CN112175404B - Preparation method of bamboo charcoal-based high-flame-retardance expansion type synergistic system - Google Patents

Preparation method of bamboo charcoal-based high-flame-retardance expansion type synergistic system Download PDF

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CN112175404B
CN112175404B CN202011183106.1A CN202011183106A CN112175404B CN 112175404 B CN112175404 B CN 112175404B CN 202011183106 A CN202011183106 A CN 202011183106A CN 112175404 B CN112175404 B CN 112175404B
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bamboo charcoal
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章亮
李文珠
张文标
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Zhejiang A&F University ZAFU
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a preparation method of a bamboo charcoal-based high-flame-retardance expansion-type synergistic system, which comprises the steps of pre-irradiating surface-modified bamboo charcoal, and grafting a nitrogen and phosphorus expansion flame retardant to the inside and outside of the bamboo charcoal and the surface of pores by adopting a low-temperature plasma activation method; heating and mixing the grafted bamboo charcoal, hydroxymethylated lignin, chitosan and expanded graphite to obtain a high-flame-retardancy mixed material B; mixing the mixed material B dispersed in ethanol, Alkyl Polyglycoside (APG), ammonia water and Tetraethoxysilane (TEOS), reacting for 2h, filtering, washing, and drying to obtain the microencapsulated synergistic material system C. The bamboo charcoal-based high-flame-retardance expansion-type synergistic system prepared by the invention is green in material and improves the additional value of bamboo wood; the bamboo charcoal has excellent heat conduction char forming property, has gas phase and condensed phase flame retardance after being grafted with the low-polymerization-degree nitrogen and phosphorus intumescent flame retardant, remarkably improves the flame retardant effect while reducing the negative influence on the mechanical property of the composite material, can be simply ploughed and abandoned, and enhances the water and fertilizer retention of soil.

Description

Preparation method of bamboo charcoal-based high-flame-retardance expansion type synergistic system
Technical Field
The invention relates to the field of production of green high-flame-retardance intumescent flame retardants, in particular to a method for preparing bamboo charcoal with high-flame-retardance characteristics.
Background
China is the biggest bamboo product production and export country all over the world, and the development of the bamboo industry promotes the economic development, but at the same time means the generation of more processing residues. Part of the waste is used as raw materials of the machine-made charcoal, and most of the waste is discarded or incinerated as garbage, so that the environment is polluted and the resource waste is caused. The bamboo charcoal is a solid product obtained by high-temperature carbonization of bamboo and processing residues thereof under the anaerobic or anoxic condition, has a high-strength carbon skeleton and a porous surface structure with a good thermoplastic composite forming foundation, and can effectively improve the thermal stability of a polymer by virtue of excellent thermal conductivity and char forming performance when being used as a special filler or auxiliary agent for preparing a composite material.
The market has a great demand for polymer products, which are themselves flammable and cause fires. At present, the flame retardant material mainly adopts an intrinsic flame retardant mode and a halogen-free additive flame retardant mode, the intrinsic flame retardant introduces flame retardant groups or flame retardant elements to the molecular chain of a high molecular polymer, and the technical difficulty is high; the additive type mainly adopts the addition of an intumescent flame retardant represented by ammonium polyphosphate and a phosphorus-nitrogen inorganic metal salt represented by aluminum hypophosphite, and can achieve excellent flame retardant effect under the condition of higher addition (more than 30%). The traditional intumescent flame retardant has many limitations, such as small molecular weight, easy moisture absorption, poor thermal stability and the like, and is usually compounded and synergistic in order to achieve an ideal flame retardant effect, so that poor compatibility is easily caused to cause the deterioration of the mechanical property of the material, and meanwhile, the preparation difficulty of the process is increased, and the application range of the composite material is limited; in addition, the addition of a large amount of flame retardant polymer materials, especially when containing heavy metal elements or toxic chemical components, can release toxic gases to endanger trapped persons and rescue workers during combustion; and if the flame retardant is not properly disposed of, a series of environmental problems are caused, which all put new demands on the flame retardant means.
