CN106893274B - A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material - Google Patents

A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material Download PDF

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CN106893274B
CN106893274B CN201710187796.XA CN201710187796A CN106893274B CN 106893274 B CN106893274 B CN 106893274B CN 201710187796 A CN201710187796 A CN 201710187796A CN 106893274 B CN106893274 B CN 106893274B
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CN106893274A (en
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杨冰雪
于法鹏
杨志远
马庆宇
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Shandong Origin Crystal Technology Co Ltd
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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Abstract

The invention discloses a kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material; the phosphate that the present invention adds can be by catalytic dehydration into carbon in burning; heat-insulated, oxygen barrier is played a part of to the material below carbon-coating; so that the surface of polymer forms firm protection type layer of charcoal; and silicon filler, graphene are enriched with to polymer layer of charcoal table and serve certain layer of charcoal humidification in combustion; breeze has certain robustness; fine and close and complete layer of charcoal is shown, serves good fire retardant performance.

Description

A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material
Technical field
The invention belongs to Material Field, and in particular to a kind of preparation side of silicon phosphorus cooperative flame retardant graphene polymer material Method.
Background technology
Polyethylene terephthalate is milky or light yellow, highly crystalline polymer, and smooth surface is glossy. There is excellent physical and mechanical properties within the scope of wider temperature, for long-term use of temperature up to 120 DEG C, electrical insulating property is excellent, Even under high-temperature high-frequency, its electrical property is still preferable, but corona resistance is poor, creep resistance, fatigue durability, rub resistance, chi Very little stability is all fine.Polyethylene terephthalate has ester bond, can occur under strong acid, highly basic and water vapor acting point Solution, organic solvent-resistant, good weatherability, is widely used in the fields such as electronic apparatus, auto industry, particularly suitable for electrically inserting Seat, circuit breaker shell, switch, motor fan shell, vehicle window controller, foot operated speed changer, distribution board cover etc.；
But pet material belongs to the combustible material of meltbility, its application is restricted, therefore Flame-retardant modified about pet material receives much concern, and develops new fire retardant or the new fire-retardant side of research Method has turned into the focus of current research to improve the fire resistance of pet material；Then traditional mode Flame resistant method is the addition of inorganic combustion inhibitor, including magnesium hydroxide, expansible graphite, aluminium hydroxide, talcum powder etc., these are inorganic Additive is easily formed in polyurethane matrix reunites, so as to reduce the stability of finished-product material.
The content of the invention
It is an object of the invention to the poor fire for pet material and tradition are inorganic fire-retarded Additive easily forms the problem of reuniting in polyester material, there is provided a kind of system of silicon phosphorus cooperative flame retardant graphene polymer material Preparation Method.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material, it is characterised in that comprise the following steps：
（1）Graphene oxide is taken, is added in the absolute ethyl alcohol of 3-10 times of its weight, rise temperature is 40-55 DEG C, is added Expoxy propane, insulated and stirred 20-30 minutes, obtain epoxy solution；
（2）Dodecyl primary amine is taken, is added in the pentaerythrite of 3-5 times of its weight, stirs, adds above-mentioned epoxy Solution, stirring reaction 10-13 hours, the phosphate aqueous solution that concentration is 4-6% is added dropwise, it is 90-100 that temperature is raised after being added dropwise DEG C, stannous octoate is added, insulation reaction 5-7 hours, filtering, precipitation is washed, 2-3 hours are dried at 70-90 DEG C of vacuum, it is cold But, phosphotidic graphene is obtained；
（3）Sorbitan monostearate is taken, is added in the ethyl acetate of 16-18 times of its weight, stirring and dissolving, adds phosphorus Graphene is esterified, 10-20 minutes are preheated at 50-60 DEG C, obtain ester dispersion liquid；
（4）Maleic anhydride, vinylacetate mixing are taken, is added in the butyl acetate of 80-100 times of compound weight, stirs Mix uniformly, add ester dispersion liquid, stir, add catalyst, be passed through nitrogen, the insulated and stirred 4-7 hours at 70-76 DEG C, Filtering, vacuum drying 1-2 hours at 50-60 DEG C will be deposited in, normal temperature is cooled to, obtains anhydride polymer；
