CN103910907B - A kind of method of graphene oxide graft modification melamine pyrophosphate fire retardant - Google Patents
A kind of method of graphene oxide graft modification melamine pyrophosphate fire retardant Download PDFInfo
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Abstract
The invention belongs to field of material technology, it is related to a kind of preparation method of graphene oxide graft modification melamine pyrophosphate fire retardant, including step in detail below：Melamine and anhydrous sodium pyrophosphate are added in distilled water, are sufficiently stirred for making system be uniformly dispersed；Added into above-mentioned system through the good graphene oxide colloidal solution of ultrasonic disperse, and be added dropwise catalysis, stabilizer Bronsted acid weak solution, adjust pH value of reaction system, heating, stirring reaction, after reaction completely, then reaction product is subjected to suction filtration, washing, product drying, you can obtain graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants.The above-mentioned preparation method that the present invention is provided is efficient, it is easy to operate, it is environmentally friendly, and the halogen-free expansion fire retardant particle diameter prepared is small, heat endurance is high, in the Halogen system that can be not only used for polyolefin, while being also applied in polyamide, polyester, rubber and dilatancy fireproof coating.
Description
Technical field
The invention belongs to field of material technology, it is related to a kind of graphene oxide graft modification melamine pyrophosphate fire-retardant
The method of agent.
Background technology
Traditional halogenated flame retardant, its flame retarding efficiency height thus the production for being largely used to fire proofing, but halogen system is fire-retardant
Product produces substantial amounts of smog and poisonous corrosive gas in burning, hinders evacuating personnel, causes serious secondary disaster.
At present, expansion type flame retardant（IFR）Paid attention to deep the advantages of its Halogen, low cigarette, low toxicity by people.Melamine (MEL)
And its esters（Cyanurate, phosphate, pyrophosphate, Quadrafos, borate, phthalate, oxalates etc.）It is one
Class nitrogen system and nitrogen-phosphorus flame retardant, are the important components (containing source of the gas and hydrochlorate) for constituting halogen-free expansion fire retardant (IFR), and
Nearly all used IFR, all containing nitrogen and（Or）Phosphorus is used as flame retardant activity component.Due to MA and its esters have it is a series of with
The characteristics of ecological environment is compatible, to the harm very little of human health, so in environmental requirement increasingly strict today, enjoying fire-retardant
Field is attracted attention and favored, and its application is just increasing, and application prospect is good.
But melamine pyrophosphate prepared by traditional synthetic method（MPP）Fire retardant not only particle size than larger,
And the mechanical performance of big, the easy reunion severe exacerbation polymer-base flame-proof material of addition, while there is also cause larger to environment
Pollution, not enough environmental protection.
The content of the invention
For problems of the prior art, it is an object of the invention to provide a kind of modification of halogen-free expansible graphene oxide
The preparation method of melamine pyrophosphate, this method has efficient, easy to operate, environmentally friendly, the good economic benefit of tool
The advantages of.The fire retardant particle diameter for using this method to prepare simultaneously is small, is added to good dispersion in polymeric matrix, and to resistance
The mechanical performance influence of combustible material is small, or even also has humidification to some performances, can be not only used for the Halogen resistance of polyolefin
Combustion system, is also admirably suitable in the engineering plastics such as polyamide, polyester.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of graphene oxide graft modification melamine pyrophosphate fire retardant, this method uses aqueous phase
Synthetic method, comprises the following steps：
（1）By melamine and anhydrous sodium pyrophosphate（Na4P2O7）It is added in distilled water, is sufficiently stirred for disperseing system
Uniformly；
（2）Then to step（1）System in, add through the good graphene oxide of ultrasonic disperse（GO）Colloidal solution, and
Be added dropwise catalysis, stabilizer function Bronsted acid weak solution, adjust pH value of reaction system, heating, stirring reaction；
（3）After reaction completely, reaction product is subjected to suction filtration, washing, product drying, that is, obtains graphene oxide and is modified three
Poly cyanamid pyrophosphate halogen-free flame retardants.
The step（1）In melamine and anhydrous sodium pyrophosphate（Na4P2O7）Mol ratio be 2：（1~1.5）.
The step（1）In stir speed (S.S.) be 400-500r/min, stirring be the time be 15-30min.
