CN107556530A - A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application - Google Patents
A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application Download PDFInfo
- Publication number
- CN107556530A CN107556530A CN201710652426.9A CN201710652426A CN107556530A CN 107556530 A CN107556530 A CN 107556530A CN 201710652426 A CN201710652426 A CN 201710652426A CN 107556530 A CN107556530 A CN 107556530A
- Authority
- CN
- China
- Prior art keywords
- fire retardant
- melamine
- phosphorus nitrogen
- nitrogen boron
- boron ternary
- 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.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of phosphorus nitrogen boron Ternary Expansive fire retardant and its preparation method and application, melamine, phosphoric acid, boric acid, crosslinking agent and surfactant, which are added in distilled water, to be dissolved, pour into supercritical reaction kettle, open CO 2 high pressure pump, and temperature of reaction kettle is raised, react 1~5 hour, open pressure relief opening and drop to normal pressure, turbid solution is obtained, is phosphorus nitrogen boron Ternary Expansive fire retardant of the present invention by solution filtration washing vacuum drying.The phosphorus nitrogen boron ternary flame retardant prepared using the method for the invention, on the basis of with excellent flame effect, also preferable smoke suppressing effect, when fire occurs, can greatly improve the survival rate of people, have great application prospect.
Description
Technical field
The invention belongs to fire retardant preparation field, and in particular to a kind of phosphorus nitrogen boron Ternary Expansive fire retardant and its preparation side
Method and application.
Background technology
High polymer material because its have low production cost, good mechanical property, nontoxic, light, corrosion-resistant, good electrical property, easily
Many advantages, such as processing, easily reclaiming, is widely used in production and living.But most of macromolecules belong to combustible material, one
As high polymer material limited oxygen index（LOI）Only 17~20 %, and can produce many poisonous during macromolecule burning and have
Mordant gas and flue dust, therefore, the consequence caused by the fire being induced by it is with regard to even more serious.The material of halogenated flame retardant
Material can produce a large amount of smog and toxic and harmful gas in burning, in today that environmental requirement is increasingly strict, halogenated flame retardant
Using will gradually tail off and be gradually backed out the arena of history.
Phosphorus-nitrogen expansion type fire retardant (IFR) is a kind of, based flame retardant foaming and intumescing when heated, generation carbonaceous foam
Layer, heat-insulated, oxygen barrier, suppression cigarette, antidrip and other effects are played, there is excellent fire resistance, be the environment-friendly type resistance of a kind of high-efficiency low-toxicity
Fire agent.Boron flame retardant mainly includes the inorganic borates such as Firebrake ZB, borax, calcium metaborate, kodalk and minority is organic
Borate fire retardant.Boron flame retardant has the advantages that heat endurance is good, toxicity is low, eliminated smoke, toxicity is low, raw material is easy to get.It is most difficult to
Can be valuable, it has very excellent effect in terms of smoke elimination.It is reported that boron flame retardant and nitrogenated flame retardant or
Phosphorus flame retardant compounding can play the fire-retardant effect of synergistic, and can significantly reduce material combustion smoke density after adding.
Therefore, phosphorus nitrogen boron fire retardant preservative is a kind of very excellent Green Flammability agent of performance, and its application potential is very big.Have been reported that synthesis
（Plastics science and technology, 2010,38：87-92）Phosphorus nitrogen boron ternary flame retardant, but it is only simple composite, does not reach microcosmic
Three-in-one fire retardant synthesis, three kinds of Elemental redistribution heterogeneities of its each several part, do not reach best flame retardant effect.
Supercritical fluid is temperature and pressure is in more than critical point fluid, and supercritical carbon dioxide is as the most frequently used
Supercritical fluid, be a kind of nontoxic, inertia and environmental sound reaction medium.It is easy to and product point after preparation terminates
From, and small pressure oscillation can triggers huge changes in solubility, and the special dissolubility of supercritical carbon dioxide
And the supercriticality of HTHP is readily synthesized unavailable product under usual preparation condition.Therefore, by overcritical dioxy
The technology that change carbon prepares nano particle is introduced into the preparation of phosphorus nitrogen boron Ternary Expansive combustion agent the real meaning for having technology and applying
Justice.
