CN114262498A - Flame-retardant polymer composite material and preparation method thereof - Google Patents
Flame-retardant polymer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant polymer composite material which comprises the following raw materials in parts by weight: 100-120 parts of epoxy resin, 20-40 parts of flame retardant, 3-6 parts of metal oxide, 4-6 parts of montmorillonite and 10-20 parts of curing agent; the preparation method of the flame-retardant polymer composite material comprises the following steps: firstly, heating epoxy resin to 85-90 ℃, then adding a flame retardant, continuing to stir for 15-30min, adding a metal oxide and montmorillonite, and uniformly stirring to obtain a first mixture; and secondly, adding a curing agent into the first mixture, stirring until no bubbles exist, pouring the mixture into a mold while the mixture is hot, curing the mixture for 2 hours at the temperature of 120-130 ℃, then heating to the temperature of 140 ℃ for curing for 1 hour, and demolding the mixture while the mixture is hot to obtain the flame-retardant polymer composite material. The flame-retardant layer formed during combustion can prevent combustion products from escaping, inhibit the thermal decomposition of materials under the layer, and play a role in flame retardance, low smoke and low toxicity.
Description
Technical Field
The invention belongs to the technical field of flame retardance, and particularly relates to a flame-retardant polymer composite material and a preparation method thereof.
Background
The flame-retardant modification technology is a key technology and a main way for improving the fireproof safety characteristics of epoxy, phenolic aldehyde and other polymers and composite materials thereof, plays an irreplaceable important role in the development process of promoting the epoxy, phenolic aldehyde and other polymers and composite materials thereof to be widely applied, and makes great contribution to the safety development and low-carbon development of the human society. However, although the flame-retardant modification method based on the traditional bromine-antimony flame retardant has the characteristics of high efficiency, low cost and the like, and can remarkably improve the flame-retardant performance of epoxy, phenolic aldehyde and other high polymers and composite materials thereof, the flame retardant can release a large amount of toxic and harmful smoke such as HBr and the like in the combustion process, and seriously harms human health, and researches show that: the most direct cause of casualty accidents in most fires is toxic and harmful smoke.
Most of the polymer matrix materials are nonpolar materials, so that the water solubility of the flame-retardant component can cause the flame-retardant component to migrate and separate out to the surface, thereby affecting the appearance on one hand, and causing the non-uniform distribution of the flame-retardant component in the material on the other hand, gradually reducing the flame-retardant effect and affecting the lasting flame-retardant performance of the material; polyols or low molecular weight polyols also have a low thermal decomposition temperature and are therefore unsuitable for use in substrates having a high processing temperature.
Disclosure of Invention
The invention provides a flame-retardant polymer composite material and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
most of the polymer matrix materials are nonpolar materials, so that the water solubility of the flame-retardant component can cause the flame-retardant component to migrate and separate out to the surface, thereby affecting the appearance on one hand, and causing the non-uniform distribution of the flame-retardant component in the material on the other hand, gradually reducing the flame-retardant effect and affecting the lasting flame-retardant performance of the material; polyols or low molecular weight polyols also have a low thermal decomposition temperature and are therefore unsuitable for use in substrates having a high processing temperature.
The purpose of the invention can be realized by the following technical scheme:
a flame-retardant polymer composite material comprises the following raw materials in parts by weight:
100-120 parts of epoxy resin, 20-40 parts of flame retardant, 3-6 parts of metal oxide, 4-6 parts of montmorillonite and 10-20 parts of curing agent;
the flame-retardant polymer composite material is prepared by the following steps:
firstly, heating epoxy resin to 85-90 ℃, then adding a flame retardant, continuing to stir for 15-30min, adding a metal oxide and montmorillonite, and uniformly stirring to obtain a first mixture;
and secondly, adding a curing agent into the first mixture, stirring until no bubbles exist, pouring the mixture into a mold while the mixture is hot, curing the mixture for 2 hours at the temperature of 120-130 ℃, then heating to the temperature of 140 ℃ for curing for 1 hour, and demolding the mixture while the mixture is hot to obtain the flame-retardant polymer composite material.
Further, the metal oxide is formed by mixing one or two of aluminum oxide and copper oxide according to any proportion; the curing agent is aromatic polyamine curing agent.
