CN107286370A - A kind of nitrogen phosphorus flame retardant and preparation method thereof - Google Patents
A kind of nitrogen phosphorus flame retardant and preparation method thereof Download PDFInfo
- Publication number
- CN107286370A CN107286370A CN201710670579.6A CN201710670579A CN107286370A CN 107286370 A CN107286370 A CN 107286370A CN 201710670579 A CN201710670579 A CN 201710670579A CN 107286370 A CN107286370 A CN 107286370A
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- flame retardant
- water
- vacuum
- catalyst
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/095—Compounds containing the structure P(=O)-O-acyl, P(=O)-O-heteroatom, P(=O)-O-CN
- C07F9/097—Compounds containing the structure P(=O)-O-N
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
Abstract
The invention belongs to technical field of flame retardant, and in particular to a kind of nitrogen phosphorus flame retardant and preparation method thereof.A kind of phosphorus-nitrogen containing flame retardant, the phosphorus-nitrogen containing flame retardant is the ammonium salt of PAPE, and structural formula is
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of nitrogen-phosphorus flame retardant and preparation method thereof.
Background technology
Containing phosphorus-nitrogen expansion type flame retardant (IFR) burning when, can generate carbonaceous froth bed in material surface, play it is heat-insulated,
Oxygen barrier, suppression cigarette, it is antidrip the effects such as, with excellent fire resistance, and low cigarette, low toxicity, non-corrosiveness gas are produced, and are a kind of rings
The Green Flammability agent of guarantor.APP (APP) is a kind of common IFR, and it has the fire retardant mechanism of acid source, source of the gas, fire-retardant effect concurrently
Fruit is efficient, and cheap.But, APP is due to meeting water facile hydrolysis into the ammonium phosphate of small molecule, with high molecular fire retardant material
Poor compatibility, occurs getting damp, separates out, the phenomenon such as frosting, the outward appearance of fire-retardant product is influenceed, especially for use in coating.
For enhancing flame retardant effect, single AP P fire retardant is overcome the shortcomings of, someone is by APP and pentaerythrite and melamine
Compounding is used in coating, but changes the essence of APP facile hydrolysis, still suffers from the problem of getting damp, and three compounds, and exists unavoidably
Scattered uneven the problem of.
In recent years, market occurs in that melamine phosphate (MP), melamine Pentaerythritol phosphate salt (MPP) etc. are a variety of
The expansion type flame retardant of containing phosphorus-nitrogen, they overcome some shortcomings of APP facile hydrolysis.But, MP and MPP poorly water-soluble, no
Just the aqueous solution of compounding high concentration, prepares suspension and deposits free settling long, disperse inequality；There is corrosion and ask in the MP aqueous solution in acidity
Topic；MPP synthesis makees phosphorus source using POCl3, and production process produces acid waste gas or waste water, and neutralization procedure raw material and production
Thing is co-precipitated, and forms the mixture almost compounded.
There is presently no nitrogen-phosphorus flame retardant that suitable water paint is used.
The content of the invention
Nitrogen-phosphorus expanding fire retardant facile hydrolysis for existing for prior art, poorly water-soluble, it is corrosive, produced
Journey not environmentally, ropy problem, the invention provides a kind of New Phosphorus-nitrogenated flame retardant and preparation method thereof.
A kind of phosphorus-nitrogenated flame retardant, the phosphorus-nitrogenated flame retardant is the ammonium salt of PAPE, and structural formula is
Wherein, R-O-P for polyalcohol at least one hydroxyl and Phosphation formed it is phosphate-based.
Further, the polyalcohol is ethylene glycol, diethylene glycol, propane diols, DPG, glycerine, Isosorbide-5-Nitrae-fourth two
Alcohol, 1,5- pentanediols, 1,6-HD, 1,4 cyclohexane dimethanol, trimethylolpropane, pentaerythrite, neopentyl glycol, polyethers
Polyalcohol or PEPA.