The content of the invention
It is inefficient for existing P-N type fire retardant, the shortcomings that without preferable smoke suppressing effect, the purpose of the present invention
It is to provide a kind of phosphorus nitrogen boron Ternary Expansive fire retardant and preparation method thereof.
Another object of the present invention is：The product that above-mentioned preparation method obtains is provided.
A further object of the present invention is：The application that above-mentioned preparation method obtains product is provided.
The object of the invention is realized by following proposal：A kind of preparation method of phosphorus nitrogen boron Ternary Expansive fire retardant, use
Supercritical methanol technology, comprise the following steps：
1）A certain amount of melamine, phosphoric acid, boric acid, crosslinking agent and surfactant are accurately weighed according to formula, is added into one
In quantitative distilled water, stirring makes it fully dissolve, and obtains mixed solution；Wherein, melamine and phosphoric acid, boric acid, crosslinking agent rub
You are than being 1:（0.2~5）:（0.2~5）:（0.001~0.5）, the mass ratio of melamine and surfactant is 1: 0.001
~0.05, the mass ratio of melamine and distilled water is 1:50~500, crosslinking agent is in season pentanediol, cyanuric acid, cellulose etc.
One or its mixing, surfactant be lauryl sodium sulfate, cetyl trimethylammonium bromide, alkylphenol-polyethenoxy
One in ether, dodecyl sodium sulfate or its mixing；
2）Above-mentioned mixed solution is poured into supercritical reaction kettle, opens CO 2 high pressure pump, and raises temperature of reaction kettle, seemingly
Reactor keep 30~100 DEG C of 10~60MPa of pressure and temperature, react 1~5 hour in this case.
3）Open pressure relief opening and the pressure in supercritical reaction kettle is dropped into normal pressure, obtain turbid solution, the solution is filtered
Washing vacuum drying is phosphorus nitrogen boron Ternary Expansive fire retardant of the present invention.
The present invention utilizes supercritical carbon dioxide to prepare the method for phosphorus nitrogen boron Ternary Expansive fire retardant：According to formula essence
A certain amount of melamine, phosphoric acid, boric acid, crosslinking agent and surfactant etc. are really weighed, is added into a certain amount of distilled water
In, stir；Then, it is added into supercritical reaction kettle, controls and react certain time in certain temperature and pressure.Release
Filtration drying produces phosphorus nitrogen boron ternary flame retardant after bleeding off pressure.
The present invention provides a kind of phosphorus nitrogen boron Ternary Expansive flame retardant products that above-mentioned preparation method obtains.
The present invention provides application of the above-mentioned phosphorus nitrogen boron Ternary Expansive flame retardant products as fire retardant.
The present invention is advantageous in that：The phosphorus nitrogen boron ternary flame retardant obtained using preparation method of the present invention, with excellent
While different flame retardant effect, also preferable smoke suppressing effect, when fire occurs, the survival rate of people can be greatly improved,
Have great application prospect.
Embodiment
The present invention, rather than limitation the scope of the present invention are further illustrated below by embodiment.
Embodiment 1
Precise melamine, phosphoric acid, boric acid, crosslinking agent and surfactant（The mol ratio of melamine and phosphoric acid is
1:1, the mol ratio of melamine and boric acid is 1:1, the mol ratio of melamine and crosslinking agent is 1:0.03, melamine and table
The mass ratio of face activating agent is 1:0.05, crosslinking agent is season pentanediol, and surfactant is lauryl sodium sulfate）, by itself plus
Enter in a certain amount of distilled water（The mass ratio of melamine and distilled water is 1:100）.Stir, be then added into overcritical
In reactor, control in 80 DEG C and 20MPa reaction 3h.Filtration drying produces phosphorus nitrogen boron ternary flame retardant after dischargeing pressure.
Embodiment 2
Precise melamine, phosphoric acid, boric acid, crosslinking agent and surfactant（The mol ratio of melamine and phosphoric acid is
1:2, the mol ratio of melamine and boric acid is 1:0.8, the mol ratio of melamine and crosslinking agent is 1:0.05, melamine with
The mass ratio of surfactant is 1:0.01, crosslinking agent is cyanuric acid, and surfactant is dodecyl sodium sulfate）, by itself plus
Enter in a certain amount of distilled water（The mass ratio of melamine and distilled water is 1:300）.Stir, be then added into overcritical
In reactor, control in 70 DEG C and 35MPa reaction 2.5h.Filtration drying produces phosphorus nitrogen boron ternary flame retardant after dischargeing pressure.
