CN103724664A - Novel fire retardant microencapsulated red phosphorus and preparation method thereof - Google Patents
Novel fire retardant microencapsulated red phosphorus and preparation method thereof Download PDFInfo
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- CN103724664A CN103724664A CN201210392786.7A CN201210392786A CN103724664A CN 103724664 A CN103724664 A CN 103724664A CN 201210392786 A CN201210392786 A CN 201210392786A CN 103724664 A CN103724664 A CN 103724664A
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Abstract
The invention discloses a novel fire retardant microencapsulated red phosphorus which is formed by wrapping phenol-formaldehyde prepolymer (PFP) on the surface of superfine red phosphorus powder. Due to addition of a high-efficient catalyst in the preparation process, the surface activity of the red phosphorus is improved, the surface of the red phosphorus is tightly wrapped with a PFP layer, and meanwhile as methanol is added to prevent formaldehyde auto-agglutination and the pH value of a reaction solution in the wrapping process is controlled to be 1-6, the stability and the resistivity of the red phosphorus are improved, the machining property is improved, and meanwhile the moisture absorption rate and the PH3 release amount are greatly reduced.
Description
Technical field
The present invention relates to a kind of BACN microcapsule red phosphorus and preparation method thereof, belong to chemical industry preparation field.
Technical background
Along with the enhancing of people's environmental consciousness, flame retardant products has become the problem of selecting fire retardant first to consider on the impact of environment.For a long time, halogenated flame retardant is one of important fire retardant kind always, but discharges toxic smog while burning due to it, causes secondary harm, has been limited gradually the trend that even has replacement.
Red phosphorus (red phosphorus, RP) be a kind of halogen-free environment-friendly type flame-proof agent efficiently, but common RP is ultra-fine RP particularly, stability and safety problem in preparation, storage and production process are more outstanding, and low, the easy spontaneous combustion of point of ignition, explosive, the easy moisture absorption of dust are disproportionated into acid and emit the problems such as hypertoxic inflammable gas phosphuret-(t)ed hydrogen and be subjected to very large attention; Common red phosphorus and resin compatible are poor simultaneously, are difficult to disperse in resin.So a kind of Novel red phosphorus fire retardant-micro encapsulation red phosphorus (microencapsulated red phosphorus, MRP) growing up in later stage 1970's.It is all generally to realize being effectively coated red phosphorus by the method for in-situ polymerization.
The feature of MRP is that inorganics or macromolecule resin film " are packed " closely continuously by the particulate of each red phosphorus one deck; so that RP and isolation; core is protected by wall material; the RP coating finally forming have more efficient flame retardant resistance, widely applicability, safety non-toxic, base material physics and mechanical property are affected to the advantages such as little, and can be by the selection of capsule material being realized to the synergistic effect of multiple ignition-proof element (fire retardant).So, by aforesaid method, can overcome common RP and do the defect of fire retardant, meet the development trend of the low cigarette of fire retardant efficient halogen-free low toxicity.
In the coated preparation of RP, use catalyzer can improve the surfactivity of RP, make organic resin more easily be coated on its surface, utilize at present the report of catalyzer a lot, Yang Fuxing
[1]once in master's problem, adopt Sodium Persulfate as catalyzer, and utilized P-F performed polymer to be coated red phosphorus, controlled the pH to 8-9 of reaction soln, prepared the good microcapsule red phosphorus of thermal stability, but the shortcoming that exists particle easily to reunite.The present invention and its difference are to add methyl alcohol to prevent formaldehyde autohemagglutination in performed polymer preparation, and in coated process, control the pH value of reaction soln to 1-6, the microencapsulated red phosphorus flame retardant surface finally obtaining is coated more fine and closely, particle dispersion is better, thermostability is higher.
Summary of the invention
The object of the invention is to propose a kind of Novel red phosphorus fire retardant microcapsule red phosphorus and preparation method thereof.Such microcapsule red phosphorus has that thermostability is high, Halogen, rate of moisture absorption are low, PH
3the features such as burst size is little.