A kind of phosphorus-nitrogenated flame retardant solution, is made up of the fire retardant and water of structure formula (I), at 15-40 DEG C, fire retardant
Concentration is 10wt%~30wt%.
A kind of preparation method of phosphorus-nitrogenated flame retardant, methods described comprises the following steps：
(1) it is esterified：Polyalcohol, phosphoric acid, catalyst and water entrainer are added in appropriate reactor, the hydroxyl of polyalcohol with
Phosphoric acid molar ratios are 1:1.0~1.2, catalyst charge is the 0.01%~8% of polyol quality, and water entrainer addition is many
1~6 times of first alcohol quality, it is 30~300r/min to control speed of agitator, at 100~150 DEG C of temperature, 1~6h is reacted, anti-
Water entrainer takes water out of during answering, and water entrainer flows back to reactor；
(2) purify：Esterification mixture is subjected to vacuum filter, tail gas condensing liquid is to reclaim water entrainer, and filter cake is that recovery is urged
Agent, filtrate carries out vacuum distillation, and distillate is to reclaim water entrainer, gradually steps up vacuum and temperature, when vacuum is 0.095
When~0.1MPa, feed temperature rise to 150 DEG C and occurred without distillate, stop distillation, remaining raffinate is semi-finished product, reclaim band
Aqua merges, and is covered together with catalyst is reclaimed for step (1)；
(3) neutralize：In the semi-finished product that step (2) is obtained, dispersant and ammonia source are added, dispersant addition is polyalcohol
1~5 times of quality, the mol ratio of ammonia and phosphoric acid contained by ammonia source is 2~3:1, in 15~120 DEG C, speed of agitator is 30~
300r/min, 0.5~2h of back flow reaction；
(4) post-process：Mixture will be neutralized and be cooled to 15~40 DEG C, vacuum filter, filter cake 20~150 DEG C, 0.05~
Dried under 0.1MPa vacuums to constant weight, obtain the ammonium salt of block granular solids product PAPE, in vacuum filter and dry
During dry, tail gas condensing reclaims dispersant and covered for step (3), and solid product is dissolved in into water or obtained solution or powder is crushed
The finished product of form.
Further, the polyalcohol is ethylene glycol, diethylene glycol, propane diols, DPG, glycerine, Isosorbide-5-Nitrae-fourth two
Alcohol, 1,5- pentanediols, 1,6-HD, 1,4 cyclohexane dimethanol, trimethylolpropane, pentaerythrite, neopentyl glycol, polyethers
Polyalcohol or PEPA.
Further, the catalyst is highly acidic resin, TiO2-Na2SO4-H2SO4Composite catalyst, Al2O3-
Na2SO4-H2SO4Composite catalyst or solid super-strong acid.
Further, the water entrainer is toluene, dimethylbenzene or ethylbenzene.
Further, the dispersant is methanol, ethanol, propyl alcohol, isopropanol or butanol.
Further, the ammonia source is ammonia, ammonium hydrogen carbonate or urea.
Phosphorus-nitrogenated flame retardant of the present invention, is the ammonium salt of PAPE, can be regarded as at least one Diammonium phosphate (DAP) point
The macromolecular for the form bridging formation that son passes through phosphate-based P-O-C with alkyl, ether chain or ester chain group.Due in molecular structure
Containing multiple ammoniums, its fire resistance and water solubility are added；Due to by phosphate-based P-O-C bridgings, relative to APP molecules
In by phosphoric acid anhydride group P-O-P bridgings, preferably, and the presence of ester group and the compatibility of organic material are preferable for hydrolytic stability.
Step (1) esterification of the preparation method of phosphorus-nitrogenated flame retardant of the present invention, using polyalcohol and phosphoric acid as raw material,
In the presence of catalyst and water entrainer, direct esterification synthetic phosphoric acid ester.Phosphoric acid can be anhydrous phosphoric acid, 85% industrial phosphoric acid or many
Polyphosphoric acid, easily, cost is relatively low for raw material sources；Esterification only produces water byproduct, it is to avoid using being corrosive and to human body
Harmful POCl3 and by-product hydrogen chloride gas or hydrochloric acid, process safety, environmental protection；Use solid acid catalyst, catalysis effect
Rate is high, and reaction temperature is low, the time is short, process energy conservation, can recovery by filtering after reaction；Using aromatic hydrocarbons water entrainer,
The water that esterification is generated in the form of azeotropic, takes out of in the very first time, promotes esterification equilibrium to react the direction to generation ester
Mobile, because the proportion of aromatic hydrocarbons water entrainer is less than water, point water is simple, convenient.
Step (2) purifying of the preparation method of phosphorus-nitrogenated flame retardant of the present invention, is first recovered by filtration catalyst, then depressurize
Distill out water entrainer.Filter and save for convenience, filtering is carried out while hot；In order to reclaim water entrainer as much as possible, it is to avoid true
In empty filter process, hot water entrainer volatilization loss sets condenser to reclaim water entrainer on the vacuum line of filtering.Recovery is urged
Agent can be recycled for several times, be changed, or bakeed using high temperature, be acidified regeneration method processing.Filtrate decompression is distilled, in order to
Energy-conservation, using high vacuum distillation.The water entrainer that filtering and still-process are reclaimed, which merges set, is used for step (1) esterification.
The preparation method of phosphorus-nitrogenated flame retardant its (3) of the present invention is neutralized, in the presence of dispersant, utilizes alkalescence
The antacid phosphorus hydroxyl P-OH of ammonia, avoids fire retardant from producing sour corrosion when in use.The effect of dispersant is dissolving phosphoric acid
Ester and ammonia source, it is to avoid band semi-finished product are wrapped up in solid product particle or ammonia source forms co-precipitation, the quality of final finished is influenceed.It is scattered
Agent selects lower boiling fatty alcohol, and excellent effect, convenient evaporation is reclaimed, and can be effectively prevented from ester hydrolysis.Ammonia source may be selected to adopt
With one of ammonia, ammoniacal liquor, ammonium hydrogen carbonate or urea.Ammonia makees ammonia source, is passed directly into reactant mixture, occurs solution-air or gas-solid
, there is the problem of reaction is not exclusively escaped, it is necessary to excessive more, a feasible method is that ammonia is dissolved in into dispersant in reaction
In, instilled by bottom insert canal in reactant mixture；And ammonium hydrogen carbonate or urea make ammonia source, operation is relatively easy, directly weighs and adds
Enter in reactant mixture, heat, decomposition discharges ammonia.
The preparation method of phosphorus-nitrogenated flame retardant its (4) post processing of the present invention, such as dispersant quantity is more, neutralizes mixing
Thing solid content under neutral temperature is less, can take and part dispersant is first evaporated under reduced pressure out, then cold crystallization method.
In order to adapt to the processing request of water paint, by product wiring solution-forming form or powder shape further can be made
Formula.
The ammonium salt fire retardant of phosphorus-nitrogen system PAPE of the present invention, by P-O-C ester groups multiple ammonium phosphate molecules
Bridging formation macromolecular, be the upgraded product of the phosphorus-nitrogenated flame retardant such as APP, MP, for preparing water paint, with point
Dissipate uniform, stable storing, excellent fireproof performance, it is compatible with polymer base material, it is corrosion-free, do not get damp, do not separate out, frost-free it is excellent
Point；The preparation method of phosphorus-nitrogenated flame retardant of the present invention, low raw-material cost is simple, convenient, process safety, environmental protection,
Energy-conservation, reliable in quality.
Embodiment
The present invention provides a kind of phosphorus-nitrogenated flame retardant, the specially ammonium salt of PAPE：
At least phosphate-based containing a P-O-C in molecular structure (I), the phosphorus hydroxyl P-OH of no esterification is changed into phosphoric acid ammonium
P-O-NH4。
At 15-40 DEG C, the fire retardant can be configured to the concentration 10wt%-30wt% aqueous solution.
