CN107417912A - Phosphorus nitrogen silicon expansion type flame retardant and its synthetic method containing triazine ring and cage structure - Google Patents
Phosphorus nitrogen silicon expansion type flame retardant and its synthetic method containing triazine ring and cage structure Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The present invention relates to a kind of phosphorus nitrogen silicon expansion type flame retardant and its synthetic method containing triazine ring and cage structure, its step is：Solvent is added in container, POCl3 is added and is dispersed with stirring, trioxa-l-phosphabicyclo [2.2.2] octane of 1 epoxide phospha, 4 methylol 2,6,7 and acid binding agent is progressively added dropwise, obtains the unitary substituent containing PEPA；Band diamine is added in another container or di-alcohols material mixes with solvent and acid binding agent, and the unitary substituent containing PEPA, isolated phosphorous diamines intermediate is slowly added dropwise；Solvent is added in the container equipped with reflux condenser etc., Cyanuric Chloride is added and is dispersed with stirring, amino silicane coupling agent and acid binding agent is progressively added dropwise, obtains siliceous unitary substituent；The mixture of phosphorous diamines intermediate and acid binding agent is slowly added dropwise in unitary substituent, it is the phosphorus nitrogen silicon expansion type flame retardant containing triazine ring and cage structure to cool down, wash, being dried to obtain pulverulent solids.It has certain degree of polymerization, and molecular weight is big, and the ratio of acid source, carbon source and source of the gas is more suitable in molecular structure, and neat coal amout is higher and the advantages that better heat stability.
Description
Technical field
The invention belongs to the technical field of environment-friendly halogen-free flame-proof product, and specifically, the present invention relates to one kind to contain triazine
Phosphorus-nitrogen-silicon the expansion type flame retardant and its synthetic method of ring and cage structure.
Background technology
High polymer material application is very extensive, is brought conveniently to production and living.But their flammable properties limit
Their uses in the higher occasion of flame-retardancy requirements, therefore, high polymer material is flame-retardant modified become its modification it is important in
One of hold.
Halogen containing flame-retardant, especially brominated flame-retardant have excellent fire resistance, but are produced during the burning of this based flame retardant
Substantial amounts of dense smoke, while corrosive gas is produced, environmental pollution is big.Consideration in terms of based on environmental protection, halogen-free flame retardants is developed, is subtracted
The toxic and harmful gas discharged during few fire retardant burning is particularly important.Expansion type flame retardant（IFR）It can be formed in burning
Fine and close layer of charcoal, play a part of heat-insulated oxygen barrier, reduce the release of toxic and harmful gas and smog, and can effectively prevent high score
A kind of generation of molten drop during sub- material combustion, it is considered to be environmental type fire retardant for having very much application prospect.Tradition
Expansion type flame retardant in, the water solubility of carbon forming agent is big, and easily migration, heat endurance be not high, it is necessary to further improve.
Triazine derivative is a kind of compound for being rich in tertiary carbon structure, has excellent carbon-forming performance.Triazines derive
The synthesis of thing is typically using Cyanuric Chloride as initiation material, by the regulation and control of reaction condition, obtains the three of different purposes and property
Piperazine analog derivative；Synthesis technique is simply ripe, cheap and easy to get, has cost advantage.
Most of patent using triazine derivative is used as carbon forming agent, such as：Japan Patent JP.Pat.No.0,
583,065, Al (1994), patent ZL200510010243.4《Macro molecular triazine series carbon forming foaming agent and its synthetic method》, specially
Profit《Triazine carbon forming agent of the chain structure containing aromatic series and preparation method thereof》（Publication number CN101586033A）All from different angles
Designed with mode and be prepared for triazines carbon forming agent, there is preferable effect.They need to answer with compoundings such as ammonium polyphosphates
For the fire-retardant of high polymer material, it is used alone without obvious flame retardant effect.
