CN104961701A - Method for preparing nano phosphorus-nitrogen inrumescent flame retardant by means of supercritical method - Google Patents
Method for preparing nano phosphorus-nitrogen inrumescent flame retardant by means of supercritical method Download PDFInfo
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- CN104961701A CN104961701A CN201510360758.0A CN201510360758A CN104961701A CN 104961701 A CN104961701 A CN 104961701A CN 201510360758 A CN201510360758 A CN 201510360758A CN 104961701 A CN104961701 A CN 104961701A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/56—Preparation of melamine
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The invention discloses a method for preparing nano phosphorus-nitrogen inrumescent flame retardant melamine phosphate (MP) by means of a supercritical method. The method comprises the steps that phospholipid melamine, phosphoric acid, surface active agents and the like are weighed, and are dissolved in a little distilled water; the dissolved solution is added to a supercritical reaction kettle, temperature and pressure are controlled, and the pressure is kept for certain time; the nano phosphorus-nitrogen inrumescent flame retardant melamine phosphate (MP) is obtained by releasing the pressure. The characteristics that supercritical carbon dioxide fluid is high in solvent resistance and environmentally friendly and can be easily separated from products after preparation is finished are utilized, and the nano phosphorus-nitrogen inrumescent flame retardant is prepared. In the preparation process of the method, toxic organic solvent is not used, and pollution to environment is avoided. The prepared phosphorus-nitrogen inrumescent flame retardant is small in particle size and easy to disperse, the problem that nano particles are poor in dispersity in polymer matrixes is solved, and therefore high fire resistance is achieved. The process is simple, and cost is low.
Description
Technical field
The invention belongs to fire retardant preparation field, be specifically related to a kind of method utilizing supercritical co to prepare nano level phosphorus-nitrogen expansion type fire retardant.
Technical background
Expansion type flame retardant (IFR) is a kind of is the main environment-friendly and green composite flame-retardant agent formed with nitrogen, phosphorus, it is not halogen-containing, do not adopt weisspiessglanz as synergist yet, this based flame retardant foaming and intumescing when being heated, effects such as generating carbonaceous foam layer, play heat insulation, oxygen barrier, press down cigarette, be antidrip, has excellent flame retardant properties, and low cigarette, low toxicity, non-corrosiveness gas produce, and are the environment friendly flame retardants of a class high-efficiency low-toxicity.After the nineties in 20th century, the research of expansion type flame retardant starts to enliven gradually, and it is acknowledged as and realizes one of non-halogen effective way of fire retardant.
The P-N type fire retardant used on the market is at present all generally micron level, and in order to reach good flame retardant effect, half addition is all comparatively large, and this often causes the decline of mechanical property, seriously limits the range of application of P-N type fire retardant.Therefore, nano level P-N type fire retardant exploitation and preparation just seem particularly important.
Supercutical fluid is the fluid that temperature and pressure are all in more than stagnation point, it has liquid property and gas property concurrently, its density is close with liquid, viscosity and velocity of diffusion and gas close, never can be dissolved into dissolving to a certain degree to the solvability of material, this makes supercritical fluid technology have great operability.Compared with Conventional nano technology of preparing, supercritical fluid technology has following characteristics: 1. operational condition is easy to control, and obtains the favorable reproducibility of the size of particulate, size-grade distribution and particle shape structure; 2. treating processes is gentle, avoids particulate and produce the shortcomings such as phase in version, high surface energy, electrostatic and chemical degradation in conventional pelletization; 3. environmental protection, pollution-free.These advantages make supercutical fluid prepare nanoparticle technology being used widely in the Pharmaceutical study of biotech drug and natural product.
Supercritical co, as the most frequently used supercutical fluid, is a kind of nontoxic, inertia and the reaction medium of environmental sound.It is easy to and product separation after preparation terminates, and small pressure surge just can cause huge changes in solubility, is easy to prepare the little nano particle of particle diameter.Therefore, prepared by supercritical co in the preparation of the technology introducing nanometer P-N type fire retardant of nano particle and possess skills and the novelty applied and creativeness.
Summary of the invention
The object of the invention is to for existing P-N type flame retardant product particle diameter large, flame retarding efficiency is not high, the shortcoming large to macromolecule matrix Effect on Mechanical Properties, provides a kind of method adopting supercritical co to prepare nanometer P-N type fire retardant.
Supercritical methanol technology prepares a method for nanometer P-N type expansion shape fire retardant, and it is characterized in that, concrete steps are as follows:
(1) accurately take trimeric cyanamide, phosphoric acid and tensio-active agent according to formula, added in distilled water, stir and make it fully dissolve and be prepared into solution;
(2) inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor by high-pressure pump after being pressurizeed; Control pressure and temperature, and pressurize certain hour;
(3) open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, obtain white powder;
(4) collect above-mentioned white powder, be nanometer P-N type expansion shape fire retardant melamine phosphate (MP).
The mass ratio of described trimeric cyanamide and phosphoric acid is 3:1 ~ 1:3.
The quality of described tensio-active agent is 0.05 of trimeric cyanamide and phosphoric acid total mass
%~ 5%.
Described pressure is 10MPa ~ 40MPa.
Described temperature is 323K ~ 383K.
The described time is 10min ~ 90min.
The consumption of described distilled water is 1% ~ 50% of trimeric cyanamide and phosphoric acid total mass.
Adopt nano melamine phosphoric acid salt prepared by the method for the invention, grain diameter is (see figure 1) between 20nm ~ 50nm usually, narrow diameter distribution, and monodispersity is fine, and it is few to reunite, and easily adds in macromolecule matrix and forms flame-retardant high-molecular.
Accompanying drawing explanation
fig. 1 nano melamine phosphoric acid salt TEM photo.
Embodiment
Further illustrate the present invention below by embodiment, instead of limit the scope of the invention.
Embodiment 1:
(mass ratio of trimeric cyanamide and phosphoric acid is 1:1 accurately to take a certain amount of trimeric cyanamide, phosphoric acid and tensio-active agent according to formula, the quality of tensio-active agent is 2% of trimeric cyanamide and phosphoric acid total mass), added (consumption of distilled water is 10% of trimeric cyanamide and phosphoric acid total mass) in a certain amount of distilled water, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Control certain pressure (30MPa) and temperature (353K), and pressurize certain hour (40min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, the nano melamine phosphate powder that number average bead diameter is 35nm can be obtained.
Embodiment 2:
(mass ratio of trimeric cyanamide and phosphoric acid is 1.5:1 accurately to take a certain amount of trimeric cyanamide, phosphoric acid and tensio-active agent according to formula, the quality of tensio-active agent is 0.5% of trimeric cyanamide and phosphoric acid total mass), added (consumption of distilled water is 50% of trimeric cyanamide and phosphoric acid total mass) in a certain amount of distilled water, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Control certain pressure (40MPa) and temperature (363K), and pressurize certain hour (20min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, the nano melamine phosphate powder that number average bead diameter is 45nm can be obtained.
Embodiment 3:
(mass ratio of trimeric cyanamide and phosphoric acid is 1:1.2 accurately to take a certain amount of trimeric cyanamide, phosphoric acid and tensio-active agent according to formula, the quality of tensio-active agent is 1% of trimeric cyanamide and phosphoric acid total mass), added (consumption of distilled water is 20% of trimeric cyanamide and phosphoric acid total mass) in a certain amount of distilled water, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Control certain pressure (35MPa) and temperature (363K), and pressurize certain hour (60min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, the nano melamine phosphate powder that number average bead diameter is 30nm can be obtained.
Embodiment 4:
(mass ratio of trimeric cyanamide and phosphoric acid is 1:1.5 accurately to take a certain amount of trimeric cyanamide, phosphoric acid and tensio-active agent according to formula, the quality of tensio-active agent is 4% of trimeric cyanamide and phosphoric acid total mass), added (consumption of distilled water is 30% of trimeric cyanamide and phosphoric acid total mass) in a certain amount of distilled water, stir and make it fully dissolve and be prepared into solution.Inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor after being pressurizeed by high-pressure pump.Control certain pressure (40MPa) and temperature (343K), and pressurize certain hour (30min); Open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, the nano melamine phosphate powder that number average bead diameter is 30nm can be obtained.
Claims (7)
1. supercritical methanol technology prepares a method for nanometer P-N type expansion shape fire retardant, and it is characterized in that, concrete steps are as follows:
(1) accurately take trimeric cyanamide, phosphoric acid and tensio-active agent according to formula, added in distilled water, stir and make it fully dissolve and be prepared into solution;
(2) inserted in supercritical reaction still by above-mentioned solution, open carbon dioxide steel cylinder, carbon dioxide is cooled to after liquid through cold, enters in reactor by high-pressure pump after being pressurizeed; Control pressure and temperature, and pressurize certain hour;
(3) open pressure relief opening and the pressure in supercritical reaction still is dropped to normal pressure, obtain white powder;
(4) collect above-mentioned white powder, be nanometer P-N type expansion shape fire retardant melamine phosphate (MP).
2. a kind of supercritical methanol technology prepares the method for nanometer P-N type expansion shape fire retardant according to claim 1, it is characterized in that, the mass ratio of described trimeric cyanamide and phosphoric acid is 3:1 ~ 1:3.
3. a kind of supercritical methanol technology prepares the method for nanometer P-N type expansion shape fire retardant according to claim 1, it is characterized in that, the quality of described tensio-active agent is 0.05 of trimeric cyanamide and phosphoric acid total mass
%~ 5%.
4. a kind of supercritical methanol technology prepares the method for nanometer P-N type expansion shape fire retardant according to claim 1, it is characterized in that, described pressure is 10MPa ~ 40MPa.
5. a kind of supercritical methanol technology prepares the method for nanometer P-N type expansion shape fire retardant according to claim 1, it is characterized in that, described temperature is 323K ~ 383K.
6. a kind of supercritical methanol technology prepares the method for nanometer P-N type expansion shape fire retardant according to claim 1, it is characterized in that, the described time is 10min ~ 90min.
7. a kind of supercritical methanol technology prepares the method for nanometer P-N type expansion shape fire retardant according to claim 1, it is characterized in that, the consumption of described distilled water is 1% ~ 50% of trimeric cyanamide and phosphoric acid total mass.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218468A (en) * | 2015-10-16 | 2016-01-06 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of ultra-fine boric acid trimeric cyanamide |
| CN107556530A (en) * | 2017-08-02 | 2018-01-09 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application |
| CN115627631A (en) * | 2022-09-26 | 2023-01-20 | 滨州亚光家纺有限公司 | Application of phosphorus-containing melamine salt nano flame-retardant antibacterial compound in preparation of flame-retardant antibacterial fabric and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757393A (en) * | 2012-07-05 | 2012-10-31 | 同济大学 | Method for synthesizing nano-scale melamine cyanurate (MCA) through hydrothermal method |
| CN103254145A (en) * | 2013-05-14 | 2013-08-21 | 同济大学 | Method for synthesizing nanoscale melamine phosphate by hydrothermal method |
| CN103989635A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing coenzyme Q10 lipidosome through supercritical carbon dioxide |
-
2015
- 2015-06-26 CN CN201510360758.0A patent/CN104961701B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757393A (en) * | 2012-07-05 | 2012-10-31 | 同济大学 | Method for synthesizing nano-scale melamine cyanurate (MCA) through hydrothermal method |
| CN103254145A (en) * | 2013-05-14 | 2013-08-21 | 同济大学 | Method for synthesizing nanoscale melamine phosphate by hydrothermal method |
| CN103989635A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing coenzyme Q10 lipidosome through supercritical carbon dioxide |
Non-Patent Citations (3)
| Title |
|---|
| 张泽江等: "三聚氰胺磷酸盐阻燃剂的合成及性能表征", 《合成化学》 * |
| 牛阿萍: "超临界二氧化碳协助制备纳米粒子一二氧化钦纳米粒子及一维碳材料/银纳米复合材料", 《郑州大学硕士学位论文》 * |
| 程娟等: "超临界CO2流体中制备纳米材料的研究进展", 《材料导报Ａ：综述篇》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218468A (en) * | 2015-10-16 | 2016-01-06 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of ultra-fine boric acid trimeric cyanamide |
| CN105218468B (en) * | 2015-10-16 | 2018-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of ultra-fine boric acid melamine |
| CN107556530A (en) * | 2017-08-02 | 2018-01-09 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application |
| CN107556530B (en) * | 2017-08-02 | 2019-04-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application |
| CN115627631A (en) * | 2022-09-26 | 2023-01-20 | 滨州亚光家纺有限公司 | Application of phosphorus-containing melamine salt nano flame-retardant antibacterial compound in preparation of flame-retardant antibacterial fabric and preparation method thereof |
| CN115627631B (en) * | 2022-09-26 | 2024-03-29 | 滨州亚光家纺有限公司 | Application of phosphorus-containing melamine salt nano flame-retardant antibacterial compound in preparation of flame-retardant antibacterial fabric and preparation method thereof |
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