CN106519239B - A kind of preparation method and its usage of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant - Google Patents
A kind of preparation method and its usage of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant Download PDFInfo
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- CN106519239B CN106519239B CN201610885221.0A CN201610885221A CN106519239B CN 106519239 B CN106519239 B CN 106519239B CN 201610885221 A CN201610885221 A CN 201610885221A CN 106519239 B CN106519239 B CN 106519239B
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- 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
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Abstract
The invention discloses a kind of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation methods for having flaky nanometer structure, it is characterized in that: taking phytic acid, melamine and solvent, the ratio between amount of substance of phytic acid and melamine is 1:3~1:15, and the dosage of solvent is that every 0.01 mol melamine adds 20~50 ml of solvent；Melamine is added into the reaction vessel equipped with thermometer and blender, is added with stirring solvent, phytic acid is added at 20~40 DEG C of temperature, be stirred to react 20~50 minutes, obtain reaction solution；Reaction solution is poured into reaction kettle, reacts 24~56h at 70~120 DEG C of temperature, it is cooling, filter, after solids ethanol washing, it is washed with water that wash to pH be 7, it is dry, it obtains.Preparation method of the present invention is simple, environmentally protective, and the containing phosphorus-nitrogen with the laminated structure-carbon poly mould assembly expansion type flame retardant and polymeric matrix of synthesis have good compatibility and flame retardant property.
Description
Technical field
The invention belongs to the preparations of aggretion type expansion type flame retardant, are related to a kind of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame-retarding
The preparation method and its usage of agent.Containing phosphorus-nitrogen prepared by the present invention-carbon poly mould assembly expansion type flame retardant has nano-sheet knot
Structure is suitable as additive flame retardant and is added to the anti-flammability for promoting polymer in polymer (i.e. flame retarded polymeric material)
Can, it can also be used in compounding with the fire retardant of other types.
Background technique
In recent years, with the continuous development of science and technology, high molecular material has become indispensable one in daily life
Also there is corresponding problem while offering convenience in part, the use of high molecular material.Due to most of high molecular materials
It is easy burning, therefore addition fire retardant carries out flame retardant treatment to it and is 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 gas source can generate intumescent layer of charcoal when burning, can effectively prevent the transmitting of heat and oxygen, improve the resistance of material
Fire performance.But traditional expansion type flame retardant, which is added in polymer (such as: polypropylene, polyethylene, nylon etc.), to be existed and adds
Dosage is larger, with the poor compatibility of polymeric matrix, smoke suppressing is poor, water resistance is poor and preparation use process in easily precipitation etc.
Problem, therefore, develop novel environment friendly, efficient expansion type flame retardant there is 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.Such compound has the characteristics that Halogen, low toxicity and low cigarette, can decompose production 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 generate can
Oxygen in combustion property gas and air, while a part of heat can be also taken away in volatilization process, reduce polymer material
The temperature on surface, to play fire retardation.Effect is bad when this kind of compound is individually used in polymer material, usually with it is poly-
Ammonium phosphate, various metal oxides, metal salt and organophosphorus 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 the seed of leguminous plant, cereal wheat bran and
Content highest in plumule.Phytic acid is very widely used.In the food industry, phytic acid can be used as food additives, in vintager
It can be used as in industry except metal agent.The toxicity of phytic acid is also lower than salt, environmentally protective.Since phytic acid itself phosphorus content is higher, and
And therefore acid source rich in and carbon source can be used to prepare environment-friendly type expansion type flame retardant.
Melamine polyphosphate (melamine polyphosphate), abbreviation MPOP have excellent thermal stability
Can (decomposition temperature reaches 300 DEG C or more), as halogen-free environment-friendly type flame-proof agent purposes it is very extensive be largely used to thermosetting property and
In thermoplastic material (7649038 B2 of patent No. US).But since melamine polyphosphate contains only acid source and gas source,
It generally requires to be used in compounding with some substances (such as pentaerythrite) for serving as charcoal source in practical applications and could have preferable effect
Fruit, while needing higher additive amount.The melamine polyphosphate of conventional method preparation is since molecular weight is small, in use process
It is middle exist with the poor compatibility of polymeric matrix, acidity is larger and solubility is higher in water the problems such as.
Summary of the invention
The purpose of the present invention is intended to overcome deficiency in the prior art, provides a kind of containing phosphorus-nitrogen-carbon poly mould assembly intumescent resistance
Fire the preparation method and its usage of 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, it is novel that the melamine phytate fire retardant of preparation is that carbon-collecting source, acid source and gas source are integrated
The expansion type flame retardant of efficient environmental protection, preparation method is simpler compared with existing melamine polyphosphate, and environment is dirty
Contaminate it is small, in water solubility it is low, with special flaky nanometer structure, polymer matrix compatability is preferable and flame retardant property is prominent
Out.
The contents of the present invention are: a kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, it is characterized in that step
Suddenly are as follows:
A, ingredient: taking raw material phytic acid, melamine and solvent, the ratio between amount of substance of phytic acid and melamine for 1:3~
1:15, the dosage of solvent is that the amount of every 0.01mol melamine addition solvent is 20~50ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 20~40 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 20
~50 minutes, obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 70
React 24~56h at~120 DEG C, it is cooling, filter, after solids ethanol washing 2~4 times, it is washed with water that wash to pH (about) be 7
(and no longer changing), then through drying, obtains containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (solid product).
In the contents of the present invention: solvent described in step a can be water, methanol, ethyl alcohol or acetone.
In the contents of the present invention: drying described in step c is in 40~70 DEG C of temperature, pressure -0.1~-0.06MPa item
It is 8~24 hours dry under part.
In the contents of the present invention: containing phosphorus-nitrogen obtained-carbon poly mould assembly expansion type flame retardant is laminated structure, lamellar spacing
It is 20~60 nanometers.
Containing phosphorus-nitrogen made from the content of present invention-carbon poly mould assembly expansion type flame retardant can be used for flame-retardant high-molecular composite material
In.
High molecular material in the flame-retardant high-molecular composite material can for polypropylene, epoxy resin, unsaturated polyester (UP),
Polyethylene, nylon or acrylonitrile-butadiene-styrene copolymer (abbreviation ABS) etc.；The method of the present invention synthesis has nanometer sheet
Shape structure containing phosphorus-nitrogen-carbon expansion type flame retardant with matrix for having preferable compatible in these thermosetting properties and thermoplastic
Property, flame retarding and smoke suppressing properties are excellent.
Containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant synthesized by the method for the present invention with flaky nanometer structure is three
Poly cyanamid phytate, is named as PAMA.
Compared with prior art, the present invention have following features and the utility model has the advantages that
(1) using the present invention, the monomer used is polyfunctional monomer, containing there are three amido, phytic acid in melamine
In containing there are six phosphoric acid, since amido is very easy to form melamine salt with Bronsted acid, so melamine and phytic acid can
React to each other into salt；Since melamine and phytic acid are polyfunctional compounds, can continue to react to each other each other, easily
Self assembly is piled up in formation dissaving structure, then by intermolecular force or pi-pi bond, ultimately forms flaky nanometer structure.
(2) it is collection charcoal that the present invention synthesized, which has flaky nanometer structure containing phosphorus-nitrogen-carbon aggretion type expansion type flame retardant,
Source, the gentle new and effective fire retardant derived from one of acid source, preparation method is simple and environmental protection, raw material are environment-protecting and non-poisonous；With traditional phosphorus-
Nitrogen expansion type combustion inhibitor is compared, and PAMA itself has charcoal source, therefore can more rapidly generate layer of charcoal and prevent to burn；Meanwhile
Six annulus of the triazine ring and phytic acid that contain in PAMA structure also have very high thermal stability；Melamine is when being thermally decomposed
A large amount of NH can be generated3、NO2、N2And CO2Equal non-flammable gases can dilute imflammable gas and oxygen, the phosphoric acid in phytic acid
Structure can promote polymer to be dehydrated into charcoal, and therefore, PAMA can give full play to the effect of P-N cooperative flame retardant；
(3) using the present invention, the melamine phytate expansion type flame retardant of the flaky nanometer structure of synthesis is applied to poly-
It closes in object, at thermal decomposition initial stage, laminated structure can play the role of certain physical barrier to heat and oxygen, and the thickness of lamella is about
20~60nm, this size will be more conducive to the dispersion of fire retardant in a polymer matrix；From structure, the present invention
One of reactant used -- 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 dispersion performance is good；
(4) product of the present invention preparation process is simple, and process is easy, easy to operate, environmentally protective, carbon-collecting source, the acid of synthesis
Gentle efficient, environmentally friendly, widely used with the good aggretion type expansion type flame retardant of matrix compatibility, the anti-flammability derived from one in source
Can be good, it is practical.
Detailed description of the invention
Fig. 1 is the expansion type flame retardant (b) and melamine (a) synthesized by the present invention with flaky nanometer structure
X-ray diffraction spectrogram；
Fig. 2 is the expansion type flame retardant (b) synthesized by melamine (a) and the present invention with flaky nanometer structure
Infrared spectrum；
Fig. 3 is the scanning electron microscope spectrum under the expansion type flame retardant low power number synthesized by the present invention with flaky nanometer structure
Figure；
Fig. 4 is the high magnification numbe scanning electron microscope spectrum of the expansion type flame retardant synthesized by the present invention with flaky nanometer structure
Figure；
Fig. 5 be pure epoxy resin and containing 6wt% the present invention synthesized by the expansion type flame retardant with flaky nanometer structure
Fire retarding epoxide resin heat release rate 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
Invention is further described, limiting the scope of the invention is not to be construed as, if person skilled in art according to
The content of aforementioned present invention makes some non-intrinsically safes to the present invention and adjusts and improve, and still falls within protection scope of the present invention.In addition,
It is worth noting that: the limit oxygen index (LOI) and vertical burn test of following embodiment each group flame-retardant smoke inhibition composite material
(UL-94) test is carried out by standard GB8624-2006 and GB20286-2006 respectively；Standard ISO5660 is pressed in taper calorimetric test
It carries out, radiant power 35kW/m2。
Embodiment 1:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
0.08mol melamine is added into the reaction vessel equipped with magnetic agitation, the ethyl alcohol of 160ml is added, 20
0.015mol phytic acid is added in stirring at DEG C, and maintenance system is temperature-resistant after addition continues stirring 50 minutes, then falls reaction solution
Enter in the reaction kettle of polytetrafluoro, 120 DEG C at a temperature of react 24 hours.Reaction product is poured out after reaction, is first used again with ethyl alcohol
Water, which is repeatedly washed to pH, to be about 7 and no longer changes, and is filtered, dry under conditions of then in 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 is shown: melamine phytate intumescent resistance
The characteristic peak of combustion agent is 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 appears in 2 θ=12.86,14.83,17.44,21.50,22.03,25.95,28.63 and 29.74 °, passes through comparison
It was found that the characteristic peak of melamine almost disappears in the XRD of fire retardant, and there is a series of new diffraction maximum and illustrate three
Poly cyanamid is reacted with phytic acid.Melamine infared spectrum (such as Fig. 2 (a)) display: 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 key, 1673,1507 and 1333cm-1It is the skeletal vibration of triazine ring, 1368cm-1
It is the stretching vibration of C-N key, 1178cm-1It is the stretching vibration of P=O double bond, 1064cm-1It is (PO3)2-Characteristic absorption peak,
982cm-1It is the stretching vibration of P-O key, 776cm-1It is the deformation vibration of ring, illustrates that phytic acid has occurred with melamine and react shape
At salt.Scanning electron microscope (such as Fig. 3) show the expansion type flame retardant structure be it is uniform, the size of laminated structure is in 5um or less.
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 maximum heat release rate of the heat release rate comparison diagram of oxygen resin and fire retarding epoxide resin, pure epoxy resin (EP) is
1050kW/m2, and after adding the PAMA1 of 6wt%, the maximum heat release rate of fire retarding epoxide resin (EP-PAMA) drops to
395.6kW/m2,, show that PAMA1 greatly improves the flame retardant property of epoxy resin.
Embodiment 2:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows: to anti-equipped with magnetic agitation
Addition 0.09mol melamine in container is answered, the distilled water of 450ml is added, 0.03mol phytic acid is added in stirring at 40 DEG C,
Maintenance system is temperature-resistant after addition continues stirring 40 minutes, then pours into reaction solution in the reaction kettle of polytetrafluoro, at 90 DEG C
At a temperature of react 56 hours.Reaction product is poured out after reaction, is first repeatedly washed with water to pH with ethyl alcohol again and is about 7 and no longer becomes
Change, filters, it is 24 hours dry under conditions of then in 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 are as follows: to anti-equipped with magnetic agitation
Addition 0.15mol melamine in container is answered, the acetone of 450ml is added, 0.01mol phytic acid is added in stirring at 25 DEG C, adds
Enter rear maintenance system it is temperature-resistant continue stirring 20 minutes, then reaction solution is poured into the reaction kettle of polytetrafluoro, at 70 DEG C
At a temperature of react 36 hours.Reaction product is poured out after reaction, is first repeatedly washed with water to pH with ethyl alcohol again and is about 7 and no longer becomes
Change, filters, it is 8 hours dry under conditions of then in 40 DEG C of temperature, pressure -0.06MPa, white solid product is obtained, that is, is contained
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 are as follows: to anti-equipped with magnetic agitation
Addition 0.07mol melamine in container is answered, the methanol of 280ml is added, 0.01mol phytic acid is added in stirring at 35 DEG C, adds
Enter rear maintenance system it is temperature-resistant continue stirring 25 minutes, then reaction solution is poured into the reaction kettle of polytetrafluoro, at 95 DEG C
At a temperature of react 48 hours.Reaction product is poured out after reaction, is first repeatedly washed with water to pH with ethyl alcohol again and is about 7 and no longer becomes
Change, filters, it is 12 hours dry under conditions of then in temperature 50 C, pressure -0.08MPa, white solid product is obtained, that is, is contained
Phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, abbreviation PAMA4.
It is that the expansion type flame retardant prepared by the embodiment of the present invention 1 is respectively used to fire retarding epoxide resin, ABS and poly- third below
Application examples in alkene.
Application examples 1-4:
This group of application examples is to be total to 1 products therefrom of embodiment and epoxy resin by solvent according to formula listed by table 1
After mixed, decompression distilled removes solvent, and oxygen index (OI), vertical combustion performance and the taper amount of composite material are detected after cured molding
Hot property the results are shown in Table 1.
Table 1:
Application examples 5-8:
This group of application examples is that 1 products therefrom of embodiment is added in polypropylene according to formula listed by table 2, through double spiral shells
Extruding pelletization after bar extruder melt blending, then through injection molding machine injection molding, the oxygen index (OI) of composite material, vertical combustion performance are shown in
Table 2.
Table 2:
Application examples 9-12:
This group of application examples is that 1 products therefrom of embodiment is added in ABS according to formula listed by table 3, through twin-screw
Extruding pelletization after extruder melt blending, then through injection molding machine injection molding, the oxygen index (OI) of composite material, 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 are as follows:
A, ingredient: raw material phytic acid, melamine and solvent are taken, the ratio between phytic acid and the amount of substance of melamine are 1:3, molten
The dosage of agent is that the amount of every 0.01mol melamine addition solvent is 20ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 20 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 50 minutes,
Obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 70
React 56h at DEG C, it is cooling, filter, after solids ethanol washing 2 times, it is washed with water that wash to pH (about) be 7 and (and no longer becomes
Change), then through drying, obtain containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (for solid product).
Embodiment 6:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
A, ingredient: taking raw material phytic acid, melamine and solvent, and the ratio between phytic acid and the amount of substance of melamine are 1:15,
The dosage of solvent is that the amount of every 0.01mol melamine addition solvent is 50ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 40 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 20 minutes,
Obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 120
It is reacted at DEG C for 24 hours, it is cooling, filter, after solids ethanol washing 4 times, it is washed with water that wash to pH (about) be 7 and (and no longer becomes
Change), then through drying, obtain containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (for solid product).
Embodiment 7:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
A, ingredient: raw material phytic acid, melamine and solvent are taken, the ratio between phytic acid and the amount of substance of melamine are 1:9, molten
The dosage of agent is that the amount of every 0.01mol melamine addition solvent is 35ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 30 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 35 minutes,
Obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 95
React 40h at DEG C, it is cooling, filter, after solids ethanol washing 3 times, it is washed with water that wash to pH (about) be 7 and (and no longer becomes
Change), then through drying, obtain containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (for solid product).
Embodiment 8:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
A, ingredient: raw material phytic acid, melamine and solvent are taken, the ratio between phytic acid and the amount of substance of melamine are 1:6, molten
The dosage of agent is that the amount of every 0.01mol melamine addition solvent is 29ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 29 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 29 minutes,
Obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 100
React 36h at DEG C, it is cooling, filter, after solids ethanol washing 3 times, it is washed with water that wash to pH (about) be 7 and (and no longer becomes
Change), then through drying, obtain containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (for solid product).
Embodiment 9:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
A, ingredient: raw material phytic acid, melamine and solvent are taken, the ratio between phytic acid and the amount of substance of melamine are 1:4, molten
The dosage of agent is that the amount of every 0.01mol melamine addition solvent is 25ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 25 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 25 minutes,
Obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 80
React 50h at DEG C, it is cooling, filter, after solids ethanol washing 2 times, it is washed with water that wash to pH (about) be 7 and (and no longer becomes
Change), then through drying, obtain containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (for solid product).
Embodiment 10:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
A, ingredient: taking raw material phytic acid, melamine and solvent, and the ratio between phytic acid and the amount of substance of melamine are 1:14,
The dosage of solvent is that the amount of every 0.01mol melamine addition solvent is 45ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 35 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 43 minutes,
Obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 110
React 30h at DEG C, it is cooling, filter, after solids ethanol washing 3 times, it is washed with water that wash to pH (about) be 7 and (and no longer becomes
Change), then through drying, obtain containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (for solid product).
Embodiment 11:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
A, ingredient: raw material phytic acid, melamine and solvent are taken, the ratio between phytic acid and the amount of substance of melamine are 1:5, molten
The dosage of agent is that the amount of every 0.01mol melamine addition solvent is 30ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at 33 DEG C of temperature, and maintaining reaction temperature is constant, continues to be stirred to react 40 minutes,
Obtain reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 90
React 36h at DEG C, it is cooling, filter, after solids ethanol washing 2~4 times, it is washed with water that wash to pH (about) be 7 and (and no longer becomes
Change), then through drying, obtain containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant (for solid product).
Embodiment 12~17:
A kind of preparation method of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant, step are as follows:
A, ingredient: taking raw material phytic acid, melamine and solvent, the ratio between amount of substance of phytic acid and melamine for 1:3~
1:15 (in embodiment 12~17, the ratio between phytic acid and the amount of substance of melamine are respectively as follows: 1:7,1:8,1:10,1:11,1:
12,1:13), the dosage of solvent be every 0.01mol melamine addition solvent amount be 20~50ml (in embodiment 12~17,
The amount of every 0.01mol melamine addition solvent is respectively 43ml, 36ml, 33ml, 30ml, 28ml, 260ml), it is spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender (can be magnetic stirring apparatus)
Solvent is added in amine under stiring, and phytic acid is added at any temperature in 20~40 DEG C of temperature, and maintaining reaction temperature is constant, continues
It is stirred to react any time in 20~50 minutes, obtains reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle (the preferably reaction kettle of polytetrafluoro), in temperature 70
React any time in 24~56h in~120 DEG C at any temperature, it is cooling, filter, solids with after ethanol washing 2~4 times,
It is washed with water that wash to pH (about) be 7 (and no longer change), then through drying, obtains containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant
(for solid product).
In above-described embodiment 5~17: solvent described in step a can be water, methanol, ethyl alcohol or acetone.
In above-described embodiment 5~17: dry described in step c to can be in 40~70 DEG C of temperature any temperature (preferably
60 DEG C), it is any in (being dried in vacuo) dry under conditions of any pressure value in pressure -0.1~-0.06MPa 8~24 hours when
Between, compared with technology.
In above-described embodiment 5~17: containing phosphorus-nitrogen obtained-carbon poly mould assembly expansion type flame retardant is laminated structure, (lamella)
With a thickness of 20~60 nanometers.
That carbon poly mould assembly expansion type flame retardant can be used for flame-retardant high-molecular to containing phosphorus-nitrogen made from above-described embodiment 5~17-is compound
In material；High molecular material in the flame-retardant high-molecular composite material can for polypropylene, epoxy resin, unsaturated polyester (UP),
Polyethylene, nylon or acrylonitrile-butadiene-styrene copolymer (abbreviation ABS) etc..
In above-described embodiment: used each raw material is commercial product.
In above-described embodiment: it is not specifically specified in used percentage, be quality (weight) percentage or
Well known to a person skilled in the art percentages；Described quality (weight) part can be gram or kilogram.
In above-described embodiment: technological parameter (temperature, time, concentration etc.) and dosage of each component numerical value in each step etc. are
Range, any point is applicable.
The technology contents being not specifically delineated in the content of present invention and above-described embodiment are compared with technology.
The present invention is not limited to the above embodiments, can be implemented described in the content of present invention and has the good result.
Claims (4)
1. a kind of containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method, it is characterized in that step are as follows:
A, ingredient: taking raw material phytic acid, melamine and solvent, and the ratio between phytic acid and the amount of substance of melamine are 1:3~1:15,
The dosage of solvent is that the amount of every 0.01 mol melamine addition solvent is 20~50 ml, spare；
B, it mixes: melamine is added into the reaction vessel equipped with thermometer and blender, solvent is added under stiring, in temperature
Phytic acid is added at 20~40 DEG C of degree, maintaining reaction temperature is constant, continues to be stirred to react 20~50 minutes, obtains reaction solution；
C, reaction and post-processing: reaction solution is poured into reaction kettle, and 24~56h, cooling, pumping are reacted at 70~120 DEG C of temperature
Filter after solids ethanol washing 2~4 times, is washed with water that wash to pH be 7, then through drying, obtains containing phosphorus-nitrogen-carbon poly and close
Type expansion type flame retardant；
The drying is 8~24 hours dry under conditions of 40~70 DEG C of temperature, pressure -0.1~-0.06 MPa；
Containing phosphorus-nitrogen-carbon poly mould assembly the expansion type flame retardant obtained is laminated structure, and lamellar spacing is 20~60 nanometers.
2. by containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method described in claim 1, it is characterized in that: in step a
The solvent is water, methanol, ethyl alcohol or acetone.
3. containing phosphorus-nitrogen as claimed in claim 1 or 2-carbon poly mould assembly expansion type flame retardant preparation method is pressed, it is characterized in that: being made
Containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant can be used for flame-retardant high-molecular composite material.
4. by containing phosphorus-nitrogen-carbon poly mould assembly expansion type flame retardant preparation method described in claim 3, it is characterized in that: described fire-retardant
High molecular material in polymer composite is polypropylene, epoxy resin, unsaturated polyester (UP), polyethylene, nylon or acrylonitrile-
Butadiene-styrene copolymer.
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