In the preparation method of phosphorus-nitrogenated flame retardant of the present invention, synthetic phosphoric acid ester first：By polyalcohol, phosphoric acid, catalysis
Agent and water entrainer are added in appropriate reactor, polyalcohol and the phosphoric acid synthetic phosphoric acid ester in the presence of catalyst, and water entrainer will
The water produced in course of reaction is taken out of.The hydroxyl of polyalcohol is 1 with phosphoric acid molar ratios:1.0~1.2, catalyst charge is many
The 0.01%~8% of first alcohol quality, water entrainer addition is 1~6 times of polyol quality, control speed of agitator be 30~
300r/min, at 100~150 DEG C of temperature, reacts 1~6h.
The use of which type of reactor is not vital, as long as meeting technological requirement.Go out from easily angle
Hair, it is preferred to use reactor well known by persons skilled in the art, such as equipped with agitator, thermometer, condenser and water knockout drum
Reactor.
Mixture containing phosphate is purified.Vacuum filter is for example first carried out, then filtrate is subjected to vacuum distillation,
To obtain semi-finished product.When vacuum is that 0.095~0.1MPa, feed temperature rise to 150 DEG C and occurred without distillate, it should stop
Distillation.
The tail gas condensing liquid produced in vacuum filter reclaims water entrainer, and filter cake is to reclaim catalyst；Vacuum distillation evaporates
Go out liquid and reclaim water entrainer.Above-mentioned recovery water entrainer can be merged, be covered together with catalyst is reclaimed for synthetic phosphoric acid ester.
The semi-finished product of acquisition are added into ammonia source to be neutralized in the presence of dispersant.Ammonia and phosphoric acid contained by ammonia source rub
You are than being 2~3:1, dispersant addition is 1~5 times of polyol quality, and in 15~120 DEG C, speed of agitator is 30~300r/
Min, 0.5~2h of back flow reaction.
Dispersant uses lower boiling fatty alcohol, and ammonia source may be selected using ammonia, ammoniacal liquor, ammonium hydrogen carbonate or urea.
Mixture will be neutralized to be purified, 15~40 DEG C are first cooled to, vacuum filter, filter cake 20~150 DEG C, 0.05
Dried under~0.1MPa vacuums to constant weight, obtain block granular solids product.
If the solid content for neutralizing mixture is less, dispersant quantity is more, and part dispersant can be first evaporated under reduced pressure out,
Cold crystallization again.
Block granular solids product is obtained, solution form or powder can be further processed into as needed.
The following examples are only intended to describe the present invention in detail, and the protection domain of invention is not limited in any way.
Example 1
(1) it is esterified：In the 1000mL reactors equipped with agitator, thermometer, condenser and water knockout drum, 90g is added
(1mol) BDO, the phosphoric acid of 242g (2.1mol) 85%, 6g NCK-9 highly acidic resins catalyst and 450g toluene, control
Speed of agitator is 60~90r/min, at 125~135 DEG C of temperature, reacts 4h, is during the course of the reaction taken out of water by toluene
To water knockout drum, moisture is separated, toluene is flowed back to reactor；
(2) purify：On tail gas pipeline in the vacuum apparatus provided with condenser, esterification mixture is subjected to vacuum mistake
Filter, vacuum degree control is in 0.03~0.05MPa, and tail gas condensing liquid is to reclaim toluene, and filter cake is to reclaim catalyst, and filtrate is transferred to
In vacuum distillation apparatus, the vacuum distillation under 0.05~0.095MPa vacuums, distillate is to reclaim toluene, gradually steps up vacuum
Degree and temperature, when vacuum is that 0.095MPa, feed temperature rise to 150 DEG C and occurred without distillate, stop vacuum distillation, remaining
Raffinate be semi-finished product, reclaim toluene merge, together with reclaim catalyst cover for step (1)；
(3) neutralize：In the semi-finished product that step (2) is obtained, 270g methanol is added, in 15~30 DEG C, speed of agitator is 90
~120r/min, in 1h, 90g ammonia is added by bottom insert canal, is added ammonia and is continued to react 0.5h；
(4) post-process：Mixture will be neutralized and be cooled to 40 DEG C, vacuum filter, filter cake 90~120 DEG C, 0.09~
Dried under 0.095MPa vacuums to constant weight, obtain 310g block granular solids products, in vacuum filter and drying process, tail gas
Condensation is reclaimed methanol and covered for step (3), and solid product is dissolved in into the solution finished product that 2067g 15wt% are made in water.
