CN113174089A - Polystyrene nano-microsphere coated red phosphorus flame retardant and preparation and application thereof - Google Patents
Polystyrene nano-microsphere coated red phosphorus flame retardant and preparation and application thereof Download PDFInfo
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- CN113174089A CN113174089A CN202110576702.4A CN202110576702A CN113174089A CN 113174089 A CN113174089 A CN 113174089A CN 202110576702 A CN202110576702 A CN 202110576702A CN 113174089 A CN113174089 A CN 113174089A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a polystyrene nano-microsphere coated red phosphorus flame retardant, and preparation and application thereof, and relates to the technical field of polymer materials. The method comprises the following steps: (1) polyvinyl alcohol modified red phosphorus; (2) emulsifying styrene; (3) polymerizing and coating styrene; (4) and preparing a finished product. According to the invention, red phosphorus is taken as a core, polyvinyl alcohol is used for modifying the surface of the red phosphorus, then styrene, a surfactant, a cross-linking agent and an initiator are added, and emulsion polymerization of styrene is utilized to generate a uniform polystyrene nano microsphere layer on the surface of the modified red phosphorus to obtain a finished product, wherein the finished product has uniform surface coating, high flame-retardant efficiency, greatly improved flame-retardant effect, environmental friendliness, high stability and easiness in storage; and the polystyrene nano-microsphere coated red phosphorus flame retardant is added into the application material, so that the obtained product has good flame retardance, excellent comprehensive performance and high cost performance.
Description
Technical Field
The invention relates to the technical field of polymer materials, in particular to a polystyrene nano-microsphere coated red phosphorus flame retardant, and preparation and application thereof.
Background
At present, most of halogen flame retardants generate harmful smoke and corrosive gases during combustion. Along with the global advocation of harmonious development of human beings and ecological environment, the rapid development of the halogen-free flame retardant technology towards the direction of high efficiency, low smoke, low toxicity and multifunction is promoted. The red phosphorus flame retardant is a representative halogen-free flame retardant, and the mechanism is that phosphoric acid is formed by combustion to serve as a dehydrating agent and promote char formation, and the heat conduction from flame to a condensed phase is reduced by the char formation. Phosphoric acid is endothermic because it prevents oxidation of CO to CO2, reducing the heating process. A thin glassy or liquid protective layer is formed on the condensed phase, so that oxygen diffusion and heat and mass transfer between a gas phase and a solid phase are reduced, a carbonization process is inhibited, and thermal decomposition of the phosphorus-containing flame retardant is reduced. However, red phosphorus is unstable in chemical properties in air, can reduce the molecular weight of polymers, and can generate toxic PH3 gas during heating processing, and when the red phosphorus is directly used as a flame retardant, the red phosphorus has strong surface hygroscopicity, poor storage stability and poor compatibility with resins.
There are many reports of using inorganic and organic coated red phosphorus flame retardant, for example, a melamine modified lignin/magnesium hydroxide double coated Honglin flame retardant provided by patent CN108912671A and its application in PA6 resin, which uses inorganic and organic double-layer coated red phosphorus, the preparation process is complex, the thermal stability of melamine coating layer is not good enough, the coating layer is not uniform and is easy to damage. There are also reports of using inorganic hydroxide to coat red phosphorus in situ, such as an inorganic material coated flame retardant microcapsule and its preparation method provided in patent CN104448934A, but the inorganic material coated flame retardant has uneven distribution of surface coating material, and its coating layer is easily damaged by strong shearing force when it is extruded by twin screw.