The step（2）In graphene oxide（GO）Colloidal solution ultrasonic disperse mode is specially：It is by solid content
0.025-0.05g/mL graphene oxide colloid is in advance in 25-35 DEG C of water temperature, 80-100HZ conditions ultrasound 4-6 hours.
The step（2）In graphene oxide have in typical quasi- two-dimensional slice structure, its structure containing abundant
Hydroxyl, epoxy radicals, carboxyl or carbonyl oxy radical, after ultrasonic disperse, into single or multiple lift structure.
The step（2）In graphene oxide colloid solid content be 0.025-0.05g/mL.
The step（2）The content of middle graphene oxide is melamine and the 5-30% of anhydrous sodium pyrophosphate quality sum.
The step（2）In one kind in hydrochloric acid, silico-tungstic acid, nitric acid or sulfuric acid of Bronsted acid weak solution or it is a kind of with
On, its concentration is 0.1-1mol/L.
The step（2）In Bronsted acid weak solution drop rate be 2-5ml/min.
The step（2）The pH value of middle regulation reaction system is between 3 and 6.
The step（2）In be warming up to 80-100 DEG C, the stirring reaction time is 2-4 hours, and stir speed (S.S.) is 360-
420rad/min。
The step（3）Middle product is in 90-100 DEG C of dry 36-48h.
The step（3）In obtained fire retardant similar " nucleocapsid " structure of structure, wherein melamine pyrophosphate structure
Into " core " of fire retardant " nucleocapsid " structure, the graphene oxide being grafted on melamine pyrophosphate is its " nucleocapsid " structure
" shell ".
Compared with prior art, advantages of the present invention and the beneficial outcomes obtained are the present invention：
（1）Graphene oxide modified cyanurotriamide pyrophosphate is because containing phosphorus and nitrogen in its molecule, with expanding fire retardant
Acid source and source of the gas, and graphene oxide is heated can directly be self-assembly of fine and close carbon-coating, the conduct in flame-retardant system, several persons
Common synergistic effect more effectively plays its fire retardation；
（2）The halogen-free expanded flame-retardant agent makes its flame retardant particle thinner because of the introducing of graphene oxide, as shown in Figure 1,
Dispersiveness is more preferable in polymer collective, not only with efficient flame retardant effect, while to the mechanical performance shadow of composite flame-proof material
Ringing can be smaller；
（3）The fire retardant particle diameter for using this method to prepare simultaneously is small, is added to good dispersion in polymeric matrix, and
Mechanical performance influence on fire proofing is small, or even also has humidification to some performances, can be not only used for the nothing of polyolefin
Halogen flame-retardant system, is also admirably suitable in the engineering plastics such as polyamide, polyester.
Brief description of the drawings
Fig. 1 is the MPP-GO in the embodiment of the present invention（Melamine pyrophosphate-graphene oxide）TEM figure.
Embodiment
The present invention is further illustrated with reference to embodiment and accompanying drawing.
All raw materials used are commercially available prod in embodiments of the invention, do not point out its producer, model specially herein
Deng.
In following examples, graphene oxide has contains abundant hydroxyl in typical quasi- two-dimensional slice structure, its structure
Base, epoxy radicals, carboxyl or carbonyl oxy radical, after ultrasonic disperse, into single or multiple lift structure.
In following examples, graphene oxide（GO）Colloidal solution ultrasonic disperse mode is specially：It is by solid content
0.025-0.05g/mL graphene oxide colloid is in advance in 25-35 DEG C of water temperature, and 80-100HZ conditions ultrasound 4-6 hours is standby.
In following examples, conversion ratio is product by purifying dried final product and initial raw material injected volume repeatedly
Mass percent ratio.
Embodiment 1
（1）In advance by 50.40g melamines and 26.59g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1, plus
Enter into 500ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, make system scattered equal
It is even；
（2）Then to step（1）System in, add 154mL through the good graphene oxide of ultrasonic disperse（GO）Colloid is molten
Liquid, the solid content of its graphene oxide colloid is 0.025g/mL, and graphene oxide GO content is melamine and anhydrous burnt phosphorus
The 5% of sour sodium quality sum, and be added dropwise catalysis, stabilizer dilute nitric acid solution, its concentration is 1mol/L, and drop rate is
2ml/min, regulation pH value of reaction system is 4, is warming up to 85 DEG C, the stirring reaction time is 2 hours, and stir speed (S.S.) is 360rad/
min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 95.7%.
