CN109797541B - PET flame-retardant monofilament - Google Patents
PET flame-retardant monofilament Download PDFInfo
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Abstract
The invention relates to the technical field of PET monofilaments, in particular to a PET flame-retardant monofilament, which comprises a PET core bundle and a flame-retardant layer coated on the outer side of the PET core bundle, wherein the flame-retardant layer comprises the following raw materials in parts by weight: 80-100 parts of ultraviolet curing resin, 20-30 parts of polyvinyl chloride resin, 20-35 parts of polyurethane resin, 3-6 parts of wood powder, 4-6 parts of porous layered silicate flame retardant, 5-9 parts of toughening agent, 5-7 parts of compatilizer, 8-12 parts of antioxidant and 80-100 parts of organic solvent.
Description
Technical Field
The invention relates to the technical field of PET monofilaments, in particular to a PET flame-retardant monofilament.
Background
PET is a milky white or light yellow highly-crystalline polymer, has smooth and glossy surface, good creep resistance, fatigue resistance and friction resistance, small abrasion and high hardness, and has the maximum toughness in thermoplastic plastics; the PET monofilament has good electrical insulation performance, small temperature influence, good weather resistance and good chemical resistance stability, but the PET monofilament has insufficient flame retardant performance, and cannot be suitable for the application field related to high flame retardant.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the PET flame-retardant monofilament which has excellent flame-retardant performance and anti-dripping performance and good smoke suppression effect.
The purpose of the invention is realized by the following technical scheme: the PET flame-retardant monofilament comprises a PET core bundle and a flame-retardant layer coated on the outer side of the PET core bundle, wherein the flame-retardant layer comprises the following raw materials in parts by weight:
according to the invention, the flame-retardant layer is prepared by adopting the raw materials, so that the prepared flame-retardant layer has excellent flame-retardant property, high-temperature resistance, good smoke suppression effect and excellent anti-dripping effect. By coating the flame-retardant layer on the outer side of the PET core bundle, the addition of a flame retardant can be reduced, and the prepared PET monofilament has a good flame-retardant effect.
The HCl gas that PVC decomposes in the in-process of fire-retardant layer burning produces can completely cut off oxygen, prevent to be wrapped up in the burning of the intraformational PET core bundle of fire-retardant, PVC dechlorination can absorb a large amount of heat simultaneously, thereby reduce the heat release rate and the heat release total amount of the fire-retardant monofilament of PET, reach fire-retardant purpose, mix PVC resin, polyurethane resin, porous phyllosilicate fire retardant and wood flour, be favorable to promoting fire-retardant layer charring, make the incomplete charcoal surface on fire-retardant layer smooth, form fine and close expanded carbon layer, play the effect that prevents heat transfer and oxygen propagation. The porous layered silicate flame retardant has a porous structure, when the porous layered silicate flame retardant is mixed with the ultraviolet curing resin, the PVC resin and the polyurethane resin, part of the mixed resin and the porous layered silicate flame retardant form a stable cross-linked structure through the porous structure, the resin matrix is cured and shrunk after being irradiated by ultraviolet light by adding the ultraviolet curing resin, part of the porous layered silicate flame retardant is exposed on the surface of the mixed resin, and due to the stable cross-linking effect between the porous layered silicate flame retardant and the mixed resin, the porous layered silicate flame retardant exposed on the surface of the mixed resin cannot fall off from the surface of the mixed resin, so that the porous layered silicate flame retardant is uniformly adhered to the surface of the cured mixed resin, is firstly contacted with a heat source when the flame retardant layer is combusted, and blocks the external heat and oxygen from being transferred and diffused to the interior of the flame retardant layer and the PET core bundle, meanwhile, the release of internal combustible volatile matters to the gas phase combustion area is blocked, and the smoke suppression effect is good. Therefore, the porous phyllosilicate flame retardant adhered to the surface of the mixed resin forms a first flame-retardant layer, the porous phyllosilicate flame retardant mixed in the mixed resin, the mixed resin and the wood powder form a second flame-retardant layer, the PET core bundle is subjected to flame-retardant protection under the synergistic effect of the two flame-retardant layers, the flame-retardant effect is excellent, and the mechanical property of the PET flame-retardant monofilament is improved.
