CN109913124B - Preparation method of intumescent phosphazene fire retardant coating - Google Patents
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Abstract
The invention provides a preparation method of an intumescent phosphazene fire-retardant coating, and belongs to the field of fire-retardant coatings. The invention adopts hexachlorocyclotriphosphazene and 4, 4-dihydroxy diphenyl sulfone as raw materials to prepare phosphazene microspheres (PZS), then adopts 1-methylimidazole and phosphomolybdic acid to react with the PZS microspheres, the phosphomolybdic acid imidazole salt is grafted to the PZS, and then the phosphomolybdic acid imidazole salt and acrylic resin are mixed according to the molar ratio of 1:1 to obtain the intumescent phosphazene fire retardant coating. The invention adopts the macromolecular phosphazene microspheres as the carbon forming catalyst and the microsphere grafted phosphomolybdate as the synergist for the first time, and the flame retardant property is greatly improved. Besides the PZS catalyst can be used as a core of char formation in the combustion process and can generate some non-combustible gases to play a role in gas-phase flame retardance when being heated and decomposed, the catalyst grafted on the PZS can be used for catalyzing the char formation in situ, so that the char formation efficiency is improved, the number and the compactness of char layers are improved, the stability of the char layers is improved, and the flame retardance of the composite material is improved.
Description
Technical Field
The invention belongs to the technical field of flame retardance, and particularly relates to a preparation method of an intumescent phosphazene fire-retardant coating.
Background
In recent years, relevant data statistics shows that the proportion of electrical fire is the largest in various national fire accidents, the number of fire accidents with larger or higher levels is the largest, and the number of the direct reasons for serious and serious fire in 2008-2016 is the electrical fire, which accounts for more than 30% of the total number of the counted fire. Among them, a fire caused by cable ignition, flame spread, and the like due to electrical causes such as short circuit of electric wires, aging of electric wires and cables, overload, and failure of electrical equipment accounts for 30% or more of the total number of fires, and tends to increase year by year. A series of fire cases have shown that once such a fire accident occurs, not only is a huge loss of property incurred, but also a major loss of life and personal injury may result. If flame protection is to be performed in the cable, a fire may reduce losses or even avoid them. Moreover, most cable materials are extremely easy to burn, flame is rapidly spread when exposed to open fire, and toxic smoke is generated, so that huge losses are caused to lives and properties of people. Therefore, how to effectively perform smokeless flame retardation on cable materials becomes a hot spot of research of people nowadays.
Through the rapid development of the last decade, the flame-retardant coating of the cable in China is an important trend for the future development. Among the flame retardants, the halogen flame retardants release toxic substances during combustion, which causes great harm to the environment and human beings, and in recent years, environmental protection laws are issued by many countries, and the halogen flame retardants will be replaced by halogen-free flame retardants. The number, compactness, thermal stability and other factors of carbon layers generated by chemical Intumescent Flame Retardant (IFR) in the halogen-free flame retardant directly determine the flame retardant performance of the flame retardant coating, different char forming synergistic catalysts and the intumescent flame retardant are adopted to cooperate with the flame retardant cable material to achieve the purpose of high-efficiency flame retardance, and the halogen-free flame retardant coating is also an important trend for future development in the field. For a power grid system, more importantly, research on a high-performance fireproof flame-retardant coating detection and evaluation technology is carried out, and establishment of a high-performance fireproof flame-retardant coating detection and evaluation system is especially important.
The cable is widely applied to places such as power enterprises, industrial and mining enterprises, communication networks, high-rise buildings and the like, and the fire prevention importance of the cable is self-evident. The coated cable fireproof paint is a simple and economic fireproof measure, is widely applied in practical engineering, and particularly, the halogen-free less-smoke cable fireproof paint can greatly reduce the fire hazard and reduce the casualties. However, cables coated with fire-retardant coatings still have a fire hazard and once the fire has spread, serious personal injury and property damage can result. Therefore, the research on the cable fireproof coating and the establishment of a high-performance fireproof flame-retardant coating detection and evaluation system thereof realize the advance prediction, which has important significance for reducing the occurrence of cable trench fire and the fire risk and can also provide a basis for improving the fireproof performance of the coating and guiding the fire-fighting design of cable places.
As a cable coating, an Intumescent Flame Retardant (IFR) is generally adopted, which has the advantages of no halogen, low toxicity and low smoke, but the IFR also has some disadvantages, such as large addition amount, low flame retardant efficiency, easy moisture absorption and the like, and the application range of the IFR is limited. Therefore, the invention adopts the self-designed phosphazene microspheres and the phosphazene microsphere catalyst modified by phosphomolybdic acid as the synergistic char forming agent respectively, and the synergistic char forming agent is compounded with IFR to be used for the fireproof coating. The quantity, compactness and thermal stability of the carbon layers in the coating are enhanced, and the aim of high-efficiency flame retardance is fulfilled.
Disclosure of Invention
The invention aims to provide a preparation method of an intumescent phosphazene fire retardant coating, aiming at the problems of large additive amount and low flame retardant efficiency of the existing intumescent fire retardant coating. According to the method, a self-designed phosphazene microsphere and phosphomolybdic acid modified phosphazene microsphere catalyst are used as a synergistic char forming agent, and the synergistic char forming agent is compounded with an Intumescent Flame Retardant (IFR) and then used for a fireproof coating, so that the high-performance fireproof flame-retardant coating with better flame retardant property, good surface fluidity and good permeability is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an intumescent phosphazene fire retardant coating comprises the following steps:
(1) preparation of phosphazene microspheres (PZS): taking Hexachlorocyclotriphosphazene (HCCP) and 4, 4-dihydroxy diphenyl sulfone (BPS) as raw materials, taking acetonitrile as a solvent, and reacting under the condition that Triethylamine (TEA) is used as a catalyst to obtain a product phosphazene microsphere (PZS);
(2) preparation of modified phosphazene microspheres (PZS-g-PMo): reacting 1-methylimidazole with the phosphazene microspheres obtained in the step (1) to obtain a transition product: reacting phosphomolybdic acid with a transition product to obtain modified phosphazene microspheres (PZS-g-PMo) with imidazole phosphomolybdate;
(3) preparation of the intumescent phosphazene fire retardant coating: and (3) selecting modified acrylic resin as a matrix material of the fire-retardant coating, and compounding the modified phosphazene microspheres (PZS-g-PMo) obtained in the step (2) and the modified acrylic resin according to the molar ratio of 1:1 to obtain a final product of the intumescent phosphazene fire-retardant coating.
The mole ratio of Hexachlorocyclotriphosphazene (HCCP) to 4, 4-dihydroxydiphenylsulfone (BPS) in step (1) is 1: 1.5-1: 2.0.
the dosage of acetonitrile solvent in the step (1) is 600 mL; the catalyst Triethylamine (TEA) was used in an amount of 51.84mmol.
And (2) reacting the mixture in the step (1) at normal temperature in an ultrasonic instrument at 40KHZ and 5400W for 15min, then centrifugally separating the mixture, and washing the mixture for 3 times by using 13.5mol/L acetone to obtain the product phosphazene microspheres (PZS).
In the step (2), the molar ratio of the phosphazene microspheres to the 1-methylimidazole is 1: 1.5-1: 2.0.
and (3) in the step (2), carrying out reflux reaction on the 1-methylimidazole and the phosphazene microspheres in 250mL of acetone solution with the concentration of 8mol/L at 60 ℃ for 24 hours to obtain a transition product.
The transition product obtained in step (2) has the following structure:
the molar ratio of the transition product to the phosphomolybdic acid in the step (2) is 2: 1.
and (3) in the step (2), in deionized water, phosphomolybdic acid and a transition product are stirred and react for 10 hours at normal temperature of 150r/min to obtain the modified phosphazene microspheres (PZS-g-PMo).
The modified acrylic resin in the step (3) has a specific modification method as follows: adding polysiloxane and acrylic resin into a three-neck flask provided with a thermometer, a condensing device and a stirring device according to the molar ratio of 1:2, adding 50mL of catalyst and 150mL of mixed solvent, starting the stirring and condensing device, heating to 80 ℃, and reacting for 2-3 h to obtain a grafted product; wherein the catalyst is: 12.5mol/L hydrochloric acid; the mixture is prepared from butyl acetate: n-butanol: toluene = 1: 2: 3, and mixing the components in a ratio of 3.
The intumescent phosphazene fire retardant coating prepared by the method.
The invention has the advantages that:
1. the reaction condition is mild, and the energy consumption is low.
2. The macromolecular phosphazene microspheres are used as a carbon forming catalyst for the first time, and the microsphere grafted phosphomolybdate is used as a synergist, so that the flame retardant property is greatly improved.