Embodiment 2
（1）In advance by 50.40g melamines and 26.59g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1, plus
Enter into 350ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 500r/min, stirring be the time be 15min, make system scattered equal
It is even；
（2）Then to step（1）System in, add 308ml through the good graphene oxide of ultrasonic disperse（GO）Colloid is molten
Liquid, the solid content of its graphene oxide colloid is 0.025g/mL, and graphene oxide GO content is melamine and anhydrous burnt phosphorus
The 10% of sour sodium quality sum, and be added dropwise catalysis, stabilizer dilute nitric acid solution, its concentration is 0.5mol/L, and drop rate is
2ml/min, regulation pH value of reaction system is 6, is warming up to 90 DEG C, the stirring reaction time is 4 hours, and stir speed (S.S.) is 360rad/
min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 97.1%.
Embodiment 3
（1）In advance by 50.40g melamines and 26.59g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1, plus
Enter into 500ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, make system scattered equal
It is even；
（2）Then to step（1）System in, add 462ml through the good graphene oxide of ultrasonic disperse（GO）Colloid is molten
Liquid, the solid content of its graphene oxide colloid is 0.05g/mL, and graphene oxide GO content is melamine and anhydrous burnt phosphorus
The 30% of sour sodium quality sum, and be added dropwise catalysis, stabilizer dilute nitric acid solution, its concentration is 0.5mol/L, and drop rate is
2ml/min, regulation pH value of reaction system is 4, is warming up to 85 DEG C, the stirring reaction time is 4 hours, and stir speed (S.S.) is 360rad/
min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 98.2%.
Embodiment 4
（1）In advance by 50.40g melamines and 27.92g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1.05,
Be added in 500ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, disperse system
Uniformly；
（2）Then to step（1）System in, add 156.6mL through the good graphene oxide of ultrasonic disperse（GO）Colloid
Solution, the solid content of its graphene oxide colloid is 0.025g/mL, and graphene oxide GO content is melamine and anhydrous Jiao
The 5% of sodium phosphate quality sum, and be added dropwise catalysis, stabilizer dilute nitric acid solution, its concentration be 0.1mol/L, drop rate
For 5ml/min, regulation pH value of reaction system is 4, is warming up to 80 DEG C, the stirring reaction time is 2 hours, stir speed (S.S.) is
420rad/min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 97.3%.
Embodiment 5
（1）In advance by 50.40g melamines and 27.92g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1.05,
Be added in 350ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, disperse system
Uniformly；
（2）Then to step（1）System in, add 313.3ml through the good graphene oxide of ultrasonic disperse（GO）Colloid
Solution, the solid content of its graphene oxide colloid is 0.025g/mL, and graphene oxide GO content is melamine and anhydrous Jiao
The 10% of sodium phosphate quality sum, and be added dropwise catalysis, stabilizer dilute nitric acid solution, its concentration be 0.5mol/L, drop rate
For 2ml/min, regulation pH value of reaction system is 3, is warming up to 90 DEG C, the stirring reaction time is 3 hours, stir speed (S.S.) is
400rad/min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 100 DEG C of dry 36h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 98.3%.
Embodiment 6
（1）In advance by 50.40g melamines and 27.92g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1.05,
Be added in 500ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, disperse system
Uniformly；
（2）Then to step（1）System in, add 469.9ml through the good graphene oxide of ultrasonic disperse（GO）Colloid
Solution, the solid content of its graphene oxide colloid is 0.05g/mL, and graphene oxide-GO content is melamine and anhydrous Jiao
The 30% of sodium phosphate quality sum, and be added dropwise catalysis, stabilizer dilute nitric acid solution, its concentration be 0.5mol/L, drop rate
For 2ml/min, regulation pH value of reaction system is 4, is warming up to 95 DEG C, the stirring reaction time is 4 hours, stir speed (S.S.) is
420rad/min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 98.8%.
The graphene oxide and melamine pyrophosphoric with lamellar structure after being peeled off as can see from Figure 1 through ultrasound
Salt reacts, and is grafted, is coated to the particle that its surface forms spheroidal, its size is between 200nm-0.1 μm, and particle
Agglomeration is not obvious between particle, and dispersive property is good, and this can effectively play its flame retardant effect in the polymer.