Preferably, the toughening agent is a mixture of vinyl acetate, epoxidized soybean oil and chlorinated polyethylene in a weight ratio of 1-3:0.5: 2-3. The vinyl acetate, the epoxidized soybean oil and the chlorinated polyethylene are compounded according to the weight ratio, so that the prepared flame-retardant layer has excellent flexibility, impact resistance and elasticity.
Preferably, the compatilizer is at least one of tri-p-sec-butylphenyl phosphate, dioctyl phthalate and methyl methacrylate-butadiene-styrene terpolymer. The compatilizer can be matched with other raw materials to act and perform synergistic reaction, so that the interfacial tension between molecules when each resin material reacts with other raw materials is effectively reduced, the interfacial bonding force is further improved, the dispersed phase and the continuous phase are uniform to form a stable structure, the mutual matching reaction of the composite resin material and each raw material is promoted, the impact strength, the toughness and the processing rheological property of the composite resin material are improved, and the surface finish and the flame retardant property are improved.
Preferably, the antioxidant is at least one of antioxidant 1076, antioxidant 168, antioxidant 445 and titanium dioxide. The antioxidant can effectively inhibit thermal aging degradation and light aging degradation of the composite material, and prolong the service life of the composite material.
Preferably, the organic solvent is a mixed solution of toluene and ethyl acetate in a weight ratio of 3-4:1, and the organic composite organic solvent can improve the cross-linking polymerization of the composite material and improve the flame retardant property and flexibility of the prepared composite material.
Wherein the grain size of the wood powder is 20-50 nm. When the grain size of wood flour is too big, the roughness on the surface of wood flour is high, the structure is loose, the compatibility between wood flour and mixed resin is poor, the flame retardant property of the prepared PET flame-retardant monofilament is reduced, meanwhile, the mixed resin melt is not easy to permeate into the wood flour, and further the wood flour is easy to form a cavity defect, the composite material is easy to form stress concentration at the defect position when bearing larger stretching force, so that the material is easy to break, therefore, the tensile strength of the composite material is reduced when the grain size of the wood flour is too big, and the flame retardant property, the bending property, the impact property and the tensile strength of the PET flame-retardant monofilament can be influenced when the grain size of the wood flour.
The preparation method of the porous layered phosphate flame retardant comprises the following steps:
(1) mixing 4-10 parts by weight of quaternary phosphonium salt and 20-30 parts by weight of inorganic montmorillonite, adding 50-60 parts by weight of 70-80% ethanol aqueous solution under the protection of inert gas, heating, keeping the temperature and stirring to prepare phosphorus-containing organic layered silicate;
(2) mixing the phosphorus-containing organic layered silicate prepared in the step (1) with 20-25 parts by weight of amino acid, heating and stirring under the protection of inert gas to prepare phosphorus-nitrogen-containing organic layered silicate;
(3) adding 6-9 parts by weight of nano cellulose into 20-40 parts by weight of ethanol water solution with volume concentration of 90-95% for ultrasonic dispersion to obtain dispersion liquid;
(4) adding 3-5 parts by weight of sodium dodecyl benzene sulfonate into the phosphorus-nitrogen-containing organic layered silicate prepared in the step (2), then adding 25-34 parts by weight of ethyl orthosilicate and the dispersion liquid prepared in the step (3), fully stirring for reaction, performing solid-liquid separation, and then performing vacuum drying to prepare the phosphorus-nitrogen-silicon pillared layered silicate;
(5) roasting the phosphorus-nitrogen-silicon containing pillared layered silicate to remove carbon, oxygen organic matters and nanocellulose to prepare the porous layered silicate flame retardant.
