CN112321895A - Nano-silica-modified macromolecular flame-retardant char-forming agent and preparation method thereof - Google Patents
Nano-silica-modified macromolecular flame-retardant char-forming agent and preparation method thereof Download PDFInfo
- Publication number
- CN112321895A CN112321895A CN202011088523.8A CN202011088523A CN112321895A CN 112321895 A CN112321895 A CN 112321895A CN 202011088523 A CN202011088523 A CN 202011088523A CN 112321895 A CN112321895 A CN 112321895A
- Authority
- CN
- China
- Prior art keywords
- reaction
- forming agent
- piperazine
- temperature
- keeping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K3/32—Phosphorus-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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with 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
- 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
-
- 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
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of macromolecular flame-retardant char-forming agents applied to polymer materials, and discloses a high-efficiency char-forming agent modified by nano-silica and a preparation method thereof. The carbon forming agent is prepared by sequentially substituting two chlorine atoms on cyanuric chloride by piperazine at different temperatures through nucleophilic substitution to form a linear macromolecular triazine intermediate taking piperazine as a chain extender, and then raising the temperature to substitute chlorine on side groups of the intermediate by nano silicon dioxide and gamma-aminopropyltriethoxysilane which are connected through hydroxyl groups in a substitution mode with piperazine and cyanuric chloride. The carbon forming agent has the characteristics of good carbon forming property, high molecular weight, migration resistance, high temperature resistance, no influence on the mechanical property of a base material and the like, solves the problem that a carbon layer with good compactness and complete shape cannot be formed due to weak migration resistance of a triazine derivative used as the carbon forming agent, and can be applied to thermoplastic polyurethane and polypropylene.
Description
Technical Field
The invention relates to the technical field of macromolecular flame-retardant char-forming agents applied to polymer materials, in particular to a high-efficiency char-forming agent modified by nano silicon dioxide and a preparation method thereof.
Background
Over the past few decades, halogen-containing Flame Retardants (FRs) have been widely used to limit the flammability of polymeric materials. However, the flame retardant process often has many negative effects, such as the generation of corrosive and toxic fumes or volatiles, which can be extremely harmful to the environment and human health. Therefore, halogen-free flame retardants, especially Intumescent Flame Retardants (IFR), can meet the requirements of various industries on personal safety and environmental protection due to their characteristics of being halogen-free, low-toxicity, droplet-inhibiting, high in flame-retardant efficiency, and low in preparation cost, and therefore, the synthesis of novel intumescent flame retardants and the design of intumescent flame retardant formulations are receiving more and more attention from research and development personnel.
The intumescent flame retardants are classified according to their action principle and can be classified into physical type and chemical type. Physical intumescent flame retardants are generally referred to as Expandable Graphite (EG), which absorbs heat from the polymer combustion system and expands rapidly (up to 280 times its original volume) with the expanded carbon residue covering the surface of the polymer. The carbon layer on the surface of the polymer may impede the transfer of heat, combustible gases and oxygen between the combustion zone and the polymer matrix. At the same time, the char residue adheres to the molten zone of the burning polymer, acting to prevent droplets and slow down the spread of the fire. However, EG hardly reacts chemically with the polymer, the force between the carbon layers is small, and the popcorn effect is easy to occur; the expanded carbon residue is observed under a scanning electron microscope to be in a worm shape, and gaps among carbon layers are large, so that the flame retardant efficiency is low. In addition, the larger the particle size of EG, the less compatible it will be with the polymer matrix. Chemical intumescent flame retardants often consist of three sources: an acid source, a carbon source, and a gas source. Commonly used acid sources consist of mineral acids and ammonium salts, such as ammonium polyphosphates, phosphates and borates, and the like; carbon sources are mainly hydroxyl-containing compounds such as polyhydric alcohols (sorbitol, pentaerythritol and dipentaerythritol), triazine derivatives, polyamides and the like; the air supply mainly comprises: melamine, urea, and urea-formaldehyde resins, and the like. Flame retardant principle of IFR: during combustion, the acid source releases inorganic acid substances containing phosphorus under the action of heat, the inorganic acid containing phosphorus can promote the carbon source to perform esterification and char formation, and simultaneously, the gas source decomposes to release a large amount of volatile gas, so that a molten substance formed between the acid source and the carbon source forms an expanded carbon foam protective layer on the surface of the polymer matrix under the action of the volatile gas, and the protective carbon layer can not only dilute the combustible gas, but also isolate the heat, oxygen and combustible substance from being transferred between a combustion area and the interior of the polymer.
