CN111574699A - Reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid and preparation method thereof - Google Patents
Reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid and preparation method thereof Download PDFInfo
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- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
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Abstract
The invention relates to the technical field of polylactic acid materials, and discloses reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid, which comprises the following formula raw materials and components: the nitrogen and phosphorus synergistic modified chitosan, D, L lactide and stannous octoate. According to the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid, glutaraldehyde is used as a cross-linking agent, the amino groups of melamine and chitosan are subjected to condensation cross-linking reaction, pyridine is used as an acid-binding agent, chlorine atoms of hexachlorocyclotriphosphazene and partial hydroxyl groups of chitosan are subjected to substitution reaction to obtain nitrogen-phosphorus synergistic modified chitosan, the hydroxyl groups in the nitrogen-phosphorus synergistic modified chitosan are used as active sites and are subjected to polymerization reaction with D, L lactide, the nitrogen-phosphorus synergistic modified chitosan is used as a branched chain monomer, a molecular chain of polylactic acid is added through chemical covalent grafting, and the nitrogen-phosphorus synergistic biomass-based intumescent flame retardant is used as a nitrogen-phosphorus synergistic biomass-based intumescent flame retardant, so that the chitosan is endowed with excellent flame retardant performance.
Description
Technical Field
The invention relates to the technical field of polylactic acid materials, in particular to reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid and a preparation method thereof.
Background
The flame retardant is a functional auxiliary agent for endowing high molecular polymer with flame retardancy, such as a brominated flame retardant, a nitrogen-phosphorus flame retardant, hexachlorocyclotriphosphazene, an intumescent flame retardant and the like, and can be divided into an additive flame retardant and a reactive flame retardant, wherein the additive flame retardant is added into the polymer by a mechanical mixing method, so that the polymer has flame retardancy, and the reactive flame retardant is used as a monomer to participate in polymerization reaction, so that the polymer contains a flame retardant component.
Polylactic acid is a novel biodegradable material, has good mechanical property and physical property and excellent biocompatibility, is suitable for various processing methods such as thermoplastic and blow molding, is convenient to process and wide in application, can be made into materials such as plastic products, packaged foods, agricultural fabrics, sanitary products and the like, but has lower fire point and poorer flame retardant property, so that the application field of the polylactic acid is limited, and the flame retardant property of the polylactic acid is enhanced by adding an additive flame retardant at present, but the mechanical property and the service performance of the polylactic acid material are influenced by the additive flame retardant.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid and a preparation method thereof, which solve the problem of poor flame retardant property of polylactic acid and simultaneously avoid the problem that the mechanical property of a polylactic acid material is influenced by an additive flame retardant.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid comprises the following raw materials and components: the nitrogen-phosphorus synergistic modified chitosan, D, L lactide and stannous octoate are in a mass ratio of 5-20:100: 0.05-0.1.
Preferably, the preparation method of the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid comprises the following steps:
(1) adding a distilled water solvent and chitosan into a reaction bottle, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, stirring at a constant speed at 50-70 ℃ for reacting for 2-5h, centrifugally separating and washing by using distilled water until the upper layer liquid is clear and neutral, and preparing the melamine cross-linked chitosan.
(2) Adding an ether solvent and melamine crosslinked chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic dispersion instrument, carrying out ultrasonic treatment for 2-4h at the ultrasonic frequency of 25-40KHz, adding hexachlorocyclotriphosphazene and acid-binding agent pyridine, carrying out uniform stirring reaction for 10-20h at the temperature of 0-5 ℃, carrying out centrifugal separation and washing on the solution by using the ether solvent and the ethanol solvent, and drying to prepare the nitrogen-phosphorus synergistic modified chitosan.