3. Besides the function of serving as a core of char formation in the combustion process and the function of gas-phase flame retardance by generating some non-combustible gases during thermal decomposition, the phosphazene microsphere (PZS) catalyst can be used for catalyzing the char formation in situ, so that the char formation efficiency is improved, the number and compactness of char layers are improved, the stability of the char layers is improved, and the flame retardance of the composite material is improved.
4. The product contains extremely low halogen content, and the amount of toxic gas generated during combustion is extremely low. During the reaction, the halogen on the phosphazene microspheres is replaced, so that the halogen content in the final product is extremely low.
5. The siloxane modified acrylic resin further improves the overall performance of the coating and provides surface fluidity and permeability for the system. The modified acrylic resin is a long straight chain, and the straight chain can reduce the surface energy and viscosity of the system, so that the surface fluidity and permeability of the system are improved.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
In this example, the molar ratio of Hexachlorocyclotriphosphazene (HCCP) to 4, 4-dihydroxydiphenylsulfone (BPS) was 1: 1.5.
a preparation method of an intumescent phosphazene fire retardant coating comprises the following steps:
(1) preparation of phosphazene microspheres (PZS): 10g (39.9 mmol) of 4, 4-dihydroxydiphenylsulfone (BPS) was dissolved in a flask containing 600mL of acetonitrile solution, stirred at room temperature until complete dissolution, and then 9.25g (26.6 mmol) of Hexachlorocyclotriphosphazene (HCCP) was added and stirred until complete dissolution. Then, 5.28g (51.84 mmol) of Triethylamine (TEA) is dropped into the flask, and the mixture reacts for 15min in a 40KHZ 5400W ultrasonic instrument, and then the mixture is centrifugally separated, washed 3 times by 13.5mol/L of acetone and dried for later use, so that phosphazene microspheres (PZS) are obtained. The reaction formula is as follows:
(2) preparation of modified phosphazene microspheres (PZS-g-PMo): 69.43g (39.9 mmol) of PZS powder is dispersed into 250mL of acetone solution with the concentration of 8mol/L, then 4.9g (59.9 mmol) of 1-methylimidazole is added, and the reaction is refluxed for 24h at the temperature of 60 ℃ to obtain 10.2g of PZS-methylimidazole chloride salt transition product. And then 110.58g (60 mmol) of phosphomolybdic acid is dissolved in 500mL of deionized water, 10.2g (120 mmol) of PZS-methylimidazole chloride salt is added, the mixture is stirred at the normal temperature at 150r/min, and after the reaction is carried out for 10 hours, the mixture is filtered and washed with deionized water for a plurality of times, so that the modified phosphazene microspheres (PZS-g-PMo) are obtained. The reaction formula is as follows:
(3) preparation of the intumescent phosphazene fire retardant coating: the modified acrylic resin is selected as a matrix material of the fireproof coating, and 12.4g of modified phosphazene microspheres and 21.6g of modified acrylic resin are stirred and reacted at 80 ℃ and constant temperature for 2.5 hours at 95r/min to obtain a final product.
The modified acrylic resin in the step (3) has a specific modification method as follows: adding polysiloxane and acrylic resin into a three-neck flask provided with a thermometer, a condensing device and a stirring device according to the molar ratio of 1:2, adding 50mL of catalyst and 150mL of mixed solvent, starting the stirring and condensing device, heating to 80 ℃, and reacting for 2-3 h to obtain a grafted product; wherein the catalyst is: 12.5mol/L hydrochloric acid; the mixture is prepared from butyl acetate: n-butanol: toluene = 1: 2: 3, and mixing the components in a ratio of 3.
Example 2
In this example, the molar ratio of Hexachlorocyclotriphosphazene (HCCP) to 4, 4-dihydroxydiphenylsulfone (BPS) was 1: 2.0.
