CN118006108B - Polycarbonate material containing polymer halogen-free flame retardant and preparation process thereof - Google Patents
Polycarbonate material containing polymer halogen-free flame retardant and preparation process thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polycarbonate, and discloses a polycarbonate material containing a polymer halogen-free flame retardant and a preparation process thereof, wherein the nitrogen-phosphorus polymer flame retardant has good compatibility with polycarbonate, and simultaneously contains a heat-resistant nitrogen heterocyclic biphenyl urea group structure, and after being mixed with the polycarbonate, the polycarbonate material can improve the thermal decomposition temperature of the polycarbonate and improve the heat resistance of the polycarbonate. Meanwhile, the flame-retardant polycarbonate resin composition contains a phosphate-indole cyclophosphates flame-retardant system, and the polycarbonate resin composition can promote polycarbonate to form a carbon layer structure after burning, so that the flame-retardant performance of the polycarbonate resin composition is enhanced. Through sulfuric acid sulfonation and potassium hydroxide salinization, a potassium sulfonate group of nitrogen and phosphorus is introduced into the side chain of the nitrogen and phosphorus polymer flame retardant to obtain the nitrogen and phosphorus sulfonate polymer flame retardant, and the sulfonate structure can catalyze polycarbonate to crosslink into carbon during combustion, so that the flame retardant property of the polycarbonate is enhanced, and the limiting oxygen index and the UL-94 fire rating are further improved.
Description
Technical Field
The invention relates to the technical field of polycarbonate, in particular to a polycarbonate material containing a polymer halogen-free flame retardant and a preparation process thereof.
Background
Polycarbonate is one of the thermoplastic engineering plastics which is emerging in recent years, and has excellent mechanical property, electrical property and oxidation resistance. Widely applied to the fields of machine manufacturing, building material industry, packaging and the like; although polycarbonates have a certain flame retardancy, polycarbonates are required to have high flame retardancy and heat resistance in special fields such as aerospace, automobile industry, electronics and electric fields, etc.
The traditional polycarbonate flame retardant mainly comprises brominated flame retardants, nitrogen and phosphorus compounds, sulfonates and the like. Wherein the brominated flame retardant is restricted in use due to the greater pollution during use. There is therefore a need to develop new halogen-free flame retardants for polycarbonates. Compared with small molecular flame retardants, the polymer-based macromolecular flame retardants have higher heat resistance, better compatibility with a material matrix, poor migration and precipitation of the flame retardants and the like. The invention improves the properties of polycarbonate material such as flame retardant property and the like through the polymer halogen-free flame retardant.
Disclosure of Invention
The invention solves the technical problems that: the novel polymer halogen-free flame retardant is utilized to improve the flame retardant property, heat resistance and other properties of the polycarbonate material, and meanwhile, the mechanical property of the polycarbonate material is not affected well.
The invention provides the technical scheme that:
a polycarbonate material containing polymer halogen-free flame retardant comprises 0.1-1.5 parts by weight of polymer halogen-free flame retardant and 98.5-99.8 parts by weight of polycarbonate.
The polymer halogen-free flame retardant is any one of a nitrogen-phosphorus polymer flame retardant or a nitrogen-phosphorus sulfonate polymer flame retardant.
The preparation process of the nitrogen-phosphorus polymer flame retardant comprises the following steps:
And step A, introducing nitrogen into a reaction container, adding N, N-dimethylformamide, toluene-2, 4-diisocyanate and phenyl bis [5- (anilino) indole ] phosphate, performing polymerization at 80-90 ℃ for 4-6 hours, adding petroleum ether for precipitation, filtering, washing with water and ethanol in sequence, and drying to obtain the nitrogen-phosphorus polymer flame retardant.
The preparation process of the nitrogen-phosphorus sulfonate polymer flame retardant comprises the following steps:
And B, adding concentrated sulfuric acid and a nitrogen-phosphorus polymer flame retardant into a reaction container, performing sulfonation reaction at the temperature of 45-60 ℃ for 30-90min, adding water for dilution, filtering, adding a water-washed product into water, adding potassium hydroxide to adjust the pH of the solution to 9-11, stirring, filtering, washing with water, and drying to obtain the nitrogen-phosphorus sulfonate polymer flame retardant.