Example 2
(1) it is esterified：In the 1000mL reactors equipped with agitator, thermometer, condenser and water knockout drum, 92g is added
(1mol) glycerine, the phosphoric acid of 363g (3.15mol) 85%, 6g TiO2-Na2SO4-H2SO4Composite catalyst and 450g toluene, control
Speed of agitator processed is 120~150r/min, at 105~115 DEG C of temperature, reacts 4.5h, during the course of the reaction will by toluene
Water is taken out of to water knockout drum, separates moisture, toluene is flowed back to reactor；
(2) purify：On tail gas pipeline in the vacuum apparatus provided with condenser, esterification mixture is subjected to vacuum mistake
Filter, vacuum degree control is in 0.03~0.06MPa, and tail gas condensing liquid is to reclaim toluene, and filter cake is to reclaim catalyst, and filtrate is transferred to
In vacuum distillation apparatus, the vacuum distillation under 0.06~0.095MPa vacuums, distillate is to reclaim toluene, gradually step up true
Reciprocal of duty cycle and temperature, when vacuum is that 0.095MPa, feed temperature rise to 150 DEG C and occurred without distillate, stops vacuum distillation, remain
Remaining raffinate is semi-finished product, reclaims toluene and merges, and is covered together with catalyst is reclaimed for step (1)；
(3) neutralize：In the semi-finished product that step (2) is obtained, in 30~40 DEG C, speed of agitator is 60~90r/min, in 1h
It is interior, the solution that 107g ammonia is dissolved in 400g methanol is added by bottom insert canal, continuation is finished and reacts 0.5h；
(4) post-process：Mixture will be neutralized and be cooled to 40 DEG C, vacuum filter, filter cake 90~120 DEG C, 0.09~
Dried under 0.095MPa vacuums to constant weight, obtain 412g block granular solids products, in vacuum filter and drying process, tail gas
Condensation is reclaimed methanol and covered for step (3), and solid product is dissolved in into the solution finished product that 1648g 25wt% are made in water.
Example 3
(1) it is esterified：In the 1000mL reactors equipped with agitator, thermometer, condenser and water knockout drum, 136g is added
(1mol) pentaerythrite, the phosphoric acid of 484g (4.2mol) 85%, 10g Al2O3-Na2SO4-H2SO4Composite catalyst and 400g ethylbenzene,
It is 90~120r/min to control speed of agitator, at 115~125 DEG C of temperature, reacts 5h, during the course of the reaction by ethylbenzene by water
Take out of to water knockout drum, separate moisture, ethylbenzene is flowed back to reactor；
(2) purify：On tail gas pipeline in the vacuum apparatus provided with condenser, esterification mixture is subjected to vacuum mistake
Filter, vacuum degree control is in 0.03~0.05MPa, and tail gas condensing liquid is to reclaim ethylbenzene, and filter cake is to reclaim catalyst, and filtrate is transferred to
In vacuum distillation apparatus, the vacuum distillation under 0.05~0.097MPa vacuums, distillate is to reclaim ethylbenzene, gradually steps up vacuum
Degree and temperature, when vacuum is that 0.097MPa, feed temperature rise to 150 DEG C and occurred without distillate, stop vacuum distillation, remaining
Raffinate be semi-finished product, reclaim ethylbenzene merge, together with reclaim catalyst cover for step (1)；
(3) neutralize：In the semi-finished product that step (2) is obtained, 400g ethanol and 640g ammonium hydrogen carbonate are added, control temperature exists
30~60 DEG C, speed of agitator is 90~120r/min, reacts 1h；
(4) post-process：Mixture will be neutralized and be cooled to 40 DEG C, vacuum filter, filter cake is in 120~150 DEG C, 0.095-
Dried under 0.1MPa vacuums to constant weight, obtain 920g block granular solids products, in vacuum filter and drying process, tail gas is cold
The solidifying ethanol that reclaims is covered for step (3), and solid product is dissolved in into the solution finished product that 3067g 30wt% are made in water.
Example 4
(1) it is esterified：In the 1000mL reactors equipped with agitator, thermometer, condenser and water knockout drum, 200g is added
N-204 PPGs (hydroxyl value 280mgKOH/g), the phosphoric acid of 121g (1.05mol) 85%, 10g solid super acid catalysts and
400g dimethylbenzene, it is 60~90r/min to control speed of agitator, at 135~145 DEG C of temperature, reacts 6h, leads to during the course of the reaction
Cross dimethylbenzene to take water to water knockout drum out of, separate moisture, dimethylbenzene is flowed back to reactor；
(2) purify：On tail gas pipeline in the vacuum apparatus provided with condenser, esterification mixture is subjected to vacuum mistake
Filter, vacuum degree control is in 0.03~0.05MPa, and tail gas condensing liquid is to reclaim dimethylbenzene, and filter cake is to reclaim catalyst, filtrate transfer
Into vacuum distillation apparatus, the vacuum distillation under 0.05~0.098MP vacuums, distillate is to reclaim dimethylbenzene, is gradually stepped up
Vacuum and temperature, when vacuum is that 0.098MPa, feed temperature rise to 150 DEG C and occurred without distillate, stop vacuum distillation,
Remaining raffinate is semi-finished product, reclaims dimethylbenzene and merges, and is covered together with catalyst is reclaimed for step (1)；
(3) neutralize：In the semi-finished product that step (2) is obtained, 300g isopropanols and 63g urea are added, control temperature is 90
~120 DEG C, speed of agitator is 60~90r/min, reacts 1h；
(4) post-process：Mixture will be neutralized and be cooled to 40 DEG C, vacuum filter, filter cake 120~150 DEG C, 0.095~
Dried under 0.1MPa vacuums to constant weight, obtain 283g block granular solids products, in vacuum filter and drying process, tail gas is cold
The solidifying isopropanol that reclaims is covered for step (3), and solid product ultra-fine grinding is made into the powder finished product that particle diameter is 10~60 μm.
Claims (9)
1. a kind of phosphorus-nitrogenated flame retardant, it is characterised in that the phosphorus-nitrogenated flame retardant is the ammonium salt of PAPE, structure
Formula is
Wherein, R-O-P for polyalcohol at least one hydroxyl and Phosphation formed it is phosphate-based.
2. phosphorus-nitrogenated flame retardant according to claim 1, it is characterised in that the polyalcohol is ethylene glycol, diethyl two
Alcohol, propane diols, DPG, glycerine, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,4 cyclohexane dimethanol,
Trimethylolpropane, pentaerythrite, neopentyl glycol, PPG or PEPA.
3. a kind of phosphorus-nitrogenated flame retardant solution, it is characterised in that be made up of the fire retardant and water of structure formula (I), at 15-40 DEG C,
The concentration of the fire retardant is 10wt%~30wt%.
4. a kind of preparation method of phosphorus-nitrogenated flame retardant, it is characterised in that methods described comprises the following steps：
(1) it is esterified：Polyalcohol, phosphoric acid, catalyst and water entrainer are added in appropriate reactor, the hydroxyl and phosphoric acid of polyalcohol
Mol ratio is 1:1.0~1.2, catalyst charge is the 0.01%~8% of polyol quality, and water entrainer addition is polyalcohol
1~6 times of quality, it is 30~300r/min to control speed of agitator, at 100~150 DEG C of temperature, reacts 1~6h, was reacting
Water entrainer takes water out of in journey, and water entrainer flows back to reactor；
(2) purify：Esterification mixture is subjected to vacuum filter, tail gas condensing liquid is to reclaim water entrainer, and filter cake is to reclaim catalyst,
Filtrate carry out vacuum distillation, distillate be reclaim water entrainer, gradually step up vacuum and temperature, when vacuum be 0.095~
When 0.1MPa, feed temperature rise to 150 DEG C and occurred without distillate, stop distillation, remaining raffinate is semi-finished product, reclaim band water
Agent merges, and is covered together with catalyst is reclaimed for step (1)；
(3) neutralize：In the semi-finished product that step (2) is obtained, dispersant and ammonia source are added, dispersant addition is polyol quality
1~5 times, the mol ratio of ammonia and phosphoric acid contained by ammonia source is 2~3:1, in 15~120 DEG C, speed of agitator is 30~300r/
Min, 0.5~2h of back flow reaction；
(4) post-process：Mixture will be neutralized and be cooled to 15~40 DEG C, vacuum filter, filter cake 20~150 DEG C, 0.05~
Dried under 0.1MPa vacuums to constant weight, obtain the ammonium salt of block granular solids product PAPE, vacuum filter and drying
During, tail gas condensing reclaims dispersant and covered for step (3), and solid product is dissolved in into water or obtained solution or powder shape is crushed
The finished product of formula.
5. method according to claim 4, it is characterised in that the polyalcohol be ethylene glycol, diethylene glycol, propane diols,
DPG, glycerine, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 1,4 cyclohexane dimethanol, trihydroxy methyl third
Alkane, pentaerythrite, neopentyl glycol, PPG or PEPA.
6. method according to claim 4, it is characterised in that the catalyst is highly acidic resin, TiO2-Na2SO4-
H2SO4Composite catalyst, Al2O3-Na2SO4-H2SO4Composite catalyst or solid super-strong acid.
7. method according to claim 4, it is characterised in that the water entrainer is toluene, dimethylbenzene or ethylbenzene.
8. method according to claim 4, it is characterised in that the dispersant be methanol, ethanol, propyl alcohol, isopropanol or
Butanol.
9. method according to claim 4, it is characterised in that the ammonia source is ammonia, ammonium hydrogen carbonate or urea.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710670579.6A CN107286370B (en) | 2017-08-08 | 2017-08-08 | A kind of nitrogen-phosphorus flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710670579.6A CN107286370B (en) | 2017-08-08 | 2017-08-08 | A kind of nitrogen-phosphorus flame retardant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107286370A true CN107286370A (en) | 2017-10-24 |
| CN107286370B CN107286370B (en) | 2019-06-25 |
Family
ID=60105525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710670579.6A Active CN107286370B (en) | 2017-08-08 | 2017-08-08 | A kind of nitrogen-phosphorus flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107286370B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912646A (en) * | 2019-03-08 | 2019-06-21 | 南通江山农药化工股份有限公司 | The preparation method of bis- (diphenyl phosphoester) fire retardants of bisphenol-A- |
| GB2581968A (en) * | 2019-03-04 | 2020-09-09 | Charles Aslin David | Liquid flame retardants from the neutralisation of oligomeric partial phosphate esters |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473962A (en) * | 2003-06-30 | 2004-02-11 | 中国石油化工集团公司 | corrosion inhibitor composition and its preparation and use |
| CN1830986A (en) * | 2006-04-11 | 2006-09-13 | 四川师范大学 | Method for preparing ammonium salts of cyclohexanpentol phosphate ester |
| CN103421227A (en) * | 2012-05-25 | 2013-12-04 | 上海派瑞特塑业有限公司 | Flame retardant high density polyethylene material and preparation method thereof |