Embodiment 3
Precise melamine, phosphoric acid, boric acid, crosslinking agent and surfactant（The mol ratio of melamine and phosphoric acid is
1:1.5, the mol ratio of melamine and boric acid is 1:2, the mol ratio of melamine and crosslinking agent is 1:0.08, melamine with
The mass ratio of surfactant is 1:0.01, crosslinking agent is cellulose, and surfactant is cetyl trimethylammonium bromide）,
It is added into a certain amount of distilled water（The mass ratio of melamine and distilled water is 1:300）.Stir, be then added into
In supercritical reaction kettle, control in 65 DEG C and 30MPa reaction 2h.Dischargeing filtration drying after pressure, to produce phosphorus nitrogen boron ternary fire-retardant
Agent.
Embodiment 4
Precise melamine, phosphoric acid, boric acid, crosslinking agent and surfactant（The mol ratio of melamine and phosphoric acid is
1:2, the mol ratio of melamine and boric acid is 1:0.7, the mol ratio of melamine and crosslinking agent is 1:0.04, melamine with
The mass ratio of surfactant is 1:0.08, crosslinking agent is cyanuric acid, and surfactant is APES）, by its
Add in a certain amount of distilled water（The mass ratio of melamine and distilled water is 1:250）.Stir, be then added into super face
In boundary's reactor, control in 60 DEG C and 40MPa reaction 4h.Filtration drying produces phosphorus nitrogen boron ternary flame retardant after dischargeing pressure.
The flame retardant effect contrast of the fire retardant that on the market prepared by fire retardant and the inventive method of subordinate list 1, using polystyrene
As substrate resin, addition is 30 parts, wherein fire retardant is the 1 of melamine phosphate and Firebrake ZB on the market:1 mixing
Fire retardant.
。
Claims (3)
1. a kind of preparation method of phosphorus nitrogen boron Ternary Expansive fire retardant, using supercritical methanol technology, it is characterised in that including following step
Suddenly：
1）A certain amount of melamine, phosphoric acid, boric acid, crosslinking agent and surfactant are accurately weighed according to formula, is added into one
In quantitative distilled water, stirring makes it fully dissolve, and obtains mixed solution；Wherein, melamine and phosphoric acid, boric acid, crosslinking agent rub
You are than being 1:（0.2~5）:（0.2~5）:（0.001~0.5）, the mass ratio of melamine and surfactant is 1: 0.001
~0.05, the mass ratio of melamine and distilled water is 1:50~500, crosslinking agent is in season pentanediol, cyanuric acid, cellulose etc.
One or its mixing, surfactant be lauryl sodium sulfate, cetyl trimethylammonium bromide, alkylphenol-polyethenoxy
One in ether, dodecyl sodium sulfate or its mixing；
2）Above-mentioned mixed solution is poured into supercritical reaction kettle, opens CO 2 high pressure pump, and raises temperature of reaction kettle, is made
Obtain reactor and keep 30~100 DEG C of 10~60MPa pressure and temperatures, react 1~5 hour in this case；
3）Open pressure relief opening and the pressure in supercritical reaction kettle is dropped into normal pressure, turbid solution is obtained, by the solution filtration washing
Vacuum drying is the phosphorus nitrogen boron Ternary Expansive fire retardant.
A kind of 2. phosphorus nitrogen boron Ternary Expansive fire retardant that preparation method described in claim 1 obtains.
3. one kind application of the phosphorus nitrogen boron Ternary Expansive fire retardant as fire retardant according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710652426.9A CN107556530B (en) | 2017-08-02 | 2017-08-02 | A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710652426.9A CN107556530B (en) | 2017-08-02 | 2017-08-02 | A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107556530A true CN107556530A (en) | 2018-01-09 |
| CN107556530B CN107556530B (en) | 2019-04-16 |
Family
ID=60975072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710652426.9A Active CN107556530B (en) | 2017-08-02 | 2017-08-02 | A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107556530B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504235A (en) * | 2018-11-15 | 2019-03-22 | 佛山科学技术学院 | A kind of environmental protection flame retardant coating suitable for electronic product |
| CN111849117A (en) * | 2020-07-17 | 2020-10-30 | 浙江王氏科技有限公司 | Flame-retardant plastic and processing technology thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306545A (en) * | 2008-06-13 | 2008-11-19 | 昆明理工大学 | Wood fire retardant and preparation method thereof |
| CN104961701A (en) * | 2015-06-26 | 2015-10-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing nano phosphorus-nitrogen inrumescent flame retardant by means of supercritical method |
| 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 |
-
2017
- 2017-08-02 CN CN201710652426.9A patent/CN107556530B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306545A (en) * | 2008-06-13 | 2008-11-19 | 昆明理工大学 | Wood fire retardant and preparation method thereof |
| CN104961701A (en) * | 2015-06-26 | 2015-10-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing nano phosphorus-nitrogen inrumescent flame retardant by means of supercritical method |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 杜春霖，洪哲: ""磷酸三聚氰胺硼酸盐阻燃剂的合成"", 《染料与染色》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504235A (en) * | 2018-11-15 | 2019-03-22 | 佛山科学技术学院 | A kind of environmental protection flame retardant coating suitable for electronic product |
| CN111849117A (en) * | 2020-07-17 | 2020-10-30 | 浙江王氏科技有限公司 | Flame-retardant plastic and processing technology thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107556530B (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104086913B (en) | The preparation method of difficult combustion eps foam heat preservation plate material and sheet material thereof | |
| CN103333370B (en) | Organic and inorganic microcapsule coating expansible graphite preparation method | |
| CN102391588B (en) | High-flame-retardant low-smoke-density polystyrene foam compound heat insulating material and preparation method thereof | |
| Yu et al. | Effects of boric acid and/or borax treatments on the fire resistance of bamboo filament | |
| CN103878847B (en) | A kind of difficult firebrand material and its preparation method and application | |
| CN112225985B (en) | Flame-retardant PP composite material and preparation method thereof | |
| US20120295996A1 (en) | Fire Retardant Composition | |
| CN102975251A (en) | Flame retardant for wood as well as preparation method and applications of flame retardant for wood | |
| CN105670231B (en) | The preparation method of inflatable carbonitride fire retarding epoxide resin | |
| Cheng et al. | Effect of chitosan/lignosulfonate microencapsulated red phosphorus on fire performance of epoxy resin | |
| Wu et al. | Design of P-decorated POSS towards flame-retardant, mechanically-strong, tough and transparent epoxy resins | |
| CN108641033A (en) | A kind of fire-retardant linear thermal expansion microcapsules and preparation method thereof | |
| CN105751346A (en) | Thin flame-retardant medium-density fiberboard and preparation method thereof | |
| CN107556530A (en) | A kind of phosphorus nitrogen boron Ternary Expansive fire retardant preparation method and products thereof and application | |
| CN102294105A (en) | Preparation method of novel anti-solvent aqueous film forming foam extinguishing agent | |
| CN104072759A (en) | P-N expanded reaction type flame retardant and preparation method thereof | |
| CN107955155B (en) | Nitrogen-boron structure type flame-retardant polyether polyol and preparation method and application thereof | |
| CN104210002B (en) | A kind of composite flame-retardant agent, preparation method and its usage | |
| CN110358141A (en) | A kind of preparation method of fire retardant high molecular material | |
| CN110306380A (en) | A kind of waterproof flame-retardant paint and preparation method thereof for corrugated board | |
| CN104961701A (en) | Method for preparing nano phosphorus-nitrogen inrumescent flame retardant by means of supercritical method | |
| CN102975253A (en) | Wood fire retardant, preparation method and applications thereof | |
| CN102975252A (en) | Wood treatment agent and preparation method thereof | |
| CN106986896B (en) | Star-like boron phosphazene derivative expansion type flame retardant and preparation method thereof | |
| CN109134939A (en) | A kind of piperazine modified lignin resin/magaldrate dual cladding red phosphorus combustion inhibitor and its application in PP |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |