CN114773615A - Phytic acid supramolecular flame retardant, preparation method and application - Google Patents
Phytic acid supramolecular flame retardant, preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C09K21/00—Fireproofing materials
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- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention provides a phytic acid supermolecule flame retardant, a preparation method and application, and belongs to the field of flame retardant materials. The preparation method of the phytic acid supermolecule flame retardant comprises the following steps: adding an organic amine compound and an aminobenzene sulfonic acid compound into a solvent, stirring and dissolving, and reacting to obtain a supramolecular solution; dissolving phytic acid in a solvent, adding the phytic acid into the obtained supramolecular solution, cooling the system to room temperature after reaction, removing the solvent, and drying to obtain the phytic acid supramolecular flame retardant. The invention has environmental friendliness, reduces the consumption of petrochemical resources and lightens the environmental burden. The nitrogen and phosphorus content of the flame retardant is high, so that the flame retardant performance of the flame retardant can be greatly improved, the flame retardant plays an important role in the thermal stability of a composite material, and the generation of smoke and toxic gas is reduced.
Description
Technical Field
The invention belongs to the field of flame retardant materials, and particularly relates to a phytic acid supramolecular flame retardant, a preparation method and application.
Background
With the increasing shortage of petrochemical resources, the global demand for bio-based materials of renewable resources is increasing. The wood is a natural material with better mechanical property, sustainable development and low cost. Essentially a hierarchical structured nanocellulose material consisting of cellulose hollow fibres embedded in hemicellulose and lignin. Wood is one of the most important materials in the construction and building industries and is the only truly sustainable resource. In recent years, it has been used in the fields of furniture, packaging, copper-clad plate substrates, and the like. However, wood is also highly flammable and subject to catastrophic damage. Therefore, the flame retardant modification of the wood with fire prevention requirements is of great significance.
The flame retardance of wood is realized mainly by two ways of enhancing insulation measures and adding a flame retardant. However, the coating insulation can fail over time and require re-coating, increasing the cost of fire resistance. The addition of the flame retardant is an effective way for improving the flame retardant property of the material. The flame retardants currently used include halogen-based, phosphorus nitrogen-based, inorganic flame retardants, and the like. Halogenated flame retardants have been gradually banned because they release toxic and harmful gases when burned; although the inorganic flame retardant has good flame retardant performance, the inorganic flame retardant has the defects of large addition amount, poor compatibility, easy precipitation and the like; the phosphorus-nitrogen flame retardant has a good flame retardant effect and is widely concerned in recent years. The Intumescent Flame Retardant (IFR) is a composite flame retardant mainly composed of nitrogen and phosphorus.
Intumescent flame retardants have three basic elements. Namely an acid source, a carbon source and a gas source. The acid source is also called dehydrating agent or charring accelerant, which is inorganic acid or compound that can generate acid in situ during burning, such as phosphoric acid, boric acid, sulfuric acid and phosphate; the carbon source is also called as a carbon forming agent, which is the basis for forming a foam carbonized layer and mainly comprises polyhydroxy compounds with high carbon content, such as starch, cane sugar, dextrin, pentaerythritol, glycol, phenolic resin and the like; the gas source, also called a blowing source, is a nitrogen-containing compound such as urea, melamine, polyamide, and the like.
Phytic acid, also known as creatine, is mainly found in seeds, roots, stems and stems of plants, and is a biobased acid source with the highest content of phosphorus, up to 28%, in seeds of leguminous plants, bran and embryo of cereals. The research of using phytic acid as the acid source of the flame retardant is gradually paid attention. Patent CN114015115A discloses an intumescent flame retardant prepared from piperazine pyrophosphate, melamine cyanurate, and ammonium polyphosphate, but the preparation process of ammonium polyphosphate is complex, and is easy to cause environmental pollution, and the compatibility of ammonium polyphosphate and polymer matrix is poor.
The supermolecule self-assembly is a simple, easy and efficient method for preparing the flame retardant. Organic amine compounds are attractive scaffolds with hydrogen bond donor and acceptor sites in supramolecular chemistry. Meanwhile, the organic amine compound is an important nitrogen-rich organic base, has a plurality of amino groups and can be stacked in a pi-pi mode. The aminobenzene sulfonic acid compound not only can provide nitrogen element, but also can generate supermolecule (AM) through pi-pi stacking with organic amine compound. The supermolecule can greatly improve the flame retardant property through the accumulation of nitrogen elements.
Therefore, AM and acidic sites in phytic acid are adopted to synthesize the supramolecular flame retardant (AMPA) through ion attraction interaction. The nitrogen and phosphorus content of the flame retardant AMPA generated by supermolecule self-assembly is very high, so that the flame retardant property of the flame retardant can be greatly improved, the flame retardant AMPA plays an important role in the thermal stability of the composite material, and the generation of smoke and toxic gas is reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a phytic acid supramolecular flame retardant and a preparation method thereof, and the phytic acid supramolecular flame retardant is used for preparing flame-retardant wood and flame-retardant polymer materials. The flame retardant has the advantages of green source, reproducibility, simple synthesis and the like; the flame retardant has high nitrogen and phosphorus content and remarkable flame retardant effect. The high nitrogen and the high phosphorus can not only greatly improve the flame retardant performance of the flame retardant, but also play an important role in the thermal stability of the composite material, and reduce the generation of smoke and toxic gas; the phytic acid is an environment-friendly raw material; the method for synthesizing the flame retardant is simple and easy to operate.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the phytic acid supramolecular flame retardant has the following structural general formula:
R+is a supermolecular self-assembly structure; wherein the number of the supermolecule self-assembly structures is n, and n is more than or equal to 1 and less than or equal to 12.
The supermolecule self-assembly structure takes an organic amine compound as a center and an aminobenzene sulfonic acid compound as an arm, and is formed by pi-pi superposition and ionic bond self-assembly.
The organic amine compound comprises one of aromatic organic amine or alicyclic organic amine compound, preferably any one of melamine, p-phenylenediamine or piperazine; the structural formula of the aminobenzene sulfonic acid compound is shown in the specification
Wherein R 'is alkyl or ester group, R' is H or alkyl, and the aminobenzenesulfonic acid compound is preferably sulfanilic acid.
A preparation method of a phytic acid supramolecular flame retardant comprises the following steps:
(1) adding an organic amine compound and an aminobenzene sulfonic acid compound into a solvent I, stirring and dissolving, and reacting at the temperature of 0-100 ℃ for 1-24 hours to obtain a supramolecular solution; wherein the molar ratio of the organic amine compound to the aminobenzene sulfonic acid compound is 0.3-0.5.
(2) Dissolving phytic acid in a solvent II, adding the phytic acid into the supermolecule solution obtained in the step (1), reacting for 1-24 hours at 0-100 ℃, cooling the system to room temperature, removing the solvent I and the solvent II, and drying to obtain the phytic acid supermolecule flame retardant; wherein the amount of phytic acid added is 2.4 to 6.0, preferably 3 to 5.4, in terms of the molar ratio of the nitrogen atoms on the amino groups of the supramolecules to the free hydroxyl groups of the phytic acid.
The solvent I is one of water, methanol, ethanol and glycol.
The solvent II is one of water, methanol, ethanol and acetone.
The reaction temperature in the step (1) is preferably 70-90 ℃, and the reaction time is preferably 2-6 h.
The reaction temperature in the step (2) is preferably 70-90 ℃, and the reaction time is preferably 4-8 h.
The phytic acid is derived from seeds, roots and stems of plants.
The application of the phytic acid supramolecular flame retardant in preparing the flame-retardant wood comprises the following steps:
(1) preparing a light wood sample with fixed size, placing the light wood sample in a buffer solution, keeping the mixture at a constant temperature of 70 ℃ to remove lignin, and replacing the buffer solution once in fixed time. After the balsawood sample is completely rinsed, washing the balsawood sample by deionized water to remove residues;
(2) putting the delignified balsawood sample into a phytic acid supermolecule flame retardant solution, stirring at a constant temperature of 70 ℃, changing the color of the sample from white to reddish brown, stopping stirring, slowly cooling to room temperature, and then freeze-drying the sample.
The light wood sample is made of Barsha wood, catalpa bungei, red wood or red pine wood.
The buffer solution is acetic acid-sodium acetate solution or peroxyacetic acid solution with pH value of 4-6.
One skilled in the art can add other optional additives to obtain better use performance, wherein the additives can be selected from anti-aging agents, preservatives, bactericides, antistatic agent crosslinking agents, pigments, fillers, perfumes and the like, and can be added simultaneously or independently.
The application of the phytic acid supermolecule flame retardant in the flame retardant polymer; the preparation process of the flame-retardant polymer comprises the following steps: and premixing the matrix polymer and the phytic acid supermolecule flame retardant, adding the premixed materials into an internal mixer, and melting and blending the premixed materials uniformly at the temperature of 180-300 ℃ to obtain the composite material.
The matrix polymer is polyamide, polyethylene, polypropylene, starch, polylactic acid, polyethylene terephthalate or polybutylene terephthalate.
The invention has the beneficial effects that:
1. the flame retardant provided by the invention is synthesized from phytic acid of a biological source, is environment-friendly, and not only reduces the consumption of petrochemical resources, but also reduces the environmental burden.
2. The flame retardant provided by the invention is synthesized by a supermolecular structure and phytic acid through ion attraction interaction, so that the nitrogen and phosphorus content of the flame retardant is high, the flame retardant can greatly improve the flame retardant performance of the flame retardant, plays an important role in the thermal stability of a composite material, and reduces the generation of smoke and toxic gas.
Detailed Description
The present invention will be further illustrated by the following detailed description, which is to be construed as merely illustrative and not limitative of the remainder of the disclosure, and it is within the scope of the present invention to be interpreted by those skilled in the art from the foregoing disclosure without being limited thereto.
Preparing the phytic acid supermolecule flame retardant:
example 1:
(1) dissolving 0.02mol of melamine and 0.06mol of sulfanilic acid in 200mL of deionized water at 70 ℃, and reacting for 2h to obtain a light red solution;
(2) weighing 0.002mol of phytic acid, dissolving in 20mL of deionized water, and mixing the light red solution obtained in the step (1), wherein the molar ratio of the phytic acid to nitrogen atoms on amino groups in supermolecules to free hydroxyl groups in the phytic acid is 3; reacting for 4 hours at the temperature of 90 ℃, cooling the system to the room temperature of 25 ℃, separating out crystals from the solution, filtering, and drying for 24 hours at the temperature of 80 ℃ to obtain the phytic acid supramolecular flame retardant which is marked as MAPA 1.
Example 2:
(1) dissolving 0.03mol of p-phenylenediamine and 0.06mol of p-aminobenzene sulfonic acid in 200mL of methanol at the temperature of 80 ℃, and reacting for 4 hours to obtain a light red solution;
(2) weighing 0.00125mol of phytic acid, dissolving in 20mL of methanol, mixing the light red solution obtained in the step (1), wherein the molar ratio of nitrogen atoms on amino groups in the phytic acid and supermolecules to free hydroxyl groups in the phytic acid is 4; reacting for 6 hours at 90 ℃, cooling the system to room temperature of 25 ℃, separating out crystals from the solution, filtering, and drying for 24 hours at 80 ℃ to obtain the phytic acid supramolecular flame retardant, which is marked as MAPA 2.
Example 3:
(1) dissolving 0.03mol of piperazine and 0.06mol of sulfanilic acid in 200mL of glycol at 90 ℃, and reacting for 6h to obtain a light red solution;
(2) weighing 0.00125mol of phytic acid, dissolving in 20mL of acetone, mixing the light red solution obtained in the step (1), wherein the molar ratio of nitrogen atoms on amino groups in the phytic acid and supermolecules to free hydroxyl groups in the phytic acid is 4; reacting for 8 hours at 70 ℃, cooling the system to 25 ℃ at room temperature, separating out crystals from the solution, performing suction filtration, and drying for 24 hours at 80 ℃ to obtain the phytic acid supramolecular flame retardant which is marked as MAPA 3.
Preparing flame-retardant wood:
example 4:
preparation of balsa wood of size 100mm 8mm, placing balsa wood in acetic acid-sodium acetate buffer solution of pH 4, keeping the mixture at constant temperature 70 ℃ to remove lignin, the buffer solution was replaced every 24 h. When the balsa sample was completely rinsed, it was washed at least 3 times with deionized water to remove residues, and then the delignified balsa sample was lyophilized for 24 h.
5 parts of the phytic acid supramolecular flame retardant MAPA1 in example 1 were dissolved in ethanol, the prepared wood sample was placed in the solution, stirred and soaked at a constant temperature of 70 ℃ for 24 hours, and then lyophilized for 48 hours, and the oxygen index of the material was measured, and the results are shown in Table 1.
Example 5
The same procedure as in example 4 was repeated except for taking 10 parts of the phytic acid supramolecular flame retardant MAPA1 from example 1.
Example 6
20 parts of the phytic acid supramolecular flame retardant MAPA1 in example 1 were taken, and the other preparation steps were the same as in example 4.
Example 7
The same procedure as in example 4 was repeated except for taking 30 parts of the phytic acid supramolecular flame retardant MAPA1 from example 1.
Comparative example 1
Preparation of balsa wood of size 100mm 8mm, placing balsa wood in buffered peroxyacetic acid at pH 5, keeping the mixture at constant temperature 70 ℃ to remove lignin, and changing the buffer every 24 h. After the balsa sample was completely rinsed, it was washed with deionized water at least 3 times to remove residues, and then the delignified balsa sample was lyophilized for 24 hours, and the oxygen index of the material was measured, and the results are shown in table 1.
TABLE 1
| Size of wood | MAPA1 | Water (W) | Oxygen index | |
| Comparative example 1 | 100mm*10mm*8mm | 0 | 200 | 23 |
| Example 4 | 100mm*10mm*8mm | 5 | 200 | 27 |
| Example 5 | 100mm*10mm*8mm | 10 | 200 | 28 |
| Example 6 | 100mm*10mm*8mm | 20 | 200 | 31 |
| Example 7 | 100mm*10mm*8mm | 30 | 200 | 33 |
In the present application example, the oxygen index of the sample of 100mm × 10mm × 8mm was 28% at 10 parts and 33% at 30 parts or more of AMPA 1. Indicating that the fire retardant can obviously inhibit the burning of wood. The aminobenzene sulfonic acid compound not only provides nitrogen elements, but also forms supermolecules with the organic amine compound through pi-pi stacking, the supermolecules are combined with acid sites of the phytic acid through ion attraction interaction, the content of nitrogen and phosphorus is greatly increased, when the sample strips are combusted, the flame retardant can release more non-combustible gas, and meanwhile, the effect of inhibiting heat transfer is achieved.
Preparation of flame retardant polymer:
example 8:
100 parts of polyamide (Akema Co., Ltd.) and 5 parts of phytic acid supramolecular flame retardant MAPA2 are premixed and added into an internal mixer, the mixture is melted and blended uniformly at the temperature of 225 ℃, the mixture is extruded and formed by a double-screw extruder to prepare a polymer sheet with the thickness of 1mm, and the oxygen index of the material is detected, and the result is shown in Table 2.
Example 9
The same procedure as in example 8 was repeated except for taking 10 parts of the phytic acid supramolecular flame retardant MAPA2 from example 2.
Example 10
The same procedure as in example 8 was repeated except for taking 20 parts of the phytic acid supramolecular flame retardant MAPA2 from example 2.
Example 11
The other preparation steps of 30 parts of the phytic acid supramolecular flame retardant MAPA2 in example 2 were the same as those in example 8.
Example 12
The same procedure as in example 11 was repeated except for taking 30 parts of the phytic acid supramolecular flame retardant MAPA3 from example 3.
Comparative example 2
Polyamide (Achima Co., Ltd.) was extruded at 225 ℃ through a twin-screw extruder to prepare a polymer sheet having a thickness of 1mm, and the oxygen index of the material was measured, and the results are shown in Table 2.
TABLE 2
| Polyamide, process for producing the same and use thereof | MAPA2 | MAPA3 | Oxygen index | |
| Comparative example 2 | 100 | 0 | 0 | 22 |
| Example 8 | 100 | 5 | 0 | 25 |
| Example 9 | 100 | 10 | 0 | 26 |
| Example 10 | 100 | 20 | 0 | 28 |
| Example 11 | 100 | 30 | 0 | 32 |
| Example 12 | 100 | 0 | 30 | 30 |
In the application example of the group, 20 parts of the sheet with the thickness of 1mm can reach 28 percent, and more than 30 parts of MAPA2 can reach 32 percent. The flame retardant property of the polyamide is obviously improved along with the increase of the addition amount of the flame retardant. By comparing the example 11 with the example 12, it can be found that the oxygen index of the example 11 is higher, and it can be preliminarily judged that the flame retardant effect of the flame retardant MAPA2 is better than that of MAPA3, mainly because the aromatic amine compound is easier to stack pi-pi than the alicyclic amine compound, the accumulation of nitrogen elements is realized, and the flame retardant performance is improved.
Example 13:
100 parts of starch, 10 parts of phytic acid supramolecular flame retardant MAPA1, 30 parts of glycerol and 15 parts of water are mixed, and then subjected to haake blending and compression molding to prepare a polymer sheet with the thickness of 1mm, and the oxygen index of the material is detected, and the result is shown in Table 3.
Comparative example 3
100 parts of starch, 30 parts of glycerol and 15 parts of water are mixed, and then the mixture is subjected to haake blending and compression molding to prepare a polymer sheet with the thickness of 1mm, and the oxygen index of the material is detected, and the result is shown in table 3.
Comparative example 4
A preparation method of a green environment-friendly choline phytate flame retardant comprises the following steps:
(1) respectively dissolving 0.7mol of sodium hydroxide and 0.7mol of choline chloride in 300g of ethanol and 200g of ethanol, mixing the two solutions, reacting at normal temperature for 1 hour, and performing suction filtration to obtain a filtrate of the choline hydroxide;
(2) weighing 0.117mol of phytic acid, dissolving in 100g of ethanol, mixing the filtrate of choline hydroxide obtained in the step (1), reacting for 1h at normal temperature, removing supernatant, washing with ethanol for multiple times until the pH is 7 and does not change, and drying for 10 hours at the temperature of 80 ℃ and under the pressure of-0.08 MPa to obtain the phytic choline flame retardant, which is recorded as CPA 1.
100 parts of starch, 10 parts of a choline phytate flame retardant CPA1, 30 parts of glycerol and 15 parts of water are mixed, then the mixture is subjected to haake blending and compression molding to prepare a polymer sheet with the thickness of 1mm, and the oxygen index of the material is detected, and the result is shown in Table 3.
TABLE 3
| Starch | MAPA1 | CPA1 | Glycerol | Water (W) | Oxygen index | |
| Comparative example 3 | 100 | 0 | 0 | 30 | 15 | 23 |
| Comparative example 4 | 100 | 0 | 10 | 30 | 15 | 33 |
| Example 13 | 100 | 10 | 0 | 30 | 15 | 37 |
As can be seen from the oxygen index data in Table 3, compared with choline phytate flame retardants with the same parts and common structures, the formed starch complex has a higher combustion oxygen index, which indicates that the phytic acid supramolecular compound is easier to stack pi-pi, the accumulation of nitrogen elements is realized, and the flame retardant performance is improved.
Those of ordinary skill in the art will understand that: the above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The phytic acid supramolecular flame retardant is characterized by having the following structural general formula:
R+is a supermolecular self-assembly structure; wherein n is the number of the supermolecule self-assembly structures, and n is more than or equal to 1 and less than or equal to 12;
the supermolecular self-assembly structure takes an organic amine compound as a center and an aminobenzene sulfonic acid compound as an arm, and is formed by pi-pi superposition and ionic bond self-assembly.
2. A phytic supramolecular flame retardant as claimed in claim 1, which is characterized in thatCharacterized in that the organic amine compound comprises one of aromatic organic amine or alicyclic organic amine compound; the structural formula of the aminobenzene sulfonic acid compound is shown as
Wherein R 'is alkyl or ester group, R' is H or alkyl.
3. The phytic supramolecular flame retardant of claim 1, wherein the organic amine compound is one of melamine, p-phenylenediamine, or piperazine; the aminobenzene sulfonic acid compound is sulfanilic acid.
4. A method for preparing a phytic acid supramolecular flame retardant as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
(1) adding an organic amine compound and an aminobenzene sulfonic acid compound into a solvent I, stirring and dissolving, and reacting at 0-100 ℃ for 1-24h to obtain a supramolecular solution; wherein the molar ratio of the organic amine compound to the aminobenzene sulfonic acid compound is 0.3-0.5;
(2) dissolving phytic acid in a solvent II, adding the phytic acid into the supermolecule solution obtained in the step (1), reacting for 1-24 hours at 0-100 ℃, cooling the system to room temperature, removing the solvent I and the solvent II, and drying to obtain the phytic acid supermolecule flame retardant; wherein the addition amount of phytic acid is 2.4-6.0 calculated by the molar ratio of nitrogen atoms on amino groups in the supramolecules to free hydroxyl groups in the phytic acid.
5. The method for preparing phytic acid supramolecular flame retardant according to claim 4, wherein the phytic acid is added in an amount of 3 to 5.4 in terms of a molar ratio of nitrogen atoms on amino groups in the supramolecules to free hydroxyl groups in phytic acid.
6. The method for preparing a phytic acid supramolecular flame retardant as claimed in claim 4, wherein the solvent I is water, methanol, ethanol or ethylene glycol; the solvent II is water, methanol, ethanol or acetone.
7. The method for preparing a phytic acid supramolecular flame retardant as claimed in claim 4, wherein the reaction temperature in the step (1) is 70-90 ℃, and the reaction time is 2-6 h; the reaction temperature in the step (2) is 70-90 ℃, and the reaction time is 4-8 h.
8. The method for preparing a phytic acid supramolecular flame retardant according to any one of claims 4 to 7, wherein the phytic acid is derived from seeds, roots and stems of plants.
9. Use of a phytic acid supramolecular flame retardant according to any one of claims 1 to 3 and a phytic acid supramolecular flame retardant prepared by the method according to any one of claims 4 to 8, comprising:
(1) application in flame-retardant wood; the preparation process of the flame-retardant wood comprises the following steps:
a. preparing a light wood sample with a fixed size, placing the light wood sample in a buffer solution, keeping the mixture at a constant temperature of 70 ℃ to remove lignin, and replacing the buffer solution once every fixed time; after the balsawood sample is completely rinsed, washing the balsawood sample by deionized water to remove residues;
b. placing the delignified balsawood sample in a phytic acid supermolecule flame retardant solution, stirring at a constant temperature of 70 ℃, changing the color of the sample from white to reddish brown, stopping stirring, slowly cooling to room temperature, and then freeze-drying the sample;
(2) use in flame retardant polymers; the preparation process of the flame-retardant polymer comprises the following steps: and premixing the matrix polymer and the phytic acid supermolecule flame retardant, adding the premixed materials into an internal mixer, and melting and blending the premixed materials uniformly at the temperature of 180-300 ℃ to obtain the composite material.
10. The use according to claim 9, wherein the light wood sample material is balsa wood, catalpa wood, rosewood or pinus koraiensis; the buffer solution is acetic acid-sodium acetate solution or peroxyacetic acid solution with pH value of 4-6; the matrix polymer is polyamide, polyethylene, polypropylene, starch, polylactic acid, polyethylene terephthalate or polybutylene terephthalate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115637078A (en) * | 2022-11-01 | 2023-01-24 | 安徽农业大学 | Preparation method of intumescent carbon layer thickness-controllable flame retardant and flame-retardant wood |
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| CN115637078A (en) * | 2022-11-01 | 2023-01-24 | 安徽农业大学 | Preparation method of intumescent carbon layer thickness-controllable flame retardant and flame-retardant wood |
| CN115637078B (en) * | 2022-11-01 | 2023-12-26 | 安徽农业大学 | Preparation method of flame retardant with controllable thickness of expanded carbon layer and flame retardant wood |
| CN115850808A (en) * | 2022-11-29 | 2023-03-28 | 华南理工大学 | Phosphorus-containing inorganic organic acid-lignin synergistic flame-retardant enhanced aerogel and preparation and application thereof |
| CN115850808B (en) * | 2022-11-29 | 2024-02-06 | 华南理工大学 | Phosphorus-containing inorganic and organic acid-lignin synergistic flame-retardant reinforced aerogel and preparation and application thereof |
| CN116554555A (en) * | 2023-07-06 | 2023-08-08 | 广州市寅源新材料股份有限公司 | Expandable graphite/phytic acid composite flame retardant, and preparation method and application thereof |
| CN116554555B (en) * | 2023-07-06 | 2023-08-29 | 广州市寅源新材料股份有限公司 | Expandable graphite/phytic acid composite flame retardant, and preparation method and application thereof |
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