CN111732709A - Phytic acid-melamine composite reaction type flame retardant modified polyurethane and preparation method thereof - Google Patents
Phytic acid-melamine composite reaction type flame retardant modified polyurethane and preparation method thereof Download PDFInfo
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- CN111732709A CN111732709A CN202010635654.7A CN202010635654A CN111732709A CN 111732709 A CN111732709 A CN 111732709A CN 202010635654 A CN202010635654 A CN 202010635654A CN 111732709 A CN111732709 A CN 111732709A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention relates to the field of flame retardant materials and discloses phytic acid-melamine composite reaction type flame retardant modified polyurethane, hydroxyl of melamine polyether polyol and phosphate groups of phytic acid modified graphene are subjected to phosphorylation esterification reaction to obtain melamine polyol-phytate modified graphene serving as a nitrogen-phosphorus composite flame retardant, polyester diol and isophorone diisocyanate are used as polymerization monomers, melamine polyol-phytate modified graphene is used as a reactive flame retardant to participate in the polymerization process, the interfacial compatibility of the composite flame retardant and polyurethane is improved, a large amount of non-combustible gases such as ammonia gas, nitrogen gas and the like are generated under high-temperature combustion, and are decomposed into a large amount of phosphoric acid derivatives, can be used as a char forming agent and an inhibitor of a combustion chain free radical reaction, and the uniformly dispersed graphene forms a continuous compact carbon layer at a high temperature.
Description
Technical Field
The invention relates to the field of flame retardant materials, in particular to phytic acid-melamine composite reaction type flame retardant modified polyurethane and a preparation method thereof.
Background
Organic high molecular polymer materials such as epoxy resin, polyurethane and the like have excellent performance and wide application, but the traditional high molecular materials have poor flame retardant property and are easy to burn, so that a flame retardant is required to be added to improve the flame retardant property of the organic high molecular materials, and the flame retardant is mainly available; the halogen-containing flame retardant, the nitrogen-based flame retardant, the nitrogen-phosphorus-based flame retardant and the like can be divided into an additive flame retardant and a reactive flame retardant, wherein the reactive flame retardant is used as a polymerization monomer to react in a high polymer matrix, and has the advantages of small using amount, excellent flame retardant effect, lasting flame retardant property, small influence on the mechanical property and the usability of a high polymer material and the like.
Polyurethane is a common organic polymer material, can be divided into polyester type and polyether type, can be made into polyurethane plastics, polyurethane fiber, polyurethane coating, polyurethane rubber elastomer and the like, has excellent rebound resilience, mechanical property and chemical resistance, and has important application in the fields of building industry, automobile manufacturing industry, aviation industry and the like, but the traditional polyurethane material has low ignition point, a large amount of dense smoke escapes during combustion, the flame retardant property is poor, and the further development and application of the polyurethane material are limited.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides phytic acid-melamine composite reaction type flame retardant modified polyurethane and a preparation method thereof, and solves the problem of poor flame retardant property of a polyurethane material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the phytic acid-melamine composite reaction type flame retardant modified polyurethane comprises the following steps:
(1) adding a deionized water solvent, hydroxylated graphene and phytic acid into a reaction bottle, placing the reaction bottle in an ultrasonic treatment instrument for ultrasonic dispersion treatment, placing the reaction bottle in a reaction kettle for heating to 150-180 ℃, reacting for 10-20h, filtering the solvent, washing with deionized water and ethanol, and drying to prepare the phytic acid modified graphene.
(2) Adding an N, N-dimethylacetamide solvent and melamine into a reaction bottle, placing the mixture into a reaction kettle after uniform ultrasonic dispersion, introducing nitrogen to keep the pressure in the reaction kettle at 0.2-0.5MPa, slowly dropwise adding epichlorohydrin and a catalyst potassium methoxide, heating to 150 ℃ and 170 ℃, reacting for 3-8h, vacuum drying to remove the solvent, washing with deionized water and ethanol, and drying to prepare the melamine polyether polyol.
(3) Adding a deionized water solvent, phytic acid modified graphene and melamine polyether polyol into a reaction bottle, adding a catalyst urea, heating to 90-120 ℃ after uniform ultrasonic dispersion, stirring at a constant speed for reaction for 12-24h, filtering the solvent, washing with deionized water and ethanol, and drying to prepare melamine polyol-phytate modified graphene.