Disclosure of Invention
The invention aims to provide a polystyrene nano-microsphere coated red phosphorus flame retardant and preparation and application thereof aiming at the defects in the prior art. Therefore, the flame retardant effect of the microcapsule red phosphorus flame retardant can be fully exerted; and the polystyrene nano-microsphere coated red phosphorus flame retardant is added into the application material, so that the obtained product has good flame retardance, excellent comprehensive performance and high cost performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a polystyrene nano-microsphere coated red phosphorus flame retardant comprises the following steps:
(1) polyvinyl alcohol-modified red phosphorus: dispersing 5-15 g of red phosphorus in water, stirring the red phosphorus and the water vigorously, then adding 0.4-0.6 ml/g of a polyvinyl alcohol aqueous solution of the red phosphorus, and stirring the mixture for a period of time to obtain a polyvinyl alcohol modified red phosphorus particle dispersion liquid;
(2) styrene emulsification: heating the red phosphorus particle dispersion liquid modified by the polyvinyl alcohol to 50-75 ℃, then adding 0.1-0.6 ml/g of red phosphorus styrene, 50-300 mg of surfactant, 10-300 mg of dispersing agent and 0.005-0.6 ml of cross-linking agent, and stirring for 0.5-3 h to obtain a mixed system of the red phosphorus particle dispersion liquid modified by the polyvinyl alcohol and styrene emulsion;
(3) styrene polymerization coating: raising the temperature of the mixed system to 65-90 ℃, then adding 5-60 mg of emulsion polymerization initiator, and continuously stirring for 2-5 h to perform emulsion polymerization reaction of styrene;
(4) preparing a finished product: and filtering, washing and drying the product to obtain the red phosphorus flame retardant coated by the polystyrene nano-microspheres.
Further, in some preferred embodiments of the present invention, the surfactant in step (2) is one or more of sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium alkyl polyoxyethylene ether sulfate, and sodium alkyl sulfonate.
Further, in some preferred embodiments of the present invention, the dispersant in step (2) is one or more of silicate, alkali metal phosphate, and sodium lauryl sulfate.
Further, in some preferred embodiments of the present invention, the crosslinking agent in step (2) is one or more of divinylbenzene, diisocyanate, and N, N-methylene bisacrylamide.
Further, in some preferred embodiments of the present invention, the initiator in step (3) is one or more of potassium persulfate, ammonium persulfate, and sodium persulfate.
The invention also provides the polystyrene nano-microsphere coated red phosphorus flame retardant prepared by the preparation method.
The invention also provides application of the polystyrene nano-microsphere coated red phosphorus flame retardant in preparation of flame-retardant polyamide resin materials.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the polystyrene nano microsphere coated red phosphorus flame retardant is prepared by using red phosphorus as a core, modifying the surface of the red phosphorus by using polyvinyl alcohol, adding styrene, a surfactant, a cross-linking agent and an initiator, generating a uniform polystyrene nano microsphere layer on the surface of the modified red phosphorus by emulsion polymerization of the styrene to obtain a finished product,
(2) the polystyrene nano-microsphere coated red phosphorus flame retardant prepared by the invention has the advantages of uniform surface coating, high flame-retardant efficiency, greatly improved flame-retardant effect, environmental friendliness, high stability and easiness in storage; and the polystyrene nano-microsphere coated red phosphorus flame retardant is added into the application material, so that the obtained product has good flame retardance, excellent comprehensive performance and high cost performance.
Drawings
FIG. 1 is a FTIR comparison of red phosphorus and a polystyrene nanosphere coated red phosphorus flame retardant of the present invention;
FIG. 2 is a thermogravimetric comparison graph of red phosphorus and a polystyrene nanosphere-coated red phosphorus flame retardant of example 1 of the present invention;
FIG. 3 is a graph comparing the release test paper for detecting phosphine release of red phosphorus and the polystyrene nanospheres coated with red phosphorus flame retardant of the present invention in examples 2 and 3;
FIG. 4 is a SEM comparison of the surface morphology of red phosphorus particles and the red phosphorus flame retardant coated with polystyrene nano-microspheres of examples 1-4 of the present invention;
FIG. 5 is a thermogravimetric comparison of PA66 with flame retardant modified PA66 of the present invention;
FIG. 6 is an SEM image of a burned surface carbon layer of a sample bar prepared in application example 1;
FIG. 7 is an SEM image of a burned surface carbon layer of a sample prepared in application example 2;
FIG. 8 is an SEM image of the burned surface carbon layer of the sample prepared in application example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
a. Adding 10g of red phosphorus and 5ml of polyvinyl alcohol aqueous solution into deionized water, and stirring for 1.5h at normal temperature to obtain a system A;
b. heating the system A to 60 ℃, then sequentially adding 3ml of styrene, 300mg of sodium dodecyl sulfate, 300mg of magnesium aluminum silicate and 90ul of divinylbenzene into the system A, and stirring and emulsifying for 1 hour to obtain a system B;
c. heating the system B to 80 ℃, adding 40mg of potassium persulfate, and carrying out styrene emulsion polymerization reaction for 3 hours;
d. and filtering, washing and drying the product to obtain the polystyrene nano-microsphere coated red phosphorus flame retardant.
Referring to fig. 1, fig. 1 is a FT-IR diagram of the red phosphorus particles and the prepared polystyrene nanospheres coated red phosphorus flame retardant used in this example, and fig. 1 shows: the prepared polystyrene nano-microsphere coated red phosphorus flame retardant well reserves the basic structure of red phosphorus.
Referring to fig. 2, fig. 2 is a TG diagram of the red phosphorus particles used in this example and the prepared polystyrene nanospheres coated red phosphorus flame retardant, and fig. 2 shows: the red phosphorus begins to lose weight at 400 ℃, the polystyrene nano-microsphere coated red phosphorus flame retardant begins to lose weight at 450 ℃, and the residual quantity of the red phosphorus is obviously reduced by a lot compared with the residual quantity of the coated red phosphorus after the combustion is finished, which indicates that the flame retardant effect of the coated red phosphorus is obviously improved.
Example 2
a. Adding 8g of red phosphorus and 4ml of polyvinyl alcohol aqueous solution into deionized water, and stirring for 1.5 hours at normal temperature to obtain a system A;
b. heating the system A to 60 ℃, then sequentially adding 3ml of styrene, 300mg of sodium dodecyl sulfate, 300mg of magnesium aluminum silicate and 30ul of divinylbenzene into the system A, and stirring and emulsifying for 1 hour to obtain a system B;
c. heating the system B to 80 ℃, adding 20mg of potassium persulfate, and carrying out styrene emulsion polymerization reaction for 3 hours;
d. and filtering, washing and drying the product to obtain the polystyrene nano-microsphere coated red phosphorus flame retardant.
Example 3
a. Adding 5g of red phosphorus and 2.5ml of polyvinyl alcohol aqueous solution into deionized water, and stirring at normal temperature for 1.5h to obtain a system A;
b. heating the system A to 60 ℃, then sequentially adding 3ml of styrene, 250mg of sodium dodecyl sulfate, 250mg of magnesium aluminum silicate and 165ul of divinylbenzene into the system A, and stirring and emulsifying for 1 hour to obtain a system B;
c. heating the system B to 80 ℃, adding 40mg of potassium persulfate, and carrying out styrene emulsion polymerization reaction for 3 hours;
d. and filtering, washing and drying the product to obtain the polystyrene nano-microsphere coated red phosphorus flame retardant.
Referring to fig. 3, fig. 3 is a graph showing the results of comparing the release of phosphine gas of the polystyrene nanosphere-coated red phosphorus flame retardant prepared in example 2(a) and example 3(b) with that of the red phosphorus particles (c) used in example, and fig. 3 shows the results of the phosphine gas test using silver nitrate test paper: the release amount of phosphine gas in the prepared polystyrene nano-microsphere coated red phosphorus flame retardants a and b is obviously reduced, and the environmental protection effect is obviously improved.
Example 4
a. Adding 15g of red phosphorus and 6ml of polyvinyl alcohol aqueous solution into deionized water, and stirring for 1.5h at normal temperature to obtain a system A;
b. heating the system A to 60 ℃, then sequentially adding 3ml of styrene, 200mg of sodium dodecyl sulfate, 200mg of magnesium aluminum silicate and 600ul of divinylbenzene into the system A, and stirring and emulsifying for 1 hour to obtain a system B;
c. heating the system B to 80 ℃, adding 60mg of potassium persulfate, and carrying out styrene emulsion polymerization reaction for 3 hours;
d. and filtering, washing and drying the product to obtain the polystyrene nano-microsphere coated red phosphorus flame retardant.
Referring to FIG. 4, FIG. 4 is a SEM comparison of the red phosphorus flame retardant (e-h) coated with polystyrene nanospheres prepared in examples 1-4 with the red phosphorus particles (d) used in the examples, and FIG. 4 shows: the red phosphorus (d) is an irregular block with a smooth surface, the volume is enlarged and the surface is rough after the red phosphorus flame retardant (e-h) is coated by the polystyrene nano-microsphere, and the polystyrene nano-microsphere is obviously coated on the red phosphorus surface.
Example 5
a. Adding 15g of red phosphorus and 6ml of polyvinyl alcohol aqueous solution into deionized water, and stirring for 1.5h at normal temperature to obtain a system A;
b. heating the system A to 60 ℃, then sequentially adding 1ml of styrene, 50mg of sodium dodecyl sulfate, 50mg of magnesium aluminum silicate and 90ul of divinylbenzene into the system A, and stirring and emulsifying for 1 hour to obtain a system B;
c. heating the system B to 80 ℃, adding 20mg of potassium persulfate, and carrying out styrene emulsion polymerization reaction for 3 hours;
d. and filtering, washing and drying the product to obtain the polystyrene nano-microsphere coated red phosphorus flame retardant.
Performance test
1. Moisture absorption test
The polystyrene nanospheres prepared in examples 1-3 were coated with red phosphorus flame retardant and red phosphorus particles (RP) used in the examples as materials, and moisture absorption rate was measured, and the measurement results are shown in Table 1.
Table 1 moisture absorption rate test
The results in table 1 show: with the time being prolonged, the moisture absorption rate of the polystyrene nano-microsphere coated red phosphorus flame retardant is obviously reduced, which shows that the flame retardant effect of the polystyrene nano-microsphere coated red phosphorus flame retardant is obviously improved.
2. Testing of ignition temperature and thermal weightlessness starting temperature
The polystyrene nanospheres prepared in examples 1-3 were coated with red phosphorus flame retardant and red phosphorus particles (RP) used in the examples as materials, and the ignition temperature and the thermal weight loss initiation temperature were measured, and the measurement results are shown in Table 2.
| Sample (I) | Ignition temperature/. degree.C | Onset temperature of thermal weight loss/. degree.C |
| RP | 270.1 | 435.9 |
| Example 1 | 434.2 | 459.5 |
| Example 2 | 465.4 | 471.5 |
| Example 3 | 417.7 | 460.7 |
The results in table 2 show: the ignition temperature of the polystyrene nano-microsphere coated red phosphorus flame retardant of the embodiments 1-3 of the invention is improved to a certain extent compared with that of red phosphorus, and the thermal weight loss starting temperature is also improved to a certain extent, which shows that the polystyrene nano-microsphere coated red phosphorus flame retardant of the invention has better thermal stability.
Application example 1
Weighing 5% of the microcapsule-coated red phosphorus flame retardant obtained in example 1, mixing the microcapsule-coated red phosphorus flame retardant with 70% of polyamide (PA66) and 25% of glass fiber in a high-speed mixer to obtain a premix, adding the premix into a double-screw extruder, carrying out melt mixing, and carrying out extrusion granulation. The temperature of a screw cylinder in the double-screw extruder is 250-300 ℃, and the rotating speed of a screw is 300 rpm; and then carrying out injection molding on the microcapsule red phosphorus flame-retardant polyamide compound particles at the injection molding temperature of 280 ℃ and the injection molding pressure of 70MPa, and taking out the sample strip after the injection molding is finished to obtain the flame-retardant modified polyamide resin. The sample specification is 125mm multiplied by 13mm multiplied by 0.8mm, and the vertical burning test grade can reach UL 94V-0 grade; the glow wire flammability index (GWIT) of the flame-retardant sample strip is 770 ℃/0.8 mm; the Comparative Tracking Index (CTI) of the flame-retardant sample strip is 400V; the tensile strength is 147MPa, and the notch impact strength is 13.1KJ/m2。
Referring to fig. 5, fig. 5 is a comparison graph of polyamide resin used in this application example and modified polyamide resin TG coated with red phosphorus flame retardant using polystyrene nano-microspheres of example 1 of the present invention, and fig. 5 shows: the residual quantity of the modified polyamide resin with the red phosphorus flame retardant coated by the polystyrene nano microspheres in the embodiment 1 of the invention after the combustion is finished is obviously improved, which shows that the flame retardant property and the thermal stability of the polyamide resin with the red phosphorus flame retardant coated by the polystyrene nano microspheres are obviously improved.
Application example 2
Weighing 5% of the microcapsule-coated red phosphorus flame retardant obtained in example 2, mixing the microcapsule-coated red phosphorus flame retardant with 70% of polyamide (PA66) and 25% of glass fiber in a high-speed mixer to obtain a premix, adding the premix into a double-screw extruder, carrying out melt mixing, and carrying out extrusion granulation. The temperature of a screw cylinder in the double-screw extruder is 250-300 ℃, and the rotating speed of a screw is 300 rpm; and then carrying out injection molding on the microcapsule red phosphorus flame-retardant polyamide compound particles at the injection molding temperature of 280 ℃ and the injection molding pressure of 70MPa, and taking out the sample strip after the injection molding is finished to obtain the flame-retardant modified polyamide resin. The sample specification is 125mm multiplied by 13mm multiplied by 0.8mm, and the vertical burning test grade can reach UL 94V-0 grade; the glow wire flammability index (GWIT) of the flame-retardant sample strip is 775 ℃/0.8 mm; the Comparative Tracking Index (CTI) of the flame-retardant sample strip is 400V; the tensile strength was 150MPa, and the notched impact strength was 14.2KJ/m 2.
Application example 3
Weighing 5% of the microcapsule-coated red phosphorus flame retardant obtained in example 3, mixing the microcapsule-coated red phosphorus flame retardant with 70% of polyamide (PA66) and 25% of glass fiber in a high-speed mixer to obtain a premix, adding the premix into a double-screw extruder for melt mixing, and extruding and granulating. The temperature of a screw cylinder in the double-screw extruder is 250-300 ℃, and the rotating speed of a screw is 300 rpm; and then carrying out injection molding on the microcapsule red phosphorus flame-retardant polyamide compound particles at the injection molding temperature of 280 ℃ and the injection molding pressure of 70MPa, and taking out the sample strip after the injection molding is finished to obtain the flame-retardant modified polyamide resin. The sample specification is 125mm multiplied by 13mm multiplied by 0.8mm, and the vertical burning test grade can reach UL 94V-0 grade; the glow wire flammability index (GWIT) of the flame-retardant sample strip is 760 ℃/0.8 mm; the Comparative Tracking Index (CTI) of the flame-retardant sample strip is 400V; the tensile strength was 148MPa, and the notched impact strength was 13.8KJ/m 2.
Referring to FIGS. 6 to 8, FIGS. 6 to 8 are SEM images of the burned carbon layers of the sample strips prepared in examples 1 to 3, respectively, and FIGS. 6 to 8 show: the carbon layer obtained by coating the red phosphorus flame retardant modified polyamide resin with the polystyrene nano microspheres of the embodiments 1-3 of the invention is compact and uniform, and the sample has good flame retardant property.
The above description is of the preferred embodiment of the present invention and is not intended to limit the invention, and those skilled in the art may make modifications and improvements within the spirit and principle of the present invention.
Claims (7)
1. A preparation method of a red phosphorus flame retardant coated by polystyrene nano microspheres is characterized by comprising the following steps:
(1) polyvinyl alcohol-modified red phosphorus: dispersing 5-15 g of red phosphorus in water, stirring the red phosphorus and the water vigorously, then adding 0.4-0.6 ml/g of a polyvinyl alcohol aqueous solution of the red phosphorus, and stirring the mixture for a period of time to obtain a polyvinyl alcohol modified red phosphorus particle dispersion liquid;
(2) styrene emulsification: heating the red phosphorus particle dispersion liquid modified by the polyvinyl alcohol to 50-75 ℃, then adding 0.1-0.6 ml/g of red phosphorus styrene, 50-300 mg of surfactant, 10-300 mg of dispersing agent and 0.005-0.6 ml of cross-linking agent, and stirring for 0.5-3 h to obtain a mixed system of the red phosphorus particle dispersion liquid modified by the polyvinyl alcohol and styrene emulsion;
(3) styrene polymerization coating: raising the temperature of the mixed system to 65-90 ℃, then adding 5-60 mg of emulsion polymerization initiator, and continuously stirring for 2-5 h to perform emulsion polymerization reaction of styrene;
(4) preparing a finished product: and filtering, washing and drying the product to obtain the red phosphorus flame retardant coated by the polystyrene nano-microspheres.
2. The preparation method of the polystyrene nano-microsphere coated red phosphorus flame retardant according to claim 1, which is characterized in that: the surfactant is one or more of sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium alkyl polyoxyethylene ether sulfate and sodium alkyl sulfonate.
3. The preparation method of the polystyrene nano-microsphere coated red phosphorus flame retardant according to claim 1, which is characterized in that: the dispersant is one or more of silicate, alkali metal phosphate and sodium dodecyl sulfate.
4. The preparation method of the polystyrene nano-microsphere coated red phosphorus flame retardant according to claim 1, which is characterized in that: the cross-linking agent is one or more of divinylbenzene, diisocyanate and N, N-methylene bisacrylamide.
5. The preparation method of the polystyrene nano-microsphere coated red phosphorus flame retardant according to claim 1, which is characterized in that: the initiator is one or more of potassium persulfate, ammonium persulfate and sodium persulfate.
6. The polystyrene nano-microsphere coated red phosphorus flame retardant prepared by the preparation method of the polystyrene nano-microsphere coated red phosphorus flame retardant according to any one of claims 1 to 5.
7. The use of the polystyrene nanosphere-coated red phosphorus flame retardant of claim 6 in the preparation of flame retardant polyamide resin material.
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| CN114835953A (en) * | 2022-06-09 | 2022-08-02 | 什邡市太丰新型阻燃剂有限责任公司 | Hydrophobic piperazine pyrophosphate and efficient preparation method thereof |
| CN115449158A (en) * | 2022-10-17 | 2022-12-09 | 广东登峰电线电缆有限公司 | Heat-resistant halogen-free low-smoke flame-retardant fire-resistant cable |
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| CN114805937A (en) * | 2022-05-05 | 2022-07-29 | 清远市一丞阻燃材料有限公司 | Styrene-coated phosphorus-containing acid source particles and preparation method thereof |
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| CN114835953A (en) * | 2022-06-09 | 2022-08-02 | 什邡市太丰新型阻燃剂有限责任公司 | Hydrophobic piperazine pyrophosphate and efficient preparation method thereof |
| CN115449158A (en) * | 2022-10-17 | 2022-12-09 | 广东登峰电线电缆有限公司 | Heat-resistant halogen-free low-smoke flame-retardant fire-resistant cable |
| CN115449158B (en) * | 2022-10-17 | 2023-08-11 | 广东登峰电线电缆有限公司 | Heat-resistant halogen-free low-smoke flame-retardant fire-resistant cable |
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