Compared with the flame-retardant mode, the flame-retardant modification of the bamboo charcoal to the polymer is added, so that the high added value utilization of the bamboo and the processing residues of the bamboo is facilitated, meanwhile, the bamboo charcoal is used as biomass charcoal with excellent performance, the flame-retardant performance of the polymer composite material is improved, the smoke toxicity during combustion is reduced, and the influence of the addition of the flame retardant to the mechanical performance of the composite material can be reduced according to the performance requirement of the product. However, under normal conditions, the flame retardant property of the polymer is improved only by using the unmodified bamboo charcoal, and the phenomenon of melt dripping of the polymer composite material cannot be obviously improved. Therefore, the bamboo charcoal needs to be reasonably modified to prepare a novel green synergistic system with high flame retardant property, and the limitation of the existing flame retardant mode is broken through.
Disclosure of Invention
Aiming at the defects of the existing flame retardant technology and the high-efficiency utilization of bamboo wood and processing residues thereof, the invention aims to provide a preparation method for constructing a bamboo charcoal-based synergistic system with high flame retardant property. The flame-retardant system prepared by the method has the effects of no toxicity, greenness and high flame retardance, gives full play to the properties of high thermal stability, char formation and the like of bamboo and residues thereof under high-temperature carbonization, and realizes the environment protection of flame retardance of polymers.
In order to solve the problems mentioned in the background technology, the invention adopts the following technical scheme: a method for preparing a bamboo charcoal based high flame retardant expansion type synergistic system,
the structure schematic formula of the modified flame-retardant grafted bamboo charcoal is as follows:
Figure RE-GDA0002789035410000021
the preparation of the bamboo charcoal based high flame retardant expansion type synergistic system comprises the following steps:
1) surface modification: selecting bamboo charcoal obtained at the carbonization temperature of 500-700 ℃, and mixing 40-60 parts of bamboo charcoal particles and 240-360 parts of hydrogen peroxide (H)2O2) The solution is mixed, 200-240 parts of nitric acid (HNO) are slowly mixed3) And adding the solution, mixing, reacting for 20-24h under the assistance of microwave, repeatedly cleaning with deionized water until the filtrate is neutral, and finally drying the cleaned bamboo charcoal to obtain the modified bamboo charcoal.
2) Flame-retardant grafting: and (2) putting 20-30 parts by mass of the modified bamboo charcoal obtained in the step 1) into an irradiation bottle, vacuumizing, filling nitrogen for several times, putting into an irradiation chamber, and performing irradiation treatment for 5-10 min. Then the irradiation bottle is vacuumized, and 40-60 parts of phosphoric acid (H) is sucked in under the condition of negative pressure3PO4) 70-110 parts of urea, slowly heating and stirringAfter reacting for 1-2h, taking out and washing with mild deionized water for several times, and vacuum drying for later use.
Placing the pre-irradiated modified bamboo charcoal in a closed vacuum glass bottle, after plasma treatment with the power set at 240W is performed for 5-10min, sucking 20-60 parts of phosphoric acid and 35-55 parts of urea under negative pressure, heating and stirring, controlling the heating speed to be 8-10 ℃/min, heating until the solution is clear and a little bubbles are generated, then continuously heating at the speed of 4-5 ℃/min until the solution is foamed and the viscosity is rapidly increased, stopping heating, and keeping the temperature for 5-15 min. And pouring the reaction materials into a small tray, putting the tray into an oven with the temperature of 200-260 ℃, heating, curing for 1.5-3 h, and discharging to obtain the intumescent flame retardant bamboo charcoal.
3) The synergistic effect is enhanced: adding the flame-retardant grafted bamboo charcoal obtained in the step 2) and 15-30 parts of the carbon source synergistic auxiliary into a planetary mixer by mass parts, and stirring at the revolution speed of 50-60r/min and the temperature of 50-60 ℃ to obtain a mixed material system B.
4) Interface modification: pouring 100-150 parts of anhydrous ethanol and 40-60 parts of deionized water into a three-neck round-bottom flask with a magnetic stirrer and a condenser according to the parts by mass, and stirring for 10-20 min at 40 ℃. Then, 10 parts of the mixed material B in the step 3), 1-2 parts of Alkyl Polyglycoside (APG) and 15-20 parts of ammonia water are added into a flask and stirred for 15-20 min. And then, dropwise adding 10-15 parts of Tetraethoxysilane (TEOS) into the mixture, keeping the same temperature for 2 hours, cooling the mixture to room temperature, washing the mixture with deionized water after filtering, and drying the mixture at 80 ℃ to obtain the microencapsulated expanded flame-retardant carbon synergistic material system C.