Wherein the molar amount of the phenyl bis [5- (anilino) indole ] phosphate in the step A is 105-120% of the molar amount of the toluene-2, 4-diisocyanate.
Wherein, the preparation process of the di [5- (anilino) indole ] phenyl phosphate comprises the following steps:
adding toluene, 5-bromoindole, pyridine and phenyl dichlorophosphate into a reaction vessel under ice bath, then reacting for 12-18h at 20-45 ℃, rotary evaporating, washing with petroleum ether, and recrystallizing the product with toluene to obtain the phenyl bis (5-bromoindole) phosphate with the structural formula of 。
And (2) adding 1, 4-dioxane, phenyl bis (5-bromoindole) phosphate, 4-aminophenylboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium, potassium carbonate and water into a reaction vessel, introducing nitrogen into the reaction vessel, condensing and refluxing the reaction vessel for 48 to 72 hours at the temperature of between 100 and 110 ℃, performing rotary evaporation, washing the water and acetone in sequence, and recrystallizing the product by toluene to obtain the bis [5- (anilino) indole ] phenyl phosphate. The structure is that。
Wherein, the molar dosage of the 5-bromoindole and the pyridine in the step (1) is 180-230 percent and 200-230 percent of the molar dosage of the phenyl dichlorophosphate.
Wherein, in the step (2), the molar amount of the 4-aminophenylboronic acid pinacol ester, the tetrakis (triphenylphosphine) palladium and the potassium carbonate is 210 to 240 percent, 5.6 to 7 percent and 260 to 320 percent of the molar amount of the phenyl bis (5-bromoindole) phosphate.
Wherein, the preparation process of the polycarbonate material containing the polymer halogen-free flame retardant comprises the steps of adding 0.1-1.5 parts by weight of the polymer halogen-free flame retardant and 98.5-99.8 parts by weight of polycarbonate into a double screw extruder for blending extrusion, wherein the temperature of each section is 220-240 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265-275 ℃, and obtaining the polycarbonate material containing the polymer halogen-free flame retardant.
The invention has the technical effects that: the invention uses 5-bromoindole and phenyl dichlorophosphate to carry out a phosphoramidation reaction, and then carries out a coupling reaction with 4-aminophenylboronic acid pinacol ester to obtain di [5- (anilino) indole ] phenyl phosphate; finally, the flame retardant is polymerized with toluene-2, 4-diisocyanate to obtain a nitrogen-phosphorus polymer flame retardant, wherein the flame retardant is a polymer macromolecule, has good compatibility with polycarbonate, contains a heat-resistant nitrogen heterocyclic biphenyl ureido structure, and can improve the thermal decomposition temperature of the polycarbonate and improve the heat resistance of the polycarbonate after being mixed with the polycarbonate. Meanwhile, the flame-retardant polycarbonate resin composition contains a phosphate-indole cyclophosphates flame-retardant system, and the polycarbonate resin composition can promote polycarbonate to form a carbon layer structure after burning, so that the flame retardant property of the polycarbonate resin composition is enhanced, and the limiting oxygen index and the UL-94 fire-retardant grade during burning are improved.
The bis [5- (anilino) indole ] phenyl phosphate structural unit in the nitrogen-phosphorus polymer flame retardant contains a plurality of benzene ring structures, and is subjected to sulfuric acid sulfonation and potassium hydroxide salinization, and a nitrogen-phosphorus sulfonate group is introduced into the side chain of the nitrogen-phosphorus polymer flame retardant to obtain the nitrogen-phosphorus sulfonate polymer flame retardant, wherein the sulfonate structure can catalyze polycarbonate to crosslink into carbon during combustion, so that the flame retardant performance of the polycarbonate is enhanced, and the limiting oxygen index and the UL-94 fire resistance are further improved.
Drawings
FIG. 1 is a scheme showing the reaction of phenyl bis [5- (anilino) indole ] phosphate.