The technical solution that realizes the object of the invention is: a kind of BACN microcapsule red phosphorus, P-F performed polymer (PFP) is coated on ultra-fine red phosphorus powder surface, forms microcapsule red phosphorus.
A preparation method for BACN microcapsule red phosphorus, comprises following preparation process:
1, ultra-fine red phosphorus is dissolved in to supersound process in water, add dispersion agent to stir;
2, add again P-F prepolymer reaction after adding persulfuric acid salt catalyzer, in reaction process, regulate pH value to 1-6;
3, after having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Dispersion agent described in step 1 is selected from sodium lauryl sulphate, Sodium hexametaphosphate 99 or Macrogol 200, preferably Macrogol 200, dispersant dosage is the 1-4% of red phosphorus quality, and described ultrasonic time is 10-20 minute, and the order number of described ultra-fine red phosphorus is 400-1000 order.
Persulfuric acid salt catalyzer described in step 2 is ammonium persulphate or Sodium Persulfate, and described catalyst levels is the 1-4% of red phosphorus quality; Reaction times is 0.5-3h; The consumption of P-F performed polymer is the 10-20% of red phosphorus quality.
PH value described in step 2 preferably 3.
P-F performed polymer described in step 2 is prepared by the following method: in water, add respectively phenol, formaldehyde and methyl alcohol, wherein, the mass ratio of phenol, formaldehyde and methyl alcohol is 20:(20-32): 1, temperature control is to 70-90 ℃, regulate pH=8-9 scope, reaction 25-35min, obtains P-F performed polymer.
The coated microcapsule red phosphorus of phenol-formaldehyde resin obtaining according to above-mentioned preparation method, its advantage is that effective catalyst has improved the surfactivity of red phosphorus, make PFP layer be coated on densely the surface of red phosphorus, added methyl alcohol to prevent formaldehyde autohemagglutination, the pH value of controlling reaction soln in coated process is to 1-6, thereby improved stability, the stability of red phosphorus, improved processing characteristics, simultaneously rate of moisture absorption and PH
3burst size significantly reduces.
Accompanying drawing explanation
Fig. 1 is process flow sheet prepared by novel microcapsules red phosphorus of the present invention.
Embodiment
Embodiment 1:
As shown in Figure 1, take phenol, formaldehyde, methyl alcohol that mass ratio is 20:20:1, mix and add appropriate amount of deionized water, control temperature of reaction 70 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, makes solution keep the weakly alkaline environment of pH=8, after reaction 25 min always, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (400 order), dissolve in suitable quantity of water, supersound process 15 min, add 0.2 g sodium laurylsulfonate, at 65 ℃, stir, then add 0.2 g Sodium Persulfate, add again 1.0 g P-F performed polymers, reaction 0.5 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 2.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 2:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:28:1, mix and add appropriate amount of deionized water, control temperature of reaction 75 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=8 always, react after 25 min, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (400 order), dissolve in suitable quantity of water, supersound process 15 min, add 0.2 g Sodium hexametaphosphate 99, at 65 ℃, stir, and then add 0.2 g ammonium persulphate, then add 1.5 g P-F performed polymers, reaction 1 h.In this process, with the NaOH aqueous solution of NaOH, 0.1 mol/L of 0.1 mol/L, regulating pH value is 6.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 3:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:20:1, mix and add appropriate amount of deionized water, control temperature of reaction 80 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=8.5 always, react after 35 min, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (800 order), dissolve in suitable quantity of water, supersound process 20 min, add 0.1 g Macrogol 200, at 65 ℃, stir, and then add 0.3 g ammonium persulphate, then add 1.0 g P-F performed polymers, reaction 1.5 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 4.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 4:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:32:1, mix and add appropriate amount of deionized water, control temperature of reaction 85 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=8.5, after reaction 25min, phenol dissolves completely always, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (800 order), dissolve in suitable quantity of water, supersound process 15 min, add 0.3 g Macrogol 200, at 70 ℃, stir, and then add Sodium Persulfate 0.1 g, then add appropriate P-F performed polymer, reaction 3 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 5.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 5:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:32:1, mix and add appropriate amount of deionized water, control temperature of reaction 90 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=9 always, react after 35 min, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (1000 order), dissolve in suitable quantity of water, supersound process 20 min, add 0.4 g sodium laurylsulfonate, at 65 ℃, stir, then add catalyzer Sodium Persulfate 0.4 g, add again 2.0 g P-F performed polymers, reaction 3 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 6.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 6:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:28:1, mix and add appropriate amount of deionized water, control temperature of reaction 80 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=8.5, after reaction 30 min, phenol dissolves completely always, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (800 order), dissolve in suitable quantity of water, supersound process 15 min, add 0.2 g Macrogol 200, at 65 ℃, stir, then add 0.3 g ammonium persulphate, add again the P-F performed polymer of 2.0 g, reaction 2.5 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 3.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 7:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:20:1, mix and add appropriate amount of deionized water, control temperature of reaction 90 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=9, after reaction 25 min, phenol dissolves completely always, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (1000 order), dissolve in suitable quantity of water, supersound process 20 min, add 0.4 g sodium laurylsulfonate, at 65 ℃, stir, then add 0.2 g ammonium persulphate, add again the P-F performed polymer of 1.5 g, reaction 1.5 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 6.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 8:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:28:1, mix and add appropriate amount of deionized water, control temperature of reaction 90 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=8, after reaction 35 min, phenol dissolves completely always, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (400 order), dissolve in suitable quantity of water, supersound process 10 min, add 0.4 g Macrogol 200, at 65 ℃, stir, then add 0.4 g Sodium Persulfate, add again the P-F performed polymer of 1.0 g, reaction 1.5 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 5.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
Embodiment 9:
Take phenol, formaldehyde, methyl alcohol that mass ratio is 20:32:1, mix and add appropriate amount of deionized water, control temperature of reaction 80 ℃ of left and right, dripping volumetric molar concentration is the NaOH solution adjusting pH of 0.1 mol/L, make solution keep the weakly alkaline environment of pH=8.5, after reaction 30 min, phenol dissolves completely always, obtain clear solution, be P-F performed polymer.
Weigh 10.0 g ultra-fine red phosphorus (1000 order), dissolve in suitable quantity of water, supersound process 20 min, add 0.1 g Sodium hexametaphosphate 99, at 65 ℃, stir, and then add 0.2 g Sodium Persulfate, then add the P-F performed polymer of 1.0 g, reaction 2 h.In this process, with the NaOH aqueous solution of HCL, 0.1 mol/L of 0.1 mol/L, regulating pH value is 2.After having reacted, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
The performance of micro encapsulation red phosphorus prepared by above-described embodiment detects as follows:
Point of ignition test: Shimadzu DTA-50, TGA-50 (Japan), 10 ℃/min of temperature rise rate, air atmosphere, α-Al
2o
3for reference substance;
Wettability test: press GB/T16913.6 – 1997 standard testings, 80 ℃, sample, places and measure moisture absorption weightening finish percentage ratio after 1 month;
PH
3test: take 40 g water, 20 g samples are put into 500 mL Erlenmeyer flasks of band plug, shake up, and place 24 h after sealing at 40 ℃ of temperature.With the phosphuret-(t)ed hydrogen (PH in ammonium molybdate colorimetric method for determining flask gas phase
3) burst size;
The above-mentioned performance perameter detected result of the microcapsule red phosphorus of being prepared by above-described embodiment is listed in table 1; The performance perameter detection method of micro encapsulation red phosphorus is not with embodiment 1-9, and the results are shown in Table 1.
?
Table 1 red phosphorus microcapsuleization is processed point of ignition, rate of moisture absorption and the PH of front and back
3burst size
Note: experimental data error is all within allowed band.
Correlation data by upper table can be found out: point of ignition, rate of moisture absorption, the PH of the micro encapsulation red phosphorus of being prepared by the embodiment of the present invention
3burst size is all due to the red phosphorus of micro encapsulation not, and the present invention has obviously improved stability and the stability of red phosphorus.
Although with preferred embodiment in detail the present invention has been described in detail, but it is not intended to limit the present invention.Any those skilled in the art, without departing from the spirit and scope of the present invention, should make various modifications and change.Therefore protection scope of the present invention should be considered as appended claims limited range.
Claims (9)
1. a BACN microcapsule red phosphorus, is characterized in that P-F performed polymer is coated on ultra-fine red phosphorus powder surface, forms microcapsule red phosphorus.
2. BACN microcapsule red phosphorus according to claim 1, is characterized in that the order number of described ultra-fine red phosphorus is 400-1000 order, and the consumption of described P-F performed polymer is the 10-20% of red phosphorus quality.
3. BACN microcapsule red phosphorus according to claim 1, P-F performed polymer described in it is characterized in that is prepared by the following method: in water, add respectively phenol, formaldehyde and methyl alcohol, wherein, the mass ratio of phenol, formaldehyde and methyl alcohol is 20:(20-32): 1, temperature control is to 70-90 ℃, regulate pH=8-9 scope, reaction 25-35min, obtains P-F performed polymer.
4. a preparation method for BACN microcapsule red phosphorus, is characterized in that described method comprises following preparation process:
Step 1, ultra-fine red phosphorus is dissolved in to supersound process in water, add dispersion agent to stir;
Step 2, add again P-F prepolymer reaction after adding persulfuric acid salt catalyzer, in reaction process, regulate pH value to 1-6;
Step 3, reacted after, solution is cooling, filter, washing, dry, obtain the coated microcapsule red phosphorus of phenol-formaldehyde resin.
5. the preparation method of BACN microcapsule red phosphorus according to claim 4, it is characterized in that the dispersion agent described in step 1 is selected from sodium lauryl sulphate, Sodium hexametaphosphate 99 or Macrogol 200, dispersant dosage is the 1-4% of red phosphorus quality, described ultrasonic time is 10-20 minute, and the order number of described ultra-fine red phosphorus is 400-1000 order.
6. the preparation method of BACN microcapsule red phosphorus according to claim 5, is characterized in that the preferred Macrogol 200 of the dispersion agent described in step 1.
7. the preparation method of BACN microcapsule red phosphorus according to claim 4, is characterized in that the persulfuric acid salt catalyzer described in step 2 is ammonium persulphate or Sodium Persulfate, and described catalyst levels is the 1-4% of red phosphorus quality; Reaction times is 0.5-3h; The consumption of P-F performed polymer is the 10-20% of red phosphorus quality.
8. the preparation method of BACN microcapsule red phosphorus according to claim 7, is characterized in that the pH value described in step 2 preferably 3.
9. the preparation method of BACN microcapsule red phosphorus according to claim 4, it is characterized in that the P-F performed polymer described in step 2 prepared by the following method: in water, add respectively phenol, formaldehyde and methyl alcohol, wherein, the mass ratio of phenol, formaldehyde and methyl alcohol is 20:(20-32): 1, temperature control is to 70-90 ℃, regulate pH=8-9 scope, reaction 25-35min, obtains P-F performed polymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108546320A (en) * | 2018-04-12 | 2018-09-18 | 安徽皖东树脂科技有限公司 | The preparation method of phenolic resin |
| CN112876327A (en) * | 2021-02-03 | 2021-06-01 | 中国工程物理研究院化工材料研究所 | Method for preparing coated boron powder and coated boron powder |
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| CN102140262A (en) * | 2011-01-19 | 2011-08-03 | 成都理工大学 | Preparation method of light-color microcapsule red phosphorus |
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| CN102140262A (en) * | 2011-01-19 | 2011-08-03 | 成都理工大学 | Preparation method of light-color microcapsule red phosphorus |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108546320A (en) * | 2018-04-12 | 2018-09-18 | 安徽皖东树脂科技有限公司 | The preparation method of phenolic resin |
| CN108546320B (en) * | 2018-04-12 | 2019-07-26 | 安徽皖东树脂科技有限公司 | The preparation method of phenolic resin |
| CN112876327A (en) * | 2021-02-03 | 2021-06-01 | 中国工程物理研究院化工材料研究所 | Method for preparing coated boron powder and coated boron powder |
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Application publication date: 20140416 |