CN116333411B - Flame-retardant EVA (ethylene vinyl acetate) heat-insulating material and preparation method thereof - Google Patents

Flame-retardant EVA (ethylene vinyl acetate) heat-insulating material and preparation method thereof Download PDF

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CN116333411B
CN116333411B CN202310613785.9A CN202310613785A CN116333411B CN 116333411 B CN116333411 B CN 116333411B CN 202310613785 A CN202310613785 A CN 202310613785A CN 116333411 B CN116333411 B CN 116333411B
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CN116333411A (en
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苗春燕
马少怀
焦建培
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Shijiazhuang Qihong New Material Products Co ltd
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
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    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

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Abstract

The invention relates to the technical field of EVA materials and discloses a flame-retardant EVA heat-insulating material and a preparation method thereof, wherein phenol diphenyl phosphate, trimellitic anhydride acyl chloride and 2-aminopyrimidine-5-formic acid are used as reactants to synthesize phenyl phosphate pyrimidine dicarboxyl monomers, and then melt polycondensation is carried out on the phenyl phosphate pyrimidine dicarboxyl monomers and 1, 6-hexamethylenediamine to prepare a novel phosphorus-containing polyaramid flame retardant, the phosphorus-containing polyaramid flame retardant and silicon dioxide aerogel are melt mixed and molded with EVA resin by using maleic anhydride grafted EVA as a compatilizer, so that the flame-retardant EVA heat-insulating material is obtained.

Description

Flame-retardant EVA (ethylene vinyl acetate) heat-insulating material and preparation method thereof
Technical Field
The invention relates to the technical field of EVA materials, in particular to a flame-retardant EVA heat-insulating material and a preparation method thereof.
Background
Ethylene-vinyl acetate copolymer (EVA) is a general polymer, has good water resistance, corrosion resistance, vibration resistance and processability, is widely applied to the fields of foaming shoe materials, functional greenhouse films, hot melt adhesives, wires and cables and the like, improves the heat insulation and flame retardance of EVA, increasingly expands the heat insulation of EVA in the functional greenhouse films, wires and cables and the like, and announces the Chinese patent with the number of CN114702625B, adopts polyimide aerogel materials as a heat insulation layer, coats modified EVA materials on the front surface, and the prepared cell therapy liquid storage bag has good tensile property, heat insulation property and lower water vapor transmittance.
EVA has excellent comprehensive performance, but has inflammability, so that development and application of EVA are limited, a novel efficient flame retardant is developed to be applied to EVA, the method is an effective method for improving flame retardant performance of EVA, and the method is disclosed in the patent with publication number of CN 109337186B.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a flame-retardant EVA heat-insulating material and a preparation method thereof, and solves the problems of low heat-insulating property and poor flame retardance of the EVA material.
(II) technical scheme
The invention provides a flame-retardant EVA heat-insulating material, which comprises the following raw materials, by weight, 2-10% of silica aerogel, 0.5-5% of phosphorus-containing polyaramid flame retardant, 0.2-3% of maleic anhydride grafted EVA and the balance of EVA resin.
The preparation method of the flame-retardant EVA heat-insulating material comprises the following steps:
(1) Adding phenyl phosphate pyrimidine dicarboxyl monomer, 1, 6-hexamethylenediamine and distilled water into a reaction kettle, then introducing nitrogen, and heating to 80-110 ℃ for pre-reaction of 1-2 h; then heating to 210-240 ℃ to perform melt polymerization for 2-4 h, and discharging water vapor in the reaction kettle in the melt polymerization reaction process; finally, vacuumizing, heating to 250-280 ℃, reacting 2-4 h, cooling after the reaction, and washing with ethanol, N-dimethylformamide and deionized water in sequence to obtain the phosphorus-containing polyaramid flame retardant.
(2) Adding the silicon dioxide aerogel, the phosphorus-containing polyaramid flame retardant, the maleic anhydride grafted EVA and the EVA resin into a double-screw extruder, extruding and granulating, and then moulding the master batch in a plate vulcanizing machine to obtain the flame-retardant EVA heat-insulating material.
Further, the molar ratio of the phenyl phosphate pyrimidine dicarboxylic monomer to the 1, 6-hexamethylenediamine in the step (1) is 1:1-1.2.
Further, nitrogen is introduced into the reaction kettle in the step (1) to control the pressure to be 0.2-0.3 MPa; the pressure of the reaction kettle is controlled to be 1.5-2.5 MPa by discharging water vapor in the melt polymerization reaction process; vacuum pumping is controlled to be 0.01-0.08 MPa.
Further, the melting temperature of the twin-screw extruder in the step (2) is controlled to be 220-230 ℃ and the extrusion temperature is controlled to be 215-225 ℃; the temperature of the vulcanizing press is controlled to be 190-210 ℃ and the pressure is controlled to be 8-12 MPa.
Further, the preparation method of the phenyl phosphate pyrimidine dicarboxylic monomer comprises the following steps:
(1) Synthesizing phenol diphenyl phosphate by using terephthalquinone and diphenyl phosphate as reactants; then dissolving the phenyl diphenyl phosphate and pyridine into a reaction solvent at 0-5 ℃, dropwise adding trimellitic anhydride acyl chloride, uniformly stirring, reacting at room temperature for 6-18 h, concentrating under reduced pressure, washing with diethyl ether, and drying to obtain the phenyl diphenyl phosphate intermediate of the trimellitic anhydride.
(2) Adding the diphenyl phosphate intermediate of the phenyl trimellitate and the 2-aminopyrimidine-5-formic acid into a dimethyl sulfoxide solvent, heating to 80-120 ℃, reacting 12-36 h, cooling, adding deionized water and ethyl acetate, extracting and separating, concentrating an upper ethyl acetate solution under reduced pressure, washing a crude product with acetone, adding the crude product into ethanol, and recrystallizing to obtain the phenyl phosphate pyrimidine dicarboxylic monomer.
Further, the molar ratio of the phenol diphenyl phosphate, the pyridine and the trimellitic anhydride acyl chloride in the step (1) is 1:1.5-2.5:1.2-1.8.
Further, the reaction solvent in (2) comprises any one of tetrahydrofuran, ethyl acetate, acetonitrile and 1, 4-dioxane.
Further, the molar ratio of the diphenyl phosphate intermediate of the phenyl trimellitate group to the 2-aminopyrimidine-5-formic acid in the step (2) is 1:1.1-1.5.
(III) beneficial technical effects
1. The invention utilizes phenol diphenyl phosphate, trimellitic anhydride acyl chloride and 2-aminopyrimidine-5-formic acid as reactants to synthesize a novel phenyl phosphate pyrimidine dicarboxyl monomer, and then the novel phenyl phosphate pyrimidine dicarboxyl monomer and 1, 6-hexamethylenediamine undergo melt polycondensation to prepare a novel phosphorus-containing polyaramide flame retardant, wherein the flame retardant contains a thermally stable polyaramide structure and nitrogen-phosphorus synergistic flame retardant elements of phenyl phosphate and pyrimidine.
2. The maleic anhydride grafted EVA is used as a compatilizer, the phosphorus-containing polyaramid flame retardant and the silica aerogel are melted and mixed with EVA resin and molded to obtain the flame-retardant EVA heat-insulating material, the maleic anhydride grafted EVA compatilizer can improve the interfacial compatibility between the phosphorus-containing polyaramid flame retardant and the silica aerogel and the EVA resin, promote the uniform dispersion of the phosphorus-containing polyaramid flame retardant and the silica aerogel in the EVA resin, and avoid the influence of the addition of the flame retardant and the aerogel on the tensile strength and the mechanical property of the EVA resin.
3. The phosphorus-containing polyaramid flame retardant has an aromatic ring structure with high carbon content, and nitrogen and phosphorus synergistic flame retardant elements, can promote the char formation of an EVA resin matrix, plays a synergistic flame retardant role with silica aerogel, prevents oxygen from entering the resin matrix, inhibits the combustion process, reduces the escape of smoke during combustion, and remarkably improves the flame retardant property of the EVA resin.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a phenyl pyrimidine dicarboxyl phosphate monomer.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of a phenyl phosphate pyrimidine dicarboxylic monomer.
FIG. 3 is an infrared spectrum of a phosphorus polyaramid flame retardant.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail. It should be noted that: the relative arrangement of the components and steps, numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless it is specifically stated otherwise.
Techniques, methods, and apparatus known to one of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of exemplary embodiments may have different values.
The preparation method of the phenol diphenyl phosphate comprises the following steps: adding 0.043 mol of diphenyl phosphate and 0.056 mol of p-benzoquinone into 30 mL toluene solvent, dropwise adding 0.011 mol of triethylamine at 0 ℃, stirring at room temperature for reaction 12 h, concentrating under reduced pressure, washing with diethyl ether, and drying to obtain phenol diphenyl phosphate; the structure is that。
The preparation method of the silica aerogel comprises the following steps: the preparation method comprises the steps of adding tetraethyl orthosilicate 30 mL, ethanol 18 mL and oxalic acid 8 mL to a concentration of 0.01 mol/L, advancing by 12 h at 50 ℃, then dropwise adding an ammonia water solution 0.6 mL to a concentration of 25%, stirring for 3 min, standing to form gel, adding ethanol 30 mL to soak 48 h, replacing the gel with reaction raw materials and water, adding n-hexane 30 mL to soak 48 h to replace ethanol, finally drying the gel at 60 ℃ for 4 days, and then heating to 180 ℃ to dry 4 h to obtain the silica aerogel.
The preparation method of the maleic anhydride grafted EVA comprises the following steps: uniformly mixing 50 g EVA resin, 2 g maleic anhydride, 0.4 g dicumyl peroxide and 100 mL acetone, volatilizing to remove acetone, and then carrying out melt grafting on the materials in a torque rheometer at 190 ℃ for 8 min to obtain the maleic anhydride grafted EVA.
Example 1:
(1) 0.2 mol of phenol diphenyl phosphate and 0.35 mol of pyridine are dissolved into 800 mL ethyl acetate solvent at the temperature of 5 ℃, 0.28 mol of trimellitic anhydride acyl chloride is added dropwise, the mixture is stirred uniformly and then reacted at room temperature for 6 h, the mixture is concentrated under reduced pressure, washed by diethyl ether and dried, and thus the intermediate of the phenyl trimellitic anhydride diphenyl phosphate is obtained.
(2) Adding 0.4 mol of diphenyl phosphate intermediate with a phenyl trimellitate group and 0.6 mol of 2-aminopyrimidine-5-formic acid into a dimethyl sulfoxide solvent of 2000 mL, heating to 100 ℃, reacting 12 h, cooling, adding deionized water and ethyl acetate, extracting and separating, concentrating an upper ethyl acetate solution under reduced pressure, washing a crude product with acetone, adding into ethanol, and recrystallizing to obtain phenyl phosphatePyrimidine dicarboxylic monomers; molecular formula C 32 H 22 N 3 O 10 P； 1 H NMR(300MHz，CDCl 3 )：δ12.10 (s，1H)，9.78 (s，1H)，8.36-8.02(m，5H)，7.79-7.48 (m，8H)，7.20-7.06 (m，1H)，7.05-6.90(m，3H)，6.88-6.73(m，3H)。 13 C NMR(400MHz，CDCl 3 ): delta 171.8. 165.2, 164.7, 162.0, 159.1, 155.9, 150.1, 138.7, 138.0, 134.6, 132.4, 130.9, 130.1, 127.2, 123.3, 122.8, 124.1, 121.3, 119.6, 119.5. The preparation route is as follows:
(3) Adding 0.4 mol of phenyl phosphate pyrimidine dicarboxylic monomer, 0.4 mol of 1, 6-hexamethylenediamine and 50 mL of distilled water into a reaction kettle, then introducing nitrogen to control the pressure of the reaction kettle to be 0.2 MPa, and heating to 100 ℃ for pre-reaction of 1 h; then heating to 240 ℃ to perform melt polymerization 2 h, discharging water vapor in the reaction kettle in the melt polymerization reaction process, and controlling the pressure of the reaction kettle to be 2 MPa; finally, vacuumizing to control the vacuum degree to be 0.01 MPa, heating to 280 ℃, reacting for 3 h, cooling after the reaction, and washing with ethanol, N-dimethylformamide and deionized water in sequence to obtain the phosphorus-containing polyaramid flame retardant; 1652 and cm in the IR spectrum -1 Is the telescopic vibration absorption peak of the amide bond C=O in the phosphorus-containing polyaramid, 1560 cm -1 Is characterized by an amide bond N-H characteristic absorption peak, 1432cm -1 At the vibration absorption peak of benzene ring skeleton, 1169 cm -1 Is the telescopic vibration absorption peak of the P=O bond of the phosphate, 1005cm -1 Is the absorption peak of phosphate P-O.
(4) Adding 10% of silicon dioxide aerogel, 0.5% of phosphorus-containing polyaramid flame retardant, 0.2% of maleic anhydride grafted EVA and 89.7% of EVA resin into a double-screw extruder, controlling the melting temperature to 220 ℃, the extrusion temperature to 215 ℃, extruding and granulating, and then molding the master batch in a flat vulcanizing machine, controlling the temperature to 200 ℃ and the pressure to 12 MPa to obtain the flame-retardant EVA heat-insulating material.
Example 2:
(1) 0.2 mol of phenol diphenyl phosphate and 0.3 mol of pyridine are dissolved in 500 mL tetrahydrofuran solvent at the temperature of 0 ℃, 0.24 mol of trimellitic anhydride acyl chloride is added dropwise, the mixture is stirred uniformly and then reacted at room temperature for 18 h, the mixture is concentrated under reduced pressure, washed by diethyl ether and dried, and thus the intermediate of the phenyl trimellitic anhydride diphenyl phosphate is obtained.
(2) 0.4 mol of the diphenyl phosphate intermediate of the phenyl trimellitate and 0.5 mol of 2-aminopyrimidine-5-formic acid are added into a dimethyl sulfoxide solvent of 1500 mL, the temperature is raised to 120 ℃, the reaction is carried out for 24 h, deionized water and ethyl acetate are cooled and added, extraction separation is carried out, the upper ethyl acetate solution is decompressed and concentrated, and then the crude product is washed by acetone and then added into ethanol for recrystallization, thus obtaining the phenyl phosphate pyrimidine dicarboxylic monomer.
(3) Adding 0.4 mol of phenyl phosphate pyrimidine dicarboxylic monomer, 0.42 mol of 1, 6-hexamethylenediamine and 80 mL distilled water into a reaction kettle, then introducing nitrogen to control the pressure of the reaction kettle to be 0.3 MPa, and heating to 100 ℃ for pre-reaction 2 h; then heating to 210 ℃ to carry out melt polymerization 4 h, discharging water vapor in the reaction kettle in the melt polymerization reaction process, and controlling the pressure of the reaction kettle to be 1.5 MPa; finally, vacuumizing to control the vacuum degree to be 0.08 MPa, heating to 280 ℃, reacting 2.2 h, cooling after the reaction, and washing sequentially with ethanol, N-dimethylformamide and deionized water to obtain the phosphorus-containing polyaramid flame retardant.
(4) Adding 6% of silicon dioxide aerogel, 2% of phosphorus-containing polyaramid flame retardant, 1.5% of maleic anhydride grafted EVA and 90.5% of EVA resin into a double-screw extruder, controlling the melting temperature to be 230 ℃, extruding at 225 ℃, extruding and granulating, and then molding the master batch in a flat vulcanizing machine, controlling the temperature to be 210 ℃ and the pressure to be 8 MPa, thus obtaining the flame-retardant EVA heat-insulating material.
Example 3:
(1) 0.2 mol of phenyl diphenyl phosphate and 0.5 mol of pyridine are dissolved in 1000 mL acetonitrile solvent at the temperature of 5 ℃, 0.36 mol of trimellitic anhydride acyl chloride is added dropwise, the mixture is stirred uniformly and then reacted at room temperature for 12 h, the mixture is concentrated under reduced pressure, and the mixture is washed by diethyl ether and dried to obtain the intermediate of the phenyl diphenyl phosphate of the trimellitic anhydride.
(2) Adding 0.4 mol of diphenyl phosphate intermediate with a phenyl trimellitate group and 0.44 mol of 2-aminopyrimidine-5-formic acid into a dimethyl sulfoxide solvent of 1500 mL, heating to 120 ℃, reacting 12 h, cooling, adding deionized water and ethyl acetate, extracting and separating, concentrating an upper ethyl acetate solution under reduced pressure, washing a crude product with acetone, adding into ethanol, and recrystallizing to obtain phenyl phosphate pyrimidine dicarboxylic monomers
(3) Adding 0.4 mol of phenyl phosphate pyrimidine dicarboxylic monomer, 0.48 mol of 1, 6-hexamethylenediamine and 100 mL of distilled water into a reaction kettle, then introducing nitrogen to control the pressure of the reaction kettle to be 0.25 MPa, and heating to 80 ℃ for pre-reaction 2 h; then heating to 230 ℃ to perform melt polymerization 4 h, discharging water vapor in the reaction kettle in the melt polymerization reaction process, and controlling the pressure of the reaction kettle to be 1.5 MPa; finally, vacuumizing to control the vacuum degree to be 0.05 MPa, heating to 260 ℃, reacting for 4 h, cooling after the reaction, and washing with ethanol, N-dimethylformamide and deionized water in sequence to obtain the phosphorus-containing polyaramid flame retardant.
(4) Adding 4% of silicon dioxide aerogel, 3% of phosphorus-containing polyaramid flame retardant, 2.2% of maleic anhydride grafted EVA and 90.8% of EVA resin into a double-screw extruder, controlling the melting temperature to 220 ℃, extruding at 215 ℃, extruding and granulating, and then molding the master batch in a flat vulcanizing machine, controlling the temperature to 190 ℃ and the pressure to 12 MPa to obtain the flame-retardant EVA heat-insulating material.
Example 4:
(1) 0.2 mol of phenyl diphenyl phosphate and 0.4 mol of pyridine are dissolved into 800 mL of 1, 4-dioxane solvent at the temperature of 0 ℃, 0.3 mol of trimellitic anhydride acyl chloride is added dropwise, after being stirred uniformly, the mixture reacts at room temperature for 12 h, and then the mixture is concentrated under reduced pressure, washed by diethyl ether and dried, thus obtaining the phenyl diphenyl phosphate intermediate of the trimellitic anhydride phenyl ester.
(2) 0.4 mol of the diphenyl phosphate intermediate with a phenyl trimellitate group and 0.55 mol of 2-aminopyrimidine-5-formic acid are added into a dimethyl sulfoxide solvent of 2000 mL, the temperature is raised to 80 ℃, the reaction is carried out at 36 h, deionized water and ethyl acetate are cooled and added, extraction separation is carried out, the upper ethyl acetate solution is decompressed and concentrated, and then the crude product is washed by acetone first and then added into ethanol for recrystallization, thus obtaining the phenyl phosphate pyrimidine dicarboxylic monomer.
(3) Adding 0.4 mol of phenyl phosphate pyrimidine dicarboxylic monomer, 0.45 mol of 1, 6-hexamethylenediamine and 100 mL of distilled water into a reaction kettle, then introducing nitrogen to control the pressure of the reaction kettle to be 0.3 MPa, and heating to 110 ℃ for pre-reaction of 1 h; then heating to 220 ℃ to carry out melt polymerization 3 h, discharging water vapor in the reaction kettle in the melt polymerization reaction process, and controlling the pressure of the reaction kettle to be 2.5 MPa; finally, vacuumizing to control the vacuum degree to be 0.08 MPa, heating to 250 ℃, reacting 2.2 h, cooling after the reaction, and washing sequentially with ethanol, N-dimethylformamide and deionized water to obtain the phosphorus-containing polyaramid flame retardant.
(4) Adding 2% of silicon dioxide aerogel, 5% of phosphorus-containing polyaramid flame retardant, 3% of maleic anhydride grafted EVA and 90% of EVA resin into a double-screw extruder, controlling the melting temperature to 225 ℃, controlling the extrusion temperature to 220 ℃, extruding and granulating, and then molding the master batch in a flat vulcanizing machine, controlling the temperature to 210 ℃ and the pressure to 10 MPa to obtain the flame-retardant EVA heat-insulating material.
Comparative example 1:
(1) 0.2 mol of phenol diphenyl phosphate and 0.4 mol of pyridine are dissolved into 800 mL tetrahydrofuran solvent at the temperature of 5 ℃, 0.3 mol of trimellitic anhydride acyl chloride is added dropwise, the mixture is stirred uniformly and then reacted at room temperature for 6 h, the mixture is concentrated under reduced pressure, washed by diethyl ether and dried, and thus the intermediate of the trimellitic anhydride phenyl diphenyl phosphate is obtained.
(2) 0.4 mol of the diphenyl phosphate intermediate with a phenyl trimellitate group and 0.44 mol of 2-aminopyrimidine-5-formic acid are added into a dimethyl sulfoxide solvent of 2000 mL, the temperature is raised to 120 ℃, the reaction is carried out for 12 h, deionized water and ethyl acetate are added after cooling, extraction separation is carried out, the upper ethyl acetate solution is decompressed and concentrated, and then the crude product is washed by acetone first and then added into ethanol for recrystallization, thus obtaining the phenyl phosphate pyrimidine dicarboxylic monomer.
(3) Adding 0.4 mol of phenyl phosphate pyrimidine dicarboxylic monomer, 0.45 mol of 1, 6-hexamethylenediamine and 80 mL distilled water into a reaction kettle, then introducing nitrogen to control the pressure of the reaction kettle to be 0.25 MPa, and heating to 100 ℃ for pre-reaction of 2 h; then heating to 220 ℃ to carry out melt polymerization 4 h, discharging water vapor in the reaction kettle in the melt polymerization reaction process, and controlling the pressure of the reaction kettle to be 1.5 MPa; finally, vacuumizing to control the vacuum degree to be 0.05 MPa, heating to 260 ℃, reacting for 4 h, cooling after the reaction, and washing with ethanol, N-dimethylformamide and deionized water in sequence to obtain the phosphorus-containing polyaramid flame retardant.
(4) Adding 10% of silicon dioxide aerogel, 0.5% of phosphorus-containing polyaramid flame retardant and 90.5% of EVA resin into a double-screw extruder, controlling the melting temperature to 225 ℃, the extrusion temperature to 220 ℃, extruding and granulating, and then molding the master batch in a flat vulcanizing machine, controlling the temperature to 200 ℃ and the pressure to 10 MPa to obtain the flame-retardant EVA heat-insulating material.
Comparative example 2:
(1) 0.2 mol of phenyl diphenyl phosphate and 0.5 mol of pyridine are dissolved in 1000 mL acetonitrile solvent at the temperature of 5 ℃, 0.36 mol of trimellitic anhydride acyl chloride is added dropwise, the mixture is stirred uniformly and then reacted at room temperature for 6 h, the mixture is concentrated under reduced pressure, and the mixture is washed by diethyl ether and dried to obtain the intermediate of the phenyl diphenyl phosphate of the trimellitic anhydride.
(2) 0.4 mol of the diphenyl phosphate intermediate with a phenyl trimellitate group and 0.5 mol of 2-aminopyrimidine-5-formic acid are added into a dimethyl sulfoxide solvent of 2000 mL, the temperature is raised to 100 ℃, the reaction is carried out for 24 h, deionized water and ethyl acetate are added after cooling, extraction separation is carried out, the upper ethyl acetate solution is decompressed and concentrated, and then the crude product is washed by acetone first, and then added into ethanol for recrystallization, thus obtaining the phenyl phosphate pyrimidine dicarboxylic monomer.
(3) Adding 0.4 mol of phenyl phosphate pyrimidine dicarboxylic monomer, 0.48 mol of 1, 6-hexamethylenediamine and 50 mL of distilled water into a reaction kettle, then introducing nitrogen to control the pressure of the reaction kettle to be 0.25 MPa, and heating to 80 ℃ for pre-reaction 2 h; then heating to 220 ℃ to carry out melt polymerization 4 h, discharging water vapor in the reaction kettle in the melt polymerization reaction process, and controlling the pressure of the reaction kettle to be 2.5 MPa; finally, vacuumizing to control the vacuum degree to be 0.08 MPa, heating to 260 ℃, reacting for 3 h, cooling after the reaction, and washing with ethanol, N-dimethylformamide and deionized water in sequence to obtain the phosphorus-containing polyaramid flame retardant.
(4) Adding 0.5% of phosphorus-containing polyaramid flame retardant, 0.2% of maleic anhydride grafted EVA and 99.3% of EVA resin into a double-screw extruder, controlling the melting temperature to 225 ℃, the extrusion temperature to 220 ℃, extruding and granulating, and then molding the master batch in a flat vulcanizing machine, controlling the temperature to 210 ℃ and the pressure to 10 MPa to obtain the flame-retardant EVA material.
Comparative example 3:
(1) Adding 2% of silicon dioxide aerogel, 0.5% of maleic anhydride grafted EVA and 97.5% of EVA resin into a double-screw extruder, controlling the melting temperature to 220 ℃, the extrusion temperature to 215 ℃, extruding and granulating, then molding the master batch in a vulcanizing press, controlling the temperature to 190 ℃ and the pressure to 12 MPa, and obtaining the flame-retardant EVA heat-insulating material.
The flame retardant property of EVA material is tested by a cone calorimeter, and the heat radiation intensity is 50 kW/m 2 Sample size 50 mm ×50 mm.
The heat conduction performance of the EVA material is tested by a double-heat-protection flat plate method heat conduction coefficient tester, and the test is referred to GB/T3399-1982 standard.
The tensile property of the EVA material is tested by a servo universal material testing machine, and the test is in reference to GB/T1040.1-2018 standard.
The EVA resin in examples 1-4 is added with silicon dioxide aerogel and phosphorus-containing polyaramid flame retardant, and maleic anhydride grafted EVA is added as a compatilizer, wherein the total heat release amount, the peak heat release rate and the peak smoke release rate of the EVA material are smaller and smaller as the use amount of the phosphorus-containing polyaramid flame retardant in examples 1-4 is increased, and the flame retardant performance is better, wherein the total heat release amount of the EVA material in example 4 is only 66.2 MJ/m 2 The peak heat release rate was only 204.3 kW/m 2 The peak smoke release rate was only 0.040 m 2 S; comparative example 3, in which no phosphorus-containing polyaramid flame retardant was added, had the worst flame retardancy.
The addition amount of silica aerogel in examples 1 to 4Smaller and bigger, larger and worse, wherein the EVA material of example 1 has the lowest heat conductivity coefficient of only 0.028W m- 1 K- 1 The heat preservation and insulation performance is best; comparative example 2, in which no silica aerogel was added, had the greatest thermal conductivity and the worst thermal insulation properties.
In the examples 1-4, maleic anhydride grafted EVA is added as a compatilizer, so that the influence of the silica aerogel and the phosphorus-containing polyaramid flame retardant on the mechanical properties of the EVA material is reduced, and the EVA material maintains good tensile strength. In comparative example 1, maleic anhydride grafted EVA was not added as a compatibilizer, and the EVA material had the lowest tensile strength of only 8.1MPa.
The foregoing is only the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent modifications made by the present invention or direct/indirect applications in other related technical fields are included in the scope of the present invention under the concept of the present invention.

Claims (7)

1. A preparation method of a flame-retardant EVA heat-insulating material is characterized by comprising the following steps: the flame-retardant EVA heat-insulating material comprises the following raw materials in parts by weight, 2-10% of silicon dioxide aerogel, 0.5-5% of phosphorus-containing polyaramid flame retardant, 0.2-3% of maleic anhydride grafted EVA and the balance of EVA resin; the preparation method of the flame-retardant EVA heat-insulating material comprises the following steps:
(1) Synthesizing phenol diphenyl phosphate by using terephthalquinone and diphenyl phosphate as reactants; then dissolving phenyl diphenyl phosphate and pyridine into a reaction solvent at 0-5 ℃, dropwise adding trimellitic anhydride acyl chloride, uniformly stirring, reacting at room temperature for 6-18 h, washing and drying to obtain a phenyl diphenyl phosphate intermediate of the trimellitic anhydride;
(2) Adding a diphenyl phosphate intermediate of phenyl trimellitate and 2-aminopyrimidine-5-formic acid into a dimethyl sulfoxide solvent, heating to 80-120 ℃, reacting 12-36 h, extracting, separating, washing and recrystallizing to obtain a phenyl phosphate pyrimidine dicarboxyl monomer;
(3) Adding phenyl phosphate pyrimidine dicarboxyl monomer, 1, 6-hexamethylenediamine and distilled water into a reaction kettle, then introducing nitrogen, and heating to 80-110 ℃ for pre-reaction of 1-2 h; then heating to 210-240 ℃ to perform melt polymerization for 2-4 h, and discharging water vapor in the reaction kettle in the melt polymerization reaction process; finally, vacuumizing, heating to 250-280 ℃, reacting 2-4 h, cooling after the reaction, and washing to obtain the phosphorus-containing polyaramid flame retardant;
(4) Adding the silicon dioxide aerogel, the phosphorus-containing polyaramid flame retardant, the maleic anhydride grafted EVA and the EVA resin into a double-screw extruder, extruding and granulating, and then moulding the master batch in a plate vulcanizing machine to obtain the flame-retardant EVA heat-insulating material.
2. The method for preparing the flame-retardant EVA heat-insulating material according to claim 1, wherein the method comprises the following steps: (1) The molar ratio of the diphenyl phosphate to the pyridine to the trimellitic anhydride acyl chloride is 1:1.5-2.5:1.2-1.8.
3. The method for preparing the flame-retardant EVA heat-insulating material according to claim 1, wherein the method comprises the following steps: (1) The reaction solvent comprises any one of tetrahydrofuran, ethyl acetate, acetonitrile and 1, 4-dioxane.
4. The method for preparing the flame-retardant EVA heat-insulating material according to claim 1, wherein the method comprises the following steps: (2) The molar ratio of the intermediate of the phenyl trimellitate diphenyl phosphate to the 2-aminopyrimidine-5-formic acid is 1:1.1-1.5.
5. The method for preparing the flame-retardant EVA heat-insulating material according to claim 1, wherein the method comprises the following steps: (3) The molar ratio of the phenyl phosphate pyrimidine dicarboxylic monomer to the 1, 6-hexamethylenediamine is 1:1-1.2.
6. The method for preparing the flame-retardant EVA heat-insulating material according to claim 1, wherein the method comprises the following steps: (3) Introducing nitrogen into the medium reaction kettle to control the pressure to be 0.2-0.3 MPa; the pressure of the reaction kettle is controlled to be 1.5-2.5 MPa by discharging water vapor in the melt polymerization reaction process; vacuum pumping is controlled to be 0.01-0.08 MPa.
7. The method for preparing the flame-retardant EVA heat-insulating material according to claim 1, wherein the method comprises the following steps: (4) The melting temperature of the medium double-screw extruder is controlled to be 220-230 ℃ and the extrusion temperature is controlled to be 215-225 ℃; the temperature of the vulcanizing press is controlled to be 190-210 ℃ and the pressure is controlled to be 8-12 MPa.
CN202310613785.9A 2023-05-29 2023-05-29 Flame-retardant EVA (ethylene vinyl acetate) heat-insulating material and preparation method thereof Active CN116333411B (en)

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DD130936A1 (en) * 1977-05-13 1978-05-17 Rolf Kurze PROCESS FOR THE PREPARATION OF PHOSPHORUS ACID REFERENCES
CN86101475A (en) * 1985-03-08 1987-01-21 普林斯顿大学托管委员会 The preparation and the application of pyrido [2,3-d] pyrimidine derivatives
CN103665031A (en) * 2008-12-19 2014-03-26 科莱恩金融(Bvi)有限公司 Hydrophosphorylation of phosphonous acid derivatives for flame retardants
WO2022176821A1 (en) * 2021-02-19 2022-08-25 本州化学工業株式会社 Powder of 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol bis(trimellitate anhydride)

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Publication number Priority date Publication date Assignee Title
US20130059952A1 (en) * 2010-01-15 2013-03-07 Basf Se Phospho-substituted alkoxyamine compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD130936A1 (en) * 1977-05-13 1978-05-17 Rolf Kurze PROCESS FOR THE PREPARATION OF PHOSPHORUS ACID REFERENCES
CN86101475A (en) * 1985-03-08 1987-01-21 普林斯顿大学托管委员会 The preparation and the application of pyrido [2,3-d] pyrimidine derivatives
CN103665031A (en) * 2008-12-19 2014-03-26 科莱恩金融(Bvi)有限公司 Hydrophosphorylation of phosphonous acid derivatives for flame retardants
WO2022176821A1 (en) * 2021-02-19 2022-08-25 本州化学工業株式会社 Powder of 2,2',3,3',5,5'-hexamethylbiphenyl-4,4'-diol bis(trimellitate anhydride)

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