(4) Adding polyester diol, isophorone diisocyanate and melamine polyol-phytate modified graphene into a reaction bottle, uniformly stirring at 75-85 ℃, adding a catalyst dibutyltin dilaurate, uniformly stirring for reacting for 4-6h, cooling to 40-50 ℃, adding an acetone solvent and triethylamine to adjust the pH of the solution to be neutral, adding 1, 4-butanediol, reacting for 1-2h, pouring into a mold for vacuum defoaming, drying and curing, and preparing the phytic acid-melamine composite reaction type flame retardant modified polyurethane.
Preferably, the mass ratio of the hydroxylated graphene to the phytic acid in the step (1) is 10: 50-100.
Preferably, the ultrasonic treatment instrument in the step (1) comprises a water bath, the inner wall of the water bath is fixedly connected with an ultrasonic device, the lower part of the water bath is fixedly connected with a base, a supporting rod is fixedly connected with the upper part of the base, a via hole is formed in the supporting rod, a moving rod is movably connected in the via hole, a clamping plate is fixedly connected with the moving rod, and a reaction bottle is movably connected with the clamping plate.
Preferably, the melamine, the epichlorohydrin and the potassium methoxide in the step (2) are 10:70-80: 0.4-0.8.
Preferably, the mass ratio of the phytic acid modified graphene, the melamine polyether polyol and the urea in the step (3) is 100:150-250: 80-120.
Preferably, the mass ratio of the polyester diol, the isophorone diisocyanate, the melamine polyol-phytate modified graphene, the dibutyltin dilaurate and the 1, 4-butanediol in the step (4) is 100:65-75:5-15:0.01-0.04: 4-6.
(III) advantageous technical effects
Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:
according to the phytic acid-melamine composite reaction type flame retardant modified polyurethane, the surface of hydroxylated graphene contains rich hydroxyl groups, phosphoric acid groups of phytic acid and a large number of hydroxyl groups are subjected to phosphorylation esterification reaction through ultrasonic dispersion and thermal reaction to obtain phytic acid modified graphene, potassium methoxide is used as a catalyst, one molecular amino group of melamine and one molecular chlorine atom of epoxy chloropropane are subjected to condensation substitution reaction, then an epoxy group and one molecular chlorine atom of epoxy chloropropane are subjected to ring opening reaction to obtain melamine polyether polyol, urea is used as a catalyst, the hydroxyl groups of the melamine polyether polyol and the unreacted phosphoric acid groups of the phytic acid modified graphene are subjected to phosphorylation esterification reaction, and the obtained melamine polyol-phytate modified graphene is used as a nitrogen-phosphorus composite flame retardant.
The phytic acid-melamine composite reaction type flame retardant modified polyurethane takes polyester diol and isophorone diisocyanate as polymerization monomers, melamine polyol-phytate modified graphene as a polyol component to replace part of the polyester diol and participates in the polymerization process as a reaction type flame retardant, so that the interface compatibility of a composite flame retardant and polyurethane is improved, the influence of the composite flame retardant on the mechanical property of the polyurethane is reduced, the melamine-phytate component in the melamine polyol-phytate modified graphene composite flame retardant is taken as a flame retardant active component, a large amount of non-combustible gases such as ammonia gas and nitrogen gas are generated under high-temperature combustion, the concentration of oxygen is diluted and meanwhile decomposed into a large amount of phosphoric acid derivatives, and the phosphoric acid derivatives can be taken as an inhibitor of the reaction of a char forming agent and a combustion chain free radical, so that the carbonization of the surface of the polyurethane is promoted and the combustion process is inhibited, meanwhile, graphene is uniformly dispersed in polyurethane, a continuous and compact carbon layer is further formed at high temperature, oxygen permeation is inhibited, and excellent flame retardant performance is shown under the synergistic effect.
Drawings
FIG. 1 is a schematic front view of an ultrasonic treatment apparatus;
FIG. 2 is an enlarged view of the support rod;
fig. 3 is a schematic view of the travel bar adjustment.
