CN111748127A - Novel red phosphorus microcapsule and preparation method thereof - Google Patents
Novel red phosphorus microcapsule and preparation method thereof Download PDFInfo
- Publication number
- CN111748127A CN111748127A CN202010561608.7A CN202010561608A CN111748127A CN 111748127 A CN111748127 A CN 111748127A CN 202010561608 A CN202010561608 A CN 202010561608A CN 111748127 A CN111748127 A CN 111748127A
- Authority
- CN
- China
- Prior art keywords
- red phosphorus
- nitrate
- microcapsule
- solution
- novel red
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- 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
-
- 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
Abstract
The invention discloses a novel red phosphorus microcapsule, which comprises the following raw materials in parts by weight: 5-80g of red phosphorus, 1-60 parts of nitrate, 5-80 parts of strong base and 0.01-10 parts of surfactant. The method comprises the steps of ball-milling red phosphorus, performing ultrasonic oscillation to obtain stable red phosphorus suspension, and simultaneously dissolving nitrate and strong base in deionized water respectively to obtain a nitrate solution and an alkali solution; then mixing, stirring, crystallizing, precipitating, filtering, washing and drying the raw materials to obtain the red phosphorus microcapsule. The red phosphorus microcapsule of the invention is used as a flame retardant additive of a high polymer material, has the performances of low moisture absorption rate, high flame retardant efficiency and the like, and does not influence the chromaticity and the mechanical properties of the material.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a novel red phosphorus microcapsule and a preparation method thereof.
Background
With the development of society and the improvement of industrial level, all trades pay attention to the combustion safety of building materials and products, and the flame retardant in the market is also endlessly available. At present, products with different elements and forms, such as flame retardants, are involved, and the effects are different.
The problems of flame retardant efficiency, moisture absorption rate, storage performance and the like of the existing phosphorus flame retardant are solved, and therefore, how to provide a stable, low-moisture-absorption rate, safe and efficient phosphorus flame retardant is a technical problem which needs to be solved by the technical personnel in the field.
Disclosure of Invention
In view of the above, the present invention provides a novel red phosphorus microcapsule flame retardant which is stable, low in moisture absorption rate, safe and efficient.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel red phosphorus microcapsule comprises the following raw materials in parts by weight: 5-80g of red phosphorus, 1-60 parts of nitrate, 5-80 parts of strong base and 0.01-10 parts of surfactant.
Further, the surfactant is any one of sodium dodecylbenzene sulfonate, sodium dodecylsulfate and sodium dodecyl sulfate.
Further, the nitrate is any two or more of magnesium nitrate, aluminum nitrate, ferric nitrate, nickel nitrate, cadmium nitrate, lead nitrate and calcium nitrate.
Adopt above-mentioned further beneficial effect to lie in: the common inorganic coating materials are single materials such as aluminum hydroxide or magnesium hydroxide, the layered double hydroxide compound is organic composite of the two materials, and the flame retardant property and the like of the layered double hydroxide compound are superior to those of the layered double hydroxide compound.
Further, the strong base is sodium hydroxide or potassium hydroxide.
Adopt above-mentioned further beneficial effect to lie in: the amphoteric substance adopted by the invention has stable property and strong alkalinity, is easy to synthesize and control, and has less alkali dosage and stronger alkalinity compared with other medium and strong alkalis with weaker alkalinity, thereby ensuring the stable control of the pH value in the synthesis process.
The invention has the beneficial effects that: the red phosphorus microcapsule of the invention is used as a flame retardant additive of a high polymer material, has the performances of low moisture absorption rate, high flame retardant efficiency and the like, and does not influence the chromaticity and the mechanical properties of the material.
The invention also provides a preparation method of the novel red phosphorus microcapsule, which comprises the following steps:
(1) weighing the raw materials according to the novel red phosphorus microcapsule;
(2) putting red phosphorus into a planetary ball mill for ball milling for 0.5-1h, then adding the red phosphorus into deionized water, and performing ultrasonic oscillation to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a nitrate solution and an alkali solution;
(4) adding a nitrate solution and an alkali solution into a reaction container, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 1-4 hours to obtain a mixed solution;
(5) crystallizing the mixed solution for 10-30h, precipitating, filtering, washing with water for 1-5 times, and oven drying to obtain red phosphorus microcapsule.
Preferably, the deionized water is boiled in advance to remove carbon dioxide.
