CN109355923B - Preparation method of flame-retardant polyurethane artificial leather - Google Patents

Preparation method of flame-retardant polyurethane artificial leather Download PDF

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CN109355923B
CN109355923B CN201811036690.0A CN201811036690A CN109355923B CN 109355923 B CN109355923 B CN 109355923B CN 201811036690 A CN201811036690 A CN 201811036690A CN 109355923 B CN109355923 B CN 109355923B
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flame retardant
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artificial leather
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CN109355923A (en
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王鑫
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Fujian xinlongshang Super Fiber Co., Ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial 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
    • D06N3/14Artificial 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
    • CCHEMISTRY; METALLURGY
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    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/50Polyethers having heteroatoms other than oxygen
    • C08G18/5096Polyethers having heteroatoms other than oxygen containing silicon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/69Polymers of conjugated dienes
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/07Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015Artificial 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial 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
    • D06N3/0059Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial 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
    • D06N3/0063Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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    • D06N2209/00Properties of the materials
    • D06N2209/06Properties of the materials having thermal properties
    • D06N2209/067Flame resistant, fire resistant
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N2211/00Specially adapted uses
    • D06N2211/12Decorative or sun protection articles
    • D06N2211/28Artificial leather

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  • Engineering & Computer Science (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

The invention relates to the technical field of artificial leather production, in particular to a preparation method of flame-retardant polyurethane artificial leather, which comprises the following steps: preparing base cloth, wherein the raw materials comprise, by weight, 70-100 parts of hydroxyl-terminated polybutadiene, 70-100 parts of diphenylmethylene diisocyanate, 5-10 parts of vinyl triethoxysilane, 2-10 parts of a silane coupling agent, 0.1-0.2 part of dibutyltin dilaurate, 3-5 parts of a flame retardant, 5-10 parts of carbon nanotubes, 5-10 parts of gas-phase hydrophobic silicon dioxide, 0-5 parts of gardenia fruit juice and 5-10 parts of silyl-terminated polyether; preparing resin layer raw materials, 100 parts by weight of polyurethane elastomer, 0-10 parts by weight of plasticizer, 1-3 parts by weight of compatilizer, 0-20 parts by weight of filler, 5-10 parts by weight of flame retardant and 3-5 parts by weight of gardenia fruit juice; and (4) casting, coating and forming. Provides a preparation method of full flame-retardant artificial leather, and avoids the influence of organic phosphine flame retardants on quality in the prior art.

Description

Preparation method of flame-retardant polyurethane artificial leather
Technical Field
The invention relates to the technical field of artificial leather production, in particular to a preparation method of flame-retardant polyurethane artificial leather.
Background
Because the polyurethane artificial leather has the hand feeling close to real leather and the cost lower than real leather, the polyurethane artificial leather replaces real leather materials to be widely applied, and can achieve more beautiful appearance, but the polyurethane artificial leather has poor flame retardant property, and can be burnt when exposed fire or high-temperature baking occurs, so that danger is brought to use, the common method for solving the problem of poor flame retardant property at present is to coat a flame retardant layer on the surface of the artificial leather, or add a flame retardant material in the surface layer of the artificial leather, so that flame is prevented from spreading to a base cloth through the flame retardant material, the combustion of the artificial leather is prevented, however, once the flame starts to burn from the base cloth layer, the flame retardant property of the artificial leather can lose effect, so that the loss difficult to save is caused to a user, and the mode that the flame retardant effect is easily attenuated in the long-term use process of the artificial leather only by adding a, the fire safety coefficient is low.