Patent 201210002709.6 discloses application of the siliceous triazines carbon forming agent in polypropylene, has preferably resistance
Fuel efficiency fruit.Patent CN103980315B discloses a kind of phosphorus-nitrogen-silicon compound containing triazine ring and preparation method thereof, the product
Phosphorus-nitrogen-silicon is concentrated on into an intramolecular, fire-retardant synergy is embodied, a chlorine be present in compound, reaction can be passed through
Fabric face is grafted to, therefore, suitable for being handled in fabrics flame resistance.But additive flame retardant is not suitable as in plastics, painting
The place such as material uses.
Therefore, silicon is introduced into fire retardant, the element such as the intensity of charcoal, phosphorus, silicon can be improved into is introduced into triazine ring and be advantageous to
Obtain more preferable flame retardant effect.
These patents and synthetic method are not suitable enough in the ratio that acid source-carbon source and source of the gas to some extent be present, into charcoal
The problems such as performance and fire resistance need to be continued to improve, therefore, it is necessary to develop performance more preferably fire retardant.
The content of the invention
The purpose of the present invention be overcome the deficiencies in the prior art and provide a kind of phosphorus-silicon containing triazine ring and cage structure-
Nitrogen expansion type combustion inhibitor, it has certain degree of polymerization, and molecular weight is big, in molecular structure the ratio of acid source, carbon source and source of the gas compared with
To be suitable, neat coal amout is higher and better heat stability；It is a still further object of the present invention to provide containing triazine ring and cage structure
The synthetic method of phosphorus-silicon-nitrogen expansion type combustion inhibitor.
In order to reach the purpose of the present invention, phosphorus-nitrogen-silicon expansion type flame-retarding of the invention containing triazine ring and cage structure
Agent, it is characterised in that its structural formula is as follows：
In formula：Y is NH or O；
R1 is one kind of the straight or branched alkyl containing 1-18 carbon, or R1 is to one kind in phenyl, a phenyl or adjacent phenyl；
R2 is amino silicane coupling agent, and amino silicane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
Base silane, γ-aminopropyltriethoxy diethoxy silane, γ-aminopropylsilane hydrolysate, γ-aminopropyltriethoxy dimethoxysilane,
N- phenyl-γ-aminopropyltrimethoxysilane, N- β-（Aminoethyl）- γ-aminopropyltriethoxy dimethoxysilane, N-N diethyl
Aminopropyl trimethoxysilane, N-N dimethyl aminopropyls trimethoxy silane, N- β-(aminoethyl)-aminopropyl trimethoxy silicon
Alkane, N- β-(aminoethyl)-aminopropyl triethoxysilane, γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane, γ-two
The aminocarbonyl propyl trimethoxy silane of ethene three, it is double-（γ-trimethoxy silicon propyl group）Amine, it is double-（γ-triethoxysilylpropyl）Amine,
γ-piperazinopropyl methyl dimethoxysilane, N- phenylaminomethyls triethoxysilane, γ-ethoxy of diethylin methyl three
One of which or their mixture in base silane.
In order to reach the purpose of the present invention, phosphorus-nitrogen-silicon expansion type flame-retarding of the invention containing triazine ring and cage structure
The synthetic method of agent, it is characterised in that including the following steps：
Step 1
Solvent is added in container, is cooled to -10 ~ 10 DEG C, adds POCl3（POCl3）And be dispersed with stirring, progressively it is added dropwise
1- epoxide phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane（PEPA）And acid binding agent, 1-4 hours are reacted, are obtained
To the unitary substituent containing PEPA（POCl2-PEPA）；Wherein POCl3（POCl3）, 1- epoxide phospha -4- methylol -2,6,
7- trioxa-l-phosphabicyclos [2.2.2] octane（PEPA）And the mol ratio of acid binding agent three is 1:1:1,1mol POCl3 50-
500mL solvent；
Step 2
Band diamine or di-alcohols material, solvent and acid binding agent are added in another container and is mixed, is cooled to -10-10 DEG C,
The unitary substituent containing PEPA obtained by step 1 is slowly added dropwise（POCl2-PEPA）, react 3-6 hours, it is isolated phosphorous
Diamines intermediate；Unitary substituent wherein containing PEPA（POCl2-PEPA）, diamine or mole of dihydric alcohol and acid binding agent
Than for 1:2:2-4；The 1mol unitary substituent containing PEPA（POCl2-PEPA）With 50-500mL solvent；
Step 3
By solvent be added to equipped with reflux condenser, agitator, constant pressure funnel container in, be cooled to -10 ~ 10 DEG C, add
Enter Cyanuric Chloride（CNC）And be dispersed with stirring, amino silicane coupling agent and acid binding agent is progressively added dropwise, pH is between 5-7 for control, reaction
Temperature control reacts 1-4 hours, obtains siliceous unitary substituent at -5 ~ 5 DEG C（CNC-Si）；Wherein Cyanuric Chloride（CNC）、
The mol ratio of amino silicane coupling agent and acid binding agent three are 1:1:1,1mol Cyanuric Chloride 50-500mL solvent；
Step 4
Under conditions of 40 ~ 50 DEG C, the phosphorous diamines intermediate that step 2 obtains is slowly added dropwise in the same container of step 3
With the mixture of acid binding agent, 3-6 hours to be reacted, then, are continuously heating to 80-130 DEG C, the reaction time is 5-10 hours, cooling,
Wash, be dried to obtain pulverulent solids, phosphorus-nitrogen-silicon expansion type flame retardant as containing triazine ring and cage structure；It is wherein siliceous
Unitary substituent（CNC-Si）, phosphorous intermediate and acid binding agent mol ratio be 1:1:2-3；1mol siliceous unitary substitution
Thing（CNC-Si）With 20-600mL solvent.
In the technical program, the solvent is acetone, acetonitrile, tetrahydrofuran, butanone, ethyl acetate, dioxane, three
One or both of chloromethanes, toluene, dimethylbenzene, trimethylbenzene, durene, dimethyl sulfoxide, DMF mix
Close liquid.
In the technical program, the acid binding agent is triethylamine, triethylene diamine, pyridine, N, in N- diisopropyl ethane
One kind.
The present invention compared with prior art the advantages of be：
1）Phosphorus is rich in the flame retardant mechanism, good acid source effect can be played, promote fire retardant into charcoal；The fire retardant contains triazine
The cage structure of ring structure and PEPA, there is good char forming ability, contain silicon compound in structure, can be formed during burning stronger
Layer of charcoal, meanwhile, be effectively combined with acid source, carbon source and source of the gas, played intramolecular flame retardant synergistic effect；
2）Product is white or white or buff powder, and yield is more than 90%, and 5% decomposition temperature is 300 under nitrogen atmosphere
More than DEG C；
3）Three source ratios of acid source, carbon source and source of the gas are reasonable in the fire retardant, product has good heat endurance, into charcoal and
Fire resistance, the layer of charcoal for the expansion densification for doing intensity can be formed in burning.
Embodiment
The embodiment of the present invention is described further below.Herein it should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but does not form limitation of the invention.In addition, invention described below
As long as involved technical characteristic does not form conflict can and is combined with each other each other in each embodiment.