FIG. 2 is a reaction mechanism of a nitrogen-phosphorus polymer flame retardant.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
To the reaction vessel were added 20mL of toluene, 5.4mmol of 5-bromoindole, 6.6mmol of pyridine, 3mmol of phenyl dichlorophosphate under ice bath, followed by reaction at 30℃for 12 hours, rotary evaporation, washing with petroleum ether, and recrystallization of the product with toluene to give phenyl bis (5-bromoindole) phosphate.
To the reaction vessel were added 60mL of 1, 4-dioxane, 5mmol of phenyl bis (5-bromoindole) phosphate, 10.5mmol of 4-aminophenylboronic acid pinacol ester, 0.35mmol of tetrakis (triphenylphosphine) palladium, 16mmol of potassium carbonate and 15mL of water, and the mixture was introduced into nitrogen gas, and the mixture was subjected to reflux reaction at 100℃for 60 hours under condensation, rotary evaporation, water and acetone were sequentially washed, and the product was recrystallized from toluene to give phenyl bis [5- (anilino) indole ] phosphate.
Introducing nitrogen into a reaction vessel, adding 20mL of N, N-dimethylformamide, 10mmol of toluene-2, 4-diisocyanate and 12mmol of di [5- (anilino) indole ] phenyl phosphate, performing polymerization reaction at the temperature of 85 ℃ for 6 hours, adding petroleum ether for precipitation, filtering, washing with water and ethanol in sequence, and drying to obtain the nitrogen-phosphorus polymer flame retardant.
Adding 1g of nitrogen-phosphorus polymer flame retardant and 999g of polycarbonate into a double screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Example 2
10ML of toluene, 5.4mmol of 5-bromoindole, 6mmol of pyridine and 3mmol of phenyl dichlorophosphate are added into a reaction vessel under ice bath, then the mixture is reacted at 45 ℃ for 18 hours, rotary evaporation and petroleum ether washing are carried out, and the product is recrystallized by toluene to obtain the phenyl bis (5-bromoindole) phosphate.
50ML of 1, 4-dioxane, 5mmol of phenyl bis (5-bromoindole) phosphate, 12mmol of 4-aminophenylboronic acid pinacol ester, 0.32mmol of tetrakis (triphenylphosphine) palladium, 13mmol of potassium carbonate and 10mL of water are added into a reaction vessel, nitrogen is introduced, the mixture is subjected to condensation reflux reaction for 72h at the temperature of 100 ℃, rotary evaporation is carried out, water and acetone are sequentially washed, and the product is recrystallized by toluene to obtain bis [5- (anilino) indole ] phenyl phosphate.
Introducing nitrogen into a reaction vessel, adding 30mL of N, N-dimethylformamide, 10mmol of toluene-2, 4-diisocyanate and 12mmol of di [5- (anilino) indole ] phenyl phosphate, performing polymerization reaction at 80 ℃ for 6 hours, adding petroleum ether for precipitation, filtering, washing with water and ethanol in sequence, and drying to obtain the nitrogen-phosphorus polymer flame retardant.
Adding 8g of nitrogen-phosphorus polymer flame retardant and 992g of polycarbonate into a double screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Example 3
To the reaction vessel were added 20mL of toluene, 6.9mmol of 5-bromoindole, 6.9mmol of pyridine, 3mmol of phenyl dichlorophosphate under ice bath, followed by reaction at 20℃for 18 hours, rotary evaporation, washing with petroleum ether, and recrystallization of the product with toluene to give phenyl bis (5-bromoindole) phosphate.
To the reaction vessel were added 60mL of 1, 4-dioxane, 5mmol of phenyl bis (5-bromoindole) phosphate, 11mmol of 4-aminophenylboronic acid pinacol ester, 0.28mmol of tetrakis (triphenylphosphine) palladium, 16mmol of potassium carbonate and 15mL of water, and the mixture was introduced into nitrogen gas at 110℃for condensation reflux reaction for 48 hours, followed by rotary evaporation, washing with water and acetone in sequence, and the product was recrystallized with toluene to give phenyl bis [5- (anilino) indole ] phosphate.