The chemical intumescent flame retardant is widely applied due to the advantages of no halogen and strong char-forming performance. However, the small-molecule char-forming agent in the traditional IFR system has the defects of low flame retardant efficiency and poor thermal stability. This has forced more and more researchers to focus on how to enhance the char-forming capability of IFR systems. The triazine diffractometer mainly comprises H, C, N and three elements, and a stable triazine ring structure is also present in the molecular structure of the triazine diffractometer, so that the triazine diffractometer can simultaneously play the roles of a gas source and a carbon source in the combustion process. Therefore, the development of new triazine-based char-forming agents is still one of the important research directions for realizing high-efficiency intumescent flame retardant. Cyanuric chloride, because of its high selectivity, is often used as a raw material for the synthesis of a series of triazine-based char-forming agents. Although the charring agent mainly comprising the triazine derivatives has many advantages compared with other charring agents, the charring agent is easy to migrate to the surface of a polymer due to the reasons of small molecular weight and the like, the problems of low flame retardant efficiency, poor thermal stability and poor charring performance exist all the time, and a carbon layer with good appearance can not be generated within the required time, so that three sources can not be coordinated and matched efficiently to achieve the ideal flame retardant effect.
Because the quality of the expanded carbon layer greatly influences the flame retardant efficiency of the IFR in the polymer material, and the quality of the expanded carbon layer is closely related to the property of the carbon forming agent, the improvement of the carbon forming performance of the carbon forming agent and the use of the synergist are two important research directions for improving the flame retardant efficiency of the IFR. The nano-silica is used as a commonly used inorganic flame retardant synergist, has a synergistic flame retardant effect with IFR, but has poor compatibility with polymers and is difficult to uniformly disperse in a matrix, and the defects influence the synergistic flame retardant effect of the nano-silica and the IFR in a polymer material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention adopts an organic-inorganic hybrid method to organically modify the nano-silica by using an organic modifier (triazine-based macromolecules) with high flame retardance to synthesize the high-efficiency char-forming agent modified by the nano-silica. The nano silicon dioxide of the novel triazine-based macromolecular charring agent with the efficient catalytic charring function can promote in-situ catalytic charring reaction of triazine-based macromolecules, and can form an expanded charcoal layer capable of isolating heat and combustible gas transmission on the surface of a polymer through esterification and charring reaction with an acid source. Meanwhile, the viscous glass melt generated by the interaction between the decomposition product of the acid source and the nano silicon dioxide can bond the carbon layer on the surface of the polymer, so that the compactness and the thermal stability of the carbon layer can be improved. Not only reduces the generation of combustible gas, but also improves the barrier property of the barrier layer. The compact carbon layer with good thermal stability greatly promotes the flame-retardant efficiency of a three-source expansion flame-retardant system, so that a barrier layer formed on the surface of a polymer melt has a certain inhibiting effect on the mass and heat transfer process between a condensed phase and a gas phase, and the char forming performance of the char forming agent is greatly improved. By the synergistic effect between the nano silicon dioxide and the expansion flame-retardant system, the flame-retardant property of the polymer material is obviously improved. The carbon forming agent has the characteristics of good carbon forming property, high molecular weight, migration resistance, high temperature resistance, no influence on the mechanical property of a base material and the like, and solves the problem that the triazine derivatives cannot form carbon forming property with good compactness and complete appearance due to the migration resistance of the triazine derivatives as the carbon forming agent. Can be used independently or cooperated with phosphorus-nitrogen flame retardant to be applied to polypropylene and thermoplastic polyurethane materials.
In order to achieve the purpose, the invention is realized by the following technical scheme: a high-efficiency carbon forming agent modified by nano silicon dioxide has a structure shown in figure 1.
Further, the raw materials of the efficient carbon forming agent modified by the nano silicon dioxide comprise the following components: nano silicon dioxide, cyanuric chloride, piperazine, triethylamine and gamma-aminopropyl triethoxysilane.
Further, the preparation method of the nano-silica modified high-efficiency carbon forming agent is shown in fig. 2.
Specifically, the preparation method of the efficient carbon forming agent modified by the nano-silica comprises the following steps:
(1) adding cyanuric chloride into an acetone solvent, keeping the temperature of the system at 0-5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving piperazine and sodium hydroxide into deionized water, dropwise adding the piperazine and the sodium hydroxide into the reaction system within 0.5-2 h, and keeping the reaction at 0-5 ℃ for 2.5-5 h after dropwise adding. After the reaction is finished, heating the reaction system to 40-60 ℃, then dropwise adding the water solution of piperazine and sodium hydroxide into the reaction system again, and controlling the dropwise adding time and the reaction time to be 0.5-2 h and 2.5-5 h respectively at the temperature. And finally, after the synthesized product is kept stand and filtered, washing the solid product by using deionized water and ethanol, and fully drying to prepare an intermediate.
(2) Dispersing nano silicon dioxide and gamma-aminopropyltriethoxysilane in dioxane, keeping the reaction temperature of 80-95 ℃, continuously stirring for 20-30 h, heating to 85-100 ℃, adding an intermediate into the reaction system, uniformly stirring, dissolving triethylamine in dioxane, dropwise adding the solution within 0.5-2 h, and keeping the reaction for 4-10 h after dropwise addition. And finally, after the synthesized product is kept stand and filtered, washing the solid product by using deionized water and ethanol, and fully drying to prepare the nano-silica modified efficient carbon forming agent.
Preferably, in the step (1), the mass ratio of cyanuric chloride to piperazine to sodium hydroxide is 2-3: 1: 1-2.
Preferably, in the step (2), the mass ratio of the nano-silica, the gamma-aminopropyltriethoxysilane, the triethylamine and the intermediate is 0.5-1: 2-3: 0.5-1: 2-3.
Has the advantages that: compared with the prior art, the invention has the following beneficial technical effects.
According to the invention, through nucleophilic substitution, two chlorine atoms on cyanuric chloride are sequentially substituted by piperazine at different temperatures to form a linear macromolecular triazine intermediate with piperazine as a chain extender, then the temperature is raised, and chlorine on the side group of the intermediate is substituted by hydroxyl-connected nano silicon dioxide and gamma-aminopropyltriethoxysilane through substitution with piperazine and cyanuric chloride, so that the nano silicon dioxide modified efficient char-forming agent is successfully prepared.
The nano silicon dioxide of the novel triazine-based macromolecular charring agent with the efficient catalytic charring function can promote in-situ catalytic charring reaction of triazine-based macromolecules, and can also form an expanded charcoal layer capable of isolating heat and combustible gas transmission on the surface of a polymer through esterification and charring reaction with an acid source. Meanwhile, the viscous glass melt generated by the interaction between the decomposition product of the acid source and the nano silicon dioxide can bond the carbon layer on the surface of the polymer, so that the compactness and the thermal stability of the carbon layer can be improved. Not only reduces the generation of combustible gas, but also improves the barrier property of the barrier layer. The compact carbon layer with good thermal stability greatly promotes the flame-retardant efficiency of a three-source expansion flame-retardant system, so that a barrier layer formed on the surface of a polymer melt has a certain inhibiting effect on the mass and heat transfer process between a condensed phase and a gas phase, and the char forming performance of the char forming agent is greatly improved. Through the synergistic effect between the nano silicon dioxide and the expansion flame-retardant system, the flame retardant property of the polymer material is obviously improved, the carbon forming agent has the characteristics of good carbon forming property, high molecular weight, migration resistance, high temperature resistance, no influence on the mechanical property of a base material and the like, and the problem that a carbon layer with good compactness and complete appearance cannot be formed due to the weak migration resistance of the triazine derivative as the carbon forming agent is solved. The specific flame retardant mechanism of the nano-silica modified high-efficiency char-forming agent is shown in fig. 3.
Drawings
FIG. 1 is a molecular structural formula of a high-efficiency carbon forming agent modified by nano-silica.