Embodiment one
The synthesis step of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure is as follows：
Step 1
250mL acetonitriles are added in 1000mL, are cooled to -10 DEG C, add 153.33g（That is 1mol）POCl3
（POCl3）It is dispersed with stirring, 180g is progressively added dropwise（That is 1mol）1- epoxide phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos
[2.2.2] octane（PEPA）And 101.20g（1mol）Triethylamine, react 4 hours, obtain the unitary substituent containing PEPA
（POCl2-PEPA）；
Step 2
120.20g is added in another container（2mol）Ethylenediamine, 50mL acetonitrile and 202.40g（2mol）Triethylamine simultaneously
Mixing, is cooled to -10 DEG C, 296.83g is slowly added dropwise（1mol）The unitary substituent containing PEPA（POCl2-PEPA）, reaction 6
Hour, isolated phosphorous diamines intermediate；
Step 3
Equipped with reflux condenser, agitator, constant pressure funnel 1000mL there-necked flasks in, add 184.5g（1mol）Three
Polychlorostyrene cyanogen, 200mL acetonitrile is then added, there-necked flask is placed in oil bath, is sufficiently stirred, Cyanuric Chloride is uniformly dispersed, it is past
221.37 g are added dropwise in there-necked flask（That is 1mol）Gamma-aminopropyl-triethoxy-silane（KH550）, by 101.20g（1mol）'s
Triethylamine is added dropwise with constant pressure funnel, and pH is between 5-7 for control, and at -5 DEG C, the reaction time is 4 hours, is obtained for reaction temperature control
The siliceous unitary substituent of Cyanuric Chloride（CNC-Si）；
Step 4
The 344.03g that step 2 is obtained（1mol）Phosphorous diamines intermediate be dissolved in 200mL acetonitrile, be then progressively added dropwise
The siliceous unitary substituent of Cyanuric Chloride is housed to step 3（CNC-Si）There-necked flask in, while be added dropwise 101.20 g（1mol）
Triethylamine, reaction temperature control at 40 DEG C, react 6 hours, then proceed to increase the temperature to 80 DEG C, then 101.20 g are added dropwise
（1mol）Triethylamine, react 10 hours, obtain white precipitate, distillation water washing, drying, obtain white solid, that is, obtain
582.76 g phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure, yield 91.0%.
In the present embodiment, the structural formula of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure is：
Embodiment two
The synthesis step of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure is as follows：
Step 1
300mL acetonitriles are added in 1000mL, are cooled to 10 DEG C, add 153.33g（1mol）POCl3（POCl3）Stirring
It is scattered, 1- epoxide phospha -4- methylols -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane is progressively added dropwise（PEPA）180g（1mol）
With triethylamine 101.20g（1mol）Acetonitrile solution, react 1 hour, obtain the unitary substituent containing PEPA（POCl2-PEPA）；
Step 2
Butanediamine 176.30g is added in another container（2mol）With acetonitrile（50mL）, triethylamine 202.40g（2mol）Mixing
Thing, 10 DEG C are cooled to, the 296.83g obtained by step 1 is slowly added dropwise（1mol）The unitary substituent containing PEPA（POCl2-
PEPA）, react 3 hours, isolated phosphorous diamines intermediate；
Step 3
Equipped with reflux condenser, agitator, constant pressure funnel 1000mL there-necked flasks in, add 184.5g（1mol）Three
Polychlorostyrene cyanogen, 200mL acetonitrile is then added, there-necked flask is placed in oil bath, is sufficiently stirred, Cyanuric Chloride is uniformly dispersed, it is past
179.3 g are added dropwise in there-necked flask（That is 1mol）γ-aminopropyltrimethoxysilane（KH551）, by 101.20g（1mol）Three
Ethamine is added dropwise with constant pressure funnel, and pH is between 5-7 for control, and at 10 DEG C, the reaction time is 1 hour, obtains three for reaction temperature control
The siliceous unitary substituent of polychlorostyrene cyanogen（CNC-Si）；
Step 4
Step 2 is obtained into 358.03g（1mol）Phosphorous diamines intermediate be dissolved in 150mL acetonitrile, be then progressively added drop-wise to
Step 3 is equipped with siliceous unitary substituent（CNC-Si）There-necked flask in, while the g of triethylamine 101.20 is added dropwise（1mol）, reaction
Temperature control is reacted 3 hours at 50 DEG C, then proceedes to increase the temperature to 130 DEG C, and 101.20 g are being added dropwise（1mol）Three second
Amine, react 5 hours, obtain white precipitate, distillation water washing, drying, obtain white solid, that is, obtain 605.32 g contains triazine
Ring and phosphorus-nitrogen of cage structure-silicon expansion type flame retardant B, yield 92.5%.
