CN111499823A - Degradable high-flame-retardancy modified polyurethane elastomer and preparation method thereof - Google Patents
Degradable high-flame-retardancy modified polyurethane elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane materials, and discloses a degradable high-flame-retardancy modified polyurethane elastomer, which comprises the following formula raw materials and components: the catalyst comprises graphene grafted chitosan, nitrogen-rich polyether polyol, polyester triol, a cocatalyst, a catalyst and 4, 4' -methylene bis (phenyl isocyanate). This degradable high flame retardant modified polyurethane elastomer, poly-caprolactone, polyglycolide, polylactic acid molecular chain among the rich-nitrogen polyether polyol have good biodegradable activity, polyurethane elastomer material excellent biodegradable performance has been given, when the burning of poly material high temperature, rich-nitrogen polyether polyol is heated and is decomposed and produce a large amount of flame retardant gas ammonia and nitrogen gas, the oxygen concentration around the material has been diluted, graphite alkene grafting chitosan and polyurethane organic combination, graphite alkene can form compact carbon layer, hinder oxygen and thermal further conduction, combustion process has been inhibited.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a degradable high-flame-retardancy modified polyurethane elastomer and a preparation method thereof.
Background
The polyurethane comprises polyester polyurethane and polyether polyurethane, the product mainly comprises polyurethane plastic, polyurethane fiber, polyurethane rubber and elastomer soft polyurethane, the product mainly has a thermoplastic linear structure, has good chemical resistance, rebound resilience and mechanical properties, has excellent sound insulation, heat insulation, shock resistance and other properties, and has wide application in the aspects of sound insulation materials, packaging materials, filtering materials and the like, the rigid polyurethane plastic has light texture, good electrical property, high sound insulation effect, excellent heat insulation performance and easy processing, and the product is mainly applied to the fields of buildings, automobiles, aviation industry and the like.
The polyurethane elastomer has the performance between that of plastic and rubber, is wear-resistant, ageing-resistant, low-temperature-resistant, good in hardness and elastic, and has good application in the shoe manufacturing industry and the medical industry, such as adhesives, coatings, synthetic leather and the like, but the existing polyurethane elastomer material has poor flame retardant property, usually needs to be added with a flame retardant, has no degradability and is easy to cause environmental pollution.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a degradable high-flame-retardancy modified polyurethane elastomer and a preparation method thereof, and solves the problems that the polyurethane elastomer material has poor flame-retardancy and no degradability.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a degradable high-flame-retardancy modified polyurethane elastomer comprises the following formula raw materials in parts by weight: 6-10 parts of graphene grafted chitosan, 23-30 parts of nitrogen-rich polyether polyol, 22-38 parts of polyester triol, 0.5-1 part of cocatalyst, 0.5-1 part of catalyst and 32-36 parts of 4, 4' -methylene bis (phenyl isocyanate).
Preferably, the catalyst is dibutyltin dilaurate, and the cocatalyst is pentamethyldiethylenetriamine.
Preferably, the preparation method of the graphene grafted chitosan comprises the following steps:
(1) adding carboxylated graphene and chitosan into a sulfuric acid solution with the pH of 4-5, wherein the carboxyl sheet diameter of the carboxylated graphene is 0.5-5 microns, the thickness of the carboxylated graphene is 0.8-1.2nm, the carboxyl content of the carboxylated graphene is 4-5%, the mass ratio of the carboxylated graphene to the chitosan is 1:3-5, carrying out ultrasonic dispersion treatment on the solution at the temperature of 40-60 ℃ for 30-60min, adding sulfuric acid into the solution to adjust the pH of the solution to 1-2, heating the solution to 70-90 ℃, reacting for 10-16h, and removing the solvent from the solution. And washing the solid product and drying to prepare the graphene grafted chitosan.
Preferably, the preparation method of the nitrogen-enriched polyether polyol comprises the following steps:
(1) adding sodium hydroxide into a formaldehyde water solution to adjust the pH value of the solution to 8-10, adding melamine, dicyanodiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, heating the solution to 60-80 ℃, reacting for 1-2h, heating the temperature to 80-90 ℃, adding polyether polyol, reacting for 10-15h, removing the solvent from the solution, washing a solid product and drying to prepare the nitrogen-enriched polyether polyol.
Preferably, the mass ratio of the formaldehyde, the melamine, the dicyandiamide, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine and the polyether polyol is 5-8:1:1-1.4:0.3-0.6: 1.8-2.3.
Preferably, the preparation method of the polyester triol comprises the following steps:
(1) introducing nitrogen into the reaction system to discharge air, adding glycerol, -caprolactone, glycolide, D L-lactide and catalyst stannous octoate, placing the mixture in an oil bath pot, heating to 155 ℃ plus materials, reacting for 25-30h, and performing extraction and purification processes on the materials to obtain the polyester triol.
Preferably, the mass ratio of the stannous octoate of the glycerol, -caprolactone, glycolide and D L-lactide is 225-235:520-535:155-165:75-85: 1.
Preferably, the oil bath pot comprises a box body (1), a console (2) is fixedly connected to the top of the box body (1), a bath pot (3) is installed on the top of the box body (1) and located on the front side of the console (2), a pot cover (4) covers the top of the bath pot (3), a handle (5) is fixedly connected to the top of the pot cover (5), a connecting port (6) is formed in the bottom of the bath pot (3), and a faucet (7) communicated with the connecting port (6) is fixedly connected to the front side of the box body (1).
Preferably, the preparation method of the degradable high-flame-retardancy modified polyurethane elastomer comprises the following steps:
(1) introducing nitrogen into the reaction system to exhaust air, adding 6-10 parts of graphene grafted chitosan, 23-30 parts of nitrogen-rich polyether polyol, 32-48 parts of polyester triol and 22-26 parts of 4, 4' -methylene bis (phenyl isocyanate), heating to 70-85 ℃, adding 0.5-1 part of cocatalyst pentamethyldiethylenetriamine and 0.5-1 part of catalyst dibutyltin dilaurate, stirring at a constant speed for reaction for 6-10h, pouring the materials into a mold, and heating and curing at 110-120 ℃ for 4-7h to prepare the degradable high-flame-retardancy modified polyurethane elastomer.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the degradable high-flame-retardancy modified polyurethane elastomer is prepared by performing addition reaction on nitrogen-rich compounds such as melamine and the like and formaldehyde, performing dehydration reaction on the produced hydroxyl and polyether polyol to enable the nitrogen-rich compounds such as melamine and the like and the polyether polyol to generate the nitrogen-rich polyether polyol, taking three hydroxyl groups of glycerol as reaction neutrality, performing ring-opening reaction on the three hydroxyl groups and caprolactone, glycolide and D L-lactide respectively, performing self-polymerization on ring-opening products of the three groups to generate polyester triol with poly-caprolactone, polyglycolide and polylactic acid molecular chains, wherein the poly-caprolactone, the polyglycolide and the polylactic acid have good biodegradation activity and endow the polyester triol with excellent degradation performance.
The degradable high-flame-retardancy modified polyurethane elastomer takes the nitrogen-rich polyether polyol and the polyester triol as monomers to react with 4, 4' -methylene bis (phenyl isocyanate) to generate the polyurethane elastomer, the polyester triol greatly enhances the biodegradability of the polyurethane, and when the polyurethane elastomer is burnt at high temperature, the nitrogen-rich polyether polyol is heated and decomposed to generate a large amount of flame-retardant gases, namely ammonia gas and nitrogen gas, so that the concentration of oxygen around the material is diluted, the further burning of the material is inhibited, and the material can have good flame-retardant property without adding an additional flame retardant.
According to the degradable high-flame-retardancy modified polyurethane elastomer, carboxylated graphene reacts with amino and hydroxyl in chitosan to graft graphene to chitosan, the hydroxyl in chitosan reacts with isocyanate groups of 4, 4' -methylene bis (phenyl isocyanate), the graphene-grafted chitosan and polyurethane are organically combined, the dispersibility and compatibility of the graphene in polyurethane are greatly improved, the mechanical property and mechanical property of the polyurethane elastomer material can be well improved by taking the graphene as a nano material, and when the polyurethane elastomer material burns, the graphene can form a compact carbon layer to hinder further conduction of oxygen and heat and further inhibit the combustion process.
Drawings
FIG. 1 is a front view of the connection structure of the present invention;
fig. 2 is a sectional view of the connection structure of the present invention.
In the figure: 1-box body, 2-console, 3-bath, 4-pot cover, 5-handle, 6-connector and 7-tap.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a degradable high-flame-retardancy modified polyurethane elastomer comprises the following formula raw materials in parts by weight: 6-10 parts of graphene grafted chitosan, 23-30 parts of nitrogen-rich polyether polyol, 22-38 parts of polyester triol, 0.5-1 part of cocatalyst, 0.5-1 part of catalyst and 32-36 parts of 4, 4' -methylene bis (phenyl isocyanate), wherein the catalyst is dibutyltin dilaurate, and the cocatalyst is pentamethyldiethylenetriamine.
The preparation method of the graphene grafted chitosan comprises the following steps:
(1) adding a sulfuric acid solution with the pH value of 4-5 into a reaction bottle, adding carboxylated graphene and chitosan, wherein the carboxyl sheet diameter of the carboxylated graphene is 0.5-5 microns, the thickness is 0.8-1.2nm, the carboxyl content is 4-5%, the mass ratio of the carboxylated graphene to the chitosan is 1:3-5, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 40-60 ℃ for 30-60min, adding sulfuric acid into the reaction bottle to adjust the pH value of the solution to 1-2, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70-90 ℃, uniformly stirring and reacting for 10-16h, cooling the solution to room temperature, filtering to remove a solvent, washing a solid product with distilled water, and fully drying to prepare the graphene grafted chitosan.
The preparation method of the nitrogen-rich polyether polyol comprises the following steps:
(1) adding a formaldehyde aqueous solution into a reaction bottle, adding sodium hydroxide to adjust the pH value of the solution to 8-10, adding melamine, dicyandiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, uniformly stirring to react for 1-2h, heating to 80-90 ℃, adding polyether polyol, wherein the mass ratio of the formaldehyde, the melamine, the dicyandiamide, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine to the polyether polyol is 5-8:1:1-1.4:0.3-0.6:1.8-2.3, uniformly stirring to react for 10-15h, decompressing and concentrating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, fully drying, preparing the nitrogen-rich polyether polyol.
The preparation method of the polyester triol comprises the following steps:
(1) introducing nitrogen into a reaction bottle to discharge air, adding glycerol, -caprolactone, glycolide and D L-lactide, uniformly stirring, adding a catalyst stannous octoate, wherein the mass ratio of the glycerol, -caprolactone, glycolide and D L-lactide is 225-.
The preparation method of the degradable high-flame-retardancy modified polyurethane elastomer comprises the following steps:
(1) introducing nitrogen into a reaction bottle to discharge air, adding 6-10 parts of graphene grafted chitosan, 23-30 parts of nitrogen-rich polyether polyol, 32-48 parts of polyester triol and 22-26 parts of 4, 4' -methylene bis (phenyl isocyanate), uniformly stirring, placing in an oil bath pot, heating to 70-85 ℃, adding 0.5-1 part of co-catalyst pentamethyldiethylenetriamine and 0.5-1 part of catalyst dibutyltin dilaurate, uniformly stirring for reaction for 6-10h, pouring the materials into a mold, and heating and curing at the temperature of 110-.
Example 1
(1) Preparing a graphene grafted chitosan component 1: adding a sulfuric acid solution with pH of 5 into a reaction bottle, adding carboxylated graphene and chitosan, wherein the mass ratio of the carboxylated graphene to chitosan is 1:3, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 40 ℃ for 30min, adding sulfuric acid into the reaction bottle to adjust the pH of the solution to 2, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring for reaction for 10h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water, and fully drying to obtain the graphene grafted chitosan component 1.
(2) Preparation of nitrogen-rich polyether polyol component 1: adding a formaldehyde aqueous solution into a reaction bottle, adding sodium hydroxide to adjust the pH value of the solution to 8, adding melamine, dicyanodiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for reaction for 1h, heating to 80 ℃, adding polyether polyol, wherein the mass ratio of the formaldehyde, the melamine, the dicyanodiamide and the 2, 4-diamino-6-phenyl-1, 3, 5-triazine to the polyether polyol is 5:1:1:0.3:1.8, stirring at a constant speed for reaction for 10h, decompressing and concentrating the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to prepare the nitrogen-enriched polyether polyol component 1.
