CN111592666A - Flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel and preparation method thereof - Google Patents
Flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of hydrogel materials, and discloses a flame-retardant beta-cyclodextrin modified polypropylene-based cellulose hydrogel which comprises the following formula raw materials and components: cellulose nanocrystal, methacrylic acid, acrylic acid, beta-cyclodextrin based flame retardant, modified carbon nanotube, acrylamide, cross-linking agent and initiator. According to the flame-retardant beta-cyclodextrin modified polypropylene-based-cellulose hydrogel, the beta-cyclodextrin, the acrylic acid, the methacrylic acid, the acrylamide and the maleic anhydride are grafted with the carbon nano tube to form a polymer, the polymer is crosslinked with the cellulose nanocrystalline to form a hydrogel material, the beta-cyclodextrin coats the benzenediol bis (diphenyl) phosphate, when the hydrogel material is burnt at high temperature, a phosphide generated by decomposition has strong dehydration property, the beta-cyclodextrin is easily carbonized under an inert atmosphere, and the carbon nano tube can form a compact carbon layer at high temperature, so that the carbonization rate of the hydrogel material is enhanced, and heat conduction and oxygen permeation are inhibited.
Description
Technical Field
The invention relates to the technical field of hydrogel materials, in particular to flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel and a preparation method thereof.
Background
The hydrogel can rapidly absorb water and swell in water, can keep a large volume of water in a swollen state without decomposition, is a very hydrophilic three-dimensional network structure gel, has a cross-linking network inside, can absorb and keep a large amount of water, has a water absorption capacity related to a cross-linking degree, is lower in water absorption capacity when the cross-linking degree is higher, is not completely solid or completely liquid in an aggregation state of the gel, can keep a certain shape and volume without deformation when the solid state is in a state, and can diffuse or permeate a solute in the hydrogel when the liquid state is in a state.
The hydrogel material can be divided into synthetic polymer hydrogel and natural polymer hydrogel, natural polymers such as polysaccharide starch, cellulose and polypeptide poly-L-glutamic acid and the like have good biocompatibility, environmental sensitivity, rich sources and low price, but the natural polymer hydrogel material has poor stability, low mechanical property and easy degradation, so that how to form a composite material by the natural polymer material and the synthetic polymer material becomes a research hotspot.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel and a preparation method thereof, and solves the problem of poor flame-retardant property of hydrogel materials.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel comprises the following formula raw materials in parts by weight: 10-46 parts of cellulose nanocrystal, 8-12 parts of methacrylic acid, 10-16 parts of acrylic acid, 8-14 parts of beta-cyclodextrin-based flame retardant, 2-6 parts of modified carbon nanotube, 14-20 parts of acrylamide, 2-4 parts of cross-linking agent and 10-18 parts of initiator.
Preferably, the crosslinking agent is N, N-methylene bisacrylamide.
Preferably, the initiator is ammonium persulfate.
Preferably, the preparation method of the beta-cyclodextrin-based flame retardant comprises the following steps:
(1) adding N, N-dimethylformamide into a reaction bottle, adding resorcinol bis (diphenyl) phosphate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50-70 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 60-90 ℃, uniformly stirring for 2-4h, standing and aging for 6-10h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the beta-cyclodextrin based flame retardant of the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate.
Preferably, the mass ratio of the resorcinol bis (diphenyl) phosphate to the beta-cyclodextrin is 2.5-5: 1.
Preferably, the preparation method of the modified carbon nanotube comprises the following steps:
(1) adding an acetone solvent and a hydroxylated carbon nanotube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, performing ultrasonic dispersion treatment for 20-40min, heating sulfuric acid to adjust the pH value to 2-4, adding maleic anhydride and a catalyst sodium p-toluenesulfonate, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the kettle in an oven, heating to 160 ℃ for reaction for 10-18h, cooling the solution to room temperature, performing reduced pressure concentration to remove the solvent, washing a solid product by using distilled water and ethanol, and fully drying to prepare the maleic anhydride grafted modified carbon nanotube.
Preferably, the mass ratio of the hydroxylated carbon nanotube to the maleic anhydride to the sodium p-toluenesulfonate is 1:6-10: 0.2-0.5.
