CN111101384A - Preparation method of super-hydrophobic ecological environment-friendly microfiber leather - Google Patents
Preparation method of super-hydrophobic ecological environment-friendly microfiber leather Download PDFInfo
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- 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
- D06N3/147—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 characterised by the isocyanates used
- D06N3/148—(cyclo)aliphatic polyisocyanates
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- 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
- D06N3/0004—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 ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/0011—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 non-woven fabrics
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- 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
- D06N3/0036—Polyester fibres
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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- 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
- D06N3/146—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 characterised by the macromolecular diols used
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- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
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- D06N2209/108—Slipping, anti-blocking, low friction
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Abstract
The invention relates to the technical field of synthetic leather preparation, and provides a preparation method of super-hydrophobic ecological environment-friendly microfiber leather, which solves the problem that microfiber leather produced by using aqueous polyurethane in the prior art is insufficient in water resistance and comprises the following steps: 1) preparing base cloth; 2) preparing a super-hydrophobic polyurethane emulsion; 3) and (5) dipping and drying.
Description
Technical Field
The invention relates to the technical field of synthetic leather preparation, in particular to a preparation method of super-hydrophobic ecological environment-friendly microfiber leather.
Background
The leather product has the characteristics of firmness, durability, elegance, comfort and the like, and is widely applied to the industries of luggage leather, sofa leather, clothes, furniture and the like. Natural leather, as the earliest leather product raw material, is widely used because of its advantages of softness, wear resistance, high strength, high hygroscopicity and comfort. With the development of society. The demand of human beings for leather has been increasing, and natural leather has not been able to satisfy people's demand. At this time, the artificial leather is produced, the application field of the artificial leather is continuously expanded, the artificial leather is increasingly determined by the market, the application range is wide, the variety is large, and the artificial leather cannot be met by the traditional natural leather. The artificial leather has undergone the third generation development, the first generation is PVC artificial leather, which is a leather-like plastic product obtained by coating or attaching a mixture consisting of polyvinyl chloride resin, plasticizer, stabilizer and the like on the basic material; the second generation artificial leather is PU synthetic leather, which is a leather-like plastic product obtained by basically coating or attaching a mixture consisting of polyurethane, an auxiliary agent, a filler and the like; the third generation artificial leather is superfine fiber synthetic leather (called superfine fiber leather for short), which is prepared by preparing superfine fiber short fibers into non-woven fabric with a three-dimensional structure network through carding and needling, and then performing polyurethane impregnation, decrement extraction and after-finishing processes. The microfiber leather is comparable to natural leather in all aspects and can be completely used as a substitute of high-grade natural leather.
In the production of microfiber leather in the prior art, a wet coagulation process is commonly adopted, wherein the wet coagulation process is to impregnate or coat a non-woven fabric with solvent type polyurethane slurry, the solvent type polyurethane slurry takes polyurethane and dimethyl formamide (DMF) as main components, and then DMF and H are fed into the solvent type polyurethane slurry2And in the solidification liquid with O as the main component, polyurethane is solidified to form a filling body or a coating with a micropore structure. The principle of polyurethane solidification is based on the reaction of polyurethane with H2O is incompatible, and DMF and H2O is unrestrictedly miscible with each other, so that DMF and H2Mutual substitution between O and DMF by H2O is extracted out, so that the polyurethane macromolecules solidify as DMF is continuously reduced. The traditional wet solidification process has two problems, one is that an organic solvent DMF is adopted, and the processing process is easy to cause environmental pollution; second is H2O cannot completely replace DMF in the polyurethane, and residual DMF influences the quality and safety of the product. At present, the most researched technology is the water-based polyurethane technology which is used for replacing solvent-based polyurethane to produce environment-friendly microfiber leather. The application of the waterborne polyurethane in the production of the microfiber leather also has the defect that hydrophilic groups are introduced into molecular chain segments of the waterborne polyurethane, so that the water resistance of the waterborne polyurethane is reduced, and the quality of microfiber leather products is influenced.