（5）Anhydride polymer is taken, is added in the deionized water of 100-120 times of its weight, the insulated and stirred at 60-70 DEG C 4-5 hours, filter, precipitation is washed, air drying, obtains hydrating polymer；
（6）Tetraethyl orthosilicate is taken, is added in the deionized water of 400-470 times of its weight, stirs, concentration, which is added dropwise, is 10-12% ammoniacal liquor, regulation pH are 10-12, stirring at normal temperature 2-3 hours, add the tert-butyl alcohol, rise temperature is 60-70 DEG C, insulation 1-2 hours are stirred, obtain hydroxylating Ludox；
（7）It is 2-3 to take mol ratio:1 ethylene glycol, terephthalic acid (TPA) mixing, are sent in reactor, are passed through nitrogen, rise High-temperature is 230-250 DEG C, and the pressure for controlling reactor is 0.2-0.3MPa, esterification 3-5 hours, is discharged, at 70-80 DEG C Lower drying, obtains phosphatization ester monomer；
（8）Hydrating polymer, the mixing of phosphatization ester monomer are taken, is sent in reactor, is arranged air in reactor with nitrogen Sky, rise temperature of reaction kettle are 270-300 DEG C, open agitating paddle, stirring reaction 4-6 hours, discharging is molten with above-mentioned hydroxyl SiClx Glue mixes, and stirring reaction 2-3 hours, cools down, dehydration, dries 1-2 hours at 90-100 DEG C of vacuum, obtains silicon phosphorus cooperative flame retardant graphite Alkene polymer material；
Described graphene oxide, expoxy propane, dodecyl primary amine, the phosphate aqueous solution that concentration is 4-6%, octanoic acid are sub- Tin, sorbitan monostearate, the tert-butyl alcohol, maleic anhydride, vinylacetate, azodiisobutyronitrile, tetraethyl orthosilicate, to benzene two The weight ratio of formic acid is 20-26:1-2:3-5:130-170：0.4-1:3-5:20-26：6-10:37-40:1.3-2:20-25: 300-370。
Described catalyst is azodiisobutyronitrile.
Advantages of the present invention：
The present invention using epoxidation graphene oxide and fatty amine reaction open loop, is then blended with phosphate aqueous solution first, The graphene of phosphotidic is obtained, is disperseed afterwards using ethyl acetate, is blended with maleic anhydride, using vinylacetate as monomer, enters Row polymerization, obtains anhydride polymer, then hydrolyzes the anhydride polymer, obtain carboxylated polymers, afterwards with positive silicic acid second Ester is presoma, colloidal sol hydroxylating is blended with carboxylated polymers, the polymerization for participating in polyethylene terephthalate is anti- Ying Zhong, in the course of the polymerization process, hydroxylated colloidal sol and carboxylated polymers form effective crosslinking, so as to enhance graphene, Dispersiveness of the silicon filler between polymeric matrix, effectively reduces reunion, improves the stability_intensity of finished product, and the present invention adds The phosphate entered can play a part of heat-insulated, oxygen barrier to the material below carbon-coating, make in burning by catalytic dehydration into carbon The surface for obtaining polymer forms firm protection type layer of charcoal, and silicon filler, graphene are in combustion to polymer layer of charcoal table And be enriched with and serve certain layer of charcoal humidification, breeze has certain robustness, shows fine and close and complete layer of charcoal, Serve good fire retardant performance.
Embodiment
Embodiment 1
A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material, comprises the following steps：
（1）Graphene oxide is taken, is added in the absolute ethyl alcohol of 10 times of its weight, rise temperature is 55 DEG C, adds epoxy Propane, insulated and stirred 30 minutes, obtains epoxy solution；
（2）Dodecyl primary amine is taken, is added in the pentaerythrite of 5 times of its weight, stirs, it is molten to add above-mentioned epoxy The phosphate aqueous solution that concentration is 6% is added dropwise in liquid, stirring reaction 13 hours, and it is 100 DEG C that temperature is raised after being added dropwise, and adds octanoic acid Stannous, insulation reaction 7 hours, filtering, precipitation is washed, dried 3 hours at 90 DEG C of vacuum, cooling, obtain phosphotidic graphene；
（3）Sorbitan monostearate is taken, is added in the ethyl acetate of 18 times of its weight, stirring and dissolving, adds phosphide Graphite alkene, preheated 20 minutes at 60 DEG C, obtain ester dispersion liquid；
（4）Maleic anhydride, vinylacetate mixing are taken, is added in the butyl acetate of 100 times of compound weight, stirring is equal It is even, ester dispersion liquid is added, is stirred, azodiisobutyronitrile is added, is passed through nitrogen, insulated and stirred 7 hours, mistake at 76 DEG C Filter, will be deposited at 60 DEG C and is dried in vacuo 2 hours, be cooled to normal temperature, obtain anhydride polymer；
（5）Anhydride polymer is taken, is added in the deionized water of 120 times of its weight, insulated and stirred 5 hours at 70 DEG C, Filter, precipitation is washed, air drying, obtains hydrating polymer；
（6）Tetraethyl orthosilicate is taken, is added in the deionized water of 470 times of its weight, stirs, it is 12% that concentration, which is added dropwise, Ammoniacal liquor, regulation pH be 12, stirring at normal temperature 3 hours, add the tert-butyl alcohol, rise temperature be 70 DEG C, insulated and stirred 2 hours, obtain hydroxyl Base SiClx colloidal sol；
（7）It is 3 to take mol ratio:1 ethylene glycol, terephthalic acid (TPA) mixing, are sent in reactor, are passed through nitrogen, raise Temperature is 250 DEG C, and the pressure for controlling reactor is 0.3MPa, esterification 5 hours, discharging, is dried at 80 DEG C, obtains phosphatization ester Monomer；
（8）Hydrating polymer, the mixing of phosphatization ester monomer are taken, is sent in reactor, is arranged air in reactor with nitrogen Sky, rise temperature of reaction kettle are 300 DEG C, open agitating paddle, stirring reaction 6 hours, discharging, are mixed with above-mentioned hydroxylating Ludox Close, stirring reaction 3 hours, cool down, be dehydrated, dried 2 hours at 90-100 DEG C of vacuum, obtain silicon phosphorus cooperative flame retardant graphene polymer Material；
Described graphene oxide, expoxy propane, dodecyl primary amine, the phosphate aqueous solution that concentration is 6%, stannous octoate, Sorbitan monostearate, the tert-butyl alcohol, maleic anhydride, vinylacetate, azodiisobutyronitrile, tetraethyl orthosilicate, terephthaldehyde The weight ratio of acid is 26:2:3: 170：0.4-1:3-5:26：10:40:2: 25:370.
Embodiment 2
A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material, comprises the following steps：
（1）Graphene oxide is taken, is added in the absolute ethyl alcohol of 3 times of its weight, rise temperature is 40-55 DEG C, adds ring Ethylene Oxide, insulated and stirred 20 minutes, obtains epoxy solution；
（2）Dodecyl primary amine is taken, is added in the pentaerythrite of 3 times of its weight, stirs, it is molten to add above-mentioned epoxy The phosphate aqueous solution that concentration is 4% is added dropwise in liquid, stirring reaction 10 hours, and it is 90 DEG C that temperature is raised after being added dropwise, and adds octanoic acid Stannous, insulation reaction 5 hours, filtering, precipitation is washed, dried 2 hours at 70 DEG C of vacuum, cooling, obtain phosphotidic graphene；
（3）Sorbitan monostearate is taken, is added in the ethyl acetate of 16 times of its weight, stirring and dissolving, adds phosphide Graphite alkene, preheated 10 minutes at 50 DEG C, obtain ester dispersion liquid；
（4）Maleic anhydride, vinylacetate mixing are taken, is added in the butyl acetate of 80 times of compound weight, stirring is equal It is even, ester dispersion liquid is added, is stirred, azodiisobutyronitrile is added, is passed through nitrogen, insulated and stirred 4 hours, mistake at 70 DEG C Filter, will be deposited at 50 DEG C and is dried in vacuo 1 hour, be cooled to normal temperature, obtain anhydride polymer；
（5）Anhydride polymer is taken, is added in the deionized water of 100 times of its weight, insulated and stirred 4 hours at 60 DEG C, Filter, precipitation is washed, air drying, obtains hydrating polymer；
（6）Tetraethyl orthosilicate is taken, is added in the deionized water of 400 times of its weight, stirs, it is 10% that concentration, which is added dropwise, Ammoniacal liquor, regulation pH be 10, stirring at normal temperature 2 hours, add the tert-butyl alcohol, rise temperature be 60 DEG C, insulated and stirred 1 hour, obtain hydroxyl Base SiClx colloidal sol；
（7）It is 2 to take mol ratio:1 ethylene glycol, terephthalic acid (TPA) mixing, are sent in reactor, are passed through nitrogen, raise Temperature is 230 DEG C, and the pressure for controlling reactor is 0.2MPa, esterification 3 hours, discharging, is dried at 70 DEG C, obtains phosphatization ester Monomer；
（8）Hydrating polymer, the mixing of phosphatization ester monomer are taken, is sent in reactor, is arranged air in reactor with nitrogen Sky, rise temperature of reaction kettle are 270 DEG C, open agitating paddle, stirring reaction 4 hours, discharging, are mixed with above-mentioned hydroxylating Ludox Close, stirring reaction 2- hours, cool down, be dehydrated, dried 1 hour at 90 DEG C of vacuum, obtain silicon phosphorus cooperative flame retardant graphene polymer material Material；
Described graphene oxide, expoxy propane, dodecyl primary amine, the phosphate aqueous solution that concentration is 4%, stannous octoate, Sorbitan monostearate, the tert-butyl alcohol, maleic anhydride, vinylacetate, azodiisobutyronitrile, tetraethyl orthosilicate, terephthaldehyde The weight ratio of acid is 20:1:3:130：0.4:3:20：6:37:1.3:20:300.
Embodiment 3
A kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material, comprises the following steps：
（1）Graphene oxide is taken, is added in the absolute ethyl alcohol of 5 times of its weight, rise temperature is 40-55 DEG C, adds ring Ethylene Oxide, insulated and stirred 25 minutes, obtains epoxy solution；
（2）Dodecyl primary amine is taken, is added in the pentaerythrite of 3 times of its weight, stirs, it is molten to add above-mentioned epoxy The phosphate aqueous solution that concentration is 4% is added dropwise in liquid, stirring reaction 12 hours, and it is 95 DEG C that temperature is raised after being added dropwise, and adds octanoic acid Stannous, insulation reaction 5 hours, filtering, precipitation is washed, dried 2 hours at 75 DEG C of vacuum, cooling, obtain phosphotidic graphene；
（3）Sorbitan monostearate is taken, is added in the ethyl acetate of 16 times of its weight, stirring and dissolving, adds phosphide Graphite alkene, preheated 15 minutes at 55 DEG C, obtain ester dispersion liquid；
（4）Maleic anhydride, vinylacetate mixing are taken, is added in the butyl acetate of 84 times of compound weight, stirring is equal It is even, ester dispersion liquid is added, is stirred, azodiisobutyronitrile is added, is passed through nitrogen, insulated and stirred 4 hours, mistake at 74 DEG C Filter, will be deposited at 54 DEG C and is dried in vacuo 1 hour, be cooled to normal temperature, obtain anhydride polymer；
（5）Anhydride polymer is taken, is added in the deionized water of 104 times of its weight, insulated and stirred 4 hours at 64 DEG C, Filter, precipitation is washed, air drying, obtains hydrating polymer；
（6）Tetraethyl orthosilicate is taken, is added in the deionized water of 404 times of its weight, stirs, it is 10% that concentration, which is added dropwise, Ammoniacal liquor, regulation pH be 10, stirring at normal temperature 2 hours, add the tert-butyl alcohol, rise temperature be 66 DEG C, insulated and stirred 1 hour, obtain hydroxyl Base SiClx colloidal sol；
（7）It is 2 to take mol ratio:1 ethylene glycol, terephthalic acid (TPA) mixing, are sent in reactor, are passed through nitrogen, raise Temperature is 230 DEG C, and the pressure for controlling reactor is 0.2MPa, esterification 3-5 hours, discharging, is dried at 77 DEG C, obtains phosphatization Ester monomer；
（8）Hydrating polymer, the mixing of phosphatization ester monomer are taken, is sent in reactor, is arranged air in reactor with nitrogen Sky, rise temperature of reaction kettle are 277 DEG C, open agitating paddle, stirring reaction 4- hours, discharging, are mixed with above-mentioned hydroxylating Ludox Close, stirring reaction 2 hours, cool down, be dehydrated, dried 1 hour at 90 DEG C of vacuum, obtain silicon phosphorus cooperative flame retardant graphene polymer material Material；
Described graphene oxide, expoxy propane, dodecyl primary amine, the phosphate aqueous solution that concentration is 4%, stannous octoate, Sorbitan monostearate, the tert-butyl alcohol, maleic anhydride, vinylacetate, azodiisobutyronitrile, tetraethyl orthosilicate, terephthaldehyde The weight ratio of acid is 24:1:3:130：0.7:3-5:23：6:37:1.3:20:307.
Performance test：
To traditional pet material and the silicon phosphorus cooperative flame retardant graphene polymer material of the present invention Carry out tapered calorimeter test and oxygen index (OI) experiment；
Tapered calorimeter test result is：
Total Heat liberation unit of traditional pet material is 34.6MJ/m2, maximum HRR For 607.5KW/m2, and total Heat liberation unit of the silicon phosphorus cooperative flame retardant graphene polymer material of the present invention is 38.9MJ/m2, Maximum HRR is 205.1KW/m2；
Oxygen index (OI) experimental result is：
The oxygen index (OI) of traditional pet material is 21.7%, and the silicon phosphorus cooperative flame retardant stone of the present invention The oxygen index (OI) of black alkene polymer material is 29.9%；
As can be seen that silicon phosphorus cooperative flame retardant graphene polymer material of the present invention has good fire resistance.

Claims (2)

1. a kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material, it is characterised in that comprise the following steps：
（1）Graphene oxide is taken, is added in the absolute ethyl alcohol of 3-10 times of its weight, rise temperature is 40-55 DEG C, adds epoxy Propane, insulated and stirred 20-30 minutes, obtain epoxy solution；
（2）Dodecyl primary amine is taken, is added in the pentaerythrite of 3-5 times of its weight, stirs, it is molten to add above-mentioned epoxy Liquid, stirring reaction 10-13 hours, the phosphate aqueous solution that concentration is 4-6% is added dropwise, it is 90-100 DEG C that temperature is raised after being added dropwise, Stannous octoate is added, insulation reaction 5-7 hours, filtering, precipitation is washed, 2-3 hours are dried at 70-90 DEG C of vacuum, cooling, are obtained Phosphotidic graphene；
（3）Sorbitan monostearate is taken, is added in the ethyl acetate of 16-18 times of its weight, stirring and dissolving, adds phosphotidic Graphene, 10-20 minutes are preheated at 50-60 DEG C, obtain ester dispersion liquid；
（4）Maleic anhydride, vinylacetate mixing are taken, is added in the butyl acetate of 80-100 times of compound weight, stirring is equal It is even, ester dispersion liquid is added, is stirred, catalyst is added, is passed through nitrogen, the insulated and stirred 4-7 hours at 70-76 DEG C, filtering, Vacuum drying 1-2 hours at 50-60 DEG C will be deposited in, normal temperature is cooled to, obtains anhydride polymer；
（5）Anhydride polymer is taken, is added in the deionized water of 100-120 times of its weight, the insulated and stirred 4-5 at 60-70 DEG C Hour, filter, precipitation is washed, air drying, obtains hydrating polymer；
（6）Tetraethyl orthosilicate is taken, is added in the deionized water of 400-470 times of its weight, stirs, dropwise addition concentration is 10- 12% ammoniacal liquor, regulation pH are 10-12, stirring at normal temperature 2-3 hours, add the tert-butyl alcohol, rise temperature is 60-70 DEG C, insulated and stirred 1-2 hours, obtain hydroxylating Ludox；
（7）It is 2-3 to take mol ratio:1 ethylene glycol, terephthalic acid (TPA) mixing, are sent in reactor, are passed through nitrogen, rise temperature Spend that for 230-250 DEG C, to control the pressure of reactor be 0.2-0.3MPa, esterification 3-5 hours, discharging, dried at 70-80 DEG C It is dry, obtain phosphatization ester monomer；
（8）Hydrating polymer, the mixing of phosphatization ester monomer are taken, is sent in reactor, is emptied air in reactor with nitrogen, rise High temperature of reaction kettle is 270-300 DEG C, opens agitating paddle, stirring reaction 4-6 hours, discharging, is mixed with above-mentioned hydroxylating Ludox Close, stirring reaction 2-3 hours, cool down, be dehydrated, 1-2 hours are dried at 90-100 DEG C of vacuum, silicon phosphorus cooperative flame retardant graphene is obtained and gathers Compound material；
The phosphate aqueous solution, stannous octoate, mountain that described graphene oxide, expoxy propane, dodecyl primary amine, concentration are 4-6% The smooth monostearate of pears, the tert-butyl alcohol, maleic anhydride, vinylacetate, azodiisobutyronitrile, tetraethyl orthosilicate, terephthalic acid (TPA) Weight ratio be 20-26:1-2:3-5:130-170：0.4-1:3-5:20-26：6-10:37-40:1.3-2:20-25:300- 370。
2. a kind of preparation method of silicon phosphorus cooperative flame retardant graphene polymer material according to claim 1, its feature exist In described catalyst is azodiisobutyronitrile.
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CN108752727B (en) * 2018-06-14 2020-07-14 北京理工大学 Method for modifying flame-retardant ethylene-vinyl acetate copolymer by sol-gel method
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