| CN106633022A (en) * | 2016-11-28 | 2017-05-10 | 宋雪晶 | Preparation method and application of three-source integrated hyperbranched structure flame retardant |
-
2017
- 2017-08-08 CN CN201710670579.6A patent/CN107286370B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1473962A (en) * | 2003-06-30 | 2004-02-11 | 中国石油化工集团公司 | corrosion inhibitor composition and its preparation and use |
| CN1830986A (en) * | 2006-04-11 | 2006-09-13 | 四川师范大学 | Method for preparing ammonium salts of cyclohexanpentol phosphate ester |
| CN103421227A (en) * | 2012-05-25 | 2013-12-04 | 上海派瑞特塑业有限公司 | Flame retardant high density polyethylene material and preparation method thereof |
| CN106633022A (en) * | 2016-11-28 | 2017-05-10 | 宋雪晶 | Preparation method and application of three-source integrated hyperbranched structure flame retardant |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2581968A (en) * | 2019-03-04 | 2020-09-09 | Charles Aslin David | Liquid flame retardants from the neutralisation of oligomeric partial phosphate esters |
| CN109912646A (en) * | 2019-03-08 | 2019-06-21 | 南通江山农药化工股份有限公司 | The preparation method of bis- (diphenyl phosphoester) fire retardants of bisphenol-A- |
| CN109912646B (en) * | 2019-03-08 | 2021-02-09 | 南通江山农药化工股份有限公司 | Preparation method of bisphenol A-bis (diphenyl phosphate) flame retardant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107286370B (en) | 2019-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175777B (en) | It is a kind of for phosphorus nitrogen concerted reaction type fire retardant of polyurethane and its preparation method and application | |
| CN102816186B (en) | HPCP resin with polyhydroxy structure and preparation method thereof | |
| CN102603799B (en) | Fire-retarding-type fire inhibiting hard polyether polyol and preparation method thereof | |
| CN102924521B (en) | Silicon-containing expansive flame retardant and preparation method and application thereof | |
| CN101280197B (en) | Preparation of water-resistant expansion type flame retardant | |
| CN101624403B (en) | Phosphorus-nitrogen quaternary ammonium as well as preparation method and application thereof | |
| CN102675372A (en) | Ethylenediamine bicyclo-tetra methylenemelamine phosphonate compound and preparation method thereof | |
| CN107286370A (en) | A kind of nitrogen phosphorus flame retardant and preparation method thereof | |
| CN106519297A (en) | Method for synthesizing flame retardant by aminolysis and phosphorous-nitrogen flame retardant | |
| CN104371031A (en) | Cellulose-based nitrogen-phosphorus flame retardant and preparation method thereof | |
| CN105924645A (en) | Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant | |
| CN104610571A (en) | Cardanol-based phosphatefire-retardant plasticizer and preparation method thereof | |
| CN102344570A (en) | Melamine carboxethyl phenylphosphinic acid condensation product and preparation method thereof | |
| CN100420706C (en) | Process for preparation of melamine polyphosphates and products thereof | |
| CN108997416B (en) | Preparation method of phosphonic acid tris (1, 3-dichloro-2-propyl) ester | |
| CN107903440A (en) | A kind of Halogen alkyl phosphoric acid ester oligomer organic fire-retardant and preparation method thereof | |
| CN115677957A (en) | Preparation method of reactive phosphorus-nitrogen flame-retardant melamine hard foam polyol | |
| US3056824A (en) | Transesterification process for producing nonsymmetrical phosphite triesters and products resulting therefrom | |
| CN102321245B (en) | Benzoguanamine carboxethyl phenylphosphinic acid condensation product and preparation method | |
| RU2370503C2 (en) | Method of producing polymer material | |
| CN107955155A (en) | A kind of nitrogen boron flame retardand polyether polyol and its preparation method and purposes | |
| CN102010586A (en) | Phosphate flame retardant for urethane foams and synthesis method of phosphate flame retardant | |
| CN109232639B (en) | Preparation method of tris (1, 3-dichloropropyl) phosphonate | |
| CN115093305A (en) | Method for synthesizing dibromoethane by solid acid catalysis | |
| CN105237410A (en) | Method for preparing tetramethyl ammonium bromide |
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 |