Disclosure of Invention
Therefore, aiming at the content, the invention provides a preparation method of super-hydrophobic ecological environment-friendly microfiber leather, and solves the problem that microfiber leather produced by using aqueous polyurethane in the prior art is insufficient in water resistance.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of super-hydrophobic ecological environment-friendly microfiber leather comprises the following steps:
1) preparation of the base Fabric
Uniformly mixing polylactic acid fiber, polycaprolactone fiber, chitosan and modified nano silicon dioxide, adding the mixture into a screw extruder for melt extrusion, and stretching and heat setting to prepare polylactic acid/polycaprolactone sea-island fiber;
sequentially opening the prepared polylactic acid/polycaprolactone sea-island fibers by an opener and carding by a carding machine to form a web, finally needling the web by using the needles on a needling machine, and repeatedly interweaving and piercing and reinforcing the barbed needles to prepare the base fabric;
2) preparation of super-hydrophobic polyurethane emulsion
Adding diphenylmethane-4, 4' -diisocyanate, dihydroxy polyether and acetone as solvents into a reactor, carrying out prepolymerization reaction for 1.5-2.5 h at 75-85 ℃, then cooling a reaction system to 40-50 ℃, gradually adding aliphatic diol, heating to 70-80 ℃, reacting for 40-80 min, and then adding 2-hydroxy-2-butyl acrylate to react for 25-50 min to obtain an aqueous polyurethane prepolymer;
adding deionized water, an emulsifier and an initiator into the aqueous polyurethane prepolymer, carrying out high-speed shearing emulsification for 30-50 min, then adding perfluoroalkyl ethyl acrylate for carrying out polymerization reaction for 2-4 h, and finally carrying out reduced pressure distillation to remove acetone to prepare a super-hydrophobic polyurethane emulsion;
3) dipping and drying treatment
Soaking the base fabric prepared in the step 1) into a soaking tank filled with super-hydrophobic polyurethane slurry, wherein the super-hydrophobic polyurethane slurry comprises the following raw materials in parts by weight: 42-56 parts of super-hydrophobic polyurethane emulsion, 3-6 parts of aqueous thickening agent, 0.8-1.5 parts of polyether modified siloxane, 1-3 parts of penetrating agent, 1.2-1.8 parts of aqueous defoaming agent, 5-10 parts of aqueous black paste and 15-25 parts of calcium carbonate;
taking the base cloth out of the dipping tank, removing redundant super-hydrophobic polyurethane slurry on the surface of the base cloth by using a scraper, then placing the base cloth into an oven, and drying for 30-50 min at 85-105 ℃;
and (3) drying the base cloth, and then washing with an organic solvent, washing with water, and drying to obtain the super-hydrophobic ecological environment-friendly microfiber leather.
The further improvement is that: the specific preparation method of the modified nano silicon dioxide comprises the following steps: weighing a certain amount of nano silicon dioxide, adding a toluene solvent, and stirring, wherein the mass ratio of the nano silicon dioxide to the toluene is 1: and 5, slowly adding a silane coupling agent with the mass fraction of 5% of nano silicon dioxide under ultrasonic oscillation, stirring and reacting for 3-5 h at the temperature of 60-80 ℃, washing with water, carrying out suction filtration, and drying to obtain the modified nano silicon dioxide.
The further improvement is that: the weight ratio of the polylactic acid fiber, the polycaprolactone fiber, the chitosan and the modified nano silicon dioxide in the step 1) is 50-70: 30-50: 8-12: 18 to 30.
The further improvement is that: the shearing rate in the step 2) is 1500-2500 r/min.
The further improvement is that: the step 2) comprises the following raw materials in parts by weight: 12-18 parts of diphenylmethane-4, 4' -diisocyanate, 50-75 parts of dihydroxy polyether, 80-100 parts of acetone, 4-6 parts of aliphatic diol, 6-8 parts of 2-hydroxy-2-butyl acrylate, 1.5-2.0 parts of an emulsifier, 0.9-1.5 parts of an initiator, 15-18 parts of perfluoroalkyl ethyl acrylate and 42-56 parts of deionized water.