By adopting the method of the invention, the phosphorus, nitrogen, silicon and nano-cellulose are inserted between montmorillonite layers and generate bonding reaction with the montmorillonite framework, and simultaneously, the carbon-oxygen organic matter and the nano-cellulose are decomposed into carbon dioxide and water gas to escape from the montmorillonite layers by roasting, so that more fine holes and nano-cellulose channels are generated between the layers, the interlayer spacing and the specific surface area of the montmorillonite are increased, the montmorillonite can be uniformly dispersed in a mixed resin system, and the flame retardant effect is improved. Meanwhile, due to the insertion of phosphorus, nitrogen and silicon and the formation of a porous structure, the flame retardant property and the thermal stability of the montmorillonite are improved, and further, the flame retardant property and the mechanical property of the PET flame retardant monofilament are improved.
Wherein the diameter of the nano-cellulose in the step (3) is 30-50nm, and the length is 1-2 μm. The long diameter and the corresponding dosage of the nano-cellulose are controlled, so that the particle diameter of the prepared porous phyllosilicate fire retardant is controlled between 150-250nm, and the pore volume channel is controlled at 150-160cm3(g) improving the crosslinking effect of the mixed resin and the porous layered silicate flame retardant to uniformly disperse the porous layered silicate flame retardant inIn the mixed resin, the migration does not occur, and the flame retardant effect is improved.
Wherein the heating temperature in the step (1) is 30-40 ℃, the stirring speed is 200-500r/min, and the stirring time is 0.5-1 h. By adopting the heating temperature and the stirring speed, phosphorus can be inserted into the montmorillonite layer more favorably, and the flame retardant effect of the porous phyllosilicate flame retardant is improved.
Wherein the heating temperature in the step (2) is 50-60 ℃, and the stirring speed is 400-600 r/min; the drying temperature in the step (4) is 100-150 ℃. By adopting the heating temperature and the stirring speed, nitrogen can be inserted into the montmorillonite layer more favorably, nitrogen and phosphorus can be used for realizing synergistic flame retardance, and the flame retardant effect of the porous layered silicate flame retardant is improved. The drying temperature in the fourth step is adopted to control the particle size of the porous phyllosilicate fire retardant to be between 150-250nm and maintain the nanometer size effect of the porous phyllosilicate fire retardant.
Wherein the roasting temperature in the step (5) is 600-700 ℃, and the roasting time is 1-2 h. By controlling the roasting temperature and time, the nanocellulose, the carbon and oxygen organic matters are fully decomposed into water and carbon dioxide to escape from the montmorillonite layer, so that more fine holes and nanocellulose channels are generated between layers, and the interlayer spacing and the specific surface area of the montmorillonite are increased.
Preferably, the quaternary phosphonium salt is at least one of tetrakis hydroxymethyl phosphonium sulfate, tetrakis hydroxymethyl phosphonium sulfate-urea condensate, and tetrakis hydroxymethyl phosphonium chloride-urea condensate.
The ultraviolet curing resin comprises the following raw materials in parts by weight:
according to the invention, the prepared ultraviolet curing resin is well combined with the PET core bundle through the selection of the acrylic monomer and the selection of the epoxy resin, and the prepared ultraviolet curing resin has good compatibility with the polyurethane resin and the polyvinyl chloride resin, so that the flame retardant property and the photocuring shrinkage property of the flame retardant layer are improved.
Preferably, the catalyst is triphenylphosphine or N, N-dimethylbenzylamine; the photoinitiator is at least one of benzophenone, diethoxyacetophenone and benzoin dimethyl ether; the polymerization inhibitor is hydroquinone.
The preparation method of the PET flame-retardant monofilament comprises the following steps:
s1, mixing and uniformly stirring the ultraviolet curing resin, the polyvinyl chloride resin, the polyurethane resin, the wood powder, the flexibilizer, the compatilizer, the antioxidant and the organic solvent according to the weight ratio to prepare a mixed solution;
s2, adding the porous layered silicate flame retardant into the mixed solution prepared in the step S1, and uniformly stirring to prepare flame-retardant mixed solution;
s3, pressurizing the flame-retardant mixed liquid prepared in the step S3 to 60-70Mpa, keeping for 0.5-1.5h, slowly releasing the pressure, and fully stirring and mixing again after the flame-retardant mixed liquid is restored to normal pressure to prepare the flame-retardant material;
and S4, immersing the PET core bundle in the flame retardant to coat the outer layer of the PET core bundle with the flame retardant, and then irradiating by ultraviolet light to cure the flame retardant to form a flame retardant layer to obtain the PET flame retardant monofilament.
