CN101497741A - Phosphine copolyamide / nano montmorillonite flame-retardant composite material and preparation thereof - Google Patents
Phosphine copolyamide / nano montmorillonite flame-retardant composite material and preparation thereof Download PDFInfo
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Abstract
The invention relates to phosphoric copolyamide/nano-meter montmorillonite flame-retardant composite material and a method for preparing the same. The invention mainly aims at solving the technical problems that the prior flame-retardant polyamide uses more inorganic flame retardant, is easy to precipitate and has poor flame-retardant effect and low mechanical property, and the halogenated flame retardant polyamide is easy to pollute the environment during combustion. The organic montmorillonite is dispersed in the form of nano-particles in phosphoric copolyamide formed by the polymerization of phosphoric prepolymer and nylon 66 salt. The method for preparing the phosphoric copolyamide/nano-meter montmorillonite flame-retardant composite material comprises the steps of preparing the solution of ethanol in hexamethylene diamine, preparing the nylon 66 salt, preparing the phosphoric prepolymer and preparing the phosphoric copolyamide/nano-meter montmorillonite flame-retardant composite material. The phosphoric copolyamide/nano-meter montmorillonite flame-retardant composite material needs less flame retardant, has high flame-retardant efficiency and high mechanical property and causes no poisonous and harmful gas during combustion to pollute the environment.
Description
Technical field
The present invention relates to a kind of phosphine copolyamide/nano montmorillonite flame-retardant composite material and preparation method thereof, it belongs to a kind of main chain and contains the copolyamide of aryl oxidized phosphine and flame-proof composite material of nano imvite and preparation method thereof.
Background technology
Polyamide (PA), be commonly called as nylon, it is the macromolecular compound that contains amide group on the main chain, have that fusing point height, intensity are big, wear-resisting, overall merits such as oil resistant and common organic solvents, be widely used in and make tricot, tire cord, filter cloth, rope, fishnet, trolley part, mechanical part, wrapping material etc.But as the nylon of macromolecular material, have relative inflammableness, limited the application of nylon at special dimensions such as aerospace, electronic apparatuss.Business-like fire-retardant nylon mainly is to realize by interpolation inorganic combustion inhibitor or halogenated flame retardant in nylon.But inorganic combustion inhibitor is a cost with the mechanical property of sacrificing nylon usually, exists poisonous, obnoxious flavour to discharge and problem of environmental pollution during the burning of halogen flame retardant nylon.For addressing the above problem, people work out a kind of preparation method as the disclosed nylon/montmorillonoid fire retarding composite material of CN1948396, flame-proof composite material with this method production, though its limiting oxygen index(LOI) is greatly improved, but its fire-retardant mode is single, still exists the defective of fire-retardant persistence weak effect.
Summary of the invention
The objective of the invention is to solve inorganic combustion inhibitor consumption that existing Flameproof polyamide exists greatly, easily move out, flame retardant effect is poor, the polymeric amide mechanical property is low and halogen easily causes the technological difficulties of environmental pollution when being the Flameproof polyamide burning, and provide that a kind of low fire retardant consumption is few, flame retardant effect is lasting, mechanical property is high and do not cause phosphine copolyamide/nano montmorillonite flame-retardant composite material of environmental pollution and preparation method thereof during burning.
The present invention solves the problems of the technologies described above the technical scheme that adopts to be: phosphine copolyamide/nano montmorillonite flame-retardant composite material, its weight part are that 1～10 part organo montmorillonite is scattered in by weight part with nanoparticle is that 5～15 parts contain phosphine prepolymer and weight part is in the phosphine copolyamide that aggregates into of 75～94 parts nylon salt.
The polymerizable molecular structure formation of described phosphine copolyamide is
x＝1-100；y＝1-100。
The intrinsic viscosity of described phosphine copolyamide is between 1.2～2.5; The fusing point of described phosphine copolyamide is between 210～270 ℃.
A kind of preparation method who produces phosphine copolyamide/nano montmorillonite flame-retardant composite material, it comprises the following steps:
A) preparation hexanediamine ethanolic soln: with weight part is that to be dissolved in weight part be to make the hexanediamine ethanolic soln in 50 parts the ethanol for 50 parts hexanodioic acid;
B) preparation nylon salt: with weight part be 54～57 parts hexanodioic acid to be dissolved in weight part be in 50 parts the ethanol, be warmed up to 60～70 ℃ after, add weight part and be 43～46 parts hexanediamine ethanolic soln; In thermostat water bath, keep 70～80 ℃ of reactions of water temperature, 2～3h, cool off then, filter, obtain nylon salt through washing with alcohol;
C) preparation contains the phosphine prepolymer: with weight part is that 77～83 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 17～23 parts hexanediamine is dissolved in the dehydrated alcohol, in thermostat water bath, keep 70 ℃ of reactions of water temperature, 3～4h, cooling then, filter, obtain containing the phosphine prepolymer or be that 77～83 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 17～23 parts hexanediamine is dissolved in N ' the N-dimethylformamide with weight part through absolute ethanol washing, in thermostat water bath, keep 50 ℃ of reactions of water temperature, 3～4h, cooling then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing;
D) preparation phosphine copolyamide/nano montmorillonite flame-retardant composite material: with weight part be 5～15 parts contain the phosphine prepolymer, weight part is that the nylon salt that 1～10 part organic montmorillonite nano particle and weight part are 75～94 parts is mixed into mixture, add weight part then and be 30～50 parts deionized water, regulate between pH value to 7.3～7.7, then above-mentioned aqueous mixture is put into the stirring-type reactor, emptying gas 4～5 times, be heated to 220～250 ℃ to reactor is airtight, under spontaneous pressure to reactant heat-insulation pressure keeping 0.5～2h, slowly be decompressed to environmental stress then, be heated to 250～280 ℃ of further reaction 1～2h simultaneously, vacuumize 0.5～1h at last, reaction is finished, and replenishes nitrogen or rare gas element when discharging.
The oxygen index of described flame-proof composite material is between 27～32; The fire-retardant rank of flame-proof composite material is the UL94V-0 level.
Because in the technical solution used in the present invention, it is reactive flame retardant that two (right-carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire retardant that uses belong to organic phosphine, can introduce in the nylon molecular backbone, therefore by the mode of copolycondensation, compare with background technology, have following advantage:
1, flame-proof composite material fire retardant consumption of the present invention is few, flame retarding efficiency is high, mechanical property is high, does not produce poisonous, obnoxious flavour after the burning, and is free from environmental pollution.
2, flame-proof composite material of the present invention has kept the original mechanical property of nylon, has increased the safety in utilization of nylon, has enlarged the use range of nylon.
3, preparation technology of the present invention is easy, can utilize the polymeric kettle polymerization fully, is convenient to produce, and can easily realize industrialization.
4, can add oxidation inhibitor, coupling agent etc. in the preparation process of the present invention, make the performance of flame-proof composite material become more excellent.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1
Phosphine copolyamide/nano montmorillonite flame-retardant composite material in the present embodiment, its weight part are that 10 parts organo montmorillonite is scattered in by weight part with nanoparticle is that 15 parts contain phosphine prepolymer and weight part is in the phosphine copolyamide that aggregates into of 75 parts nylon salt.
The polymerizable molecular structure formation of above-mentioned phosphine copolyamide is
x＝1-100；y＝1-100。
The intrinsic viscosity of above-mentioned phosphine copolyamide is between 1.2～2.5; The fusing point of above-mentioned phosphine copolyamide is between 210～270 ℃.
Produce the preparation method of above-mentioned phosphine copolyamide/nano montmorillonite flame-retardant composite material, it comprises the following steps:
A) preparation hexanediamine ethanolic soln: with weight part is that to be dissolved in weight part be to make the hexanediamine ethanolic soln in 50 parts the ethanol for 50 parts hexanodioic acid;
B) preparation nylon salt: with weight part be 54 parts hexanodioic acid to be dissolved in weight part be in 50 parts the ethanol, be warmed up to 60～70 ℃ after, add weight part and be 46 parts hexanediamine ethanolic soln; In thermostat water bath, keep 70～80 ℃ of reactions of water temperature, 2～3h, cool off then, filter, obtain nylon salt through washing with alcohol;
C) preparation contains the phosphine prepolymer: with weight part is that 77 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 23 parts hexanediamine is dissolved in the dehydrated alcohol, in thermostat water bath, keep 70 ℃ of reactions of water temperature, 3～4h, cool off then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing; Its reaction equation is as follows:
D) preparation phosphine copolyamide/nano montmorillonite flame-retardant composite material: with weight part be 15 parts contain the phosphine prepolymer, weight part is that the nylon salt that 10 parts organic montmorillonite nano particle and weight part are 75 parts is mixed into mixture, add weight part then and be 50 parts deionized water, regulate between pH value to 7.3～7.7, then above-mentioned aqueous mixture is put into the stirring-type reactor, emptying gas 4～5 times, be heated to 220～250 ℃ to reactor is airtight, under spontaneous pressure to reactant heat-insulation pressure keeping 0.5～2h, slowly be decompressed to environmental stress then, be heated to 250～280 ℃ of further reaction 1～2h simultaneously, vacuumize 0.5～1h at last, reaction is finished, and replenishes nitrogen or rare gas element when discharging.Its reaction equation is as follows:
The oxygen index of the flame-proof composite material for preparing in the foregoing description is between 27～32; The fire-retardant rank of flame-proof composite material is a UL94 V-0 level.
Embodiment 2
Phosphine copolyamide/nano montmorillonite flame-retardant composite material in the present embodiment, its weight part are that 7 parts organo montmorillonite is scattered in by weight part with nanoparticle is that 7 parts contain phosphine prepolymer and weight part is in the phosphine copolyamide that aggregates into of 86 parts nylon salt.
The polymerizable molecular structure formation of above-mentioned phosphine copolyamide is
x＝1-100；y＝1-100。
The intrinsic viscosity of above-mentioned phosphine copolyamide is between 1.2～2.5; The fusing point of above-mentioned phosphine copolyamide is between 210～270 ℃.
Produce the preparation method of above-mentioned phosphine copolyamide/nano montmorillonite flame-retardant composite material, it comprises the following steps:
A) preparation hexanediamine ethanolic soln: with weight part is that to be dissolved in weight part be to make the hexanediamine ethanolic soln in 50 parts the ethanol for 50 parts hexanodioic acid;
B) preparation nylon salt: with weight part be 55 parts hexanodioic acid to be dissolved in weight part be in 50 parts the ethanol, be warmed up to 60～70 ℃ after, add weight part and be 45 parts hexanediamine ethanolic soln; In thermostat water bath, keep 70～80 ℃ of reactions of water temperature, 2～3h, cool off then, filter, obtain nylon salt through washing with alcohol;
C) preparation contains the phosphine prepolymer: with weight part is that 79 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 21 parts hexanediamine is dissolved in the dehydrated alcohol, in thermostat water bath, keep 70 ℃ of reactions of water temperature, 3～4h, cool off then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing; Its reaction equation is as follows:
D) preparation phosphine copolyamide/nano montmorillonite flame-retardant composite material: with weight part be 7 parts contain the phosphine prepolymer, weight part is that the nylon salt that 7 parts organic montmorillonite nano particle and weight part are 86 parts is mixed into mixture, add weight part then and be 30 parts deionized water, regulate between pH value to 7.3～7.7, then above-mentioned aqueous mixture is put into the stirring-type reactor, emptying gas 4～5 times, be heated to 220～250 ℃ to reactor is airtight, under spontaneous pressure to reactant heat-insulation pressure keeping 0.5～2h, slowly be decompressed to environmental stress then, be heated to 250～280 ℃ of further reaction 1～2h simultaneously, vacuumize 0.5～1h at last, reaction is finished, and replenishes nitrogen or rare gas element when discharging.Its reaction equation is as follows:
The oxygen index of the flame-proof composite material for preparing in the foregoing description is between 27～32; The fire-retardant rank of flame-proof composite material is the UL94V-0 level.
Embodiment 3
Phosphine copolyamide/nano montmorillonite flame-retardant composite material in the present embodiment, its weight part are that 5 parts organo montmorillonite is scattered in by weight part with nanoparticle is that 10 parts contain phosphine prepolymer and weight part is in the phosphine copolyamide that aggregates into of 85 parts nylon salt.
The polymerizable molecular structure formation of above-mentioned phosphine copolyamide is
x＝1-100；y＝1-100。
The intrinsic viscosity of above-mentioned phosphine copolyamide is between 1.2～2.5; The fusing point of above-mentioned phosphine copolyamide is between 210～270 ℃.
Produce the preparation method of above-mentioned phosphine copolyamide/nano montmorillonite flame-retardant composite material, it comprises the following steps:
A) preparation hexanediamine ethanolic soln: with weight part is that to be dissolved in weight part be to make the hexanediamine ethanolic soln in 50 parts the ethanol for 50 parts hexanodioic acid;
B) preparation nylon salt: with weight part be 56 parts hexanodioic acid to be dissolved in weight part be in 50 parts the ethanol, be warmed up to 60～70 ℃ after, add weight part and be 44 parts hexanediamine ethanolic soln; In thermostat water bath, keep 70～80 ℃ of reactions of water temperature, 2～3h, cool off then, filter, obtain nylon salt through washing with alcohol;
C) preparation contains the phosphine prepolymer: with weight part is that 81 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 19 parts hexanediamine is dissolved in the dehydrated alcohol, in thermostat water bath, keep 70 ℃ of reactions of water temperature, 3～4h, cool off then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing; Its reaction equation is as follows:
D) preparation phosphine copolyamide/nano montmorillonite flame-retardant composite material: with weight part be 10 parts contain the phosphine prepolymer, weight part is that the nylon salt that 5 parts organic montmorillonite nano particle and weight part are 85 parts is mixed into mixture, add weight part then and be 40 parts deionized water, regulate between pH value to 7.3～7.7, then above-mentioned aqueous mixture is put into the stirring-type reactor, emptying gas 4～5 times, be heated to 220～250 ℃ to reactor is airtight, under spontaneous pressure to reactant heat-insulation pressure keeping 0.5～2h, slowly be decompressed to environmental stress then, be heated to 250～280 ℃ of further reaction 1～2h simultaneously, vacuumize 0.5～1h at last, reaction is finished, and replenishes nitrogen or rare gas element when discharging.Its reaction equation is as follows:
The oxygen index of the flame-proof composite material for preparing in the foregoing description is between 27～32; The fire-retardant rank of flame-proof composite material is a UL94 V-0 level.
Embodiment 4
Phosphine copolyamide/nano montmorillonite flame-retardant composite material, its weight part are that 3 parts organo montmorillonite is scattered in by weight part with nanoparticle is that 13 parts contain phosphine prepolymer and weight part is in the phosphine copolyamide that aggregates into of 84 parts nylon salt.
The polymerizable molecular structure formation of above-mentioned phosphine copolyamide is
x＝1-100；y＝1-100。
The intrinsic viscosity of above-mentioned phosphine copolyamide is between 1.2～2.5; The fusing point of above-mentioned phosphine copolyamide is between 210～270 ℃.
Produce the preparation method of above-mentioned phosphine copolyamide/nano montmorillonite flame-retardant composite material, it comprises the following steps:
A) preparation hexanediamine ethanolic soln: with weight part is that to be dissolved in weight part be to make the hexanediamine ethanolic soln in 50 parts the ethanol for 50 parts hexanodioic acid;
B) preparation nylon salt: with weight part be 57 parts hexanodioic acid to be dissolved in weight part be in 50 parts the ethanol, be warmed up to 60～70 ℃ after, add weight part and be 43 parts hexanediamine ethanolic soln; In thermostat water bath, keep 70～80 ℃ of reactions of water temperature, 2～3h, cool off then, filter, obtain nylon salt through washing with alcohol;
C) preparation contains the phosphine prepolymer: with weight part is that 83 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 17 parts hexanediamine is dissolved in the dehydrated alcohol, in thermostat water bath, keep 70 ℃ of reactions of water temperature, 3～4h, cool off then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing; Its reaction equation is as follows:
D) preparation phosphine copolyamide/nano montmorillonite flame-retardant composite material: with weight part be 13 parts contain the phosphine prepolymer, weight part is that the nylon salt that 3 parts organic montmorillonite nano particle and weight part are 84 parts is mixed into mixture, add weight part then and be 45 parts deionized water, regulate between pH value to 7.3～7.7, then above-mentioned aqueous mixture is put into the stirring-type reactor, emptying gas 4～5 times, be heated to 220～250 ℃ to reactor is airtight, under spontaneous pressure to reactant heat-insulation pressure keeping 0.5～2h, slowly be decompressed to environmental stress then, be heated to 250～280 ℃ of further reaction 1～2h simultaneously, vacuumize 0.5～1h at last, reaction is finished, and replenishes nitrogen or rare gas element when discharging.Its reaction equation is as follows:
The oxygen index of the flame-proof composite material for preparing in the foregoing description is between 27～32; The fire-retardant rank of flame-proof composite material is a UL94 V-0 level.
Embodiment 5
Phosphine copolyamide/nano montmorillonite flame-retardant composite material in the present embodiment, its weight part are that 1 part organo montmorillonite is scattered in by weight part with nanoparticle is that 5 parts contain phosphine prepolymer and weight part is in the phosphine copolyamide that aggregates into of 94 parts nylon salt.
The polymerizable molecular structure formation of above-mentioned phosphine copolyamide is
x＝1-100；y＝1-100。
The intrinsic viscosity of above-mentioned phosphine copolyamide is between 1.2～2.5; The fusing point of above-mentioned phosphine copolyamide is between 210～270 ℃.
Produce the preparation method of above-mentioned phosphine copolyamide/nano montmorillonite flame-retardant composite material, it comprises the following steps:
A) preparation hexanediamine ethanolic soln: with weight part is that to be dissolved in weight part be to make the hexanediamine ethanolic soln in 50 parts the ethanol for 50 parts hexanodioic acid;
B) preparation nylon salt: with weight part be 57 parts hexanodioic acid to be dissolved in weight part be in 50 parts the ethanol, be warmed up to 60～70 ℃ after, add weight part and be 43 parts hexanediamine ethanolic soln; In thermostat water bath, keep 70～80 ℃ of reactions of water temperature, 2～3h, cool off then, filter, obtain nylon salt through washing with alcohol;
C) preparation contains the phosphine prepolymer: with weight part is that 83 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 17 parts hexanediamine is dissolved in the dehydrated alcohol, in thermostat water bath, keep 70 ℃ of reactions of water temperature, 3～4h, cool off then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing; Its reaction equation is as follows:
D) preparation phosphine copolyamide/nano montmorillonite flame-retardant composite material: with weight part be 5 parts contain the phosphine prepolymer, weight part is that the nylon salt that 1 part organic montmorillonite nano particle and weight part are 94 parts is mixed into mixture, add weight part then and be 45 parts deionized water, regulate between pH value to 7.3～7.7, then above-mentioned aqueous mixture is put into the stirring-type reactor, emptying gas 4～5 times, be heated to 220～250 ℃ to reactor is airtight, under spontaneous pressure to reactant heat-insulation pressure keeping 0.5～2h, slowly be decompressed to environmental stress then, be heated to 250～280 ℃ of further reaction 1～2h simultaneously, vacuumize 0.5～1h at last, reaction is finished, and replenishes nitrogen or rare gas element when discharging.Identical among its reaction equation and the embodiment 4.
The oxygen index of the flame-proof composite material for preparing in the foregoing description is between 27～32; The fire-retardant rank of flame-proof composite material is a UL94 V-0 level.
The c of preparation method in the foregoing description 1～5) the preparation step that contains the phosphine prepolymer can also replace with the following step: with weight part is that 77～83 parts contain two (to the carboxyphenyl) phenyl phosphine oxides (BCPPO) of the fire-retardant monomer altogether of phosphine reaction type and weight part is that 17～23 parts hexanediamine is dissolved in N ' the N-dimethylformamide, in thermostat water bath, keep 50 ℃ of reactions of water temperature, 3～4h, cool off then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing.
In order to investigate the prepared phosphine copolyamide/nano montmorillonite flame-retardant composite material mechanical property of the present invention and the effect of flame retardant resistance, to the prepared phosphine copolyamide/nano montmorillonite flame-retardant composite material of the foregoing description, carried out tensile strength, carried out notched Izod impact strength, carried out limiting oxygen index(LOI), carried out the vertical combustion test by ASTM D3801 standard by the GB/T2406-1993 standard by the GB/T1843-1996 standard by the GB/T1040-2006 standard respectively with pure nylon 66, test result sees the following form respectively.
Claims (5)
1, a kind of phosphine copolyamide/nano montmorillonite flame-retardant composite material is characterized in that: weight part is that 1～10 part organo montmorillonite is scattered in by weight part with nanoparticle is that 5～15 parts contain phosphine prepolymer and weight part is in the phosphine copolyamide that aggregates into of 75～94 parts nylon salt.
2, phosphine copolyamide/nano montmorillonite flame-retardant composite material according to claim 1 is characterized in that: the polymerizable molecular structure formation of described phosphine copolyamide is
x＝1-100；y＝1-100。
3, phosphine copolyamide/nano montmorillonite flame-retardant composite material according to claim 1 and 2 is characterized in that: the intrinsic viscosity of described phosphine copolyamide is between 1.2～2.5; The fusing point of described phosphine copolyamide is between 210～270 ℃.
4, a kind of preparation method who produces phosphine copolyamide/nano montmorillonite flame-retardant composite material is characterized in that: comprise the following steps:
A) preparation hexanediamine ethanolic soln: with weight part is that to be dissolved in weight part be to make the hexanediamine ethanolic soln in 50 parts the ethanol for 50 parts hexanodioic acid;
B) preparation nylon salt: with weight part be 54～57 parts hexanodioic acid to be dissolved in weight part be in 50 parts the ethanol, be warmed up to 60～70 ℃ after, add weight part and be 43～46 parts hexanediamine ethanolic soln; In thermostat water bath, keep 70～80 ℃ of reactions of water temperature, 2～3h, cool off then, filter, obtain nylon salt through washing with alcohol;
C) preparation contains the phosphine prepolymer: with weight part is that 77～83 parts contain phosphine reaction type two (to the carboxyphenyl) phenyl phosphine oxides of fire-retardant monomer altogether and weight part is that 17～23 parts hexanediamine is dissolved in the dehydrated alcohol, in thermostat water bath, keep 70 ℃ of reactions of water temperature, 3～4h, cooling then, filter, obtain containing the phosphine prepolymer or be that 77～83 parts contain phosphine reaction type two (to the carboxyphenyl) phenyl phosphine oxides of fire-retardant monomer altogether and weight part is that 17～23 parts hexanediamine is dissolved in N ' the N-dimethylformamide with weight part through absolute ethanol washing, in thermostat water bath, keep 50 ℃ of reactions of water temperature, 3～4h, cooling then, filter, obtain containing the phosphine prepolymer through absolute ethanol washing;
D) preparation phosphine copolyamide/nano montmorillonite flame-retardant composite material: with weight part be 5～15 parts contain the phosphine prepolymer, weight part is that the nylon salt that 1～10 part organic montmorillonite nano particle and weight part are 75～94 parts is mixed into mixture, add weight part then and be 30～50 parts deionized water, regulate between pH value to 7.3～7.7, then above-mentioned aqueous mixture is put into the stirring-type reactor, emptying gas 4～5 times, be heated to 220～250 ℃ to reactor is airtight, under spontaneous pressure to reactant heat-insulation pressure keeping 0.5～2h, slowly be decompressed to environmental stress then, be heated to 250～280 ℃ of further reaction 1～2h simultaneously, vacuumize 0.5～1h at last, reaction is finished, and replenishes nitrogen or rare gas element when discharging.
5, the preparation method of production phosphine copolyamide/nano montmorillonite flame-retardant composite material according to claim 4 is characterized in that: the oxygen index of described flame-proof composite material is between 27～32; The fire-retardant rank of flame-proof composite material is a UL94 V-0 level.
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