Introducing nitrogen into a reaction vessel, adding 30mL of N, N-dimethylformamide, 10mmol of toluene-2, 4-diisocyanate and 10.5mmol of di [5- (anilino) indole ] phenyl phosphate, performing polymerization reaction at 90 ℃ for 4 hours, adding petroleum ether for precipitation, filtering, washing with water and ethanol in sequence, and drying to obtain the nitrogen-phosphorus polymer flame retardant.
15G of nitrogen-phosphorus polymer flame retardant and 985g of polycarbonate are added into a double screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Example 4
Adding 60mL of 98% concentrated sulfuric acid and 5g of nitrogen-phosphorus polymer flame retardant (the same as the preparation process of the embodiment 1) into a reaction container, carrying out sulfonation reaction at the temperature of 60 ℃ for 30min, adding water for dilution, filtering, adding the water-washed product into water, adding potassium hydroxide to adjust the pH of the solution to 11, stirring, filtering, washing with water, and drying to obtain the nitrogen-phosphorus sulfonate polymer flame retardant.
Adding 1g of nitrogen phosphorus sulfonate polymer flame retardant and 999g of polycarbonate into a double screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Example 5
Adding 80mL of 98% concentrated sulfuric acid and 5g of nitrogen-phosphorus polymer flame retardant (the same as the preparation process of the embodiment 1) into a reaction container, carrying out sulfonation reaction at 50 ℃ for 30min, adding water for dilution, filtering, adding the water-washed product into water, adding potassium hydroxide to adjust the pH of the solution to 9, stirring, filtering, washing with water, and drying to obtain the nitrogen-phosphorus sulfonate polymer flame retardant.
Adding 8g of nitrogen phosphorus sulfonate polymer flame retardant and 992g of polycarbonate into a double screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Example 6
Adding 80mL of 98% concentrated sulfuric acid and 5g of nitrogen-phosphorus polymer flame retardant (the same as the preparation process of the embodiment 1) into a reaction container, carrying out sulfonation reaction at 45 ℃ for 90min, adding water for dilution, filtering, adding the water-washed product into water, adding potassium hydroxide to adjust the pH of the solution to 11, stirring, filtering, washing with water, and drying to obtain the nitrogen-phosphorus sulfonate polymer flame retardant.
15G of nitrogen phosphorus sulfonate polymer flame retardant and 985g of polycarbonate are added into a double screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Comparative example 1
Adding polycarbonate into a double-screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Comparative example 2
1G of toluene-2, 4-diisocyanate and 999g of polycarbonate are added into a double screw extruder for blending extrusion, and the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Comparative example 3
1G of phenyl bis [5- (anilino) indole ] phosphate (the same preparation process as in example 1) and 999g of polycarbonate are added into a double screw extruder for blending extrusion, wherein the temperature of each section is 220 ℃, 235 ℃, 240 ℃, 235 ℃ and 235 ℃; granulating, injection molding, wherein the temperature of each section of the injection molding machine is 265 ℃, 275 ℃ and 270 ℃ to obtain the polycarbonate material containing the polymer halogen-free flame retardant.
Thermal performance test: the temperature rising rate of the TG thermogravimetric analyzer is 10 ℃/min under the nitrogen atmosphere, and the test temperature is 25-800 ℃.
And (3) testing the flame retardant property, and testing the limiting oxygen index according to GB/T2406.1-2008 standard. The sample sizes were 120mm by 6mm by 3mm. Vertical burn performance was measured according to UL94 standard, and the sample size was 120mm X14 mm X3 mm. The test results are shown in Table 1.
TABLE 1 thermal and flame retardant Property testing of polycarbonate materials
T 5% is the 5% mass loss temperature; weight is the amount of carbon residue at 800 ℃. LOI is limiting oxygen index.
The impact strength of the polycarbonates was measured according to GB/T1843-2008. The test results are shown in Table 2.
Table 2 impact strength testing of polycarbonate materials
Example 1-3 polymerization of toluene-2, 4-diisocyanate and phenyl bis [5- (anilino) indole ] phosphate to give a flame retardant comprising a nitrogen-phosphorus polymer which is a polymer macromolecule, has good compatibility with polycarbonate, has excellent dispersibility in polycarbonate and contains a heat-resistant azabiphenylureido structure) After being mixed with the polycarbonate, the polycarbonate can raise the thermal decomposition temperature and improve the heat resistance of the polycarbonate. Meanwhile, the flame-retardant polycarbonate resin composition contains a phosphate-indole cyclophosphates flame-retardant system, the polycarbonate can be promoted to form a carbon layer structure by burning, and the high-temperature carbon residue reaches 25.6-29.4%. The flame retardant property of the polycarbonate is enhanced, and the limiting oxygen index in combustion is improved to 28.6-34.4%; UL-94 fire rating is V-1 to V-0.
The bis [5- (anilino) indole ] phenyl phosphate structural unit in the nitrogen-phosphorus polymer flame retardant contains a plurality of benzene ring structures, and is subjected to sulfuric acid sulfonation and potassium hydroxide salinization, and a nitrogen-phosphorus sulfonate group is introduced into the side chain of the nitrogen-phosphorus polymer flame retardant to obtain the nitrogen-phosphorus sulfonate polymer flame retardant, wherein the sulfonate structure can catalyze polycarbonate to crosslink into carbon during combustion, and the high-temperature carbon residue of the polycarbonate in examples 4-6 reaches 27.0-32.1%, so that the flame retardant property of the polycarbonate is further enhanced; the limiting oxygen index is further improved to 30.6-39.1%, and the UL-94 fireproof grade reaches the V-0 grade.
The halogen-free flame retardant in examples 1-6 is used as a macromolecular polymer, has good compatibility with polycarbonate, has small influence on the impact strength and mechanical property of the polycarbonate when the addition amount is small, and does not influence the service performance of the polycarbonate.
Comparative example 1 is a pure polycarbonate, and has low initial thermal decomposition temperature and high-temperature carbon residue, and poor flame retardant property. The polycarbonate of comparative example 3, to which toluene-2, 4-diisocyanate was added, had no flame retardant property, and could not improve the heat resistance and flame retardant property of the polycarbonate.
The polycarbonate of comparative example 2, which incorporates phenyl bis [5- (anilino) indole ] phosphate, contains a phosphate-indole cyclophosphates flame retardant system, can increase the limiting oxygen index and UL-94 flame retardant rating of the polycarbonate; but does not contain sulfonate flame retardant groups, and the heat resistant azabiphenylurea structure, the heat resistance and flame retardant properties are inferior to those of each example. And toluene-2, 4-diisocyanate and di [5- (anilino) indole ] phenyl phosphate are taken as small molecules, so that the compatibility with polycarbonate is poor, and the impact strength of the polycarbonate is obviously reduced after the addition.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A polycarbonate material containing polymer halogen-free flame retardant is characterized by comprising 0.1-1.5 parts by weight of polymer halogen-free flame retardant and 98.5-99.8 parts by weight of polycarbonate;
the polymer halogen-free flame retardant is any one of a nitrogen-phosphorus polymer flame retardant or a nitrogen-phosphorus sulfonate polymer flame retardant;
the preparation process of the nitrogen-phosphorus polymer flame retardant comprises the following steps:
step A, introducing nitrogen into a reaction container, adding N, N-dimethylformamide, toluene-2, 4-diisocyanate and di [5- (anilino) indole ] phenyl phosphate, performing polymerization reaction, precipitating, filtering, washing and drying to obtain a nitrogen-phosphorus polymer flame retardant;
the preparation process of the nitrogen-phosphorus sulfonate polymer flame retardant comprises the following steps:
Adding concentrated sulfuric acid and a nitrogen-phosphorus polymer flame retardant into a reaction container, performing sulfonation reaction, adding water for dilution, filtering, adding the washed product into water, adding potassium hydroxide, stirring, filtering, washing, and drying to obtain the nitrogen-phosphorus sulfonate polymer flame retardant;
The structural formula of the di [5- (anilino) indole ] phenyl phosphate is as follows:
。
2. The polycarbonate material containing a polymer-halogen-free flame retardant according to claim 1, wherein the molar amount of the phenyl bis [5- (anilino) indole ] phosphate in the step a is 105 to 120% of the molar amount of toluene-2, 4-diisocyanate.
3. The polycarbonate material containing the polymer halogen-free flame retardant according to claim 1, wherein the polymerization reaction in the step A is controlled at 80-90 ℃ for 4-6 hours.
4. The polycarbonate material containing the polymer halogen-free flame retardant according to claim 1, wherein the sulfonation reaction in the step B is controlled at 45-60 ℃ for 30-90min.
5. The polycarbonate material containing the polymer halogen-free flame retardant according to claim 1, wherein potassium hydroxide is added in the step B to adjust the pH of the solution to 9-11.
6. The polycarbonate material containing the polymer halogen-free flame retardant according to claim 1, wherein the preparation process of the di [5- (anilino) indole ] phenyl phosphate is as follows:
Adding toluene, 5-bromoindole, pyridine and phenyl dichlorophosphate into a reaction vessel under ice bath, then reacting for 12-18h at 20-45 ℃, rotary evaporating, washing, and recrystallizing to obtain phenyl bis (5-bromoindole) phosphate;
And (2) adding 1, 4-dioxane, phenyl bis (5-bromoindole) phosphate, 4-aminophenylboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium, potassium carbonate and water into a reaction vessel, introducing nitrogen into the reaction vessel, condensing and refluxing the reaction vessel for 48 to 72 hours at the temperature of between 100 and 110 ℃, performing rotary evaporation, washing and recrystallizing to obtain the phenyl bis [5- (anilino) indole ] phosphate.
7. The polycarbonate material containing the polymer halogen-free flame retardant according to claim 6, wherein the molar amount of 5-bromoindole and pyridine in the step (1) is 180-230% and 200-230% of the molar amount of phenyl dichlorophosphate.
8. The polycarbonate material containing a polymer halogen-free flame retardant according to claim 6, wherein the molar amount of 4-aminophenylboronic acid pinacol ester, tetrakis (triphenylphosphine) palladium and potassium carbonate in the step (2) is 210-240%, 5.6-7% and 260-320% of the molar amount of phenyl bis (5-bromoindole) phosphate.
9. A process for preparing a polycarbonate material containing a polymer-halogen-free flame retardant according to any one of claims 1 to 8, wherein 0.1 to 1.5 parts by weight of the polymer-halogen-free flame retardant and 98.5 to 99.8 parts by weight of the polycarbonate are added into a twin screw extruder to be blended and extruded, pelletized and injection molded, thereby obtaining the polycarbonate material containing the polymer-halogen-free flame retardant.
10. The process for preparing a polycarbonate material containing a polymer halogen-free flame retardant according to claim 9, wherein the temperature of each section of the twin screw extruder is 220-240 ℃; the temperature of injection molding is 265-275 ℃.
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| CN105838389A (en) * | 2016-04-13 | 2016-08-10 | 浙江大学宁波理工学院 | High-efficiency polyphosphate ester fire retardant and preparation method thereof |
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| CN114292299A (en) * | 2021-12-28 | 2022-04-08 | 福建新安科技有限责任公司 | Phosphorus-containing, nitrogen-containing and sulfonate-containing compound, and preparation method and application thereof |
| CN116376031A (en) * | 2023-04-04 | 2023-07-04 | 上海圣奎塑业有限公司 | A polymeric phosphorus nitrogen silicon flame retardant and halogen-free polystyrene flame retardant masterbatch |
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| CN101914208A (en) * | 2010-08-19 | 2010-12-15 | 中国科学技术大学 | A kind of phosphorus, nitrogen expansion flame retardant polymer and preparation method thereof |
| CN105838389A (en) * | 2016-04-13 | 2016-08-10 | 浙江大学宁波理工学院 | High-efficiency polyphosphate ester fire retardant and preparation method thereof |
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