a preparation method of an intumescent phosphazene fire retardant coating comprises the following steps:
(1) preparation of phosphazene microspheres (PZS): 10g (39.9 mmol) of 4, 4-dihydroxydiphenylsulfone (BPS) was dissolved in a flask containing 600mL of acetonitrile solution, stirred at room temperature until complete dissolution, and then 6.94g (20 mmol) of Hexachlorocyclotriphosphazene (HCCP) was added and stirred until complete dissolution. Then, 5.28g (51.84 mmol) of Triethylamine (TEA) is dropped into the flask, and the mixture reacts for 15min in a 40KHZ 5400W ultrasonic instrument, and then the mixture is centrifugally separated, washed 3 times by 13.5mol/L of acetone and dried for later use, so that phosphazene microspheres (PZS) are obtained. The reaction formula is as follows:
(2) preparation of modified phosphazene microspheres (PZS-g-PMo): 69.43g (39.9 mmol) of PZS powder is dispersed into 250mL of acetone solution with the concentration of 8mol/L, then 6.54g (79.8 mmol) of 1-methylimidazole is added, and the reaction is refluxed for 24h at the temperature of 60 ℃ to obtain 10.2g of PZS-methylimidazole chloride salt. And then dissolving 110.58g (60 mmol) of phosphomolybdic acid into 500mL of deionized water, adding 10.2g (120 mmol) of PZS-methylimidazolium chloride, stirring at the normal temperature for 150r/min, reacting for 10h, filtering, and washing with deionized water for several times to obtain the modified phosphazene microspheres (PZS-g-PMo). The reaction formula is as follows:
(3) preparation of the intumescent phosphazene fire retardant coating: and (3) selecting modified acrylic resin as a matrix material of the fireproof coating, and stirring 12.4g of the modified phosphazene microspheres obtained in the step (2) and 21.6g of the modified acrylic resin at the constant temperature of 80 ℃ for reaction for 2.5 hours at 95r/min to obtain a final product.
The modified acrylic resin in the step (3) has a specific modification method as follows: adding polysiloxane and acrylic resin into a three-neck flask provided with a thermometer, a condensing device and a stirring device according to the molar ratio of 1:2, adding 50mL of catalyst and 150mL of mixed solvent, starting the stirring and condensing device, heating to 80 ℃, and reacting for 3 hours to obtain a grafted product; wherein the catalyst is: 12.5mol/L hydrochloric acid; the mixture is prepared from butyl acetate: n-butanol: toluene = 1: 2: 3, and mixing the components in a ratio of 3.
Example 3
In this example, the molar ratio of Hexachlorocyclotriphosphazene (HCCP) to 4, 4-dihydroxydiphenylsulfone (BPS) was 1: 1.8.
a preparation method of an intumescent phosphazene fire retardant coating comprises the following steps:
(1) preparation of phosphazene microspheres (PZS): 10g (39.9 mmol) of 4, 4-dihydroxydiphenylsulfone (BPS) was dissolved in a flask containing 600mL of acetonitrile solution, stirred at room temperature until complete dissolution, and then 7.71g (22.17 mmol) of Hexachlorocyclotriphosphazene (HCCP) was added and stirred until complete dissolution. Then, 5.28g (51.84 mmol) of Triethylamine (TEA) is dropped into the flask, and the mixture reacts for 15min in a 40KHZ 5400W ultrasonic instrument, and then the mixture is centrifugally separated, washed 3 times by 13.5mol/L of acetone and dried for later use, so that phosphazene microspheres (PZS) are obtained. The reaction formula is as follows:
(2) preparation of modified phosphazene microspheres (PZS-g-PMo): 69.43g (39.9 mmol) of PZS powder is dispersed into 250mL of an acetone solution with a concentration of 8mol/L, then 5.88g (71.8 mmol) of 1-methylimidazole is added, and the reaction is refluxed for 24h at 60 ℃ to obtain 10.2g of PZS-methylimidazole chloride salt. And then 110.58g (60 mmol) of phosphomolybdic acid is dissolved in 500mL of deionized water, 10.2g (120 mmol) of PZS-methylimidazole chloride salt is added, the mixture is stirred at the normal temperature, and after 10 hours of reaction, the mixture is filtered and washed with deionized water for several times to obtain the modified phosphazene microspheres (PZS-g-PMo). The reaction formula is as follows:
(3) preparation of the intumescent phosphazene fire retardant coating: and (3) selecting modified acrylic resin as a matrix material of the fireproof coating, and stirring and reacting 12.4g of the modified phosphazene microspheres obtained in the step (2) with 21.6g of the modified acrylic resin at 80 ℃ and constant temperature for 2.5h at 95r/min to obtain a final product.
The modified acrylic resin in the step (3) has a specific modification method as follows: adding polysiloxane and acrylic resin into a three-neck flask provided with a thermometer, a condensing device and a stirring device according to the molar ratio of 1:2, adding 50mL of catalyst and 150mL of mixed solvent, starting the stirring and condensing device, heating to 80 ℃, and reacting for 2.5h to obtain a grafted product; wherein the catalyst is: 12.5mol/L hydrochloric acid; the mixture is prepared from butyl acetate: n-butanol: toluene = 1: 2: 3, and mixing the components in a ratio of 3.
Comparative example
An intumescent phosphazene fire retardant coating, wherein the molar ratio of Hexachlorocyclotriphosphazene (HCCP) to 4, 4-dihydroxy diphenyl sulfone (BPS) is 1: 1.5, the rest of the steps are the same as example 1, but step (2) in example 1 is not included. The halogen content of the finally obtained product is high, and the amount of toxic gas generated during combustion is large; and the performance test result of the product is poorer than that of the product obtained by the three examples of the invention.
Performance detection
The performance of the intumescent phosphazene fire-retardant coating products prepared in examples 1-3 and the intumescent phosphazene fire-retardant coating products in the comparative examples were tested, and the test performance results are shown in table 1.
TABLE 1 fireproof coating product Performance test results
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. The preparation method of the intumescent phosphazene fire retardant coating is characterized by comprising the following steps:
(1) preparation of phosphazene microspheres: taking hexachlorocyclotriphosphazene and 4, 4-dihydroxy diphenyl sulfone as raw materials, taking acetonitrile as a solvent, and reacting under the condition that triethylamine is used as a catalyst to obtain a product phosphazene microsphere;
(2) preparing modified phosphazene microspheres: reacting 1-methylimidazole with the phosphazene microspheres obtained in the step (1) to obtain a transition product; reacting phosphomolybdic acid with the transition product to obtain modified phosphazene microspheres with phosphomolybdic acid imidazole salt;
(3) preparation of the intumescent phosphazene fire retardant coating: selecting modified acrylic resin as a matrix material of the fire retardant coating, and compounding the modified phosphazene microspheres obtained in the step (2) with the modified acrylic resin to obtain a final product of the intumescent phosphazene fire retardant coating;
in the step (1), the molar ratio of hexachlorocyclotriphosphazene to 4, 4-dihydroxydiphenylsulfone is 1: 1.5-1: 2.0;
the dosage of acetonitrile solvent in the step (1) is 600 mL; the dosage of triethylamine as a catalyst is 51.84 mmol;
reacting for 15min in an ultrasonic instrument with the power of 40kHz and 5400W at the normal temperature of the reaction in the step (1), then centrifugally separating, and washing for 3 times by using 13.5mol/L acetone to obtain a product phosphazene microsphere;
in the step (2), the molar ratio of the phosphazene microspheres to the 1-methylimidazole is 1: 1.5-1: 2.0; carrying out reflux reaction on 1-methylimidazole and phosphazene microspheres in 250mL of 8mol/L acetone solution at 60 ℃ for 24 hours to obtain a transition product;
the structure of the transition product obtained in the step (2) is as follows:
the molar ratio of the transition product to the phosphomolybdic acid in the step (2) is 2: 1, in deionized water, phosphomolybdic acid and a transition product are stirred and react for 10 hours at the normal temperature of 150r/min to obtain modified phosphazene microspheres;
the acrylic resin is modified in the step (3), and the specific modification method comprises the following steps: mixing polysiloxane and acrylic resin according to a molar ratio of 1:2, adding the mixture into a three-neck flask provided with a thermometer, a condensing device and a stirring device in proportion, adding 50mL of catalyst and 150mL of mixed solvent, starting the stirring and condensing device, heating to 80 ℃, and reacting for 2-3 hours to obtain a grafted product; wherein the catalyst is: 12.5mol/L hydrochloric acid; the mixed solvent comprises the following components in percentage by mass: butyl acetate: n-butanol: toluene = 1: 2: 3, mixing the components in proportion;
the mol ratio of the modified phosphazene microspheres to the modified acrylic resin in the step (3) is 1: 1.
2. an intumescent phosphazene fire retardant coating prepared by the method of claim 1.
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| CN103435844A (en) * | 2013-07-23 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Flame retardation catalyst and supported flame retardation catalyst composed of same |
Non-Patent Citations (2)
| Title |
|---|
| 《环交联聚磷腈微球的合成及阻燃聚碳酸酯的研究》;赵师师等;《中国科学》;20181231;第48卷(第3期);第282-288页 * |
| 《钢结构膨胀型防火防腐涂料的制备与研究》;邹铭等;《涂料工业》;20111031;第41卷(第10期);第54-57、70页 * |
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