(3) And (2) preparing a polyester triol component 1, namely introducing nitrogen into a reaction bottle to discharge air, adding glycerol, -caprolactone, glycolide and D L-lactide, uniformly stirring, adding a catalyst stannous octoate, wherein the mass ratio of the glycerol, -caprolactone, glycolide and D L-lactide is 225:520:155:75:1, placing the reaction bottle into an oil bath pot, the oil bath pot comprises a box body, the top of the box body is fixedly connected with a control console, the top of the box body and the front side of the control console are provided with a bath pot, the top of the bath pot is covered with a pot cover, the top of the pot cover is fixedly connected with a handle, the bottom of the bath pot is provided with a connector, the front side of the box body is fixedly connected with a tap communicated with the connector, heating to 135 ℃, uniformly stirring and reacting for 25 hours, cooling the materials to room temperature, adding a mixed solvent of ethyl acetate and dichloromethane, adding distilled water to perform an extraction process, taking a mixed organic.
(4) Preparing degradable high-flame-retardancy modified polyurethane elastomer material 1: introducing nitrogen into a reaction bottle to discharge air, adding 6 parts of graphene grafted chitosan component 1, 23 parts of nitrogen-rich polyether polyol component 1, 48 parts of polyester triol component 1 and 22 parts of 4, 4' -methylenebis (phenyl isocyanate), uniformly stirring, placing in an oil bath pot, heating to 70 ℃, adding 0.5 part of co-catalyst pentamethyldiethylenetriamine and 0.5 part of catalyst dibutyltin dilaurate, uniformly stirring for reaction for 6 hours, pouring the materials into a mold, and heating and curing at 110 ℃ for 4 hours to prepare the degradable high-flame-retardancy modified polyurethane elastomer material 1.
Example 2
(1) Preparing a graphene grafted chitosan component 2: adding a sulfuric acid solution with pH of 5 into a reaction bottle, adding carboxylated graphene and chitosan, wherein the mass ratio of the carboxylated graphene to chitosan is 1:3, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 60 ℃ for 60min, adding sulfuric acid into the reaction bottle to adjust the pH of the solution to 1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring for reaction for 16h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water, and sufficiently drying to obtain the graphene grafted chitosan component 2.
(2) Preparation of nitrogen-rich polyether polyol component 2: adding a formaldehyde aqueous solution into a reaction bottle, adding sodium hydroxide to adjust the pH value of the solution to 10, adding melamine, dicyanodiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for reaction for 1h, heating to 90 ℃, adding polyether polyol, wherein the mass ratio of the formaldehyde, the melamine, the dicyanodiamide and the 2, 4-diamino-6-phenyl-1, 3, 5-triazine to the polyether polyol is 8:1:1:0.6:1.8, stirring at a constant speed for reaction for 15h, decompressing and concentrating the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to prepare the nitrogen-enriched polyether polyol component 2.
(3) And (2) preparing a polyester triol component 2, namely introducing nitrogen into a reaction bottle to discharge air, adding glycerol, -caprolactone, glycolide and D L-lactide, uniformly stirring, adding a catalyst stannous octoate, wherein the mass ratio of the glycerol, -caprolactone, glycolide and D L-lactide is 235:520:155:85:1, placing the reaction bottle into an oil bath pot, the oil bath pot comprises a box body, the top of the box body is fixedly connected with a control console, the top of the box body and the front side of the control console are provided with a bath pot, the top of the bath pot is covered with a pot cover, the top of the pot cover is fixedly connected with a handle, the bottom of the bath pot is provided with a connector, the front side of the box body is fixedly connected with a tap communicated with the connector, heating to 135 ℃, uniformly stirring and reacting for 30 hours, cooling the materials to room temperature, adding a mixed solvent of ethyl acetate and dichloromethane, adding distilled water to perform an extraction process, taking a mixed organic.
(4) Preparing a degradable high-flame-retardancy modified polyurethane elastomer material 2: introducing nitrogen into a reaction bottle to discharge air, adding 7 parts of graphene grafted chitosan component 2, 24.7 parts of nitrogen-rich polyether polyol component 2, 44 parts of polyester triol component 2 and 23 parts of 4, 4' -methylenebis (phenyl isocyanate), uniformly stirring, placing in an oil bath pot, heating to 85 ℃, adding 0.6 co-catalyst pentamethyldiethylenetriamine and 0.7 part of catalyst dibutyltin dilaurate, uniformly stirring and reacting for 6 hours, pouring the materials into a mold, and heating and curing for 7 hours at 120 ℃ to prepare the degradable high-flame-retardancy modified polyurethane elastomer material 2.
Example 3
(1) Preparing a graphene grafted chitosan component 3: adding a sulfuric acid solution with pH of 5 into a reaction bottle, adding carboxylated graphene and chitosan, wherein the mass ratio of the carboxylated graphene to chitosan is 1:4, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 50 ℃ for 45min, adding sulfuric acid into the reaction bottle to adjust the pH of the solution to 2, placing the reaction bottle into a constant-temperature water bath kettle, heating to 80 ℃, uniformly stirring for reaction for 13h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water, and sufficiently drying to obtain the graphene grafted chitosan component 3.
(2) Preparation of nitrogen-rich polyether polyol component 3: adding a formaldehyde aqueous solution into a reaction bottle, adding sodium hydroxide to adjust the pH value of the solution to 9, adding melamine, dicyanodiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring to react for 1.5h, heating to 85 ℃, adding polyether polyol, wherein the mass ratio of the formaldehyde, the melamine, the dicyanodiamide, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine to the polyether polyol is 6.5:1:1.2:0.4:2, uniformly stirring to react for 12h, decompressing and concentrating the solution to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the nitrogen-enriched polyether polyol component 3.
(3) And (2) preparing a polyester triol component 3, namely introducing nitrogen into a reaction bottle to discharge air, adding glycerol, -caprolactone, glycolide and D L-lactide, uniformly stirring, adding a catalyst stannous octoate, wherein the mass ratio of the glycerol, -caprolactone, glycolide and D L-lactide is 230:528:160:80:1, placing the reaction bottle into an oil bath pot, the oil bath pot comprises a box body, the top of the box body is fixedly connected with a control console, the top of the box body and the front side of the control console are provided with a bath pot, the top of the bath pot is covered with a pot cover, the top of the pot cover is fixedly connected with a handle, the bottom of the bath pot is provided with a connector, the front side of the box body is fixedly connected with a tap communicated with the connector, heating to 140 ℃, uniformly stirring and reacting for 28 hours, cooling the materials to room temperature, adding a mixed solvent of ethyl acetate and dichloromethane, adding distilled water to perform an extraction process, taking a mixed organic.
(4) Preparing a degradable high-flame-retardancy modified polyurethane elastomer material 3: introducing nitrogen into a reaction bottle to discharge air, adding 8 parts of graphene grafted chitosan component 3, 26.5 parts of nitrogen-rich polyether polyol component 3, 40 parts of polyester triol component 3 and 24 parts of 4, 4' -methylenebis (phenyl isocyanate), uniformly stirring, placing in an oil bath pot, heating to 80 ℃, adding 0.7 co-catalyst pentamethyldiethylenetriamine and 0.8 part catalyst dibutyltin dilaurate, uniformly stirring for reaction for 8 hours, pouring the materials into a mold, and heating and curing at 115 ℃ for 5.5 hours to prepare the degradable high-flame-retardancy modified polyurethane elastomer material 3.
Example 4
(1) Preparing a graphene grafted chitosan component 4: adding a sulfuric acid solution with pH of 5 into a reaction bottle, adding carboxylated graphene and chitosan, wherein the mass ratio of the carboxylated graphene to chitosan is 1:3, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, performing ultrasonic dispersion treatment at 60 ℃ for 60min, adding sulfuric acid into the reaction bottle to adjust the pH of the solution to 1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, uniformly stirring for reaction for 16h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water, and sufficiently drying to obtain the graphene grafted chitosan component 4.
(2) Preparation of nitrogen-rich polyether polyol component 4: adding a formaldehyde aqueous solution into a reaction bottle, adding sodium hydroxide to adjust the pH value of the solution to 8, adding melamine, dicyanodiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for reaction for 2 hours, heating to 80 ℃, adding polyether polyol, wherein the mass ratio of the formaldehyde, the melamine, the dicyanodiamide and the 2, 4-diamino-6-phenyl-1, 3, 5-triazine to the polyether polyol is 8:1:1:0.3:2.3, stirring at a constant speed for reaction for 15 hours, decompressing and concentrating the solution to remove the solvent, washing a solid product with distilled water and ethanol, and fully drying to prepare the nitrogen-enriched polyether polyol component 4.
(3) And (2) preparing a polyester triol component 4, namely introducing nitrogen into a reaction bottle to discharge air, adding glycerol, -caprolactone, glycolide and D L-lactide, uniformly stirring, adding a catalyst stannous octoate, wherein the mass ratio of the glycerol, -caprolactone, glycolide and D L-lactide is 235:520:155:75:1, placing the reaction bottle into an oil bath pot, the oil bath pot comprises a box body, the top of the box body is fixedly connected with a control console, the top of the box body and the front side of the control console are provided with a bath pot, the top of the bath pot is covered with a pot cover, the top of the pot cover is fixedly connected with a handle, the bottom of the bath pot is provided with a connector, the front side of the box body is fixedly connected with a tap communicated with the connector, heating to 155 ℃, uniformly stirring and reacting for 30 hours, cooling the materials to room temperature, adding a mixed solvent of ethyl acetate and dichloromethane, adding distilled water to perform an extraction process, taking a mixed organic.
(4) Preparing a degradable high-flame-retardancy modified polyurethane elastomer material 4: introducing nitrogen into a reaction bottle to discharge air, adding 9 parts of graphene grafted chitosan component 4, 28.4 parts of nitrogen-rich polyether polyol component 4, 36 parts of polyester triol component 4 and 25 parts of 4, 4' -methylenebis (phenyl isocyanate), uniformly stirring, placing in an oil bath pot, heating to 70 ℃, adding 0.8 co-catalyst pentamethyldiethylenetriamine and 0.8 part catalyst dibutyltin dilaurate, uniformly stirring and reacting for 10 hours, pouring the materials into a mold, and heating and curing at 120 ℃ for 6 hours to prepare the degradable high-flame-retardancy modified polyurethane elastomer material 4.
Example 5
(1) Preparing a graphene grafted chitosan component 5: adding a sulfuric acid solution with the pH value of 4 into a reaction bottle, adding carboxylated graphene and chitosan, wherein the mass ratio of the carboxylated graphene to the chitosan is 1:5, uniformly stirring, placing the reaction bottle into an ultrasonic dispersion instrument, carrying out ultrasonic dispersion treatment at 60 ℃ for 60min, adding sulfuric acid into the reaction bottle to adjust the pH value of the solution to 1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 90 ℃, uniformly stirring for reaction for 16h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with distilled water, and fully drying to obtain the graphene grafted chitosan component 5.
(2) Preparation of nitrogen-rich polyether polyol component 5: adding a formaldehyde aqueous solution into a reaction bottle, adding sodium hydroxide to adjust the pH value of the solution to 10, adding melamine, dicyanodiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, placing the reaction bottle in a constant-temperature water bath kettle, heating to 80 ℃, stirring at a constant speed for reaction for 2 hours, heating to 85 ℃, adding polyether polyol, wherein the mass ratio of the formaldehyde, the melamine, the dicyanodiamide and the 2, 4-diamino-6-phenyl-1, 3, 5-triazine to the polyether polyol is 8:1:1.4:0.6:2.3, stirring at a constant speed for reaction for 12 hours, decompressing and concentrating the solution to remove the solvent, washing the solid product with distilled water and ethanol, fully drying, and preparing the nitrogen-enriched polyether polyol component 5.
(3) And (2) preparing a polyester triol component 5, namely introducing nitrogen into a reaction bottle to discharge air, adding glycerol, -caprolactone, glycolide and D L-lactide, uniformly stirring, adding a catalyst stannous octoate, wherein the mass ratio of the glycerol, -caprolactone, glycolide and D L-lactide is 235:535:165:85:1, placing the reaction bottle into an oil bath pot, the oil bath pot comprises a box body, the top of the box body is fixedly connected with a control console, the top of the box body and the front side of the control console are provided with a bath pot, the top of the bath pot is covered with a pot cover, the top of the pot cover is fixedly connected with a handle, the bottom of the bath pot is provided with a connector, the front side of the box body is fixedly connected with a tap communicated with the connector, heating to 155 ℃, uniformly stirring and reacting for 30 hours, cooling the materials to room temperature, adding a mixed solvent of ethyl acetate and dichloromethane, adding distilled water to perform an extraction process, taking a mixed organic.
(4) Preparing a degradable high-flame-retardancy modified polyurethane elastomer material 5: introducing nitrogen into a reaction bottle to discharge air, adding 10 parts of graphene grafted chitosan component 5, 30 parts of nitrogen-rich polyether polyol component 5, 32 parts of polyester triol component 5 and 26 parts of 4, 4' -methylenebis (phenyl isocyanate), uniformly stirring, placing in an oil bath pot, heating to 85 ℃, adding 1 cocatalyst pentamethyldiethylenetriamine and 1 part catalyst dibutyltin dilaurate, uniformly stirring and reacting for 10 hours, pouring the materials into a mold, and heating and curing at 120 ℃ for 7 hours to prepare the degradable high-flame-retardancy modified polyurethane elastomer material 5.
The limit oxygen index of the degradable high-flame-retardancy modified polyurethane elastomer material in the examples 1 to 5 is tested by using a PY-653D limit oxygen index tester integrated machine, and the test standard GB8624-2006 is adopted.
In summary, the degradable high-flame-retardancy modified polyurethane elastomer is prepared by performing addition reaction on nitrogen-rich compounds such as melamine and the like and formaldehyde, performing dehydration reaction on the produced hydroxyl and polyether polyol to enable the nitrogen-rich compounds such as melamine and the like and the polyether polyol to generate the nitrogen-rich polyether polyol, taking three hydroxyl groups of glycerol as neutral reaction, performing ring-opening reaction on the three hydroxyl groups and caprolactone, glycolide and D L-lactide respectively, and performing self-polymerization on ring-opening products of the three groups to generate the polyester triol with poly-caprolactone, polyglycolide and polylactic acid molecular chains, wherein the poly-caprolactone, polyglycolide and polylactic acid have good biodegradation activity and excellent degradation performance of the polyester triol is endowed.
The nitrogen-rich polyether polyol and the polyester triol are used as monomers and react with 4, 4' -methylene bis (phenyl isocyanate) to generate the polyurethane elastomer, the polyester triol greatly enhances the biodegradability of polyurethane, and when the polyurethane elastomer is burnt at high temperature, the nitrogen-rich polyether polyol is heated and decomposed to generate a large amount of flame retardant gases, namely ammonia gas and nitrogen gas, so that the concentration of oxygen around the material is diluted, the further burning of the material is inhibited, and the material can have good flame retardant performance without adding an additional flame retardant.
The carboxylated graphene reacts with amino and hydroxyl in the chitosan to graft the graphene to chitosan, the hydroxyl in the chitosan reacts with isocyanate groups of 4, 4' -methylene bis (phenyl isocyanate), the graphene grafted chitosan is organically combined with polyurethane, the dispersibility and compatibility of the graphene in the polyurethane are greatly improved, the graphene serving as a nano material can well improve the mechanical property and mechanical property of a polyurethane elastomer material, and when the polyurethane elastomer material burns, the graphene can form a compact carbon layer to block further conduction of oxygen and heat, further inhibit the combustion process, and meanwhile, the chitosan serving as a nano material also has good biodegradability and can enhance the degradation property of the polyurethane elastomer material.
Claims (9)
1. A degradable high-flame-retardancy modified polyurethane elastomer comprises the following formula raw materials and components in parts by weight, and is characterized in that: 6-10 parts of graphene grafted chitosan, 23-30 parts of nitrogen-rich polyether polyol, 22-38 parts of polyester triol, 0.5-1 part of cocatalyst, 0.5-1 part of catalyst and 32-36 parts of 4, 4' -methylene bis (phenyl isocyanate).
2. The degradable high-flame-retardancy modified polyurethane elastomer according to claim 1, wherein: the catalyst is dibutyltin dilaurate, and the cocatalyst is pentamethyl diethylenetriamine.
3. The degradable high-flame-retardancy modified polyurethane elastomer according to claim 1, wherein: the preparation method of the graphene grafted chitosan comprises the following steps:
(1) adding carboxylated graphene and chitosan into a sulfuric acid solution with the pH of 4-5, wherein the carboxyl sheet diameter of the carboxylated graphene is 0.5-5 microns, the thickness of the carboxylated graphene is 0.8-1.2nm, the carboxyl content of the carboxylated graphene is 4-5%, the mass ratio of the carboxylated graphene to the chitosan is 1:3-5, carrying out ultrasonic dispersion treatment on the solution at the temperature of 40-60 ℃ for 30-60min, adding sulfuric acid into the solution to adjust the pH of the solution to 1-2, heating the solution to 70-90 ℃, reacting for 10-16h, and removing the solvent from the solution. And washing the solid product and drying to prepare the graphene grafted chitosan.
4. The degradable high-flame-retardancy modified polyurethane elastomer according to claim 1, wherein: the preparation method of the nitrogen-rich polyether polyol comprises the following steps:
(1) adding sodium hydroxide into a formaldehyde water solution to adjust the pH value of the solution to 8-10, adding melamine, dicyanodiamide and 2, 4-diamino-6-phenyl-1, 3, 5-triazine, heating the solution to 60-80 ℃, reacting for 1-2h, heating the temperature to 80-90 ℃, adding polyether polyol, reacting for 10-15h, removing the solvent from the solution, washing a solid product and drying to prepare the nitrogen-enriched polyether polyol.
5. The degradable high-flame-retardancy modified polyurethane elastomer according to claim 4, wherein: the mass ratio of the formaldehyde, the melamine, the dicyandiamide, the 2, 4-diamino-6-phenyl-1, 3, 5-triazine and the polyether polyol is 5-8:1:1-1.4:0.3-0.6: 1.8-2.3.
6. The degradable high-flame-retardancy modified polyurethane elastomer according to claim 1, wherein: the preparation method of the polyester triol comprises the following steps:
(1) introducing nitrogen into the reaction system to discharge air, adding glycerol, -caprolactone, glycolide, D L-lactide and catalyst stannous octoate, placing the mixture in an oil bath pot, heating to 155 ℃ plus materials, reacting for 25-30h, and performing extraction and purification processes on the materials to obtain the polyester triol.
7. The degradable high flame retardant modified polyurethane elastomer as claimed in claim 6, wherein the mass ratio of stannous octoate of the glycerol, -caprolactone, glycolide and D L-lactide is 225-235:520-535:155-165:75-85: 1.
8. The degradable high-flame-retardancy modified polyurethane elastomer according to claim 6, wherein: the oil bath pot comprises a box body (1), a control console (2) is fixedly connected to the top of the box body (1), a bath pot (3) is installed at the top of the box body (1) and located on the front side of the control console (2), a pot cover (4) covers the top of the bath pot (3), a handle (5) is fixedly connected to the top of the pot cover (5), a connector (6) is arranged at the bottom of the bath pot (3), and a faucet (7) communicated with the connector (6) is fixedly connected to the front side of the box body (1).
9. The degradable high-flame-retardancy modified polyurethane elastomer according to claim 1, wherein: the preparation method of the degradable high-flame-retardancy modified polyurethane elastomer comprises the following steps:
(1) introducing nitrogen into the reaction system to exhaust air, adding 6-10 parts of graphene grafted chitosan, 23-30 parts of nitrogen-rich polyether polyol, 32-48 parts of polyester triol and 22-26 parts of 4, 4' -methylene bis (phenyl isocyanate), heating to 70-85 ℃, adding 0.5-1 part of cocatalyst pentamethyldiethylenetriamine and 0.5-1 part of catalyst dibutyltin dilaurate, stirring at a constant speed for reaction for 6-10h, pouring the materials into a mold, and heating and curing at 110-120 ℃ for 4-7h to prepare the degradable high-flame-retardancy modified polyurethane elastomer.
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