As a further improvement of the invention, the ash and impurities on the surface of the bamboo charcoal are removed by using deionized water assisted ultrasonic treatment in the step 1), and the particle size of the ash and impurities is 100-200 meshes (74-150 μm).
As a further development of the invention, H in step 1) is2O2The mass fraction of the solution is 30-35 percent; HNO3The concentration of the solution is 65-70%.
As a further improvement of the invention, in the step 2), the irradiation source is gamma-ray, the irradiation dose rate is set to be 6-8kGy/h, and the irradiation dose is 100-150 kGy.
As a further improvement of the invention, the low-temperature oxygen plasma is adopted as the plasma in the step 2), and the flow rate of the carrier gas is kept at 10SCCM (standard cubic centimeter per minute).
As a further improvement of the invention, the prepolymerization temperature and the polymerization temperature in the step 2) are respectively controlled to be 120-130 ℃ and 230-240 ℃, and the prepolymerization time and the polymerization time are respectively controlled to be 20-30min and 140-150 min.
As a further improvement of the invention, the carbon source synergistic auxiliary agent in the step 3) mainly comprises 10-20 parts of hydroxymethylated lignin, 5-10 parts of chitosan and 0.1-0.5 part of expanded graphite.
As a further development of the invention, the ammonia water concentration in step 4) is 20 to 30 wt.%.
After the technical scheme is adopted, the invention has the following beneficial effects:
1) the bamboo charcoal based high flame retardation expansion type synergistic system is prepared from the main raw materials of bamboo charcoal particles, lignin, chitosan and expanded graphite, and the used materials are green and pollution-free, wherein the bamboo charcoal is grafted with the low-polymerization-degree nitrogen and phosphorus synergistic expansion type flame retardant after surface modification treatment, and the bamboo charcoal can be used as a nitrogen fertilizer and a phosphorus fertilizer in agriculture by combining the water and fertilizer retention performance of the bamboo charcoal, and the waste treatment of the nitrogen fertilizer and the phosphorus fertilizer can be simply ploughed back, so that the treatment difficulty is reduced.
2) According to the invention, the bamboo charcoal has gas-phase and condensed-phase flame retardant effects by adopting the intumescent flame retardant for graft modification of the bamboo charcoal, and the addition types and the amount of the flame retardant additives can be reduced by combining the excellent heat conduction and carbon formation performance of the bamboo charcoal, so that the problem that the mechanical properties of the composite material are influenced due to poor compatibility and easy agglomeration of the bamboo charcoal is solved, and the additional value of the bamboo charcoal and the processing residues thereof is improved.
3) According to the invention, the surface of the bamboo charcoal is etched while more oxygen-containing groups are endowed to the bamboo charcoal through plasma modification, the modified and grafted bamboo charcoal units are uniformly combined with the carbon source synergistic auxiliary under low-temperature stirring, when the modified and grafted bamboo charcoal is added as a flame-retardant polymer filler, the negative influence on the mechanical property of the composite material is reduced, and an ideal flame-retardant effect is provided by simultaneously playing the flame-retardant effects of a gas phase and a condensed phase.
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FIG. 1 is FTIR images of the bamboo charcoal surface modification in examples 1, 2 and 3 of the present invention.
Detailed Description
The substance of the present invention will be described in further detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment 1 discloses a manufacturing process of a bamboo charcoal based high flame retardant expansion type synergistic system, which comprises the following preparation steps:
1) according to the mass fraction, 40 parts of bamboo charcoal particles with the particle diameter of 150 meshes (106 mu m) and the mass fraction of 30 percent of H are taken, wherein the bamboo charcoal particles are obtained at the carbonization temperature of 500-700 DEG C2O2The solution was mixed and 200 parts of 68% strength HNO were slowly added3And adding the solution, mixing, reacting for 24h under the assistance of microwaves, repeatedly cleaning with deionized water until the filtrate is neutral, and finally drying the cleaned bamboo charcoal to obtain the modified bamboo charcoal. FIG. 1 shows an FTIR chart of the modified flame-retardant grafted bamboo charcoal prepared by the present embodiment, from which it can be seen that the modified bamboo charcoal is at 3400--1、1600-1700cm-1、1380-1400cm-1The absorption peaks are obviously enhanced, which respectively correspond to the increase of the contents of hydroxyl, carboxyl and lactone, and the result shows that more oxygen-containing functional groups are introduced into the surface of the modified bamboo charcoal, so that extremely powerful conditions are provided for grafting.