The invention of the publication No. CN 106087389B discloses a preparation method of flame-retardant polyurethane synthetic leather, 12g of thermoplastic polyurethane and 3g of styrene-butadiene-styrene block copolymer, 3g of styrene-ethylene-butylene-styrene block copolymer, 7g of polyamide type thermoplastic elastomer, 2g of colorant and a substance A2g are extruded by an extruder at 90-370 ℃ to prepare a polyurethane film with the thickness of 0.8 mm; before cooling the modified polyurethane film, compounding and pressing the modified polyurethane film and flame-retardant base cloth by an extrusion roller under the pressure of 1.0Mpa, then embossing by a roller with grains under the pressure of 0.2Mpa, and cooling to obtain primary synthetic leather; firstly, the base cloth is only subjected to surface flame retardant treatment, and after long-term use and friction, the flame retardant material on the surface can fall off and lose the flame retardant function; and the flame retardant adopts an organic phosphine flame retardant, which has good flame retardant effect and is relatively environment-friendly, but has the problems of high inherent volatility, poor thermal stability, poor light stability and poor compatibility with polymers, and influences the later quality of the artificial leather.
Disclosure of Invention
Therefore, aiming at the above contents, the invention provides a preparation method of flame-retardant polyurethane artificial leather, provides a preparation method of full flame-retardant artificial leather, and avoids the influence of the prior art using organic phosphine flame retardant on quality.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of flame-retardant polyurethane artificial leather comprises the following steps:
the method comprises the following steps: preparing base cloth, namely preparing raw materials, wherein the raw materials comprise, by weight, 70-100 parts of hydroxyl-terminated polybutadiene, 70-100 parts of diphenylmethylene diisocyanate, 5-10 parts of vinyl triethoxysilane, 2-10 parts of a silane coupling agent, 0.1-0.2 part of dibutyltin dilaurate, 3-5 parts of a flame retardant, 5-10 parts of carbon nanotubes, 5-10 parts of gas-phase hydrophobic silicon dioxide, 0-5 parts of gardenia fruit juice and 5-10 parts of silyl-terminated polyether: hydroxyl polybutadiene is added into a reaction vessel, nitrogen is introduced, vacuum dehydration is carried out for 2 to 3 hours at the temperature of 100-Heating to 50-60 ℃, adding diphenyl methylene diisocyanate, vinyl triethoxysilane, a silane coupling agent and dibutyltin dilaurate, heating to 80-100 ℃ for reaction for 1-2h, adding a flame retardant, a carbon nano tube, gas-phase hydrophobic silicon dioxide and color master, dropwise adding a blocking agent silyl-terminated polyether, stirring for reaction for 2-6 h, preparing flame-retardant fibers by a melt spinning process, weaving into base cloth, and ironing the base cloth for later use; the flame retardant is silane flame retardant SFR1000, inorganic flame retardant aluminum hydroxide and phosphorus-nitrogen flame retardant CN-329, and the weight parts are as follows: (5-10): (1-5) compounding; the silyl terminated polyether has the formula (C)3H6O)n C12H30O5Si2(ii) a The tube diameter of the carbon nano tube is 2-20nm, and the tube length is 100-;
step two: preparing resin layer raw materials, namely uniformly mixing 100 parts by weight of polyurethane elastomer, 0-10 parts by weight of plasticizer, 1-3 parts by weight of compatilizer, 0-20 parts by weight of filler, 5-10 parts by weight of flame retardant and 3-5 parts by weight of gardenia fruit juice in a high-speed dispersion mixer, stirring at the temperature of 110-130 ℃ for 60-200 s; the flame retardant is the same as the flame retardant in the first step;
step three: and (3) casting, coating and forming, namely discharging the uniformly mixed materials in the step two into an internal mixer for mixing at the mixing temperature of 130-150 ℃ for 200-plus-one 300s, coating the mixture on the surface of the ironed base fabric through a casting coating process with the coating thickness of 0.1-1.0mm, ironing the mixture by an ironing machine at the temperature of 160-180 ℃, the production speed of 30 +/-10 m/min and the ironing pressure of 30-50MPa, and cooling and shaping to obtain a finished product.
The further improvement is that: the filler is prepared by compounding superfine calcium carbonate and gas-phase hydrophobic silica according to the ratio of 1: 1.
The further improvement is that: the plasticizer is PB-3A produced by Diesent investments Co.
The further improvement is that: the silane coupling agent is Z-6011, available from Dow Corning, USA.
By adopting the technical scheme, the invention has the beneficial effects that:
organosilane is introduced into a base cloth formula, a silane end is introduced into a polymer connecting section, the flame retardant property of the base cloth is improved, and the traditional color master batch is replaced by gardenia juice, so that the overall environmental protection property is improved; the compounded flame retardant improves the dispersibility of aluminum hydroxide and enhances the thermal stability of the phosphorus-nitrogen flame retardant through the compatibility of the organic silane, and the synergistic effect is exerted among the flame retardant and exceeds the flame retardant effect of a single component, when a high polymer is heated, a uniform carbonaceous foam layer can be generated on the surface to play the roles of heat insulation, oxygen isolation and smoke suppression, and the generation of a molten drop phenomenon is prevented, so that the compounded flame retardant has good flame retardant property, no volatility, high thermal stability, good light stability and good compatibility with a polymer; the flame-retardant artificial leather has the flame-retardant effect from the base cloth to the resin layer, and realizes the full flame retardance of the artificial leather.
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 1
A preparation method of flame-retardant polyurethane artificial leather comprises the following steps:
the method comprises the following steps: preparing base cloth, namely preparing raw materials, wherein the raw materials comprise the following components, by weight, 70 parts of hydroxyl-terminated polybutadiene, 70 parts of diphenylmethane diisocyanate, 5 parts of vinyl triethoxysilane, 12 parts of a silane coupling agent Z-60112, 0.1 part of dibutyltin dilaurate, 3 parts of a flame retardant, 5 parts of a carbon nano tube, 5 parts of gas-phase hydrophobic silicon dioxide, 0 part of gardenia fruit juice and 5 parts of silyl-terminated polyether: adding hydroxyl polybutadiene into a reaction vessel, introducing nitrogen, vacuum dehydrating at 100 deg.C for 3 hr, cooling to 50 deg.C, adding diphenylmethyleneHeating diisocyanate, vinyl triethoxysilane, silane coupling agent Z-6011 and dibutyltin dilaurate to 80 ℃ for reaction for 1h, adding a flame retardant, carbon nano tubes, gas-phase hydrophobic silicon dioxide, color master, dropwise adding end capping agent silyl-terminated polyether, stirring for reaction for 2 hours, preparing flame-retardant fibers by a melt spinning process, weaving into base cloth, and ironing the base cloth for later use; the flame retardant is silane flame retardant SFR1000, inorganic flame retardant aluminum hydroxide and phosphorus-nitrogen flame retardant CN-329, and the weight parts are as follows: 5: 1 is compounded; the silyl terminated polyether has the formula (C)3H6O)n C12H30O5Si2(ii) a The pipe diameter of the carbon nano tube is 2nm, and the pipe length is 100 mu m;
step two: preparing resin layer raw materials, uniformly mixing 100 parts by weight of polyurethane elastomer, 0 part by weight of plasticizer PB-3A, 1 part by weight of compatilizer, 0 part by weight of filler, 5 parts by weight of flame retardant and 3 parts by weight of gardenia fruit juice in a high-speed dispersion mixer, stirring at the temperature of 110 ℃ for 60 s; the flame retardant is the same as the flame retardant in the first step; the filler is formed by compounding superfine calcium carbonate and gas-phase hydrophobic silica according to the ratio of 1: 1;
step three: and (3) casting, coating and forming, namely discharging the uniformly mixed materials in the step two into an internal mixer for mixing at the mixing temperature of 130-150 ℃ for 200s, coating the mixture on the surface of the ironed base fabric by a casting coating process at the coating thickness of 0.1mm, ironing by an ironing machine at the ironing temperature of 160 ℃, the production speed of 20m/min and the ironing pressure of 30MPa, and cooling and shaping to obtain a finished product.
