CN110016178B - Ternary organic-inorganic hybrid material composite flame retardant and application thereof - Google Patents

Ternary organic-inorganic hybrid material composite flame retardant and application thereof Download PDF

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CN110016178B
CN110016178B CN201910347968.4A CN201910347968A CN110016178B CN 110016178 B CN110016178 B CN 110016178B CN 201910347968 A CN201910347968 A CN 201910347968A CN 110016178 B CN110016178 B CN 110016178B
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杨志旺
李丽
王蕊娜
叶娟
魏红
花逢林
胡少平
牛力同
曾巍
雷自强
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Northwest Normal University
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Abstract

The invention discloses a ternary organic-inorganic hybrid material composite flame retardant and application thereof.A DOPO and benzoquinone are dissolved in ethoxyethanol and react to obtain ODOPB; dissolving dicyanodiamine and boric acid in water, stirring and mixing at a certain temperature until water is evaporated completely, and calcining in a tubular furnace to obtain boron-doped g-C3N4(ii) a Dissolving ammonium molybdate and thiourea in water completely, stirring and mixing at a certain temperature until the water is evaporated completely, and calcining in a tubular furnace to obtain MoS2；ODOPB、g‑C3N4And MoS2And mixing, dissolving in sulfuric acid solution with proper concentration, uniformly stirring, centrifugally washing, and drying in vacuum to obtain the ternary composite flame retardant. The composite flame retardant disclosed by the invention adopts a clean and efficient inorganic flame retardant as a main flame retardant component, and is assisted with an organic flame retardant, so that the flame retardant effect of a polymer is enhanced, and the mechanical properties of the original material are kept.

Description

Ternary organic-inorganic hybrid material composite flame retardant and application thereof
Technical Field
The invention belongs to the technical field of material treatment, relates to a flame retardant, and particularly relates to a ternary organic-inorganic hybrid material composite flame retardant; the invention also relates to an application of the composite flame retardant.
Background
Ethylene-vinyl acetate copolymer (EVA) is an indispensable thermoplastic plastic in life and has wide application in the fields of food packaging, wire and cable insulating materials, hot melt adhesives and the like. EVA is greatly convenient for people to live, and has the defect of high flammability, which affects the life and property safety of people. Therefore, it becomes a research hotspot to explore a method for synthesizing the EVA material with the flame retardant effect.
In order to improve the flame retardance of EVA materials, a series of modified palygorskite-added EVA composite flame retardant materials have been prepared in the prior art by utilizing the property that EVA is easy to blend. However, palygorskite as silicate clay added into EVA has poor compatibility, and can reduce the mechanical property of the material.
Molybdenum disulfide (MoS)2) The graphene oxide/graphene composite material has a two-dimensional network structure similar to graphene, is large in surface area and high in activity, and is applied to the fields of lubricants, catalysts, intercalation chemistry and the like. Currently, many researchers have exchanged MoS2The nano sheet is used for enhancing the thermal property, the flame retardant property and the mechanical property of the polymer material. MoS2The nano thin sheet can obstruct the release of heat and improve the flame retardant capability of the material in the aspect of condensed phase.
Disclosure of Invention
The invention aims to provide a ternary organic-inorganic hybrid material composite flame retardant capable of enhancing the flame retardant property of an ethylene-vinyl acetate copolymer.
The invention also aims to provide application of the composite flame retardant.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a ternary organic-inorganic hybrid material composite flame retardant is prepared by the following steps:
1) adding 15-20 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 15-25 g of benzoquinone into 20-50 mL of ethoxyethanol, respectively taking the ethoxyethanol, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 110-130 ℃ for 5 hours to obtain phosphaphenanthrene oxide (ODOPB);
respectively taking boric acid and dicyanodiamine according to a mass ratio of 1: 2-8, completely dissolving the boric acid and the dicyanodiamine in water, stirring and mixing at the temperature of 60-80 ℃ until the water is completely evaporated, and calcining for 3-7 hours in an environment at the temperature of 500-700 ℃ to obtain boron-doped carbon nitride (g-C)3N4）；
Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 1-4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 60-80 ℃ until the water is completely evaporated, and calcining for 3-7 hours in an environment with the temperature of 500-700 ℃ to obtain molybdenum disulfide (MoS)2)；
2) Respectively taking ODOPB and g-C according to the mass ratio of 1: 1-53N4And MoS2Mixing, dissolving in a sulfuric acid solution with the molar volume concentration of 3-8 mol/L, uniformly stirring, washing with distilled water to be neutral, and drying in vacuum at the temperature of 50-80 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant (ODOPB @ g-C)3N4@MoS2）。
The other technical scheme adopted by the invention is as follows: an application of the composite flame retardant in enhancing the flame retardant property of the ethylene-vinyl acetate copolymer. The method specifically comprises the following steps: weighing EVA, placing in a plastic refining machine, melting at 110 deg.C, and adding Expandable Graphite (EG) and ODOPB @ g-C3N4@MoS2Then pouring the mixture into a mold (130 mm multiplied by 6.5 mm multiplied by 3.2 mm) to be hot-pressed on a hydraulic press for 240s, moving the mold to a hydraulic press to be cooled for 1min, and demolding to obtain the composite material sample strip. (EVA, EG and ODOPB @ g-C3N4@MoS2The dosage is shown in the following table 1)
The MoS with the two-dimensional lamellar structure is selected as the composite flame retardant2，g-C3N4The flame retardant material has excellent thermal stability, can obviously enhance the flame retardant property of a high polymer material, and is compounded with an organic phosphorus flame retardant ODOPB to maintain or optimize the mechanical property of a polymer.
Drawings
FIG. 1 shows ODOPB, g-C3N4And ODOPB @ g-C3N4@MoS2Infrared contrast chart of (1).
FIG. 2 is a scanning electron microscope image of the fracture surface of a composite flame retardant material formed by adding the composite flame retardant prepared in example 1 into EVA.
Detailed Description
The preparation process of the present invention is described in more detail below with reference to specific examples.
Example 1
Dissolving 15g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 15g of benzoquinone in 20mL of ethoxy ethanol, and reacting at 110 ℃ for 5 hours to obtain phosphaphenanthrene oxide; respectively taking boric acid and dicyanodiamine according to the mass ratio of 1: 2, completely dissolving the boric acid and the dicyanodiamine in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 500 ℃ to obtain boron-doped carbon nitride; respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 1, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 500 ℃ to obtain molybdenum disulfide; respectively taking phosphaphenanthrene oxide, boron-doped carbon nitride and molybdenum disulfide according to the mass ratio of 1: 1, mixing, dissolving in a sulfuric acid solution with the molar volume concentration of 3mol/L, uniformly stirring, washing with distilled water to be neutral, and drying in vacuum at the temperature of 50 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant (ODOPB @ g-C)3N4 @MoS2）。
Weighing 70g of EVA, placing the EVA in a plastic refining machine, melting the EVA at 110 ℃, and then mixing EG and ODOPB @ g-C according to a certain proportion3N4@MoS2(see Table 1), then pouring into a mould (130 mm multiplied by 6.5 mm multiplied by 3.2 mm), hot-pressing on a hydraulic press for 240s, moving to a hydraulic press, cooling for 1min, and demoulding to obtain the composite material sample strips.
Structure and Properties of composite flame retardant obtained in example 1
1. Infrared analysis
FIG. 1 shows ODOPB, g-C3N4And ODOPB @ C3N4-B@MoS2Is infrared ray ofCompare the figures. In the spectrum of ODOPB, 1456 cm-1Is located at CH2And CH31195 cm of in-plane oscillation peak of-1At P = O peak of stretching vibration, 756 cm-1The formula (I) represents the existence of an m-substituted aromatic ring, and the existence of a phosphorus-containing functional group proves that the ODOPB is synthesized; boron doped g-C3N4In the spectrum of (2), 1639 cm-1Is the peak of the stretching vibration with C = N and is g-C3N4Typical characteristic peaks and appear at ODOPB @ g-C3N4@MoS2And 937 cm-1And 1100 cm-1Corresponding to MoS2The S-S and Mo-O bonds, and the ternary composite flame retardant can be proved to be synthesized.
2. Compatibility analysis
FIG. 2 is a scanning electron microscope image of the fracture surface of a composite flame retardant material formed by adding the composite flame retardant prepared in example 1 into EVA. As can be seen from the figure, the EVA surface after adding the composite flame retardant is uniform, flat, compact and non-porous, which shows that the composite flame retardant has good compatibility with the matrix material and does not damage the original mechanical property of the EVA material.
3. Analysis of mechanism
MoS2In the combustion process, the barrier effect similar to graphene and montmorillonite is exerted, and MoS2The compact reticular structure is coated on the surface of the polymer, so that the combustion of a matrix in the polymer can be reduced, and the heat transfer is blocked under the synergistic effect of the expansion effect of the expandable graphite; the phosphaphenanthrene functional group in the ODOPB is heated to decompose to form PO & and phenoxy free radicals, capture H & OH & free radicals and play a quenching role to inhibit a combustion reaction; boron doped g-C3N4During the pyrolysis, NO and NO are released2Oxygen is consumed and a part of heat is taken away, and the boron-containing compound promotes the formation of a compact carbon layer, so that a barrier effect is generated, and the generation of smoke is reduced.
The ODOPB can increase the temperature of the borate to be converted into a glass state, enhance the compatibility of the flame retardant and the polymer and reduce the damage of the added flame retardant to the mechanical property of the polymer. The synergistic effect of the ternary flame retardant has excellent flame retardant effect on the EVA material in both gas phase and condensed phase.
Example 2
Adding 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 16g of benzoquinone into 30mL of ethoxyethanol, respectively taking the ethoxyethanol, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 110 ℃ for 5 hours to obtain the phosphaphenanthrene oxide; respectively taking boric acid and dicyanodiamine according to the mass ratio of 1: 3, completely dissolving the boric acid and the dicyanodiamine in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 500 ℃ to obtain boron-doped carbon nitride; respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 2, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 500 ℃ to obtain molybdenum disulfide; respectively taking the phosphaphenanthrene oxide, the boron-doped carbon nitride and the molybdenum disulfide according to the mass ratio of 1: 1, mixing, dissolving in a sulfuric acid solution with the molar volume concentration of 3mol/L, uniformly stirring, washing with distilled water to be neutral, and drying in vacuum at the temperature of 50 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 3
Adding 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 16g of benzoquinone into 35mL of ethoxyethanol, respectively taking the ethoxyethanol, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 110 ℃ for 5 hours to obtain the phosphaphenanthrene oxide; respectively taking boric acid and dicyanodiamine according to the mass ratio of 1: 4, completely dissolving the boric acid and the dicyanodiamine in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 550 ℃ to obtain boron-doped carbon nitride; respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 3, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 550 ℃ to obtain molybdenum disulfide; respectively taking ODOPB and g-C according to the mass ratio of 1: 13N4And MoS2Mixing, dissolving in sulfuric acid solution with the molar volume concentration of 3mol/L, stirring uniformly,washing the mixture to be neutral by distilled water, and drying the mixture in vacuum at the temperature of 50 ℃ to prepare the ternary organic-inorganic hybrid material composite flame retardant.
Example 4
Adding 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 16g of benzoquinone into 40mL of ethoxyethanol, respectively taking the ethoxyethanol, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 115 ℃ for 5 hours to obtain ODOPB; respectively taking boric acid and dicyanodiamine according to the mass ratio of 1: 5, completely dissolving the boric acid and the dicyanodiamine in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 4 hours in an environment with the temperature of 550 ℃ to obtain boron-doped carbon nitride g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 550 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 13N4And MoS2Mixing, dissolving in sulfuric acid solution with the molar volume concentration of 3mol/L, stirring uniformly, washing with distilled water to be neutral, and drying in vacuum at the temperature of 50 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 5
Adding 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 16g of benzoquinone into 40mL of ethoxyethanol, respectively taking the ethoxyethanol, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 115 ℃ for 5 hours to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 6, stirring and mixing at 60 deg.C until water is completely evaporated, calcining at 550 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 60 ℃ until the water is completely evaporated, and calcining for 3 hours in an environment with the temperature of 550 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 13N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 3mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 50 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 6
Adding 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 16g of benzoquinone into 45mL of ethoxyethanol, respectively taking the ethoxyethanol, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 115 ℃ for 5 hours to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 7, stirring and mixing at 60 deg.C until water is completely evaporated, calcining at 550 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 2, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 65 ℃ until the water is completely evaporated, and calcining for 4 hours in an environment with the temperature of 500 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 23N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 4mol/L after mixing, uniformly stirring, washing to be neutral by distilled water, and drying in vacuum at the temperature of 55 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 7
Adding 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 16g of benzoquinone into 50mL of ethoxyethanol, respectively taking the ethoxyethanol, the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 115 ℃ for 5 hours to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 8, stirring and mixing at 60 deg.C until water is completely evaporated, calcining at 550 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively dissolving ammonium molybdate and thiourea in water at a mass ratio of 1: 3, stirring and mixing at 65 deg.C until water is completely evaporated, calcining at 550 deg.C for 4 hr to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 23N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 4mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 55 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 8
Adding 15g of DOPO and 15g of benzoquinone into 25mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 115 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 2, stirring and mixing at 65 deg.C until water is completely evaporated, calcining at 550 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 65 ℃ until the water is completely evaporated, and calcining for 4 hours in an environment with the temperature of 550 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 23N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 4mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 55 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 9
Adding 16g of DOPO and 17g of benzoquinone into 30mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 120 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 3, stirring and mixing at 65 deg.C until water is completely evaporated, calcining at 600 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 2, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 70 ℃ until the water is completely evaporated, and calcining for 4 hours in an environment with the temperature of 550 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 23N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 4mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 60 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 10
Adding 17g of DOPO and 17g of benzoquinone into 30mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 120 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 4, stirring and mixing at 70 deg.C until water is completely evaporated, calcining at 600 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 2, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 75 ℃ until the water is completely evaporated, and calcining for 4 hours in the environment at the temperature of 600 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 23N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 5mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 60 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 11
Adding 18g of DOPO and 18g of benzoquinone into 30mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 120 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 4, stirring and mixing at 75 deg.C until water is completely evaporated, calcining at 600 deg.C for 5 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 2, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 80 ℃ until the water is completely evaporated, and calcining for 5 hours in an environment with the temperature of 600 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 23N4And MoS2Mixing, dissolving in 5mol/L sulfuric acid solution, stirring, washing with distilled waterAnd (3) drying the mixture in vacuum at the temperature of 60 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 12
Adding 17g of DOPO and 18g of benzoquinone into 30mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 120 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 4, stirring and mixing at 80 deg.C until water is completely evaporated, calcining at 600 deg.C for 5 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 3, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 65 ℃ until the water is completely evaporated, and calcining for 5 hours in an environment with the temperature of 600 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 33N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 5mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 65 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 13
Adding 19g of DOPO and 19g of benzoquinone into 30mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 120 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 5, stirring and mixing at 65 deg.C until water is completely evaporated, calcining at 600 deg.C for 6 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 3, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 65 ℃ until the water is completely evaporated, and calcining for 6 hours in an environment with the temperature of 600 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 33N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 5mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 65 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 14
Adding 20g of DOPO and 20g of benzoquinone into 30mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 120 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 5, stirring and mixing at 70 deg.C until water is completely evaporated, calcining at 650 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 3, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 70 ℃ until the water is completely evaporated, and calcining for 4 hours in an environment with the temperature of 650 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 33N4And MoS2Mixing, dissolving in 5mol/L sulfuric acid solution, stirring, washing with distilled water to neutrality, and vacuum drying at 70 deg.C to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 15
Adding 15g of DOPO and 16g of benzoquinone into 35mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 125 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 6, stirring and mixing at 70 deg.C until water is completely evaporated, calcining at 650 deg.C for 5 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 3, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 75 ℃ until the water is completely evaporated, and calcining for 5 hours in an environment with the temperature of 650 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 43N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 5mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 70 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 16
In the amount of 35mL ethoxyAdding 16g of DOPO and 16g of benzoquinone into ethanol, respectively taking ethoxyethanol, DOPO and benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 125 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 6, stirring and mixing at 75 deg.C until water is completely evaporated, calcining at 650 deg.C for 6 hr to obtain g-C3N4(ii) a Respectively dissolving ammonium molybdate and thiourea in water at a mass ratio of 1: 3, stirring and mixing at 80 deg.C until water is completely evaporated, calcining at 650 deg.C for 6 hr to obtain (MoS)2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 33N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 5mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 70 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 17
Adding 17g of DOPO and 17g of benzoquinone into 35mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 125 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 6, stirring and mixing at 75 deg.C until water is completely evaporated, calcining at 650 deg.C for 7 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 65 ℃ until the water is completely evaporated, and calcining for 7 hours in an environment with the temperature of 650 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 43N4And MoS2And dissolving the mixture in sulfuric acid solution with the molar volume concentration of 6mol/L after mixing, uniformly stirring, washing the mixture to be neutral by distilled water, and drying the mixture in vacuum at the temperature of 75 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 18
Adding 18g of DOPO and 18g of benzoquinone into 35mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, and mixing the DOPO and the benzeneDissolving quinone in ethoxy ethanol, and reacting at 125 deg.C for 5 hr to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 6, stirring and mixing at 80 deg.C until water is completely evaporated, calcining at 700 deg.C for 4 hr to obtain g-C3N4(ii) a Respectively dissolving ammonium molybdate and thiourea in water at a mass ratio of 1: 4, stirring and mixing at 70 deg.C until water is completely evaporated, and standing at 700 deg.C℃Calcining for 4 hours in the environment to obtain the molybdenum disulfide (MoS)2) (ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 43N4And MoS2And dissolving the mixture in sulfuric acid solution with the molar volume concentration of 6mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 75 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 19
Adding 19g of DOPO and 19g of benzoquinone into 35mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 125 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 7, stirring and mixing at 65 deg.C until water is completely evaporated, calcining at 700 deg.C for 5 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 75 ℃ until the water is completely evaporated, and calcining for 5 hours in an environment with the temperature of 700 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 43N4And MoS2And dissolving the mixture in sulfuric acid solution with the molar volume concentration of 6mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 75 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 20
Adding 18g of DOPO and 18g of benzoquinone into 40mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 125 ℃ to obtain ODOPB; push buttonRespectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 7, stirring and mixing at 70 deg.C until water is completely evaporated, calcining at 700 deg.C for 5 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 75 ℃ until the water is completely evaporated, and calcining for 5 hours in an environment with the temperature of 700 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 43N4And MoS2And dissolving the mixture in sulfuric acid solution with the molar volume concentration of 6mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 75 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 21
Adding 19g of DOPO and 19g of benzoquinone into 40mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 125 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 7, stirring and mixing at 75 deg.C until water is completely evaporated, calcining at 700 deg.C for 6 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 80 ℃ until the water is completely evaporated, and calcining for 6 hours in an environment with the temperature of 700 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 53N4And MoS2And dissolving the mixture in sulfuric acid solution with the molar volume concentration of 6mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 80 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 22
Adding 18g of DOPO and 18g of benzoquinone into 45mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 130 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 8, stirring and mixing at 70 deg.CUntil the water is completely evaporated, calcining for 7h in an environment with the temperature of 700 ℃ to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 80 ℃ until the water is completely evaporated, and calcining for 6 hours in an environment with the temperature of 700 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 53N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 7mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 80 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 23
Adding 19g of DOPO and 19g of benzoquinone into 45mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 130 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 8, stirring and mixing at 70 deg.C until water is completely evaporated, calcining at 700 deg.C for 7 hr to obtain g-C3N4(ii) a Respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 80 ℃ until the water is completely evaporated, and calcining for 7 hours in an environment with the temperature of 700 ℃ to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 53N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 8mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 80 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 24
Adding 20g of DOPO and 20g of benzoquinone into 45mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 130 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 8, stirring and mixing at 80 deg.C until water is completely evaporated, calcining at 700 deg.C for 7 hr to obtain g-C3N4(ii) a Push buttonRespectively taking ammonium molybdate and thiourea at a mass ratio of 1: 4, completely dissolving in water, stirring and mixing at 80 ℃ until water is completely evaporated, and calcining at 700 ℃ for 7h to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 53N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 8mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 80 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
Example 25
Adding 20g of DOPO and 20g of benzoquinone into 50mL of ethoxyethanol, respectively taking the ethoxyethanol, the DOPO and the benzoquinone, dissolving the DOPO and the benzoquinone in the ethoxyethanol, and reacting for 5 hours at the temperature of 130 ℃ to obtain ODOPB; respectively dissolving boric acid and dicyanodiamine in water at a mass ratio of 1: 8, stirring and mixing at 80 deg.C until water is completely evaporated, calcining at 700 deg.C for 7 hr to obtain g-C3N4(ii) a Respectively dissolving ammonium molybdate and thiourea in water at a mass ratio of 1: 4, stirring and mixing at 80 deg.C until water is completely evaporated, standing at 700 deg.C℃Calcining for 7 hours in the environment to obtain MoS2(ii) a Respectively taking ODOPB and g-C according to the mass ratio of 1: 53N4And MoS2And dissolving the mixture in a sulfuric acid solution with the molar volume concentration of 8mol/L after mixing, uniformly stirring, washing the mixture to be neutral by using distilled water, and drying the mixture in vacuum at the temperature of 80 ℃ to obtain the ternary organic-inorganic hybrid material composite flame retardant.
The ternary organic-inorganic hybrid material composite flame retardant prepared in each embodiment is compounded with Expandable Graphite (EG) and then applied to an EVA matrix material, and the oxygen index (LOI) of the composite flame retardant is shown in Table 1.
TABLE 1 oxygen index of the composites
Figure 807278DEST_PATH_IMAGE001
As can be seen from the data in the table, when the obtained composite flame retardant and Expandable Graphite (EG) are compounded and applied to an EVA material, the flame retardant effect is optimal when the mass ratio of the composite flame retardant to EG is 1:9, and the oxygen index is 32.5%.

Claims (3)

1. The ternary organic-inorganic hybrid material composite flame retardant for enhancing the flame retardant property of the EVA is characterized by being prepared by the following steps:
1) adding 15-20 g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 15-25 g of benzoquinone into 20-50 mL of ethoxyethanol, respectively taking ethoxyethanol, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzoquinone, dissolving the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the benzoquinone in the ethoxyethanol, and reacting at the temperature of 110-130 ℃ for 5 hours to obtain the phosphaphenanthrene oxide;
respectively taking boric acid and dicyanodiamine according to a mass ratio of 1: 2-8, completely dissolving the boric acid and the dicyanodiamine in water, stirring and mixing at the temperature of 60-80 ℃ until the water is completely evaporated, and calcining for 3-7 hours in an environment at the temperature of 500-700 ℃ to obtain boron-doped carbon nitride;
respectively taking ammonium molybdate and thiourea according to the mass ratio of 1: 1-4, completely dissolving the ammonium molybdate and the thiourea in water, stirring and mixing at the temperature of 60-80 ℃ until the water is completely evaporated, and calcining for 3-7 hours in the environment at the temperature of 500-700 ℃ to obtain molybdenum disulfide;
2) and respectively taking the phosphaphenanthrene oxide, the boron-doped carbon nitride and the molybdenum disulfide according to the mass ratio of 1: 1-5, mixing, dissolving in a sulfuric acid solution, uniformly stirring, washing to be neutral, and drying in vacuum to obtain the ternary organic-inorganic hybrid material composite flame retardant for enhancing the EVA flame retardant performance.
2. The ternary organic-inorganic hybrid material composite flame retardant for enhancing the EVA flame retardant property of claim 1, wherein in the step 2), the molar volume concentration of the sulfuric acid solution is 3-8 mol/L.
3. The use of the ternary organic-inorganic hybrid material composite flame retardant for enhancing the flame retardant property of EVA of claim 1 in the preparation of ethylene-vinyl acetate copolymer flame retardant materials.
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