Preferably, the ultrasonic frequency in the step (2) is 30-60Hz, and the ultrasonic time is 10-60 min.
Preferably, in the step (3), the concentration of the nitrate solution is 5-20%, and the concentration of the strong alkali solution is 5-20%.
Preferably, the operation method for keeping the pH stable in the step (4) is to control the dropping speed of the alkali liquor through a fine constant pressure funnel and monitor the change of the acidity through a pH electrode in real time, wherein the optimal dropping speed is 1 drop/s.
Preferably, the drying temperature in the step (5) is 60-100 ℃, and the drying time is 12-48 h.
Compared with the prior art, the invention has the beneficial effects that: when the red phosphorus microcapsule prepared by the invention is used as a flame retardant additive of a high polymer material, the red phosphorus microcapsule has the performances of low moisture absorption rate, high flame retardant efficiency and the like, and the preparation method is simple and has excellent industrialization prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the novel red phosphorus microcapsule comprises the following steps:
(1) boiling deionized water, removing carbon dioxide, weighing 10g of red phosphorus, 15.36g of magnesium nitrate, 7.5g of aluminum nitrate, 0.1g of sodium dodecyl sulfate and 6.4g of sodium hydroxide;
(2) putting red phosphorus into a planetary ball mill for ball milling, then adding the red phosphorus into deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 40Hz to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a 10% nitrate solution and a 10% alkali solution;
(4) adding a nitrate solution and an alkali solution into a reaction container, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 2 hours to obtain a mixed solution;
(5) and (3) crystallizing and precipitating the mixed solution, filtering, washing for 3 times with water, and drying for 24 hours to obtain the red phosphorus microcapsule.
Example 2
The preparation method of the novel red phosphorus microcapsule comprises the following steps:
(1) boiling deionized water, removing carbon dioxide, weighing 10g of red phosphorus, 15.36g of magnesium nitrate, 4.84g of ferric nitrate, 0.1g of sodium dodecyl sulfate and 6.4g of sodium hydroxide;
(2) putting red phosphorus into a planetary ball mill for ball milling, then adding the red phosphorus into deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 40Hz to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a 10% nitrate solution and a 10% alkali solution;
(4) adding a nitrate solution and an alkali solution into a reaction container, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 2 hours to obtain a mixed solution;
(5) and (3) crystallizing and precipitating the mixed solution, filtering, washing for 3 times with water, and drying for 24 hours to obtain the red phosphorus microcapsule.
Example 3
The preparation method of the novel red phosphorus microcapsule comprises the following steps:
(1) boiling deionized water, removing carbon dioxide, weighing 10g of red phosphorus, 15.36g of magnesium nitrate, 3.65g of nickel nitrate, 0.1g of sodium dodecyl sulfate and 6.4g of sodium hydroxide;
(2) putting red phosphorus into a planetary ball mill for ball milling, then adding the red phosphorus into deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 40Hz to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a 10% nitrate solution and a 10% alkali solution;
(4) adding a nitrate solution and an alkali solution into a reaction container, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 2 hours to obtain a mixed solution;
(5) and (3) crystallizing and precipitating the mixed solution, filtering, washing for 3 times with water, and drying for 24 hours to obtain the red phosphorus microcapsule.
Example 4
The preparation method of the novel red phosphorus microcapsule comprises the following steps:
(1) boiling deionized water, removing carbon dioxide, weighing 10g of red phosphorus, 15.36g of magnesium nitrate, 4.73g of cadmium nitrate, 0.1g of sodium dodecyl sulfate and 6.4g of sodium hydroxide;
(2) putting red phosphorus into a planetary ball mill for ball milling, then adding the red phosphorus into deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 40Hz to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a 10% nitrate solution and a 10% alkali solution;
(4) adding a nitrate solution and an alkali solution into a reaction container, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 2 hours to obtain a mixed solution;
(5) and (3) crystallizing and precipitating the mixed solution, filtering, washing for 3 times with water, and drying for 24 hours to obtain the red phosphorus microcapsule.
Example 5
The preparation method of the novel red phosphorus microcapsule comprises the following steps:
(1) boiling deionized water, removing carbon dioxide, weighing 10g of red phosphorus, 15.36g of magnesium nitrate, 6.62g of lead nitrate, 0.1g of sodium dodecyl sulfate and 6.4g of sodium hydroxide;
(2) putting red phosphorus into a planetary ball mill for ball milling, then adding the red phosphorus into deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 40Hz to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a 10% nitrate solution and a 10% alkali solution;
(4) adding a nitrate solution and an alkali solution into a reaction container, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 2 hours to obtain a mixed solution;
(5) and (3) crystallizing and precipitating the mixed solution, filtering, washing for 3 times with water, and drying for 24 hours to obtain the red phosphorus microcapsule.
Example 6
The preparation method of the novel red phosphorus microcapsule comprises the following steps:
(1) boiling deionized water, removing carbon dioxide, weighing 10g of red phosphorus, 15.36g of magnesium nitrate, 3.28g of calcium nitrate, 0.1g of sodium dodecyl sulfate and 6.4g of sodium hydroxide;
(2) putting red phosphorus into a planetary ball mill for ball milling, then adding the red phosphorus into deionized water, and carrying out ultrasonic oscillation for 30min at the frequency of 40Hz to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a 10% nitrate solution and a 10% alkali solution;
(4) adding a nitrate solution and an alkali solution into a reaction container, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 2 hours to obtain a mixed solution;
(5) and (3) crystallizing and precipitating the mixed solution, filtering, washing for 3 times with water, and drying for 24 hours to obtain the red phosphorus microcapsule.
Test examples
Because red phosphorus is easy to react with water to generate H3PO4、H3PO3、H3PO2And a small amount of toxic gas PH3Resulting in deterioration of red phosphorus and deterioration of flame retardant effect.
The oxidability means that the coated red phosphorus is dissolved in water, the coating layer is removed, and the red phosphorus reacts with the water to obtain various series of phosphoric acids, so that the solution becomes acidic. The red phosphorus coated by the aluminum hydroxide is far lower than the red phosphorus coated by the hydrotalcite.
Based on the above, the experiment of the LDH novel red phosphorus microcapsule prepared in the embodiment 1 of the invention is carried out, the weighed dry dust is placed in a moisture-keeping device with the relative humidity controlled between 80 and 90 percent at the temperature of between 20 and 30 ℃, and the weighing is carried out once every 24 hours until the weight change is within 5 percent; the dust weight gain is the amount of moisture it absorbs from the ambient air over a certain range of temperature and relative humidity over that time: the ratio of the amount of moisture absorbed to the mass of dry dust characterizes the hygroscopicity of the dust. The test results are shown in Table 1.
TABLE 1
In the table: MH: magnesium hydroxide; AH: aluminum hydroxide; LDH: a layered double hydroxide compound. The mass fraction is the percentage of the coating raw material mass in the red phosphorus mass.
As can be seen from the above data, the uncoated red phosphorus has high moisture absorption rate and poor stability, and is easy to release PH3. Three coatings with 50 percent of the mass of red phosphorus are adopted in the schemes 1, 2 and 3. The experimental results show that: LDH moisture absorption rate lower than AH and MH-coated red phosphorus, high stability, and pH of discharged solution3The gas is little.
Compared with three coating schemes 4, 5 and 6 with the weight of 85 percent of the red phosphorus, the moisture absorption rate of the LDH is obviously lower than that of red phosphorus coated with AH and MH, the stability is high, and the released PH is high3The gas is little.
Three coatings with the mass of 114 percent of the mass of the red phosphorus are adopted, and the LDH has certain moisture absorption rate along with the increase of the mass. Excessive MH prevents complete coating and reduces the red phosphorus coating effect.
The moisture absorption rate of the unmodified LDH was 4.82%, and the moisture absorption rate of red phosphorus was 4.57%. The coating effect of the invention is obvious.
Claims (10)
1. The novel red phosphorus microcapsule is characterized by comprising the following raw materials in parts by weight: 5-80g of red phosphorus, 1-60 parts of nitrate, 5-80 parts of strong base and 0.01-10 parts of surfactant.
2. The novel red phosphorus microcapsule according to claim 1, wherein the surfactant is any one of sodium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate and sodium dodecylsulfate.
3. A novel red phosphorus microcapsule according to claim 1, wherein said nitrate is any two or more selected from the group consisting of magnesium nitrate, aluminum nitrate, ferric nitrate, nickel nitrate, cadmium nitrate, lead nitrate and calcium nitrate.
4. A novel red phosphorus microcapsule according to claim 1, wherein said strong base is sodium hydroxide or potassium hydroxide.
5. A preparation method of a novel red phosphorus microcapsule is characterized by comprising the following steps:
(1) weighing the raw materials according to the novel red phosphorus microcapsule of any one of claims 1 to 4;
(2) putting red phosphorus into a planetary ball mill for ball milling for 0.5-1h, then adding the red phosphorus into deionized water, and performing ultrasonic oscillation to obtain a stable red phosphorus suspension for later use;
(3) respectively dissolving nitrate and strong base in deionized water to obtain a nitrate solution and an alkali solution;
(4) adding a nitrate solution into a reaction container, dropwise adding an alkali solution into the nitric acid solution, stirring, keeping the pH stable at 10-11, then adding a red phosphorus suspension and a surfactant into the reaction container, and stirring for 1-4 hours to obtain a mixed solution;
(5) crystallizing the mixed solution for 10-30h, precipitating, filtering, washing with water for 1-5 times, and oven drying to obtain red phosphorus microcapsule.
6. The method for preparing novel red phosphorus microcapsules of claim 5, wherein the deionized water is boiled beforehand to remove carbon dioxide.
7. The method for preparing the novel red phosphorus microcapsule according to claim 5, wherein the ultrasonic frequency in the step (2) is 30-60Hz, and the ultrasonic time is 10-60 min.
8. The method for preparing novel red phosphorus microcapsules of claim 5, wherein the nitrate solution concentration in step (3) is 5-20%, and the strong alkali solution concentration is 5-20%.
9. The method for preparing novel red phosphorus microcapsules of claim 5, wherein the pH stabilization in step (4) is performed by controlling the dropping rate of the alkali solution through a fine constant pressure funnel and monitoring the change of acidity through a pH electrode in real time.
10. The method for preparing novel red phosphorus microcapsules of claim 5, wherein the drying temperature in step (5) is 60-100 ℃ and the drying time is 12-48 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010561608.7A CN111748127A (en) | 2020-06-18 | 2020-06-18 | Novel red phosphorus microcapsule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010561608.7A CN111748127A (en) | 2020-06-18 | 2020-06-18 | Novel red phosphorus microcapsule and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111748127A true CN111748127A (en) | 2020-10-09 |
Family
ID=72675773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010561608.7A Pending CN111748127A (en) | 2020-06-18 | 2020-06-18 | Novel red phosphorus microcapsule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111748127A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437411A (en) * | 2022-03-08 | 2022-05-06 | 邵阳市富森阻燃材料有限公司 | Modified hydrotalcite coated red phosphorus flame retardant and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02111611A (en) * | 1988-10-20 | 1990-04-24 | Nippon Chem Ind Co Ltd | Stabilized red phosphorus and production thereof |
| JPH05194787A (en) * | 1992-01-20 | 1993-08-03 | Asahi Chem Ind Co Ltd | Red phosphorus flame retardant and its production |
| JP2004161924A (en) * | 2002-11-14 | 2004-06-10 | Rin Kagaku Kogyo Kk | Red phosphorus-based flame retardant and method for producing the same, and flame-retardant resin composition containing the same |
| CN1775664A (en) * | 2005-12-08 | 2006-05-24 | 南京理工大学 | Method for preparing microcapsulated superfine red phosphorus |
| CN101684186A (en) * | 2008-09-27 | 2010-03-31 | 比亚迪股份有限公司 | Microcapsule red phosphorus and preparation method thereof and antiflaming mother material and polphenyl ether alloy containing same |
| CN104448934A (en) * | 2014-12-19 | 2015-03-25 | 南京化工职业技术学院 | Flame retardant microcapsule red phosphorus coated with inorganic material and preparation method of flame retardant microcapsule red phosphorus coated with inorganic material |
| CN104945661A (en) * | 2015-06-29 | 2015-09-30 | 合肥工业大学 | Microencapsulated red phosphorus, flame retardant wood-plastic composite material based on microencapsulated red phosphorus and preparation method of microencapsulated red phosphorus |
| CN105037805A (en) * | 2015-07-05 | 2015-11-11 | 张炳雄 | Fire retardant |
-
2020
- 2020-06-18 CN CN202010561608.7A patent/CN111748127A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02111611A (en) * | 1988-10-20 | 1990-04-24 | Nippon Chem Ind Co Ltd | Stabilized red phosphorus and production thereof |
| JPH05194787A (en) * | 1992-01-20 | 1993-08-03 | Asahi Chem Ind Co Ltd | Red phosphorus flame retardant and its production |
| JP2004161924A (en) * | 2002-11-14 | 2004-06-10 | Rin Kagaku Kogyo Kk | Red phosphorus-based flame retardant and method for producing the same, and flame-retardant resin composition containing the same |
| CN1775664A (en) * | 2005-12-08 | 2006-05-24 | 南京理工大学 | Method for preparing microcapsulated superfine red phosphorus |
| CN101684186A (en) * | 2008-09-27 | 2010-03-31 | 比亚迪股份有限公司 | Microcapsule red phosphorus and preparation method thereof and antiflaming mother material and polphenyl ether alloy containing same |
| CN104448934A (en) * | 2014-12-19 | 2015-03-25 | 南京化工职业技术学院 | Flame retardant microcapsule red phosphorus coated with inorganic material and preparation method of flame retardant microcapsule red phosphorus coated with inorganic material |
| CN104945661A (en) * | 2015-06-29 | 2015-09-30 | 合肥工业大学 | Microencapsulated red phosphorus, flame retardant wood-plastic composite material based on microencapsulated red phosphorus and preparation method of microencapsulated red phosphorus |
| CN105037805A (en) * | 2015-07-05 | 2015-11-11 | 张炳雄 | Fire retardant |
Non-Patent Citations (3)
| Title |
|---|
| 任明: "超细红磷微胶囊及其在无卤阻燃聚丙烯中的应用", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
| 张东山等: "红磷的微胶囊化及其在尼龙6中的应用", 《能源化工》 * |
| 熊联明: "微胶囊红磷阻燃剂的制备、应用及阻燃抑烟机理研究", 《中国优秀博硕士学位论文全文数据库（博士） 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437411A (en) * | 2022-03-08 | 2022-05-06 | 邵阳市富森阻燃材料有限公司 | Modified hydrotalcite coated red phosphorus flame retardant and preparation method thereof |
| CN114437411B (en) * | 2022-03-08 | 2023-10-13 | 邵阳市富森阻燃材料有限公司 | Modified hydrotalcite coated red phosphorus flame retardant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106009045B (en) | A kind of microcapsule red phosphorus, preparation method and application | |
| CN111116987B (en) | Method for synthesizing fine-grained aluminum hypophosphite composite flame retardant | |
| CN110804445A (en) | Preparation method of bio-based flame-retardant microcapsule | |
| CN105295100A (en) | Preparation method of surface modification and flame retardance enhancement dual-function nano hydroxyl zinc stannate flame retardant | |
| CN111748127A (en) | Novel red phosphorus microcapsule and preparation method thereof | |
| CN105367604A (en) | Phosphorus-nitrogen-containing star-type charring agent and preparation method thereof | |
| CN103497299A (en) | Preparing method of norganic nanoparticle enhanced inflaming retarding polyurethane material | |
| CN111559762A (en) | Preparation method of cobalt hydroxide | |
| CN108623850B (en) | Environment-friendly cellulose-based flame-retardant heat-insulating material and preparation method thereof | |
| CN106390930B (en) | A kind of method that glycine prepares active carbon loading silver with silver nitrate complexing | |
| CN112480474A (en) | Smoke suppression intumescent flame retardant containing multiple anion intercalated Ca-based ternary hydrotalcite and preparation method thereof | |
| CN107501636A (en) | A kind of preparation method of Beta-cyclodextrin-based phosphorus flame retardant | |
| CN114620698B (en) | Large-particle zirconium phosphate and preparation method thereof | |
| CN116396761A (en) | Gel foam containing super absorbent resin-antioxidant and preparation method and application thereof | |
| CN1332113A (en) | Prepn of sodium percarbonate | |
| CN106219544B (en) | The preparation method of wood activated charcoal containing lanthanum | |
| CN114433014B (en) | Preparation method of 5A molecular sieve adsorbent | |
| CN105084337B (en) | A kind of method of the type APP of polyphosphoric acid catalysis method synthetic crystallization II | |
| CN101284993A (en) | Nano magnesium hydrate combustion inhibitor using agustite as crystal nucleon component and preparation method | |
| CN111533149A (en) | Preparation method of light high-dispersion calcium oxide | |
| JP3506772B2 (en) | Manufacturing method of inorganic builder | |
| CN114345295B (en) | Impurity removal process for chemical auxiliary agent | |
| CN108589397A (en) | A kind of special compound flame retardant of paper | |
| CN108822003A (en) | A kind of purifying technique of sulfosalicylic acid | |
| CN107875845A (en) | A kind of novel air purifies particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |