CN109180952A - A kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme and preparation method thereof - Google Patents
A kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme and preparation method thereof Download PDFInfo
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- CN109180952A CN109180952A CN201810783112.7A CN201810783112A CN109180952A CN 109180952 A CN109180952 A CN 109180952A CN 201810783112 A CN201810783112 A CN 201810783112A CN 109180952 A CN109180952 A CN 109180952A
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- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
Abstract
The invention belongs to technical field of flame retardant, relate generally to a kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants and preparation method thereof of graft grapheme, and 3- aminopropyl-triethoxysilane is synthesized octa-aminopropyl cage type silsesquioxane by hydrolytic condensation polymerization；Graphene is prepared into graphene oxide after chemical oxidation and removing by improved hummers method；The graft product 1 through situ aggregation method anamorphic zone reactive functional by the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy and graphene oxide；Octa-aminopropyl cage type silsesquioxane synthesizes the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme with graft product 1 through situ aggregation method.The preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme prepared by the present invention has many advantages, such as that preparation process is simple, safety and environmental protection, it can be widely applied to the fire-retardant of the fields such as electronic apparatus, automobile, cable, packaging, aviation, there is vast potential for future development.
Description
Technical field
The invention belongs to technical field of flame retardant, relate generally to a kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme
And preparation method thereof.
Background technique
Polyhedral oligomeric silsesquioxane (POSS) is a kind of nano-organosilicon material, has unique polyhedron cage modle knot
Structure, cage modle skeleton are made of Si-O-Si key, and the Si atom of polyhedron apex angle can connect different organo-functional groups.This spy
Different structure makes POSS have unique physicochemical properties, i.e., inorganic kernel and the organic and inorganic that organo-functional group is constituted are miscellaneous
Changing structure assigns polyhedral oligomeric silsesquioxane excellent heat resistance and higher reactivity；Nano-grade size assigns its spy
Different thermodynamics, magnetics and optical property；By MOLECULE DESIGN, various functionalization polyhedral oligomeric silsesquioxanes are prepared, it can
To assign its different reactivity and functionality.Compared with other polymers, organosilicon polymer and polyhedral oligomeric silicon sesquialter oxygen
The compatibility of alkane is more preferable, and by method physically or chemically, functionalization polyhedral oligomeric silsesquioxane is applied to macromolecule material
The preparation and modification of material, can significantly improve the physical and chemical performance of material, widen its application field.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) contains active P-H key, with alkenyl, alkynes
Base, epoxy group, carbonyl, imines, cyano, amine etc. can react, and phospho hetero phenanthrene group have non-co-planar, with intramolecular or
The features such as interaction, massive structure, the molecular polarity of intermolecular group, as modified group for constructing small molecule
And polymer, molecule can be made to obtain flame-retarding characteristic, unique aggregated structure, luminescent properties and good organic-dissolvable respectively
Can, therefore, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as a kind of environmental protection fire retarding agent, in addition to having
Halogen, low toxicity, it is smokeless the features such as, also have very high flame retarding efficiency.Therefore, no matter from environmental protection or reduce cost consideration,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide base flame-retardant system all shows apparent advantage, has good answer
Use prospect.
Graphene oxide (GO) is the intermediate product that graphene is prepared using oxidation-reduction method, by with polymer is compound can
Mechanical property, the hot property etc. for improving polymer, have obtained good application in field of compound material.However, research discovery oxygen
Graphite alkene in other fields such as chemistry, chemical industry in addition to equally showing other than Material Field is to be used to prepare the presoma of graphene
Good application prospect is shown.Graphene oxide, which removes, has special two-dimensional slice structure, and surface is also contained a large amount of oxygen-containing
Functional group, this not only assigns its good dispersion performance in polar solvent, but also assigns its good surface reaction activity,
This is just that structure basis has been established in the chemical reaction of its functionalization and participation synthesis noval chemical compound.
High polymer material chemical composition is based on the elements such as carbon, hydrogen, oxygen, and most limit oxygen index are low, easily fire
It burns and causes fire, can bring about great losses to the people's lives and property, it is therefore necessary to carry out fire-retardant, development to high molecular material
With the high performance halogen-free flame retardants of exploitation.Fire retardant for high molecular material mainly include halogenated flame retardant, inorganic fire retardants,
Halogen-free flame retardants etc..Traditional halogenated flame retardant advantage is that flame retarding efficiency is higher, additive amount is less, but halogenated flame retardant is in fire-retardant system
Product can discharge a large amount of toxic, pernicious gases and smog when burning, seriously damage personal and property safety.It is inorganic in halogen-free flame retardants
Fire retardant such as magnesium hydroxide with high security, suppression cigarette, it is nontoxic, inexpensive the advantages that, but the disadvantage is that additive amount is big (generally 50%
~60%) it, is affected to material mechanical and electric property, when burning is also easy to produce molten drop.In addition to inorganic fire retardants, other Halogens
Fire retardant such as nitrogen phosphorus system is preferable with flame retardant effect, low cigarette, nontoxic, additive amount relatively Shaozheng are gradually concerned by people,
Especially have the advantages that other type fire retardants are incomparable on solving the flame-retarded molten drop problem of composite material.Therefore, with
Growing interest of the people to health and environmental protection, halogenated flame retardant will be gradually forbidden to use, the sheet of development environment close friend
The multielement synergistic halogen-free intumescent flame-retardant compound of sign type or addition type has highly important scientific meaning and wide city
Prospect and very necessary.
The developing direction of the following fire retardant is: complying with environmental requirement, develops the substitution of halogenated flame retardant such as deca-BDE
For example certain halogen-free flame retardants and expansion type flame retardant for having special performance of product, the good mobility of imparting flame retarded polymeric material,
Low-permeability, compatibility, easily recycling and good dimensional stability.
In order to preferably utilize the high thermal stability of POSS, DOPO and GO, suppression cigarette suppression to fire and can be catalyzed in polymer surfaces
Charcoal is melted into the effect of the protection layer of charcoal of high quality, and the reaction between three between the functional group with strong reactivity is utilized in we,
POSS and DOPO is grafted on a kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants in GO lamellar structure by preparation.The fire retardant has
High stability and structural controllability, to realize the highly effective flame-retardant of system, this fire retardant is at home and abroad had not been reported.
Summary of the invention
The present invention solves the technical problem of: can generate a large amount of smog when halogen flame burns at present and discharge has
Poison, corrosive hydrogen halide, causes secondary pollution；Although halogen-free flame-retardant system such as aluminium hydroxide, magnesium hydroxide etc. is no
Toxic hydrogen halide is generated, but its flame-retarded efficiency is low, need very big loading, there could be anti-flammability, influence material
Processing performance and mechanical property；On the other hand, there is dispersibility and between polymeric matrix in general anti-flaming nano composite material
Consistency problem, limit its use.For this purpose, the present invention provides a kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme
Preparation method, preparation process is simple, environmental-friendly.
A kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme provided by the invention is octa-aminopropyl cage type silicon sesquialter
Miscellaneous -10- phospho hetero phenanthrene -10- oxide three's the situ-formed graft of oxygen alkane, graphene oxide, 9,10- dihydro-9-oxy forms.
The preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of the graft grapheme, including following procedure:
Step 1: by 3- aminopropyl-triethoxysilane under acetonitrile and tetraethyl ammonium hydroxide catalytic action hydrolytic condensation
It polymerize synthetic reaction intermediate product 1, i.e. octa-aminopropyl cage type silsesquioxane；Synthesize the anti-of octa-aminopropyl cage type silsesquioxane
Answering temperature is 50-70 DEG C, and preferably 55-65 DEG C, catalysts are effumability and can regulate and control the triethylamine of solution ph, acetonitrile
At least one of with tetraethyl ammonium hydroxide solution.Reaction product is washed with acetone soln, is extracted by methanol.
Step 2: by graphene by improved hummers method the concentrated sulfuric acid, concentrated phosphoric acid and potassium permanganate effect under through changing
Graphene oxide is prepared after learning oxidation and removing；The reaction temperature for synthesizing graphene oxide is no more than 95 DEG C.The present invention synthesizes oxygen
Oxidant metering is than being the concentrated sulfuric acid: concentrated phosphoric acid=9/1 in graphite alkene solution.