2) According to the mass parts, 20 parts of the modified bamboo charcoal obtained in the step 1) are placed in an irradiation bottle, the irradiation bottle is vacuumized and filled with nitrogen for a plurality of times and then placed in an irradiation chamber, gamma rays are selected as an irradiation source, the irradiation dose rate is set to be 6kGy/h, the irradiation dose is 100kGy, and the irradiation treatment is carried out for 5 min. And then, vacuumizing an irradiation bottle, sucking 40 parts of phosphoric acid and 70 parts of urea under the negative pressure condition, slowly heating, stirring, reacting for 2 hours, taking out, washing with mild deionized water for several times, and drying in vacuum for later use.
Placing the pre-irradiation modified bamboo charcoal in a closed vacuum glass bottle, treating with plasma with power set at 240W and carrier gas flow rate kept at 10SCCM (standard cubic centimeter per minute) for 10min, sucking 20 parts of phosphoric acid and 35 parts of urea under negative pressure, heating and stirring, raising temperature at 8 ℃/min, controlling prepolymerization temperature at 120 ℃ and polymerization time at 30min, then continuing raising temperature at 5 ℃/min to 230 ℃, keeping polymerization time for 150min, and finally keeping temperature for 15 min. And pouring the reaction materials into a small tray, putting the tray into a baking oven with the temperature of 200 ℃, heating, curing for 2 hours, and discharging to obtain the intumescent flame retardant bamboo charcoal.
3) Adding the flame-retardant grafted bamboo charcoal obtained in the step 2) with 10 parts of hydroxymethylated lignin, 5 parts of chitosan and 0.1 part of expanded graphite into a planetary mixer by weight, and stirring at 60 ℃ under the condition of revolution speed of 60r/min to obtain a mixed material system B.
4) 100 parts by weight of absolute ethanol and 40 parts by weight of deionized water were poured into a three-necked round bottom flask equipped with a magnetic stirrer and a condenser and stirred at 40 ℃ for 20 min. Then, 10 parts of the mixture B in the step 3), 2 parts of Alkyl Polyglycoside (APG) and 20 parts of ammonia water with the mass fraction of 25 wt.% are added into the flask and stirred for 20 min. And then, adding 15 parts of Tetraethoxysilane (TEOS) into the mixture dropwise, keeping the same temperature for 2 hours, cooling the mixture to room temperature, washing the mixture with deionized water after filtering, and drying the mixture at 80 ℃ to obtain the microencapsulated intumescent flame retardant carbon synergistic material system C.
The embodiment 2 discloses a manufacturing process of a bamboo charcoal based high flame retardant intumescent synergistic system, which comprises the following preparation steps:
1) according to the mass fraction, 40 parts of bamboo charcoal particles with the particle diameter of 150 meshes (106 mu m) and the mass fraction of 35 percent of H are taken, wherein the bamboo charcoal particles are obtained at the carbonization temperature of 500-700 DEG C2O2The solution was mixed and 220 parts of 68% HNO were slowly added3And adding and mixing the solution, reacting for 24 hours under the assistance of microwaves, repeatedly washing the solution by using deionized water until the filtrate is neutral, and finally drying the washed bamboo charcoal to obtain the modified bamboo charcoal. FIG. 1 shows an FTIR chart of the modified flame-retardant grafted bamboo charcoal prepared by the present embodiment, from which it can be seen that the bamboo charcoal modified by the present embodiment is at 3400--1(hydroxyl group) 1600-1700cm-1(carboxyl group) 1380-1400cm-1The absorption peak at the (lactone group) position is obviously enhanced compared with that of the example 1, which shows that the oxygen-containing function is introduced into the surface of the modified bamboo charcoalThe bolus is more effective.