The porous layered silicate flame retardant and the mixed liquid are mixed and pressurized to 60-70Mpa, the mixed liquid is crosslinked with the porous layered silicate flame retardant through the porous structure under the action of pressure, the crosslinking effect is improved through pressurization, the porous layered silicate flame retardant and the mixed resin are combined more stably, when the mixed resin is cured and shrunk under ultraviolet illumination, the porous layered silicate flame retardant is not easy to migrate or fall off, part of the porous layered silicate flame retardant is firmly attached to the surface of the mixed resin, the moisture absorption rate of the flame-retardant layer is reduced, and the flame-retardant effect is also improved.
The thickness of the flame-retardant layer is 0.01-0.02mm, the diameter of the PET core bundle is 0.04-0.5mm, when the thickness of the flame-retardant layer is too large, the toughness of the prepared PET monofilament is lower, and when the thickness of the flame-retardant layer is too small, the flame-retardant effect of the prepared PET monofilament is reduced.
The invention has the beneficial effects that: according to the invention, the porous phyllosilicate flame retardant is mixed with the ultraviolet curing resin, the PVC resin and the polyurethane resin, so that part of the mixed resin forms a stable cross-linking structure with the porous phyllosilicate flame retardant through the porous structure, the porous phyllosilicate flame retardant is uniformly and stably distributed in a mixed resin system, the migration is not easy to occur, and the flame retardant effect is improved;
according to the invention, the ultraviolet curing resin is added, so that the resin matrix is cured and shrunk after being irradiated by ultraviolet light, part of the porous phyllosilicate flame retardant is exposed on the surface of the mixed resin, the porous phyllosilicate flame retardant is firstly contacted with a heat source when the flame retardant layer is combusted, the transmission and diffusion of external heat and oxygen to the inside of the flame retardant layer and a PET core bundle are blocked, the release of internal combustible volatile matters to a gas phase combustion area is blocked, and the smoke suppression effect is good. The porous phyllosilicate flame retardant adhered to the surface of the mixed resin forms a first flame-retardant layer, the porous phyllosilicate flame retardant mixed in the mixed resin, the mixed resin and the wood powder form a second flame-retardant layer, and the PET core bundle is subjected to flame-retardant protection under the synergistic effect of the two flame-retardant layers, so that the flame-retardant effect is excellent, and the mechanical property of the PET flame-retardant monofilament is improved.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The PET flame-retardant monofilament comprises a PET core bundle and a flame-retardant layer coated on the outer side of the PET core bundle, wherein the flame-retardant layer comprises the following raw materials in parts by weight:
specifically, the toughening agent is a mixture of vinyl acetate, epoxidized soybean oil and chlorinated polyethylene in a weight ratio of 2:0.5: 2.5; the compatilizer is a mixture of tri-p-sec-butylphenyl phosphate, dioctyl phthalate and a methyl methacrylate-butadiene-styrene terpolymer in a weight ratio of 1:1: 1; the antioxidant is a mixture of antioxidant 1076, antioxidant 168 and titanium dioxide in a weight ratio of 1:1: 1; the organic solvent is a mixed solution of toluene and ethyl acetate according to the weight ratio of 3.5: 1.
Wherein the particle size of the wood powder is 35 nm.