Step 3: the graphene oxide that the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy and step 2 are synthesized in
Reaction intermediate 2 through situ aggregation method anamorphic zone reactive functional under nitrogen protection in tetrahydrofuran solution；
Step 4: by the reaction intermediate 2 synthesized in reaction intermediate 1 and step 3 synthesized in step 1 in four
A kind of graft grapheme is synthesized by situ aggregation method under nitrogen protection through dicyclohexylcarbodiimide catalysis in hydrogen tetrahydrofuran solution
Nitrogen phosphorus silicon synergistic halogen-free flame retardants, wherein above-mentioned halogen-free flame retardants be by octa-aminopropyl cage type silsesquioxane, graphite oxide
Compound made of the miscellaneous -10- phospho hetero phenanthrene -10- oxide three grafting of alkene, 9,10- dihydro-9-oxy.
The required cleaning solvent of the present invention is anhydrous methanol and tetrahydrofuran.
Catalyst needed for step 4 is dicyclohexylcarbodiimide.
Synthetic reaction reactive intermediate 2 and Nitrogen-and Phosphorus-containing silicon synergistic halogen-free flame retardants need to be protected in tetrahydrofuran solution with nitrogen
Shield, and filtered with 0.2-0.45 microns of polytetrafluoroethylene film.
Nitrogen phosphorus silicon synergistic halogen-free flame retardants of a kind of graft grapheme of the present invention and preparation method thereof has following excellent
Point:
1, the nitrogenous-phosphorus-Halogen of silicon ignition-proof element on the surface of graphene is realized for the first time to be combined to, and can give full play to three kinds
The barrier action of polynary the synergistic fire retardation and graphene of ignition-proof element, with important science and actual innovative significance.
2, generated in combustion process without noxious pollutant, and smoke-producing amount is few, environment-friendly high-efficiency, use value with higher and
Good application prospect.
3, under the conditions of long term high temperature, stability and flame resistance effect are still significant, can be suitably used for more extreme environments.
4, it can be compounded with common expansibility flame-proof agent, metal fire retardant, biomass fire retardant and play synergistic fire retardation, drop
The additive amount of low fire retardant simultaneously improves flame retardant effect, widens it in the application of flame retardant area.
5, with inexpensive, the environmental-friendly graphene oxide of preparation, the miscellaneous -10- phospho hetero phenanthrene -10- of 9,10- dihydro-9-oxy
Oxide, octa-aminopropyl cage type silsesquioxane synthesize Trinitarian Nitrogen-and Phosphorus-containing silicon synergistic Halogen resistance as halogen-free flame retardants
Agent is fired, there is environmentally protective, cheap, sustainable development advantage.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made according to the present invention.
Embodiment 1
500ml there-necked flask is placed in 50 DEG C of constant temperature waters, then by 40ml distilled water, 10ml isopropanol, 2ml acetonitrile,
10ml triethylamine and 2ml tetraethyl ammonium hydroxide are added sequentially in there-necked flask, and moderate-speed mixer makes to be uniformly mixed.By 80g 3-
Aminopropyl triethoxysilane is added dropwise in the mixed liquor, in 50 DEG C of constant temperature back flow reaction 12h.It after reaction, will be upper
Reaction solution vacuum distillation is stated, standing there are a large amount of white solids to be precipitated.It is filtered through decompression, acetone washing is finally extracted with methanol.Very
Sky drying finally obtains yellow solid product octa-aminopropyl cage type silsesquioxane, i.e. reaction intermediate 1.
Graphene oxide 500mg is taken to be added in 500ml tetrahydrofuran, ultrasonic disperse 1h.By dispersion liquid be transferred to filled with
In the three-necked flask of nitrogen, then it is added thereto containing 5g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
100ml tetrahydrofuran solution, and stir.Mixed liquor is heated to 50 DEG C of back flow reaction 12h under a nitrogen.Terminate in functionalization
Afterwards, mixed liquor filters out product by 0.2 μm of polytetrafluoroethylene film.Then it is thoroughly washed simultaneously with anhydrous tetrahydro furan and acetone
Remaining reactant is removed, is finally dried in vacuo at 80-90 DEG C, reaction dissolvent is removed, obtains reaction intermediate 2.
