CN108164809B - Anti-dripping integrated intumescent halogen-free flame retardant and preparation method thereof - Google Patents

Anti-dripping integrated intumescent halogen-free flame retardant and preparation method thereof Download PDF

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CN108164809B
CN108164809B CN201711096548.0A CN201711096548A CN108164809B CN 108164809 B CN108164809 B CN 108164809B CN 201711096548 A CN201711096548 A CN 201711096548A CN 108164809 B CN108164809 B CN 108164809B
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ammonia gas
triazine compound
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free flame
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CN108164809A (en
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李章武
周侃
刘华夏
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Presafer Qingyuan Phosphor Chemical Co ltd
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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/22—Halogen free composition

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Abstract

The invention discloses an anti-dripping integrated intumescent halogen-free flame retardant and a preparation method thereof, wherein the preparation method of the halogen-free flame retardant comprises the following steps: preparation of a triazine compound prepolymer solution, preparation of ammonium polyphosphate with polytetrafluoroethylene, and coating of a triazine compound on the surface of the ammonium polyphosphate. According to the invention, polytetrafluoroethylene is sprayed and dispersed in ammonium polyphosphate in the form of emulsion in the synthesis process of ammonium polyphosphate, and then the triazine compound is wrapped on the surface of the ammonium polyphosphate in the form of microcapsules, so that on one hand, the water solubility of the flame retardant is effectively reduced, on the other hand, the processing resistance and precipitation resistance of the flame retardant are improved, and the finally obtained flame retardant can obtain more uniform and stable flame retardant performance when used in polyolefin.

Description

Anti-dripping integrated intumescent halogen-free flame retardant and preparation method thereof
Technical Field
The invention relates to an anti-dripping integrated intumescent halogen-free flame retardant and a preparation method thereof.
Background
The ammonium polyphosphate (APP) intumescent flame retardant has excellent flame retardant effect, particularly has superiority when being used for flame retardance of polyolefin plastics such as polyethylene, polypropylene and the like, and is a research hotspot in the field of the current halogen-free flame retardant material. However, ammonium polyphosphate has certain water solubility, and is partially degraded after being processed, which leads to further increase of water solubility and finally serious precipitation, so that the ammonium polyphosphate is often required to be coated to improve the water solubility, which is not only troublesome to process, but also has a common treatment effect. In addition, when people prepare the flame-retardant polyolefin material, in order to achieve a better flame-retardant effect, an anti-dripping agent is usually added to improve the flame-retardant efficiency, but because the anti-dripping agent has thicker particles, the anti-dripping agent cannot be uniformly dispersed in the flame-retardant polyolefin material no matter the anti-dripping agent is added in the compounding process of the flame retardant or the material is added in the extrusion process of the material, so that the prepared sample strip and the product have uneven and unstable flame retardance, the addition of the anti-dripping agent is further improved, and the production cost is finally increased.
Disclosure of Invention
The invention aims to provide an anti-dripping integrated intumescent halogen-free flame retardant and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of an anti-dripping integrated intumescent halogen-free flame retardant comprises the following steps:
1) adding a triazine compound, a dispersing agent and water into a reaction kettle, adding a formaldehyde solution, and reacting at 60-100 ℃ for 2-8 h to obtain a triazine compound prepolymer solution;
2) adding phosphorus pentoxide and diammonium phosphate into a kneading machine, preheating to 180-350 ℃, introducing ammonia gas for reaction, and stopping introducing ammonia gas after the reaction is finished;
3) spraying polytetrafluoroethylene emulsion on the surface of powder in a kneader through spraying equipment, heating, introducing ammonia gas, and sintering;
4) stopping introducing ammonia gas and heating, and introducing nitrogen gas to obtain ammonium polyphosphate with polytetrafluoroethylene;
5) controlling the temperature in the kneader to be 80-150 ℃, adding the triazine compound prepolymer solution obtained in the step 1), reacting for 2-8 h, adding the curing agent, reacting for 4-12 h, and introducing ammonia gas to absorb unreacted formaldehyde to obtain the anti-dripping integral intumescent halogen-free flame retardant.