Further, the flame retardant is prepared by the following steps:
step A1, adding the component A into a reaction kettle, adding glacial acetic acid, stirring for 10-20min at the temperature of 0-5 ℃, adding the component B, keeping the temperature unchanged after adding, continuing stirring for 10-20min, raising the temperature to 20-25 ℃, stirring for 50-60min, raising the temperature to 120 ℃, continuing to react for 5-6h, performing post-treatment after the reaction is finished, mixing the obtained reaction liquid with deionized water ten times the volume of the reaction liquid, performing suction filtration under reduced pressure, and drying the obtained filter cake to constant weight at 40 ℃ to obtain the flame retardant.
Further, the dosage ratio of the component A, the glacial acetic acid and the component B in the step A1 is 10-12.9 g: 600 mL: 15-15.2 g.
Further, component a was prepared by the following steps:
step S11, adding p-hydroxybenzaldehyde, dichloromethane and triethylamine into a reaction kettle, controlling the temperature to be 0-5 ℃, adding phenylphosphoryl dichloride under the protection of nitrogen, monitoring the reaction by using a TLC plate in the reaction process, carrying out post-treatment after the reaction is finished, washing the obtained reaction solution by using deionized water and a sodium hydroxide solution with the mass fraction of 5% in sequence, washing the reaction solution to be neutral by using the deionized water, drying the reaction solution by using anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain an intermediate 1;
the reaction process is as follows:
step S12, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene into a reaction kettle, adding the intermediate 1, heating and refluxing under the conditions of 110 ℃ and nitrogen protection, monitoring the reaction by a TLC plate in the reaction process, cooling the temperature of the reaction liquid to room temperature after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the obtained reaction liquid, washing the reaction liquid for three times by hot toluene, and drying the reaction liquid at 60 ℃ to constant weight after the washing is finished to obtain an intermediate 2;
the reaction process is as follows:
step S13, adding chlorinated trimellitic anhydride into a reaction kettle, adding pyridine, precipitating white solid, adding the intermediate 2 and acetone, stirring at room temperature, stopping reaction after 12h of reaction, performing post-treatment after the reaction is finished, performing vacuum filtration on the obtained reaction liquid, performing rotary evaporation on the obtained filtrate by using a rotary evaporator, removing the solvent, and recrystallizing the obtained solid for 3-5 times by using toluene and acetic anhydride to obtain the component A.
The reaction process is as follows:
further, in the step S11, the dosage ratio of the p-hydroxybenzaldehyde, the dichloromethane, the triethylamine and the phenylphosphoryl dichloride is 25-26 g: 80mL of: 20-20.2 g: 19-20 g;
in step S12, the ratio of the amounts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene and intermediate 1 was 43 g: 90mL of: 36-37 g;
the dosage ratio of the chlorinated trimellitic anhydride, the pyridine, the intermediate 2 and the acetone in the step S13 is 12.4-12.6 g: 4.64 g: 23 g: 400 mL.
Further, component B was prepared by the following steps:
step S21, adding phenyltriethoxysilane into a reaction kettle, adding a hydrochloric acid solution with the mass fraction of 15% as a catalyst, dropwise adding N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane, heating to 50 ℃ at the heating rate of 5 ℃/min, keeping the temperature unchanged, heating and refluxing for 4h, adding hexamethyldisiloxane for end capping, keeping the temperature unchanged for reaction for 1h, adjusting the pH value to 8-9 with ammonia water after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the reaction solution after the pH value is adjusted, washing the obtained filter cake with deionized water for three times, and drying at 80 ℃ under a vacuum condition to constant weight to obtain a component B.
Wherein, in the step S21, the dosage ratio of the phenyltriethoxysilane, the hydrochloric acid solution with the mass fraction of 15 percent to the N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane is 21-22 g: 10mL of: 2-2.2 g.
The reaction process is as follows:
further, the preparation method of the flame-retardant polymer composite material comprises the following steps:
firstly, heating epoxy resin to 85-90 ℃, then adding a flame retardant, continuing to stir for 15-30min, adding a metal oxide and montmorillonite, and uniformly stirring to obtain a first mixture;
and secondly, adding a curing agent into the first mixture, stirring until no bubbles exist, pouring the mixture into a mold while the mixture is hot, curing the mixture for 2 hours at the temperature of 120-130 ℃, then heating to the temperature of 140 ℃ for curing for 1 hour, and demolding the mixture while the mixture is hot to obtain the flame-retardant polymer composite material.
The invention has the beneficial effects that:
under the protection of nitrogen, hydroxybenzaldehyde and phenyl phosphoryl dichloride are subjected to esterification reaction to prepare an intermediate 1; the intermediate 1 and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide undergo nucleophilic addition to prepare an intermediate 2, and the intermediate 2 reacts with chlorinated trimellitic anhydride to prepare a component A; phenyl triethoxysilane reacts with N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane, and the mixture is hydrolyzed and polycondensed to synthesize organic silicon resin containing phenyl and amino, namely component B; then the amino groups in the prepared component A and the component B are subjected to imidization reaction to prepare the flame retardant.
Phenyl phosphate diester (phosphorus valence state is +3) and DOPO (phosphorus valence state is +1) are combined to prepare a component A with a flame retardant function by utilizing two different phosphorus valence states, then the component A is connected to a molecular chain of a component B, an imide ring structure unit is formed at the same time to endow the flame retardant with heat stability, phosphorus is introduced into the molecular structure of the component A, and the phosphorus and the existing silicon and nitrogen elements have a synergistic effect, so that the flame retardant effect can be improved, and the problems of uneven dispersion and poor compatibility in the processing of the flame retardant can be solved. The benzene ring in the flame retardant has a rigid structure, is thermally stable and rich in carbon source, and the Si-O, Si-C bond in the flame retardant is an oxygen-insulating and heat-insulating flame-retardant layer which can prevent combustion products from escaping outwards, inhibit the thermal decomposition of materials below the layer, play a role in flame retardance, low smoke and low toxicity, improve the processability of the materials, reduce the smoke amount and heat release amount of the materials during combustion, reduce the generation of CO and improve the flame retardance of the materials.
Al2O3Can improve the barrier property of the carbon residue layer, and CuO can inhibit CO and CO2Is thus Al2O3The CuO and the composite flame-retardant system has the best synergistic flame-retardant and smoke-suppression performance, improves the condensed phase flame-retardant capability, reduces the dosage of organic flame retardant, and improves the flame-retardant performance and the fire safety.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 flame-retardant polymer composite material comprises the following raw materials in parts by weight:
100 parts of epoxy resin, 20 parts of flame retardant, 3 parts of metal oxide, 4 parts of montmorillonite and 10 parts of curing agent;
the flame-retardant polymer composite material is prepared by the following steps:
firstly, heating epoxy resin to 85 ℃, then adding a flame retardant, continuing stirring for 15min, adding a metal oxide and montmorillonite, and uniformly stirring to obtain a first mixture;
and secondly, adding a curing agent into the first mixture, stirring until no bubbles exist, pouring the mixture into a mold while the mixture is hot, curing the mixture for 2 hours at the temperature of 120 ℃, then heating the mixture to the temperature of 140 ℃, curing the mixture for 1 hour, and demolding the mixture while the mixture is hot to obtain the flame-retardant polymer composite material.
Wherein, the metal oxide is formed by mixing one or two of aluminum oxide and copper oxide according to any proportion; the curing agent is 4,4' -diaminodiphenylmethane.
Wherein, the flame retardant is prepared by the following steps:
step A1, adding the component A into a reaction kettle, adding glacial acetic acid, stirring for 10min at the temperature of 0 ℃, adding the component B, keeping the temperature unchanged after the component A is added, continuing stirring for 10min, raising the temperature to 20 ℃, stirring for 50min, raising the temperature to 120 ℃, continuing to react for 5h, performing post-treatment after the reaction is finished, mixing the obtained reaction liquid with deionized water ten times the volume of the reaction liquid, performing suction filtration under reduced pressure, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ to obtain the flame retardant.
Wherein, the dosage ratio of the component A, the glacial acetic acid and the component B in the step A1 is 10 g: 600 mL: 15 g.
Wherein, the component A is prepared by the following steps:
step S11, adding p-hydroxybenzaldehyde, dichloromethane and triethylamine into a reaction kettle, controlling the temperature to be 0 ℃, adding phenylphosphoryl dichloride under the protection of nitrogen, monitoring the reaction by using a TLC plate in the reaction process, performing post-treatment after the reaction is finished, washing the obtained reaction solution by using deionized water and a sodium hydroxide solution with the mass fraction of 5% in sequence, washing the reaction solution to be neutral by using the deionized water, drying the reaction solution by using anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain an intermediate 1;
step S12, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene into a reaction kettle, adding the intermediate 1, heating and refluxing under the conditions of 110 ℃ and nitrogen protection, monitoring the reaction by a TLC plate in the reaction process, cooling the temperature of the reaction liquid to room temperature after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the obtained reaction liquid, washing the reaction liquid for three times by hot toluene, and drying the reaction liquid at 60 ℃ to constant weight after the washing is finished to obtain an intermediate 2;
step S13, adding chlorinated trimellitic anhydride into a reaction kettle, adding pyridine, precipitating white solid, adding the intermediate 2 and acetone, stirring at room temperature, stopping reaction after 12 hours of reaction, performing post-treatment after the reaction is finished, performing vacuum filtration on the obtained reaction liquid, performing rotary evaporation on the obtained filtrate by using a rotary evaporator, removing the solvent, and recrystallizing the obtained solid for 3 times by using toluene and acetic anhydride to obtain the component A.
Wherein the dosage ratio of the p-hydroxybenzaldehyde, the dichloromethane, the triethylamine and the phenylphosphoryl dichloride in the step S11 is 25 g: 80mL of: 20 g: 19g of a mixture; in step S12, the ratio of the amounts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene and intermediate 1 was 43 g: 90mL of: 36g of a mixture; the use amount ratio of the chlorinated trimellitic anhydride, pyridine, intermediate 2 and acetone in step S13 was 12.4 g: 4.64 g: 23 g: 400 mL.
Wherein the component B is prepared by the following steps:
step S21, adding phenyltriethoxysilane into a reaction kettle, adding a hydrochloric acid solution with the mass fraction of 15% as a catalyst, dropwise adding N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane, heating to 50 ℃ at the heating rate of 5 ℃/min, keeping the temperature unchanged, heating and refluxing for 4h, adding hexamethyldisiloxane for end capping, keeping the temperature unchanged for reaction for 1h, adjusting the pH value to 8 by using ammonia water after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the reaction solution after the pH value is adjusted, washing the obtained filter cake for three times by using deionized water, and drying at 80 ℃ under a vacuum condition to constant weight to obtain the component B.
Wherein, in the step S21, the dosage ratio of the phenyltriethoxysilane, the hydrochloric acid solution with the mass fraction of 15 percent and the N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane is 21 g: 10mL of: 2g of the total weight.
Example 2
A flame-retardant polymer composite material comprises the following raw materials in parts by weight:
110 parts of epoxy resin, 30 parts of flame retardant, 5 parts of metal oxide, 5 parts of montmorillonite and 15 parts of curing agent;
the flame-retardant polymer composite material is prepared by the following steps:
firstly, heating epoxy resin to 88 ℃, then adding a flame retardant, continuing stirring for 20min, adding a metal oxide and montmorillonite, and uniformly stirring to obtain a first mixture;
and secondly, adding a curing agent into the first mixture, stirring until no bubbles exist, pouring the mixture into a mold while the mixture is hot, curing the mixture for 2 hours at the temperature of 125 ℃, then heating the mixture to the temperature of 140 ℃, curing the mixture for 1 hour, and demolding the mixture while the mixture is hot to obtain the flame-retardant polymer composite material.
Wherein, the metal oxide is formed by mixing one or two of aluminum oxide and copper oxide according to any proportion; the curing agent is 4,4' -diaminodiphenylmethane.
Wherein, the flame retardant is prepared by the following steps:
step A1, adding the component A into a reaction kettle, adding glacial acetic acid, stirring for 15min at the temperature of 2 ℃, adding the component B, keeping the temperature unchanged after the component A is added, continuing stirring for 15min, raising the temperature to 22 ℃, stirring for 55min, raising the temperature to 120 ℃, continuing to react for 5.5h, performing post-treatment after the reaction is finished, mixing the obtained reaction liquid with deionized water ten times the volume of the reaction liquid, performing suction filtration under reduced pressure, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ to obtain the flame retardant.
Wherein the dosage ratio of the component A, the glacial acetic acid and the component B in the step A1 is 11 g: 600 mL: 15 g.
Wherein, the component A is prepared by the following steps:
step S11, adding p-hydroxybenzaldehyde, dichloromethane and triethylamine into a reaction kettle, controlling the temperature to be 2 ℃, adding phenylphosphoryl dichloride under the protection of nitrogen, monitoring the reaction by using a TLC plate in the reaction process, performing post-treatment after the reaction is finished, washing the obtained reaction solution by using deionized water and a sodium hydroxide solution with the mass fraction of 5% in sequence, washing the reaction solution to be neutral by using the deionized water, drying the reaction solution by using anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain an intermediate 1;
step S12, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene into a reaction kettle, adding the intermediate 1, heating and refluxing under the conditions of 110 ℃ and nitrogen protection, monitoring the reaction by a TLC plate in the reaction process, cooling the temperature of the reaction liquid to room temperature after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the obtained reaction liquid, washing the reaction liquid for three times by hot toluene, and drying the reaction liquid at 60 ℃ to constant weight after the washing is finished to obtain an intermediate 2;
step S13, adding chlorinated trimellitic anhydride into a reaction kettle, adding pyridine, precipitating white solid, adding the intermediate 2 and acetone, stirring at room temperature, stopping reaction after 12 hours of reaction, performing post-treatment after the reaction is finished, performing vacuum filtration on the obtained reaction liquid, performing rotary evaporation on the obtained filtrate by using a rotary evaporator, removing the solvent, and recrystallizing the obtained solid for 4 times by using toluene and acetic anhydride to obtain the component A.
Wherein the dosage ratio of the p-hydroxybenzaldehyde, the dichloromethane, the triethylamine and the phenylphosphoryl dichloride in the step S11 is 25 g: 80mL of: 20 g: 19g of a mixture; in step S12, the ratio of the amounts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene and intermediate 1 was 43 g: 90mL of: 36g of a mixture; the use amount ratio of the chlorinated trimellitic anhydride, pyridine, intermediate 2 and acetone in step S13 was 12.5 g: 4.64 g: 23 g: 400 mL.
Wherein the component B is prepared by the following steps:
step S21, adding phenyltriethoxysilane into a reaction kettle, adding a hydrochloric acid solution with the mass fraction of 15% as a catalyst, dropwise adding N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane, heating to 50 ℃ at the heating rate of 5 ℃/min, keeping the temperature unchanged, heating and refluxing for 4h, adding hexamethyldisiloxane for end capping, keeping the temperature unchanged for reaction for 1h, adjusting the pH value to 8 by using ammonia water after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the reaction solution after the pH value is adjusted, washing the obtained filter cake for three times by using deionized water, and drying at 80 ℃ under a vacuum condition to constant weight to obtain the component B.
Wherein, in the step S21, the dosage ratio of the phenyltriethoxysilane, the hydrochloric acid solution with the mass fraction of 15 percent and the N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane is 21 g: 10mL of: 2g of the total weight.
Example 3
A flame-retardant polymer composite material comprises the following raw materials in parts by weight:
120 parts of epoxy resin, 40 parts of flame retardant, 6 parts of metal oxide, 6 parts of montmorillonite and 20 parts of curing agent;
the flame-retardant polymer composite material is prepared by the following steps:
firstly, heating epoxy resin to 90 ℃, then adding a flame retardant, continuing stirring for 30min, adding a metal oxide and montmorillonite, and uniformly stirring to obtain a first mixture;
and secondly, adding a curing agent into the first mixture, stirring until no bubbles exist, pouring the mixture into a mold while the mixture is hot, curing the mixture for 2 hours at the temperature of 130 ℃, then heating the mixture to the temperature of 140 ℃, curing the mixture for 1 hour, and demolding the mixture while the mixture is hot to obtain the flame-retardant polymer composite material.
Wherein, the metal oxide is formed by mixing one or two of aluminum oxide and copper oxide according to any proportion; the curing agent is 4,4' -diaminodiphenylmethane.
Wherein, the flame retardant is prepared by the following steps:
step A1, adding the component A into a reaction kettle, adding glacial acetic acid, stirring for 20min at the temperature of 5 ℃, adding the component B, keeping the temperature unchanged after the component A is added, continuing stirring for 20min, raising the temperature to 25 ℃, stirring for 60min, raising the temperature to 120 ℃, continuing to react for 6h, performing post-treatment after the reaction is finished, mixing the obtained reaction liquid with deionized water ten times the volume of the reaction liquid, performing suction filtration under reduced pressure, and drying the obtained filter cake to constant weight at the temperature of 40 ℃ to obtain the flame retardant.
Wherein, the dosage ratio of the component A, the glacial acetic acid and the component B in the step A1 is 12.9 g: 600 mL: 15.2 g.
Wherein, the component A is prepared by the following steps:
step S11, adding p-hydroxybenzaldehyde, dichloromethane and triethylamine into a reaction kettle, controlling the temperature to be 5 ℃, adding phenylphosphoryl dichloride under the protection of nitrogen, monitoring the reaction by using a TLC plate in the reaction process, performing post-treatment after the reaction is finished, washing the obtained reaction solution by using deionized water and a sodium hydroxide solution with the mass fraction of 5% in sequence, washing the reaction solution to be neutral by using the deionized water, drying the reaction solution by using anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain an intermediate 1;
step S12, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene into a reaction kettle, adding the intermediate 1, heating and refluxing under the conditions of 110 ℃ and nitrogen protection, monitoring the reaction by a TLC plate in the reaction process, cooling the temperature of the reaction liquid to room temperature after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the obtained reaction liquid, washing the reaction liquid for three times by hot toluene, and drying the reaction liquid at 60 ℃ to constant weight after the washing is finished to obtain an intermediate 2;
step S13, adding chlorinated trimellitic anhydride into a reaction kettle, adding pyridine, precipitating white solid, adding the intermediate 2 and acetone, stirring at room temperature, stopping reaction after 12 hours of reaction, performing post-treatment after the reaction is finished, performing vacuum filtration on the obtained reaction liquid, performing rotary evaporation on the obtained filtrate by using a rotary evaporator, removing the solvent, and recrystallizing the obtained solid for 5 times by using toluene and acetic anhydride to obtain the component A.
Wherein the dosage ratio of the p-hydroxybenzaldehyde, the dichloromethane, the triethylamine and the phenylphosphoryl dichloride in the step S11 is 26 g: 80mL of: 20.2 g: 20g of the total weight of the mixture; in step S12, the ratio of the amounts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene and intermediate 1 was 43 g: 90mL of: 37g of a soybean milk powder; the use amount ratio of the chlorinated trimellitic anhydride, pyridine, intermediate 2 and acetone in step S13 was 12.6 g: 4.64 g: 23 g: 400 mL.
Wherein the component B is prepared by the following steps:
step S21, adding phenyltriethoxysilane into a reaction kettle, adding a hydrochloric acid solution with the mass fraction of 15% as a catalyst, dropwise adding N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane, heating to 50 ℃ at the heating rate of 5 ℃/min, keeping the temperature unchanged, heating and refluxing for 4h, adding hexamethyldisiloxane for end capping, keeping the temperature unchanged for reaction for 1h, adjusting the pH value to 9 by using ammonia water after the reaction is finished, performing post-treatment, performing reduced pressure suction filtration on the reaction solution after the pH value is adjusted, washing the obtained filter cake for three times by using deionized water, and drying at 80 ℃ under a vacuum condition to constant weight to obtain the component B.
Wherein, the dosage ratio of the phenyltriethoxysilane, the hydrochloric acid solution with the mass fraction of 15 percent and the N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane in the step S21 is 22 g: 10mL of: 2.2 g.
Comparative example 1
The flame retardant in example 1 was replaced with one commonly available on the market, and the rest of the raw materials and the preparation process were kept unchanged.
Comparative example 2
The metal oxide in example 1 was removed and the remaining raw materials and preparation process remained unchanged.
The materials obtained in examples 1 to 3 and comparative examples 1 to 2 were tested; the flame retardant property test adopts a cone calorimetric tester, and the sample size is 100 multiplied by 3mm according to ISO5660-1 standard3The test heat flow is 50kW/m25 bars were tested per sample and then calculated according to the correction specified in the standard,
the test results are shown in table 1 below:
TABLE 1
| Categories | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Total Heat Release amount (MJ/m)2) | 83.2 | 83.1 | 83.6 | 96.4 | 90.2 |
| Total amount of smoke released (m/m) | 3655.6 | 3651.8 | 3658 | 4631.7 | 3744.8 |
| Total time of combustion(s) | 336 | 354 | 321 | 405 | 370 |
| Total time of smoke release(s) | 230 | 241 | 240 | 272 | 253 |
From the above table 1, it can be seen that the flame-retardant polymer composite material prepared by the present invention prevents the release of heat and smoke, greatly shortens the combustion duration, and greatly shortens the smoke release duration.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. The flame-retardant polymer composite material is characterized by comprising the following raw materials in parts by weight:
100-120 parts of epoxy resin, 20-40 parts of flame retardant, 3-6 parts of metal oxide, 4-6 parts of montmorillonite and 10-20 parts of curing agent;
the flame retardant is prepared by the following steps:
step A1, adding the component A into a reaction kettle, adding glacial acetic acid, stirring for 10-20min at the temperature of 0-5 ℃, adding the component B, keeping the temperature unchanged after the component A is added, continuing stirring for 10-20min, raising the temperature to 20-25 ℃, stirring for 50-60min, raising the temperature to 120 ℃, continuing to react for 5-6h, and performing post-treatment after the reaction is finished to obtain the flame retardant.
2. The flame-retardant polymer composite material according to claim 1, wherein the metal oxide is one or two of aluminum oxide and copper oxide mixed in any proportion; the curing agent is aromatic polyamine curing agent.
3. The flame-retardant polymer composite material according to claim 1, wherein the component A is prepared by the following steps:
step S11, adding p-hydroxybenzaldehyde, dichloromethane and triethylamine into a reaction kettle, controlling the temperature to be 0-5 ℃, adding phenylphosphoryl dichloride under the condition of nitrogen protection, and performing post-treatment after the reaction is finished to obtain an intermediate 1;
step S12, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and toluene into a reaction kettle, adding the intermediate 1, heating and refluxing for reaction at the temperature of 110 ℃ under the protection of nitrogen, cooling the reaction solution to room temperature after the reaction is finished, and performing post-treatment to obtain an intermediate 2;
and step S13, adding chlorinated trimellitic anhydride into a reaction kettle, adding pyridine, adding the intermediate 2 and acetone when white solids are separated out, stirring at room temperature, stopping the reaction after reacting for 12 hours, and performing post-treatment after the reaction is finished to obtain the component A.
4. The flame-retardant polymer composite material according to claim 1, wherein the component B is prepared by the following steps:
step S21, adding phenyltriethoxysilane into a reaction kettle, adding a hydrochloric acid solution with the mass fraction of 15% as a catalyst, dropwise adding N- (beta-aminoethyl-) -gamma-aminopropylmethyl-dimethoxysilane, heating to 50 ℃ at the heating rate of 5 ℃/min, keeping the temperature unchanged, heating and refluxing for 4h, adding hexamethyldisiloxane for end capping, keeping the temperature unchanged for reaction for 1h, adjusting the pH value to 8-9 by using ammonia water after the reaction is finished, and performing post-treatment to obtain a component B.
5. The preparation method of the flame-retardant polymer composite material according to claim 1, which is characterized by comprising the following steps:
firstly, heating epoxy resin to 85-90 ℃, then adding a flame retardant, continuing to stir for 15-30min, adding a metal oxide and montmorillonite, and uniformly stirring to obtain a first mixture;
and secondly, adding a curing agent into the first mixture, stirring until no bubbles exist, pouring the mixture into a mold while the mixture is hot, curing the mixture for 2 hours at the temperature of 120-130 ℃, then heating to the temperature of 140 ℃ for curing for 1 hour, and demolding the mixture while the mixture is hot to obtain the flame-retardant polymer composite material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854213A (en) * | 2022-06-15 | 2022-08-05 | 千年舟新材科技集团股份有限公司 | Plate flame-retardant additive and application thereof |
| CN115304636A (en) * | 2022-08-15 | 2022-11-08 | 铨盛聚碳科技股份有限公司 | Organic silicon flame retardant containing phosphorus and nitrogen, and preparation method and application thereof |
| CN115558324A (en) * | 2022-10-25 | 2023-01-03 | 青岛科技大学 | Flame retardant and preparation method thereof, and fireproof coating and preparation method thereof |
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2022
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854213A (en) * | 2022-06-15 | 2022-08-05 | 千年舟新材科技集团股份有限公司 | Plate flame-retardant additive and application thereof |
| CN114854213B (en) * | 2022-06-15 | 2023-03-21 | 千年舟新材科技集团股份有限公司 | Plate flame-retardant additive and application thereof |
| CN115304636A (en) * | 2022-08-15 | 2022-11-08 | 铨盛聚碳科技股份有限公司 | Organic silicon flame retardant containing phosphorus and nitrogen, and preparation method and application thereof |
| CN115558324A (en) * | 2022-10-25 | 2023-01-03 | 青岛科技大学 | Flame retardant and preparation method thereof, and fireproof coating and preparation method thereof |
| CN115558324B (en) * | 2022-10-25 | 2023-04-28 | 青岛科技大学 | Flame retardant and preparation method thereof, and fireproof coating and preparation method thereof |
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