In the present embodiment, the structural formula of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure is：
Embodiment three
The synthesis step of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure is as follows：
Step 1
300mL acetonitriles are added in 1000mL, are cooled to 0 DEG C, add 153.33g（1mol）POCl3（POCl3）Stir
Mix scattered, 180g is progressively added dropwise（1mol）1- epoxide phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane
（PEPA）And 101.20g（1mol）Triethylamine, react 2.5 hours, obtain the unitary substituent containing PEPA（POCl2-PEPA）；
Step 2
120.20g is added in another container（2mol）Ethylenediamine, 50mL acetonitrile, 202.40g（2mol）Triethylamine simultaneously
Mixing, is cooled to 0 DEG C, is slowly added dropwise obtained by step 1 and contains 296.83g（1mol）PEPA unitary substituent（POCl2-
PEPA）, react 4.5 hours, isolated phosphorous diamines intermediate；
Step 3
Equipped with reflux condenser, agitator, constant pressure funnel 1000mL there-necked flasks in, add 184.5g（1mol）Three
Polychlorostyrene cyanogen, 200mL acetone is then added, there-necked flask is placed in oil bath, is sufficiently stirred, Cyanuric Chloride is uniformly dispersed, it is past
191.34 g are added dropwise in there-necked flask（That is 1mol）γ-aminopropyltriethoxy diethoxy silane（KH552）, by 101.20g
（1mol）Triethylamine be added dropwise with constant pressure funnel, pH is between 5-7 for control, and reaction temperature control is at 0 DEG C, the reaction time 2.5
Hour, obtain the siliceous unitary substituent of Cyanuric Chloride（CNC-Si）；
Step 4
The 344.03g that step 2 is obtained（1mol）Phosphorous diamines intermediate be dissolved in 250mL acetonitrile, be then progressively added dropwise
Siliceous unitary substituent is housed to step 3（CNC-Si）There-necked flask in, while be added dropwise 101.20 g（1mol）Triethylamine,
Reaction temperature is controlled at 45 DEG C, is reacted 4.5 hours, is then proceeded to increase the temperature to 105 DEG C, then 101.20 g are added dropwise（1mol）Three
Ethamine, react 7.5 hours, obtain white precipitate, distillation water washing, drying, obtain white solid, that is, obtain the three of 558.49g
Phosphorus-nitrogen-silicon expansion type flame retardant of piperazine ring and cage structure, yield 91.5%.
In the present embodiment, the structural formula of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure is：
Phosphorus-nitrogen of the structural formula 3 containing triazine ring and cage structure-silicon expansion type flame retardant C structural formula
Above is embodiments of the present invention are explained in detail, but the present invention is not limited to described embodiment.It is right
For one of ordinary skill in the art, these embodiments are entered in the case where not departing from the principle and objective of the present invention
The a variety of changes of row, modification, replacement and deformation are still fallen within the scope of the present invention.
Claims (4)
1. a kind of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure, it is characterised in that its structural formula is as follows：
In formula：Y is NH or O；
R1 is one kind of the straight or branched alkyl containing 1-18 carbon, or R1 is to one kind in phenyl, a phenyl or adjacent phenyl；
R2 is amino silicane coupling agent, and amino silicane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
Base silane, γ-aminopropyltriethoxy diethoxy silane, γ-aminopropylsilane hydrolysate, γ-aminopropyltriethoxy dimethoxysilane,
N- phenyl-γ-aminopropyltrimethoxysilane, N- β-（Aminoethyl）- γ-aminopropyltriethoxy dimethoxysilane, N-N diethyl
Aminopropyl trimethoxysilane, N-N dimethyl aminopropyls trimethoxy silane, N- β-(aminoethyl)-aminopropyl trimethoxy silicon
Alkane, N- β-(aminoethyl)-aminopropyl triethoxysilane, γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane, γ-two
The aminocarbonyl propyl trimethoxy silane of ethene three, it is double-（γ-trimethoxy silicon propyl group）Amine, it is double-（γ-triethoxysilylpropyl）Amine,
γ-piperazinopropyl methyl dimethoxysilane, N- phenylaminomethyls triethoxysilane, γ-ethoxy of diethylin methyl three
One of which or their mixture in base silane.