Embodiment 7
（1）In advance by 50.40g melamines and 29.25g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1.1,
Be added in 350ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, disperse system
Uniformly；
（2）Then to step（1）System in, add 159.3ml through the good graphene oxide of ultrasonic disperse（GO）Colloid
Solution, the solid content of its graphene oxide colloid is 0.025g/mL, and graphene oxide GO content is melamine and anhydrous Jiao
The 5% of sodium phosphate quality sum, and be added dropwise catalysis, stabilizer dilute nitric acid solution, its concentration be 0.5mol/L, drop rate
For 2ml/min, regulation pH value of reaction system is 6, is warming up to 85 DEG C, the stirring reaction time is 4 hours, stir speed (S.S.) is
360rad/min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 98.0%.
Embodiment 8
（1）In advance by 50.40g melamines and 29.25g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1.1,
Be added in 350ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, disperse system
Uniformly；
（2）Then to step（1）System in, add 318.6ml through the good graphene oxide of ultrasonic disperse（GO）Colloid
Solution, the solid content of its graphene oxide colloid is 0.025g/mL, and graphene oxide GO content is melamine and anhydrous Jiao
The 10% of sodium phosphate quality sum, and be added dropwise catalysis, stabilizer dilute hydrochloric acid solution, its concentration be 0.1mol/L, drop rate
For 5ml/min, regulation pH value of reaction system is 3, is warming up to 90 DEG C, the stirring reaction time is 4 hours, stir speed (S.S.) is
360rad/min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 97.9%.
Embodiment 9
（1）In advance by 50.40g melamines and 29.25g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1.1,
Be added in 500ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 400r/min, stirring be the time be 30min, disperse system
Uniformly；
（2）Then to step（1）System in, add 477.9ml through the good graphene oxide of ultrasonic disperse（GO）Colloid
Solution, the solid content of its graphene oxide colloid is 0.05g/mL, and graphene oxide GO content is melamine and anhydrous Jiao
The 30% of sodium phosphate quality sum, and be added dropwise catalysis, stabilizer dilution heat of sulfuric acid, its concentration is 1mol/L, and drop rate is
3ml/min, regulation pH value of reaction system is 4, is warming up to 95 DEG C, the stirring reaction time is 4 hours, and stir speed (S.S.) is 420rad/
min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 90 DEG C of dry 48h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 98.2%.
Embodiment 10
（1）In advance by 50.40g melamines and 39.88g anhydrous sodium pyrophosphates（Na4P2O7）, its mol ratio is 2:1.5,
Be added in 500ml distilled water, be sufficiently stirred for, stir speed (S.S.) is 450r/min, stirring be the time be 20min, disperse system
Uniformly；
（2）Then to step（1）System in, add 154mL through the good graphene oxide of ultrasonic disperse（GO）Colloid is molten
Liquid, the solid content of its graphene oxide colloid is 0.025g/mL, and graphene oxide GO content is melamine and anhydrous burnt phosphorus
The 5% of sour sodium quality sum, and be added dropwise catalysis, stabilizer dilute silico-tungstic acid solution, its concentration is 1mol/L, and drop rate is
2ml/min, regulation pH value of reaction system is 5, is warming up to 100 DEG C, the stirring reaction time is 2 hours, and stir speed (S.S.) is 360rad/
min；
（3）After reaction completely, reaction product is then subjected to suction filtration, washing, product is in 100 DEG C of dry 36h, you can obtain
Graphene oxide modified cyanurotriamide pyrophosphate halogen-free flame retardants, similar " nucleocapsid " structure of structure of the fire retardant, wherein three
Poly cyanamid pyrophosphate constitutes " core " of fire retardant " nucleocapsid " structure, is grafted to the graphite oxide on melamine pyrophosphate
Alkene is " shell " of its " nucleocapsid " structure.The feed stock conversion of product is 96.7%.
Embodiment 11
By the fire-retartant agent MP P-GO prepared in embodiment 6 and synergist pentaerythrite（PER）Compounding, is added to nylon 6（PA
6）In, its weight part ratio is 20：2：78, in addition, primary antioxidant is antioxidant 1010, auxiliary anti-oxidant is irgasfos 168, lubricant
For ethylene bis-fatty acid amides（EBS）, dispersant is high molecular weight silicone oxygen alkane P121, after extruding pelletization, is molded by standard
Into standard batten, it is formulated and performance see the table below 1.