FIG. 2 is a schematic diagram of a synthetic route of a high-efficiency carbon-forming agent modified by nano-silica.
FIG. 3 is a schematic diagram of the flame retardant mechanism of the efficient char-forming agent modified by nano-silica.
Detailed Description
The invention is further illustrated by the following specific examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass, 16 parts by mass and 4 parts by mass. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 2
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of the thermoplastic polyurethane, 15 parts by mass of the diethyl aluminum hypophosphite and 5 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 3
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. After the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano silicon dioxide modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of the thermoplastic polyurethane, 14 parts by mass of the diethyl aluminum hypophosphite and 6 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 4
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of the thermoplastic polyurethane, 13 parts by mass of the diethyl aluminum hypophosphite and 7 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 5
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass, 12 parts by mass and 8 parts by mass. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 6
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before polypropylene, ammonium polyphosphate and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of polypropylene, 16 parts by mass of ammonium polyphosphate and 4 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic charring function. First, polypropylene was heated and melted for 2min in a torque rheometer (set temperature and rotation speed were 180 ℃ and 50r/min, respectively), and then a premixed flame retardant was added and banburying was carried out for 13 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 7
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before polypropylene, ammonium polyphosphate and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of polypropylene, 15 parts by mass of ammonium polyphosphate and 5 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic charring function. First, polypropylene was heated and melted for 2min in a torque rheometer (set temperature and rotation speed were 180 ℃ and 50r/min, respectively), and then a premixed flame retardant was added and banburying was carried out for 13 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 8
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before polypropylene, ammonium polyphosphate and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of polypropylene, 14 parts by mass of ammonium polyphosphate and 6 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic charring function. First, polypropylene was heated and melted for 2min in a torque rheometer (set temperature and rotation speed were 180 ℃ and 50r/min, respectively), and then a premixed flame retardant was added and banburying was carried out for 13 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 9
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before polypropylene, ammonium polyphosphate and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of polypropylene, 13 parts by mass of ammonium polyphosphate and 7 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic charring function. First, polypropylene was heated and melted for 2min in a torque rheometer (set temperature and rotation speed were 180 ℃ and 50r/min, respectively), and then a premixed flame retardant was added and banburying was carried out for 13 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 10
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 1g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before polypropylene, ammonium polyphosphate and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the polypropylene, the ammonium polyphosphate and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of polypropylene, 12 parts by mass of ammonium polyphosphate and 8 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic charring function. First, polypropylene was heated and melted for 2min in a torque rheometer (set temperature and rotation speed were 180 ℃ and 50r/min, respectively), and then a premixed flame retardant was added and banburying was carried out for 13 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 11
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 5g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass, 16 parts by mass and 4 parts by mass. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 12
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 5g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of the thermoplastic polyurethane, 15 parts by mass of the diethyl aluminum hypophosphite and 5 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 13
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 5g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of the thermoplastic polyurethane, 14 parts by mass of the diethyl aluminum hypophosphite and 6 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 14
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 5g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass of the thermoplastic polyurethane, 13 parts by mass of the diethyl aluminum hypophosphite and 7 parts by mass of the novel triazine-based macromolecular charring agent with the efficient catalytic. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Example 15
(1) Adding 18g of cyanuric chloride and 200mL of acetone into a 500mL flask, keeping the temperature of the system below 5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving 3.05g of piperazine and 4.00g of sodium hydroxide into 20mL of deionized water, dropwise adding the solution into the reaction system within 1.5h, and keeping the reaction at 0-5 ℃ for 3h after the dropwise adding is finished. After the reaction was completed, the reaction system was heated to 45 ℃ and then an aqueous solution of piperazine (3.05g) and sodium hydroxide (4.00g) was again added dropwise to the above reaction system at that temperature for 1.5 hours and 3 hours, respectively. And finally, after standing and filtering the synthesized product, alternately washing the product with ethanol and deionized water for three times, and drying the product in a vacuum oven at 70 ℃ for 12 hours to obtain an intermediate.
(2) Dispersing 5g of nano silicon dioxide and 11.07g of KH550 in 300mL of dioxane, keeping the reaction temperature of 90 ℃ and continuously stirring for 24h, heating to 95 ℃, adding 10g of intermediate into the reaction system, uniformly stirring, dissolving 5.06g of triethylamine in 25mL of 1, 4-dioxane, dropwise adding into the solution within 1.5h, and keeping the reaction for 6h after dropwise adding. And after the reaction is finished, filtering the obtained solid, alternately washing the solid for three times by using distilled water and ethanol, and drying the solid for 24 hours at the temperature of 80 ℃ to obtain the nano-silica modified efficient carbon forming agent.
(3) Before thermoplastic polyurethane, diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent with the efficient catalytic charring function are used, the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are placed in a 70 ℃ drying oven to be dried for 8 hours, and then the thermoplastic polyurethane, the diethyl aluminum hypophosphite and the novel triazine-based macromolecular charring agent are weighed according to 100 parts by mass, 12 parts by mass and 8 parts by mass. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Comparative example 1
Before the thermoplastic polyurethane and the diethyl aluminum hypophosphite are used, the thermoplastic polyurethane and the diethyl aluminum hypophosphite are placed in an oven at 70 ℃ for drying for 8 hours, and then the weight of the thermoplastic polyurethane is 100 parts by weight, and the weight of the diethyl aluminum hypophosphite is 20 parts by weight. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Comparative example 2
Before the polypropylene and the aluminum diethyl hypophosphite are used, the polypropylene and the aluminum diethyl hypophosphite are placed in an oven at 70 ℃ for drying for 8 hours, and then 100 parts by mass of thermoplastic polyurethane and 20 parts by mass of the aluminum diethyl hypophosphite are weighed. Firstly, thermoplastic polyurethane is added into a torque rheometer (the set temperature and the set rotating speed are respectively 175 ℃ and 50r/min) to be heated and melted for 2min, and then premixed flame retardant is added to be banburied for 6 min. And (3) placing the internally mixed sample into a mold with a test size specification, placing the mold into a flat vulcanizing machine with a set temperature of 180 ℃ for preheating for 3min, maintaining the pressure for 4min, and naturally cooling to room temperature to obtain the standard sample strip required by the analysis test.
Effect verification
The standard samples obtained in the above examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 1 and 2 were subjected to a vertical burning test in accordance with GB/T2408 + 2008(3.2 mm); carrying out a limit oxygen index test according to GB/T2406.2-2009; performing carbon residue rate test by thermogravimetric analysis, wherein the heating rate is 5 ℃/min, the test range is 15-700 ℃, and the N2 flow rate is 40 mL/min; tensile tests were carried out according to GB/T1040.3-2006; a simple beam impact test (unnotched) was performed according to GB/T1043.1-2008. The test results are shown in table 1.
TABLE 1 flame retardancy and mechanical Properties test results
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (6)
1. A high-efficiency carbon forming agent modified by nano silicon dioxide is characterized in that: the structure is as follows:
2. the nanosilica-modified high-efficiency char-forming agent according to claim 1, wherein: the raw materials comprise the following components: nano silicon dioxide, cyanuric chloride, piperazine, triethylamine and gamma-aminopropyl triethoxysilane.
3. The nanosilica-modified high-efficiency char-forming agent according to claim 1, wherein: the preparation method comprises the following steps:
4. the nanosilica-modified high-efficiency char-forming agent according to claim 1, wherein: the preparation method comprises the following steps:
(1) adding cyanuric chloride into an acetone solvent, keeping the temperature of the system at 0-5 ℃ to completely dissolve the cyanuric chloride, simultaneously dissolving piperazine and sodium hydroxide into deionized water, dropwise adding the piperazine and the sodium hydroxide into the reaction system within 0.5-2 h, and keeping the reaction at 0-5 ℃ for 2.5-5 h after dropwise adding; after the reaction is finished, heating the reaction system to 40-60 ℃, then dropwise adding the aqueous solution of piperazine and sodium hydroxide into the reaction system again, and controlling the dropwise adding time and the reaction time to be 0.5-2 h and 2.5-5 h respectively at the temperature; finally, after the synthesized product is kept stand and filtered, washing the solid product by using deionized water and ethanol, and fully drying to prepare an intermediate;
(2) dispersing nano silicon dioxide and gamma-aminopropyltriethoxysilane in dioxane, keeping the reaction temperature of 80-95 ℃, continuously stirring for 20-30 h, heating to 85-100 ℃, adding an intermediate into the reaction system, uniformly stirring, dissolving triethylamine in dioxane, dropwise adding the solution within 0.5-2 h, and keeping the reaction for 4-10 h after dropwise adding; and finally, after the synthesized product is kept stand and filtered, washing the solid product by using deionized water and ethanol, and fully drying to prepare the nano-silica modified efficient carbon forming agent.