Example 2
A preparation method of flame-retardant polyurethane artificial leather comprises the following steps:
the method comprises the following steps: preparing base cloth, namely preparing raw materials, wherein the raw materials comprise the following components, by weight, 100 parts of hydroxyl-terminated polybutadiene, 100 parts of diphenylmethane diisocyanate, 10 parts of vinyl triethoxysilane, 5 parts of a silane coupling agent Z-601110, 0.2 part of dibutyltin dilaurate, 10 parts of a flame retardant, 10 parts of carbon nanotubes, 10 parts of gas-phase hydrophobic silicon dioxide, 5 parts of gardenia fruit juice and 10 parts of silyl-terminated polyether: in thatAdding hydroxyl polybutadiene into a reaction vessel, introducing nitrogen, dehydrating for 2h in vacuum at 120 ℃, cooling to 60 ℃, adding diphenylmethylene diisocyanate, vinyl triethoxysilane, silane coupling agent Z-6011 and dibutyltin dilaurate, heating to 100 ℃, reacting for 2h, adding a flame retardant, carbon nano tubes, gas-phase hydrophobic silica, color master, dropwise adding end capping agent silyl-terminated polyether, stirring and reacting for 6 h, preparing flame-retardant fibers through a melt spinning process, weaving into base cloth, and ironing the base cloth for later use; the flame retardant is silane flame retardant SFR1000, inorganic flame retardant aluminum hydroxide and phosphorus-nitrogen flame retardant CN-329, and the weight parts are as follows: 10: 5, compounding; the silyl terminated polyether has the formula (C)3H6O)n C12H30O5Si2(ii) a The pipe diameter of the carbon nano tube is 20nm, and the pipe length is 120 mu m;
step two: preparing resin layer raw materials, uniformly mixing 100 parts by weight of polyurethane elastomer, 10 parts by weight of plasticizer PB-3A, 3 parts by weight of compatilizer A-6651, 20 parts by weight of filler, 10 parts by weight of flame retardant and 5 parts by weight of gardenia fruit juice in a high-speed dispersion mixer, stirring at the temperature of 130 ℃ for 200 s; the flame retardant is the same as the flame retardant in the first step; the filler is formed by compounding superfine calcium carbonate and gas-phase hydrophobic silica according to the ratio of 1: 1;
step three: and (3) casting, coating and forming, namely discharging the uniformly mixed materials in the step two into an internal mixer for mixing at the mixing temperature of 130-150 ℃ for 300s, coating the mixture on the surface of the ironed base fabric by a casting coating process, wherein the coating thickness is 1.0mm, ironing by an ironing machine, the ironing temperature is 180 ℃, the production speed is 40m/min, the ironing pressure is 50MPa, and cooling and shaping are carried out to obtain a finished product.
Example 2
A preparation method of flame-retardant polyurethane artificial leather comprises the following steps:
the method comprises the following steps: preparing base cloth, preparing raw materials, and preparing the base cloth by weight parts of 100 parts of hydroxyl-terminated polybutadiene, 100 parts of diphenylmethane diisocyanate, 10 parts of vinyl triethoxysilane, Z-601110 parts of a silane coupling agent and dibutyl dilaurate0.2 part of tin base, 5 parts of flame retardant, 10 parts of carbon nano tube, 10 parts of gas-phase hydrophobic silicon dioxide, 5 parts of gardenia fruit juice, 10 parts of silyl-terminated polyether: adding hydroxyl polybutadiene into a reaction vessel, introducing nitrogen, dehydrating for 2h in vacuum at 120 ℃, cooling to 60 ℃, adding diphenylmethylene diisocyanate, vinyl triethoxysilane, silane coupling agent Z-6011 and dibutyltin dilaurate, heating to 100 ℃, reacting for 2h, adding a flame retardant, carbon nano tubes, gas-phase hydrophobic silica, color master, dropwise adding end capping agent silyl-terminated polyether, stirring and reacting for 6 h, preparing flame-retardant fibers by a melt spinning process, weaving into base cloth, and ironing the base cloth for later use; the flame retardant is silane flame retardant SFR1000, inorganic flame retardant aluminum hydroxide and phosphorus-nitrogen flame retardant CN-329, and the weight parts are as follows: 10: 5, compounding; the silyl terminated polyether has the formula (C)3H6O)n C12H30O5Si2(ii) a The pipe diameter of the carbon nano tube is 20nm, and the pipe length is 120 mu m;