(3) Adding a dimethyl sulfoxide solvent and nitrogen-phosphorus synergistic modified chitosan into a reaction bottle, placing the reaction bottle in an oil bath pot after uniform ultrasonic dispersion, heating the reaction bottle to the temperature of 100 ℃ plus 120 ℃, adding D, L lactide and stannous octoate, stirring at a constant speed for reaction for 24-48h, placing the solution in an ice-water bath for cooling, adding distilled water until a large amount of precipitate is separated out, centrifugally separating and washing the solution by using distilled water and ethanol, drying the solution, placing a solid product in a trichloromethane solvent, pouring the solution into a film forming mold after uniform ultrasonic dispersion, and naturally casting, drying and pressing the solution into a film to prepare the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid.
Preferably, the ultrasonic dispersion instrument comprises an ultrasonic device, an ultrasonic probe fixedly connected to the lower portion of the ultrasonic device, a base fixedly connected to the lower portion of the inner portion of the ultrasonic dispersion instrument, a regulating valve arranged above the base, a regulating valve fixedly connected to a regulating rod, a regulating rotating ball movably connected to the regulating rod, a moving rod movably connected to the regulating rotating ball, and an objective table movably connected to the moving rod, wherein a reaction bottle is arranged above the objective table.
Preferably, the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:6-10: 15-20.
Preferably, the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding agent pyridine is 10:2-5: 0.5-1.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid takes glutaraldehyde as a cross-linking agent, the amino groups of melamine and chitosan are subjected to condensation cross-linking reaction, then pyridine is taken as an acid-binding agent, the chlorine atoms of hexachlorocyclotriphosphazene and part of hydroxyl groups of chitosan are subjected to substitution reaction to obtain nitrogen-phosphorus synergistic modified chitosan, in the ring-opening polymerization process of D, L lactide, hydroxyl groups in the nitrogen-phosphorus synergistic modified chitosan are taken as active sites and are subjected to polymerization reaction with D, L lactide under the action of stannous octoate, the nitrogen-phosphorus synergistic modified chitosan is taken as a branched chain monomer, a molecular chain of polylactic acid is added by chemical covalent grafting, the compatibility of the polylactic acid and the polylactic acid is improved, the influence on the mechanical property of the polylactic acid is reduced, and the uniformly dispersed nitrogen-phosphorus synergistic modified chitosan is taken as a nitrogen-phosphorus synergistic biomass-based intumescent flame retardant, the chitosan is used as a carbon source, the melamine structure is used as a nitrogen source, and the hexachlorocyclotriphosphazene is used as a nitrogen source and a phosphorus source, so that the excellent flame retardant property of the chitosan is endowed.
Drawings
FIG. 1 is a schematic front view of an ultrasonic disperser;
FIG. 2 is an enlarged schematic view of the regulator valve;
FIG. 3 is a schematic view of stage adjustment;
FIG. 4 is an X-ray diffraction pattern of nitrogen and phosphorus synergistically modified chitosan.
1-ultrasonic dispersion instrument; 2-an ultrasonic device; 3-an ultrasonic probe; 4-a base; 5-adjusting the valve; 6-adjusting the rod; 7-adjusting the rotary ball; 8-a moving rod; 9-an object stage; 10-reaction flask.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid comprises the following raw materials and components: the nitrogen-phosphorus synergistic modified chitosan, D, L lactide and stannous octoate are in a mass ratio of 5-20:100: 0.05-0.1.
The preparation method of the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid comprises the following steps:
(1) adding a distilled water solvent and chitosan into a reaction bottle, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, wherein the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:6-10:15-20, stirring at a constant speed at 50-70 ℃ for reaction for 2-5h, centrifugally separating and washing by using distilled water until the upper layer liquid is clear and neutral, and preparing to obtain the melamine cross-linked chitosan.
