CN105968060B - A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution - Google Patents
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution Download PDFInfo
- Publication number
- CN105968060B CN105968060B CN201610302087.7A CN201610302087A CN105968060B CN 105968060 B CN105968060 B CN 105968060B CN 201610302087 A CN201610302087 A CN 201610302087A CN 105968060 B CN105968060 B CN 105968060B
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- melamine
- hours
- reaction
- acid
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a kind of preparation methods of the melamine polyphosphate of Narrow Molecular Weight Distribution, the following steps are included: step 1: melamine is completely dissolved in deionized water, phosphoric acid is added dropwise, modifying agent is added dropwise in reaction in the solution after a period of time, reaction a period of time is then proceeded to, final reaction product is cooling, filter, dry and crushing obtains modified intermediate；Step 2: by the modified intermediate under inert atmosphere protection and/or vacuum condition; thermal condensation reaction is carried out, the melamine polyphosphate of Narrow Molecular Weight Distribution is obtained, polymerization degree n range is 170-190; for molecular weight distributing index D less than 2.0, the temperature of weightlessness 1% is greater than 375 DEG C.The present invention solve the melamine polyphosphate of the prior art as molecular weight distribution it is wide caused by thermal stability is low, flame retarding efficiency is low and phase tolerance the problems such as, can satisfy glass fiber enhanced nylon and the molding processing request of polyester flame-retardant.
Description
Technical field
The present invention relates to a kind of preparation methods of the melamine polyphosphate of Narrow Molecular Weight Distribution, more particularly to one kind
The preparation method of the melamine polyphosphate of the high polymerization degree and high thermal stability of Narrow Molecular Weight Distribution.
Background technique
In recent years, high molecular material is widely used in production and life due to having the characteristics that light, easy processing molding
In work.However most high molecular materials are easy burning, and in the process of burning along with the generation of toxic and harmful gas,
Therefore there are serious fire hazards.Under such circumstances, flame-retardant modified to high molecular material progress to seem especially important.Mesh
Preceding flame retarded polymeric material mainly adds bromide fire retardant, although additive amount is few also to can guarantee efficient flame retardant effect,
Toxic and corrosive dense smoke can be generated, biggish harm is caused to the health of environment and human body.Therefore various countries are increased to nothing
The exploitation of halogen fire retardant, wherein halogen-free expansion fire retardant is exactly one of the countermeasure solved.At high temperature, expansion type flame retardant exists
Polymer surface forms fine and close layer of charcoal, can be with starvation and heat, and raw smoke is few, does not generate poisonous and harmful gas
Body, flame retardant effect are good.
Melamine polyphosphate, English name are melamine polyphosphate, abbreviation MPP, are a kind of phosphorus-nitrogen
Expansion type flame retardant, have thermal stability is good, excellent fireproof performance, with the compatibility of substrate is good, Halogen, low cigarette and low toxicity etc. are special
Point is widely used in the fields such as plastics, resin and polyurethane elastomer, especially suitable for the work processed at relatively high temperatures
Engineering plastics, such as the high molecular materials such as nylon66 fiber, nylon 46 and polyester of fiberglass reinforced.
The synthetic method of known melamine polyphosphate is divided into one-step method and two-step method.One-step method is using melamine
Amine reacts direct synthesis with polyphosphoric acid under certain condition；Two-step method is first with melamine and phosphatase reaction synthetic intermediate；
Then melamine polyphosphate is made in thermal condensation again.Since all there are three reactive groups for melamine and phosphoric acid, in higher temperatures
It is more complicated to spend lower reactive mode, therefore the degree of polymerization and molecular weight of the obtained melamine polyphosphate of different synthesis technologies
Differing distribution is very big.In one-step synthesis method melamine polyphosphate, since easy hydrolysis is therefore most in water for polyphosphoric acid
It must synthesize in organic solvent, and the degree of polymerization is limited by the polyphosphoric acid degree of polymerization.Opposite one-step method, two-step method have raw material
It is easy to get, the advantages that melamine polyphosphate degree of polymerization of generation is high, molecular weight is easy to control, however seen document report at present
Road, two-step method are that the intermediate (melamine phosphate) of synthesis is directly warming up to certain temperature then to keep reaction one mostly
It fixes time to prepare melamine polyphosphate, this method is since equipment and technology controlling and process are widely different, gained melamine
The degree of polymerization and molecular weight distribution of Quadrafos differ greatly, and especially molecular weight distribution is wide, and starting thermal decomposition temperature is low.China
Invention patent publication number is to disclose metallic ion modified polyphosphoric acid melamine salt and its preparation in CN200510010255.7
Method.The dissolution of metal hydroxides, oxide or carbonate is distributed in the phosphoric acid solution that concentration is 80%-90%, by water
It is reacted in a kettle 2 hours with the phosphoric acid solution containing dihydric phosphate and melamine, by modified melamine phosphate
Salt heats under the conditions of 260 DEG C -330 DEG C, polymerization reaction 8-12 hours, obtains target product polyphosphoric acid melamine salt.The production
The initial decomposition temperature of object is 340 DEG C -350 DEG C, is easily decomposed in the nylon machine-shaping of fiberglass reinforced, flame retardant effect compares
Difference.
According to known technique synthesized melamine polyphosphate due to molecular weight distribution it is wide, product is water-soluble
Greatly, thermal stability is low, flame retarding efficiency is low, the poor compatibility with polymer.