step two: preparing resin layer raw materials, uniformly mixing 100 parts by weight of polyurethane elastomer, 10 parts by weight of plasticizer PB-3A, 3 parts by weight of compatilizer A-6651, 20 parts by weight of filler, 10 parts by weight of flame retardant and 5 parts by weight of gardenia fruit juice in a high-speed dispersion mixer, stirring at the temperature of 130 ℃ for 200 s; the flame retardant is the same as the flame retardant in the first step; the filler is formed by compounding superfine calcium carbonate and gas-phase hydrophobic silica according to the ratio of 1: 1;
step three: and (3) casting, coating and forming, namely discharging the uniformly mixed materials in the step two into an internal mixer for mixing at the mixing temperature of 130-150 ℃ for 300s, coating the mixture on the surface of the ironed base fabric by a casting coating process, wherein the coating thickness is 1.0mm, ironing by an ironing machine, the ironing temperature is 180 ℃, the production speed is 40m/min, the ironing pressure is 50MPa, and cooling and shaping are carried out to obtain a finished product.
Example 3
A preparation method of flame-retardant polyurethane artificial leather comprises the following steps:
the method comprises the following steps: preparing base cloth, preparing raw materials, and preparing hydroxyl-terminated polybutylene terephthalate80 parts of alkene, 60 parts of diphenyl methylene diisocyanate, 7 parts of vinyl triethoxysilane, 18 parts of silane coupling agent Z-60118 parts, 0.2 part of dibutyltin dilaurate, 4 parts of flame retardant, 7 parts of carbon nano tube, 7 parts of gas-phase hydrophobic silicon dioxide, 4 parts of gardenia fruit juice and 8 parts of silyl-terminated polyether: adding hydroxyl polybutadiene into a reaction vessel, introducing nitrogen, dehydrating for 2.5 hours in vacuum at 110 ℃, cooling to 55 ℃, adding diphenyl methylene diisocyanate, vinyl triethoxysilane, silane coupling agent Z-6011 and dibutyltin dilaurate, heating to 90 ℃, reacting for 1.5 hours, adding a flame retardant, a carbon nano tube, gas-phase hydrophobic silica, color master, dropwise adding end-capping agent silyl end-capped polyether, stirring and reacting for 3 hours, preparing flame-retardant fibers by a melt spinning process, weaving into base cloth, and ironing the base cloth for later use; the flame retardant is silane flame retardant SFR1000, inorganic flame retardant aluminum hydroxide and phosphorus-nitrogen flame retardant CN-329, and the weight parts are as follows: 6: 3, compounding; the silyl terminated polyether has the formula (C)3H6O)n C12H30O5Si2(ii) a The pipe diameter of the carbon nano tube is 10nm, and the pipe length is 110 mu m;
step two: preparing resin layer raw materials, uniformly mixing 100 parts by weight of polyurethane elastomer, 5 parts by weight of plasticizer PB-3A, 2 parts by weight of compatilizer A-6651, 10 parts by weight of filler, 6 parts by weight of flame retardant and 4 parts by weight of gardenia fruit juice in a high-speed dispersion mixer, stirring at 120 ℃ for 100 s; the flame retardant is the same as the flame retardant in the first step; the filler is formed by compounding superfine calcium carbonate and gas-phase hydrophobic silica according to the ratio of 1: 1;
step three: and (3) casting, coating and forming, namely discharging the uniformly mixed materials in the step two into an internal mixer for mixing at the mixing temperature of 130-150 ℃ for 250s, coating the mixture on the surface of the ironed base fabric by a casting coating process, wherein the coating thickness is 0.5mm, ironing by an ironing machine at the ironing machine temperature of 170 ℃, the production speed of 30m/min and the ironing pressure of 40MPa, and cooling and shaping to obtain a finished product.
In the invention, the silane flame retardant SFR1000 is produced by GE company in America; CN-329 is produced by CN-329 developed by GreatLake, USA, and the compatilizer A-6651 is produced by Shenzhen Jinda Total science and technology, Inc.
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 (4)

1. A preparation method of flame-retardant polyurethane artificial leather is characterized by comprising the following steps:
step one, preparing base cloth, and preparing raw materials, wherein the raw materials comprise the following components in parts by weight: 70-100 parts of hydroxyl-terminated polybutadiene, 70-100 parts of diphenylmethylene diisocyanate, 5-10 parts of vinyl triethoxysilane, 2-10 parts of a silane coupling agent, 0.1-0.2 part of dibutyltin dilaurate, 3-5 parts of a flame retardant, 5-10 parts of carbon nanotubes, 5-10 parts of gas-phase hydrophobic silica, 0-5 parts of gardenia fruit juice and 5-10 parts of silyl-terminated polyether;
adding hydroxyl polybutadiene into a reaction container, introducing nitrogen, dehydrating for 2-3h in vacuum at the temperature of 100-120 ℃, cooling to 50-60 ℃, adding diphenylmethylene diisocyanate, vinyl triethoxysilane, a silane coupling agent and dibutyltin dilaurate, heating to 80-100 ℃, reacting for 1-2h, adding a flame retardant, a carbon nano tube, gas-phase hydrophobic silica and a color master, dropwise adding a silyl-terminated polyether serving as a terminating agent, stirring and reacting for 2-6 h, preparing flame-retardant fibers by a melt spinning process, weaving into base cloth, and ironing the base cloth for later use; the flame retardant is silane flame retardant SFR1000, inorganic flame retardant aluminum hydroxide and phosphorus-nitrogen flame retardant CN-329, and the weight parts are as follows: (5-10): (1-5) compounding; the silyl terminated polyether has the formula (C)3H6O)n C12H30O5Si2(ii) a The tube diameter of the carbon nano tube is 2-20nm, and the tube length is 100-;
step two, preparing resin layer raw materials, namely uniformly mixing 100 parts by weight of polyurethane elastomer, 0-10 parts by weight of plasticizer, 1-3 parts by weight of compatilizer, 0-20 parts by weight of filler, 5-10 parts by weight of flame retardant and 3-5 parts by weight of gardenia fruit juice in a high-speed dispersion mixer, stirring at the temperature of 110-130 ℃ for 60-200 s; the flame retardant is the same as the flame retardant in the first step;
and step three, tape casting coating forming, namely discharging the uniformly mixed materials in the step two into an internal mixer for mixing at the mixing temperature of 130-150 ℃ for 200-plus-one 300s, coating the uniformly mixed materials on the surface of the ironed base fabric through a tape casting coating process with the coating thickness of 0.1-1.0mm, ironing the base fabric through an ironing machine at the temperature of 160-180 ℃, the production speed of 30 +/-10 m/min and the ironing pressure of 30-50MPa, and cooling and shaping to obtain a finished product.
2. The method for preparing flame-retardant polyurethane artificial leather according to claim 1, wherein the filler is formed by compounding superfine calcium carbonate and gas-phase hydrophobic silica according to a ratio of 1: 1.
3. The method of preparing flame retardant polyurethane artificial leather according to claim 2, wherein the plasticizer is PB-3A produced by deice co.
4. The method of preparing flame retardant polyurethane artificial leather according to claim 3, wherein the silane coupling agent is Z-6011, available from Dow Corning, USA.
CN201811036690.0A 2018-09-06 2018-09-06 Preparation method of flame-retardant polyurethane artificial leather Active CN109355923B (en)

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CN112267306B (en) * 2020-10-18 2023-05-09 广东柏奴斯股份有限公司 Flame-retardant antistatic fabric and preparation method thereof
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1400573A (en) * 2001-08-04 2003-03-05 大连路明发光科技股份有限公司 Luminous-reflecting mark band and its making method
JP2006124888A (en) * 2004-11-01 2006-05-18 Teijin Cordley Ltd Leather-like sheetlike material
CN102493210A (en) * 2011-11-18 2012-06-13 四川大学 Artificial Fireproof polyvinyl chloride (PVC) leather for cushion furniture and preparation method thereof
CN103590138A (en) * 2013-11-06 2014-02-19 浙江华峰氨纶股份有限公司 Preparation method for anti-flaming polyurethane elastic fiber
CN105237782A (en) * 2015-10-09 2016-01-13 滁州环球聚氨酯科技有限公司 Water-resistant polyurethane composite material
CN105238034A (en) * 2015-10-09 2016-01-13 滁州环球聚氨酯科技有限公司 Carbon nanotube modified polyurethane composite material
CN105860510A (en) * 2016-04-19 2016-08-17 滁州环球聚氨酯科技有限公司 High-flame-retardancy polyurethane composite material
CN106245231A (en) * 2016-08-01 2016-12-21 薛常刚 A kind of preparation method of the acoustical cotton used on car engine lid
CN106757488A (en) * 2016-12-20 2017-05-31 吴中区穹窿山福顺生物技术研究所 A kind of nano modified polyurethane fibrous material and preparation method thereof
CN107164973A (en) * 2017-06-01 2017-09-15 无锡市曼优丽新型复合材料有限公司 A kind of preparation method of environmental-protection flame-retardant uvioresistant TPU synthetic leather
CN108084400A (en) * 2017-12-29 2018-05-29 美瑞新材料股份有限公司 A kind of preparation method of high-performance thermoplastic polyurethane elastomer
CN108330704A (en) * 2018-02-02 2018-07-27 天守(福建)超纤科技股份有限公司 A kind of graphene superfine fiber polyurethane leather and preparation method thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1400573A (en) * 2001-08-04 2003-03-05 大连路明发光科技股份有限公司 Luminous-reflecting mark band and its making method
JP2006124888A (en) * 2004-11-01 2006-05-18 Teijin Cordley Ltd Leather-like sheetlike material
CN102493210A (en) * 2011-11-18 2012-06-13 四川大学 Artificial Fireproof polyvinyl chloride (PVC) leather for cushion furniture and preparation method thereof
CN103590138A (en) * 2013-11-06 2014-02-19 浙江华峰氨纶股份有限公司 Preparation method for anti-flaming polyurethane elastic fiber
CN105237782A (en) * 2015-10-09 2016-01-13 滁州环球聚氨酯科技有限公司 Water-resistant polyurethane composite material
CN105238034A (en) * 2015-10-09 2016-01-13 滁州环球聚氨酯科技有限公司 Carbon nanotube modified polyurethane composite material
CN105860510A (en) * 2016-04-19 2016-08-17 滁州环球聚氨酯科技有限公司 High-flame-retardancy polyurethane composite material
CN106245231A (en) * 2016-08-01 2016-12-21 薛常刚 A kind of preparation method of the acoustical cotton used on car engine lid
CN106757488A (en) * 2016-12-20 2017-05-31 吴中区穹窿山福顺生物技术研究所 A kind of nano modified polyurethane fibrous material and preparation method thereof
CN107164973A (en) * 2017-06-01 2017-09-15 无锡市曼优丽新型复合材料有限公司 A kind of preparation method of environmental-protection flame-retardant uvioresistant TPU synthetic leather
CN108084400A (en) * 2017-12-29 2018-05-29 美瑞新材料股份有限公司 A kind of preparation method of high-performance thermoplastic polyurethane elastomer
CN108330704A (en) * 2018-02-02 2018-07-27 天守(福建)超纤科技股份有限公司 A kind of graphene superfine fiber polyurethane leather and preparation method thereof

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