5. The nanosilica-modified high-efficiency char-forming agent according to claim 4, wherein: in the step (1), the mass ratio of cyanuric chloride to piperazine to sodium hydroxide is 2-3: 1: 1-2.
6. The nanosilica-modified high-efficiency char-forming agent according to claim 4, wherein: in the step (2), the mass ratio of the nano silicon dioxide, the gamma-aminopropyltriethoxysilane, the triethylamine and the intermediate is 0.5-1: 2-3: 0.5-1: 2-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011088523.8A CN112321895A (en) | 2020-10-13 | 2020-10-13 | Nano-silica-modified macromolecular flame-retardant char-forming agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011088523.8A CN112321895A (en) | 2020-10-13 | 2020-10-13 | Nano-silica-modified macromolecular flame-retardant char-forming agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112321895A true CN112321895A (en) | 2021-02-05 |
Family
ID=74313832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011088523.8A Pending CN112321895A (en) | 2020-10-13 | 2020-10-13 | Nano-silica-modified macromolecular flame-retardant char-forming agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112321895A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845725A (en) * | 2021-10-19 | 2021-12-28 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
| CN114752098A (en) * | 2022-04-12 | 2022-07-15 | 界首市锦丰塑业有限公司 | Plastic basin for flower planting and preparation method thereof |
| CN114805935A (en) * | 2022-04-20 | 2022-07-29 | 江西永通科技股份有限公司 | Preparation method of composite ultraviolet absorbent |
| CN115194144A (en) * | 2022-07-15 | 2022-10-18 | 三峡大学 | Preparation method of iron-coordinated covalent triazine polymer derived nanocluster material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130281620A1 (en) * | 2010-11-02 | 2013-10-24 | Nissan Chemical Industries, Ltd. | Film-forming composition |
| CN105061761A (en) * | 2015-08-14 | 2015-11-18 | 华南理工大学 | Nano zirconium phosphate-modified triazine macromolecular charring agent, and preparation method and application thereof |
| CN105968352A (en) * | 2016-06-29 | 2016-09-28 | 广州大学 | Preparation methods of amino triazine derivative macromolecular char forming agent and polypropylene flame retardant |
| CN106810720A (en) * | 2016-12-30 | 2017-06-09 | 中国科学院宁波材料技术与工程研究所 | A kind of network structure carbon forming agent and its preparation method and application |
| CN109776795A (en) * | 2018-12-12 | 2019-05-21 | 深圳市比克动力电池有限公司 | Novel triazines are at carbon foamed flame retardant additive and its preparation method and application |
-
2020
- 2020-10-13 CN CN202011088523.8A patent/CN112321895A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130281620A1 (en) * | 2010-11-02 | 2013-10-24 | Nissan Chemical Industries, Ltd. | Film-forming composition |
| CN105061761A (en) * | 2015-08-14 | 2015-11-18 | 华南理工大学 | Nano zirconium phosphate-modified triazine macromolecular charring agent, and preparation method and application thereof |
| CN105968352A (en) * | 2016-06-29 | 2016-09-28 | 广州大学 | Preparation methods of amino triazine derivative macromolecular char forming agent and polypropylene flame retardant |
| CN106810720A (en) * | 2016-12-30 | 2017-06-09 | 中国科学院宁波材料技术与工程研究所 | A kind of network structure carbon forming agent and its preparation method and application |
| CN109776795A (en) * | 2018-12-12 | 2019-05-21 | 深圳市比克动力电池有限公司 | Novel triazines are at carbon foamed flame retardant additive and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| SUKJOON YOO: "Engineering Nanospaces: OMS/Dendrimer Hybrids Possessing Controllable Chemistry and Porosity", 《CHEM.MATER.》 * |
| Y.LOU: "Not all nitrogen atoms are equal: contribution of peripheral versus internal amines to the observed reactivity and capture properties of melamine dendrons on SBA-15", 《CHEMCOMM》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845725A (en) * | 2021-10-19 | 2021-12-28 | 青岛塑科高分子科技有限公司 | Flame-retardant polypropylene material with good water resistance and preparation method thereof |
| CN114752098A (en) * | 2022-04-12 | 2022-07-15 | 界首市锦丰塑业有限公司 | Plastic basin for flower planting and preparation method thereof |
| CN114805935A (en) * | 2022-04-20 | 2022-07-29 | 江西永通科技股份有限公司 | Preparation method of composite ultraviolet absorbent |
| CN115194144A (en) * | 2022-07-15 | 2022-10-18 | 三峡大学 | Preparation method of iron-coordinated covalent triazine polymer derived nanocluster material |
| CN115194144B (en) * | 2022-07-15 | 2023-09-19 | 三峡大学 | Preparation method of iron coordinated covalent triazine polymer derived nanocluster material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112321895A (en) | Nano-silica-modified macromolecular flame-retardant char-forming agent and preparation method thereof | |
| Chen et al. | Synthesis of chitosan-based flame retardant and its fire resistance in epoxy resin | |
| Zheng et al. | Preparation of a novel phosphorus‐and nitrogen‐containing flame retardant and its synergistic effect in the intumescent flame‐retarding polypropylene system | |
| Zhan et al. | Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant | |
| Wang et al. | Synthesis of N-methyl triazine-ethylenediamine copolymer charring foaming agent and its enhancement on flame retardancy and water resistance for polypropylene composites | |
| CN105542160A (en) | Single-component phosphor-nitrogen double-ring cage-shaped macromolecular intumescent flame retardant as well as preparation method and application thereof | |
| CN111040293B (en) | Intumescent flame-retardant polypropylene and preparation method thereof | |
| CN108264720B (en) | Precipitation-free halogen-free flame retardant composition | |
| CN111690171B (en) | Flame retardant and flame-retardant PC plastic | |
| CN109206665B (en) | A kind of hybrid modification hypo-aluminum orthophosphate and preparation method thereof | |
| CN109369957A (en) | It is a kind of to have both UV absorption and fire-retardant difunctional phosphorus flame retardant and preparation and application | |
| WO2019144331A1 (en) | Aluminum amino trimethylene phosphonate, preparation method therefor and use thereof | |
| Qi et al. | The flame retardant and thermal performances of polypropylene with a novel intumescent flame retardant | |
| CN109627758B (en) | Halogen-free flame-retardant glass fiber reinforced nylon | |
| CN112940475A (en) | Flame-retardant composite material and preparation method thereof | |
| CN109679138B (en) | Halogen-free flame retardant melamine polyphosphate borate salt and preparation method and application thereof | |
| CN108948348B (en) | Triazine-silicon-containing Schiff base flame retardant and synthesis method thereof | |
| CN112608485B (en) | Organic-inorganic hybrid efficient synergistic flame-retardant char-forming agent and preparation method thereof | |
| CN103739851A (en) | Polymeric flame retardant containing silicon, phosphorus and nitrogen elements and flame retardant polylactic acid material therefrom | |
| Zhang et al. | Synthesis of a novel organic–inorganic hybrid flame retardant based on Ca (H2PO4) 2 and hexachlorocyclotriphosphazene and its performance in polyvinyl alcohol | |
| CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
| CN113845725A (en) | Flame-retardant polypropylene material with good water resistance and preparation method thereof | |
| CN110922637B (en) | DOPO derivative flame-retardant photo-thermal stabilizer and preparation method and application thereof | |
| US20160075862A1 (en) | Nanoclays containing flame retardant chemicals for fire retardant applications | |
| CN110628085B (en) | Mesoporous silicon resin flame retardant, preparation method and flame-retardant composite material thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210205 |
|
| RJ01 | Rejection of invention patent application after publication |