2) According to the mass parts, 20 parts of the modified bamboo charcoal obtained in the step 1) are placed in an irradiation bottle, the irradiation bottle is vacuumized and filled with nitrogen for a plurality of times and then placed in an irradiation chamber, gamma rays are selected as an irradiation source, the irradiation dose rate is set to be 8kGy/h, the irradiation dose is 100kGy, and the irradiation treatment is carried out for 8 min. And then, vacuumizing the irradiation bottle, sucking 50 parts of phosphoric acid and 100 parts of urea under the negative pressure condition, slowly heating, stirring, reacting for 2 hours, taking out, washing with mild deionized water for several times, and drying in vacuum for later use.
Placing the pre-irradiation modified bamboo charcoal in a closed vacuum glass bottle, treating with plasma with power set at 240W and carrier gas flow rate kept at 10SCCM (standard cubic centimeter per minute) for 10min, sucking 40 parts of phosphoric acid and 45 parts of urea under negative pressure, heating and stirring, raising temperature at 8 ℃/min, controlling prepolymerization temperature at 125 ℃ and polymerization time at 30min, then continuing raising temperature to 240 ℃ at 5 ℃/min, keeping polymerization time at 150min, and finally keeping the temperature for 15 min. And pouring the reaction materials into a small tray, putting the tray into a baking oven with the temperature of 200 ℃, heating, curing for 2 hours, and discharging to obtain the intumescent flame retardant bamboo charcoal.
3) Adding the flame-retardant grafted bamboo charcoal obtained in the step 2), 15 parts of hydroxymethylated lignin, 8 parts of chitosan and 0.3 part of expanded graphite into a planetary mixer by mass, and stirring at a revolution speed of 60r/min and a temperature of 60 ℃ to obtain a mixed material system B.
4) 100 parts by weight of absolute ethanol and 40 parts by weight of deionized water were poured into a three-necked round bottom flask equipped with a magnetic stirrer and a condenser and stirred at 40 ℃ for 20 min. Then, 10 parts of the mixture B in the step 3), 2 parts of Alkyl Polyglycoside (APG) and 20 parts of ammonia water with the mass fraction of 25 wt.% are added into the flask and stirred for 20 min. And then, adding 15 parts of Tetraethoxysilane (TEOS) into the mixture dropwise, keeping the same temperature for 2 hours, cooling the mixture to room temperature, washing the mixture with deionized water after filtering, and drying the mixture at 80 ℃ to obtain the microencapsulated intumescent flame retardant carbon synergistic material system C.
The embodiment 3 discloses a manufacturing process of a bamboo charcoal based high flame retardant expansion type synergistic system, which comprises the following preparation steps:
1) according to the mass fraction,40 parts of bamboo charcoal particles with the carbonization temperature of 500-700 ℃, the particle diameter of 150 meshes (106 mu m) and 360 parts of H with the mass fraction of 35 percent2O2The solution was mixed and 240 parts of 68% strength HNO were slowly added3And adding the solution, mixing, reacting for 24h under the assistance of microwaves, repeatedly cleaning with deionized water until the filtrate is neutral, and finally drying the cleaned bamboo charcoal to obtain the modified bamboo charcoal. FIG. 1 shows FTIR chart of modified flame retardant grafted bamboo charcoal prepared by this embodiment, from which it can be seen that comparative example 2 of modified bamboo charcoal of this embodiment is at 3400--1(hydroxyl group) 1600-1700cm-1(carboxyl group) 1380-1400cm-1The absorption peak at the (lactone group) position is enhanced more obviously, which shows that the introduction of the oxygen-containing functional group on the surface of the modified bamboo charcoal is very effective.
2) According to the mass parts, 20 parts of the modified bamboo charcoal obtained in the step 1) are placed in an irradiation bottle, the irradiation bottle is vacuumized and filled with nitrogen for a plurality of times and then placed in an irradiation chamber, gamma rays are selected as an irradiation source, the irradiation dose rate is set to be 8kGy/h, the irradiation dose is 150kGy, and the irradiation treatment is carried out for 8 min. And then, vacuumizing an irradiation bottle, sucking 60 parts of phosphoric acid and 110 parts of urea under the negative pressure condition, slowly heating, stirring, reacting for 2 hours, taking out, washing with mild deionized water for several times, and drying in vacuum for later use.
Placing the pre-irradiation modified bamboo charcoal in a closed vacuum glass bottle, treating with plasma with power set at 240W and carrier gas flow rate kept at 10SCCM (standard cubic centimeter per minute) for 10min, sucking 60 parts of phosphoric acid and 55 parts of urea under negative pressure, heating and stirring, raising temperature at 8 ℃/min, controlling prepolymerization temperature at 125 ℃ and polymerization time at 30min, then continuing raising temperature to 240 ℃ at 5 ℃/min, keeping polymerization time at 150 min, and finally keeping the temperature for 15 min. And pouring the reaction materials into a small tray, putting the tray into a baking oven with the temperature of 200 ℃, heating, curing for 2 hours, and discharging to obtain the intumescent flame retardant bamboo charcoal.
3) Adding the flame-retardant grafted bamboo charcoal obtained in the step 2), 20 parts of hydroxymethylated lignin, 10 parts of chitosan and 0.5 part of expanded graphite into a planetary mixer by mass, and stirring at a revolution speed of 60r/min and a temperature of 60 ℃ to obtain a mixed material system B.
4) 100 parts by weight of absolute ethanol and 40 parts by weight of deionized water were poured into a three-necked round bottom flask equipped with a magnetic stirrer and a condenser and stirred at 40 ℃ for 20 min. Then, 10 parts of the mixture B in the step 3), 2 parts of Alkyl Polyglycoside (APG) and 20 parts of ammonia water with the mass fraction of 25 wt.% are added into the flask and stirred for 20 min. And then, adding 15 parts of Tetraethoxysilane (TEOS) into the mixture dropwise, keeping the same temperature for 2 hours, cooling the mixture to room temperature, washing the mixture with deionized water after filtering, and drying the mixture at 80 ℃ to obtain the microencapsulated intumescent flame retardant carbon synergistic material system C.
The analysis and test of the element content and the physical and chemical properties of the examples 1 to 3 are carried out, as shown in the following table 1:
TABLE 1
Mass fraction (%) C H N O P Ash content Fixed carbon Volatile component
BC 75.5 3.1 0.8 11.0 0.1 9.3 75.5 15.2
BC-1 52.7 8.3 9.2 16.6 5.7 7.5 52.7 39.8
BC-2 51.5 8.4 10.3 16.1 6.6 7.1 51.5 41.4
BC-3 43.8 8.8 12.1 18.3 7.9 9.1 43.8 47.1
It can be seen that the N, P element content of the modified flame-retardant grafted bamboo charcoal prepared in example 1 is significantly increased, the amplification is over 1000%, and the volatile component is over 2 times that before the modification, which indicates that N, P synergistic flame retardant is successfully grafted on the surface of bamboo charcoal through functional groups, and inert gases and active free radicals can be released in a pyrolysis state, so that a good gas-phase flame-retardant effect is achieved. The N, P element content and the volatile component of the modified flame-retardant grafted bamboo charcoal prepared in example 2 are increased by 12.0% and 15.8% respectively compared with those of example 1, and the volatile component is increased by 4.0%, which shows that N, P synergistic flame-retardant graft has higher polymerization degree and better grafting effect. The N, P element content and the volatile component of the modified flame-retardant grafted bamboo charcoal prepared in example 3 are increased by 17.5% and 19.7% respectively, and the volatile component is further increased by 13.8%, which indicates that the grafting effect of N, P synergistic flame-retardant graft on the surface of bamboo charcoal is effectively improved, the degree of polymerization is higher, and a more uniform and continuous flame-retardant gas phase is provided in a pyrolysis state.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned examples, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that, for those skilled in the art, modifications and improvements can be made on the technical solutions described in the foregoing embodiments, or equivalent replacements can be made on some of the technical features, and these modifications and improvements should also be considered as the protection scope of the present invention.

