CN112143193A - Halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and preparation method thereof - Google Patents

Halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and preparation method thereof Download PDF

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CN112143193A
CN112143193A CN201910561372.4A CN201910561372A CN112143193A CN 112143193 A CN112143193 A CN 112143193A CN 201910561372 A CN201910561372 A CN 201910561372A CN 112143193 A CN112143193 A CN 112143193A
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向红建
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Abstract

The invention provides a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and a preparation method thereof, and relates to the technical field of flame retardant production. The flame retardant is prepared from the following raw materials in parts by weight: 40-45 parts of polyphosphoric acid, 20-25 parts of pentaerythritol, 18-22 parts of melamine, 6-8 parts of titanium dioxide, 3-5 parts of wollastonite powder, 5-7 parts of aluminum hydroxide, 2-4 parts of hydrotalcite, 4-6 parts of sodium hexametaphosphate, 2-4 parts of potassium diphenylsulfone sulfonate, 3-5 parts of m-phenylene tetra (xylyl) diphosphate, 6-8 parts of polycarbonate, 2-4 parts of 2, 5-diaminoadipic acid tetramethylene phosphate and 2-4 parts of silicon phosphate. The invention overcomes the defects of the prior art, effectively enhances the synergistic effect of nitrogen and phosphorus, does not contain halogen and heavy metal, has no toxicity and corrosion, does not generate dense smoke during firing, and expands and foams when meeting fire, thereby effectively prolonging the fire resistance limit of the composite material.

Description

Halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and preparation method thereof
Technical Field
The invention relates to the technical field of flame retardant production, in particular to a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and a preparation method thereof.
Background
Flame retardants, i.e., functional adjuvants that impart flame retardancy to flammable polymers. The flame retardants are of various types, and are classified into additive type flame retardants and reactive type flame retardants according to the method of use. The additive flame retardant is added into a polymer such as a fireproof coating by a mechanical mixing method to enable the polymer to have flame retardance. At present, the additive flame retardant mainly comprises an organic flame retardant, an inorganic flame retardant, a halogen flame retardant (organic chloride and organic bromide) and non-halogen. The halogen flame retardant can generate toxic substances in the using process, so that the halogen flame retardant is harmful to the environment and the health of people. Halogen-free flame retardants are therefore gaining increasing popularity.
The conventional halogen-free flame retardant has unreasonable formula composition and production process, so that the stability and flame retardant durability of the flame retardant are poor, the expansion effect is poor, the addition amount is large, the use requirements of users are not met, and great troubles are brought to people.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and a preparation method thereof, the halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant overcomes the defects of the prior art, effectively enhances the nitrogen-phosphorus synergistic effect, does not contain halogen and heavy metal, has no toxic or corrosive effect, does not generate dense smoke during firing, and expands and foams when meeting fire, thereby effectively prolonging the fire resistance limit of the flame retardant.
In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:
a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant is prepared from the following raw materials in parts by weight: 40-45 parts of polyphosphoric acid, 20-25 parts of pentaerythritol, 18-22 parts of melamine, 6-8 parts of titanium dioxide, 3-5 parts of wollastonite powder, 5-7 parts of aluminum hydroxide, 2-4 parts of hydrotalcite, 4-6 parts of sodium hexametaphosphate, 2-4 parts of potassium diphenylsulfone sulfonate, 3-5 parts of m-phenylene tetra (xylyl) diphosphate, 6-8 parts of polycarbonate, 2-4 parts of 2, 5-diaminoadipic acid tetramethylene phosphate and 2-4 parts of silicon phosphate.
Preferably, the flame retardant is prepared from the following raw materials in parts by weight: 42 parts of polyphosphoric acid, 24 parts of pentaerythritol, 20 parts of melamine, 8 parts of titanium dioxide, 4 parts of wollastonite powder, 6 parts of aluminum hydroxide, 3 parts of hydrotalcite, 5 parts of sodium hexametaphosphate, 3 parts of potassium diphenylsulfone sulfonate, 4 parts of m-phenylene tetra (xylyl) diphosphate, 7 parts of polycarbonate, 3 parts of 2, 5-diaminoadipic acid tetramethylene phosphoric acid and 3 parts of silicon phosphate.
The preparation method of the flame retardant comprises the following steps:
(1) adding polyphosphoric acid into a reaction kettle, heating, adding pentaerythritol while stirring, uniformly stirring, heating again, and carrying out heat preservation reaction to obtain a reaction material for later use;
(2) adding melamine into a stirrer, adding the prepared reaction material, and stirring and mixing to obtain a base material for later use;
(3) putting titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a refrigerator for freezing, pouring the frozen titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a ball mill for mixing and grinding, putting the mixture into a high-temperature furnace, preserving heat, roasting, and naturally cooling to room temperature to obtain a mixture for later use;
(4) mixing potassium diphenylsulfone sulfonate, m-phenylene tetra (xylyl) diphosphate and polycarbonate, adding the mixture into an autoclave, uniformly stirring, heating and boosting pressure, maintaining pressure for a period of time, then recovering to normal pressure, adding 2, 5-diaminoadipic acid tetramethylene phosphoric acid and silicon phosphate, maintaining the temperature, mixing, boosting pressure again, maintaining the pressure, recovering to normal pressure after permeation, and then maintaining the temperature and standing to obtain auxiliary materials for later use;
(5) and adding the prepared base material, mixture and auxiliary materials into a high-speed dispersion machine, naturally cooling to room temperature after high-speed dispersion, and pouring the mixture into a pulverizer to pulverize to obtain the product.
Preferably, in the step (1), the temperature is raised to 125 ℃ for the first time at 115-.
Preferably, the rotation speed of the stirrer in the step (2) is 200-220r/min, and the stirring time is 30-40 min.
Preferably, in the step (3), the freezing temperature is minus 40 ℃ to minus 30 ℃, the freezing time is 1.5 to 2 hours, the mixture is ground until the mixture is sieved by a 200-mesh sieve, the roasting temperature is 400 ℃ and 420 ℃, and the roasting time is 1 to 1.5 hours.
Preferably, the rotation speed of the stirring in the step (4) is 180-.
Preferably, the rotation speed of the high-speed dispersion in the step (5) is 600-800r/min, the high-speed dispersion time is 30-50min, and the powder is crushed and sieved by a 600-mesh sieve.
The invention provides a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and a preparation method thereof, and compared with the prior art, the halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant has the advantages that:
(1) the invention adopts polyphosphoric acid and pentaerythritol to synthesize through chemical reaction, can effectively enhance the synergistic effect of nitrogen-phosphorus, and simultaneously improve the stability of the flame retardant, and the pentaerythritol is added while stirring, so that reactants can be fully contacted and mixed, the reaction rate is improved, and the reactants are mixed with melamine, therefore, the flame retardant has good flame retardant effect and is convenient to use;
(2) according to the invention, titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate are adopted to prepare a mixture, and the mixture is subjected to freezing modification, mixed grinding and roasting modification in sequence, so that the dispersibility of the flame retardant can be effectively improved, the flame retardant has good compatibility with polymers such as fire-retardant coatings and the like, the addition amount is small, and the phenomena of deposition, bubbling and the like are avoided;
(3) according to the invention, the auxiliary materials are prepared from potassium diphenylsulfone sulfonate, m-phenylene tetra (xylyl) diphosphate, polycarbonate, 2, 5-diaminoadipic acid tetramethylene phosphoric acid and silicon phosphate, and the components are mutually cross-linked, modified and fused under the conditions of high temperature and high pressure, so that the auxiliary materials can be matched with a mixture, the flame retardant property of the flame retardant can be further improved, the flame retardant durability of the flame retardant can be effectively improved, and the use effect of the flame retardant is good;
(4) the flame retardant does not contain halogen and heavy metal, is nontoxic and free of corrosion, does not generate dense smoke during ignition, expands and foams when encountering fire, and gradually forms a honeycomb-shaped compact carbon layer, so that the fire resistance limit of the flame retardant is effectively prolonged, the overall performance of the flame retardant is excellent, and the flame retardant is suitable for popularization.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant is prepared from the following raw materials in parts by weight: 40 parts of polyphosphoric acid, 20 parts of pentaerythritol, 18 parts of melamine, 6 parts of titanium dioxide, 3 parts of wollastonite powder, 5 parts of aluminum hydroxide, 2 parts of hydrotalcite, 4 parts of sodium hexametaphosphate, 2 parts of potassium diphenylsulfone sulfonate, 3 parts of m-phenylene tetra (xylyl) diphosphate, 6 parts of polycarbonate, 2 parts of 2, 5-diaminoadipic acid tetramethylene phosphoric acid and 2 parts of silicon phosphate.
The preparation method of the flame retardant comprises the following steps:
(1) adding polyphosphoric acid into a reaction kettle, heating, adding pentaerythritol while stirring, uniformly stirring, heating again, and carrying out heat preservation reaction to obtain a reaction material for later use;
(2) adding melamine into a stirrer, adding the prepared reaction material, and stirring and mixing to obtain a base material for later use;
(3) putting titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a refrigerator for freezing, pouring the frozen titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a ball mill for mixing and grinding, putting the mixture into a high-temperature furnace, preserving heat, roasting, and naturally cooling to room temperature to obtain a mixture for later use;
(4) mixing potassium diphenylsulfone sulfonate, m-phenylene tetra (xylyl) diphosphate and polycarbonate, adding the mixture into an autoclave, uniformly stirring, heating and boosting pressure, maintaining pressure for a period of time, then recovering to normal pressure, adding 2, 5-diaminoadipic acid tetramethylene phosphoric acid and silicon phosphate, maintaining the temperature, mixing, boosting pressure again, maintaining the pressure, recovering to normal pressure after permeation, and then maintaining the temperature and standing to obtain auxiliary materials for later use;
(5) and adding the prepared base material, mixture and auxiliary materials into a high-speed dispersion machine, naturally cooling to room temperature after high-speed dispersion, and pouring the mixture into a pulverizer to pulverize to obtain the product.
Wherein, in the step (1), the temperature is raised to 125 ℃ for the first time, the stirring speed is 80-100r/min, the temperature is raised to 135 ℃ for the second time, and the reaction time is 2.5-3.5 h; the rotating speed of the stirrer in the step (2) is 200-220r/min, and the stirring time is 30-40 min; in the step (3), the freezing temperature is minus 40 ℃ to minus 30 ℃, the freezing time is 1.5 to 2 hours, the mixture is ground until the mixture is sieved by a 200-mesh sieve, the roasting temperature is 400 ℃ and 420 ℃, and the roasting time is 1 to 1.5 hours; the stirring speed in the step (4) is 180-fold sand 200r/min, the stirring time is 30-40min, the temperature is increased to 240 ℃ for 220-fold sand, the pressure is increased to 10-12MPa for the first time, the pressure maintaining treatment time is 40-60min, the heat preservation mixing time is 1-2h, the pressure is increased to 8-10MPa for the second time, the pressure maintaining permeation time is 30-50min, and the heat preservation standing time is 2-3 h; the rotating speed of the high-speed dispersion in the step (5) is 600-800r/min, the high-speed dispersion time is 30-50min, and the powder is crushed and sieved by a 600-mesh sieve.
Example 2:
a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant is prepared from the following raw materials in parts by weight: 42 parts of polyphosphoric acid, 24 parts of pentaerythritol, 20 parts of melamine, 8 parts of titanium dioxide, 4 parts of wollastonite powder, 6 parts of aluminum hydroxide, 3 parts of hydrotalcite, 5 parts of sodium hexametaphosphate, 3 parts of potassium diphenylsulfone sulfonate, 4 parts of m-phenylene tetra (xylyl) diphosphate, 7 parts of polycarbonate, 3 parts of 2, 5-diaminoadipic acid tetramethylene phosphoric acid and 3 parts of silicon phosphate.
The preparation method of the flame retardant comprises the following steps:
(1) adding polyphosphoric acid into a reaction kettle, heating, adding pentaerythritol while stirring, uniformly stirring, heating again, and carrying out heat preservation reaction to obtain a reaction material for later use;
(2) adding melamine into a stirrer, adding the prepared reaction material, and stirring and mixing to obtain a base material for later use;
(3) putting titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a refrigerator for freezing, pouring the frozen titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a ball mill for mixing and grinding, putting the mixture into a high-temperature furnace, preserving heat, roasting, and naturally cooling to room temperature to obtain a mixture for later use;
(4) mixing potassium diphenylsulfone sulfonate, m-phenylene tetra (xylyl) diphosphate and polycarbonate, adding the mixture into an autoclave, uniformly stirring, heating and boosting pressure, maintaining pressure for a period of time, then recovering to normal pressure, adding 2, 5-diaminoadipic acid tetramethylene phosphoric acid and silicon phosphate, maintaining the temperature, mixing, boosting pressure again, maintaining the pressure, recovering to normal pressure after permeation, and then maintaining the temperature and standing to obtain auxiliary materials for later use;
(5) and adding the prepared base material, mixture and auxiliary materials into a high-speed dispersion machine, naturally cooling to room temperature after high-speed dispersion, and pouring the mixture into a pulverizer to pulverize to obtain the product.
Wherein, in the step (1), the temperature is raised to 125 ℃ for the first time, the stirring speed is 80-100r/min, the temperature is raised to 135 ℃ for the second time, and the reaction time is 2.5-3.5 h; the rotating speed of the stirrer in the step (2) is 200-220r/min, and the stirring time is 30-40 min; in the step (3), the freezing temperature is minus 40 ℃ to minus 30 ℃, the freezing time is 1.5 to 2 hours, the mixture is ground until the mixture is sieved by a 200-mesh sieve, the roasting temperature is 400 ℃ and 420 ℃, and the roasting time is 1 to 1.5 hours; the stirring speed in the step (4) is 180-fold sand 200r/min, the stirring time is 30-40min, the temperature is increased to 240 ℃ for 220-fold sand, the pressure is increased to 10-12MPa for the first time, the pressure maintaining treatment time is 40-60min, the heat preservation mixing time is 1-2h, the pressure is increased to 8-10MPa for the second time, the pressure maintaining permeation time is 30-50min, and the heat preservation standing time is 2-3 h; the rotating speed of the high-speed dispersion in the step (5) is 600-800r/min, the high-speed dispersion time is 30-50min, and the powder is crushed and sieved by a 600-mesh sieve.
Example 3:
a halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant is prepared from the following raw materials in parts by weight: 45 parts of polyphosphoric acid, 25 parts of pentaerythritol, 22 parts of melamine, 8 parts of titanium dioxide, 5 parts of wollastonite powder, 7 parts of aluminum hydroxide, 4 parts of hydrotalcite, 6 parts of sodium hexametaphosphate, 4 parts of potassium diphenylsulfone sulfonate, 5 parts of m-phenylene tetra (xylyl) diphosphate, 8 parts of polycarbonate, 4 parts of 2, 5-diaminoadipic acid tetramethylene phosphoric acid and 4 parts of silicon phosphate.
The preparation method of the flame retardant comprises the following steps:
(1) adding polyphosphoric acid into a reaction kettle, heating, adding pentaerythritol while stirring, uniformly stirring, heating again, and carrying out heat preservation reaction to obtain a reaction material for later use;
(2) adding melamine into a stirrer, adding the prepared reaction material, and stirring and mixing to obtain a base material for later use;
(3) putting titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a refrigerator for freezing, pouring the frozen titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a ball mill for mixing and grinding, putting the mixture into a high-temperature furnace, preserving heat, roasting, and naturally cooling to room temperature to obtain a mixture for later use;
(4) mixing potassium diphenylsulfone sulfonate, m-phenylene tetra (xylyl) diphosphate and polycarbonate, adding the mixture into an autoclave, uniformly stirring, heating and boosting pressure, maintaining pressure for a period of time, then recovering to normal pressure, adding 2, 5-diaminoadipic acid tetramethylene phosphoric acid and silicon phosphate, maintaining the temperature, mixing, boosting pressure again, maintaining the pressure, recovering to normal pressure after permeation, and then maintaining the temperature and standing to obtain auxiliary materials for later use;
(5) and adding the prepared base material, mixture and auxiliary materials into a high-speed dispersion machine, naturally cooling to room temperature after high-speed dispersion, and pouring the mixture into a pulverizer to pulverize to obtain the product.
Wherein, in the step (1), the temperature is raised to 125 ℃ for the first time, the stirring speed is 80-100r/min, the temperature is raised to 135 ℃ for the second time, and the reaction time is 2.5-3.5 h; the rotating speed of the stirrer in the step (2) is 200-220r/min, and the stirring time is 30-40 min; in the step (3), the freezing temperature is minus 40 ℃ to minus 30 ℃, the freezing time is 1.5 to 2 hours, the mixture is ground until the mixture is sieved by a 200-mesh sieve, the roasting temperature is 400 ℃ and 420 ℃, and the roasting time is 1 to 1.5 hours; the stirring speed in the step (4) is 180-fold sand 200r/min, the stirring time is 30-40min, the temperature is increased to 240 ℃ for 220-fold sand, the pressure is increased to 10-12MPa for the first time, the pressure maintaining treatment time is 40-60min, the heat preservation mixing time is 1-2h, the pressure is increased to 8-10MPa for the second time, the pressure maintaining permeation time is 30-50min, and the heat preservation standing time is 2-3 h; the rotating speed of the high-speed dispersion in the step (5) is 600-800r/min, the high-speed dispersion time is 30-50min, and the powder is crushed and sieved by a 600-mesh sieve.
Example 4:
the flame retardant performance of the common flame retardant on the market and the flame retardants in examples 1-3 was tested, and the specific test procedure was as follows:
(1) setting 3 different common flame retardants on the market as a control group 1-3, and setting the flame retardants prepared in examples 1-3 as an experimental group 1-3;
(2) taking 30mL of polyvinyl acetate emulsion, adding a flame retardant accounting for 50% of the mass of the polyvinyl acetate emulsion, uniformly stirring, grinding the mixture by using a conical mill until the granularity is 60 mu m, adding 20mL of distilled water, and uniformly stirring to obtain a coating sample;
(3) preparing the rest 5 groups of paint samples according to the method in the step (2), uniformly coating each group of paint on the wood board, burning by adopting the outer flame of the alcohol lamp, and detecting the carbonization time and the combustion phenomenon of each group of paint.
The results are shown in the following table:
Figure DEST_PATH_IMAGE002
as can be seen from the above table, the flame retardant prepared in example 2 has the best flame retardancy because the flame retardant of experiment group 2 requires the longest carbonization time, has the best expansion effect, and has the most abundant bubbles.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (8)

1. The halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant is characterized by being prepared from the following raw materials in parts by weight: 40-45 parts of polyphosphoric acid, 20-25 parts of pentaerythritol, 18-22 parts of melamine, 6-8 parts of titanium dioxide, 3-5 parts of wollastonite powder, 5-7 parts of aluminum hydroxide, 2-4 parts of hydrotalcite, 4-6 parts of sodium hexametaphosphate, 2-4 parts of potassium diphenylsulfone sulfonate, 3-5 parts of m-phenylene tetra (xylyl) diphosphate, 6-8 parts of polycarbonate, 2-4 parts of 2, 5-diaminoadipic acid tetramethylene phosphate and 2-4 parts of silicon phosphate.
2. The halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant of claim 1, characterized in that the flame retardant is prepared from the following raw materials in parts by weight: 42 parts of polyphosphoric acid, 24 parts of pentaerythritol, 20 parts of melamine, 8 parts of titanium dioxide, 4 parts of wollastonite powder, 6 parts of aluminum hydroxide, 3 parts of hydrotalcite, 5 parts of sodium hexametaphosphate, 3 parts of potassium diphenylsulfone sulfonate, 4 parts of m-phenylene tetra (xylyl) diphosphate, 7 parts of polycarbonate, 3 parts of 2, 5-diaminoadipic acid tetramethylene phosphoric acid and 3 parts of silicon phosphate.
3. The preparation method of the halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant is characterized by comprising the following steps of:
(1) adding polyphosphoric acid into a reaction kettle, heating, adding pentaerythritol while stirring, uniformly stirring, heating again, and carrying out heat preservation reaction to obtain a reaction material for later use;
(2) adding melamine into a stirrer, adding the prepared reaction material, and stirring and mixing to obtain a base material for later use;
(3) putting titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a refrigerator for freezing, pouring the frozen titanium dioxide, wollastonite powder, aluminum hydroxide, hydrotalcite and sodium hexametaphosphate into a ball mill for mixing and grinding, putting the mixture into a high-temperature furnace, preserving heat, roasting, and naturally cooling to room temperature to obtain a mixture for later use;
(4) mixing potassium diphenylsulfone sulfonate, m-phenylene tetra (xylyl) diphosphate and polycarbonate, adding the mixture into an autoclave, uniformly stirring, heating and boosting pressure, maintaining pressure for a period of time, then recovering to normal pressure, adding 2, 5-diaminoadipic acid tetramethylene phosphoric acid and silicon phosphate, maintaining the temperature, mixing, boosting pressure again, maintaining the pressure, recovering to normal pressure after permeation, and then maintaining the temperature and standing to obtain auxiliary materials for later use;
(5) and adding the prepared base material, mixture and auxiliary materials into a high-speed dispersion machine, naturally cooling to room temperature after high-speed dispersion, and pouring the mixture into a pulverizer to pulverize to obtain the product.
4. The method as claimed in claim 3, wherein the temperature in step (1) is raised to 125 ℃ for the first time, the stirring speed is 80-100r/min, the temperature is raised to 135 ℃ for the second time, and the reaction time is 2.5-3.5 h.
5. The method as claimed in claim 3, wherein the rotation speed of the stirrer in step (2) is 200-220r/min, and the stirring time is 30-40 min.
6. The method for preparing the halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant as claimed in claim 3, wherein in the step (3), the freezing temperature is-40 ℃ to-30 ℃, the freezing time is 1.5 to 2 hours, the mixture is ground until the mixture passes through a 200-mesh sieve, the roasting temperature is 400-420 ℃, and the roasting time is 1 to 1.5 hours.
7. The method for preparing the halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant of claim 3, wherein the stirring speed in the step (4) is 180-200r/min, the stirring time is 30-40min, the temperature is increased to 240 ℃, the pressure is increased to 10-12MPa for the first time, the pressure maintaining treatment time is 40-60min, the heat preservation and mixing time is 1-2h, the pressure is increased to 8-10MPa for the second time, the pressure maintaining permeation time is 30-50min, and the heat preservation and standing time is 2-3 h.
8. The method for preparing the halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant as claimed in claim 3, wherein the rotation speed of the high-speed dispersion in the step (5) is 600-800r/min, the high-speed dispersion time is 30-50min, and the mixture is crushed to pass through a 600-mesh sieve.
CN201910561372.4A 2019-06-26 2019-06-26 Halogen-free nitrogen-phosphorus-containing macromolecular intumescent flame retardant and preparation method thereof Pending CN112143193A (en)

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