The further improvement is that: the viscosity of the super-hydrophobic polyurethane slurry in the step 3) is controlled within the range of 6-12 Pa.s.
The further improvement is that: in the step 2), the aliphatic diol is any one of 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol and 1, 8-octanediol.
The further improvement is that: the organic solvent used for washing after the base cloth is dried in the step 3) is dimethylbenzene.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the microfiber leather prepared by the invention belongs to an ecological environment-friendly material, and is specifically represented as follows: (1) the base cloth is prepared by using degradable fiber raw materials, namely polylactic acid fiber and polycaprolactone fiber, and the degradation products can not cause new pollution to the environment; (2) compared with solvent type polyurethane slurry, the super-hydrophobic polyurethane slurry is used for impregnating the base cloth, so that the use of a large amount of organic solvent is reduced, the discharge of waste gas and waste water generated by the organic solvent in the production process is avoided, the environmental pollution is avoided in the production and manufacturing process, the requirements of ecological environment protection are met, the physical health of operators is not harmed, and the quality of the produced super-fiber leather product is ensured.
2. The super-hydrophobic polyurethane emulsion is prepared on the premise of not changing the excellent performance of polyurethane, and the water resistance of the polyurethane is improved. The produced microfiber leather is subjected to a series of post-finishing processes such as dyeing, buffing and the like, so that final products with different purposes and various styles can be obtained, the post-finishing process requires that polyurethane on the surface of the microfiber leather has good water resistance, high temperature resistance and other functions, common waterborne polyurethane cannot meet the requirements of the post-finishing process and cannot replace solvent type polyurethane, and after the prepared superhydrophobic polyurethane emulsion is used for surface treatment of base cloth, the obtained microfiber leather can be subjected to the post-finishing process to produce various high-quality leather products.
3. The preparation method of the super-hydrophobic polyurethane emulsion comprises the following steps: (1) adding diphenylmethane-4, 4' -diisocyanate, dihydroxy polyether and acetone as solvents into a reactor, carrying out prepolymerization reaction for 1.5-2.5 h at 75-85 ℃, then cooling a reaction system to 40-50 ℃, gradually adding aliphatic diol, heating to 70-80 ℃, reacting for 40-80 min, and then adding 2-hydroxy-2-butyl acrylate to react for 25-50 min to obtain an aqueous polyurethane prepolymer; (2) adding deionized water, an emulsifier, an initiator and a catalyst into the waterborne polyurethane prepolymer, carrying out high-speed shearing emulsification for 30-50 min, then adding perfluoroalkyl ethyl acrylate for carrying out polymerization reaction for 2-4 h, and finally carrying out reduced pressure distillation to remove acetone to prepare the super-hydrophobic polyurethane emulsion. The invention takes diphenylmethane-4, 4' -diisocyanate and dihydroxy polyether as raw materials to carry out prepolymerization reaction; then adding aliphatic diol to extend molecular chain diffusion, obviously increase molecular mass and improve mechanical property of the product and viscosity of the system; and then adding 2-hydroxy-2-butyl acrylate to obtain a double-bond-containing waterborne polyurethane prepolymer, shearing the waterborne polyurethane prepolymer in a water medium at a high speed to form an initial emulsion, adding perfluoroalkyl ethyl acrylate, and carrying out free radical polymerization under the action of an initiator and a catalyst to finally form the super-hydrophobic polyurethane emulsion. After free radical polymerization, a fluorine-containing chain segment is grafted in a polyurethane molecular chain, and the organic combination of the fluorine-containing chain segment and the polyurethane molecular chain can fully exert respective performance advantages, so that the emulsion has good hydrophobicity, low surface energy and good lubricity.