Preferably, the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring fixedly connected inside the water tank, a water tank upper part movably connected with a top cover, a regulating ring arranged on the surface of the top cover, a regulating fan sheet arranged on the regulating ring, a regulator fixedly connected with the regulating fan sheet, a water outlet pipe fixedly connected below the water tank, one end of the water outlet pipe movably connected with a water valve, a heat preservation inner container arranged on the outer wall of the water tank, a heat preservation inner container outer layer fixedly connected with a vacuum heat preservation inner layer, and a heat preservation outer container fixedly connected with the outside of the vacuum.
Preferably, the preparation method of the flame-retardant beta-cyclodextrin modified polypropylene-based cellulose hydrogel comprises the following steps:
(1) adding distilled water solvent, 10-46 parts of cellulose nanocrystalline and 2-6 parts of modified carbon nano tube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 40-80 ℃ for 30-60min, wherein the ultrasonic frequency is 20-30KHz, adding 8-12 parts of methacrylic acid, 10-16 parts of acrylic acid, 8-14 parts of beta-cyclodextrin-based flame retardant, 14-20 parts of acrylamide, 2-4 parts of cross-linking agent N, N-methylene bisacrylamide and 10-18 parts of initiator potassium persulfate into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50-70 ℃, uniformly stirring for reaction for 6-12h, carrying out vacuum drying on the solution to remove the solvent, placing the solid product into a dialysis bag, adding distilled water for dialysis and impurity removal, preparing the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel, maleic anhydride and hydroxylated carbon nanotubes are used, ring-opening esterification is improved, maleic anhydride is successfully grafted to the carbon nanotubes, potassium persulfate is used as an initiator, N, N-methylene bisacrylamide is used as a cross-linking agent, beta-cyclodextrin, acrylic acid, methacrylic acid, acrylamide and alkenyl groups in the maleic anhydride grafted carbon nanotubes are subjected to free radical polymerization to form a high polymer, and then the high polymer is crosslinked with cellulose nanocrystals to form a gel material, and the grafting hydrogel effect of maleic anhydride well improves the dispersibility and compatibility of the carbon nanotubes in the polymer hydrogel, so that the mechanical property of the hydrogel material is prevented from being influenced due to the fact that the carbon nanotubes are not uniformly dispersed in the hydrogel.
The flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel has a three-dimensional structure, the phosphate flame retardant benzenediol bis (diphenyl) phosphate can be well coated in the cavity of the beta-cyclodextrin to form a composite material, when the hydrogel material burns at high temperature, the beta-cyclodextrin coated diphenol bis (diphenyl) phosphate is heated and decomposed, the generated phosphide has strong dehydration property, the carbonization of the material is promoted, meanwhile, the beta-cyclodextrin is easy to be carbonized under inert atmosphere, and the carbon nano tube can also form a compact carbon layer at high temperature, the charring rate of the hydrogel material is greatly enhanced under the synergistic effect, and the compact carbon layer can inhibit the conduction of heat and the permeation of oxygen, so that the combustion process of the material is hindered, and the hydrogel material is endowed with excellent flame retardant property.
Drawings
FIG. 1 is a schematic front view of a heat preservation structure of an ultrasonic disperser;
fig. 2 is a schematic diagram of a top cover adjusting ring structure.
1. A water tank; 2. heating a ring; 3. a top cover; 4. an adjusting ring; 5. a regulator; 6. a water outlet pipe; 7. a water valve; 8. a heat preservation liner; 9. vacuum heat preservation; 10. a heat-insulating outer liner; 11. the fan blade is adjusted.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel comprises the following formula raw materials in parts by weight: 10-46 parts of cellulose nanocrystal, 8-12 parts of methacrylic acid, 10-16 parts of acrylic acid, 8-14 parts of beta-cyclodextrin-based flame retardant, 2-6 parts of modified carbon nanotube, 14-20 parts of acrylamide, 2-4 parts of cross-linking agent and 10-18 parts of initiator, wherein the cross-linking agent is N, N-methylene bisacrylamide, and the initiator is ammonium persulfate.
The preparation method of the beta-cyclodextrin based flame retardant comprises the following steps:
(1) adding N, N-dimethylformamide into a reaction bottle, adding resorcinol bis (diphenyl) phosphate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50-70 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 60-90 ℃, wherein the mass ratio of resorcinol bis (diphenyl) phosphate to beta-cyclodextrin is 2.5-5:1, stirring at a constant speed for 2-4h, standing and aging for 6-10h, cooling the solution to room temperature, centrifugally separating to remove a solvent, washing a solid product with distilled water and ethanol, and fully drying to prepare the beta-cyclodextrin based flame retardant of the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate.
The preparation method of the modified carbon nanotube comprises the following steps:
(1) adding acetone solvent and hydroxylated carbon nano tubes into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, wherein the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring fixedly connected inside the water tank, a top cover movably connected above the water tank, a regulating ring arranged on the surface of the top cover, a regulating fan arranged on the regulating ring, a regulator fixedly connected with the regulating fan, a water outlet pipe fixedly connected below the water tank, one end of the water outlet pipe movably connected with a water valve, a heat preservation inner container arranged on the outer wall of the water tank, a heat preservation inner container fixedly connected with the outer layer of the heat preservation inner container, a heat preservation outer container fixedly connected outside the vacuum heat preservation inner layer, performing ultrasonic dispersion treatment for 20-40min, heating sulfuric acid to regulate the dissolved pH to 2-4, adding maleic anhydride and catalyst sodium p-toluenesulfonate, wherein the mass ratio of the hydroxylated carbon nano tubes, the maleic anhydride and the sodium p-toluenesulfonate is 1, transferring the solution into a high-pressure hydrothermal reaction kettle, placing the high-pressure hydrothermal reaction kettle in an oven, heating the solution to 160 ℃, reacting for 10-18h, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the maleic anhydride grafted modified carbon nanotube.
The preparation method of the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel comprises the following steps:
(1) adding distilled water solvent, 10-46 parts of cellulose nanocrystalline and 2-6 parts of modified carbon nano tube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 40-80 ℃ for 30-60min, wherein the ultrasonic frequency is 20-30KHz, adding 8-12 parts of methacrylic acid, 10-16 parts of acrylic acid, 8-14 parts of beta-cyclodextrin-based flame retardant, 14-20 parts of acrylamide, 2-4 parts of cross-linking agent N, N-methylene bisacrylamide and 10-18 parts of initiator potassium persulfate into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50-70 ℃, uniformly stirring for reaction for 6-12h, carrying out vacuum drying on the solution to remove the solvent, placing the solid product into a dialysis bag, adding distilled water for dialysis and impurity removal, preparing the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel.
Example 1
(1) Preparing a beta-cyclodextrin-based flame retardant component 1: adding N, N-dimethylformamide into a reaction bottle, adding resorcinol bis (diphenyl) phosphate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 60 ℃, wherein the mass ratio of resorcinol bis (diphenyl) phosphate to beta-cyclodextrin is 2.5:1, stirring at a constant speed for 2h, standing and aging for 6h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the beta-cyclodextrin based flame retardant component 1 of the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate.
(2) Preparing a modified carbon nanotube component 1: adding an acetone solvent and a hydroxylated carbon nano tube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, wherein the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring is fixedly connected inside the water tank, the upper part of the water tank is movably connected with a top cover, the surface of the top cover is provided with an adjusting ring, the adjusting ring is provided with an adjusting fan sheet, the adjusting fan sheet is fixedly connected with an adjuster, the lower part of the water tank is fixedly connected with a water outlet pipe, one end of the water outlet pipe is movably connected with a water valve, the outer wall of the water tank is provided with a heat-insulating inner liner, the outer layer of the heat-insulating inner liner is fixedly connected with a vacuum heat-insulating inner layer, the outer part of the vacuum heat-insulating inner layer is fixedly connected with a heat-insulating outer liner, carrying out ultrasonic dispersion treatment for 20min, heating sulfuric acid to adjust the dissolved pH to 4, adding maleic anhydride and, and placing the mixture in an oven, heating the mixture to 120 ℃, reacting for 10 hours, cooling the solution to room temperature, concentrating the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying the solid product to prepare the modified carbon nanotube component 1 grafted by maleic anhydride.
(3) Preparing a flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 1: adding a distilled water solvent, 46 parts of cellulose nanocrystalline and 2 parts of modified carbon nanotube component 1 into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 40 ℃ for 30min, wherein the ultrasonic frequency is 20KHz, adding 8 parts of methacrylic acid, 10 parts of acrylic acid and 8 parts of beta-cyclodextrin-based flame retardant component 1, 14 parts of acrylamide, 2 parts of cross-linking agent N, N-methylene bisacrylamide and 10 parts of initiator potassium persulfate into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50 ℃, carrying out uniform stirring reaction for 6h, carrying out vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding distilled water, carrying out dialysis and impurity removal processes, and preparing the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 1.
Example 2
(1) Preparing a beta-cyclodextrin-based flame retardant component 2: adding N, N-dimethylformamide into a reaction bottle, adding resorcinol bis (diphenyl) phosphate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 60 ℃, wherein the mass ratio of resorcinol bis (diphenyl) phosphate to beta-cyclodextrin is 5:1, stirring at a constant speed for 2h, standing and aging for 6h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the beta-cyclodextrin based flame retardant component 2 of the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate.
(2) Preparing a modified carbon nanotube component 2: adding an acetone solvent and a hydroxylated carbon nano tube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, wherein the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring is fixedly connected inside the water tank, the upper part of the water tank is movably connected with a top cover, the surface of the top cover is provided with an adjusting ring, the adjusting ring is provided with an adjusting fan sheet, the adjusting fan sheet is fixedly connected with an adjuster, the lower part of the water tank is fixedly connected with a water outlet pipe, one end of the water outlet pipe is movably connected with a water valve, the outer wall of the water tank is provided with a heat-insulating inner liner, the outer layer of the heat-insulating inner liner is fixedly connected with a vacuum heat-insulating inner layer, the outer part of the vacuum heat-insulating inner layer is fixedly connected with a heat-insulating outer liner, carrying out ultrasonic dispersion treatment for 20min, heating sulfuric acid to adjust the dissolved pH to 4, adding maleic anhydride and, and placing the mixture in an oven, heating the mixture to 160 ℃, reacting for 10 hours, cooling the solution to room temperature, concentrating the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying the solid product to prepare the modified carbon nano tube component 2 grafted by maleic anhydride.
(3) Preparing a flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 2: adding distilled water solvent, 39 parts of cellulose nanocrystalline and 3 parts of modified carbon nanotube component 2 into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 40 ℃ for 60min, wherein the ultrasonic frequency is 30KHz, adding 9 parts of methacrylic acid, 11 parts of acrylic acid, 9 parts of beta-cyclodextrin-based flame retardant component 2, 15 parts of acrylamide, 2.5 parts of cross-linking agent N, N-methylene bisacrylamide and 11.5 parts of initiator potassium persulfate into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 50 ℃, carrying out uniform-speed stirring reaction for 12h, carrying out vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding distilled water, and carrying out dialysis impurity removal to prepare the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 2.
Example 3
(1) Preparing a beta-cyclodextrin-based flame retardant component 3: adding N, N-dimethylformamide into a reaction bottle, adding resorcinol bis (diphenyl) phosphate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 75 ℃, wherein the mass ratio of resorcinol bis (diphenyl) phosphate to beta-cyclodextrin is 4:1, stirring at a constant speed for 3h, standing and aging for 8h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare a beta-cyclodextrin based flame retardant component 3 of the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate.
(2) Preparing a modified carbon nanotube component 3: adding an acetone solvent and a hydroxylated carbon nano tube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, wherein the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring is fixedly connected inside the water tank, the upper part of the water tank is movably connected with a top cover, the surface of the top cover is provided with an adjusting ring, the adjusting ring is provided with an adjusting fan sheet, the adjusting fan sheet is fixedly connected with an adjuster, the lower part of the water tank is fixedly connected with a water outlet pipe, one end of the water outlet pipe is movably connected with a water valve, the outer wall of the water tank is provided with a heat-insulating inner liner, the outer layer of the heat-insulating inner liner is fixedly connected with a vacuum heat-insulating inner layer, the outer part of the vacuum heat-insulating inner layer is fixedly connected with a heat-insulating outer liner, carrying out ultrasonic dispersion treatment for 30min, heating sulfuric acid to adjust the dissolved pH to 3, adding maleic anhydride and, and placing the mixture in an oven, heating the mixture to 140 ℃, reacting for 14h, cooling the solution to room temperature, concentrating the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying the solid product to prepare the modified carbon nanotube component 3 grafted by maleic anhydride.
(3) Preparing a flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 3: adding distilled water solvent, 28 parts of cellulose nanocrystalline and 4 parts of modified carbon nanotube component 3 into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 60 ℃ for 45min, wherein the ultrasonic frequency is 25KHz, adding 10 parts of methacrylic acid, 13 parts of acrylic acid and 11 parts of beta-cyclodextrin-based flame retardant component 3, 17 parts of acrylamide, 3 parts of cross-linking agent N, N-methylene bisacrylamide and 14 parts of initiator potassium persulfate into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, carrying out uniform stirring reaction for 8h, carrying out vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding distilled water, and carrying out dialysis impurity removal process to prepare the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 3.
Example 4
(1) Preparing a beta-cyclodextrin-based flame retardant component 4: adding N, N-dimethylformamide into a reaction bottle, adding resorcinol bis (diphenyl) phosphate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 70 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 80 ℃, wherein the mass ratio of resorcinol bis (diphenyl) phosphate to beta-cyclodextrin is 5:1, stirring at a constant speed for 3h, standing and aging for 6h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the beta-cyclodextrin based flame retardant component 4 of the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate.
(2) Preparing a modified carbon nanotube component 4: adding an acetone solvent and a hydroxylated carbon nano tube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, wherein the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring is fixedly connected inside the water tank, the upper part of the water tank is movably connected with a top cover, the surface of the top cover is provided with an adjusting ring, the adjusting ring is provided with an adjusting fan sheet, the adjusting fan sheet is fixedly connected with an adjuster, the lower part of the water tank is fixedly connected with a water outlet pipe, one end of the water outlet pipe is movably connected with a water valve, the outer wall of the water tank is provided with a heat-insulating inner liner, the outer layer of the heat-insulating inner liner is fixedly connected with a vacuum heat-insulating inner layer, the outer part of the vacuum heat-insulating inner layer is fixedly connected with a heat-insulating outer liner, carrying out ultrasonic dispersion treatment for 40min, heating sulfuric acid to adjust the dissolved pH to 2, adding maleic anhydride and, and placing the mixture in an oven, heating the mixture to 160 ℃, reacting for 10 hours, cooling the solution to room temperature, concentrating the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying the solid product to prepare the modified carbon nano tube component 4 grafted by maleic anhydride.
(3) Preparing a flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 4: adding distilled water solvent, 18 parts of cellulose nanocrystalline and 5 parts of modified carbon nanotube component 4 into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 40 ℃ for 30min, wherein the ultrasonic frequency is 20KHz, adding 11 parts of methacrylic acid, 15 parts of acrylic acid and 13 parts of beta-cyclodextrin-based flame retardant component 4, 18 parts of acrylamide, 3.5 parts of cross-linking agent N, N-methylene bisacrylamide and 16.5 parts of initiator potassium persulfate into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, carrying out uniform-speed stirring reaction for 12h, carrying out vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding distilled water, and carrying out dialysis impurity removal to prepare the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 4.
Example 5
(1) Preparing a beta-cyclodextrin-based flame retardant component 5: adding N, N-dimethylformamide into a reaction bottle, adding resorcinol bis (diphenyl) phosphate, placing the reaction bottle in a constant-temperature water bath kettle, heating to 70 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 90 ℃, wherein the mass ratio of resorcinol bis (diphenyl) phosphate to beta-cyclodextrin is 5:1, stirring at a constant speed for 4h, standing and aging for 10h, cooling the solution to room temperature, centrifugally separating to remove the solvent, washing the solid product with distilled water and ethanol, and fully drying to prepare the beta-cyclodextrin based flame retardant component 5 of the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate.
(2) Preparing a modified carbon nanotube component 5: adding an acetone solvent and a hydroxylated carbon nano tube into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, wherein the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring is fixedly connected inside the water tank, the upper part of the water tank is movably connected with a top cover, the surface of the top cover is provided with an adjusting ring, the adjusting ring is provided with an adjusting fan sheet, the adjusting fan sheet is fixedly connected with an adjuster, the lower part of the water tank is fixedly connected with a water outlet pipe, one end of the water outlet pipe is movably connected with a water valve, the outer wall of the water tank is provided with a heat-insulating inner liner, the outer layer of the heat-insulating inner liner is fixedly connected with a vacuum heat-insulating inner layer, the outer part of the vacuum heat-insulating inner layer is fixedly connected with a heat-insulating outer liner, carrying out ultrasonic dispersion treatment for 40min, heating sulfuric acid to adjust the dissolved pH to 2, adding maleic anhydride and, and placing the mixture in an oven, heating the mixture to 160 ℃, reacting for 18h, cooling the solution to room temperature, concentrating the solution under reduced pressure to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying the solid product to prepare the modified carbon nanotube component 5 grafted by maleic anhydride.
