows: 1-3%; the dosage ratio of the mixed solution (mL) to the saturated sodium dodecyl sulfate aqueous solution (mL) is 1: 2-4.
(5) Pre-polymerization: adding polypropylene glycol and dimethylolpropionic acid into a reaction kettle, dehydrating for 1-2 hours in vacuum at 100-120 ℃, slowly cooling to 50-60 ℃, dropwise adding a mixed solution of toluene diisocyanate, butanone and catalyst stannous octoate, heating to 80-90 ℃, and reacting for 3-4 hours.
Preferably, the molecular weight of the polypropylene glycol is 200, the molar ratio of the polypropylene glycol to the dimethylolpropionic acid to the toluene diisocyanate is 1: 1-3: 3-5, and the volume-mass ratio of the stannous octoate (mL) to the butanone (mL) is 1: 20-30.
(6) Chain extension: and (3) cooling the reaction kettle in the step (5) to 40-45 ℃, adding monohydroxy acrylic acid for 2-4 times in 1-1.5 h, heating to 60-80 ℃, and carrying out heat preservation reaction for 1-2 h.
Preferably, the molar ratio of the monohydroxyacrylic acid to the dimethylolpropionic acid is 1: 1-2.
(7) Emulsification: and (3) adding a certain amount of deionized water into the solution obtained in the step (6) under the action of high shear force in an emulsification pump, carrying out reverse emulsification, and simultaneously dropwise adding triethylamine for neutralization.
Preferably, the shear rate of the emulsification pump is 6000-15000 r/min;
(8) solvent removal: and (4) removing butanone from the emulsion obtained in the step (7) by adopting a reduced pressure low temperature distillation method to obtain the waterborne polyurethane emulsion.
(9) Mixing the emulsion: and (3) mixing the O/W type wool keratin emulsion prepared in the step (4) with the aqueous polyurethane emulsion prepared in the step (8), and stirring the mixed solution on a high-speed dispersion homogenizer for 0.5-1 h at the stirring temperature of 40-45 ℃ to obtain the wool keratin/aqueous polyurethane composite emulsion coating agent with the warm-keeping function.
Preferably, the volume ratio of the O/W type wool keratin emulsion prepared in the step (4) to the aqueous polyurethane emulsion prepared in the step (8) is 1: 5-7.
The invention has the following remarkable characteristics:
(1) after the wool keratin/waterborne polyurethane composite emulsion coating agent prepared by the invention is used for coating finishing of cotton fabrics, the heat preservation rate of the cotton fabrics is increased from 24.7% to more than 66%, which indicates that the coating agent has a good heat preservation function.
(2) According to the invention, the wool keratin emulsion and the aqueous polyurethane emulsion are mixed, so that the prepared wool keratin/aqueous polyurethane composite emulsion coating agent has stable performance, and does not delaminate after being placed for 90 days.
(3) The raw material source of the wool keratin/waterborne polyurethane composite emulsion coating agent is wide, and the waste wool is efficiently applied; in addition, the waterborne polyurethane coating agent is further modified, so that the performance of the waterborne polyurethane coating agent is obviously improved.
(4) The preparation process is simple, the production process has no pollution to the environment, and the method is favorable for further popularization and application.
Detailed Description
The examples described below illustrate the invention in detail.
Example 1
In this embodiment, the wool keratin/aqueous polyurethane composite emulsion coating agent with a warm-keeping function is prepared by the following method, including the following steps:
(1) selecting waste wool: the waste clothes made of wool are selected, washed by a clothes washing agent, washed by a large amount of water and dried.
(2) Preparation of wool keratin solution: and (2) dissolving 10g of waste clothes treated in the step (1) in a mixed solution of 150mL of tricarboxyethylphosphine and 15g of urea at 70 ℃, continuously stirring in the dissolving process, wherein the dissolving time is 5h, filtering, and concentrating to obtain a wool keratin solution, wherein the solid content of the wool keratin solution is 48.7%.
(3) Preparation of wool keratin powder: freeze-drying the wool keratin solution prepared in the step (2) on a freeze dryer at the following freezing temperature: -55 ℃, drying time: and (4) 14h, preparing the wool keratin powder.
(4) Preparation of O/W emulsion: adding 10g of wool keratin solid into a round-bottom flask, adding 75 mLN-methylmorpholine, and continuously stirring and completely dissolving the wool keratin solid at 40 ℃ on a constant-temperature electromagnetic stirrer; after the wool keratin is completely dissolved, adding 1.5g of span 60 into the mixed solution, and stirring to uniformly mix the mixture; adding the mixed solution into 225mL of saturated sodium dodecyl sulfate aqueous solution, and uniformly stirring by using a magnetic rotor to obtain the O/W type wool keratin emulsion.
(5) Pre-polymerization: adding 0.1mol of polypropylene glycol with the molecular weight of 200 and 0.2mol of dimethylolpropionic acid into a reaction kettle, dehydrating for 1.5h under vacuum at 110 ℃, slowly cooling to 55 ℃, dropwise adding a mixed solution of 0.4mol of toluene diisocyanate, 25mL of butanone and 1mL of catalyst stannous octoate, heating to 85 ℃, and reacting for 3.5 h.
(6) Chain extension: and (3) cooling the reaction kettle in the step (5) to 43 ℃, adding 0.13mol of monohydroxy acrylic acid into the reaction kettle for 1.2h in 3 times, heating to 70 ℃, and reacting for 1.5h under the condition of heat preservation.
(7) Emulsification: and (3) adding 300mL of deionized water into the solution obtained in the step (6) under the action of high shear force in an emulsification pump with the shear rate of 9000r/min for reverse emulsification, and simultaneously dropwise adding triethylamine for neutralization.
(8) Solvent removal: and (4) removing butanone from the emulsion obtained in the step (7) by adopting a reduced pressure low temperature distillation method to obtain the waterborne polyurethane emulsion.
(9) Mixing the emulsion: mixing 100mL of the O/W type wool keratin emulsion prepared in the step (4) with 600mL of the aqueous polyurethane emulsion prepared in the step (8), and stirring the mixed solution on a high-speed dispersion homogenizer for 0.75h at the stirring temperature of 43 ℃ to obtain the wool keratin/aqueous polyurethane composite emulsion coating agent a with the heat preservation function.
Example 2
In this embodiment, the wool keratin/aqueous polyurethane composite emulsion coating agent with a warm-keeping function is prepared by the following method, including the following steps:
(1) selecting waste wool: the waste clothes made of wool are selected, washed by a clothes washing agent, washed by a large amount of water and dried.
(2) Preparation of wool keratin solution: dissolving 10g of waste clothes treated in the step (1) in 100mL of mixed solution of tricarboxyethylphosphine and 10g of urea at 60 ℃, continuously stirring in the dissolving process, wherein the dissolving time is 4h, filtering, and concentrating to obtain a wool keratin solution, wherein the solid content of the wool keratin solution is 43.5%.
(3) Preparation of wool keratin powder: freeze-drying the wool keratin solution prepared in the step (2) on a freeze dryer at the following freezing temperature: -50 ℃ and drying time: and (4) obtaining the wool keratin powder after 18 hours.
(4) Preparation of O/W emulsion: adding 10g of wool keratin solid into a round-bottom flask, adding 50 mLN-methylmorpholine, and continuously stirring and completely dissolving the wool keratin solid at 40 ℃ on a constant-temperature electromagnetic stirrer; after the wool keratin is completely dissolved, adding 0.5g of span 60 into the mixed solution, and stirring to uniformly mix the mixed solution; adding the mixed solution into 120mL of saturated sodium dodecyl sulfate aqueous solution, and uniformly stirring by using a magnetic rotor to obtain the O/W type wool keratin emulsion.