4. The polylactic acid fiber lacks hydrophilic groups in the molecular structure and shows good hydrophobicity, and the surface of the base fabric prepared by the polylactic acid fiber generates certain hydrophobicity, so that the overall hydrophobic effect of the microfiber leather material can be improved. The silane coupling agent is utilized to modify the surface of the nano silicon dioxide, so that the surface energy of the nano silicon dioxide is reduced, the nano silicon dioxide can be fully mixed with polylactic acid fiber, polycaprolactone fiber and chitosan, and the rigidity and heat resistance of the base fabric can be improved while the production cost of the base fabric is reduced. .
Detailed Description
The following detailed description will be provided for the embodiments of the present invention with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagents used are indicated at the first appearance.
Example one
A preparation method of super-hydrophobic ecological environment-friendly microfiber leather comprises the following steps:
1) preparation of the base Fabric
Uniformly mixing polylactic acid fiber, polycaprolactone fiber, chitosan and modified nano-silica, adding the mixture into a screw extruder for melt extrusion, and stretching and heat setting to prepare the polylactic acid/polycaprolactone sea-island fiber, wherein the weight ratio of the polylactic acid fiber to the polycaprolactone fiber to the chitosan to the modified nano-silica is 50: 50: 8: 30, the specific preparation method of the modified nano silicon dioxide comprises the following steps: weighing a certain amount of nano silicon dioxide, adding a toluene solvent, and stirring, wherein the mass ratio of the nano silicon dioxide to the toluene is 1: slowly adding a silane coupling agent KH-550 with the mass fraction of 5% of nano-silica under ultrasonic oscillation, stirring at 60 ℃ for reaction for 5 hours, washing with water, performing suction filtration, and drying to obtain modified nano-silica;
sequentially opening the prepared polylactic acid/polycaprolactone sea-island fibers by an opener and carding by a carding machine to form a web, finally needling the web by using the needles on a needling machine, and repeatedly interweaving and piercing and reinforcing the barbed needles to prepare the base fabric;
2) preparation of super-hydrophobic polyurethane emulsion
Adding 12 parts of diphenylmethane-4, 4' -diisocyanate, 50 parts of dihydroxy polyether N-210 and 80 parts of acetone serving as a solvent into a reactor, carrying out prepolymerization reaction for 2.5 hours at 75 ℃, then cooling a reaction system to 40 ℃, gradually adding 4 parts of 1, 5-pentanediol, heating to 70 ℃, reacting for 80min, and then adding 6 parts of 2-hydroxy-2-butyl acrylate, and reacting for 25min to obtain an aqueous polyurethane prepolymer;
adding 42 parts of deionized water, 1.5 parts of nonylphenol polyoxyethylene ether and 1.2 parts of azodiisobutyl imidazoline hydrochloride into the aqueous polyurethane prepolymer, carrying out high-speed shearing emulsification at 1500r/min for 30min, then adding 15 parts of perfluoroalkyl ethyl acrylate for carrying out polymerization reaction for 2h, and finally carrying out reduced pressure distillation to remove acetone to prepare the super-hydrophobic polyurethane emulsion;
3) dipping and drying treatment
Soaking the base fabric prepared in the step 1) into a soaking tank filled with super-hydrophobic polyurethane slurry, wherein the super-hydrophobic polyurethane slurry comprises the following raw materials in parts by weight: 42 parts of super-hydrophobic polyurethane emulsion, 3 parts of aqueous thickening agent (manufactured by Denzhou chemical technology Co., Ltd., model N-906), 1.5 parts of polyether modified siloxane (manufactured by Orna polymer Co., Ltd., model F340), 1 part of penetrating agent JFC, 1.5 parts of aqueous defoaming agent (manufactured by Guangzhou Tianfeng defoaming agent Co., Ltd., model F-326), 7 parts of aqueous black paste (Xinshuo chemical Co., Ltd.), and 25 parts of calcium carbonate, wherein the viscosity of the super-hydrophobic polyurethane slurry is controlled within the range of 6-12 Pa.s;
taking the base cloth out of the dipping tank, removing redundant super-hydrophobic polyurethane slurry on the surface of the base cloth by using a scraper, then placing the base cloth into an oven, and drying for 50min at 85 ℃;
and after drying the base fabric, carrying out xylene washing, water washing and drying to obtain the super-hydrophobic ecological environment-friendly microfiber leather.
Example two
A preparation method of super-hydrophobic ecological environment-friendly microfiber leather comprises the following steps:
1) preparation of the base Fabric
Uniformly mixing polylactic acid fiber, polycaprolactone fiber, chitosan and modified nano-silica, adding the mixture into a screw extruder for melt extrusion, and stretching and heat setting to prepare the polylactic acid/polycaprolactone sea-island fiber, wherein the weight ratio of the polylactic acid fiber to the polycaprolactone fiber to the chitosan to the modified nano-silica is 60: 40: 10: 24, the specific preparation method of the modified nano silicon dioxide comprises the following steps: weighing a certain amount of nano silicon dioxide, adding a toluene solvent, and stirring, wherein the mass ratio of the nano silicon dioxide to the toluene is 1: slowly adding a silane coupling agent KH-560 with the mass fraction of 5% of nano-silica under ultrasonic oscillation, stirring at 70 ℃ for reacting for 4 hours, washing with water, performing suction filtration, and drying to obtain modified nano-silica;
sequentially opening the prepared polylactic acid/polycaprolactone sea-island fibers by an opener and carding by a carding machine to form a web, finally needling the web by using the needles on a needling machine, and repeatedly interweaving and piercing and reinforcing the barbed needles to prepare the base fabric;
2) preparation of super-hydrophobic polyurethane emulsion
Adding 15 parts of diphenylmethane-4, 4' -diisocyanate, 60 parts of dihydroxy polyether N-210 and 90 parts of acetone serving as a solvent into a reactor, carrying out prepolymerization reaction for 2 hours at the temperature of 80 ℃, then cooling a reaction system to 45 ℃, gradually adding 5 parts of 3-methyl-1, 5-pentanediol, heating to 75 ℃, reacting for 60 minutes, and then adding 7 parts of 2-hydroxy-2-butyl acrylate, and reacting for 35 minutes to obtain an aqueous polyurethane prepolymer;
adding 50 parts of deionized water, 1.8 parts of nonylphenol polyoxyethylene ether and 1.5 parts of 1.2 parts of azodiisobutyl imidazoline hydrochloride into the aqueous polyurethane prepolymer, carrying out high-speed shearing emulsification at 2000r/min for 40min, then adding 16 parts of perfluoroalkyl ethyl acrylate to carry out polymerization reaction for 3h, and finally carrying out reduced pressure distillation to remove acetone to prepare a super-hydrophobic polyurethane emulsion;
3) dipping and drying treatment
Soaking the base fabric prepared in the step 1) into a soaking tank filled with super-hydrophobic polyurethane slurry, wherein the super-hydrophobic polyurethane slurry comprises the following raw materials in parts by weight: 48 parts of super-hydrophobic polyurethane emulsion, 6 parts of aqueous thickening agent (model N-906, produced by Denzhong chemical technology Co., Ltd.), 0.8 part of polyether modified siloxane (model F340, produced by Orna Polymer Co., Ltd.), 2 parts of penetrating agent JFC, 1.8 parts of aqueous defoaming agent (model F-326, produced by Guangzhou Tianfeng defoaming agent Co., Ltd.), 5 parts of aqueous black paste (Xinshuo chemical Co., Ltd.), and 20 parts of talcum powder, wherein the viscosity of the super-hydrophobic polyurethane slurry is controlled within the range of 6-12 Pa.s;
taking the base cloth out of the dipping tank, removing redundant super-hydrophobic polyurethane slurry on the surface of the base cloth by using a scraper, then placing the base cloth into an oven, and drying for 40min at 95 ℃;
and after drying the base fabric, carrying out xylene washing, water washing and drying to obtain the super-hydrophobic ecological environment-friendly microfiber leather.
EXAMPLE III
A preparation method of super-hydrophobic ecological environment-friendly microfiber leather comprises the following steps:
1) preparation of the base Fabric
Uniformly mixing polylactic acid fiber, polycaprolactone fiber, chitosan and modified nano-silica, adding the mixture into a screw extruder for melt extrusion, and stretching and heat setting to prepare the polylactic acid/polycaprolactone sea-island fiber, wherein the weight ratio of the polylactic acid fiber to the polycaprolactone fiber to the chitosan to the modified nano-silica is 70: 30: 12: 18, the specific preparation method of the modified nano silicon dioxide comprises the following steps: weighing a certain amount of nano silicon dioxide, adding a toluene solvent, and stirring, wherein the mass ratio of the nano silicon dioxide to the toluene is 1: slowly adding a silane coupling agent KH-151 with the mass fraction of 5% of nano-silica under ultrasonic oscillation, stirring at 80 ℃ for reaction for 3 hours, washing with water, performing suction filtration, and drying to obtain modified nano-silica;
sequentially opening the prepared polylactic acid/polycaprolactone sea-island fibers by an opener and carding by a carding machine to form a web, finally needling the web by using the needles on a needling machine, and repeatedly interweaving and piercing and reinforcing the barbed needles to prepare the base fabric;
2) preparation of super-hydrophobic polyurethane emulsion
Adding 18 parts of diphenylmethane-4, 4' -diisocyanate, 75 parts of dihydroxy polyether N-210 and 100 parts of acetone serving as a solvent into a reactor, carrying out prepolymerization reaction for 1.5h at 85 ℃, then cooling a reaction system to 50 ℃, gradually adding 6 parts of 1, 8-octanediol, heating to 80 ℃, reacting for 40min, and then adding 8 parts of 2-hydroxy-2-butyl acrylate, and reacting for 50min to obtain an aqueous polyurethane prepolymer;
adding 56 parts of deionized water, 2 parts of nonylphenol polyoxyethylene ether emulsifier and 0.9 part of azobisisobutyronitrile hydrochloride into the aqueous polyurethane prepolymer, shearing and emulsifying at a high speed of 2500r/min for 50min, then adding 18 parts of perfluoroalkyl ethyl acrylate to perform polymerization reaction for 4h, and finally performing reduced pressure distillation to remove acetone to prepare the super-hydrophobic polyurethane emulsion;
3) dipping and drying treatment
Soaking the base fabric prepared in the step 1) into a soaking tank filled with super-hydrophobic polyurethane slurry, wherein the super-hydrophobic polyurethane slurry comprises the following raw materials in parts by weight: 56 parts of super-hydrophobic polyurethane emulsion, 4.5 parts of aqueous thickening agent (model N-906, produced by Denzhong chemical technology Co., Ltd.), 1.2 parts of polyether modified siloxane (model F340, produced by Orna Polymer Co., Ltd.), 3 parts of penetrating agent JFC, 1.2 parts of aqueous defoaming agent (model F-326, produced by Guangzhou Tianfeng defoaming agent Co., Ltd.), 10 parts of aqueous black paste (Xinshuo chemical Co., Ltd.), and 15 parts of titanium dioxide, wherein the viscosity of the super-hydrophobic polyurethane slurry is controlled within the range of 6-12 Pa.s;
taking the base cloth out of the dipping tank, removing redundant super-hydrophobic polyurethane slurry on the surface of the base cloth by using a scraper, then placing the base cloth into an oven, and drying for 30min at 105 ℃;
and after drying the base fabric, carrying out xylene washing, water washing and drying to obtain the super-hydrophobic ecological environment-friendly microfiber leather.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (8)
1. A preparation method of super-hydrophobic ecological environment-friendly microfiber leather is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of the base Fabric
Uniformly mixing polylactic acid fiber, polycaprolactone fiber, chitosan and modified nano silicon dioxide, adding the mixture into a screw extruder for melt extrusion, and stretching and heat setting to prepare polylactic acid/polycaprolactone sea-island fiber;
sequentially opening the prepared polylactic acid/polycaprolactone sea-island fibers by an opener and carding by a carding machine to form a web, finally needling the web by using the needles on a needling machine, and repeatedly interweaving and piercing and reinforcing the barbed needles to prepare the base fabric;
2) preparation of super-hydrophobic polyurethane emulsion
Adding diphenylmethane-4, 4' -diisocyanate, dihydroxy polyether and acetone as solvents into a reactor, carrying out prepolymerization reaction for 1.5-2.5 h at 75-85 ℃, then cooling a reaction system to 40-50 ℃, gradually adding aliphatic diol, heating to 70-80 ℃, reacting for 40-80 min, and then adding 2-hydroxy-2-butyl acrylate to react for 25-50 min to obtain an aqueous polyurethane prepolymer;
adding deionized water, an emulsifier and an initiator into the aqueous polyurethane prepolymer, carrying out high-speed shearing emulsification for 30-50 min, then adding perfluoroalkyl ethyl acrylate for carrying out polymerization reaction for 2-4 h, and finally carrying out reduced pressure distillation to remove acetone to prepare a super-hydrophobic polyurethane emulsion;
3) dipping and drying treatment
Soaking the base fabric prepared in the step 1) into a soaking tank filled with super-hydrophobic polyurethane slurry, wherein the super-hydrophobic polyurethane slurry comprises the following raw materials in parts by weight: 42-56 parts of super-hydrophobic polyurethane emulsion, 3-6 parts of thickening agent, 0.8-1.5 parts of flatting agent, 1-3 parts of penetrating agent, 1.2-1.8 parts of defoaming agent, 5-10 parts of color paste and 15-25 parts of filler;
taking the base cloth out of the dipping tank, removing redundant super-hydrophobic polyurethane slurry on the surface of the base cloth by using a scraper, then placing the base cloth into an oven, and drying for 30-50 min at 85-105 ℃;
and (3) drying the base cloth, and then washing with an organic solvent, washing with water, and drying to obtain the super-hydrophobic ecological environment-friendly microfiber leather.
2. The preparation method of the super-hydrophobic ecological environment-friendly microfiber leather according to claim 1, wherein the preparation method comprises the following steps: the specific preparation method of the modified nano silicon dioxide comprises the following steps: weighing a certain amount of nano silicon dioxide, adding a toluene solvent, and stirring, wherein the mass ratio of the nano silicon dioxide to the toluene is 1: and 5, slowly adding a silane coupling agent with the mass fraction of 5% of nano silicon dioxide under ultrasonic oscillation, stirring and reacting for 3-5 h at the temperature of 60-80 ℃, washing with water, carrying out suction filtration, and drying to obtain the modified nano silicon dioxide.
3. The preparation method of the super-hydrophobic ecological environment-friendly microfiber leather according to claim 1, wherein the preparation method comprises the following steps: the weight ratio of the polylactic acid fiber, the polycaprolactone fiber, the chitosan and the modified nano silicon dioxide in the step 1) is 50-70: 30-50: 8-12: 18 to 30.
4. The preparation method of the super-hydrophobic ecological environment-friendly microfiber leather according to claim 1, wherein the preparation method comprises the following steps: the shearing rate in the step 2) is 1500-2500 r/min.
5. The preparation method of the super-hydrophobic ecological environment-friendly microfiber leather according to claim 1, wherein the preparation method comprises the following steps: the step 2) comprises the following raw materials in parts by weight: 12-18 parts of diphenylmethane-4, 4' -diisocyanate, 50-75 parts of dihydroxy polyether, 80-100 parts of acetone, 4-6 parts of aliphatic diol, 6-8 parts of 2-hydroxy-2-butyl acrylate, 1.5-2.0 parts of an emulsifier, 0.9-1.5 parts of an initiator, 15-18 parts of perfluoroalkyl ethyl acrylate and 42-56 parts of deionized water.
6. The preparation method of the super-hydrophobic ecological environment-friendly microfiber leather according to claim 1, wherein the preparation method comprises the following steps: the viscosity of the super-hydrophobic polyurethane slurry in the step 3) is controlled within the range of 6-12 Pa.s.
7. The preparation method of the super-hydrophobic ecological environment-friendly microfiber leather according to claim 1, wherein the preparation method comprises the following steps: in the step 2), the aliphatic diol is any one of 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol and 1, 8-octanediol.
8. The preparation method of the super-hydrophobic ecological environment-friendly microfiber leather according to claim 1, wherein the preparation method comprises the following steps: the organic solvent used for washing after the base cloth is dried in the step 3) is dimethylbenzene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112127156A (en) * | 2020-09-25 | 2020-12-25 | 珠海华大浩宏新材料有限公司 | Environment-friendly fluorine-containing waterproof agent and preparation method thereof |
| CN113062123A (en) * | 2021-03-30 | 2021-07-02 | 英德市匠心新材料股份有限公司 | High-solid-content mirror-surface PU leather and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998038340A1 (en) * | 1997-02-26 | 1998-09-03 | Bayer Aktiengesellschaft | Biologically degradable leather |
| CN103866582A (en) * | 2014-03-27 | 2014-06-18 | 张子亮 | Natural product-containing degradable water-based synthetic leather and production process thereof |
| CN104420331A (en) * | 2013-08-20 | 2015-03-18 | 上海华峰超纤材料股份有限公司 | Environmental-protective waterproof oilproof microfiber synthetic leather and preparation method thereof |
| CN106948181A (en) * | 2017-05-27 | 2017-07-14 | 福建宝利特科技股份有限公司 | The preparation method of superfine fiber chemical leather and preparation method thereof and its bottom base |
| CN110144737A (en) * | 2019-05-31 | 2019-08-20 | 疏博（上海）纳米科技有限公司 | A kind of preparation method of super-hydrophobic ecological, environmental protective super fiber leather |
-
2019
- 2019-12-21 CN CN201911331658.XA patent/CN111101384A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998038340A1 (en) * | 1997-02-26 | 1998-09-03 | Bayer Aktiengesellschaft | Biologically degradable leather |
| CN104420331A (en) * | 2013-08-20 | 2015-03-18 | 上海华峰超纤材料股份有限公司 | Environmental-protective waterproof oilproof microfiber synthetic leather and preparation method thereof |
| CN103866582A (en) * | 2014-03-27 | 2014-06-18 | 张子亮 | Natural product-containing degradable water-based synthetic leather and production process thereof |
| CN106948181A (en) * | 2017-05-27 | 2017-07-14 | 福建宝利特科技股份有限公司 | The preparation method of superfine fiber chemical leather and preparation method thereof and its bottom base |
| CN110144737A (en) * | 2019-05-31 | 2019-08-20 | 疏博（上海）纳米科技有限公司 | A kind of preparation method of super-hydrophobic ecological, environmental protective super fiber leather |
Non-Patent Citations (4)
| Title |
|---|
| 刘淑强著: "《聚乳酸纤维》", 30 November 2012, 东华大学出版社 * |
| 强涛涛编著: "《合成革化学品》", 31 July 2016, 中国轻工业出版社 * |
| 李新功 等: "用于生物降解膜的聚己内酯与聚乳酸共混物制备及性能分析", 《农业工程学报》 * |
| 柴春鹏 等编著: "《高分子合成材料学》", 31 January 2019, 北京理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112127156A (en) * | 2020-09-25 | 2020-12-25 | 珠海华大浩宏新材料有限公司 | Environment-friendly fluorine-containing waterproof agent and preparation method thereof |
| CN113062123A (en) * | 2021-03-30 | 2021-07-02 | 英德市匠心新材料股份有限公司 | High-solid-content mirror-surface PU leather and preparation method thereof |
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Effective date of registration: 20200927 Address after: 366100 Datian County of Sanming City Fujian province Jingkou Industrial Zone Applicant after: Fujian xinlongshang Super Fiber Co.,Ltd. Address before: Gold town, West Ring Road of Jinjiang city in Fujian province 362200 Quanzhou city edge (Technology Industrial Zone) Applicant before: FUJIAN LONGSHANG MICROFIBER Co.,Ltd. |
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