CN116554555B - Expandable graphite/phytic acid composite flame retardant, and preparation method and application thereof - Google Patents
Expandable graphite/phytic acid composite flame retardant, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 93
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 title claims abstract description 84
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229940068041 phytic acid Drugs 0.000 title claims abstract description 84
- 235000002949 phytic acid Nutrition 0.000 title claims abstract description 84
- 239000000467 phytic acid Substances 0.000 title claims abstract description 84
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 78
- 239000010439 graphite Substances 0.000 title claims abstract description 78
- 239000003063 flame retardant Substances 0.000 title claims abstract description 58
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 229950000244 sulfanilic acid Drugs 0.000 claims abstract description 19
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 15
- 239000000779 smoke Substances 0.000 claims abstract description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims abstract description 7
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000010517 secondary reaction Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001629 suppression Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 40
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- 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
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- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an expandable graphite/phytic acid composite flame retardant, wherein the surface of the expandable graphite is loaded with a phytic acid layer, and the surface of the phytic acid layer is grafted with a sulfanilic acid layer, wherein phytic acid in the phytic acid layer is chelated with nickel ions. The invention also discloses a preparation method of the expandable graphite/phytic acid composite flame retardant, which comprises the following steps: uniformly mixing the solution A with a phytic acid aqueous solution, performing primary reaction, and performing solid-liquid separation to obtain an intermediate; uniformly mixing the intermediate with an aqueous solution of sulfanilic acid, carrying out secondary reaction, and carrying out solid-liquid separation to obtain the expandable graphite/phytic acid composite flame retardant; wherein the solution A is a solution containing expandable graphite, nickel ions and a silane coupling agent. The invention also discloses a low-smoke flame-retardant polymer, which comprises the following raw materials: polymer, diethyl aluminum hypophosphite and the expandable graphite/phytic acid composite flame retardant. The invention has good flame retardance and good smoke suppression performance.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to an expandable graphite/phytic acid composite flame retardant, and a preparation method and application thereof.
Background
The graphite crystal has a hexagonal network planar layered structure composed of carbon elements. The carbon atoms on the layer plane are bonded by strong covalent bonds, while the layers are bonded by van der Waals forces between the layers, the bond is very weak, and the interlayer distance is large. Thus, under appropriate conditions, various chemicals such as acids, alkali metals, salts, etc. can intercalate between graphite layers and combine with carbon atoms to form new chemical phases, graphite intercalation compounds. When heated to a proper temperature, the interlayer compound can be instantaneously and rapidly decomposed to generate a large amount of gas, so that the graphite is expanded into a worm-like new substance along the axial direction, namely, expanded graphite. The unexpanded graphite intercalation compound is an expandable graphite.
The expandable graphite delays or inhibits the combustion of the polymer mainly by virtue of an expansion heat insulation layer formed by self volume expansion. However, the vermiform graphites formed after the expandable graphite is expanded have weaker adhesion force with each other, after the polymer matrix is combusted, the expandable graphite can not form a firm expanded carbon layer, and under the action of flame pressure or heat convection, the surface expanded graphite layer can be damaged, so that the heat insulation expanded layer is lost, and the flame retardant efficiency is limited; and the damaged expanded graphite layer may generate fly ash, resulting in a large amount of smoke.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides an expandable graphite/phytic acid composite flame retardant, and a preparation method and application thereof; the invention has good flame retardance and good smoke suppression performance.
The invention provides an expandable graphite/phytic acid composite flame retardant, wherein the surface of the expandable graphite is loaded with a phytic acid layer, and the surface of the phytic acid layer is grafted with a sulfanilic acid layer, wherein phytic acid in the phytic acid layer is chelated with nickel ions.
The invention also provides a preparation method of the expandable graphite/phytic acid composite flame retardant, which comprises the following steps: uniformly mixing the solution A with a phytic acid aqueous solution, performing primary reaction, and performing solid-liquid separation to obtain an intermediate; uniformly mixing the intermediate with an aqueous solution of sulfanilic acid, carrying out secondary reaction, and carrying out solid-liquid separation to obtain the expandable graphite/phytic acid composite flame retardant; wherein the solution A is a solution containing expandable graphite, nickel ions and a silane coupling agent.
The invention uniformly disperses the expandable graphite, nickel ions and silane coupling agent in water, then reacts with the phytic acid, so that the surface of the expandable graphite is loaded with a phytic acid layer, the nickel ions can be chelated with the phytic acid and uniformly distributed in the phytic acid layer, and then the residual active hydroxyl in the phytic acid can be subjected to grafting reaction with the sulfanilic acid, so that the sulfanilic acid layer is formed on the surface of the phytic acid.
Preferably, the silane coupling agent is an amino group-containing silane coupling agent.
The amino group-containing silane coupling agent may be 3-aminopropyl triethoxysilane or the like. The nickel ions mentioned above may be added in the form of a water-soluble nickel salt, such as nickel nitrate or the like.
Preferably, the weight ratio of the expandable graphite to the silane coupling agent is 1:0.1-0.2; the ratio of the expandable graphite to the phytic acid is 1g to 0.05-0.1mol.
Preferably, the molar ratio of nickel ions to phytic acid is 1:120-150.
Preferably, the temperature of the primary reaction is 65-75 ℃ and the time is 3.5-4.5h; the temperature of the secondary reaction is 65-75 ℃ and the time is 1-2h.
Preferably, the concentration of expandable graphite in solution A is 0.005-0.01g/ml.
Preferably, the mass fraction of the aqueous solution of sulfanilic acid is 1-3% by weight.
The dosage of the sulfanilic acid aqueous solution is not specified, and the intermediate can be completely soaked.
Preferably, the solvent of the solution A is ethanol water solution; the volume fraction of ethanol in the ethanol aqueous solution is 70-80%.
The expandable graphite/phytic acid composite flame retardant can be used alone or in combination with other flame retardants.
The invention also provides a low-smoke flame-retardant polymer, which comprises the following raw materials: a polymer, aluminum diethylphosphinate, and the expandable graphite/phytic acid composite flame retardant; the weight ratio of the diethyl aluminum hypophosphite to the expandable graphite/phytic acid composite flame retardant is 1:1.4-1.6.
Preferably, the polymer is at least one of polypropylene, polyethylene, nylon.
The total content of aluminum diethylphosphinate and expandable graphite/phytic acid composite flame retardant in the polymer may be 10-30wt%. The diethyl aluminum hypophosphite and the expandable graphite/phytic acid composite flame retardant are compounded, so that the carbon forming rate can be improved, and the flame retardant property of the polymer can be improved.
The polymer may further contain: filler, antioxidant, lubricant, etc.
The beneficial effects are that:
1. in the expandable graphite/phytic acid composite flame retardant, nickel ions can promote phytic acid and polymers (such as polypropylene, polyamide and the like) to quickly form a graphitized carbon layer during combustion, so that the compactness of the carbon layer is improved; the benzene ring in the sulfanilic acid can provide an inner core, so that the formation of a graphitized carbon layer is further promoted, and the compactness of the graphitized carbon layer is improved; thereby effectively isolating oxygen and inhibiting the generation of smoke;
2. the expandable graphite can expand to construct an expanded carbon layer when being combusted, and the formed compact graphitized carbon layer is combined, so that cracks and fly ash of the carbon layer can be greatly reduced, the impact of decomposed gas is resisted, oxygen is isolated, the blocking effect of the carbon layer on heat transfer and mass transfer and the adsorption effect on smoke are enhanced, and therefore good smoke suppression and flame retardance performances are achieved, and the expanded carbon layer and the compact graphitized carbon layer are mutually matched, so that the thermal degradation rate of carbon residue can be reduced;
3. the expandable graphite is loaded by the phytic acid layer and the sulfanilic acid layer, so that the dispersibility of the expandable graphite and the polymer is greatly improved, and the mechanical property of the polymer can be improved; and the diethyl aluminum hypophosphite and the expandable graphite/phytic acid composite flame retardant are compounded, so that the carbon forming rate can be improved, and the flame retardant property can be improved.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
The expandable graphite/phytic acid composite flame retardant has the advantages that the surface of the expandable graphite is loaded with a phytic acid layer, and the surface of the phytic acid layer is grafted with a sulfanilic acid layer, wherein phytic acid and nickel ions in the phytic acid layer are chelated.
The preparation method of the expandable graphite/phytic acid composite flame retardant comprises the following steps:
taking 4L of ethanol water solution with the volume fraction of 70%, sequentially adding 0.013mol of nickel nitrate, 4g of 3-aminopropyl triethoxysilane and 20g of expandable graphite, stirring and dispersing uniformly, then adding 2L of 1mol/L of phytic acid water solution, heating to 65 ℃, preserving heat and stirring for reacting for 4.5 hours, filtering, washing a filter cake, and vacuum drying to obtain an intermediate;
adding the intermediate into 2L of sulfanilic acid water solution with the mass fraction of 1wt%, stirring for 30min, uniformly mixing, adjusting the temperature to 65 ℃, preserving heat, stirring for 2h, filtering, washing a filter cake by water, and drying in vacuum to obtain the expandable graphite/phytic acid composite flame retardant.
Example 2
The expandable graphite/phytic acid composite flame retardant has the advantages that the surface of the expandable graphite is loaded with a phytic acid layer, and the surface of the phytic acid layer is grafted with a sulfanilic acid layer, wherein phytic acid and nickel ions in the phytic acid layer are chelated.
The preparation method of the expandable graphite/phytic acid composite flame retardant comprises the following steps:
taking 2L of ethanol water solution with the volume fraction of 80%, sequentially adding 0.008mol of nickel nitrate, 2g of 3-aminopropyl triethoxysilane and 20g of expandable graphite, stirring and dispersing uniformly, then adding 1L of phytic acid water solution with the volume fraction of 1mol/L, heating to 75 ℃, preserving heat and stirring for reaction for 3.5h, filtering, washing a filter cake, and vacuum drying to obtain an intermediate;
adding the intermediate into 2L of sulfanilic acid water solution with the mass fraction of 3wt%, stirring for 30min, uniformly mixing, adjusting the temperature to 75 ℃, preserving heat, stirring for reaction for 1h, filtering, washing a filter cake with water, and vacuum drying to obtain the expandable graphite/phytic acid composite flame retardant.
Example 3
The expandable graphite/phytic acid composite flame retardant has the advantages that the surface of the expandable graphite is loaded with a phytic acid layer, and the surface of the phytic acid layer is grafted with a sulfanilic acid layer, wherein phytic acid and nickel ions in the phytic acid layer are chelated.
The preparation method of the expandable graphite/phytic acid composite flame retardant comprises the following steps:
taking 3L of ethanol water solution with the volume fraction of 75%, sequentially adding 0.01mol of nickel nitrate, 3g of 3-aminopropyl triethoxysilane and 20g of expandable graphite, stirring and dispersing uniformly, then adding 1.5L of 1mol/L of phytic acid water solution, heating to 70 ℃, preserving heat and stirring for reaction for 4 hours, filtering, washing a filter cake, and vacuum drying to obtain an intermediate;
adding the intermediate into 2L of 2wt% sulfanilic acid water solution, stirring for 30min, mixing, adjusting the temperature to 70 ℃, preserving heat, stirring for reaction for 1.5h, filtering, washing the filter cake with water, and vacuum drying to obtain the expandable graphite/phytic acid composite flame retardant.
Comparative example 1
Expandable graphite.
Comparative example 2
Nickel nitrate was not added, and the procedure of example 3 was followed.
Comparative example 3
Intermediate in example 3.
The flame retardants of examples 1 to 3 and comparative examples 1 to 3 were taken, and polymers were prepared according to the formulation of Table 1, respectively, and the mechanical properties, flame retardant properties and smoke suppression properties of the polymers were examined. The results are shown in Table 2.
Table 1 polymer formulation
Comparative example 4
The flame retardant in the polymer was 20g of the flame retardant of example 3, and the other results are shown in Table 1.
Comparative example 5
The flame retardant in the polymer was 20g of diethyl aluminum hypophosphite, and the other materials are shown in Table 1.
TABLE 2 detection results
Remarks: UL94 and limiting oxygen index were measured according to GB-T10707-2008, the test piece thickness was 1.6mm; smoke density was measured according to EN 45545-2; the tensile strength was measured according to GB/T1039-1992.
As can be seen from table 2: when the expandable graphite/phytic acid composite flame retardant is simply used, the flame retardant has better flame retardant property and smoke suppression property, and the mechanical property of the polymer can be improved; when the flame retardant is matched with the diethyl aluminum hypophosphite, the limiting oxygen index can be further improved while the mechanical property and the smoke suppression property are maintained, and the flame retardance is improved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (11)
1. The preparation method of the expandable graphite/phytic acid composite flame retardant is characterized by comprising the following steps of: uniformly mixing the solution A with a phytic acid aqueous solution, performing primary reaction, and performing solid-liquid separation to obtain an intermediate; uniformly mixing the intermediate with an aqueous solution of sulfanilic acid, carrying out secondary reaction, and carrying out solid-liquid separation to obtain the expandable graphite/phytic acid composite flame retardant; wherein the solution A is a solution containing expandable graphite, nickel ions and a silane coupling agent.
2. The method for preparing an expandable graphite/phytic acid composite flame retardant according to claim 1, wherein the silane coupling agent is an amino group-containing silane coupling agent.
3. The preparation method of the expandable graphite/phytic acid composite flame retardant according to claim 1, wherein the weight ratio of the expandable graphite to the silane coupling agent is 1:0.1-0.2; the ratio of the expandable graphite to the phytic acid is 1g to 0.05-0.1mol.
4. The method for preparing the expandable graphite/phytic acid composite flame retardant according to claim 1, wherein the molar ratio of nickel ions to phytic acid is 1:120-150.
5. The method for preparing the expandable graphite/phytic acid composite flame retardant according to claim 1, wherein the temperature of one reaction is 65-75 ℃ and the time is 3.5-4.5h; the temperature of the secondary reaction is 65-75 ℃ and the time is 1-2h.
6. The method for preparing the expandable graphite/phytic acid composite flame retardant according to claim 1, wherein the concentration of the expandable graphite in the solution A is 0.005-0.01g/ml.
7. The preparation method of the expandable graphite/phytic acid composite flame retardant according to claim 1, wherein the mass fraction of the sulfanilic acid aqueous solution is 1-3wt%.
8. The method for preparing the expandable graphite/phytic acid composite flame retardant according to claim 1, wherein the solvent of the solution A is an ethanol water solution; the volume fraction of ethanol in the ethanol aqueous solution is 70-80%.
9. An expandable graphite/phytic acid composite flame retardant, characterized in that it is produced according to the production method of an expandable graphite/phytic acid composite flame retardant according to any one of claims 1 to 8.
10. The expandable graphite/phytic acid composite flame retardant according to claim 9, wherein the surface of the expandable graphite is loaded with a phytic acid layer, and the surface of the phytic acid layer is grafted with a sulfanilic acid layer, wherein phytic acid in the phytic acid layer is chelated with nickel ions.
11. A low smoke flame retardant polymer, characterized in that the raw materials thereof comprise: a polymer, aluminum diethylphosphinate, and the expandable graphite/phytic acid composite flame retardant of claim 9 or 10; the weight ratio of the diethyl aluminum hypophosphite to the expandable graphite/phytic acid composite flame retardant is 1:1.4-1.6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310819970.3A CN116554555B (en) | 2023-07-06 | 2023-07-06 | Expandable graphite/phytic acid composite flame retardant, and preparation method and application thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930002234A (en) * | 1991-07-11 | 1993-02-22 | 오정무 | Method of producing expanded graphite |
| CN105603734A (en) * | 2016-03-28 | 2016-05-25 | 西南大学 | Method for preparing functional cotton fabric by divalent nickel ion complex phytic acid |
| CN106519239A (en) * | 2016-10-11 | 2017-03-22 | 西南科技大学 | Preparation method and application of phosphorus-nitrogen-carbon-containing aggregate and intumescent flame retardant |
| CN111363312A (en) * | 2020-04-26 | 2020-07-03 | 张杨全 | Phytic acid ammonium salt-graphene modified epoxy resin flame-retardant material and preparation method thereof |
| CN113429628A (en) * | 2021-07-20 | 2021-09-24 | 北京理工大学 | Expandable phytate flame retardant, flame-retardant epoxy resin, and preparation method and application thereof |
| CN114573876A (en) * | 2022-03-01 | 2022-06-03 | 天津职业技术师范大学(中国职业培训指导教师进修中心) | Phytic acid modified graphene oxide, preparation method thereof and anticorrosive water-based epoxy coating |
| CN114773615A (en) * | 2022-04-28 | 2022-07-22 | 江南大学 | Phytic acid supramolecular flame retardant, preparation method and application |
| CN115558164A (en) * | 2022-09-20 | 2023-01-03 | 江西龙泰新材料股份有限公司 | Nano flame retardant with core-shell structure and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8691129B2 (en) * | 2007-05-08 | 2014-04-08 | Nanotek Instruments, Inc. | Method of producing exfoliated graphite composite compositions for fuel cell flow field plates |
-
2023
- 2023-07-06 CN CN202310819970.3A patent/CN116554555B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930002234A (en) * | 1991-07-11 | 1993-02-22 | 오정무 | Method of producing expanded graphite |
| CN105603734A (en) * | 2016-03-28 | 2016-05-25 | 西南大学 | Method for preparing functional cotton fabric by divalent nickel ion complex phytic acid |
| CN106519239A (en) * | 2016-10-11 | 2017-03-22 | 西南科技大学 | Preparation method and application of phosphorus-nitrogen-carbon-containing aggregate and intumescent flame retardant |
| CN111363312A (en) * | 2020-04-26 | 2020-07-03 | 张杨全 | Phytic acid ammonium salt-graphene modified epoxy resin flame-retardant material and preparation method thereof |
| CN113429628A (en) * | 2021-07-20 | 2021-09-24 | 北京理工大学 | Expandable phytate flame retardant, flame-retardant epoxy resin, and preparation method and application thereof |
| CN114573876A (en) * | 2022-03-01 | 2022-06-03 | 天津职业技术师范大学(中国职业培训指导教师进修中心) | Phytic acid modified graphene oxide, preparation method thereof and anticorrosive water-based epoxy coating |
| CN114773615A (en) * | 2022-04-28 | 2022-07-22 | 江南大学 | Phytic acid supramolecular flame retardant, preparation method and application |
| CN115558164A (en) * | 2022-09-20 | 2023-01-03 | 江西龙泰新材料股份有限公司 | Nano flame retardant with core-shell structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "可膨胀石墨的修饰构筑对 ABS 阻燃抑烟性能的影响";孙昊一;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第02期);B016-1750 * |
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