1-ultrasonic treatment instrument; 2-water bath; 3-an ultrasonic device; 4-a base; 5-a support rod; 6-via holes; 7-moving the rod; 8-clamping plate; 9-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a phytic acid-melamine composite reaction type flame retardant modified polyurethane is prepared by the following steps:
(1) adding a deionized water solvent into a reaction bottle, placing the hydroxylated graphene and the phytic acid with the mass ratio of 10:50-100 into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a water bath, the inner wall of the water bath is fixedly connected with an ultrasonic device, the lower part of the water bath is fixedly connected with a base, a support rod is fixedly connected above the base, a through hole is formed in the support rod, a moving rod is movably connected in the through hole and fixedly connected with a clamping plate, the clamping plate is movably connected with the reaction bottle for ultrasonic dispersion treatment, placing the reaction bottle in a reaction kettle, heating to 150 degrees centigrade and 180 degrees centigrade, reacting for 10-20 hours, filtering the solvent, washing and drying by using deionized water and ethanol, and preparing the phytic acid modified graphene.
(2) Adding an N, N-dimethylacetamide solvent and melamine into a reaction bottle, placing the mixture into a reaction kettle after uniform ultrasonic dispersion, introducing nitrogen to keep the pressure in the reaction kettle at 0.2-0.5MPa, slowly dropwise adding epichlorohydrin and a catalyst potassium methoxide, wherein the ratio of melamine, epichlorohydrin and potassium methoxide is 10:70-80:0.4-0.8, heating to 150-170 ℃, reacting for 3-8h, vacuum drying to remove the solvent, washing with deionized water and ethanol, and drying to prepare the melamine polyether polyol.
(3) Adding a deionized water solvent, phytic acid modified graphene and melamine polyether polyol into a reaction bottle, adding a catalyst urea at a mass ratio of 100: 150-.
(4) Adding polyester diol, isophorone diisocyanate and melamine polyol-phytate modified graphene into a reaction bottle, stirring at 75-85 deg.C, adding dibutyltin dilaurate as catalyst, stirring at uniform speed for reaction for 4-6 hr, cooling to 40-50 deg.C, adding acetone solvent and triethylamine to adjust pH of the solution to neutrality, adding 1, 4-butanediol, wherein the mass ratio of the polyester diol to the isophorone diisocyanate to the melamine polyol-phytate modified graphene to the dibutyltin dilaurate to the 1, 4-butanediol is 100:65-75:5-15:0.01-0.04:4-6, the reaction is carried out for 1-2h, and the reaction product is poured into a mold for vacuum defoaming, drying and curing to prepare the phytic acid-melamine composite reaction type flame retardant modified polyurethane.
Example 1
(1) Adding a deionized water solvent into a reaction bottle, placing the hydroxylated graphene and the phytic acid with the mass ratio of 10:50 into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a water bath, the inner wall of the water bath is fixedly connected with an ultrasonic device, the lower part of the water bath is fixedly connected with a base, a support rod is fixedly connected above the base, a through hole is formed in the support rod, a moving rod is movably connected in the through hole, a clamping plate is fixedly connected with the moving rod, the clamping plate is movably connected with the reaction bottle, carrying out ultrasonic dispersion treatment, placing the reaction bottle in a reaction kettle, heating to 150 ℃, reacting for 10 hours, filtering the solvent, washing with deionized water and ethanol, and drying to prepare the phytic acid modified graphene.
(2) Adding an N, N-dimethylacetamide solvent and melamine into a reaction bottle, placing the mixture into a reaction kettle after uniform ultrasonic dispersion, introducing nitrogen to keep the pressure in the reaction kettle at 0.2MPa, slowly dropwise adding epichlorohydrin and a catalyst potassium methoxide, wherein the ratio of 10:70:0.4 of melamine, epichlorohydrin and potassium methoxide is 10, heating the mixture to 150 ℃, reacting for 3 hours, vacuum drying to remove the solvent, washing the mixture with deionized water and ethanol, and drying the mixture to prepare the melamine polyether polyol.
(3) Adding a deionized water solvent, phytic acid modified graphene and melamine polyether polyol into a reaction bottle, adding a catalyst urea at a mass ratio of 100:150:80, uniformly dispersing by ultrasonic, heating to 90 ℃, uniformly stirring for reaction for 12 hours, filtering the solvent, washing with deionized water and ethanol, and drying to obtain melamine polyol-phytate modified graphene.
(4) Adding polyester diol, isophorone diisocyanate and melamine polyol-phytate modified graphene into a reaction bottle, stirring uniformly at 75 ℃, adding a catalyst dibutyltin dilaurate, stirring at a constant speed for reaction for 4 hours, cooling to 40 ℃, adding an acetone solvent and triethylamine to adjust the pH of the solution to be neutral, adding 1, 4-butanediol, wherein the mass ratio of the polyester diol, isophorone diisocyanate, melamine polyol-phytate modified graphene, dibutyltin dilaurate to 1, 4-butanediol is 100:65:5:0.01:4, reacting for 1 hour, pouring into a mold, and carrying out vacuum defoamation and drying curing to prepare the phytic acid-melamine composite reaction type flame retardant modified polyurethane 1.
Example 2
(1) Adding a deionized water solvent into a reaction bottle, placing the hydroxylated graphene and the phytic acid with the mass ratio of 10:60 into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a water bath, the inner wall of the water bath is fixedly connected with an ultrasonic device, the lower part of the water bath is fixedly connected with a base, a supporting rod is fixedly connected above the base, a through hole is formed in the supporting rod, a moving rod is movably connected in the through hole, a clamping plate is fixedly connected with the moving rod, the clamping plate is movably connected with the reaction bottle, carrying out ultrasonic dispersion treatment, placing the reaction bottle in a reaction kettle, heating to 180 ℃, reacting for 10 hours, filtering the solvent, washing with deionized water and ethanol, and drying to prepare the phytic acid modified graphene.
(2) Adding an N, N-dimethylacetamide solvent and melamine into a reaction bottle, placing the mixture into a reaction kettle after uniform ultrasonic dispersion, introducing nitrogen to keep the pressure in the reaction kettle at 0.3MPa, slowly dropwise adding epichlorohydrin and a catalyst potassium methoxide, wherein the ratio of melamine to epichlorohydrin to potassium methoxide is 10:74:0.5, heating to 170 ℃, reacting for 8 hours, vacuum drying to remove the solvent, washing with deionized water and ethanol, and drying to prepare the melamine polyether polyol.
(3) Adding a deionized water solvent, phytic acid modified graphene and melamine polyether polyol into a reaction bottle, adding a catalyst urea at a mass ratio of 100:180:90, uniformly dispersing by ultrasonic, heating to 120 ℃, uniformly stirring for reaction for 24 hours, filtering the solvent, washing with deionized water and ethanol, and drying to obtain melamine polyol-phytate modified graphene.
(4) Adding polyester diol, isophorone diisocyanate and melamine polyol-phytate modified graphene into a reaction bottle, stirring uniformly at 75 ℃, adding a catalyst dibutyltin dilaurate, stirring at a constant speed for reaction for 4 hours, cooling to 50 ℃, adding an acetone solvent and triethylamine to adjust the pH of the solution to be neutral, adding 1, 4-butanediol, wherein the mass ratio of the polyester diol, isophorone diisocyanate, melamine polyol-phytate modified graphene, dibutyltin dilaurate to 1, 4-butanediol is 100:68:8:0.02:4.5, reacting for 2 hours, pouring into a mold, and carrying out vacuum defoamation, drying and curing to prepare the phytic acid-melamine composite reaction type flame retardant modified polyurethane 2.
Example 3
(1) Adding a deionized water solvent into a reaction bottle, placing the hydroxylated graphene and the phytic acid with the mass ratio of 10:65 into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a water bath, the inner wall of the water bath is fixedly connected with an ultrasonic device, the lower part of the water bath is fixedly connected with a base, a supporting rod is fixedly connected above the base, a through hole is formed in the supporting rod, a moving rod is movably connected in the through hole, a clamping plate is fixedly connected with the moving rod, the clamping plate is movably connected with the reaction bottle, carrying out ultrasonic dispersion treatment, placing the reaction bottle in a reaction kettle, heating to 170 ℃, reacting for 15 hours, filtering the solvent, washing with deionized water and ethanol, and drying to prepare the phytic acid modified graphene.
(2) Adding an N, N-dimethylacetamide solvent and melamine into a reaction bottle, placing the mixture into a reaction kettle after uniform ultrasonic dispersion, introducing nitrogen to keep the pressure in the reaction kettle at 0.4MPa, slowly dropwise adding epichlorohydrin and a catalyst potassium methoxide, wherein the ratio of the melamine to the epichlorohydrin to the potassium methoxide is 10:78:0.65, heating to 160 ℃, reacting for 5 hours, vacuum drying to remove the solvent, washing with deionized water and ethanol, and drying to prepare the melamine polyether polyol.
(3) Adding a deionized water solvent, phytic acid modified graphene and melamine polyether polyol into a reaction bottle, adding a catalyst urea at a mass ratio of 100:220:105, uniformly dispersing by ultrasonic, heating to 100 ℃, uniformly stirring for reacting for 18h, filtering the solvent, washing with deionized water and ethanol, and drying to obtain melamine polyol-phytate modified graphene.
(4) Adding polyester diol, isophorone diisocyanate and melamine polyol-phytate modified graphene into a reaction bottle, stirring uniformly at 80 ℃, adding a catalyst dibutyltin dilaurate, stirring at a constant speed for reaction for 5 hours, cooling to 45 ℃, adding an acetone solvent and triethylamine to adjust the pH of the solution to be neutral, adding 1, 4-butanediol, wherein the mass ratio of the polyester diol, isophorone diisocyanate, melamine polyol-phytate modified graphene, dibutyltin dilaurate to 1, 4-butanediol is 100:72:12:0.03:5.5, reacting for 1.5 hours, pouring into a mold for vacuum defoamation and drying and curing, and preparing the phytic acid-melamine composite reaction type flame retardant modified polyurethane 3.
Example 4
(1) Adding a deionized water solvent into a reaction bottle, placing the hydroxylated graphene and the phytic acid with the mass ratio of 10:100 into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a water bath, the inner wall of the water bath is fixedly connected with an ultrasonic device, the lower part of the water bath is fixedly connected with a base, a supporting rod is fixedly connected above the base, a through hole is formed in the supporting rod, a moving rod is movably connected in the through hole, a clamping plate is fixedly connected with the moving rod, the clamping plate is movably connected with the reaction bottle, carrying out ultrasonic dispersion treatment, placing the reaction bottle in a reaction kettle, heating to 180 ℃, reacting for 20 hours, filtering the solvent, washing with deionized water and ethanol, and drying to prepare the phytic acid modified graphene.
(2) Adding an N, N-dimethylacetamide solvent and melamine into a reaction bottle, placing the mixture into a reaction kettle after uniform ultrasonic dispersion, introducing nitrogen to keep the pressure in the reaction kettle at 0.5MPa, slowly dropwise adding epichlorohydrin and a catalyst potassium methoxide, wherein the ratio of the melamine to the epichlorohydrin to the potassium methoxide is 10:80:0.8, heating to 170 ℃, reacting for 8 hours, vacuum drying to remove the solvent, washing with deionized water and ethanol, and drying to prepare the melamine polyether polyol.
(3) Adding a deionized water solvent, phytic acid modified graphene and melamine polyether polyol into a reaction bottle, adding a catalyst urea at a mass ratio of 100:250:120, uniformly dispersing by using ultrasonic waves, heating to 120 ℃, uniformly stirring for reaction for 24 hours, filtering the solvent, washing with deionized water and ethanol, and drying to obtain melamine polyol-phytate modified graphene.
(4) Adding polyester diol, isophorone diisocyanate and melamine polyol-phytate modified graphene into a reaction bottle, stirring uniformly at 85 ℃, then adding a catalyst dibutyltin dilaurate, stirring at a constant speed for reaction for 6 hours, cooling to 50 ℃, adding an acetone solvent and triethylamine to adjust the pH of the solution to be neutral, then adding 1, 4-butanediol, wherein the mass ratio of the polyester diol, isophorone diisocyanate, melamine polyol-phytate modified graphene, dibutyltin dilaurate to 1, 4-butanediol is 100:75:15:0.04:6, reacting for 2 hours, pouring into a mold for vacuum defoamation and drying and curing, and preparing the phytic acid-melamine composite reaction type flame retardant modified polyurethane 4.
Comparative example 1
(1) Adding a deionized water solvent into a reaction bottle, placing the hydroxylated graphene and the phytic acid with the mass ratio of 10:40 into an ultrasonic treatment instrument, wherein the ultrasonic treatment instrument comprises a water bath, the inner wall of the water bath is fixedly connected with an ultrasonic device, the lower part of the water bath is fixedly connected with a base, a supporting rod is fixedly connected above the base, a through hole is formed in the supporting rod, a moving rod is movably connected in the through hole, a clamping plate is fixedly connected with the moving rod, the clamping plate is movably connected with the reaction bottle, carrying out ultrasonic dispersion treatment, placing the reaction bottle in a reaction kettle, heating to 180 ℃, reacting for 10 hours, filtering the solvent, washing with deionized water and ethanol, and drying to prepare the phytic acid modified graphene.
(2) Adding an N, N-dimethylacetamide solvent and melamine into a reaction bottle, placing the mixture into a reaction kettle after uniform ultrasonic dispersion, introducing nitrogen to keep the pressure in the reaction kettle at 0.5MPa, slowly dropwise adding epichlorohydrin and a catalyst potassium methoxide, wherein the ratio of melamine to epichlorohydrin to potassium methoxide is 10:65:0.3, heating to 170 ℃, reacting for 4 hours, vacuum drying to remove the solvent, washing with deionized water and ethanol, and drying to prepare the melamine polyether polyol.
(3) Adding a deionized water solvent, phytic acid modified graphene and melamine polyether polyol into a reaction bottle, adding a catalyst urea at a mass ratio of 100:120:70, uniformly dispersing by ultrasonic, heating to 90 ℃, uniformly stirring for reaction for 24 hours, filtering the solvent, washing with deionized water and ethanol, and drying to obtain melamine polyol-phytate modified graphene.
(4) Adding polyester diol, isophorone diisocyanate and melamine polyol-phytate modified graphene into a reaction bottle, stirring uniformly at 85 ℃, then adding a catalyst dibutyltin dilaurate, stirring at a constant speed for reaction for 4 hours, cooling to 50 ℃, adding an acetone solvent and triethylamine to adjust the pH of the solution to be neutral, then adding 1, 4-butanediol, wherein the mass ratio of the polyester diol, isophorone diisocyanate, melamine polyol-phytate modified graphene, dibutyltin dilaurate to 1, 4-butanediol is 100:60:3:0.008:3.5, reacting for 2 hours, pouring into a mold for vacuum defoamation and drying and curing, and preparing the phytic acid-melamine composite reaction type flame retardant modified polyurethane comparative 1.
The flame retardant performance of the phytic acid-melamine composite reaction type flame retardant modified polyurethane in the examples and the comparative examples is tested by using an SH-8350 horizontal and vertical combustion tester, and the test standard is UL94 flame retardant test method and standard.
| Testing | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| UL94 rating | V-0 | V-0 | V-0 | V-0 | V-1 |
Claims (6)
1. A phytic acid-melamine composite reaction type flame retardant modified polyurethane is characterized in that: the preparation method of the phytic acid-melamine composite reaction type flame retardant modified polyurethane comprises the following steps:
(1) adding hydroxylated graphene and phytic acid into a deionized water solvent, placing the mixture into an ultrasonic treatment instrument for ultrasonic dispersion treatment, placing the mixture into a reaction kettle for heating to 150 ℃ and 180 ℃, reacting for 10-20h, filtering, washing and drying to prepare phytic acid modified graphene;
(2) adding melamine into an N, N-dimethylacetamide solvent, placing the mixture into a reaction kettle after ultrasonic dispersion is uniform, introducing nitrogen to keep the pressure in the reaction kettle at 0.2-0.5MPa, slowly dropwise adding epichlorohydrin and catalyst potassium methoxide, heating to 150 ℃ and 170 ℃, reacting for 3-8h, washing and drying to prepare melamine polyether polyol;
(3) adding phytic acid modified graphene and melamine polyether polyol into a deionized water solvent, adding a catalyst urea, uniformly dispersing by ultrasonic, heating to 90-120 ℃, reacting for 12-24h, filtering, washing and drying to prepare melamine polyol-phytate modified graphene;
(4) adding isophorone diisocyanate and melamine polyol-phytate modified graphene into polyester diol, stirring at 75-85 ℃, adding a catalyst dibutyltin dilaurate, reacting for 4-6h, cooling to 40-50 ℃, adding an acetone solvent and triethylamine to adjust the pH of the solution to be neutral, adding 1, 4-butanediol, reacting for 1-2h, pouring into a mold, performing vacuum defoaming, drying and curing, and preparing the phytic acid-melamine composite reaction type flame retardant modified polyurethane.
2. The phytic acid-melamine composite reaction type flame retardant modified polyurethane as claimed in claim 1, wherein: the mass ratio of the hydroxylated graphene to the phytic acid in the step (1) is 10: 50-100.
3. The phytic acid-melamine composite reaction type flame retardant modified polyurethane as claimed in claim 1, wherein: the ultrasonic treatment instrument in the step (1) comprises a water bath, an ultrasonic device is fixedly connected to the inner wall of the water bath, a base is fixedly connected to the lower portion of the water bath, a supporting rod is fixedly connected to the upper portion of the base, a via hole is formed in the supporting rod, a moving rod is movably connected to the inner portion of the via hole, a clamping plate is fixedly connected to the moving rod, and a reaction bottle is movably connected to the clamping plate.
4. The phytic acid-melamine composite reaction type flame retardant modified polyurethane as claimed in claim 1, wherein: the ratio of melamine, epichlorohydrin to potassium methoxide in the step (2) is 10:70-80: 0.4-0.8.
5. The phytic acid-melamine composite reaction type flame retardant modified polyurethane as claimed in claim 1, wherein: the mass ratio of the phytic acid modified graphene, the melamine polyether polyol and the urea in the step (3) is 100:150-250: 80-120.
6. The phytic acid-melamine composite reaction type flame retardant modified polyurethane as claimed in claim 1, wherein: the mass ratio of the polyester diol, the isophorone diisocyanate, the melamine polyol-phytate modified graphene, the dibutyltin dilaurate and the 1, 4-butanediol in the step (4) is 100:65-75:5-15:0.01-0.04: 4-6.
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Cited By (6)
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| CN113088066A (en) * | 2021-04-07 | 2021-07-09 | 福州大学 | Flame-retardant thermoplastic polyurethane composite material |
| CN113150522A (en) * | 2021-05-25 | 2021-07-23 | 江南大学 | Modified flame-retardant polyester material containing all-bio-based flame retardant and preparation method thereof |
| CN113354680A (en) * | 2021-06-23 | 2021-09-07 | 河北科技大学 | Bio-based reactive flame retardant, flame-retardant waterborne polyurethane emulsion and preparation method |
| CN113621176A (en) * | 2021-07-26 | 2021-11-09 | 四川大学 | Single-molecule intumescent flame retardant MPPR and MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material |
| CN114516935A (en) * | 2021-12-07 | 2022-05-20 | 徐州飞云泡沫制品有限责任公司 | Reactive flame retardant modified polystyrene foam material and preparation method thereof |
| CN114890960A (en) * | 2022-05-17 | 2022-08-12 | 淮阴师范学院 | Preparation method and application of hydroxyl modified melamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113088066A (en) * | 2021-04-07 | 2021-07-09 | 福州大学 | Flame-retardant thermoplastic polyurethane composite material |
| CN113088066B (en) * | 2021-04-07 | 2022-03-08 | 福州大学 | Flame-retardant thermoplastic polyurethane composite material |
| CN113150522A (en) * | 2021-05-25 | 2021-07-23 | 江南大学 | Modified flame-retardant polyester material containing all-bio-based flame retardant and preparation method thereof |
| CN113354680A (en) * | 2021-06-23 | 2021-09-07 | 河北科技大学 | Bio-based reactive flame retardant, flame-retardant waterborne polyurethane emulsion and preparation method |
| CN113621176A (en) * | 2021-07-26 | 2021-11-09 | 四川大学 | Single-molecule intumescent flame retardant MPPR and MPPR/POSS composite synergistic halogen-free flame retardant polypropylene composite material |
| CN113621176B (en) * | 2021-07-26 | 2023-03-10 | 四川大学 | Single-molecule intumescent flame retardant MPPR (modified Polypropylene) and MPPR/POSS (polyhedral oligomeric silsesquioxane) composite synergistic halogen-free flame retardant polypropylene composite material |
| CN114516935A (en) * | 2021-12-07 | 2022-05-20 | 徐州飞云泡沫制品有限责任公司 | Reactive flame retardant modified polystyrene foam material and preparation method thereof |
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| CN114890960A (en) * | 2022-05-17 | 2022-08-12 | 淮阴师范学院 | Preparation method and application of hydroxyl modified melamine |
| CN114890960B (en) * | 2022-05-17 | 2023-09-15 | 淮阴师范学院 | Preparation method and application of hydroxyl modified melamine |
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