Comparative example 1
By simple MPP and synergist pentaerythrite（PER）Compounding, is added to nylon 6（PA 6）In, its weight part ratio is
20：2：67, in addition, primary antioxidant is antioxidant 1010, auxiliary anti-oxidant is irgasfos 168, and lubricant is ethylene bis-fatty acid acyl
Amine（EBS）, dispersant is high molecular weight silicone oxygen alkane P121, after extruding pelletization, and standard batten is molded into by standard, and it is formulated
And performance see the table below 1.
The fire proofing formula of table 1 and its correlated performance
As shown in Table 1, the fire-retartant agent MP P-GO prepared in embodiment 6 and synergist pentaerythrite（PER）Compounding, compared to
Simple MPP and synergist pentaerythrite（PER）Compounding, either from mechanical performance or fire resistance, all with comparing
Big advantage.It can be seen that the fire retardant particle diameter that use this method is prepared is small, it is added to good dispersion in polymeric matrix, and
Mechanical performance influence on fire proofing is small, or even also has humidification to some performances, can be not only used for the nothing of polyolefin
Halogen flame-retardant system, is also admirably suitable in the engineering plastics such as polyamide, polyester.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to implementation here
Example, those skilled in the art do not depart from improvement that scope made and change all should be according to the announcement of the present invention
Within protection scope of the present invention.
Claims (12)
1. a kind of method of graphene oxide graft modification melamine pyrophosphate fire retardant, it is characterised in that：Including following
Step：
(1) melamine and anhydrous sodium pyrophosphate are added in distilled water, are sufficiently stirred for making system be uniformly dispersed；
(2) then into the system of step (1), add through the good graphene oxide colloidal solution of ultrasonic disperse, and to be added dropwise
Catalysis, the Bronsted acid weak solution of stabilizer function, adjust pH value of reaction system, heating, stirring reaction；
(3) after reacting completely, reaction product is subjected to suction filtration, washing, product drying, that is, obtains graphene oxide and is modified melamine
Amine pyrophosphate halogen-free flame retardants.
2. according to the method described in claim 1, it is characterised in that：Melamine and anhydrous pyrophosphoric acid in the step (1)
The mol ratio of sodium is 2:(1~1.5).
3. according to the method described in claim 1, it is characterised in that：Stir speed (S.S.) in the step (1) is 400-500r/
Min, mixing time is 15-30min.
4. according to the method described in claim 1, it is characterised in that：Graphene oxide in the step (2) has typical
Containing one or more of hydroxyl, epoxy radicals, carboxyl or carbonyl in quasi- two-dimensional slice structure, its structure, after ultrasonic disperse,
Into single or multiple lift structure.
5. according to the method described in claim 1, it is characterised in that：Consolidating for graphene oxide colloid in the step (2) contains
Measure as 0.025-0.05g/mL.
6. according to the method described in claim 1, it is characterised in that：The content of graphene oxide is trimerization in the step (2)
The 5-30% of cyanamide and anhydrous sodium pyrophosphate quality sum.
7. according to the method described in claim 1, it is characterised in that：Bronsted acid weak solution in the step (2) be selected from hydrochloric acid,
One or more of silico-tungstic acid, nitric acid or sulfuric acid, its concentration are 0.1-1mol/L.
8. according to the method described in claim 1, it is characterised in that：The dropwise addition speed of Bronsted acid weak solution in the step (2)
Rate is 2-5ml/min.
9. according to the method described in claim 1, it is characterised in that：The pH value of regulation reaction system is in 3-6 in the step (2)
Between.
10. according to the method described in claim 1, it is characterised in that：80-100 DEG C is warming up in the step (2), stirring is anti-
It it is 2-4 hours between seasonable, stir speed (S.S.) is 360-420rad/min.
11. according to the method described in claim 1, it is characterised in that：Product is in 90-100 DEG C of dry 36- in the step (3)
48h。
12. according to the method described in claim 1, it is characterised in that：The structure of obtained fire retardant is in the step (3)
" nucleocapsid " structure, wherein melamine pyrophosphate constitute " core " of fire retardant " nucleocapsid " structure, are grafted to melamine burnt
Graphene oxide on phosphate is " shell " of its " nucleocapsid " structure.
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