(5) Pre-polymerization: adding 0.1mol of polypropylene glycol with the molecular weight of 200 and 0.1mol of dimethylolpropionic acid into a reaction kettle, dehydrating for 1.5h under vacuum at 110 ℃, slowly cooling to 50 ℃, dropwise adding a mixed solution of 0.3mol of toluene diisocyanate, 20mL of butanone and 1mL of catalyst stannous octoate, heating to 85 ℃, and reacting for 3 h.
(6) Chain extension: and (3) cooling the reaction kettle in the step (5) to 40 ℃, adding 0.1mol of monohydroxy acrylic acid into the reaction kettle for 1 hour in 2 times, heating to 70 ℃, and reacting for 1.5 hours under the condition of heat preservation.
(7) Emulsification: and (3) adding 250mL of deionized water into the solution obtained in the step (6) under the action of high shear force in an emulsification pump with the shear rate of 6000r/min for reverse emulsification, and simultaneously dropwise adding triethylamine for neutralization.
(8) Solvent removal: and (4) removing butanone from the emulsion obtained in the step (7) by adopting a reduced pressure low temperature distillation method to obtain the waterborne polyurethane emulsion.
(9) Mixing the emulsion: and (3) mixing 100mL of the O/W type wool keratin emulsion prepared in the step (4) with 500mL of the aqueous polyurethane emulsion prepared in the step (8), and stirring the mixed solution on a high-speed dispersion homogenizer for 0.75h at the stirring temperature of 43 ℃ to obtain the wool keratin/aqueous polyurethane composite emulsion coating agent b with the heat preservation function.
Example 3
In this embodiment, the wool keratin/aqueous polyurethane composite emulsion coating agent with a warm-keeping function is prepared by the following method, including the following steps:
(1) selecting waste wool: the waste clothes made of wool are selected, washed by a clothes washing agent, washed by a large amount of water and dried.
(2) Preparation of wool keratin solution: dissolving 10g of waste clothes treated in the step (1) in 200mL of mixed solution of tricarboxyethylphosphine and 20g of urea at 80 ℃, continuously stirring in the dissolving process, wherein the dissolving time is 6h, filtering, and concentrating to obtain a wool keratin solution, wherein the solid content of the wool keratin solution is 60.3%.
(3) Preparation of wool keratin powder: freeze-drying the wool keratin solution prepared in the step (2) on a freeze dryer at the following freezing temperature: -60 ℃ and drying time: and (4) obtaining the wool keratin powder after 18 hours.
(4) Preparation of O/W emulsion: adding 10g of wool keratin solid into a round-bottom flask, adding 100 mLN-methylmorpholine, and continuously stirring and completely dissolving the wool keratin solid at 40 ℃ on a constant-temperature electromagnetic stirrer; after the wool keratin is completely dissolved, adding 3g of span 60 into the mixed solution, and stirring to uniformly mix the mixture; the mixed solution is added into 350mL of saturated sodium dodecyl sulfate aqueous solution, and the mixture is uniformly stirred by a magnetic rotor to obtain O/W type wool keratin emulsion.
(5) Pre-polymerization: adding 0.1mol of polypropylene glycol with the molecular weight of 200 and 0.3mol of dimethylolpropionic acid into a reaction kettle, dehydrating for 1.5h under vacuum at 120 ℃, slowly cooling to 55 ℃, dropwise adding a mixed solution of 0.5mol of toluene diisocyanate, 30mL of butanone and 1mL of catalyst stannous octoate, heating to 90 ℃, and reacting for 4 h.
(6) Chain extension: and (3) cooling the reaction kettle in the step (5) to 45 ℃, adding 0.15mol of monohydroxy acrylic acid into the reaction kettle for 1.2h in 3 times, heating to 70 ℃, and reacting for 1.5h under the condition of heat preservation.
(7) Emulsification: and (3) adding 400mL of deionized water into the solution obtained in the step (6) under the action of high shear force in an emulsification pump with the shear rate of 15000r/min for reverse emulsification, and simultaneously dropwise adding triethylamine for neutralization.
(8) Solvent removal: and (4) removing butanone from the emulsion obtained in the step (7) by adopting a reduced pressure low temperature distillation method to obtain the waterborne polyurethane emulsion.
(9) Mixing the emulsion: and (3) mixing 100mL of the O/W type wool keratin emulsion prepared in the step (4) with 700mL of the aqueous polyurethane emulsion prepared in the step (8), and stirring the mixed solution on a high-speed dispersion homogenizer for 0.75h at the stirring temperature of 43 ℃ to obtain the wool keratin/aqueous polyurethane composite emulsion coating agent c with the heat preservation function.
Application performance examples:
the wool keratin/waterborne polyurethane composite emulsion coating agents a, b and c prepared in the embodiments 1-3 are used for coating finishing of cotton fabrics: tightening the cotton fabric on a tightening frame, uniformly coating the coating agent on the cotton fabric by using a scraper, wherein the coating weight and dry weight are 20-25 g/m2Drying at 90 ℃ for 2 minutes, and baking at 150 ℃ for 3 minutes to prepare the cotton fabric finished by the wool keratin/waterborne polyurethane composite emulsion coating agents a, b and c.
Testing the heat preservation performance: according to the requirements of a method A in a textile thermal insulation performance test method (GB 11048-89), the insulation rate of cotton fabrics finished by the wool keratin/waterborne polyurethane composite emulsion coating agents a, b and c is tested by adopting a YG606 type flat-plate type thermal insulation instrument. During the test, a sample with the size of 300mm multiplied by 300mm is covered on a test board with the size of 250mm multiplied by 250mm, the constant temperature is kept in a power-on and power-off mode, the heating time required for keeping the constant temperature of the test board in a certain time is measured, and the sample heat preservation rate is calculated. The test results are shown in the following table:
as can be seen from the table, the heat preservation rate of the cotton fabrics finished by the wool keratin/waterborne polyurethane composite emulsion coating agents a, b and c prepared by the invention is more than 66 percent and is obviously higher than that of the cotton fabrics which are not finished. This indicates that: the wool keratin/waterborne polyurethane composite emulsion coating agents a, b and c prepared by the invention have good warm-keeping function.
Claims (3)
1. The wool keratin/waterborne polyurethane composite emulsion coating agent with the warm-keeping function is characterized by being prepared by the following method: taking waste wool as a raw material, and extracting wool keratin from the waste wool; then preparing keratin into O/W type wool keratin emulsion; the aqueous polyurethane emulsion is prepared, and the wool keratin emulsion and the aqueous polyurethane emulsion are compounded and mixed to prepare the wool keratin/aqueous polyurethane composite emulsion coating agent with the warm-keeping function.
2. The preparation method of the wool keratin/waterborne polyurethane composite emulsion coating agent with the warm-keeping function of claim 1, which is characterized by comprising the following steps:
(1) selecting waste wool: selecting waste clothes made of wool, cleaning the clothes with a clothes cleaning agent, cleaning with a large amount of water, and drying;
(2) preparation of wool keratin solution: dissolving the waste clothes treated in the step (1) in a mixed solution of tricarboxyethylphosphine and urea at the temperature of 60-80 ℃, continuously stirring in the dissolving process, wherein the dissolving time is 4-6 h, filtering, and concentrating to obtain a wool keratin solution, wherein the solid content of the wool keratin solution is 40-60%; the volume-mass ratio of the waste wool (g), the tricarboxyethylphosphine (mL) and the urea (g) is 1: 10-20: 1-2;
(3) preparation of wool keratin powder: freeze-drying the wool keratin solution prepared in the step (2) on a freeze dryer to prepare wool keratin powder; the freezing temperature is as follows: -50 to-60 ℃, and the drying time is as follows: 10-18 h;
(4) preparation of O/W emulsion: adding wool keratin solid into a round-bottom flask, adding N-methylmorpholine, and continuously stirring and completely dissolving the wool keratin solid at 40 ℃ on a constant-temperature electromagnetic stirrer; after the wool keratin is completely dissolved, adding the mixed solution into span 60, and stirring to uniformly mix the mixed solution; adding the mixed solution into saturated sodium dodecyl sulfate aqueous solution, and uniformly stirring by using a magnetic rotor to obtain O/W type wool keratin emulsion; the solid-to-liquid ratio of the wool keratin (g) to the N-methylmorpholine (mL) is as follows: 1: 5-10; the dosage ratio of the span 60 to the N-methylmorpholine is as follows: 1-3%; the dosage ratio of the mixed solution (mL) to the saturated sodium dodecyl sulfate aqueous solution (mL) is 1: 2-4;
(5) pre-polymerization: adding polypropylene glycol and dimethylolpropionic acid into a reaction kettle, dehydrating for 1-2 hours in vacuum at 100-120 ℃, slowly cooling to 50-60 ℃, dropwise adding a mixed solution of toluene diisocyanate, butanone and catalyst stannous octoate, heating to 80-90 ℃, and reacting for 3-4 hours; the molecular weight of the polypropylene glycol is 200; the molar ratio of the polypropylene glycol to the dimethylolpropionic acid to the toluene diisocyanate is 1: 1-3: 3-5; the volume-mass ratio of the stannous octoate (mL) to the butanone (mL) is 1: 20-30;
(6) chain extension: cooling the reaction kettle in the step (5) to 40-45 ℃, adding monohydroxy acrylic acid for 2-4 times in 1-1.5 h, heating to 60-80 ℃, and carrying out heat preservation reaction for 1-2 h; the molar ratio of the monohydroxy acrylic acid to the dimethylolpropionic acid is 1: 1-2;
(7) emulsification: adding a certain amount of deionized water into the solution obtained in the step (6) under the action of high shear force in an emulsification pump with the shear rate of 6000-15000 r/min, carrying out reverse emulsification, and simultaneously dropwise adding triethylamine for neutralization;
(8) solvent removal: removing butanone from the emulsion obtained in the step (7) by adopting a reduced pressure low temperature distillation method to obtain a waterborne polyurethane emulsion;
(9) mixing the emulsion: and (3) mixing the O/W type wool keratin emulsion prepared in the step (4) with the aqueous polyurethane emulsion prepared in the step (8), and stirring the mixed solution on a high-speed dispersion homogenizer for 0.5-1 h at the stirring temperature of 40-45 ℃ to obtain the wool keratin/aqueous polyurethane composite emulsion coating agent with the warm-keeping function.
3. The preparation method of the wool keratin/aqueous polyurethane composite emulsion coating agent with the warm-keeping function according to claim 2, characterized in that: the volume ratio of the O/W type wool keratin emulsion prepared in the step (4) in the step (9) to the aqueous polyurethane emulsion prepared in the step (8) is 1: 5-7.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471316A (en) * | 2020-03-19 | 2020-07-31 | 当阳市鸿阳新材料科技有限公司 | Extraction method of microbial pigment and method for dyeing lyocell fibers by using microbial pigment |
| CN113355914A (en) * | 2021-06-29 | 2021-09-07 | 武汉纺织大学 | Wool fabric shrink-proof finishing liquid containing lignin, and preparation method and application thereof |
| CN113622190A (en) * | 2021-08-06 | 2021-11-09 | 武汉纺织大学 | Leather-imitated color functional yarn for clothing and preparation method thereof |
| CN115785770A (en) * | 2022-11-25 | 2023-03-14 | 武汉纺织大学 | Paint doped with wool powder and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171877A (en) * | 2001-11-30 | 2003-06-20 | Kyoeisha Chem Co Ltd | Method for treating textile product |
| CN101585903A (en) * | 2009-06-23 | 2009-11-25 | 丽水市优耐克水性树脂科技有限公司 | A kind of aqueous polyurethane and preparation method thereof |
| CN102391459A (en) * | 2011-08-25 | 2012-03-28 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for modified polyurethane |
| CN104017230A (en) * | 2014-06-13 | 2014-09-03 | 东华大学 | Preparation method of polyurethane-keratin composite film |
| CN108360264A (en) * | 2018-04-04 | 2018-08-03 | 常州五荣化工有限公司 | A kind of preparation method of waterproof ventilating type weaving polyurethane coating agent |
| CN108589302A (en) * | 2018-05-28 | 2018-09-28 | 江苏阳光股份有限公司 | A kind of preparation method of wool keratin polyurethane comixing dressing liquid |
| CN109023713A (en) * | 2018-08-29 | 2018-12-18 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of superfine fiber synthetic leather base cloth |
| CN109322166A (en) * | 2018-11-20 | 2019-02-12 | 武汉纺织大学 | A kind of preparation method and application of radix saposhnikoviae dacron coating agent |
| CN109518474A (en) * | 2018-11-20 | 2019-03-26 | 武汉纺织大学 | A kind of preparation method of heat insulation type cotton fabric coating |
-
2019
- 2019-10-06 CN CN201910946652.7A patent/CN110685170B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003171877A (en) * | 2001-11-30 | 2003-06-20 | Kyoeisha Chem Co Ltd | Method for treating textile product |
| CN101585903A (en) * | 2009-06-23 | 2009-11-25 | 丽水市优耐克水性树脂科技有限公司 | A kind of aqueous polyurethane and preparation method thereof |
| CN102391459A (en) * | 2011-08-25 | 2012-03-28 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for modified polyurethane |
| CN104017230A (en) * | 2014-06-13 | 2014-09-03 | 东华大学 | Preparation method of polyurethane-keratin composite film |
| CN108360264A (en) * | 2018-04-04 | 2018-08-03 | 常州五荣化工有限公司 | A kind of preparation method of waterproof ventilating type weaving polyurethane coating agent |
| CN108589302A (en) * | 2018-05-28 | 2018-09-28 | 江苏阳光股份有限公司 | A kind of preparation method of wool keratin polyurethane comixing dressing liquid |
| CN109023713A (en) * | 2018-08-29 | 2018-12-18 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of superfine fiber synthetic leather base cloth |
| CN109322166A (en) * | 2018-11-20 | 2019-02-12 | 武汉纺织大学 | A kind of preparation method and application of radix saposhnikoviae dacron coating agent |
| CN109518474A (en) * | 2018-11-20 | 2019-03-26 | 武汉纺织大学 | A kind of preparation method of heat insulation type cotton fabric coating |
Non-Patent Citations (1)
| Title |
|---|
| 张晶等: "端乙烯基水性聚氨酯乳液的合成研究", 《化学推进剂与高分子材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471316A (en) * | 2020-03-19 | 2020-07-31 | 当阳市鸿阳新材料科技有限公司 | Extraction method of microbial pigment and method for dyeing lyocell fibers by using microbial pigment |
| CN113355914A (en) * | 2021-06-29 | 2021-09-07 | 武汉纺织大学 | Wool fabric shrink-proof finishing liquid containing lignin, and preparation method and application thereof |
| CN113355914B (en) * | 2021-06-29 | 2022-07-22 | 武汉纺织大学 | Lignin-containing wool fabric shrink-proof finishing liquid and preparation method and application thereof |
| CN113622190A (en) * | 2021-08-06 | 2021-11-09 | 武汉纺织大学 | Leather-imitated color functional yarn for clothing and preparation method thereof |
| CN115785770A (en) * | 2022-11-25 | 2023-03-14 | 武汉纺织大学 | Paint doped with wool powder and preparation method thereof |
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