Summary of the invention
The purpose of the present invention is to solve, prior art melamine polyphosphate thermal stability is low, flame retarding efficiency is low, phase
The problems such as tolerance, a kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution is provided, is especially to provide a kind of narrow
The preparation method of the melamine polyphosphate of the high polymerization degree and high thermal stability of molecular weight distribution.The present invention uses three first
Poly cyanamid and phosphatase reaction generate melamine phosphate, while adding heteropoly acid in the synthesis process, and effect is in pyrocondensation
Catalytic dehydration is played when closing reaction, and thermal condensation reaction is accelerated to carry out；Secondly it in thermal condensation reaction process, is set by using program
It counts and carries out thermal condensation reaction under temperature gradient, avoid initial reaction stage because of branching etc. caused by the polynary group of melamine and phosphoric acid
The generation of side reaction makes molecular weight of product distribution broaden and influence initial decomposition temperature.Product molecular weight distribution of the invention is narrow,
The degree of polymerization is larger, and product and resin have preferable compatibility, and thermal stability is prominent, and the temperature of weightlessness 1% is greater than 375 DEG C,
It is able to satisfy the machine-shaping requirement of glass fiber enhanced nylon and polyester, and has preferable flame retardant effect.
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution of the invention, comprising the following steps:
Step 1: melamine is completely dissolved in deionized water, phosphoric acid is added dropwise, after reaction a period of time in the solution
Modifying agent is added dropwise, then proceedes to reaction a period of time；Final reaction product is cooling, be filtered, washed, dry and crushing is modified
Intermediate；
Step 2: thermal condensation reaction is carried out by the modified intermediate under inert atmosphere protection and/or vacuum condition,
Obtain the melamine polyphosphate of Narrow Molecular Weight Distribution；
The thermal condensation reaction process are as follows:
It is first warming up to 200 DEG C and is then warming up to 300 DEG C by 1-5 DEG C/min, maintain 1-4 hours, maintenance is finished by 5-10
350 DEG C DEG C/min are warming up to, is maintained 1-4 hour, maintains to finish to be warming up to 380 DEG C of maintenances 1-4 hours by 10-15 DEG C/min；
Alternatively, being protected respectively by temperature gradient in 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C conditions
Hold progress substep thermal condensation reaction in 1-4 hours；
The molecular structural formula of the melamine polyphosphate of the Narrow Molecular Weight Distribution are as follows:
Wherein, polymerization degree n range is 170-190；
The molecular weight distributing index D of the melamine polyphosphate of the Narrow Molecular Weight Distribution is less than 2.0, weightlessness 1%
Temperature is greater than 375 DEG C.
As a preferred technical scheme:
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution as described above, the melamine are complete
Being dissolved in deionized water entirely is in 50-95 DEG C of temperature range, and the mass ratio of the melamine and the deionized water is 1:
5-1:50；The melamine is 1:0.5-2 with the molar ratio of reacting of the phosphoric acid；The phosphoric acid is industrial phosphoric acid, the work
Industry phosphoric acid concentration is 80wt%-90wt%, and time for adding is 0.5-3 hours；Reaction time after the industrial phosphoric acid is added dropwise is
2-5 hours, reaction temperature was 50-95 DEG C.
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution as described above, the modifying agent are phosphorus
One or more of wolframic acid, silico-tungstic acid, wolframic acid, fluorine metaantimmonic acid, stannic acid, molybdic acid and phosphomolybdic acid；The modifying agent is in the reaction system
Mass fraction be 0.5-5%, time for adding 0.2-1h, be added dropwise modifying agent after reaction time be 1-3 hours, reaction temperature
It is 50-95 DEG C.Then cool down at normal temperature, in convection oven 80-150 DEG C it is 1-12 hours dry.
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution as described above, the inert atmosphere are protected
Shield is nitrogen protection；The relative degree of vacuum of the vacuum condition is≤- 0.08MPa；It is described in inert atmosphere protection and/or true
Thermal condensation reaction is carried out under empty condition, the overall process that can be thermal condensation reaction all carries out under inert atmosphere protection, either
It in a certain specific warm area and is reacted under inert atmosphere protection in the time, another section of warm area and time are anti-under vacuum conditions
It answers or overall process is all reacted under vacuum conditions.
The method that the present invention prepares melamine polyphosphate is that melamine first is made using melamine and phosphatase reaction
Amine phosphate intermediate, then the intermediate carries out thermal condensation reaction at a certain temperature and generates melamine polyphosphate.By
In melamine tool, there are three identical active amino, and phosphoric acid is a kind of ternary strong acid, therefore in melamine and phosphatase reaction
It is easy to cause thermal condensation reaction complicated since the active group that can participate in reaction is more during generating intermediate.In order to close
At the target compound of Narrow Molecular Weight Distribution, according to the structure of the intermediate it is desirable that reaction is as follows to carry out straight chain pyrocondensation
Close reaction, (III) again can the reaction was continued with (I) and/or (II), and so on until reach it is anticipated that molecular weight and its
Distribution:
But since the dehydration of ammonium salt will also occur at different conditions for the difference of technique, the amino on triazine ring is mutual
The side reactions such as the reaction of deamination gas are acted on, to influence molecular weight and its distribution of product.Therefore, the present invention is reacted in thermal condensation
In the process, by using thermal condensation reaction is carried out under programming temperature gradient, avoid initial reaction stage because of melamine and phosphorus
The polynary group of acid causes the generation of the side reactions such as branching, makes molecular weight of product distribution narrow to improve its initial decomposition temperature
And flame retarding efficiency.
The utility model has the advantages that
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution of the invention, advantage are as follows:
1, melamine polyphosphate narrow molecular weight distribution obtained, the degree of polymerization is larger, and thermal stability is high, weightlessness 1%
Temperature is greater than 375 DEG C, can satisfy glass fiber enhanced nylon and the requirement of polyester flame-retardant processing and forming.
2, melamine polyphosphate and polymer produced by the present invention have preferable compatibility, improve the resistance to of fire retardant
Migration.
3, melamine polyphosphate produced by the present invention is using monomeric form as expansion type flame retardant, and nitrogen phosphorus is at same point
In son, phosphorus-nitrogen synergistic effect is played during fire-retardant, improves the flame retardant effect of flame-retardant system.