The reaction intermediate 2 of preparation is initially dispersed in tetrahydrofuran 500ml and is ultrasonically treated 2h and obtains suspension, so
Afterwards by reaction intermediate 1 and N, N- dicyclohexyl carbodiimide is added in above-mentioned gained suspension, is ultrasonically treated 1h.It will
Mixture under nitrogen protection at 65 DEG C magnetic agitation and flow back for 24 hours.After reaction, solution is passed through into 0.2 μm of polytetrafluoro
Vinyl film is filtered by vacuum, and is washed three times with enough anhydrous methanols and anhydrous tetrahydro furan.Finally by obtained solid true
It is dried overnight removing solvent under the conditions of 80 DEG C and 0.1MPa in empty baking oven, obtains product.
Embodiment 2
500ml there-necked flask is placed in 60 DEG C of constant temperature waters, then by 60ml distilled water, 20ml isopropanol, 2ml acetonitrile,
10ml triethylamine and 2ml tetraethyl ammonium hydroxide are added sequentially in there-necked flask, and moderate-speed mixer makes to be uniformly mixed.By 100g 3-
Aminopropyl triethoxysilane is added dropwise in the mixed liquor, 60 DEG C of constant temperature back flow reactions for 24 hours.It after reaction, will be upper
Reaction solution vacuum distillation is stated, standing there are a large amount of white solids to be precipitated.It is filtered through decompression, acetone washing is finally extracted with methanol.Very
Sky drying finally obtains yellow solid product octa-aminopropyl cage type silsesquioxane, i.e. reaction intermediate 1.
Graphene oxide 500mg is taken to be added in 500ml tetrahydrofuran, ultrasonic disperse 1h.By dispersion liquid be transferred to filled with
In the three-necked flask of nitrogen, then it is added thereto containing 10g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
100ml tetrahydrofuran solution, and stir.Mixed liquor is heated to 60 DEG C, and back flow reaction is for 24 hours under a nitrogen.Terminate in functionalization
Afterwards, mixed liquor filters out product by 0.45 μm of polytetrafluoroethylene film.Then it is thoroughly washed with anhydrous tetrahydro furan and acetone
And remaining reactant is removed, it is finally dried in vacuo at 80-90 DEG C, removes reaction dissolvent, obtain reaction intermediate 2.
The reaction intermediate 2 of preparation is initially dispersed in tetrahydrofuran 500ml and is ultrasonically treated 2h and obtains suspension, so
Afterwards by reaction intermediate 1 and N, N- dicyclohexyl carbodiimide is added in above-mentioned gained suspension, is ultrasonically treated 1h.It will
Mixture magnetic agitation and the 36h that flows back at 75 DEG C under nitrogen protection.After reaction, solution is passed through into 0.45 μm of polytetrafluoro
Vinyl film is filtered by vacuum, and is washed three times with enough anhydrous methanols and anhydrous tetrahydro furan.Finally by obtained solid true
It is dried overnight removing solvent under the conditions of 80 DEG C and 0.1MPa in empty baking oven, obtains product.
Embodiment 3
500ml there-necked flask is placed in 65 DEG C of constant temperature waters, then by 80ml distilled water, 30ml isopropanol, 2ml acetonitrile,
10ml triethylamine and 2ml tetraethyl ammonium hydroxide are added sequentially in there-necked flask, and moderate-speed mixer makes to be uniformly mixed.By 120g 3-
Aminopropyl triethoxysilane is added dropwise in the mixed liquor, in 65 DEG C of constant temperature back flow reaction 36h.It after reaction, will be upper
Reaction solution vacuum distillation is stated, standing there are a large amount of white solids to be precipitated.It is filtered through decompression, acetone washing is finally extracted with methanol.Very
Sky drying finally obtains yellow solid product octa-aminopropyl cage type silsesquioxane, i.e. reaction intermediate 1.
Graphene oxide 1g is taken to be added in 500ml tetrahydrofuran, ultrasonic disperse 1h.Dispersion liquid is transferred to filled with nitrogen
Three-necked flask in, then the 100ml containing 15g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added thereto
Tetrahydrofuran solution, and stir.Mixed liquor is heated to 65 DEG C of back flow reaction 36h under a nitrogen.After functionalization, mix
It closes liquid and product is filtered out by 0.22 μm of polytetrafluoroethylene film.Then it is thoroughly washed and is removed with anhydrous tetrahydro furan and acetone
Remaining reactant is finally dried in vacuo at 80-90 DEG C, is removed reaction dissolvent, is obtained reaction intermediate 2.
The reaction intermediate 2 of preparation is initially dispersed in tetrahydrofuran 500ml and is ultrasonically treated 2h and obtains suspension, so
Afterwards by reaction intermediate 1 and N, N- dicyclohexyl carbodiimide is added in above-mentioned gained suspension, is ultrasonically treated 1h.It will
Mixture magnetic agitation and the 48h that flows back at 80 DEG C under nitrogen protection.After reaction, solution is passed through into 0.22 μm of polytetrafluoro
Vinyl film is filtered by vacuum, and is washed three times with enough anhydrous methanols and anhydrous tetrahydro furan.Finally by obtained solid true
It is dried overnight removing solvent under the conditions of 80 DEG C and 0.1MPa in empty baking oven, obtains product.
Embodiment 4
500ml there-necked flask is placed in 65 DEG C of constant temperature waters, then by 80ml distilled water, 30ml isopropanol, 2ml acetonitrile,
It is added sequentially in there-necked flask with 2ml tetraethyl ammonium hydroxide, moderate-speed mixer, makes to be uniformly mixed.By three second of 120g3- aminopropyl
Oxysilane is added dropwise in the mixed liquor, in 65 DEG C of constant temperature back flow reaction 36h.After reaction, above-mentioned reaction solution is subtracted
Pressure distillation, standing have a large amount of white solids to be precipitated.It is filtered through decompression, acetone washing is finally extracted with methanol.Vacuum drying is final
Obtain yellow solid product octa-aminopropyl cage type silsesquioxane, i.e. reaction intermediate 1.
Graphene oxide 1g is taken to be added in 500ml tetrahydrofuran, ultrasonic disperse 1h.Dispersion liquid is transferred to filled with nitrogen
Three-necked flask in, then thereto be added contain 20g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 100ml tetra-
Hydrogen tetrahydrofuran solution, and stir.Mixed liquor is heated to 70 DEG C of back flow reaction 36h under a nitrogen.After functionalization, mixing
Liquid filters out product by 0.3 μm of polytetrafluoroethylene film.Then it is thoroughly washed and is removed residual with anhydrous tetrahydro furan and acetone
The reactant stayed is finally dried in vacuo at 80-90 DEG C, is removed reaction dissolvent, is obtained reaction intermediate 2.
The reaction intermediate 2 of preparation is initially dispersed in tetrahydrofuran 500ml and is ultrasonically treated 2h and obtains suspension, so
Afterwards by reaction intermediate 1 and N, N- dicyclohexyl carbodiimide is added in above-mentioned gained suspension, is ultrasonically treated 1h.It will
Mixture magnetic agitation and the 48h that flows back at 80 DEG C under nitrogen protection.After reaction, solution is passed through into 0.3 μm of polytetrafluoro
Vinyl film is filtered by vacuum, and is washed three times with enough anhydrous methanols and anhydrous tetrahydro furan.Finally by obtained solid true
It is dried overnight removing solvent under the conditions of 80 DEG C and 0.1MPa in empty baking oven, obtains product.
Embodiment 5
500ml there-necked flask is placed in 65 DEG C of constant temperature waters, then by 80ml distilled water, 20ml isopropanol, 2ml acetonitrile,
10ml triethylamine is added sequentially in there-necked flask, moderate-speed mixer, makes to be uniformly mixed.By 120g 3- aminopropyl triethoxysilane
Be added dropwise in the mixed liquor, 65 DEG C of constant temperature back flow reactions for 24 hours.After reaction, above-mentioned reaction solution is evaporated under reduced pressure, it is quiet
It is equipped with white solid precipitation.It is filtered through decompression, acetone washing is finally extracted with methanol.Vacuum drying finally obtains yellow solid
Product octa-aminopropyl cage type silsesquioxane, i.e. reaction intermediate 1.
Graphene oxide 2g is taken to be added in 500ml tetrahydrofuran, ultrasonic disperse 1h.Dispersion liquid is transferred to filled with nitrogen
Three-necked flask in, then thereto be added contain 20g 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 100ml tetra-
Hydrogen tetrahydrofuran solution, and stir.Mixed liquor is heated to 70 DEG C of back flow reaction 36h under a nitrogen.After functionalization, mixing
Liquid filters out product by 0.4 μm of polytetrafluoroethylene film.Then it is thoroughly washed and is removed residual with anhydrous tetrahydro furan and acetone
The reactant stayed is finally dried in vacuo at 80-90 DEG C, is removed reaction dissolvent, is obtained reaction intermediate 2.
The reaction intermediate 2 of preparation is initially dispersed in tetrahydrofuran 500ml and is ultrasonically treated 2h and obtains suspension, so
Reaction intermediate 1 is added in above-mentioned gained suspension afterwards, is ultrasonically treated 1h.By mixture under nitrogen protection in 80 DEG C
Lower magnetic agitation and the 48h that flows back.After reaction, solution is filtered by vacuum by 0.4 μm of polytetrafluoroethylene film, and with enough
Measure anhydrous methanol and anhydrous tetrahydro furan washing three times.Finally by obtained solid in vacuum drying oven in 80 DEG C and 0.1MPA condition
Under be dried overnight removing solvent, obtain product.
The above content is combine specific preferred embodiment to the further description done of the present invention, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (8)
1. a kind of nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme, which is characterized in that be octa-aminopropyl cage type silicon sesquialter oxygen
Miscellaneous -10- phospho hetero phenanthrene -10- oxide three's the situ-formed graft of alkane, graphene oxide, 9,10- dihydro-9-oxy forms.
2. the preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme according to claim 1, feature exist
In, including following procedure:
(1) 3- aminopropyl-triethoxysilane is passed through into hydrolytic condensation polymerization synthetic reaction reactive intermediate 1: octa-aminopropyl
Cage type silsesquioxane；
(2) graphene is prepared into graphene oxide after chemical oxidation and removing by improved hummers method；
(3) by the miscellaneous -10- phospho hetero phenanthrene -10- oxide of 9,10- dihydro-9-oxy and graphene oxide through situ aggregation method synthetic reaction
Reactive intermediate 2；
(4) reactive intermediate 1 and reactive intermediate 2 are synthesized into Nitrogen-and Phosphorus-containing silicon synergistic halogen-free flameproof through situ aggregation method
Agent.
3. the preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme according to claim 2, feature exist
In step (1) is synthesized the reaction of octa-aminopropyl cage type silsesquioxane by 3- aminopropyl-triethoxysilane, and catalyst is easy
Volatility and the triethylamine, acetonitrile and tetraethyl ammonium hydroxide solution that solution PH can be regulated and controled.
4. the preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme according to claim 3, feature exist
In the reaction time that step (1) synthesizes octa-aminopropyl cage type silsesquioxane is 1-3 days, and reaction temperature is 50-70 DEG C, is used in combination
Acetone soln washing reaction product, is finally extracted with methanol.
5. the preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme according to claim 2, feature exist
In the reaction temperature that step (2) prepares graphene oxide is no more than 95 DEG C；It synthesizes oxidant in graphene oxide solution and measures ratio
For the concentrated sulfuric acid: concentrated phosphoric acid=9/1, and potassium permanganate is slowly added in batches, hydrogen peroxide is eventually adding.
6. the preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme according to claim 2, feature exist
It is 1-5 days in the reaction time that, step (3) prepares reactive intermediate 2, with being closed under nitrogen protection in tetrahydrofuran solution
At product is filtered by vacuum with 0.2-0.45 microns of polytetrafluoroethylene film.
7. the preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of graft grapheme according to claim 2, feature exist
In step (4) synthesizes in Nitrogen-and Phosphorus-containing silicon synergistic halogen-free flame retardants, is catalyzed with dicyclohexylcarbodiimide, in tetrahydrofuran solution
It is middle with being synthesized under nitrogen protection.
8. the preparation method of the nitrogen phosphorus silicon synergistic halogen-free flame retardants of the graft grapheme according to claim 2 or 7, feature
It is, step (4) further includes washing product anhydrous methanol and tetrahydrofuran for several times, with 0.2-0.45 microns of polytetrafluoroethyl-ne
Alkene film vacuum filters.
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| CN110041612A (en) * | 2019-04-01 | 2019-07-23 | 四川大学 | Oligomeric silsesquioxane increase-volume and synergistic halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN111269461A (en) * | 2020-03-09 | 2020-06-12 | 贵州民族大学 | Phosphaphenanthrene silane grafted and modified graphene and preparation method thereof |
| CN111662475A (en) * | 2020-06-17 | 2020-09-15 | 山东师范大学 | Intelligent early warning flame-retardant material prepared from modified high-molecular polymer, and preparation method and application thereof |
| CN112341825A (en) * | 2020-11-06 | 2021-02-09 | 陕西科技大学 | Environment-friendly flame-retardant ternary composite material POSS/GO/ZIF-8 and preparation method thereof |
| CN112938955A (en) * | 2021-04-02 | 2021-06-11 | 青岛量子元基环保科技有限公司 | Chemical preparation method of single-layer porous graphene |
| CN115247371A (en) * | 2021-04-26 | 2022-10-28 | 北京服装学院 | Graphene oxide-based flame retardant and preparation method thereof, graphene oxide-based flame-retardant copolyester and preparation method thereof |
| CN115477827A (en) * | 2022-10-18 | 2022-12-16 | 北京服装学院 | Preparation method and application of phosphorus-nitrogen-silicon composite intumescent flame retardant |
| CN115536910A (en) * | 2022-09-29 | 2022-12-30 | 南京鸿瑞塑料制品有限公司 | Preparation method of DOPO derivative grafted graphene oxide/layered double hydroxide composite flame retardant |
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| CN110041612A (en) * | 2019-04-01 | 2019-07-23 | 四川大学 | Oligomeric silsesquioxane increase-volume and synergistic halogen-free flame retardant polypropylene composite material and preparation method thereof |
| CN110041612B (en) * | 2019-04-01 | 2021-03-30 | 四川大学 | Halogen-free flame-retardant polypropylene composite material compatibilized by oligomeric silsesquioxane and synergistic effect and preparation method thereof |
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| CN112938955A (en) * | 2021-04-02 | 2021-06-11 | 青岛量子元基环保科技有限公司 | Chemical preparation method of single-layer porous graphene |
| CN112938955B (en) * | 2021-04-02 | 2022-11-08 | 青岛量子元基环保科技有限公司 | Chemical preparation method of single-layer porous graphene |
| CN115247371A (en) * | 2021-04-26 | 2022-10-28 | 北京服装学院 | Graphene oxide-based flame retardant and preparation method thereof, graphene oxide-based flame-retardant copolyester and preparation method thereof |
| CN115247371B (en) * | 2021-04-26 | 2024-04-26 | 北京服装学院 | Graphene oxide-based flame retardant and preparation method thereof, and graphene oxide-based flame-retardant copolyester and preparation method thereof |
| CN115536910A (en) * | 2022-09-29 | 2022-12-30 | 南京鸿瑞塑料制品有限公司 | Preparation method of DOPO derivative grafted graphene oxide/layered double hydroxide composite flame retardant |
| CN115477827A (en) * | 2022-10-18 | 2022-12-16 | 北京服装学院 | Preparation method and application of phosphorus-nitrogen-silicon composite intumescent flame retardant |
| CN115477827B (en) * | 2022-10-18 | 2023-09-26 | 北京服装学院 | Preparation method and application of phosphorus-nitrogen-silicon composite intumescent flame retardant |
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