(2) Adding an ether solvent and melamine crosslinked chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic disperser, wherein the ultrasonic disperser comprises an ultrasonic device, an ultrasonic probe fixedly connected below the ultrasonic device, a base fixedly connected below the inner part of the ultrasonic disperser, a regulating valve arranged above the base, a regulating rod fixedly connected with the regulating valve, a regulating rotating ball movably connected with the regulating rod, a moving rod movably connected with the moving rod, a carrying platform movably connected with the moving rod, a reaction bottle arranged above the carrying platform, carrying out ultrasonic treatment for 2-4h with the ultrasonic frequency of 25-40KHz, adding hexachlorocyclotriphosphazene and acid-binding pyridine, wherein the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding pyridine is 10:2-5:0.5-1, carrying out uniform stirring reaction for 10-20h at the temperature of 0-5 ℃, carrying out centrifugal separation and washing on the solution by using the ether solvent and the ethanol solvent, and drying to prepare the nitrogen-phosphorus synergistic modified chitosan.
(3) Adding a dimethyl sulfoxide solvent and nitrogen-phosphorus synergistic modified chitosan into a reaction bottle, placing the reaction bottle in an oil bath pot after uniform ultrasonic dispersion, heating the reaction bottle to the temperature of 100 ℃ plus 120 ℃, adding D, L lactide and stannous octoate, stirring at a constant speed for reaction for 24-48h, placing the solution in an ice-water bath for cooling, adding distilled water until a large amount of precipitate is separated out, centrifugally separating and washing the solution by using distilled water and ethanol, drying the solution, placing a solid product in a trichloromethane solvent, pouring the solution into a film forming mold after uniform ultrasonic dispersion, and naturally casting, drying and pressing the solution into a film to prepare the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid.
Example 1
(1) Adding a distilled water solvent and chitosan into a reaction bottle, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, wherein the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:6:15, stirring at a constant speed at 50 ℃ for reaction for 2 hours, centrifugally separating and washing by using distilled water until the upper layer liquid is clear and neutral, and preparing the melamine cross-linked chitosan.
(2) Adding ether solvent and melamine cross-linked chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic dispersion instrument, the ultrasonic dispersion instrument comprises an ultrasonic device, an ultrasonic probe fixedly connected below the ultrasonic device, a base fixedly connected below the inner part of the ultrasonic dispersion instrument, a regulating valve arranged above the base, a regulating rod fixedly connected with the regulating valve, a regulating rotating ball movably connected with the regulating rod, a moving rod movably connected with the regulating rotating ball, a carrying platform movably connected with the moving rod, a reaction bottle arranged above the carrying platform, ultrasonic treatment for 2 hours with ultrasonic frequency of 25KHz, and then hexachlorocyclotriphosphazene and acid-binding pyridine are added, wherein the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding agent pyridine is 10:2:0.5, stirring at a constant speed at 5 ℃ for reaction for 10h, centrifugally separating and washing the solution by using an ether and ethanol solvent, and drying to prepare the nitrogen-phosphorus synergistic modified chitosan.
(3) Adding dimethyl sulfoxide solvent and nitrogen-phosphorus synergistic modified chitosan into a reaction bottle, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, heating the mixture to 100 ℃, adding D, L lactide and stannous octoate in a mass ratio of 5:100:0.05, stirring at a constant speed for reaction for 24 hours, placing the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is separated out, centrifugally separating and washing the precipitate by using distilled water and ethanol, drying, placing a solid product into trichloromethane solvent, pouring the solution into a film forming mold after uniform ultrasonic dispersion, and naturally casting, drying and pressing the solution into a film to prepare the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid material 1.
Example 2
(1) Adding a distilled water solvent and chitosan into a reaction bottle, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, wherein the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:8:18, stirring at a constant speed at 60 ℃ for reaction for 4 hours, centrifugally separating and washing by using distilled water until the upper layer liquid is clear and neutral, and preparing the melamine cross-linked chitosan.
(2) Adding ether solvent and melamine cross-linked chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic dispersion instrument, the ultrasonic dispersion instrument comprises an ultrasonic device, an ultrasonic probe fixedly connected below the ultrasonic device, a base fixedly connected below the inner part of the ultrasonic dispersion instrument, a regulating valve arranged above the base, a regulating rod fixedly connected with the regulating valve, a regulating rotating ball movably connected with the regulating rod, a moving rod movably connected with the regulating rotating ball, a carrying platform movably connected with the moving rod, a reaction bottle arranged above the carrying platform, ultrasonic treatment for 3 hours with ultrasonic frequency of 30KHz, and then hexachlorocyclotriphosphazene and acid-binding pyridine are added, wherein the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding agent pyridine is 10:3.5:0.8, stirring at a constant speed at 2 ℃ for reaction for 15h, centrifugally separating and washing the solution by using an ether and ethanol solvent, and drying to prepare the nitrogen-phosphorus synergistic modified chitosan.
(3) Adding dimethyl sulfoxide solvent and nitrogen-phosphorus synergistic modified chitosan into a reaction bottle, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, heating the mixture to 110 ℃, adding D, L lactide and stannous octoate in a mass ratio of 12:100:0.08, stirring at a constant speed for reaction for 36 hours, placing the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is separated out, centrifugally separating and washing the precipitate by using distilled water and ethanol, drying, placing a solid product into trichloromethane solvent, pouring the solution into a film forming mold after uniform ultrasonic dispersion, and naturally casting, drying and pressing the solution into a film to prepare the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid material 2.
Example 3
(1) Adding a distilled water solvent and chitosan into a reaction bottle, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, wherein the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:10:20, stirring at a constant speed at 70 ℃ for reaction for 5 hours, centrifugally separating and washing by using distilled water until the upper layer liquid is clear and neutral, and preparing the melamine cross-linked chitosan.
(2) Adding ether solvent and melamine cross-linked chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic dispersion instrument, the ultrasonic dispersion instrument comprises an ultrasonic device, an ultrasonic probe fixedly connected below the ultrasonic device, a base fixedly connected below the inner part of the ultrasonic dispersion instrument, a regulating valve arranged above the base, a regulating rod fixedly connected with the regulating valve, a regulating rotating ball movably connected with the regulating rod, a moving rod movably connected with the regulating rotating ball, a carrying platform movably connected with the moving rod, a reaction bottle arranged above the carrying platform, ultrasonic treatment for 4 hours with ultrasonic frequency of 40KHz, and then hexachlorocyclotriphosphazene and acid-binding pyridine are added, wherein the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding agent pyridine is 10:5:1, stirring at 0 deg.C for 20h, centrifuging, washing, and drying to obtain nitrogen-phosphorus synergistic modified chitosan.
(3) Adding dimethyl sulfoxide solvent and nitrogen-phosphorus synergistic modified chitosan into a reaction bottle, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, heating the mixture to 120 ℃, adding D, L lactide and stannous octoate in a mass ratio of 20:100:0.1, stirring at a constant speed for reaction for 48 hours, placing the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is separated out, centrifugally separating and washing the precipitate by using distilled water and ethanol, drying, placing a solid product into trichloromethane solvent, pouring the solution into a film forming mold after uniform ultrasonic dispersion, and naturally casting, drying and pressing the solution into a film to prepare the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid material 3.
Comparative example 1
(1) Adding a distilled water solvent and chitosan into a reaction bottle, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, wherein the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:4:12, stirring at a constant speed at 70 ℃ for reaction for 2 hours, centrifugally separating and washing by using distilled water until the upper layer liquid is clear and neutral, and preparing the melamine cross-linked chitosan.
(2) Adding ether solvent and melamine cross-linked chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic dispersion instrument, the ultrasonic dispersion instrument comprises an ultrasonic device, an ultrasonic probe fixedly connected below the ultrasonic device, a base fixedly connected below the inner part of the ultrasonic dispersion instrument, a regulating valve arranged above the base, a regulating rod fixedly connected with the regulating valve, a regulating rotating ball movably connected with the regulating rod, a moving rod movably connected with the regulating rotating ball, a carrying platform movably connected with the moving rod, a reaction bottle arranged above the carrying platform, ultrasonic treatment for 2 hours with ultrasonic frequency of 40KHz, and then hexachlorocyclotriphosphazene and acid-binding pyridine are added, wherein the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding agent pyridine is 10:1:0.3, stirring at a constant speed at 5 ℃ for reaction for 20h, centrifugally separating and washing the solution by using an ether and ethanol solvent, and drying to prepare the nitrogen-phosphorus synergistic modified chitosan.
(3) Adding dimethyl sulfoxide solvent and nitrogen-phosphorus synergistic modified chitosan into a reaction bottle, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, heating the mixture to 120 ℃, adding D, L lactide and stannous octoate in a mass ratio of 2:100:0.04, stirring at a constant speed for reaction for 24 hours, placing the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is separated out, centrifugally separating and washing the precipitate with distilled water and ethanol, drying, placing a solid product into trichloromethane solvent, pouring the solution into a film forming mold after uniform ultrasonic dispersion, and naturally casting, drying and pressing to form a film to prepare the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid contrast material 1.
Comparative example 2
(1) Adding a distilled water solvent and chitosan into a reaction bottle, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, wherein the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:12:25, stirring at a constant speed at 70 ℃ for reaction for 2 hours, centrifugally separating and washing by using distilled water until the upper layer liquid is clear and neutral, and preparing the melamine cross-linked chitosan.
(2) Adding ether solvent and melamine cross-linked chitosan into a reaction bottle, placing the reaction bottle in an ultrasonic dispersion instrument, the ultrasonic dispersion instrument comprises an ultrasonic device, an ultrasonic probe fixedly connected below the ultrasonic device, a base fixedly connected below the inner part of the ultrasonic dispersion instrument, a regulating valve arranged above the base, a regulating rod fixedly connected with the regulating valve, a regulating rotating ball movably connected with the regulating rod, a moving rod movably connected with the regulating rotating ball, a carrying platform movably connected with the moving rod, a reaction bottle arranged above the carrying platform, ultrasonic treatment for 4 hours with ultrasonic frequency of 40KHz, and then hexachlorocyclotriphosphazene and acid-binding pyridine are added, wherein the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding agent pyridine is 10:6:1.2, stirring at a constant speed at 5 ℃ for reaction for 10h, centrifugally separating and washing the solution by using an ether and ethanol solvent, and drying to prepare the nitrogen-phosphorus synergistic modified chitosan.
(3) Adding dimethyl sulfoxide solvent and nitrogen-phosphorus synergistic modified chitosan into a reaction bottle, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, heating the mixture to 120 ℃, adding D, L lactide and stannous octoate in a mass ratio of 25:100:0.012, stirring at a constant speed for reaction for 48 hours, placing the solution into an ice water bath for cooling, adding distilled water until a large amount of precipitate is separated out, centrifugally separating and washing the precipitate by using distilled water and ethanol, drying, placing a solid product into trichloromethane solvent, pouring the solution into a film forming mold after uniform ultrasonic dispersion, and naturally casting, drying and pressing the solution into a film to prepare the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid contrast material 2.
The limiting oxygen index and the flame retardant performance of the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid in the examples and the comparative examples are tested by using a GB2406 limiting oxygen index tester, and the test standard is GB/T29284-2012.
The reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid takes glutaraldehyde as a cross-linking agent, the amino groups of melamine and chitosan are subjected to condensation cross-linking reaction, then pyridine is taken as an acid-binding agent, the chlorine atoms of hexachlorocyclotriphosphazene and part of hydroxyl groups of chitosan are subjected to substitution reaction to obtain nitrogen-phosphorus synergistic modified chitosan, in the ring-opening polymerization process of D, L lactide, hydroxyl groups in the nitrogen-phosphorus synergistic modified chitosan are taken as active sites and are subjected to polymerization reaction with D, L lactide under the action of stannous octoate, the nitrogen-phosphorus synergistic modified chitosan is taken as a branched chain monomer, a molecular chain of polylactic acid is added by chemical covalent grafting, the compatibility of the polylactic acid and the polylactic acid is improved, the influence on the mechanical property of the polylactic acid is reduced, and the uniformly dispersed nitrogen-phosphorus synergistic modified chitosan is taken as a nitrogen-phosphorus synergistic biomass-based intumescent flame retardant, the chitosan is used as a carbon source, the melamine structure is used as a nitrogen source, and the hexachlorocyclotriphosphazene is used as a nitrogen source and a phosphorus source, so that the excellent flame retardant property of the chitosan is endowed.
Claims (5)
1. The reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid comprises the following raw materials and components, and is characterized in that: the nitrogen-phosphorus synergistic modified chitosan, D, L lactide and stannous octoate are in a mass ratio of 5-20:100: 0.05-0.1.
2. The reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid according to claim 1, wherein: the preparation method of the reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid comprises the following steps:
(1) adding chitosan into a distilled water solvent, slowly dropwise adding a hydrochloric acid solution until the chitosan is dissolved, then adding melamine and a cross-linking agent glutaraldehyde, reacting for 2-5h at 50-70 ℃, performing centrifugal separation and washing until the upper-layer liquid is clear and neutral, and preparing to obtain melamine cross-linked chitosan;
(2) adding melamine cross-linked chitosan into an ether solvent, placing the mixture into an ultrasonic dispersion instrument, carrying out ultrasonic treatment for 2-4h at the ultrasonic frequency of 25-40KHz, adding hexachlorocyclotriphosphazene and acid-binding agent pyridine, reacting for 10-20h at the temperature of 0-5 ℃, carrying out centrifugal separation, washing and drying to prepare nitrogen-phosphorus synergistic modified chitosan;
(3) adding nitrogen and phosphorus synergistic modified chitosan into a dimethyl sulfoxide solvent, placing the mixture into an oil bath pot after uniform ultrasonic dispersion, heating the mixture to 120 ℃ for reaction for 24-48h, adding D, L lactide and stannous octoate, cooling, precipitating, centrifugally separating, washing and drying the mixture, placing a solid product into a chloroform solvent, pouring the solution into a film forming die after uniform ultrasonic dispersion, and naturally casting, drying and pressing the solution into a film to prepare the reactive nitrogen and phosphorus synergistic biomass-based flame retardant grafted polylactic acid.
3. The reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid according to claim 2, wherein: ultrasonic dispersion appearance includes ultrasonic ware, ultrasonic ware below fixedly connected with ultrasonic probe, the inside below fixedly connected with base of ultrasonic dispersion appearance, base top are provided with governing valve, governing valve fixedly connected with regulation pole, regulation pole swing joint have adjust the ball, adjust ball swing joint have the carriage release lever, carriage release lever swing joint have the objective table, the objective table top is provided with the reaction bottle.
4. The reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid according to claim 2, wherein: the mass ratio of the chitosan to the melamine to the cross-linking agent glutaraldehyde is 10:6-10: 15-20.
5. The reactive nitrogen-phosphorus synergistic biomass-based flame retardant grafted polylactic acid according to claim 2, wherein: the mass ratio of the melamine crosslinked chitosan to the hexachlorocyclotriphosphazene to the acid-binding agent pyridine is 10:2-5: 0.5-1.
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| CN113121809A (en) * | 2021-05-12 | 2021-07-16 | 温多利遮阳材料（德州）股份有限公司 | Nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant and preparation method thereof |
| CN113121809B (en) * | 2021-05-12 | 2022-05-20 | 温多利遮阳材料（德州）股份有限公司 | Nitrogen-phosphorus synergistic chitosan grafted polylactic acid flame retardant and preparation method thereof |
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Application publication date: 20200825 |