4, raw material is simple and easy to get, and preparation method is simple.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 50 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:5；Keep temperature-resistant, it is 80wt%'s that concentration is added dropwise into solution in 0.5 hour
Industrial phosphoric acid, melamine are 1:0.5 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 2 hours；Keep temperature
It spends constant, is added dropwise a certain amount of phosphotungstic acid into solution in 0.2h, the mass fraction of phosphotungstic acid in the reaction system is 0.5%,
Rear insulation reaction is added dropwise 1 hour；Finally by reaction product natural cooling, filtering, washing, in 80 DEG C of dryings of air dry oven
Modified intermediate is obtained with crushing within 12 hours.
Obtained modification intermediate is placed in box atmosphere furnace, thermal condensation reaction is carried out under nitrogen protection, first heats up
300 DEG C then are warming up to by 1 DEG C/min to 200 DEG C, is maintained 1 hour, maintenance, which is finished, is warming up to 350 DEG C by 5 DEG C/min, maintains
1 hour, maintenance, which is finished, was warming up to 380 DEG C of maintenances 1 hour by 10 DEG C/min, finally cools down, filters, washes and is dried to obtain and is narrow
The melamine polyphosphate of molecular weight distribution, test show that the degree of polymerization of the melamine polyphosphate of preparation is 170, molecule
Measuring profile exponent D is 1.9, and the temperature of weightlessness 1% is 376 DEG C.
Embodiment 2
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 60 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:50；Keep temperature-resistant, it is 83wt%'s that concentration is added dropwise into solution in 1.0 hours
Industrial phosphoric acid, melamine are 1:0.8 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It spends constant, is added dropwise a certain amount of silico-tungstic acid into solution in 0.4h, the mass fraction of silico-tungstic acid in the reaction system is 1%, drop
Insulation reaction 2 hours after adding；Finally by reaction product natural cooling, filtering, washing, in 150 DEG C of dryings of air dry oven
Modified intermediate is obtained with crushing within 12 hours.
Obtained modification intermediate is placed in progress thermal condensation reaction in box atmosphere furnace, is first warming up under nitrogen protection
Then 200 DEG C are warming up to 300 DEG C by 2 DEG C/min, maintain 2 hours, then vacuumize system, the relative vacuum of control system
Degree is -0.08MPa, is warming up to 350 DEG C by 7 DEG C/min, maintains 2 hours, and maintenance, which is finished, is warming up to 380 DEG C of dimensions by 12 DEG C/min
It holds 2 hours, finally cools down, filters, washes and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows to make
The degree of polymerization of standby melamine polyphosphate is 175, and molecular weight distributing index D is 1.8, and the temperature of weightlessness 1% is 380 DEG C.
Embodiment 3
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 60 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:10；Keep temperature-resistant, it is 85wt%'s that concentration is added dropwise into solution in 1.0 hours
Industrial phosphoric acid, melamine are 1:1 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It is constant, a certain amount of silico-tungstic acid is added dropwise into solution in 0.5h, the mass fraction of silico-tungstic acid in the reaction system is 1%, is added dropwise
After insulation reaction 2 hours；Finally by reaction product natural cooling, filtering, washing, small in 90 DEG C of dryings 2 of air dry oven
When and crushing obtain modified intermediate.
Obtained modification intermediate is placed in progress thermal condensation reaction in box atmosphere furnace, first system is vacuumized, is controlled
The relative degree of vacuum of system is -0.08MPa, is warming up to 200 DEG C and is then warming up to 300 DEG C by 2 DEG C/min, maintains 2 hours, so
350 DEG C are warming up to by 7 DEG C/min under nitrogen protection afterwards, is maintained 2 hours, maintenance, which is finished, is warming up to 380 DEG C by 12 DEG C/min
It maintains 2 hours, finally cools down, filters, washes and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows
The degree of polymerization of the melamine polyphosphate of preparation is 173, and molecular weight distributing index D is 1.8, and the temperature of weightlessness 1% is 381
℃。
Embodiment 4
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 68 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:15；Keep temperature-resistant, it is 85wt%'s that concentration is added dropwise into solution in 1.5 hours
Industrial phosphoric acid, melamine are 1:1.2 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It spends constant, is added dropwise a certain amount of wolframic acid into solution in 0.5h, the mass fraction of wolframic acid in the reaction system is 2%, is dripped
Insulation reaction 3 hours after finishing；Finally by reaction product natural cooling, filtering, washing, in the drying 4 hours of 100 DEG C of air dry oven
Modified intermediate is obtained with crushing.
Obtained modification intermediate is placed in progress thermal condensation reaction in box atmosphere furnace, is first warming up under nitrogen protection
Then 200 DEG C are warming up to 300 DEG C by 4 DEG C/min, maintain 3 hours, and maintenance, which is finished, is warming up to 350 DEG C by 8 DEG C/min, maintain 3
Hour, then system is vacuumized, the relative degree of vacuum of control system is -0.06MPa, is warming up to 380 DEG C of dimensions by 14 DEG C/min
It holds 3 hours, finally cools down, filters, washes and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows to make
The degree of polymerization of standby melamine polyphosphate is 180, and molecular weight distributing index D is 1.6, and the temperature of weightlessness 1% is 382 DEG C.
Embodiment 5
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 68 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:20；Keep temperature-resistant, it is 85wt%'s that concentration is added dropwise into solution in 1.5 hours
Industrial phosphoric acid, melamine are 1:1.2 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It spends constant, is added dropwise a certain amount of wolframic acid into solution in 0.5h, the mass fraction of wolframic acid in the reaction system is 2%, is dripped
Insulation reaction 3 hours after finishing；Finally by reaction product natural cooling, filtering, washing, in the drying 5 hours of 120 DEG C of air dry oven
Modified intermediate is obtained with crushing.