2. a kind of synthetic method of phosphorus-nitrogen-silicon expansion type flame retardant containing triazine ring and cage structure, it is characterised in that including such as
Under several steps：
Step 1
Solvent is added in container, is cooled to -10-10 DEG C, adds POCl3（POCl3）And be dispersed with stirring, 1- is progressively added dropwise
Epoxide phospha -4- methylol -2,6,7- trioxa-l-phosphabicyclos [2.2.2] octane（PEPA）And acid binding agent, 1-4 hours are reacted, are obtained
Unitary substituent containing PEPA（POCl2-PEPA）；Wherein POCl3（POCl3）, 1- epoxide phospha -4- methylols -2,6,7-
Trioxa-l-phosphabicyclo [2.2.2] octane（PEPA）And the mol ratio of acid binding agent three is 1:1:1,1mol POCl3 50-
500mL solvent；
Step 2
Band diamine or di-alcohols material, solvent and acid binding agent are added in another container and is mixed, is cooled to -10-10 DEG C,
The unitary substituent containing PEPA obtained by step 1 is slowly added dropwise（POCl2-PEPA）, react 3-6 hours, it is isolated phosphorous
Diamines intermediate；Unitary substituent wherein containing PEPA（POCl2-PEPA）, diamine or mole of dihydric alcohol and acid binding agent
Than for 1:2:2-4；The 1mol unitary substituent containing PEPA（POCl2-PEPA）With 50-500mL solvent；
Step 3
By solvent be added to equipped with reflux condenser, agitator, constant pressure funnel container in, be cooled to -10-10 DEG C, add
Enter Cyanuric Chloride（CNC）And be dispersed with stirring, amino silicane coupling agent and acid binding agent is progressively added dropwise, pH is between 5-7 for control, reaction
Temperature control reacts 1-4 hours, obtains siliceous unitary substituent at -5-5 DEG C（CNC-Si）；Wherein Cyanuric Chloride（CNC）、
The mol ratio of amino silicane coupling agent and acid binding agent three are 1:1:1,1mol Cyanuric Chloride 50-500mL solvent；
Step 4
Under conditions of 40-50 DEG C, the phosphorous diamines intermediate that step 2 obtains is slowly added dropwise in the same container of step 3
And with the mixture of acid binding agent, react 3-6 hours, then, be continuously heating to 80-130 DEG C, the reaction time is 5-10 hours, cold
But, wash, be dried to obtain pulverulent solids, phosphorus-nitrogen-silicon expansion type flame retardant as containing triazine ring and cage structure；Wherein
Siliceous unitary substituent（CNC-Si）, phosphorous intermediate and acid binding agent mol ratio be 1:1:2-3；1mol siliceous unitary
Substituent（CNC-Si）With 20-600mL solvent.
3. the synthesis side of phosphorus-nitrogen-silicon expansion type flame retardant according to claim 2 containing triazine ring and cage structure
Method, it is characterised in that the solvent is acetone, acetonitrile, tetrahydrofuran, butanone, ethyl acetate, dioxane, chloroform, first
The mixed liquor of one or both of benzene, dimethylbenzene, trimethylbenzene, durene, dimethyl sulfoxide, DMF.
4. the synthesis side of phosphorus-nitrogen-silicon expansion type flame retardant according to claim 2 containing triazine ring and cage structure
Method, it is characterised in that the acid binding agent is triethylamine, triethylene diamine, pyridine, N, one kind in N- diisopropyl ethane.
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| CN201710665574.4A CN107417912B (en) | 2017-08-07 | 2017-08-07 | Phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure and synthesis method thereof |
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| CN107417912B CN107417912B (en) | 2020-02-14 |
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Cited By (16)
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| CN108948348A (en) * | 2018-07-30 | 2018-12-07 | 顺德职业技术学院 | Containing triazine-silicon schiff bases fire retardant and its synthetic method |
| CN108948362A (en) * | 2018-08-10 | 2018-12-07 | 江苏凯尔消防工程设备有限公司 | A kind of expanding flame-proof material and preparation method thereof of novel siliceous nitrogen phosphorus |
| CN108976416A (en) * | 2018-05-11 | 2018-12-11 | 顺德职业技术学院 | Phosphorous intumescent carbon forming agent and its synthetic method |
| CN109093803A (en) * | 2018-08-13 | 2018-12-28 | 江苏凯尔消防工程设备有限公司 | A kind of novel timber flame retardant composite material and preparation method thereof |
| CN109265689A (en) * | 2018-08-10 | 2019-01-25 | 南京万和新材料有限公司 | A kind of expanding flame-proof material and preparation method thereof of siliceous nitrogen phosphorus |
| CN109294243A (en) * | 2018-08-14 | 2019-02-01 | 南京万和新材料有限公司 | A kind of inflaming retarding core material and preparation method thereof |
| CN109370231A (en) * | 2018-10-04 | 2019-02-22 | 南京万和新材料有限公司 | A kind of rubber-plastic foamed thermal insulation material of antibacterial hydrophobic |
| CN109385004A (en) * | 2018-10-04 | 2019-02-26 | 南京万和新材料有限公司 | A kind of low temperature resistant rubber-plastic foamed thermal insulation material |
| CN110776635A (en) * | 2019-10-12 | 2020-02-11 | 华南理工大学 | Single-component intumescent flame retardant with free radical quenching function and preparation method and application thereof |
| CN112646252A (en) * | 2020-12-11 | 2021-04-13 | 顺德职业技术学院 | Polyethylene flame-retardant composite material containing 'four-in-one' flame retardant and preparation method thereof |
| CN112646267A (en) * | 2020-12-11 | 2021-04-13 | 顺德职业技术学院 | Polypropylene composite material containing triazine ring and cage-like structure flame retardant and preparation method thereof |
| CN112812510A (en) * | 2020-12-11 | 2021-05-18 | 南宁绿趣环保科技有限公司 | Fully-degradable PBAT flame-retardant composite material and preparation method thereof |
| CN112812524A (en) * | 2020-12-11 | 2021-05-18 | 南宁绿趣环保科技有限公司 | Flame-retardant full-degradable polylactic acid flame-retardant composite material and preparation method thereof |
| CN113637160A (en) * | 2021-07-19 | 2021-11-12 | 武汉理工大学 | Phosphorus-nitrogen star-shaped flame retardant containing triazine structure and preparation method and application thereof |
| CN114507380A (en) * | 2022-01-24 | 2022-05-17 | 华南理工大学 | MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof |
| CN114574983A (en) * | 2022-03-22 | 2022-06-03 | 苏州世名科技股份有限公司 | Flame-retardant slurry and preparation method and application thereof |
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| CN108976416A (en) * | 2018-05-11 | 2018-12-11 | 顺德职业技术学院 | Phosphorous intumescent carbon forming agent and its synthetic method |
| CN108948348A (en) * | 2018-07-30 | 2018-12-07 | 顺德职业技术学院 | Containing triazine-silicon schiff bases fire retardant and its synthetic method |