The preparation method of the porous layered phosphate flame retardant comprises the following steps:
(1) mixing 7 parts by weight of quaternary phosphonium salt and 25 parts by weight of inorganic montmorillonite, adding 55 parts by weight of 75% ethanol aqueous solution in volume concentration under the protection of inert gas nitrogen, heating to 35 ℃, keeping the temperature and stirring at the stirring speed of 350r/min for 0.75h to prepare the phosphorus-containing organic layered silicate;
(2) mixing the phosphorus-containing organic layered silicate prepared in the step (1) with 22.5 parts by weight of amino acid, heating to 55 ℃ under the protection of inert gas nitrogen, and stirring at the stirring speed of 500r/min to prepare the phosphorus-nitrogen-containing organic layered silicate;
(3) adding 7.5 parts by weight of nano-cellulose into 30 parts by weight of ethanol water solution with volume concentration of 92.5% for ultrasonic dispersion to obtain dispersion liquid;
(4) adding 4 parts by weight of sodium dodecyl benzene sulfonate into the phosphorus-nitrogen-containing organic layered silicate prepared in the step (2), then adding 29.5 parts by weight of ethyl orthosilicate and the dispersion liquid prepared in the step (3), fully stirring and reacting, then carrying out solid-liquid separation, and then carrying out vacuum drying at the drying temperature of 125 ℃ to prepare the phosphorus-nitrogen-silicon pillared layered silicate;
(5) roasting the phosphorus-nitrogen-silicon containing pillared layered silicate at 650 ℃ for 1.5h to remove carbon, oxygen organic matters and nanocellulose, thus obtaining the porous layered silicate flame retardant.
Wherein the diameter of the nano-cellulose in the step (3) is 40nm, and the length of the nano-cellulose is 1.5 μm.
Wherein the quaternary phosphonium salt is a mixture of tetrakis hydroxymethyl phosphonium sulfate, tetrakis hydroxymethyl phosphonium sulfate-urea condensate and tetrakis hydroxymethyl phosphonium chloride-urea condensate in a weight ratio of 1:1: 1.
The ultraviolet curing resin comprises the following raw materials in parts by weight:
specifically, the catalyst is triphenylphosphine; the photoinitiator is a mixture consisting of benzophenone, diethoxyacetophenone and benzoin dimethyl ether according to the weight ratio of 1:1.5: 1; the polymerization inhibitor is hydroquinone.
The preparation method of the PET flame-retardant monofilament comprises the following steps:
s1, mixing and uniformly stirring the ultraviolet curing resin, the polyvinyl chloride resin, the polyurethane resin, the wood powder, the flexibilizer, the compatilizer, the antioxidant and the organic solvent according to the weight ratio to prepare a mixed solution;
s2, adding the porous layered silicate flame retardant into the mixed solution prepared in the step S1, and uniformly stirring to prepare flame-retardant mixed solution;
s3, pressurizing the flame-retardant mixed liquid prepared in the step S3 to 65Mpa, keeping the temperature at 55 ℃ for 1h, slowly releasing the pressure, and fully stirring and mixing the flame-retardant mixed liquid again after the flame-retardant mixed liquid is restored to normal pressure to prepare the flame retardant;
and S4, immersing the PET core bundle in the flame retardant to coat the outer layer of the PET core bundle with the flame retardant, and then irradiating by ultraviolet light to cure the flame retardant to form a flame retardant layer to obtain the PET flame retardant monofilament.
Wherein the thickness of the flame-retardant layer is 0.015mm, and the diameter of the PET core bundle is 0.25 mm.
Example 2
The PET flame-retardant monofilament comprises a PET core bundle and a flame-retardant layer coated on the outer side of the PET core bundle, wherein the flame-retardant layer comprises the following raw materials in parts by weight:
specifically, the toughening agent is a mixture of vinyl acetate, epoxidized soybean oil and chlorinated polyethylene in a weight ratio of 1:0.5: 2. The compatilizer is tri-p-sec-butylphenyl phosphate, the antioxidant is antioxidant 1076, and the organic solvent is a mixed solution of toluene and ethyl acetate in a weight ratio of 3: 1.
Wherein the particle size of the wood powder is 20 nm.
The preparation method of the porous layered phosphate flame retardant comprises the following steps:
(1) mixing 4 parts by weight of quaternary phosphonium salt and 20 parts by weight of inorganic montmorillonite, adding 50 parts by weight of ethanol aqueous solution with the volume concentration of 70% under the protection of inert gas nitrogen, heating, keeping the temperature and stirring, wherein the heating temperature is 30 ℃, the stirring speed is 200r/min, and the stirring time is 0.5h, so as to prepare the phosphorus-containing organic layered silicate;
(2) mixing the phosphorus-containing organic layered silicate prepared in the step (1) with 20 parts by weight of amino acid, heating and stirring under the protection of inert gas nitrogen, wherein the heating temperature is 50 ℃, and the stirring speed is 400r/min, so as to prepare the phosphorus-nitrogen containing organic layered silicate;
(3) adding 6 parts by weight of nano-cellulose into 20 parts by weight of ethanol water solution with volume concentration of 90% for ultrasonic dispersion to obtain dispersion liquid;
(4) adding 3 parts by weight of sodium dodecyl benzene sulfonate into the phosphorus-nitrogen-containing organic layered silicate prepared in the step (2), then adding 25 parts by weight of tetraethoxysilane and the dispersion liquid prepared in the step (3), fully stirring for reaction, carrying out solid-liquid separation, and then carrying out vacuum drying at the drying temperature of 100 ℃ to prepare the phosphorus-nitrogen-silicon pillared layered silicate;
(5) roasting the phosphorus-nitrogen-silicon containing pillared layered silicate at the roasting temperature of 600 ℃ for 1h, and removing carbon, oxygen organic matters and nanocellulose to obtain the porous layered silicate flame retardant.
Wherein the diameter of the nano-cellulose in the step (3) is 30nm, and the length of the nano-cellulose is 1 μm.
Specifically, the quaternary phosphonium salt is tetrakis hydroxymethyl phosphonium sulfate.
The ultraviolet curing resin comprises the following raw materials in parts by weight:
specifically, the catalyst is N, N-dimethylbenzylamine; the photoinitiator is benzophenone; the polymerization inhibitor is hydroquinone.
The preparation method of the flame-retardant layer comprises the following steps:
s1, mixing and uniformly stirring the ultraviolet curing resin, the polyvinyl chloride resin, the polyurethane resin, the wood powder, the flexibilizer, the compatilizer, the antioxidant and the organic solvent according to the weight ratio to prepare a mixed solution;
s2, adding the porous layered silicate flame retardant into the mixed solution prepared in the step S1, and uniformly stirring to prepare flame-retardant mixed solution;
s3, pressurizing the flame-retardant mixed liquid prepared in the step S3 to 60Mpa, keeping for 0.5h, slowly releasing pressure, fully stirring and mixing again after the flame-retardant mixed liquid is restored to normal pressure to prepare the flame-retardant material;
s4, immersing the PET core bundle in the flame retardant to coat the outer layer of the PET core bundle with the flame retardant, and then irradiating the flame retardant by ultraviolet light to solidify the flame retardant to form the flame retardant layer.
Wherein, the thickness of fire-retardant layer is 0.01mm, the diameter of PET core bundle is 0.04 mm.
Example 3
The PET flame-retardant monofilament comprises a PET core bundle and a flame-retardant layer coated on the outer side of the PET core bundle, wherein the flame-retardant layer comprises the following raw materials in parts by weight:
specifically, the toughening agent is a mixture of vinyl acetate, epoxidized soybean oil and chlorinated polyethylene in a weight ratio of 3:0.5: 3. The compatilizer is dioctyl phthalate. The antioxidant is antioxidant 168. The organic solvent is a mixed solution of toluene and ethyl acetate according to the weight ratio of 4:1
Wherein the particle size of the wood powder is 50 nm.
The preparation method of the porous layered phosphate flame retardant comprises the following steps:
(1) mixing 10 parts by weight of quaternary phosphonium salt and 30 parts by weight of inorganic montmorillonite, adding 60 parts by weight of 80% ethanol aqueous solution under the protection of inert gas nitrogen, heating, keeping the temperature and stirring, wherein the heating temperature is 40 ℃, the stirring speed is 500r/min, and the stirring time is 1h to prepare the phosphorus-containing organic layered silicate;
(2) mixing the phosphorus-containing organic layered silicate prepared in the step (1) with 25 parts by weight of amino acid, heating and stirring under the protection of inert gas, wherein the heating temperature is 60 ℃, and the stirring speed is 600r/min, so as to prepare the phosphorus-nitrogen-containing organic layered silicate;
(3) adding 9 parts by weight of nano-cellulose into 40 parts by weight of ethanol aqueous solution with volume concentration of 95% for ultrasonic dispersion to obtain dispersion liquid;
(4) adding 5 parts by weight of sodium dodecyl benzene sulfonate into the phosphorus-nitrogen-containing organic layered silicate prepared in the step (2), then adding 34 parts by weight of ethyl orthosilicate and the dispersion liquid prepared in the step (3), fully stirring for reaction, performing solid-liquid separation, and then performing vacuum drying at the drying temperature of 150 ℃ to prepare the phosphorus-nitrogen-silicon pillared layered silicate;
(5) roasting the phosphorus-nitrogen-silicon containing pillared layered silicate at the roasting temperature of 700 ℃ for 2 hours to remove carbon, oxygen organic matters and nanocellulose to prepare the porous layered silicate flame retardant.
Wherein the diameter of the nano-cellulose in the step (3) is 50nm, and the length of the nano-cellulose is 2 μm.
Specifically, the quaternary phosphonium salt is a tetrakis hydroxymethyl phosphonium sulfate-urea condensate.
The ultraviolet curing resin comprises the following raw materials in parts by weight:
specifically, the catalyst is N, N-dimethylbenzylamine; the photoinitiator is diethoxyacetophenone; the polymerization inhibitor is hydroquinone.
The preparation method of the flame-retardant layer comprises the following steps:
s1, mixing and uniformly stirring the ultraviolet curing resin, the polyvinyl chloride resin, the polyurethane resin, the wood powder, the flexibilizer, the compatilizer, the antioxidant and the organic solvent according to the weight ratio to prepare a mixed solution;
s2, adding the porous layered silicate flame retardant into the mixed solution prepared in the step S1, and uniformly stirring to prepare flame-retardant mixed solution;
s3, pressurizing the flame-retardant mixed liquid prepared in the step S3 to 70Mpa, keeping for 1.5h, slowly releasing pressure, fully stirring and mixing again after the flame-retardant mixed liquid is restored to normal pressure to prepare the flame-retardant material;
s4, immersing the PET core bundle in the flame retardant to coat the outer layer of the PET core bundle with the flame retardant, and then irradiating the flame retardant by ultraviolet light to solidify the flame retardant to form the flame retardant layer.
Wherein, the thickness of fire-retardant layer is 0.02mm, the diameter of PET core bundle is 0.5 mm.
Performance testing
The PET flame-retardant monofilaments prepared in the above examples 1 to 3 were subjected to performance tests such as flame retardancy, smoke suppression, tensile strength, heat distortion temperature, water resistance, and anti-dripping, and the test results are shown in table 1.
The test method of the waterproof performance comprises the following steps: soaking the prepared PET flame-retardant monofilament in water for 48h, and testing the weight g of the PET flame-retardant monofilament before soaking1Weight g of the impregnated PET flame-retardant monofilament2And according to (g)2-g1)/g1Calculating the moisture absorption rate of the PET flame-retardant monofilament.
TABLE 1 summary of the performance test results for the flame retardant PET monofilaments made in examples 1-3
The performance test results in the table 1 show that the PET flame-retardant monofilament prepared by the invention has a smoke density grade of 8-10 and a good smoke suppression effect; the tensile strength is between 84 and 89MPa, and the tensile property is good; the flame retardant grade of the prepared PET flame retardant monofilament is grade A, the thermal deformation temperature is 152-180 ℃, the flame retardant property is excellent, the property is stable, the thermal deformation is not easy to occur, the anti-dripping property is good, and the waterproof property is good.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
- The PET flame-retardant monofilament is characterized in that: the PET core bundle flame-retardant coating comprises a PET core bundle and a flame-retardant layer coated on the outer side of the PET core bundle, wherein the flame-retardant layer comprises the following raw materials in parts by weight:
the ultraviolet curing resin comprises the following raw materials in parts by weight:
- 2. the PET flame retardant monofilament according to claim 1, wherein: the preparation method of the porous layered phosphate flame retardant comprises the following steps:(1) mixing 4-10 parts by weight of quaternary phosphonium salt and 20-30 parts by weight of inorganic montmorillonite, adding 50-60 parts by weight of 70-80% ethanol aqueous solution under the protection of inert gas, heating, keeping the temperature and stirring to prepare phosphorus-containing organic layered silicate;(2) mixing the phosphorus-containing organic layered silicate prepared in the step (1) with 20-25 parts by weight of amino acid, heating and stirring under the protection of inert gas to prepare phosphorus-nitrogen-containing organic layered silicate;(3) adding 6-9 parts by weight of nano cellulose into 20-40 parts by weight of ethanol water solution with volume concentration of 90-95% for ultrasonic dispersion to obtain dispersion liquid;(4) adding 3-5 parts by weight of sodium dodecyl benzene sulfonate into the phosphorus-nitrogen-containing organic layered silicate prepared in the step (2), then adding 25-34 parts by weight of ethyl orthosilicate and the dispersion liquid prepared in the step (3), fully stirring for reaction, performing solid-liquid separation, and then performing vacuum drying to prepare the phosphorus-nitrogen-silicon pillared layered silicate;(5) roasting the phosphorus-nitrogen-silicon containing pillared layered silicate to remove carbon, oxygen organic matters and nanocellulose to prepare the porous layered silicate flame retardant.
- 3. The PET flame retardant monofilament according to claim 2, wherein: the diameter of the nano-cellulose in the step (3) is 30-50nm, and the length is 1-2 μm.
- 4. The PET flame retardant monofilament according to claim 2, wherein: the heating temperature in the step (1) is 30-40 ℃, the stirring speed is 200-500r/min, and the stirring time is 0.5-1 h.
- 5. The PET flame retardant monofilament according to claim 2, wherein: the heating temperature in the step (2) is 50-60 ℃, and the stirring speed is 400-600 r/min; the drying temperature in the step (4) is 100-150 ℃.
- 6. The PET flame retardant monofilament according to claim 2, wherein: the roasting temperature in the step (5) is 600-700 ℃, and the roasting time is 1-2 h.
- 7. The PET flame retardant monofilament according to claim 1, wherein: the grain size of the wood powder is 20-50 nm.
- 8. The PET flame retardant monofilament according to claim 1, wherein: the toughening agent is a mixture of vinyl acetate, epoxidized soybean oil and chlorinated polyethylene in a weight ratio of 1-3:0.5: 2-3.
- 9. The PET flame retardant monofilament according to claim 1, wherein: the preparation method of the PET flame-retardant monofilament comprises the following steps:s1, mixing and uniformly stirring the ultraviolet curing resin, the polyvinyl chloride resin, the polyurethane resin, the wood powder, the flexibilizer, the compatilizer, the antioxidant and the organic solvent according to the weight ratio to prepare a mixed solution;s2, adding the porous layered silicate flame retardant into the mixed solution prepared in the step S1, and uniformly stirring to prepare flame-retardant mixed solution;s3, pressurizing the flame-retardant mixed liquid prepared in the step S3 to 60-70Mpa, keeping for 0.5-1.5h, slowly releasing the pressure, and fully stirring and mixing again after the flame-retardant mixed liquid is restored to normal pressure to prepare the flame-retardant material;and S4, immersing the PET core bundle in the flame retardant to coat the outer layer of the PET core bundle with the flame retardant, and then irradiating by ultraviolet light to cure the flame retardant to form a flame retardant layer to obtain the PET flame retardant monofilament.
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