Obtained modification intermediate is placed in progress thermal condensation reaction in box atmosphere furnace, first system is vacuumized, is controlled
The relative degree of vacuum of system is -0.06MPa, is warming up to 200 DEG C and is then warming up to 300 DEG C by 4 DEG C/min, maintains 3 hours, dimension
It holds to finish and is warming up to 350 DEG C by 8 DEG C/min, maintain 3 hours, be then warming up to 380 DEG C by 14 DEG C/min under nitrogen protection
It maintains 3 hours, finally cools down, filters, washes and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows
The degree of polymerization of the melamine polyphosphate of preparation is 180, and molecular weight distributing index D is 1.6, and the temperature of weightlessness 1% is 382
℃。
Embodiment 6
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 73 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:25；Keep temperature-resistant, it is 86wt%'s that concentration is added dropwise into solution in 1.8 hours
Industrial phosphoric acid, melamine are 1:1.5 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 4 hours；Keep temperature
It spends constant, is added dropwise a certain amount of fluorine metaantimmonic acid into solution in 0.6h, the mass fraction of fluorine metaantimmonic acid in the reaction system is 3%, drop
Insulation reaction 1 hour after adding；Finally by reaction product natural cooling, filtering, washing, in 130 DEG C of dryings 7 of air dry oven
Hour and crushing obtain modified intermediate.
Obtained modification intermediate is placed in box atmosphere furnace, in the case where relative degree of vacuum is the vacuum condition of -0.05Mpa
Thermal condensation reaction is carried out, 200 DEG C is first warming up to and is then warming up to 300 DEG C by 5 DEG C/min, maintain 4 hours, maintenance is finished by 10
350 DEG C DEG C/min are warming up to, is maintained 4 hours, maintenance, which is finished, to be warming up to 380 DEG C by 15 DEG C/min and maintain 4 hours, last cold
But, the melamine polyphosphate of Narrow Molecular Weight Distribution is filtered, washes and is dried to obtain, test shows that the melamine of preparation is poly-
The phosphatic degree of polymerization is 185, and molecular weight distributing index D is 1.5, and the temperature of weightlessness 1% is 385 DEG C.
Embodiment 7
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 80 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:30；Keep temperature-resistant, it is 88wt%'s that concentration is added dropwise into solution in 2.5 hours
Industrial phosphoric acid, melamine are 1:1.8 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 5 hours；Keep temperature
It spends constant, is added dropwise a certain amount of stannic acid into solution in 0.8h, the mass fraction of stannic acid in the reaction system is 4%, is dripped
Insulation reaction 2 hours after finishing；Finally by reaction product natural cooling, filtering, washing, in the drying 12 hours of 80 DEG C of air dry oven
Modified intermediate is obtained with crushing.
Obtained modification intermediate is placed in box atmosphere furnace, carries out substep thermal condensation reaction under nitrogen protection,
Kept respectively under the conditions of 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C 1 hour, 1 hour, 1 hour, it is 1 small
When, 1 hour, 1 hour and 1 hour, finally cool down, filter, wash and be dried to obtain the poly- phosphorus of melamine of Narrow Molecular Weight Distribution
Hydrochlorate, test show that the degree of polymerization of the melamine polyphosphate of preparation is 190, and molecular weight distributing index D is 1.9, weightlessness 1%
Temperature be 376 DEG C.
Embodiment 8
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 95 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:35；It keeps temperature-resistant, the work that concentration is 90wt% is added dropwise into solution in 3 hours
Industry phosphoric acid, melamine are 1:2 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 5 hours；Keep temperature not
Become, a certain amount of molybdic acid is added dropwise into solution in 1h, the mass fraction of molybdic acid in the reaction system is 5%, is protected after being added dropwise
Temperature reaction 3 hours；Finally by reaction product natural cooling, filtering, washing, the drying 12 hours of 80 DEG C of air dry oven and crush
Obtain modified intermediate.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, first in nitrogen protection
Under, kept for 2 hours at 200 DEG C, then vacuumize system, the relative degree of vacuum of control system is -0.08MPa, 230 DEG C,
Under the conditions of 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C, kept for 2 hours, 2 hours, 2 hours, 2 hours, 2 hours and 2 respectively
Hour, the melamine polyphosphate of Narrow Molecular Weight Distribution is finally cooled down, filters, washes and is dried to obtain, test shows to prepare
Melamine polyphosphate the degree of polymerization be 170, molecular weight distributing index D be 1.8, weightlessness 1% temperature be 379 DEG C.
Embodiment 9
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 50 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:40；Keep temperature-resistant, it is 80wt%'s that concentration is added dropwise into solution in 0.5 hour
Industrial phosphoric acid, melamine are 1:0.5 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 2 hours；Keep temperature
It spends constant, is added dropwise a certain amount of phosphomolybdic acid into solution in 0.2h, the mass fraction of phosphomolybdic acid in the reaction system is 0.5%,
Rear insulation reaction is added dropwise 1 hour；Finally by reaction product natural cooling, filtering, washing, dry at 150 DEG C of air dry oven
Modified intermediate is obtained with crushing within dry 1 hour.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, is first taken out system true
Sky, the relative degree of vacuum of control system are -0.08MPa, keep 3 hours at 200 DEG C, then under nitrogen protection, 230 DEG C,
Under the conditions of 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C, kept for 3 hours, 3 hours, 3 hours, 3 hours, 3 hours and 3 respectively
Hour, the melamine polyphosphate of Narrow Molecular Weight Distribution is finally cooled down, filters, washes and is dried to obtain, test shows to prepare
Melamine polyphosphate the degree of polymerization be 175, molecular weight distributing index D be 1.7, weightlessness 1% temperature be 382 DEG C.
Embodiment 10
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 60 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:45；Keep temperature-resistant, it is 83wt%'s that concentration is added dropwise into solution in 1.0 hours
Industrial phosphoric acid, melamine are 1:0.8 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It spends constant, the mixture of a certain amount of phosphotungstic acid and silico-tungstic acid, the quality of phosphotungstic acid and silico-tungstic acid is added dropwise into solution in 0.4h
Than for 1:1, the mass fraction of the mixture of phosphotungstic acid and silico-tungstic acid in the reaction system is 1%, rear insulation reaction 2 is added dropwise
Hour；Finally by reaction product natural cooling, filtering, washing, changed in the drying 4 hours of 100 DEG C of air dry oven and crushing
Property intermediate.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, first in nitrogen protection
Under, it is kept for 1 hour and 2 hours, is then vacuumized system, the relative degree of vacuum of control system respectively at 200 DEG C and 230 DEG C
1 hour, 2 hours, 2 hours, 1 are kept respectively under the conditions of 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C for -0.06MPa
Hour and 2 hours finally cool down, filter, wash and are dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test table
The degree of polymerization of the melamine polyphosphate of bright preparation is 180, and molecular weight distributing index D is 1.7, and the temperature of weightlessness 1% is 380
℃。
Embodiment 11
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 68 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:5；Keep temperature-resistant, it is 85wt%'s that concentration is added dropwise into solution in 1.5 hours
Industrial phosphoric acid, melamine are 1:1.2 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It spends constant, the mixture of a certain amount of wolframic acid Yu fluorine metaantimmonic acid is added dropwise into solution in 0.5h, the mass ratio of wolframic acid and fluorine metaantimmonic acid is
The mass fraction of the mixture of 1:2, wolframic acid and fluorine metaantimmonic acid in the reaction system is 2%, rear insulation reaction is added dropwise 3 hours；
Finally by reaction product natural cooling, filtering, washing, among the drying 6 hours of 120 DEG C of air dry oven and crushing are modified
Body.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, is first taken out system true
Sky, the relative degree of vacuum of control system are -0.05MPa, are kept for 2 hours and 2 hours respectively at 200 DEG C and 230 DEG C, then in nitrogen
Under gas shielded, under the conditions of 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C, keep respectively 1 hour, 1 hour, 2 hours, it is 3 small
When and 2 hours, finally cool down, filter, wash and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows
The degree of polymerization of the melamine polyphosphate of preparation is 185, and molecular weight distributing index D is 1.5, and the temperature of weightlessness 1% is 381
℃。
Embodiment 12
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 73 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:50；Keep temperature-resistant, it is 86wt%'s that concentration is added dropwise into solution in 1.8 hours
Industrial phosphoric acid, melamine are 1:1.5 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 4 hours；Keep temperature
It spends constant, is added dropwise the mixture of a certain amount of stannic acid and molybdic acid into solution in 0.6h, the mass ratio of stannic acid and molybdic acid is 1:1,
The mass fraction of the mixture of stannic acid and molybdic acid in the reaction system is 3%, rear insulation reaction is added dropwise 1 hour；Finally will
Reaction product natural cooling, washing, obtains being modified intermediate in the drying 10 hours of 90 DEG C of air dry oven and crushing filtering.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, first in nitrogen protection
Under, it is kept for 1 hour, 1 hour and 1 hour at 200 DEG C, 230 DEG C and 260 DEG C, then vacuumizes system respectively, control system
Relative degree of vacuum is -0.04MPa, under the conditions of 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C, keep respectively 2 hours, 3 hours, it is 1 small
When and 2 hours, finally cool down, filter, wash and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows
The degree of polymerization of the melamine polyphosphate of preparation is 190, and molecular weight distributing index D is 1.7, and the temperature of weightlessness 1% is 382
℃。
Embodiment 13
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 80 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:10；Keep temperature-resistant, it is 88wt%'s that concentration is added dropwise into solution in 2.5 hours
Industrial phosphoric acid, melamine are 1:1.8 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 5 hours；Keep temperature
It spends constant, is added dropwise the mixture of a certain amount of molybdic acid and phosphomolybdic acid into solution in 0.8h, the mass ratio of molybdic acid and phosphomolybdic acid is
The mass fraction of the mixture of 2:1, molybdic acid and phosphomolybdic acid in the reaction system is 4%, rear insulation reaction is added dropwise 2 hours；
Finally by reaction product natural cooling, filtering, washing, among the drying 12 hours of 80 DEG C of air dry oven and crushing are modified
Body.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, is first taken out system true
Sky, the relative degree of vacuum of control system are -0.04MPa, are kept for 2 hours, 1 hour and 2 respectively at 200 DEG C, 230 DEG C and 260 DEG C
Hour, then under nitrogen protection, under the conditions of 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C, 1 hour, 3 hours, 1 are kept respectively
Hour and 1 hour finally cool down, filter, wash and are dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test table
The degree of polymerization of the melamine polyphosphate of bright preparation is 170, and molecular weight distributing index D is 1.5, and the temperature of weightlessness 1% is 379
℃。
Embodiment 14
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 95 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:20；It keeps temperature-resistant, the work that concentration is 90wt% is added dropwise into solution in 3 hours
Industry phosphoric acid, melamine are 1:2 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 5 hours；Keep temperature not
Become, is added dropwise the mixture of a certain amount of phosphotungstic acid, silico-tungstic acid and wolframic acid into solution in 1h, phosphotungstic acid, silico-tungstic acid and wolframic acid
Mass ratio is 1:1:1, and the mass fraction of the mixture of phosphotungstic acid, silico-tungstic acid and wolframic acid in the reaction system is 5%, is added dropwise
Insulation reaction 3 hours afterwards；Finally by reaction product natural cooling, filtering, washing, in the drying 2 hours of 150 DEG C of air dry oven and
Crushing obtains modified intermediate.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, first in nitrogen protection
Under, it keeps 2 hours, 1 hour, 3 hours and 1 hour, then takes out system true respectively at 200 DEG C, 230 DEG C, 260 DEG C and 290 DEG C
Sky, the relative degree of vacuum of control system is≤- 0.08MPa, under the conditions of 320 DEG C, 350 DEG C and 380 DEG C, keep respectively 1 hour,
2 hours and 1 hour, the melamine polyphosphate of Narrow Molecular Weight Distribution is finally cooled down, filtered, washed and be dried to obtain, is tested
The degree of polymerization for showing the melamine polyphosphate of preparation is 172, and molecular weight distributing index D is 1.6, and the temperature of weightlessness 1% is
381℃。
Embodiment 15
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 50 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:30；Keep temperature-resistant, it is 80wt%'s that concentration is added dropwise into solution in 0.5 hour
Industrial phosphoric acid, melamine are 1:0.5 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 2 hours；Keep temperature
It spends constant, the mixture of a certain amount of fluorine metaantimmonic acid, stannic acid and molybdic acid, fluorine metaantimmonic acid, stannic acid and molybdic acid is added dropwise into solution in 0.2h
Mass ratio be 1:1:2, the mass fraction of the mixture of fluorine metaantimmonic acid, stannic acid and molybdic acid in the reaction system be 0.5%, drip
Insulation reaction 1 hour after finishing；Finally by reaction product natural cooling, filtering, washing, small in 100 DEG C of dryings 10 of air dry oven
When and crushing obtain modified intermediate.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, is first taken out system true
Sky, the relative degree of vacuum of control system are -0.06MPa, kept respectively at 200 DEG C, 230 DEG C, 260 DEG C and 290 DEG C 3 hours, it is 1 small
When, 1 hour and 1 hour, then under nitrogen protection, under the conditions of 320 DEG C, 350 DEG C and 380 DEG C, keep respectively 2 hours, it is 3 small
When and 3 hours, finally cool down, filter, wash and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows
The degree of polymerization of the melamine polyphosphate of preparation is 175, and molecular weight distributing index D is 1.4, and the temperature of weightlessness 1% is 385
℃。
Embodiment 16
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 60 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:40；Keep temperature-resistant, it is 83wt%'s that concentration is added dropwise into solution in 1.0 hours
Industrial phosphoric acid, melamine are 1:0.8 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It spends constant, the mixture of a certain amount of stannic acid, molybdic acid and phosphomolybdic acid, stannic acid, molybdic acid and phosphomolybdic acid is added dropwise into solution in 0.4h
Mass ratio be 1:2:1, the mass fraction of the mixture of stannic acid, molybdic acid and phosphomolybdic acid in the reaction system be 1%, be added dropwise
Insulation reaction 2 hours afterwards；Finally by reaction product natural cooling, filtering, washing, in the drying 6 hours of 80 DEG C of air dry oven and
Crushing obtains modified intermediate.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, first in nitrogen protection
Under, 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C and 320 DEG C respectively keep 2 hours, 3 hours, 3 hours, 1 hour and 1 hour, so
System is vacuumized afterwards, the relative degree of vacuum of control system is that -0.03MPa keeps 1 under the conditions of 350 DEG C and 380 DEG C respectively
Hour and 1 hour finally cool down, filter, wash and are dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test table
The degree of polymerization of the melamine polyphosphate of bright preparation is 178, and molecular weight distributing index D is 1.7, and the temperature of weightlessness 1% is 382
℃。
Embodiment 17
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 68 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:50；Keep temperature-resistant, it is 85wt%'s that concentration is added dropwise into solution in 1.5 hours
Industrial phosphoric acid, melamine are 1:1.2 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 3 hours；Keep temperature
It spends constant, the mixture of a certain amount of fluorine metaantimmonic acid, stannic acid, molybdic acid and phosphomolybdic acid, fluorine metaantimmonic acid, tin is added dropwise into solution in 0.5h
Acid, molybdic acid and phosphomolybdic acid mass ratio be 1:1:1:1, fluorine metaantimmonic acid, stannic acid, molybdic acid and phosphomolybdic acid mixture in the reaction system
Mass fraction be 2%, rear insulation reaction is added dropwise 3 hours；Finally by reaction product natural cooling, filtering, washing, in drum
The drying 1 hour of 150 DEG C of wind drying box and crushing obtain modified intermediate.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, is first taken out system true
Sky, the relative degree of vacuum of control system are -0.04MPa, keep 2 small respectively at 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C and 320 DEG C
When, then under nitrogen protection 3 hours, 1 hour, 1 hour and 1 hour under the conditions of 350 DEG C and 380 DEG C, keeps 2 small respectively
When and 1 hour, finally cool down, filter, wash and be dried to obtain the melamine polyphosphate of Narrow Molecular Weight Distribution, test shows
The degree of polymerization of the melamine polyphosphate of preparation is 182, and molecular weight distributing index D is 1.8, and the temperature of weightlessness 1% is 384
℃。
Embodiment 18
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 73 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:5；Keep temperature-resistant, it is 86wt%'s that concentration is added dropwise into solution in 1.8 hours
Industrial phosphoric acid, melamine are 1:1.5 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 4 hours；Keep temperature
It spends constant, is added dropwise a certain amount of phosphotungstic acid into solution in 0.6h, the mass fraction of phosphotungstic acid in the reaction system is 3%, drop
Insulation reaction 1 hour after adding；Finally by reaction product natural cooling, filtering, washing, in 100 DEG C of dryings of air dry oven
Modified intermediate is obtained with crushing within 10 hours.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, first in nitrogen protection
Under, kept respectively at 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C, 320 DEG C and 350 DEG C 1 hour, 2 hours, 3 hours, 3 hours, it is 4 small
When and 4 hours, then system is vacuumized, the relative degree of vacuum of control system is -0.08MPa, under the conditions of 380 DEG C, keeps 3
Hour, the melamine polyphosphate of Narrow Molecular Weight Distribution is finally cooled down, filters, washes and is dried to obtain, test shows to prepare
Melamine polyphosphate the degree of polymerization be 186, molecular weight distributing index D be 1.4, weightlessness 1% temperature be 387 DEG C.
Embodiment 19
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 80 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:20；Keep temperature-resistant, it is 88wt%'s that concentration is added dropwise into solution in 2.5 hours
Industrial phosphoric acid, melamine are 1:1.8 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 5 hours；Keep temperature
It spends constant, is added dropwise a certain amount of silico-tungstic acid into solution in 0.8h, the mass fraction of silico-tungstic acid in the reaction system is 4%, drop
Insulation reaction 2 hours after adding；Finally by reaction product natural cooling, filtering, washing, in 80 DEG C of dryings 12 of air dry oven
Hour and crushing obtain modified intermediate.
Obtained modification intermediate is placed in progress substep thermal condensation reaction in box atmosphere furnace, is first taken out system true
The relative degree of vacuum of sky, control system is -0.05MPa, in 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C, 320 DEG C and 350 DEG C difference
It is kept for 4 hours, 3 hours, 2 hours, 1 hour, 1 hour and 1 hour, then under nitrogen protection, under the conditions of 380 DEG C, keeps 2
Hour, the melamine polyphosphate of Narrow Molecular Weight Distribution is finally cooled down, filters, washes and is dried to obtain, test shows to prepare
Melamine polyphosphate the degree of polymerization be 188, molecular weight distributing index D be 1.6, weightlessness 1% temperature be 385 DEG C.
Embodiment 20
A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, under the conditions of 95 DEG C, equipped with stirring
Device, dropping funel, reflux condensing tube and thermometer four-hole boiling flask in melamine is completely dissolved in deionized water, melamine
Amine and the mass ratio of deionized water are 1:50；It keeps temperature-resistant, the work that concentration is 90wt% is added dropwise into solution in 3 hours
Industry phosphoric acid, melamine are 1:2 with the molar ratio of reacting of industrial phosphoric acid, rear insulation reaction are added dropwise 5 hours；Keep temperature not
Become, a certain amount of wolframic acid is added dropwise into solution in 1h, the mass fraction of wolframic acid in the reaction system is 5%, is protected after being added dropwise
Temperature reaction 3 hours；Finally by reaction product natural cooling, filtering, washing, the drying 1 hour of 150 DEG C of air dry oven and crush
Obtain modified intermediate.
Obtained modification intermediate is placed in box atmosphere furnace, in the case where relative degree of vacuum is the vacuum condition of -0.04Mpa
Substep thermal condensation reaction is carried out, is kept respectively under the conditions of 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C
4 hours, 4 hours, 4 hours, 4 hours, 4 hours, 4 hours and 4 hours, finally cool down, filter, wash and be dried to obtain narrow molecule
The melamine polyphosphate of distribution is measured, test shows that the degree of polymerization of the melamine polyphosphate of preparation is 190, molecular weight point
Cloth index D is 1.3, and the temperature of weightlessness 1% is 389 DEG C.
Claims (4)
1. a kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution, it is characterized in that the following steps are included:
Step 1: melamine is completely dissolved in deionized water, phosphoric acid is added dropwise, reaction is added dropwise in the solution after a period of time
Modifying agent then proceedes to reaction a period of time；Final reaction product is cooling, filter, dry and crushing obtains modified intermediate, institute
Stating modifying agent is one or more of phosphotungstic acid, silico-tungstic acid, wolframic acid, fluorine metaantimmonic acid, stannic acid, molybdic acid and phosphomolybdic acid；
Step 2: carrying out thermal condensation reaction by the modified intermediate under inert atmosphere protection and/or vacuum condition, obtaining
The melamine polyphosphate of Narrow Molecular Weight Distribution；
The thermal condensation reaction process are as follows:
It is first warming up to 200 DEG C and is then warming up to 300 DEG C by 1-5 DEG C/min, maintain 1-4 hours, maintenance is finished by 5-10 DEG C/minute
Clock is warming up to 350 DEG C, maintains 1-4 hours, and maintenance, which is finished, is warming up to 380 DEG C of maintenances 1-4 hours by 10-15 DEG C/min；
Alternatively, keeping 1- respectively in 200 DEG C, 230 DEG C, 260 DEG C, 290 DEG C, 320 DEG C, 350 DEG C and 380 DEG C conditions by temperature gradient
Progress substep thermal condensation reaction in 4 hours；
The molecular structural formula of the melamine polyphosphate of the Narrow Molecular Weight Distribution are as follows:
Wherein, polymerization degree n range is 170-190；
The molecular weight distributing index D of the melamine polyphosphate of the Narrow Molecular Weight Distribution is less than 2.0, the temperature of weightlessness 1%
Greater than 375 DEG C.
2. a kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution according to claim 1, feature
It is, it is in 50-95 DEG C of temperature range that the melamine, which is completely dissolved in deionized water, and the melamine is gone with described
The mass ratio of ionized water is 1:5-1:50；The melamine is 1:0.5-2 with the molar ratio of reacting of the phosphoric acid；The phosphoric acid
For industrial phosphoric acid, the industrial phosphoric acid concentration is 80wt%-90wt%, and time for adding is 0.5-3 hours；The industrial phosphorus is added dropwise
Reaction time after acid is 2-5 hours, and reaction temperature is 50-95 DEG C.
