CN103992481A - Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof - Google Patents
Hyperbranched polyphosphazene flame retardant charring agent and preparing method thereof Download PDFInfo
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Abstract
An efficient hyperbranched polyphosphazene flame retardant charring agent is prepared by reacting hexachlorocyclotriphosphazene with a binary compound containing two active groups. The charring agent has characteristics of good foaming charring performance, excellent flame retardant effects and good processing performance, and can be widely used in plastics, rubber, coating, adhesives, and other polymer materials. A preparing method adopts a one-pot method, and has characteristics of continuous reaction process, short reaction time and high production efficiency. By controlling the mole ratio of the hexachlorocyclotriphosphazene to the binary compound, no end-capping agent is added in the reaction process. When compared with the addition of end-capping agents in synthesis processes in triazine type charring agent patents, the synthetic process of the charring agent is simplified.
Description
Technical field
The invention belongs to field of polymer material preparing technology, relate to a kind of expansion type flame-retarding char-forming agent and preparation method thereof, relate in particular to fire-retardant char-forming agent of a kind of hyperbranched poly phosphonitrile and preparation method thereof.
Background technology
Expansion type flame retardant is one of environment-friendly flame retardant agent type of widespread use in recent years, it has not only overcome halogenated flame retardant and when burning, has easily emitted pungency and corrosive gas and smog, many molten drops, shortcoming that easily personnel that cause suffocate, and has overcome the detrimentally affect that inorganic combustion inhibitor brings the mechanics of materials, processibility the subject of knowledge and the object of knowledge greatly due to addition.Expansion type flame retardant (IFR), because the charcoal layer of its unique fire retardant mechanism and Halogen, low cigarette, low toxicity, generation can prevent the characteristics such as polymkeric substance molten drop effectively, meets the requirement of preserving the ecological environment now.
Generally speaking, IFR comprises 3 parts, i.e. carbon source (being often polyol, as tetramethylolmethane), acid source (as ammonium polyphosphate) and source of the gas (as trimeric cyanamide).In traditional Intumscent Flame Retardant System polyphosphoric acid amine-tetramethylolmethane-trimeric cyanamide, tetramethylolmethane (PER) is a kind of compound with strong polarity, in use with bad, the easy reunion of macromolecular material consistency, exist poor heat stability, water-fast and poor durability, be easy to move to water-soluble large, the shortcoming such as addition is large, viscosity is high, processing characteristics is not good, charring rate is poor of matrix surface, greatly limited further applying of IFR.And existing triazines char-forming agent exists synthesis technique complexity, the shortcomings such as production cycle length.Therefore, the exploitation of novel char-forming agent is one of important directions of current expansion type flame retardant research.In recent years, phosphazene flame retardant as a kind of environmentally friendly flame retardant products development rapidly, is studied widely and is applied.
Phosphazene polymer is that a class skeleton has phosphorus, nitrogen Dan Shuanjian alternative arrangement as backbone structure, by connect different functional substituted radicals on phosphorus atom, obtain a class novel inorganic organic hybrid macromole of property, they have inorganics and organic excellent properties concurrently: be easy to functionalized, main chain is soft, optical clear, good biocompatibility, biodegradable etc., therefore be widely used in biological medicine material, fire retardant material, optical material etc.Have the characteristic that traditional organic polymer and inorganics hardly match, the phosphorus on main chain, nitrogen have been given its good flame retardant properties simultaneously; Organic constituent on side chain has been given the consistency good with matrix, and polyphosphonitrile environmental protection.Thereby can give the water tolerance that organic polymer matrix is good, high temperature resistant, low temperature resistant, resistance to solvent, oil resistant class and chemical, radiation hardness, mechanical property and optical transparence are good, photo and thermal stability is high and do not burn and the premium properties such as fire-retardant by the polyphosphonitrile of Choice and design different structure.
In the molecule of cyclic phosphazene compound, on phosphorus atom, contain two commutable active chlorine atoms, by various substitution reactions, can obtain multiple derivative, and phosphazene derivative has higher phosphorus, nitrogen content, this has just determined no matter be as flame retardant type functional materials or the flame-retardant additive of various materials, and this compounds is all with a wide range of applications and good application prospect.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, and the fire-retardant char-forming agent of hyperbranched poly phosphonitrile that a kind of thermostability is better, charring rate is higher is provided.
Another object of the present invention is to provide that a kind of reaction process is continuous, the reaction times is short, the preparation method of the fire-retardant char-forming agent of the simple above-mentioned hyperbranched poly phosphonitrile of synthesis technique.
For solving above technical problem, the technical scheme that the present invention takes is:
The fire-retardant char-forming agent of hyperbranched poly phosphonitrile, it has following general structure:
Wherein, Z is NH, N, S or O; R is a kind of in piperazine ring, straight chained alkyl, branched-chain alkyl, cycloalkyl and aryl.
Further, in R structure, also can contain one or more in S, O, N, Si and P atom.
Further, R can be on straight chain with between the straight chained alkyl of phenyl ring, a plurality of phenyl ring with aryl, cycloalkaryl or the cycloalkyl aryl of alkyl.
The preparation method of the above-mentioned fire-retardant char-forming agent of hyperbranched poly phosphonitrile, can represent by following reaction equation:
Wherein, HZ-R-ZH is the binary compound that contains two active groups, described active group can with hexachlorocyclotriphosphazene structure in chlorine atom generation substitution reaction;
Described preparation method comprises the steps:
(1), by hexachlorocyclotriphosphazene and general structure, being HZ-R-ZH, binary compound is dispersed in respectively in solvent, obtains hexachlorocyclotriphosphazene solution and binary compound solution;
(2), under the temperature condition of 0 ℃～10 ℃, in the described binary compound solution stirring, dropwise add described hexachlorocyclotriphosphazene solution, after dropwising, maintain temperature of reaction constant, continue reaction 1-4 hour; The mol ratio of described binary compound and described hexachlorocyclotriphosphazene is between 4:1～6:1;
(3) temperature of the reaction system through step (2) is increased to 30 ℃-70 ℃, and adds wherein acid binding agent, continue reaction 3-6 hour; The mol ratio of described acid binding agent and described hexachlorocyclotriphosphazene is between 6:1-7:1;
(4) temperature of the reaction system through step (3) is increased to 90 ℃-150 ℃, continues reaction 6-10 hour;
(5) stop stirring, and gained solid is carried out to suction filtration, washing, dry, obtain the fire-retardant char-forming agent of described hyperbranched poly phosphonitrile.
Preferably, the concentration of hexachlorocyclotriphosphazene solution described in step (1) is between 0.5mol/L～10mol/L.
Preferably, described binary compound is Ursol D, quadrol, hexanediamine, butanediamine, piperazine, N, N-dimethyl-1,3-propylene diamine, N-aminoethyl piperazine, 4,4 '-diaminodiphenyl oxide, DDS, 4,4 '-diaminodiphenylmethane, adjacent biphenyl methylamine, O-Phenylene Diamine, 1,2-propylene diamine, 1,3-propylene diamine, 2 methyl pentamethylenediamine, 2,6-tolylene diamine, 2,4 di amino toluene, 3 diethyl aminopropylamine, diethyl toluene diamine, hydroxyethylethylene diamine, 1,2-cyclohexanediamine, 4,5-dichloro O-Phenylene Diamine, 2,2 '-bis-[4-(4-amino-benzene oxygen phenyl)] propane, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl disulfide, Resorcinol, pentanediol, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dioxydiphenyl methane, BDO, ethylene glycol, 1,3 butylene glycol, 1,3-pentanediol, 1,3 cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 2-ethyl-1,3-hexylene glycol, pyrocatechol, Resorcinol, 1,5-dihydroxy naphthlene, 1,3-naphthalenediol, 2,7 dihydroxy naphthalene, toluhydroquinone, 4,4 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl disulfide, Isosorbide-5-Nitrae-benzene dimethanethiol, 4,4 '-dimercapto diphenyl sulfide, 4, the combination of one or more in 4 '-dimercapto diphenyl disulfide and Isosorbide-5-Nitrae-thioresorcin.
Preferably, described acid binding agent is one or several mixtures that mix with arbitrary proportion in alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate; And the volumetric molar concentration of described acid binding agent is 1-10mol/L.
Further, described alkali metal hydroxide is NaOH or KOH; Described alkaline carbonate is Na
2cO
3or K
2cO
3; Described alkali metal hydrocarbonate is NaHCO
3or KHCO
3.
Preferably, drying conditions is vacuum-drying 2～10 hours at 50 ℃～100 ℃ in step (5), to reach good drying effect.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention designs by dissaving structure, make full use of that super branched molecule end group is many, viscosity is low, easily process with other additive mixtures, high temperature easily becomes the advantages such as charcoal, prepared the fire-retardant char-forming agent of a kind of efficient polyphosphonitrile, weightless 1% temperature is all more than 340 ℃, the carbon residue amount of 600 ℃ of high temperature substantially can reach 60% and more than; It has fabulous charcoal, excellent flame retardant effect and the good processing characteristics of being foamed into, and owing to being hyperbranched structure, so flame retardant effect is lasting, there is not the problem of volatilization, stripping and migration, can be widely used in the macromolecular materials such as plastics, rubber, coating, tackiness agent.
Preparation method of the present invention adopts one kettle way, has reaction process continuous, and the reaction times is short, the feature that production efficiency is high.By controlling the mol ratio of hexachlorocyclotriphosphazene and binary compound, in reaction process, need not add end-capping reagent, and in building-up process, add end-capping reagent to compare in some triazines char-forming agent patents, simplified synthesis technique.
Accompanying drawing explanation
Fig. 1 is the infrared spectra comparison diagram of the prepared fire-retardant char-forming agent of hyperbranched poly phosphonitrile (a) of embodiment 1 and hexachlorocyclotriphosphazene (b).
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention will be further described in detail, but be not limited to these embodiment.
Embodiment 1
0.2mol piperazine is dissolved in to 70mL ethanol, joins in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, start stirring; 0.05mol hexachlorocyclotriphosphazene is dissolved in 100mL dioxane, and is dropwise added drop-wise in above-mentioned piperazine solution by constant pressure funnel, maintain the temperature at 0 ℃ and react 4 hours; Then temperature of reaction is risen to 50 ℃, 0.3molNaOH is dissolved in 20mL water, be slowly added drop-wise to above-mentioned reaction system, at this temperature, continue reaction 6 hours; Finally temperature of reaction is risen to 95 ℃ again, continue reaction 9 hours, stop stirring, suction filtration, washing while hot 3 times, 80 ℃ of vacuum-dryings 8 hours, obtains micro-yellow solid product 22.54g.
Products therefrom is carried out to ultimate analysis, and result shows, sample actual measurement C, and N, the quality percentage composition of H is respectively 39.2%, 30.5%, 6.37%, and C in the fire-retardant char-forming agent of hyperbranched poly phosphonitrile, N, the theoretical percentage composition of H is respectively 41.0%, 32.9%, 6.8%, and both are basically identical.Fig. 1 is the infrared spectrogram of products therefrom (a) and hexachlorocyclotriphosphazene (b), can find out 3420cm from Fig. 1 (a)
-1the stretching vibration peak that has occurred N-H, 2970-2840cm
-1for the stretching vibration peak of C-H, 1220cm
-1for the stretching vibration peak of P=N, 827cm
-1for the stretching vibration peak of C-N, and 567cm
-1the stretching vibration peak of the P-Cl at place is vanished from sight, and illustrates that Cl is substituted.Comprehensive above analysis, thinks that the fire-retardant char-forming agent of hyperbranched poly phosphonitrile of the present invention is successfully prepared.
The productive rate of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile of the present embodiment gained is 95.4%, and the lower 357 ℃ of weightlessness of nitrogen atmosphere are that 1%, 600 ℃ of carbon residue amount is 68.1%.The fire-retardant char-forming agent of this hyperbranched poly phosphonitrile is joined in polypropylene matrix with 30% ratio, and its oxygen index is that 29, UL-94 reaches V-0 level.
In the present embodiment, the standard of oxygen index test institute foundation is ASTM D2863; The testing standard of vertical combustion UL-94 institute foundation is ASTM D3801-1996.
Embodiment 2
0.25mol quadrol is dissolved in to 25mL water, join the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in the tetrahydrofuran (THF) of 10mL, is dropwise added drop-wise in above-mentioned ethylenediamine solution, at 10 ℃, react 1 hour; Then be warming up to 70 ℃, by the Na of 0.32mol
2cO
3be dissolved in 40mL water, be slowly added drop-wise in this system, and continue reaction 3 hours at this temperature, be finally warming up to again 150 ℃, react 6 hours; Stop stirring, suction filtration, washing while hot 3 times is dried 2 hours at 100 ℃, obtains micro-yellow solid product 8.79g, and productive rate is 93.2%.In the present embodiment, the results of elemental analyses of products therefrom shows, C in the fire-retardant char-forming agent of hyperbranched poly phosphonitrile, and N, the theoretical percentage composition of H is respectively 28.4%, 43.1%, 7.1%, and measured value is respectively 27.2%, 42.5%, 6.18%, both are basically identical.Under nitrogen atmosphere, 342 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 58.7%.
Embodiment 3:
0.3mol Ursol D is dissolved in to 100mL ethanol, join in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in the benzene of 5mL, is dropwise added drop-wise in above-mentioned Ursol D solution, and at 5 ℃, react 3 hours; Then temperature of reaction is risen to 30 ℃, the KOH of 0.35mol is dissolved in the water of 50mL, be slowly added drop-wise in this reaction system, and continue reaction 8 hours at this temperature, be finally warming up to again 150 ℃, react 10 hours; Stop stirring, suction filtration, washing while hot 3 times, 50 ℃ of vacuum-dryings 10 hours, obtains micro-yellow solid product 36.7g, and productive rate is 94.6%.In the present embodiment, the results of elemental analyses of products therefrom shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, the theoretical percentage composition of H is respectively 51.8%, 27.7%, 4.3%, and measured value is respectively 50.3%, 25.6%, 3.9%, both are basically identical.Under nitrogen atmosphere, 397 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 69.8%.
Embodiment 4:
By 0.2mol4,4 '-diaminodiphenylsulfone(DDS) is dissolved in 80mL acetone, join in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in to 10mL tetra-carbonoxides, dropwise be added drop-wise to above-mentioned 4, in 4 '-diaminodiphenylsulfone(DDS) solution, and at 10 ℃, react 1.5 hours; Then be warming up to 65 ℃, by 0.31molNaHCO
3be dissolved in 40mL water, be slowly added drop-wise in this reaction system, and continue reaction 3 hours at this temperature, be finally warming up to 110 ℃, then continue reaction 7 hours; Stop stirring, suction filtration, washing while hot 3 times, is dried 2 hours at 100 ℃, obtains white solid product 49.9g, and productive rate is 89.2%.In the present embodiment, the results of elemental analyses of product shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, H, the theoretical percentage composition of S is respectively 51.6%, 11.8%, 3.5%, 11.4%, and measured value is respectively 50.3%, 10.3%, 2.9%, 10.5%, both are basically identical.Under nitrogen atmosphere, 387 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 65.8%.
Embodiment 5:
0.25mol Resorcinol is dissolved in to 60mL ethanol, join the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again the hexachlorocyclotriphosphazene of 0.05mol is dissolved in 50mL benzene, is dropwise added drop-wise in above-mentioned Resorcinol solution, and at 0 ℃, react 2 hours; Then the temperature of reaction system is risen to 60 ℃, by the K of 0.16mol
2cO
3be dissolved in 50mL water, be slowly added drop-wise in this reaction system, and continue reaction 7 hours at this temperature; Finally again the temperature of reaction system is risen to 100 ℃, continue reaction 9 hours; Stop stirring, suction filtration, washing while hot 3 times, 50 ℃ of vacuum-dryings 10 hours, obtains white solid product 24.5g, and productive rate is 86.2%.In the present embodiment, the results of elemental analyses of products therefrom shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, the theoretical percentage composition of H is respectively 51.0%, 7.4%, 2.8%, and measured value is respectively 49.8%, 6.7%, 2.6%, both are basically identical.Under nitrogen atmosphere, 365 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 60.4%.
Embodiment 6:
0.23mol ethylene glycol is dissolved in to 25mL acetone, join in the 500mL there-necked flask that reflux condensing tube, constant pressure funnel, agitator are housed, again 0.05mol hexachlorocyclotriphosphazene is dissolved in to 70mL tetrahydrofuran (THF), is dropwise added drop-wise in above-mentioned ethylene glycol solution, and react 2.5 hours at 3 ℃; Then the temperature of reaction system is risen to 56 ℃, by the KHCO of 0.32mol
3be dissolved in 40mL water, be slowly added drop-wise in this reaction system, and continue reaction 3 hours at this temperature; Finally the temperature of reaction system is risen to 89 ℃, then react 7 hours; Stop stirring, suction filtration, washing while hot 3 times, is dried 2 hours at 100 ℃, obtains white solid product 14.9g, and productive rate is 79.4%.In the present embodiment, the results of elemental analyses of product shows, C in hyperbranched poly phosphonitrile char-forming agent, and N, the theoretical percentage composition of H is respectively 25.2%, 11.0%, 6.3%, and measured value is respectively 24.9%, 10.5%, 5.9%, both are basically identical.Under nitrogen atmosphere, 335 ℃ of weightlessness of obtained flame-retardant char-forming agent are that 1%, 600 ℃ of carbon residue amount is 52.6%.
The fire-retardant char-forming agent of hyperbranched poly phosphonitrile of gained of the present invention, Heat stability is good, charring rate is high, no matter be to be used in conjunction with as char-forming agent and other acid sources, source of the gas, or self joins in polymeric matrix as fire retardant, can both reach desirable flame retardant effect.And the fire-retardant char-forming agent synthesis technique of hyperbranched poly phosphonitrile of the present invention is simple, and reaction process is continuous, and the reaction times is short, be applicable to very much suitability for industrialized production, there is fabulous fire-retardant application prospect.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (9)
1. the fire-retardant char-forming agent of hyperbranched poly phosphonitrile, is characterized in that: the fire-retardant char-forming agent of described hyperbranched poly phosphonitrile has following general structure:
Wherein, Z is NH, N, S or O; R is a kind of in piperazine ring, straight chained alkyl, branched-chain alkyl, cycloalkyl and aryl.
2. the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 1, is characterized in that: in R structure, contain one or more in S, O, N, Si and P atom.
3. the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 1 and 2, is characterized in that: R be on straight chain with between the straight chained alkyl of phenyl ring, a plurality of phenyl ring with aryl, cycloalkaryl or the cycloalkyl aryl of alkyl.
4. a preparation method for the fire-retardant char-forming agent of hyperbranched poly phosphonitrile claimed in claim 1, is characterized in that:
Described preparation method represents by following reaction equation:
Described preparation method comprises the steps:
(1), by hexachlorocyclotriphosphazene and general structure, being HZ-R-ZH, binary compound is dispersed in respectively in solvent, obtains hexachlorocyclotriphosphazene solution and binary compound solution;
(2), under the temperature condition of 0 ℃～10 ℃, in the described binary compound solution stirring, dropwise add described hexachlorocyclotriphosphazene solution, after dropwising, maintain temperature of reaction constant, continue reaction 1-4 hour; The mol ratio of described binary compound and described hexachlorocyclotriphosphazene is between 4:1～6:1;
(3) temperature of the reaction system through step (2) is increased to 30 ℃-70 ℃, and adds wherein acid binding agent, continue reaction 3-6 hour; The mol ratio of described acid binding agent and described hexachlorocyclotriphosphazene is between 6:1-7:1;
(4) temperature of the reaction system through step (3) is increased to 90 ℃-150 ℃, continues reaction 6-10 hour;
(5) stop stirring, and gained solid is carried out to suction filtration, washing, dry, obtain the fire-retardant char-forming agent of described hyperbranched poly phosphonitrile.
5. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: in step (1), the concentration of hexachlorocyclotriphosphazene solution is between 0.5mol/L～10mol/L.
6. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: described binary compound is Ursol D, quadrol, hexanediamine, butanediamine, piperazine, N, N-dimethyl-1,3-propylene diamine, N-aminoethyl piperazine, 4,4 '-diaminodiphenyl oxide, DDS, 4,4 '-diaminodiphenylmethane, adjacent biphenyl methylamine, O-Phenylene Diamine, 1,2-propylene diamine, 1,3-propylene diamine, 2 methyl pentamethylenediamine, 2,6-tolylene diamine, 2,4 di amino toluene, 3 diethyl aminopropylamine, diethyl toluene diamine, hydroxyethylethylene diamine, 1,2-cyclohexanediamine, 4,5-dichloro O-Phenylene Diamine, 2,2 '-bis-[4-(4-amino-benzene oxygen phenyl)] propane, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl sulfide, 4,4 '-diamino diphenyl disulfide, Resorcinol, pentanediol, 4,4 '-dihydroxy diphenyl ether, 4,4 '-dioxydiphenyl methane, BDO, ethylene glycol, 1,3 butylene glycol, 1,3-pentanediol, 1,3 cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 2-ethyl-1,3-hexylene glycol, pyrocatechol, Resorcinol, 1,5-dihydroxy naphthlene, 1,3-naphthalenediol, 2,7 dihydroxy naphthalene, toluhydroquinone, 4,4 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxyl diphenyl disulfide, Isosorbide-5-Nitrae-benzene dimethanethiol, 4,4 '-dimercapto diphenyl sulfide, 4, the combination of one or more in 4 '-dimercapto diphenyl disulfide and Isosorbide-5-Nitrae-thioresorcin.
7. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: described acid binding agent is one or several mixtures that mix with arbitrary proportion in alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate; And the volumetric molar concentration of described acid binding agent is 1-10mol/L.
8. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 7, is characterized in that: described alkali metal hydroxide is NaOH or KOH; Described alkaline carbonate is Na
2cO
3or K
2cO
3; Described alkali metal hydrocarbonate is NaHCO
3or KHCO
3.
9. the preparation method of the fire-retardant char-forming agent of hyperbranched poly phosphonitrile according to claim 4, is characterized in that: in step (5), drying conditions is vacuum-drying 2～10 hours at 50 ℃～100 ℃.
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