The triazine compound in the step 1) is one of compounds shown in structural formulas (1) and (2):
Figure BDA0001462339310000021
wherein R is1And R2Independently of one another represent-NH2、
Figure BDA0001462339310000022
Figure BDA0001462339310000023
-NHCyH2yOR31 is more than or equal to y is less than or equal to 8, R3is-H, C1～C8Alkyl of (C)2～C6X is one of the alkenyl groups of (A), X is
Figure BDA0001462339310000024
2≤Z≤6。
The molar ratio of the triazine compound and formaldehyde in the step 1) is 1: (1-6).
The mass ratio of the dispersing agent to the water in the step 1) is 1: (1-20).
The addition amount of the triazine compound in the step 1) is 0.5-5 times of the total mass of the dispersing agent and water.
The dispersing agent in the step 1) is at least one of aliphatic alcohol with a boiling point of 50-150 ℃ and aliphatic ketone with a boiling point of 50-150 ℃.
The mass fraction of the formaldehyde solution in the step 1) is 35-40%.
The phosphorus pentoxide in the step 2) is in a crystal H type.
The total addition amount of the phosphorus pentoxide and the diammonium hydrogen phosphate in the step 2) is 2-10 times of the mass of the triazine compound.
The mol ratio of the phosphorus pentoxide to the diammonium phosphate in the step 2) is 1: (1.0-1.1).
The introduction flow rate of the ammonia gas in the step 2) is 20-25 m3And/h, the ammonia gas introduction time is 2-4 h.
The addition amount of the polytetrafluoroethylene emulsion in the step 3) is 0.5-2% of the total mass of the phosphorus pentoxide, the diammonium hydrogen phosphate and the triazine compound.
The introduction flow of the ammonia gas in the step 3) is 8-15 m3And/h, the ammonia gas introduction time is 1-3 h.
The flow of the nitrogen introduced in the step 4) is 2-5 m3/h。
And 5) the curing agent is at least one of ammonium chloride, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate acid salt, citric acid and acetic acid.
The addition amount of the curing agent in the step 5) is 0.5-10% of the weight of the triazine compound prepolymer solution.
The introduction flow rate of the ammonia gas in the step 5) is 0.5-2 m3And/h, the ammonia gas introduction time is 1-2 h.
The invention has the beneficial effects that: according to the invention, polytetrafluoroethylene is sprayed and dispersed in ammonium polyphosphate in the form of emulsion in the synthesis process of ammonium polyphosphate, and then the triazine compound is wrapped on the surface of the ammonium polyphosphate in the form of microcapsules, so that on one hand, the water solubility of the flame retardant is effectively reduced, on the other hand, the processing resistance and precipitation resistance of the flame retardant are improved, and the finally obtained flame retardant can obtain more uniform and stable flame retardant performance when used in polyolefin.
Drawings
FIG. 1 is an SEM image of the drip resistant integral intumescent halogen free flame retardant of example 1.
Detailed Description
A preparation method of an anti-dripping integrated intumescent halogen-free flame retardant comprises the following steps:
1) adding a triazine compound, a dispersing agent and water into a reaction kettle, adding a formaldehyde solution, and reacting at 60-100 ℃ for 2-8 h to obtain a triazine compound prepolymer solution;
2) adding phosphorus pentoxide and diammonium phosphate into a kneading machine, preheating to 180-350 ℃, introducing ammonia gas for reaction, and stopping introducing ammonia gas after the reaction is finished;
3) spraying polytetrafluoroethylene emulsion on the surface of powder in a kneader through spraying equipment, heating, introducing ammonia gas, and sintering;
4) stopping introducing ammonia gas and heating, and introducing nitrogen gas to obtain ammonium polyphosphate with polytetrafluoroethylene;
5) controlling the temperature in the kneader to be 80-150 ℃, adding the triazine compound prepolymer solution obtained in the step 1), reacting for 2-8 h, adding the curing agent, reacting for 4-12 h, and introducing ammonia gas to absorb unreacted formaldehyde to obtain the anti-dripping integral intumescent halogen-free flame retardant.
Preferably, the triazine compound in step 1) is one of compounds represented by structural formulas (1) and (2):
Figure BDA0001462339310000031
wherein R is1And R2Independently of one another represent-NH2、
Figure BDA0001462339310000032
Figure BDA0001462339310000033
-NHCyH2yOR31 is more than or equal to y is less than or equal to 8, R3is-H, C1～C8Alkyl of (C)2～C6X is one of the alkenyl groups of (A), X is
Figure BDA0001462339310000034
2≤Z≤6。
Preferably, the molar ratio of the triazine compound and formaldehyde in the step 1) is 1: (1-6).
