CN104403128A - Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant - Google Patents
Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant Download PDFInfo
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Abstract
The invention relates to a phosphorus-containing fire retardant, a preparation method of the phosphorus-containing fire retardant and a flame-retardant epoxy resin prepared from the phosphorus-containing fire retardant, and especially relates to a phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, a preparation method of the phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from the phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant. The flame-retardant epoxy resin solves the problem that the existing epoxy resin has low flame retardation efficiency and poor compatibility between a polymer matrix and a fire retardant. The preparation method comprises the following steps of 1, dissolving p-hydroxybenzaldehyde and tetrahydrofuran, adding triethylamine into the solution and carrying out stirring, 2, dissolving phosphonitrilic chloride trimer in tetrahydrofuran, dropwisely adding the solution into the reaction system, and carrying out heating and stirring, 3, cooling the reaction system, concentrating the filtrate, pouring the filtrate into water for precipitate separation, carrying out pumping filtration, carrying out recrystallization on the precipitates and carrying out drying to obtain intermediates, and 4, dissolving the intermediates by a solvent, adding p-aminophenol into the solution, carrying out heating reflux, adding DOPO into the reflux product, carrying out condensation, pouring the concentrate into cold ethanol for solid precipitation, and washing and drying the solids to obtain the phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant. The flame-retardant epoxy resin comprises epoxy resin, a curing agent and the phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant. The preparation method is used for preparing the phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant.
Description
Technical field
The fire retarding epoxide resin that the present invention relates to a kind of phosphonium flame retardant, its preparation method and be raw material with it.
Background technology
Polymer materials has excellent over-all properties and is widely used in the fields such as aerospace, electronic apparatus, automotive industry, but the harm such as the inflammableness of polymer materials and burning release toxic gas hinders them applies widely.Fire retardant is the functional aid that a class can give polymer materials flame retardancy, and halogenated flame retardant especially brominated flame-retardant has the advantages such as flame retarding efficiency is high, cheap and is widely used.But halogenated flame retardant can generate a large amount of dense smoke and corrosive toxic gas when thermo-cracking or burning, as: polybrominated dibenzo-furan, dioxin etc., based on the requirement of environmental protection and Sustainable development, some halogen containing flame-retardants are disabled, from the promulgation of European Union RoHS and WEEE in 2003 two instructions, make the cry of developing green halogen-free environment-friendlyflame flame retardant more and more higher.
Organic phosphonium flame retardant has low cigarette, the advantage such as nontoxic in combustion, more environmental protection during use, and being recognized is one of the staple product of alternative halogen containing flame-retardant, has good development prospect.The direction of novel flame-retardant macromolecular material development requires that flame-retardant system not only has good flame retardant properties, also will meet flame retarding efficiency high; Fire retardant and matrix phase capacitive good, not easily move and ooze out, exceeding the physical and mechanical properties, electric property and the processing characteristics that affect material; During burning Poisonous Gas and raw smoke which few as much as possible, environmentally friendly.Current organic phosphonium flame retardant great majority are liquid, as BDP, RDP, TPP etc., there is flame retarding efficiency not high, poor heat resistance and facile hydrolysis, bad with the consistency of polymkeric substance, the problems such as processing difficulties.Ring three phosphonitrile compounds has excellent thermal stability, corrosion resistance nature, water tolerance, chemical-resistant, good with material compatibility, minimum on material property impact, also there is excellent flame retardant properties simultaneously, and the flame retardant effect of phospho hetero phenanthrene (DOPO) compounds is remarkable.
Summary of the invention
The present invention is the problem that will solve low, the polymeric matrix of flame retarding efficiency that existing epoxide resin material exists and fire retardant poor compatibility, provides containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant, its preparation method and the fire retarding epoxide resin that is raw material with it.
The present invention containing the structural formula of phosphonitrile/DOPO double-basis structure phosphonium flame retardant is:
The above-mentioned preparation method containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant, carries out according to the following steps:
One, on four mouthfuls of round-bottomed flasks, spherical condensation tube, nitrogen protection device, mechanical stirrer, constant pressure funnel and heating unit are installed, high pure nitrogen is blown into after vacuumizing in round-bottomed flask, anaerobic anhydrous condition is reached to flask, then in flask, p-Hydroxybenzaldehyde is added, then add dried tetrahydrofuran (THF) fully to dissolve, add triethylamine again as acid binding agent, be stirred to reaction system clear;
Two, hexachlorocyclotriphosphazene is dissolved in dried tetrahydrofuran (THF) and obtains solution A, by constant pressure funnel, solution A is added drop-wise in the reaction system of Keep agitation, after dropwising, system temperature is elevated to reflux temperature with the heat-up rate of 5 DEG C/min, continues stirring reaction 24h;
Three, after reaction terminates, by reaction system cool to room temperature, filter to obtain glassy yellow filtrate, gained glassy yellow filtrate is concentrated with Rotary Evaporators, then be poured into water and separate out precipitation, after suction filtration, obtain pale yellow precipitate, obtaining white crystal by putting into vacuum drying oven dry 24h at 50 DEG C after gained pale yellow precipitate re-crystallizing in ethyl acetate twice, being intermediate product six pairs of aldehyde radical phenoxy cyclotriphosphazenes;
Four, six pairs of aldehyde radical phenoxy cyclotriphosphazenes that step 3 is synthesized are joined mechanical stirring is housed, in the four-hole bottle of reflux condensing tube and nitrogen protection device, add 1, 4-dioxane fully dissolves as solvent, p-aminophenol is added again in four-hole bottle, add DOPO after reflux 12h wherein and continue heating reflux reaction 12h, after reaction terminates, solution in four-hole bottle is concentrated, then pour in cold ethanol and separate out faint yellow solid product, 3 ~ 5 times are washed respectively with cold ethanol and 70 DEG C of hot water, be placed in vacuum drying oven at 60 DEG C of dry 24h, namely obtain containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant---six-[4-(para hydroxybenzene amine-phospho hetero phenanthrene-methylene radical) phenoxy group] ring three phosphonitriles (CTP-DOPO).
Fire retarding epoxide resin of the present invention is by epoxy resin, solidifying agent DDS and form containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant, and its epoxy resin, solidifying agent DDS and the mass ratio containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant are 100:31:(14 ~ 16).
The inventive method has been synthesized and has been contained phosphonitrile and DOPO structure simultaneously, and the polymkeric substance such as epoxy resin are had to the phosphonium flame retardant of highly effective flame-retardant effect, product is white or flaxen powder, productive rate is more than 91%, 1% initial thermal weight loss decomposition temperature is 269 DEG C, in a nitrogen atmosphere, neat coal amout when 700 DEG C is 42.7%, and product has good thermostability and carbon-forming performance.
Compared with prior art, the inventive method is without the use of the poisonous hazardous materials such as sodium hydride, hexanaphthene in building-up process, and reaction conditions milder, operate safer, combined coefficient is higher.The consistency of the fire retardant simultaneously synthesized and blended polymeric substrate is good, not easily moves, can ensure Flame Retardancy can weather resistance, overcome small molecules phosphate flame retardant heat decomposition temperature low, with polymeric matrix poor compatibility and the shortcoming of easily moving.Compared with existing organic phosphorus flame retardant, its flame retarding efficiency is higher, during for fire retarding epoxide resin, when the addition of fire retardant is only 10.6wt%, the limiting oxygen index(LOI) of epoxy resin cured product has brought up to 36.6% by 21.7%, and vertical combustion grade reaches UL-94 V-0 level.
Accompanying drawing explanation
Fig. 1 is the infrared conversion spectrum figure of Fourier of experiment Raw hexachlorocyclotriphosphazene (HCCP), intermediate product six pairs of aldehyde radical phenoxy cyclotriphosphazenes (HAPCP); Fig. 2 be intermediate product HAPCP proton magnetic (
1hNMR) spectrogram; Fig. 3 is product C TP-DOPO infrared spectrogram; Fig. 4 is the 1H NMR spectrogram of the product C TP-DOPO of synthesis; Fig. 5 is product C TP-DOPO's
31p NMR spectrogram.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment containing the structural formula of phosphonitrile/DOPO double-basis structure phosphonium flame retardant is:
Embodiment two: present embodiment, containing the preparation method of phosphonitrile/DOPO double-basis structure phosphonium flame retardant, is carried out according to the following steps:
One, on four mouthfuls of round-bottomed flasks, spherical condensation tube, nitrogen protection device, mechanical stirrer, constant pressure funnel and heating unit are installed, high pure nitrogen is blown into after vacuumizing in round-bottomed flask, anaerobic anhydrous condition is reached to flask, then in flask, p-Hydroxybenzaldehyde is added, then add dried tetrahydrofuran (THF) fully to dissolve, add triethylamine again as acid binding agent, be stirred to reaction system clear;
Two, hexachlorocyclotriphosphazene is dissolved in dried tetrahydrofuran (THF) and obtains solution A, by constant pressure funnel, solution A is added drop-wise in the reaction system of Keep agitation, after dropwising, system temperature is elevated to reflux temperature with the heat-up rate of 5 DEG C/min, continues stirring reaction 24h;
Three, after reaction terminates, by reaction system cool to room temperature, filter to obtain glassy yellow filtrate, gained glassy yellow filtrate is concentrated with Rotary Evaporators, then be poured into water and separate out precipitation, after suction filtration, obtain pale yellow precipitate, obtaining white crystal by putting into vacuum drying oven dry 24h at 50 DEG C after gained pale yellow precipitate re-crystallizing in ethyl acetate twice, being intermediate product six pairs of aldehyde radical phenoxy cyclotriphosphazenes;
Four, six pairs of aldehyde radical phenoxy cyclotriphosphazenes that step 3 is synthesized are joined mechanical stirring is housed, in the four-hole bottle of reflux condensing tube and nitrogen protection device, add 1, 4-dioxane fully dissolves as solvent, p-aminophenol is added again in four-hole bottle, add DOPO after reflux 12h wherein and continue heating reflux reaction 12h, after reaction terminates, solution in four-hole bottle is concentrated, then pour in cold ethanol and separate out faint yellow solid product, 3 ~ 5 times are washed respectively with cold ethanol and 70 DEG C of hot water, be placed in vacuum drying oven at 60 DEG C of dry 24h, namely obtain containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant---six-[4-(para hydroxybenzene amine-phospho hetero phenanthrene-methylene radical) phenoxy group] ring three phosphonitriles (CTP-DOPO).
Phosphonitrile and DOPO structure are incorporated in flame retardant molecule structure by present embodiment simultaneously, and preparation has excellent properties phosphonium flame retardant.The fire retardant of synthesis is applied to the fire-retardant of epoxy resin simultaneously, solves the problems such as low, the polymeric matrix of flame retarding efficiency that epoxide resin material exists and fire retardant poor compatibility.
P-Hydroxybenzaldehyde in step one also can be replaced p-Aminobenzaldehyde or to sulfydryl phenyl aldehyde.
P-aminophenol in step 4 also can be replaced p-NP or aniline.
Embodiment three: present embodiment and embodiment two unlike: in step one, the purity of high pure nitrogen is 99.99%.Other is identical with embodiment two.
Embodiment four: present embodiment and embodiment two or three unlike: in step one, the mass ratio of p-Hydroxybenzaldehyde, tetrahydrofuran (THF) and triethylamine is 1:(1 ~ 1.2): (3 ~ 10).Other is identical with embodiment two or three.
Embodiment five: one of present embodiment and embodiment two to four unlike: in step 2, the mass ratio of hexachlorocyclotriphosphazene and tetrahydrofuran (THF) is 1:(5 ~ 10).Other is identical with one of embodiment two to four.
Embodiment six: one of present embodiment and embodiment two to five unlike: cold ethanol described in step 4 is the ethanol of 0 DEG C, and the volumetric concentration of cold ethanol is 95%.Other is identical with one of embodiment two to five.
Embodiment seven: present embodiment fire retarding epoxide resin is by epoxy resin, solidifying agent DDS and form containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant, and its epoxy resin, solidifying agent DDS and the mass ratio containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant are 100:31:(14 ~ 16).
For verifying beneficial effect of the present invention, carry out following experiment:
This experiment, containing the preparation method of phosphonitrile/DOPO double-basis structure phosphonium flame retardant, is carried out according to the following steps:
One, on 1000mL tetra-mouthfuls of round-bottomed flasks, spherical condensation tube, nitrogen protection device, mechanical stirrer, constant pressure funnel and heating unit are installed, it is fully dry before all glassware use, high pure nitrogen is blown into after vacuumizing in round-bottomed flask, anaerobic anhydrous condition is reached to flask, then in flask, 140g p-Hydroxybenzaldehyde is added, then add dried tetrahydrofuran (THF) fully to dissolve, add 100g triethylamine again as acid binding agent, be stirred to reaction system clear, now solution colour is reddish brown;
Two, 56.8g hexachlorocyclotriphosphazene is dissolved in dried tetrahydrofuran (THF) and obtains solution A, by constant pressure funnel, solution A is added drop-wise in the reaction system of Keep agitation, now system temperature raises gradually, system color is taken off gradually, adularescent crystal is separated out, after dropwising, system temperature is elevated to reflux temperature with the heat-up rate of 5 DEG C/min, continues stirring reaction 24h;
Three, after reaction terminates, by reaction system cool to room temperature, filter to obtain glassy yellow filtrate, gained glassy yellow filtrate Rotary Evaporators is concentrated remove portion solvent (concentrated after for can flow state), then be poured into water and separate out precipitation, after suction filtration, obtain pale yellow precipitate, obtaining white crystal by putting into vacuum drying oven dry 24h at 50 DEG C after gained pale yellow precipitate re-crystallizing in ethyl acetate twice, being intermediate product six pairs of aldehyde radical phenoxy cyclotriphosphazenes;
Four, six pairs of aldehyde radical phenoxy cyclotriphosphazenes that 17.2g step 3 is synthesized are joined mechanical stirring is housed, in the 250mL four-hole bottle of reflux condensing tube and nitrogen protection device, add 1, 4-dioxane fully dissolves as solvent, 15g p-aminophenol is added again in four-hole bottle, add 30g DOPO after reflux 12h wherein and continue heating reflux reaction 12h, after reaction terminates, solution in four-hole bottle is concentrated, then pouring volumetric concentration into is separate out faint yellow solid product in the cold ethanol of 95%, first by cold washing with alcohol 3 times, use 70 DEG C of hot washes 3 times again, be placed in vacuum drying oven at 60 DEG C of dry 24h, namely obtain containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant---six-[4-(para hydroxybenzene amine-phospho hetero phenanthrene-methylene radical) phenoxy group] ring three phosphonitriles (CTP-DOPO).
The synthetic route of the present embodiment six-[4-(para hydroxybenzene amine-phospho hetero phenanthrene-methylene radical) phenoxy group] ring three phosphonitrile is as follows:
The productive rate that step 3 obtains intermediate product six pairs of aldehyde radical phenoxy cyclotriphosphazenes is 90.5%.
By Thermogravimetric analysis (TGA), product is tested, result shows that the initial pyrolyzation temperature (temperature when mass loss is 1wt%) of product is 269 DEG C, carbon left when 700 DEG C reaches 42.7wt%, shows that this compound has good thermostability and carbon-forming performance.
The present embodiment method abandons the use of the poisonous hazardous materials such as sodium hydride, hexanaphthene, reaction conditions milder, and operate safer, combined coefficient is higher.
(1) sign of intermediate six pairs of aldehyde radical phenoxy cyclotriphosphazenes (HAPCP)
Fig. 1 is the infrared conversion spectrum figure of Fourier of raw material hexachlorocyclotriphosphazene (HCCP), intermediate product six pairs of aldehyde radical phenoxy cyclotriphosphazenes (HAPCP).As can be seen from spectrogram, curve a is the infared spectrum of raw material HCCP, at 1208cm
-1place can observe very strong absorption peak, corresponds to P=N charateristic avsorption band in phosphonitrile ring, at 608cm
-1and 526cm
-1place is P-Cl charateristic avsorption band; Corresponding in the infrared curve b of intermediate product HAPCP, can see at 1208cm
-1the charateristic avsorption band of place's phosphonitrile ring still exists, but at 608cm
-1and 526cm
-1the absorption peak that place corresponds to P-Cl is vanished from sight, and the substitute is, at 2823cm
-1and 1706cm
-1there is the charateristic avsorption band of aldehyde radical (-CHO) in place, at 1600cm
-1there is the stretching vibration absorption peak of-CH-on phenyl ring skeleton in place, these phenomenons illustrate that the chlorine atom on raw material hexachlorocyclotriphosphazene all successfully replaces by p-Hydroxybenzaldehyde.
Fig. 2 be intermediate product HAPCP proton magnetic (
1hNMR) spectrogram.As can be seen from HAPCP hydrogen nuclear magnetic spectrogram, a place δ=9.93ppm is the resonance peak of-CHO aldehyde radical hydrogen, and b place δ=7.75ppm and 7.13ppm is the resonance peak of hydrogen on phenyl ring, and the hydrogen atom in its molecular structure is all mutually corresponding with the peak in 1H NMR spectrogram.
(2) sign of product six-[4-(para hydroxybenzene amine-phospho hetero phenanthrene-methylene radical) phenoxy group] ring three phosphonitrile (CTP-DOPO)
Figure 3 shows that product C TP-DOPO infrared spectrogram.As can be seen from the figure, 2432cm
-1p (O)-H charateristic avsorption band in place DOPO is vanished from sight, but remaining charateristic avsorption band of DOPO still can observe 1595cm
-1and 1476cm
-1place is the charateristic avsorption band of P-Ph in DOPO, 1044cm
-1place is the charateristic avsorption band of P-O-C.In addition, the charateristic avsorption band belonging to phosphonitrile ring structure appears at 1200cm
-1near, and 3300cm
-1there is N-H charateristic avsorption band in place.These all prove the phosphonitrile ring structure and the DOPO structure that there is design introducing in the product structure of synthesis gained.
Fig. 4 is the 1H NMR spectrogram of the product C TP-DOPO of synthesis, as shown in mark in figure, appear at 8.44 and the peak at 8.42ppm place belong to the chemical shift of phenolic hydroxyl group-OH proton on mark a place phenyl ring, the chemical shift that more complicated group peak corresponds to proton on DOPO group is divided between 6.86 to 8.11ppm, and the peak appeared between 6.33 and 6.49ppm belongs to identify in figure 1, 2, 3, the chemical shift of proton on 4 place's phenyl ring, the peak occurred at 5.52ppm and 5.98ppm place represents the chemical shift of secondary amine (NH), the peak representative graph being arranged in 5.63ppm and 6.02ppm marks the chemical shift of 5 place's protons.Each position in the target product of synthesis has two chemical shifts to correspond in nuclear magnetic spectrogram.
Fig. 5 is product C TP-DOPO's
31p NMR spectrogram.As can be seen from the figure chemical shift is P atom on DOPO group at 31.43ppm and 28.47ppm, and demonstrate containing two groups of non-corresponding isomeries in synthetic product CTP-DOPO, chemical shift is P atom in phosphonitrile ring at 7.78ppm place.
In conjunction with infrared spectra, hydrogen nuclear magnetic spectrogram and phosphorus nuclear magnetic spectrogram analytical results, demonstrating final synthetic product CTP-DOPO is target product.
(3) product six-[4-(para hydroxybenzene amine-phospho hetero phenanthrene-methylene radical) phenoxy group] ring three phosphonitrile (CTP-DOPO) is to the flame retardant properties of epoxide resin material:
The fire retardant CTP-DOPO of ordinary epoxy resin, solidifying agent DDS and synthesis is mixed by different ratios, melt at 180 DEG C, vigorous stirring mixes to be poured in previously prepared mould, 180 DEG C of Procuring 2h, continue solidification 3h at 200 DEG C, be cooled to room temperature and obtain fire retarding epoxide resin cured article.
Table 1 is the composition of fire retarding epoxide resin cured article and the flame retardant properties test result of material thereof.As can be seen from the table, the oxygen index of pure epoxy resin sample S1 is only 21.7%, UL-94 test without rank.When fire retardant addition is 9.8wt% (now sample system phosphorus content is 1.0%), limiting oxygen index(LOI) (LOI) value of sample S2 obtains very large raising, reach 34.3%, and 3mm thick specimens can smoothly by UL-94 V-1 level that vertical combustion is tested.When the content of fire retardant in sample is increased to 10.6wt% (in sample, phosphorus content is 1.1%), the sample S3 of 3mm thickness can smoothly by UL-94 V-0 level and LOI value reaches 36.6%.Test result shows, the double-basis phosphonium flame retardant containing phosphonitrile/DOPO while synthesis has very excellent flame retarding efficiency to epoxide resin material.
The oxygen index of table 1 cured epoxy resin sample and vertical combustion test data
Claims (7)
1., containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant, it is characterized in that the structural formula of this fire retardant is:
2., containing the preparation method of phosphonitrile/DOPO double-basis structure phosphonium flame retardant, it is characterized in that the method is carried out according to the following steps:
One, on four mouthfuls of round-bottomed flasks, spherical condensation tube, nitrogen protection device, mechanical stirrer, constant pressure funnel and heating unit are installed, high pure nitrogen is blown into after vacuumizing in round-bottomed flask, anaerobic anhydrous condition is reached to flask, then in flask, p-Hydroxybenzaldehyde is added, then add dried tetrahydrofuran (THF) fully to dissolve, add triethylamine again as acid binding agent, be stirred to reaction system clear;
Two, hexachlorocyclotriphosphazene is dissolved in dried tetrahydrofuran (THF) and obtains solution A, by constant pressure funnel, solution A is added drop-wise in the reaction system of Keep agitation, after dropwising, system temperature is elevated to reflux temperature with the heat-up rate of 5 DEG C/min, continues stirring reaction 24h;
Three, after reaction terminates, by reaction system cool to room temperature, filter to obtain glassy yellow filtrate, gained glassy yellow filtrate is concentrated with Rotary Evaporators, then be poured into water and separate out precipitation, after suction filtration, obtain pale yellow precipitate, obtaining white crystal by putting into vacuum drying oven dry 24h at 50 DEG C after gained pale yellow precipitate re-crystallizing in ethyl acetate twice, being intermediate product six pairs of aldehyde radical phenoxy cyclotriphosphazenes;
Four, six pairs of aldehyde radical phenoxy cyclotriphosphazenes that step 3 is synthesized are joined mechanical stirring is housed, in the four-hole bottle of reflux condensing tube and nitrogen protection device, add 1, 4-dioxane fully dissolves as solvent, p-aminophenol is added again in four-hole bottle, add DOPO after reflux 12h wherein and continue heating reflux reaction 12h, after reaction terminates, solution in four-hole bottle is concentrated, then pour in cold ethanol and separate out faint yellow solid product, 3 ~ 5 times are washed respectively with cold ethanol and 70 DEG C of hot water, be placed in vacuum drying oven at 60 DEG C of dry 24h, namely obtain containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant.
3. the preparation method containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant according to claim 2, is characterized in that the purity of high pure nitrogen in step one is 99.99%.
4. the preparation method containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant according to Claims 2 or 3, is characterized in that the mass ratio of p-Hydroxybenzaldehyde in step one, tetrahydrofuran (THF) and triethylamine is 1:(1 ~ 1.2): (3 ~ 10).
5. the preparation method containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant according to claim 4, is characterized in that the mass ratio of hexachlorocyclotriphosphazene and tetrahydrofuran (THF) in step 2 is 1:(5 ~ 10).
6. the preparation method containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant according to claim 5, it is characterized in that cold ethanol described in step 4 is the ethanol of 0 DEG C, the volumetric concentration of cold ethanol is 95%.
7. with containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant be the fire retarding epoxide resin of raw material, it is characterized in that this fire retarding epoxide resin is by epoxy resin, solidifying agent DDS with form containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant, its epoxy resin, solidifying agent DDS and the mass ratio containing phosphonitrile/DOPO double-basis structure phosphonium flame retardant are 100:31:(14 ~ 16).
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