Claims (7)

1. A preparation method of a bamboo charcoal based high flame retardant expansion type synergistic system is characterized by comprising the following steps: the structural schematic diagram of the modified flame-retardant grafted bamboo charcoal is as follows:
Figure FDA0003539768490000011
the preparation steps and conditions are as follows:
1) according to the mass portion, 20-30 portions of modified bamboo charcoal are put into an irradiation bottle, and are vacuumized, filled with nitrogen for a plurality of times and then put into an irradiation chamber for irradiation treatment for 5-10 min; then, vacuumizing an irradiation bottle, sucking 40-60 parts of phosphoric acid and 70-110 parts of urea under the negative pressure condition, slowly heating, stirring, reacting for 1-2 hours, taking out, washing with mild deionized water for several times, and drying in vacuum for later use;
2) placing the pre-irradiated modified bamboo charcoal in a closed vacuum glass bottle, after plasma treatment with the power set at 240W is performed for 5-10min, sucking 20-60 parts of phosphoric acid and 35-55 parts of urea under negative pressure, heating and stirring, controlling the heating speed to be 8-10 ℃/min, heating until the solution is clear and a little bubbles are generated, then continuously heating at the speed of 4-5 ℃/min until the solution is foamed and the viscosity is rapidly increased, stopping heating, and keeping the temperature for 5-15 min; pouring the reaction materials into a small tray, putting the tray into an oven with the temperature of 200-260 ℃, heating, curing for 1.5-3 h, and discharging to obtain the intumescent flame retardant bamboo charcoal;
3) Adding the flame-retardant grafted bamboo charcoal obtained in the step 2) and 15-30 parts of the carbon source synergistic auxiliary into a planetary mixer according to parts by weight, and stirring at a revolution speed of 50-60r/min and a temperature of 50-60 ℃ to obtain a mixed material system B;
4) pouring 100-150 parts of anhydrous ethanol and 40-60 parts of deionized water into a three-neck round-bottom flask with a magnetic stirrer and a condenser according to the parts by weight, and stirring for 10-20min at 40 ℃; then 10 parts of the mixed material B in the step 3) are taken,Adding 1-2 parts of Alkyl Polyglycoside (APG) and 15-20 parts of ammonia water into a flask, and stirring for 15-20 min; then, dropwise adding 10-15 parts of Tetraethoxysilane (TEOS) into the mixture, keeping the same temperature for 2 hours, cooling the mixture to room temperature, washing the mixture with deionized water after filtering, and drying the mixture at 80 ℃ to prepare a microencapsulated expanded flame-retardant carbon synergistic material system C; the preparation method of the modified bamboo charcoal in the step 1) comprises the following steps: selecting bamboo charcoal obtained at the carbonization temperature of 500-2O2Mixing the solution, slowly adding 200-240 parts of HNO3And adding the solution, mixing, reacting for 20-24h under the assistance of microwave, repeatedly cleaning with deionized water until the filtrate is neutral, and finally drying the cleaned bamboo charcoal to obtain the modified bamboo charcoal.
2. The preparation method of the bamboo charcoal based high flame retardant intumescent synergistic system according to claim 1, characterized in that: gamma rays are selected for the irradiation treatment in the step 1), the irradiation dose rate is set to be 6-8kGy/h, and the irradiation dose is 100-150 kGy.
3. The preparation method of the bamboo charcoal-based high flame retardant intumescent synergistic system according to claim 1, characterized in that: the plasma in the step 2) is low-temperature oxygen plasma, and the flow rate of the carrier gas is kept at 10SCCM (standard cubic centimeter per minute).
4. The preparation method of the bamboo charcoal-based high flame retardant intumescent synergistic system according to claim 1, characterized in that: the prepolymerization temperature in the step 2) is controlled to be 120 ℃ and 130 ℃, and the prepolymerization time is controlled to be 20-30 min; the polymerization temperature is controlled to be 230-240 ℃, and the polymerization time is controlled to be 140-150 min.
5. The preparation method of the bamboo charcoal-based high flame retardant intumescent synergistic system according to claim 1, characterized in that: the carbon source auxiliary agent in the step 3) comprises 10-20 parts of hydroxymethylated lignin, 5-10 parts of chitosan and 0.1-0.5 part of expanded graphite.
6. The preparation method of the bamboo charcoal-based high flame retardant intumescent synergistic system according to claim 1, characterized in that: the concentration of the ammonia water adopted in the step 4) is 20-30 wt.%.
7. The preparation method of the bamboo charcoal based high flame retardant intumescent synergistic system according to claim 1, characterized in that: in the step 4), the particle size of the bamboo charcoal is 100-200 meshes, and deionized water is used for assisting ultrasonic vibration cleaning treatment before modification.
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