Preferably, the mass ratio of the dispersant to the water in the step 1) is 1: (1-20).
Preferably, the addition amount of the triazine compound in the step 1) is 0.5-5 times of the total mass of the dispersing agent and the water.
Preferably, the dispersant in the step 1) is at least one of aliphatic alcohol with a boiling point of 50-150 ℃ and aliphatic ketone with a boiling point of 50-150 ℃.
Preferably, the mass fraction of the formaldehyde solution in the step 1) is 35-40%.
Preferably, the phosphorus pentoxide in step 2) is in a crystalline H form.
Preferably, the total addition amount of the phosphorus pentoxide and the diammonium phosphate in the step 2) is 2-10 times of the mass of the triazine compound.
Preferably, the molar ratio of the phosphorus pentoxide to the diammonium phosphate in the step 2) is 1: (1.0-1.1).
Preferably, the flow rate of the ammonia gas introduced in the step 2) is 20-25 m3And/h, the ammonia gas introduction time is 2-4 h.
Preferably, the addition amount of the polytetrafluoroethylene emulsion in the step 3) is 0.5-2% of the total mass of the phosphorus pentoxide, the diammonium hydrogen phosphate and the triazine compound.
Preferably, the flow rate of the ammonia gas introduced in the step 3) is 8-15 m3And/h, the ammonia gas introduction time is 1-3 h.
Preferably, the flow rate of the nitrogen introduced in the step 4) is 2-5 m3/h。
Preferably, the curing agent in the step 5) is at least one of ammonium chloride, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate acid salt, citric acid and acetic acid.
Preferably, the addition amount of the curing agent in the step 5) is 0.5-10% of the weight of the triazine compound prepolymer solution.
Preferably, the flow rate of the ammonia gas introduced in the step 5) is 0.5-2 m3And/h, the ammonia gas introduction time is 1-2 h.
Preferably, the triazine compound prepolymer solution and the curing agent in step 5) are added dropwise.
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of an anti-dripping integrated intumescent halogen-free flame retardant comprises the following steps:
1) adding 32.2kg of triazine compound, 5kg of methanol and 25kg of water into a reaction kettle, adding 24.35kg of formaldehyde solution with the mass fraction of 37%, and reacting at 80 ℃ for 2h to obtain a triazine compound prepolymer solution;
2) 81.44kg of phosphorus pentoxide and 79.56kg of diammonium phosphate were added to the kneader, preheated to 330 ℃ at 20m3Introducing ammonia gas at a flow rate of/h for reaction for 2h, and stopping introducing the ammonia gas after the reaction is finished;
3) 1.9kg of polytetrafluoroethylene emulsion (DISP40, DuPont, mass fraction 60%) was uniformly sprayed onto the powder surface in the kneader by means of a spraying device on the kneader, heated and sprayed at 8m3Introducing ammonia gas for 2h at a flow rate of/h, and sintering at 330 ℃;
4) stopping introducing ammonia gas and heating at 3.5m3Introducing nitrogen at the flow rate of/h to obtain ammonium polyphosphate with polytetrafluoroethylene;
5) adjusting the temperature in the kneader to 80 ℃, slowly dripping the triazine compound prepolymer solution obtained in the step 1) for 8 hours, then slowly dripping 4.33kg of acetic acid for reacting for 4 hours at a speed of 0.5m3Introducing ammonia gas at a flow rate of/h for 2h to absorb unreacted formaldehyde and cooling to room temperature to obtain 193.18kg of anti-dripping integral intumescent halogen-free flame retardant (shown in an SEM picture of figure 1, and shown in figure 1, wherein the surface of the particles is provided with an obvious coating layer);
wherein, the triazine compounds added in the step 1) are as follows:
Figure BDA0001462339310000051
example 2:
a preparation method of an anti-dripping integrated intumescent halogen-free flame retardant comprises the following steps:
1) adding 18kg of triazine compound, 2kg of ethanol and 20kg of water into a reaction kettle, adding 32.46kg of formaldehyde solution with the mass fraction of 37%, and reacting for 4h at 90 ℃ to obtain a triazine compound prepolymer solution;
2) 74.60kg of phosphorus pentoxide and 69.40kg of diammonium phosphate were added to the kneader, preheated to 280 ℃ at 22m3Introducing ammonia gas at a flow rate of/h for reaction for 3h, and stopping introducing the ammonia gas after the reaction is finished;
3) 1.6kg of a polytetrafluoroethylene emulsion (D3211, Suwei, mass fraction 60%) was uniformly sprayed on the kneading by means of a spraying device on a kneaderHeating the surface of the powder in the machine at 12m3Introducing ammonia gas for 3h at the flow rate of/h, and sintering at 280 ℃;
4) stopping introducing ammonia gas and heating at 2m3Introducing nitrogen at the flow rate of/h to obtain ammonium polyphosphate with polytetrafluoroethylene;
5) adjusting the temperature in the kneader to 125 ℃, slowly dripping the triazine compound prepolymer solution obtained in the step 1) for 4 hours, then slowly dripping 0.36kg of ammonium chloride, reacting for 8 hours, and reacting for 1.5m3Introducing ammonia gas at a flow rate of/h for 80min to absorb unreacted formaldehyde, and cooling to room temperature to obtain 169.72kg of anti-dripping integrated intumescent halogen-free flame retardant;
wherein, the triazine compounds added in the step 1) are as follows:
Figure BDA0001462339310000052
example 3:
a preparation method of an anti-dripping integrated intumescent halogen-free flame retardant comprises the following steps:
1) adding 19.5kg of triazine compound, 2kg of acetone alcohol and 30kg of water into a reaction kettle, adding 28.41kg of formaldehyde solution with the mass fraction of 37%, and reacting for 8h at 70 ℃ to obtain a triazine compound prepolymer solution;
2) 77.10kg of phosphorus pentoxide and 78.90kg of diammonium phosphate were added to a kneader, preheated to 200 ℃ at 25m3Introducing ammonia gas at a flow rate of/h for reaction for 4h, and stopping introducing the ammonia gas after the reaction is finished;
3) 1.8kg of polytetrafluoroethylene emulsion (D-210C, Dajin, 60% by mass) was uniformly sprayed onto the surface of the powder in the kneader by means of a spraying device on the kneader, heated, and sprayed at 15m3Introducing ammonia gas for 1h at the flow rate of/h, and sintering at the temperature of 200 ℃;
4) stopping introducing ammonia gas and heating at 5m3Introducing nitrogen at the flow rate of/h to obtain ammonium polyphosphate with polytetrafluoroethylene;
5) adjusting the temperature in the kneader to 150 ℃, slowly dripping the triazine compound prepolymer solution obtained in the step 1) for 6 hours, then slowly dripping 7.99kg of citric acid, reacting for 10 hours, and reacting for 2m3H ofIntroducing ammonia gas at the flow rate for 1h to absorb unreacted formaldehyde and cooling to room temperature to obtain 174kg of anti-dripping integrated intumescent halogen-free flame retardant;
wherein, the triazine compounds added in the step 1) are as follows:
Figure BDA0001462339310000061
comparative example 1:
the procedure of example 1 was repeated except that the polytetrafluoroethylene emulsion was not added, and 1.14kg of anti-dripping agent M532 (Dajin) was added to the obtained intumescent halogen-free flame retardant and mixed.
Comparative example 2:
the procedure of example 1 was repeated except that the polytetrafluoroethylene emulsion was not added, and 1.33kg of M532 (Dajin) as an anti-dripping agent was added to the obtained intumescent halogen-free flame retardant and mixed.
Comparative example 3:
the procedure of example 1 was repeated except that the polytetrafluoroethylene emulsion was not added, and 1.52kg of M532 (Dajin) as an anti-dripping agent was added to the obtained intumescent halogen-free flame retardant and mixed.
Comparative example 4:
the procedure of example 2 was repeated except that no polytetrafluoroethylene emulsion was added, and 0.96kg of anti-dripping agent M532 (Dajin) was added to the obtained intumescent halogen-free flame retardant and mixed.
Comparative example 5:
the procedure of example 3 was repeated except that the polytetrafluoroethylene emulsion was not added, and 1.08kg of a dripping inhibitor M532 (Dajin) was added to the obtained intumescent halogen-free flame retardant and mixed.
Test example:
the intumescent halogen-free flame retardant prepared in the examples 1-3 and the comparative examples 1-5 is applied to PP to prepare a flame-retardant PP material, and the specific raw material composition is shown in the following table:
TABLE 1 raw Material composition Table (parts by mass) of flame retardant PP material
Figure BDA0001462339310000062
Figure BDA0001462339310000071
The flame-retardant PP materials in the table 1 are prepared into samples (samples 1-8 in sequence) and are subjected to flame-retardant performance test, and the test results are shown in the following table:
TABLE 2 flame retardancy test results of flame retardant PP materials
Figure BDA0001462339310000072
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A preparation method of an anti-dripping integrated intumescent halogen-free flame retardant is characterized by comprising the following steps: the method comprises the following steps:
1) adding a triazine compound, a dispersing agent and water into a reaction kettle, adding a formaldehyde solution, and reacting at 60-100 ℃ for 2-8 h to obtain a triazine compound prepolymer solution;
2) adding phosphorus pentoxide and diammonium phosphate into a kneading machine, preheating to 180-350 ℃, introducing ammonia gas for reaction, and stopping introducing ammonia gas after the reaction is finished;
3) spraying polytetrafluoroethylene emulsion on the surface of powder in a kneader through spraying equipment, heating, introducing ammonia gas, and sintering;
4) stopping introducing ammonia gas and heating, and introducing nitrogen gas to obtain ammonium polyphosphate with polytetrafluoroethylene;
5) controlling the temperature in a kneader to be 80-150 ℃, adding the triazine compound prepolymer solution obtained in the step 1), reacting for 2-8 h, adding a curing agent, reacting for 4-12 h, and introducing ammonia gas to absorb unreacted formaldehyde to obtain an anti-dripping integrated intumescent halogen-free flame retardant;
the total addition amount of the phosphorus pentoxide and the diammonium phosphate in the step 2) is 2-10 times of the mass of the triazine compound;
the mol ratio of the phosphorus pentoxide to the diammonium phosphate in the step 2) is 1: (1.0-1.1);
the addition amount of the polytetrafluoroethylene emulsion in the step 3) is 0.5-2% of the total mass of the phosphorus pentoxide, the diammonium hydrogen phosphate and the triazine compound.
2. The method of claim 1, wherein: the triazine compound in the step 1) is one of compounds shown in structural formulas (1) and (2):
Figure FDA0002609730170000011
wherein R is1And R2Independently of one another represent-NH2、
Figure FDA0002609730170000012
Figure FDA0002609730170000013
-NHCyH2yOR31 is more than or equal to y is less than or equal to 8, R3is-H, C1～C8Alkyl of (C)2～C6X is one of the alkenyl groups of (A), X is
Figure FDA0002609730170000014
2≤Z≤6。
3. The method of claim 1, wherein: the molar ratio of the triazine compound and formaldehyde in the step 1) is 1: (1-6).
4. The method of claim 1, wherein: the mass ratio of the dispersing agent to the water in the step 1) is 1: (1-20); the addition amount of the triazine compound in the step 1) is 0.5-5 times of the total mass of the dispersing agent and water.
5. The method of claim 1, wherein: the dispersing agent in the step 1) is at least one of aliphatic alcohol with a boiling point of 50-150 ℃ and aliphatic ketone with a boiling point of 50-150 ℃; the mass fraction of the formaldehyde solution in the step 1) is 35-40%; the phosphorus pentoxide in the step 2) is in a crystal H type.
6. The method of claim 1, wherein: the curing agent in the step 5) is at least one of ammonium chloride, diammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate acid salt, citric acid and acetic acid; the addition amount of the curing agent in the step 5) is 0.5-10% of the weight of the triazine compound prepolymer solution.
7. The method of claim 1, wherein: the introduction flow rate of the ammonia gas in the step 2) is 20-25 m3The ammonia gas is introduced for 2-4 hours; the introduction flow of the ammonia gas in the step 3) is 8-15 m3The ammonia gas is introduced for 1-3 hours; the flow of the nitrogen introduced in the step 4) is 2-5 m3H; the introduction flow rate of the ammonia gas in the step 5) is 0.5-2 m3And/h, the ammonia gas introduction time is 1-2 h.
8. The anti-dripping integral intumescent halogen-free flame retardant prepared by the preparation method of any one of claims 1 to 7.
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CN101812186A (en) * 2010-03-11 2010-08-25 中科院广州化学有限公司 Microencapsulation expansion type flame retardant and application in epoxy resin composite material thereof
CN103265500A (en) * 2013-04-17 2013-08-28 清远市普塞呋磷化学有限公司 Preparation method and application of halogen-free intumescent flame retardant with crosslinking structure

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