3. a kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution according to claim 1, feature
It is, the mass fraction of the modifying agent in the reaction system is 0.5-5%, time for adding 0.2-1h, after modifying agent is added dropwise
Reaction time be 1-3 hour, reaction temperature be 50-95 DEG C.
4. a kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution according to claim 1, feature
It is, the inert atmosphere protection is nitrogen protection；The relative degree of vacuum of the vacuum condition is≤- 0.08MPa；It is described
Thermal condensation reaction is carried out under inert atmosphere protection and/or vacuum condition, can be the overall process of thermal condensation reaction all in indifferent gas
Atmosphere protection is lower to be carried out, or in a certain specific warm area and is reacted under inert atmosphere protection in the time, another section of warm area and when
Between be to react under vacuum conditions or overall process is all reacted under vacuum conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610302087.7A CN105968060B (en) | 2016-05-09 | 2016-05-09 | A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610302087.7A CN105968060B (en) | 2016-05-09 | 2016-05-09 | A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105968060A CN105968060A (en) | 2016-09-28 |
| CN105968060B true CN105968060B (en) | 2019-02-26 |
Family
ID=56991325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610302087.7A Active CN105968060B (en) | 2016-05-09 | 2016-05-09 | A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105968060B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574751B (en) * | 2020-05-11 | 2022-03-04 | 湖北航天化学技术研究所 | Preparation method of modified melamine polyphosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733778A (en) * | 2005-08-10 | 2006-02-15 | 东北林业大学 | Metallic ion modified polyphosphoric acid melamine salt and its preparation method |
| CN102127230A (en) * | 2010-01-19 | 2011-07-20 | 中化蓝天集团有限公司 | New process for preparing modified melamine polyphosphate |
| CN105504292A (en) * | 2015-12-24 | 2016-04-20 | 瓮福（集团）有限责任公司 | Preparation method of MPOP |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001026597A (en) * | 1999-07-13 | 2001-01-30 | Nippon Carbide Ind Co Inc | Melamine polyphosphate and its production |
-
2016
- 2016-05-09 CN CN201610302087.7A patent/CN105968060B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1733778A (en) * | 2005-08-10 | 2006-02-15 | 东北林业大学 | Metallic ion modified polyphosphoric acid melamine salt and its preparation method |
| CN102127230A (en) * | 2010-01-19 | 2011-07-20 | 中化蓝天集团有限公司 | New process for preparing modified melamine polyphosphate |
| CN105504292A (en) * | 2015-12-24 | 2016-04-20 | 瓮福（集团）有限责任公司 | Preparation method of MPOP |
Non-Patent Citations (1)
| Title |
|---|
| 无卤阻燃剂三聚氰胺聚磷酸盐的合成;王伟伟等;《塑料工业》;20150131;第43卷(第1期);97-100 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105968060A (en) | 2016-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105924651B (en) | A kind of preparation method of the melamine polyphosphate of high polymerization degree | |
| Zhao et al. | Synthesis of a novel bridged-cyclotriphosphazene flame retardant and its application in epoxy resin | |
| CN107417912B (en) | Phosphorus-nitrogen-silicon intumescent flame retardant containing triazine ring and cage structure and synthesis method thereof | |
| Peng et al. | A facile crosslinking strategy endows the traditional additive flame retardant with enormous flame retardancy improvement | |
| CN104725428B (en) | Cyanurotriamide modified poly- amino ring three phosphonitrile and preparation method thereof | |
| CN105542160A (en) | Single-component phosphor-nitrogen double-ring cage-shaped macromolecular intumescent flame retardant as well as preparation method and application thereof | |
| CN106749413B (en) | A kind of preparation method for applying the reactive flame retardant of phosphorus-nitrogen containing sulphur in the epoxy | |
| CN103923347B (en) | A kind of containing triazine ring hexaphenyl phosphate flame retardant and preparation method thereof | |
| CN103275129B (en) | A kind of preparation method of Caged Bicyclic Phosphate Flame Retardants | |
| CN107501493B (en) | Phosphorus nitrogen expansion type combustion inhibitor and its preparation method and application | |
| CN104497041A (en) | Melamine aminotrimethylene phosphonate and preparation method thereof | |
| CN110818948A (en) | Halogen-free phosphorus-nitrogen additive type flame retardant and preparation method thereof | |
| CN107868255A (en) | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification | |
| CN105968060B (en) | A kind of preparation method of the melamine polyphosphate of Narrow Molecular Weight Distribution | |
| CN106916188B (en) | (dimethyl phosphate base amido)-three-melamine salts of -1,3,5- triazines of 2,4,6- tri- and preparation and application | |
| Lv et al. | Synthesis of a melamine‐cyclotriphosphazene derivative and its application as flame retardant on cotton gauze | |
| CN104131463A (en) | Metal ion-modified ammonium polyphosphate and its preparation method and use | |
| CN109400649A (en) | A kind of one pack system expansion type flame retardant preparation and its application in fire retarding epoxide resin | |
| CN106700084B (en) | Bis-phenol acidic group fire retardant of polyphosphate of the structure containing DOPO and preparation method thereof | |
| Zhang et al. | Bio-based trivalent phytate: A novel strategy for enhancing fire performance of rigid polyurethane foam composites | |
| CN109679138A (en) | A kind of halogen-free flame retardants polyphosphoric acid boric acid melamine salt and its preparation method and application | |
| CN104356242A (en) | Halogen-free cellulose based phosphorus flame retardant and preparation method thereof | |
| CN102911505A (en) | Polymer type phosphorus, nitrogen and boron containing flame retardant and preparation method thereof | |
| CN106349178A (en) | Preparation method of macromolecular three-element-integrated low-smoke halogen-free intumescent flame retardant | |
| CN104017163A (en) | Applications of cyclic phosphorus-nitrogen synergic halogen-free flame retardant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |