CN106519239A - Preparation method and application of phosphorus-nitrogen-carbon-containing aggregate and intumescent flame retardant - Google Patents

Preparation method and application of phosphorus-nitrogen-carbon-containing aggregate and intumescent flame retardant Download PDF

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CN106519239A
CN106519239A CN201610885221.0A CN201610885221A CN106519239A CN 106519239 A CN106519239 A CN 106519239A CN 201610885221 A CN201610885221 A CN 201610885221A CN 106519239 A CN106519239 A CN 106519239A
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flame retardant
phosphorus
nitrogen
expansion type
type flame
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CN106519239B (en
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胡小平
王鹏吉
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Southwest University of Science and Technology
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    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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

Abstract

The invention discloses a preparation method of a phosphorus-nitrogen-carbon-containing aggregate and intumescent flame retardant of a nano-sheet structure. The preparation method is characterized in that phytic acid, melamine and a solvent are prepared, the substance amount ratio of the phytic acid to the melamine is 1: 3 to 1: 15, and 20-50 ml of the solvent is added into every 0.01 mol of the melamine; the melamine is added into a reaction container provided with a thermometer and a stirrer, the solvent is added with stirring, the phytic acid is added at the temperature of 20-40 DEG C, and a reaction is conducted with stirring for 20-50 minutes, so that reaction liquid is obtained; and the reaction liquid is poured into a reaction still to react for 24-56 h at the temperature of 70-120 DEG C, cooling and suction filtration are conducted, solid is washed with ethyl alcohol and then washed with water till the pH is 7, and the solid is dried, so that the flame retardant is obtained. The preparation method is simple and environmentally friendly, and the synthesized phosphorus-nitrogen-carbon-containing aggregate and intumescent flame retardant of the nano-sheet structure has good compatibility with a polymer matrix and has good flame retardance.

Description

A kind of preparation method and its usage of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant
Technical field
The invention belongs to the preparation of aggretion type expansion type flame retardant, is related to a kind of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame-retarding The preparation method and its usage of agent.There is containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant prepared by the present invention nano-sheet to tie Structure, it is adaptable to be added in polymer (i.e. flame retarded polymeric material) anti-flammability for lifting polymer as additive flame retardant Can, it is also possible to the fire retardant compounding use of other species etc..
Background technology
In recent years, with the continuous development of science and technology, macromolecular material has become indispensable one in daily life Part, the use of macromolecular material also occur in that corresponding problem while offering convenience.Due to most of macromolecular materials Easily burn, therefore add fire retardant flame treatment to be carried out to which be necessary.
Expansion type flame retardant (Intumescent Flame Retardant, abbreviation IFR) be it is a kind of it is typical it is phosphorous, contain The halogen-free flame retardants of nitrogen, and one of preferable fire retardant of effect at present.It mainly includes three parts, is charcoal source, acid respectively Source and source of the gas, when burning can produce intumescent layer of charcoal, can effectively prevent the transmission of heat and oxygen, improve the resistance of material Combustion performance.But traditional expansion type flame retardant is added in polymer (for example：Polypropylene, polyethylene, nylon etc.) exist and add Dosage is larger, and polymeric matrix poor compatibility, smoke suppressing is poor, resistance to water is poor and easily separates out during preparing use etc. Problem, therefore, novel environment friendly, efficient expansion type flame retardant is developed with very great meaning.
Melamine (Melamine, abbreviation MA, chemical formula：C3N6H6) it is a kind of triazines nitrogen heterocyclic ring organic compound, It is used as industrial chemicals and flame retardant area.The features such as such compound has Halogen, low toxicity and low cigarette, can decompose product in burning Raw CO2、N2、NH3And H2The non-flammable gases such as O, and these non-flammable gases can with diluted polymer by thermal decomposition produce can Oxygen in combustion property gas and air, while a part of heat also can be taken away in volatilization process, reduces polymeric material The temperature on surface, so that play fire retardation.When this kind of compound is individually used in polymeric material, effect is bad, generally with it is poly- Ammonium phosphate, various metal oxides, slaine and organic phosphorus series compound combine, and reach preferable synergistic fire retardation.
Phytic acid (Phytic acid, PA) chemical name phytic acid, is a kind of organic phosphoric acid extracted from plant seed Class compound.It is primarily present in that the seed of plant, root be dry and stem in, wherein with fabaceous seed, the wheat bran of cereal and Content highest in plumule.The application of phytic acid is widely.In the food industry, phytic acid can be used as food additives, in vintager Can be used as except metal agent in industry.The toxicity of phytic acid is also lower than salt, environmental protection.Due to phytic acid itself phosphorus content it is higher, and And containing abundant acid source and carbon source, therefore, it can be used for preparing environment-friendly type expansion type flame retardant.
Melamine polyphosphate (melamine polyphosphate), abbreviation MPOP, with excellent heat endurance Can (decomposition temperature reaches more than 300 DEG C), as halogen-free environment-friendly type flame-proof agent purposes it is quite varied be largely used to thermosetting and In thermoplastic (7649038 B2 of patent No. US).But, as melamine polyphosphate comprises only acid source and source of the gas, Material (such as the pentaerythrite) compounding use for generally requiring in actual applications to serve as charcoal source with some could have preferably effect Really, while needing higher addition.Melamine polyphosphate prepared by conventional method is little due to molecular weight, is using process It is middle there are problems that with the poor compatibility of polymeric matrix, it is acid larger and in water solubility is relatively.
The content of the invention
The purpose of the present invention is intended to overcome deficiency of the prior art, there is provided a kind of containing phosphorus-nitrogen-carbon poly mould assembly intumescent resistance The preparation method and its usage of combustion agent.The present invention provides a kind of expansion type flame retardant with special appearance -- melamine phytic acid The preparation method of salt fire retardant, the melamine phytate fire retardant of preparation be carbon-collecting source, acid source and source of the gas be integrated it is new The expansion type flame retardant of efficient environmental protection, compared with existing melamine polyphosphate, preparation method is simpler, and environment is dirty Dye is little, in water, solubility is low, preferable with special flaky nanometer structure, polymer matrix compatability and fire resistance is prominent Go out.
Present disclosure is：A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, is characterized in that step Suddenly it is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:3～ 1:15, it is 20～50ml that the consumption of solvent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 20～40 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 20 ～50 minutes, obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 70 At～120 DEG C react 24～56h, cooling, suction filtration, after solids ethanol wash 2～4 times, be washed with water wash to pH (about) be 7 (and no longer changing), then drying, that is, be obtained containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (solid product).
In present disclosure：Solvent described in step a can be water, methyl alcohol, ethanol or acetone.
In present disclosure：Drying described in step c is the bar in 40～70 DEG C of temperature, -0.1～-0.06MPa of pressure It is dried 8～24 hours under part.
In present disclosure：Obtained containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant be laminated structure, lamellar spacing For 20～60 nanometers.
Containing phosphorus-nitrogen obtained in present invention-carbon poly mould assembly expansion type flame retardant can be used for flame-retardant high-molecular composite In.
Macromolecular material in the flame-retardant high-molecular composite can for polypropylene, epoxy resin, unsaturated polyester (UP), Polyethylene, nylon or acrylonitrile-butadiene-styrene copolymer (abbreviation ABS) etc.；The inventive method synthesis with nanometer sheet The expansion type flame retardant of shape structure containing phosphorus-nitrogen-carbon is used in these thermosettings and thermoplastic, has preferably compatible with matrix Property, flame retarding and smoke suppressing properties are excellent.
The containing phosphorus-nitrogen with flaky nanometer structure synthesized by the inventive method-carbon poly mould assembly expansion type flame retardant is three Poly cyanamid phytate, is named as PAMA.
Compared with prior art, the present invention has following features and beneficial effect：
(1) using the present invention, the monomer for using is polyfunctional monomer, contains three amidos, phytic acid in melamine In contain six phosphoric acid, as amido is very easy to form melamine salt with Bronsted acid, so melamine and phytic acid can React to each other into salt；As melamine is polyfunctional compound with phytic acid, can continue to each other react to each other, easily In formation dissaving structure, then self assembly is piled up by intermolecular force or pi-pi bond, ultimately form flaky nanometer structure.
(2) the aggretion type expansion type flame retardant with flaky nanometer structure containing phosphorus-nitrogen-carbon of present invention synthesis is collection charcoal Source, the gentle new and effective fire retardant for coming from one of acid source, preparation method are simple and environmentally friendly, raw material environment-protecting asepsis；With traditional phosphorus- Nitrogen expansion type combustion inhibitor is compared, and PAMA itself has charcoal source, therefore, it is possible to more rapidly producing layer of charcoal and preventing burning；Meanwhile, The triazine ring contained in PAMA structures and six annulus of phytic acid also have very high heat endurance；Melamine is when being thermally decomposed Substantial amounts of NH can be produced3、NO2、N2And CO2Imflammable gas and oxygen can be diluted Deng non-flammable gases, the phosphoric acid in phytic acid Structure can promote polymer to be dehydrated into charcoal, therefore, PAMA can give full play to the effect of P-N cooperative flame retardants；
(3) using the present invention, the melamine phytate expansion type flame retardant of the flaky nanometer structure of synthesis is applied to gather In compound, at the thermal decomposition initial stage, laminated structure can play certain physical barrier effect to heat and oxygen, and the thickness of lamella is about 20～60nm, the dispersion that this size will advantageously in fire retardant in polymeric matrix；In structure, the present invention One of reactant for using -- phytic acid is a kind of organic acid, according to similar compatibility principle, participates in the fire retardant and polymer of synthesis With good compatibility, and dispersive property is good；
(4) product preparation process of the present invention is simple, and operation is easy, easily operates, environmental protection, the carbon-collecting source of synthesis, acid Source is gentle come from one it is efficient, environmentally friendly, and the good aggretion type expansion type flame retardant of matrix compatibility it is of many uses, anti-flammability Can be good, it is practical.
Description of the drawings
Fig. 1 is the expansion type flame retardant (b) with flaky nanometer structure and the melamine (a) synthesized by the present invention X-ray diffraction spectrogram；
Fig. 2 is melamine (a) and the expansion type flame retardant (b) with flaky nanometer structure synthesized by the present invention Infrared spectrum；
Fig. 3 is the ESEM spectrum under the expansion type flame retardant low power number with flaky nanometer structure synthesized by the present invention Figure；
Fig. 4 is the high magnification numbe ESEM spectrum of the expansion type flame retardant with flaky nanometer structure synthesized by the present invention Figure；
Fig. 5 be pure epoxy resin and containing 6wt% it is of the invention synthesized by the expansion type flame retardant with flaky nanometer structure Fire retarding epoxide resin HRR comparison diagram.
Specific embodiment
Specific description has been carried out to the present invention below by embodiment.It is important to point out that the following example is served only for To invention be further described, be not to be construed as limiting the scope of the invention, if person skilled in art according to The content of the invention described above is made some non-intrinsically safes and adjusts and improve to the present invention, still falls within protection scope of the present invention.In addition, What deserves to be explained is：The limited oxygen index (LOI) of following examples each group flame-retardant smoke inhibition composite and vertical burn test (UL-94) test is carried out by standard GB8624-2006 and GB20286-2006 respectively；Taper calorimetric test is by standard ISO5660 Carry out, radiant power is 35kW/m2。
Embodiment 1：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
0.08mol melamines are added in the reaction vessel equipped with magnetic agitation, the ethanol of 160ml is added, 20 At DEG C, stirring adds 0.015mol phytic acid, and after addition, maintenance system is temperature-resistant continues stirring 50 minutes, then falls reactant liquor Enter in the reactor of polytetrafluoro, react 24 hours at a temperature of 120 DEG C.Product is poured out after reaction, is first used with ethanol again Water is repeatedly washed to pH about 7 and is no longer changed, suction filtration, in the then drying under conditions of temperature 60 C, pressure -0.08MPa 10 hours, white solid product is obtained, i.e. containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, abbreviation PAMA1.
The X ray diffracting spectrum (such as Fig. 1 (b)) of the expansion type flame retardant shows：The melamine phytate intumescent hinders The characteristic peak of combustion agent be respectively 2 θ=14.1,15.0,17.9,25.6,26.9 and 27.7 °, and the XRD (Fig. 1 (a)) of melamine Characteristic peak then occur in 2 θ=12.86,14.83,17.44,21.50,22.03,25.95,28.63 and 29.74 °, by contrast It was found that the characteristic peak of melamine almost disappears in the XRD of fire retardant, and occur in that a series of new diffraction maximum explanation three Poly cyanamid there occurs reaction with phytic acid.Melamine infared spectrum (such as Fig. 2 (a)) shows：In melamine, 3469 Hes 3419cm-1It is free NH respectively2Symmetric and anti-symmetric stretching vibration, 1654,1553 and 1439cm-1It is the skeleton of triazine ring Vibration, 813cm-1It is the deformation vibration of triazine ring.And 3361cm in PAMA-1It is the stretching vibration of NH, 3128cm-1It is NH3 +Stretch Contracting vibration, 2843cm-1It is the stretching vibration of CH keys, 1673,1507 and 1333cm-1It is the skeletal vibration of triazine ring, 1368cm-1 It is the stretching vibration of C-N keys, 1178cm-1It is the stretching vibration of P=O double bonds, 1064cm-1It is (PO3)2-Characteristic absorption peak, 982cm-1It is the stretching vibration of P-O keys, 776cm-1It is the deformation vibration of ring, illustrates that phytic acid there occurs reaction shape with melamine Into salt.ESEM (such as Fig. 3) shows that the expansion type flame retardant structure is homogeneous, and the size of laminated structure is in below 5um. Fig. 4 is the scanning electron microscope (SEM) photograph under the fire retardant high magnification numbe, and as can be seen from the figure the thickness of lamella is about 50nm.Fig. 5 is pure ring The HRR comparison diagram of oxygen tree fat and fire retarding epoxide resin, the maximum HRR of pure epoxy resin (EP) is 1050kW/m2, and after adding the PAMA1 of 6wt%, the maximum HRR of fire retarding epoxide resin (EP-PAMA) drops to 395.6kW/m2,, show that PAMA1 drastically increases the fire resistance of epoxy resin.
Embodiment 2：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：To anti-equipped with magnetic agitation 0.09mol melamines are added in answering container, the distilled water of 450ml is added, the stirring at 40 DEG C add 0.03mol phytic acid, After addition, maintenance system is temperature-resistant continues stirring 40 minutes, then pours reactant liquor in the reactor of polytetrafluoro, at 90 DEG C At a temperature of react 56 hours.Product is poured out after reaction, is first repeatedly washed to pH about 7 and is no longer become with water with ethanol again Change, suction filtration, in then drying 24 hours under conditions of temperature 70 C, pressure -0.1MPa, white solid product is obtained, that is, is contained Phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, abbreviation PAMA2.
Embodiment 3：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：To anti-equipped with magnetic agitation 0.15mol melamines are added in answering container, the acetone of 450ml is added, the stirring at 25 DEG C adds 0.01mol phytic acid, plus Enter the temperature-resistant continuation stirring of rear maintenance system 20 minutes, then reactant liquor is poured in the reactor of polytetrafluoro, at 70 DEG C At a temperature of react 36 hours.Product is poured out after reaction, is first repeatedly washed to pH about 7 and is no longer become with water with ethanol again Change, suction filtration, in then drying 8 hours under conditions of 40 DEG C of temperature, pressure -0.06MPa, obtain white solid product, that is, contain Phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, abbreviation PAMA3.
Embodiment 4：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：To anti-equipped with magnetic agitation 0.07mol melamines are added in answering container, the methyl alcohol of 280ml is added, the stirring at 35 DEG C adds 0.01mol phytic acid, plus Enter the temperature-resistant continuation stirring of rear maintenance system 25 minutes, then reactant liquor is poured in the reactor of polytetrafluoro, at 95 DEG C At a temperature of react 48 hours.Product is poured out after reaction, is first repeatedly washed to pH about 7 and is no longer become with water with ethanol again Change, suction filtration, in then drying 12 hours under conditions of temperature 50 C, pressure -0.08MPa, obtain white solid product, that is, contain Phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, abbreviation PAMA4.
The following is fire retarding epoxide resin, ABS and poly- third is respectively used to expansion type flame retardant prepared by the embodiment of the present invention 1 Application examples in alkene.
Application examples 1-4：
This group of application examples is 1 products therefrom of embodiment is common through solvent with epoxy resin according to the formula listed by table 1 After mixed, decompression distilled removes solvent, detects oxygen index (OI), vertical combustion performance and the taper amount of composite after cured shaping Hot property, the results are shown in Table 1.
Table 1：
Application examples 5-8：
This group of application examples is 1 products therefrom of embodiment to be added in polypropylene according to the formula listed by table 2, the double spiral shells of Jing Extruding pelletization after bar extruder melt blending, then Jing injection machine injection mo(u)ldings, the oxygen index (OI) of composite, vertical combustion performance are shown in Table 2.
Table 2：
Application examples 9-12：
This group of application examples is 1 products therefrom of embodiment to be added in ABS according to the formula listed by table 3, Jing twin-screws Extruding pelletization after extruder melt blending, then Jing injection machine injection mo(u)ldings, the oxygen index (OI) of composite, vertical combustion performance are shown in Table 3。
Table 3：
Embodiment 5：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:3, it is molten It is 20ml that the consumption of agent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 20 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 50 minutes, Obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 70 React 56h at DEG C, cooling, suction filtration, after solids ethanol wash 2 times, are washed with water to wash to pH (about) and (and no longer become for 7 Change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
Embodiment 6：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:15, It is 50ml that the consumption of solvent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 40 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 20 minutes, Obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 120 React 24h at DEG C, cooling, suction filtration, after solids ethanol wash 4 times, are washed with water to wash to pH (about) and (and no longer become for 7 Change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
Embodiment 7：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:9, it is molten It is 35ml that the consumption of agent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 30 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 35 minutes, Obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 95 React 40h at DEG C, cooling, suction filtration, after solids ethanol wash 3 times, are washed with water to wash to pH (about) and (and no longer become for 7 Change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
Embodiment 8：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:6, it is molten It is 29ml that the consumption of agent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 29 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 29 minutes, Obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 100 React 36h at DEG C, cooling, suction filtration, after solids ethanol wash 3 times, are washed with water to wash to pH (about) and (and no longer become for 7 Change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
Embodiment 9：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:4, it is molten It is 25ml that the consumption of agent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 25 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 25 minutes, Obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 80 React 50h at DEG C, cooling, suction filtration, after solids ethanol wash 2 times, are washed with water to wash to pH (about) and (and no longer become for 7 Change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
Embodiment 10：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:14, It is 45ml that the consumption of solvent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 35 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 43 minutes, Obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 110 React 30h at DEG C, cooling, suction filtration, after solids ethanol wash 3 times, are washed with water to wash to pH (about) and (and no longer become for 7 Change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
Embodiment 11：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine：5, it is molten It is 30ml that the consumption of agent is the amount of every 0.01mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid at 33 DEG C of temperature, maintains reaction temperature constant, continues stirring reaction 40 minutes, Obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 90 React 36h at DEG C, cooling, suction filtration, after solids ethanol wash 2～4 times, are washed with water to wash to pH (about) and (and no longer become for 7 Change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
Embodiment 12～17：
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:3～ 1:15 (in embodiment 12～17, phytic acid is respectively with the ratio of the amount of the material of melamine：1:7、1:8、1:10、1:11、1: 12、1:13), the consumption of solvent be the amount of every 0.01mol melamines addition solvent be 20～50ml (in embodiment 12～17, 43ml, 36ml, 33ml, 30ml, 28ml, 260ml are respectively per the amount of 0.01mol melamines addition solvent), it is standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator (can be magnetic stirring apparatus) Amine, adds solvent under agitation, adds phytic acid, maintained reaction temperature constant, continue in 20～40 DEG C of temperature at arbitrary temperature Stirring reaction any time in 20～50 minutes, obtain reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor (the preferably reactor of polytetrafluoro), in temperature 70 React at arbitrary temperature in 24～56h any time in～120 DEG C, cooling, suction filtration, after solids ethanol washs 2～4 times, It is washed with water that to wash to pH (about) be 7 (and no longer change), then drying, that is, containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant is obtained (for solid product).
In above-described embodiment 5～17：Solvent described in step a can be water, methyl alcohol, ethanol or acetone.
In above-described embodiment 5～17：Drying described in step c can be that arbitrary temperature is (preferably in 40～70 DEG C of temperature 60 DEG C), be dried under conditions of arbitrary pressure value (be vacuum dried) 8～24 hours in -0.1～-0.06MPa of pressure in it is arbitrary when Between, compared with technology.
In above-described embodiment 5～17：Obtained containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant be laminated structure, (lamella) Thickness is 20～60 nanometers.
Containing phosphorus-nitrogen obtained in above-described embodiment 5～17-carbon poly mould assembly expansion type flame retardant can be used for flame-retardant high-molecular and be combined In material；Macromolecular material in the flame-retardant high-molecular composite can for polypropylene, epoxy resin, unsaturated polyester (UP), Polyethylene, nylon or acrylonitrile-butadiene-styrene copolymer (abbreviation ABS) etc..
In above-described embodiment：The each raw material for being adopted is commercially available prod.
In above-described embodiment：It is in the percentage for being adopted, especially not dated, be quality (weight) percentage or Well known to a person skilled in the art percentage；Quality (weight) part can be gram or kilogram.
In above-described embodiment：Technological parameter (temperature, time, concentration etc.) and each component numerical quantity in each step etc. are Scope, any point is applicable.
The technology contents being not specifically delineated in present invention and above-described embodiment are compared with technology.
The invention is not restricted to above-described embodiment, can implement described in present invention and there is the good result.

Claims (6)

1. a kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, is characterized in that step is：
A, dispensing：Raw material phytic acid, melamine and solvent is taken, phytic acid is 1 with the ratio of the amount of the material of melamine:3～1:15, It is 20～50 ml that the consumption of solvent is the amount of every 0.01 mol melamines addition solvent, standby；
B, mixing：Melamine is added in the reaction vessel equipped with thermometer and agitator, solvent is added under agitation, in temperature Phytic acid is added at 20～40 DEG C of degree, is maintained reaction temperature constant, is continued stirring reaction 20～50 minutes, obtains reactant liquor；
C, reaction and post processing：Reactant liquor is poured in reactor, 24～56h is reacted at 70～120 DEG C of temperature, is cooled down, takes out Filter, after solids ethanol wash 2～4 times, is washed with water that to wash to pH be 7, and then drying is obtained containing phosphorus-nitrogen-carbon poly conjunction Type expansion type flame retardant.
2. as described in claim 1 containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method, it is characterized in that：In step a The solvent is water, methyl alcohol, ethanol or acetone.
3. as described in claim 1 or 2 containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method, it is characterized in that：Step c Described in drying be under conditions of 40～70 DEG C of temperature, -0.1～-0.06 MPa of pressure be dried 8～24 hours.
4. as described in claim 1 or 2 containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method, it is characterized in that：It is obtained Containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant be laminated structure, lamellar spacing be 20～60 nanometers.
5. as described in claim 1 or 2 containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method, it is characterized in that：It is obtained Containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant can be used for flame-retardant high-molecular composite.
6. as described in claim 5 containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method, it is characterized in that：It is described fire-retardant Macromolecular material in polymer composite be polypropylene, epoxy resin, unsaturated polyester (UP), polyethylene, nylon or acrylonitrile- BS.
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CN108047494A (en) * 2017-11-15 2018-05-18 四川大学 Phytic acid ammonium salt fire retardant and preparation method thereof and the fire-retardant toughened poly-lactic acid material to prepare
CN108314951A (en) * 2018-01-12 2018-07-24 沈阳化工大学 A kind of preparation method of steel structure aqueous anti-corrosion fire resistant coating material
CN108314951B (en) * 2018-01-12 2020-05-19 沈阳化工大学 Preparation method of water-based anticorrosive fireproof coating material for steel structure
CN109320548A (en) * 2018-09-14 2019-02-12 浙江工业大学 A kind of biology base three-source-in-one expansion type fire retardant and preparation method thereof, application
CN110408199A (en) * 2019-08-02 2019-11-05 横店集团得邦工程塑料有限公司 A kind of novel anti-precipitation flame-proof PA 6 composite material and preparation method
CN111019239A (en) * 2019-12-03 2020-04-17 武汉理工大学 Flame-retardant polypropylene barrier explosion-proof material and preparation method and application thereof
CN111040399B (en) * 2019-12-13 2021-05-14 江南大学 Flame-retardant polylactic acid composite material and preparation method thereof
CN111040399A (en) * 2019-12-13 2020-04-21 江南大学 Flame-retardant polylactic acid composite material and preparation method thereof
CN110951191A (en) * 2019-12-16 2020-04-03 无锡市华美电缆有限公司 Cable material containing supramolecular self-assembly flame retardant and preparation method thereof
CN111244483B (en) * 2020-01-15 2021-06-15 先进能源产业研究院(广州)有限公司 N-P co-doped porous carbon-coated NiCo2O4Oxygen reduction catalyst and process for producing the same
CN111244483A (en) * 2020-01-15 2020-06-05 朱旭烈 N-P co-doped porous carbon-coated NiCo2O4Oxygen reduction catalyst and process for producing the same
CN111484732A (en) * 2020-04-23 2020-08-04 江南大学 Phytate composite flame retardant for polyamide and preparation method thereof
CN111484732B (en) * 2020-04-23 2021-08-10 江南大学 Phytate composite flame retardant for polyamide and preparation method thereof
CN112679789A (en) * 2021-01-20 2021-04-20 江苏威久科技发展有限公司 Flame-retardant n-pentane foaming agent for polyurethane and preparation method thereof
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