(3) Preparing a flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 5: adding a distilled water solvent, 10 parts of cellulose nanocrystalline and 6 parts of modified carbon nanotube component 5 into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic treatment instrument, carrying out ultrasonic dispersion treatment at 80 ℃ for 60min, wherein the ultrasonic frequency is 30KHz, adding 12 parts of methacrylic acid, 16 parts of acrylic acid and 14 parts of beta-cyclodextrin-based flame retardant component 5, 20 parts of acrylamide, 4 parts of cross-linking agent N, N-methylene bisacrylamide and 18 parts of initiator potassium persulfate into the reaction bottle, placing the reaction bottle into a constant-temperature water bath kettle, heating to 70 ℃, carrying out uniform stirring reaction for 12h, carrying out vacuum drying on the solution to remove the solvent, placing a solid product into a dialysis bag, adding distilled water, and carrying out dialysis impurity removal process to prepare the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel material 5.
The flame retardant beta-cyclodextrin modified polypropylene-based cellulose hydrogel materials of examples 1-5 were tested for flame retardant performance using a WK-310 horizontal vertical flame tester, with the test standard being UL94 standard.
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| UL-94 rating | V-0 | V-0 | V-0 | V-0 | V-0 |
According to the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel, maleic anhydride and hydroxylated carbon nanotubes are used, ring-opening esterification is improved, maleic anhydride is successfully grafted to the carbon nanotubes, potassium persulfate is used as an initiator, N, N-methylene bisacrylamide is used as a cross-linking agent, beta-cyclodextrin, acrylic acid, methacrylic acid, acrylamide and alkenyl groups in the maleic anhydride grafted carbon nanotubes are subjected to free radical polymerization to form a high polymer, and then the high polymer is crosslinked with cellulose nanocrystals to form a gel material, and the grafting hydrogel effect of maleic anhydride well improves the dispersibility and compatibility of the carbon nanotubes in the polymer hydrogel, so that the mechanical property of the hydrogel material is prevented from being influenced due to the fact that the carbon nanotubes are not uniformly dispersed in the hydrogel.
The beta-cyclodextrin has a three-dimensional structure, a phosphate flame retardant, namely benzenediol bis (diphenyl) phosphate, can be well coated in a cavity of the beta-cyclodextrin to form a composite material, when a hydrogel material burns at high temperature, the beta-cyclodextrin coated benzenediol bis (diphenyl) phosphate is decomposed by heating, a generated phosphide has strong dehydration performance, carbonization of the material is promoted, the beta-cyclodextrin is easily carbonized under an inert atmosphere, the carbon nanotube also forms a compact carbon layer at high temperature, the carbonization rate of the hydrogel material is greatly enhanced under the synergistic effect, and the compact carbon layer can inhibit heat conduction and oxygen permeation, so that the combustion process of the material is hindered, and the excellent flame retardant performance is endowed to the hydrogel material.
Claims (9)
1. The flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel comprises the following formula raw materials and components in parts by weight, and is characterized in that: 10-46 parts of cellulose nanocrystal, 8-12 parts of methacrylic acid, 10-16 parts of acrylic acid, 8-14 parts of beta-cyclodextrin-based flame retardant, 2-6 parts of modified carbon nanotube, 14-20 parts of acrylamide, 2-4 parts of cross-linking agent and 10-18 parts of initiator.
2. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 1, wherein: the cross-linking agent is N, N-methylene bisacrylamide.
3. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 1, wherein: the initiator is ammonium persulfate.
4. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 1, wherein: the preparation method of the beta-cyclodextrin based flame retardant comprises the following steps:
(1) adding resorcinol bis (diphenyl) phosphate into N, N-dimethylformamide, heating the solution to 50-70 ℃, stirring and dissolving, adding beta-cyclodextrin, heating to 60-90 ℃, uniformly stirring for 2-4h, standing and aging for 6-10h, removing the solvent from the solution, washing a solid product, and drying to prepare the beta-cyclodextrin based flame retardant of the beta-cyclodextrin coated hydroquinone bis (diphenyl) phosphate.
5. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 4, wherein: the mass ratio of the resorcinol bis (diphenyl) phosphate to the beta-cyclodextrin is 2.5-5: 1.
6. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 1, wherein: the preparation method of the modified carbon nanotube comprises the following steps:
(1) adding a hydroxylated carbon nanotube into an acetone solvent, carrying out ultrasonic dispersion treatment on the solution for 20-40min, heating sulfuric acid to adjust the pH value to 2-4, adding maleic anhydride and a catalyst sodium p-toluenesulfonate, transferring the solution into a reaction kettle, heating to 120-160 ℃, reacting for 10-18h, removing the solvent from the solution, washing a solid product and drying to prepare the maleic anhydride grafted modified carbon nanotube.
7. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 6, wherein: the mass ratio of the hydroxylated carbon nanotube to the maleic anhydride to the sodium p-toluenesulfonate is 1:6-10: 0.2-0.5.
8. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 1, wherein: the constant-temperature ultrasonic treatment instrument comprises a water tank, a heating ring fixedly connected inside the water tank, a water tank upper part and a top cover movably connected, a regulating ring is arranged on the surface of the top cover, a regulating fan sheet is arranged on the regulating ring, a regulator fixedly connected with the regulating fan sheet, a water outlet pipe fixedly connected below the water tank, one end of the water outlet pipe is movably connected with a water valve, a heat preservation inner container is arranged on the outer wall of the water tank, the outer layer of the heat preservation inner container is fixedly connected with a vacuum heat preservation inner layer, and a heat preservation outer container.
9. The flame retardant β -cyclodextrin modified polypropylene-based cellulose hydrogel of claim 1, wherein: the preparation method of the flame-retardant beta-cyclodextrin modified polypropylene-based cellulose hydrogel comprises the following steps:
(1) adding 10-46 parts of cellulose nanocrystalline and 2-6 parts of modified carbon nano tube into a distilled water solvent, carrying out ultrasonic dispersion treatment on the solution at 40-80 ℃ for 30-60min, wherein the ultrasonic frequency is 20-30KHz, then adding 8-12 parts of methacrylic acid, 10-16 parts of acrylic acid, 8-14 parts of beta-cyclodextrin-based flame retardant, 14-20 parts of acrylamide, 2-4 parts of cross-linking agent N, N-methylene bisacrylamide and 10-18 parts of initiator potassium persulfate, heating the solution to 50-70 ℃, reacting for 6-12h, removing the solvent from the solution, removing impurities from a solid product, and preparing the flame-retardant beta-cyclodextrin modified polypropylene-cellulose hydrogel.
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| CN112851860A (en) * | 2021-01-08 | 2021-05-28 | 杭州所予科技有限公司 | Degradable cellulose-polyacrylamide composite water-retaining agent and preparation method thereof |
| CN115449266A (en) * | 2022-10-20 | 2022-12-09 | 辽宁中亿五兄弟科技有限公司 | Building wall coating with heat-insulating and fireproof characteristics and production method thereof |
| CN117442921A (en) * | 2023-11-01 | 2024-01-26 | 四川峰邦消防科技有限公司 | Novel polymer gel fire-extinguishing flame retardant and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112851860A (en) * | 2021-01-08 | 2021-05-28 | 杭州所予科技有限公司 | Degradable cellulose-polyacrylamide composite water-retaining agent and preparation method thereof |
| CN115449266A (en) * | 2022-10-20 | 2022-12-09 | 辽宁中亿五兄弟科技有限公司 | Building wall coating with heat-insulating and fireproof characteristics and production method thereof |
| CN117442921A (en) * | 2023-11-01 | 2024-01-26 | 四川峰邦消防科技有限公司 | Novel polymer gel fire-extinguishing flame retardant and preparation method thereof |
| CN117442921B (en) * | 2023-11-01 | 2024-05-24 | 四川峰邦消防科技有限公司 | Polymer gel fire-extinguishing flame retardant and preparation method thereof |
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