| CN108948362A (en) * | 2018-08-10 | 2018-12-07 | 江苏凯尔消防工程设备有限公司 | A kind of expanding flame-proof material and preparation method thereof of novel siliceous nitrogen phosphorus |
| CN109265689A (en) * | 2018-08-10 | 2019-01-25 | 南京万和新材料有限公司 | A kind of expanding flame-proof material and preparation method thereof of siliceous nitrogen phosphorus |
| CN109093803A (en) * | 2018-08-13 | 2018-12-28 | 江苏凯尔消防工程设备有限公司 | A kind of novel timber flame retardant composite material and preparation method thereof |
| CN109294243A (en) * | 2018-08-14 | 2019-02-01 | 南京万和新材料有限公司 | A kind of inflaming retarding core material and preparation method thereof |
| CN109370231A (en) * | 2018-10-04 | 2019-02-22 | 南京万和新材料有限公司 | A kind of rubber-plastic foamed thermal insulation material of antibacterial hydrophobic |
| CN109385004A (en) * | 2018-10-04 | 2019-02-26 | 南京万和新材料有限公司 | A kind of low temperature resistant rubber-plastic foamed thermal insulation material |
| CN110776635A (en) * | 2019-10-12 | 2020-02-11 | 华南理工大学 | Single-component intumescent flame retardant with free radical quenching function and preparation method and application thereof |
| CN112646252A (en) * | 2020-12-11 | 2021-04-13 | 顺德职业技术学院 | Polyethylene flame-retardant composite material containing 'four-in-one' flame retardant and preparation method thereof |
| CN112646267A (en) * | 2020-12-11 | 2021-04-13 | 顺德职业技术学院 | Polypropylene composite material containing triazine ring and cage-like structure flame retardant and preparation method thereof |
| CN112812510A (en) * | 2020-12-11 | 2021-05-18 | 南宁绿趣环保科技有限公司 | Fully-degradable PBAT flame-retardant composite material and preparation method thereof |
| CN112812524A (en) * | 2020-12-11 | 2021-05-18 | 南宁绿趣环保科技有限公司 | Flame-retardant full-degradable polylactic acid flame-retardant composite material and preparation method thereof |
| CN113637160A (en) * | 2021-07-19 | 2021-11-12 | 武汉理工大学 | Phosphorus-nitrogen star-shaped flame retardant containing triazine structure and preparation method and application thereof |
| CN113637160B (en) * | 2021-07-19 | 2023-09-19 | 武汉理工大学 | Triazine structure-containing phosphorus-nitrogen star flame retardant, and preparation method and application thereof |
| CN114507380A (en) * | 2022-01-24 | 2022-05-17 | 华南理工大学 | MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof |
| CN114507380B (en) * | 2022-01-24 | 2022-11-18 | 华南理工大学 | MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof |
| CN114574983A (en) * | 2022-03-22 | 2022-06-03 | 苏州世名科技股份有限公司 | Flame-retardant slurry and preparation method and application thereof |
| CN114574983B (en) * | 2022-03-22 | 2023-08-29 | 苏州世名科技股份有限公司 | Flame-retardant slurry and preparation method and application thereof |
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Effective date of registration: 20210408 Address after: 510700 room 701, 7th floor, building 4, 20 Guanda Road, YUNPU Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province Patentee after: Guangzhou Guangtong Technology Co., Ltd Address before: 528300 Desheng Road, Shunde District, Foshan, Guangdong, Daliang Patentee before: Shunde Polytechnic |
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Correction item: Patentee|Address Correct: Shunde Vocational and Technical College|528300 Desheng East Road, Daliang, Shunde District, Foshan City, Guangdong Province False: Guangzhou Guangtong Technology Co.,Ltd.|510700 701, 7th Floor, Building 4, No. 20, Guanda Road, Yunpu Industrial Zone, Huangpu District, Guangzhou City, Guangdong Province Number: 17-01 Volume: 37 |