CN108084496A - The preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance - Google Patents
The preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance Download PDFInfo
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- CN108084496A CN108084496A CN201711388077.0A CN201711388077A CN108084496A CN 108084496 A CN108084496 A CN 108084496A CN 201711388077 A CN201711388077 A CN 201711388077A CN 108084496 A CN108084496 A CN 108084496A
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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Abstract
The present invention provides a kind of melamine resin coated ammonium polyphosphate preparation method having excellent water-resistance, be related to phosphate fine chemistry industry preparation field, method such as Xia the ﹕ pretreatment solutions that mix ammonium polyphosphate addition alcohol with activating agent in, react to obtain pre-treatment APP；Addition conditioner, which reacts, in melamine resin solution must coat treatment fluid；Pre-treatment APP with cladding treatment fluid is mixed, initiator is added, reacts to obtain reaction solution, reaction solution is separated into obtain wet stock, re-dry to get.The present invention carries out coating modification processing for the ammonium polyphosphate of common quality in a creative way, and preparation process is simple, easy to operate, and prepared melamine resin coated ammonium polyphosphate product has good water resistance, normal-temperature dissolution degree<0.8g/100mL water realizes the effect that comprehensive water resistance is substantially improved after common quality ammonium polyphosphate raw material coats, is the more feasible method of common quality ammonium polyphosphate coating modification.
Description
Technical field
The present invention relates to phosphate fine chemistry industry preparation field more particularly to a kind of melamine resin claddings having excellent water-resistance
Ammonium polyphosphate preparation method.
Background technology
Ammonium polyphosphate (hereinafter referred to as APP) product is a kind of important inorganic phosphorous flame-retardant developed rapidly in recent years
Agent, belong to additive flame retardant, be expansion type flame retardant main component, have good flame retarding function, suppression cigarette, be halogen-free,
Toxicity is relatively low, becomes the product for realizing the non-halogen most prospect of fire retardant.
With continuous reinforcement of the China to flame-retarded technology requirement dynamics, sound related flame retardant regulation is gradually built up, to APP's
Demand increasingly increases, and especially proposes higher requirement to the properties particularly water resistance of product.But APP is because of it
Itself chemical constitution feature, hygroscopicity is very strong in the case of high temperature, high humility, can migrate and be oozed out (especially to material surface
It is the APP of low polymerization degree), reduce flame-retarded efficiency；In addition, APP, which is added in organic material, can make the mechanical strength of material in itself
It reduces, influences its normal use, so as to limit APP extensively should in flame retardant area, particularly high molecular material flame retardant area
With.
Hygroscopicity can be reduced by improving the APP products degree of polymerization (being more than 1000), enhanced thermal stability, but only improved APP
The degree of polymerization, it is impossible to avoid essence of the APP as inorganic matter completely, however it remains it is bad with the compatibility of high polymer, be not easy
The problems such as disperseing in high molecular material.Its Yuan of Jiu is because of ﹕ one side polymeric body surface oleophyllie hydrophobics, and APP hydrophilic and oleophobics, and two
Surface polarity differs greatly and causes objectionable intermingling between person, and the interaction force very little between interface；On the other hand due to nothing
Surface tension between machine particle is big, easily reunites, and is unfavorable in a polymer matrix scattered.
Therefore, it is necessary to carry out appropriate surface modification treatment to APP products, hygroscopicity is reduced, enhances thermal stability, to change
It is apt to its dispersiveness and compatibility in high molecular material, expands extensive uses of the APP in high molecular material flame retardant area.Using
Microcapsules technology is that there are one of effective ways of self-defect in application process for solution APP products.
Microcapsules technology is to utilize natural or synthetic macromolecule as covering material (such as melamine resin, epoxy resin, ureaformaldehyde
Resin etc.), the small core substance of solid, liquid or gas is coated, a diameter of 1~50 μm of formation has semi permeability or envelope
Close the microencapsulation of film.APP coating modifications are exactly outside the outer surface of APP solid particles cladding last layer resin not soluble in water
Film, effect are similar to the effect of sugar-coat in drug.After cladding processing, since outer membrane has completely cut off APP and extraneous contact,
The water solubility of APP can be effectively reduced, promotes its water resistance.Simultaneously because the resin outer membrane category high molecular material used, with
The compatibility of high polymer is substantially better than APP, and cladding processing can improve the compatibility of APP and high polymer, and that widens APP uses model
It encloses.
There is patent to carry out surface of microcapsule processing to II types APP both at home and abroad, to improve its shortcoming, preferably play APP
The effect of fire retardant.The patents such as US5700575, US5700575 are disclosed coats II type APP with melamine formaldehyde resin, prepares tool
The method of II types APP that have hydrolytic Resistance, improvement compatibility.
In terms of existing open source information, mainly for high-quality APP, (degree of polymerization is more than in APP product modifications
1000, II type APP) product carries out, and to the common quality APP that occupies domestic market overwhelming majority share, (degree of polymerization is left 100
It is right) the rare concern of product, still, the water resistance of such APP is worse (having higher water solubility), studies specifically for general
The inexpensive surface modification technologies of logical quality APP products, are highly beneficial to the application range for widening APP.
The content of the invention
For the drawbacks described above and problem of the prior art, the object of the present invention is to provide a kind of poly- phosphorus for common quality
Sour ammonium raw material (average degree of polymerization ＜ 100, normal-temperature dissolution degree ＜ 5.0g/100mL water) is handled by melamine resin coating modification,
The melamine resin coated ammonium polyphosphate being had excellent water-resistance, normal-temperature dissolution degree ＜ 0.8g/100mL water.It solves existing general
The problem of leading to the poor water resistance of the ammonium polyphosphate raw material of quality, it caused to be of limited application.
In order to achieve the above object, the present invention provides following Ji art Fang An ﹕
A kind of preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance, through the following steps that realizing ﹕
Step 1: at the Qian of ammonium polyphosphate Li ﹕ in the mass ratio of alcohol and activating agent be 10~100 ﹕ 1 ratio, by alcohol with
Activating agent mixes, and obtains pretreatment solution；Ammonium polyphosphate is added in pretreatment solution, under 35~55 DEG C of reaction temperature, is stirred
Reaction is mixed, obtains pre-treatment ammonium polyphosphate solidliquid mixture, wherein, the addition of ammonium polyphosphate is pretreatment solution quality
20%~60%, the C atomicities of alcohol are 1-5；
Step 2: the Bei ﹕ processed of cladding treatment fluid add in conditioner in 40~65 DEG C of melamine resin solution, heat preservation is anti-
Should, obtain cladding treatment fluid；Wherein, the addition of conditioner is 0.5%~10% of melamine quality in melamine resin solution；
Step 3: the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Mass ratio be 1 ﹕ (0.5~10) ratio, by pre-treatment ammonium polyphosphate solidliquid mixture with coat treatment fluid be uniformly mixed
Mixed liquor, then initiator is added in into mixed liquor, cladding system is obtained, the addition of the initiator is cladding treatment fluid quality
5~30%, the pH value of cladding system is adjusted to 2.5~5.5, is then reacted 30~180 minutes at a temperature of 55~100 DEG C,
Reaction system is obtained, then is dried by the isolated wet stock of reaction system, then by wet stock, obtains melamine resin cladding polyphosphoric acid
Ammonium completes the preparation method of melamine resin coated ammonium polyphosphate.
Further, ammonium polyphosphate described in step 1 is average degree of polymerization ＜ 100, normal-temperature dissolution degree ＜ 5.0g/100mL
The common ammonium polyphosphate of water.
Further, activating agent described in step 1 is selected from lauryl sodium sulfate, neopelex, dodecane
One or more kinds of mixtures in base sodium sulfonate, when for a variety of mixtures when, with arbitrary than mixing.
Further, the alcohol described in step 1 is absolute methanol or absolute ethyl alcohol.
Specifically, alcohol is mixed with activating agent in the ratio that the mass ratio of alcohol and activating agent is 30~80 ﹕ 1 in step 1,
Obtain pretreatment solution.More specifically, in the ratio that the mass ratio of alcohol and activating agent is 50 ﹕ 1, alcohol is mixed with activating agent.
Specifically, the addition of ammonium polyphosphate is the 50%~60% of pretreatment solution quality in step 1.
Further, the time is stirred to react in step 1 as 5~30 minutes；
Further, melamine resin solution described in step 2 with the following method Zhi for get Dao ﹕ according to melamine, first
The mass ratio of aldehyde solution and water is followed successively by 1:(1~10):The ratio of (30~100) mixes melamine, formalin and water
Mixed liquor is obtained, the pH value of mixed liquor is adjusted to 5.5~9.5, then at a temperature of 45~100 DEG C, is stirred to react 30~180 points
Clock obtains melamine resin solution.Wherein, the mass ratio of melamine, formalin and water is followed successively by 1:(1~10):(30~
100) what is represented is that the mass ratio of melamine and formalin is 1:The mass ratio of (1~10), melamine and water is 1:(30
~100).
Specifically, the melamine uses technical grade.
Specifically, it is followed successively by 1 according to the mass ratio of melamine, formalin and water:(2~8):The ratio of (45~80)
Example, mixed liquor is mixed to obtain by melamine, formalin and water.More specifically, the matter according to melamine, formalin and water
Amount ratio is followed successively by 1:(2~5):The ratio of (45~60).
Preferably, in the preparation method of melamine resin solution described in step 2, adjust the pH value of mixed liquor to 7.5~
9.0.More preferably, the pH value of mixed liquor is adjusted to 8.0~8.5.
Further, conditioner described in step 2 is formulated by urea, polyvinyl alcohol, resorcinol.
Specifically, the conditioner be by the mass ratio of urea and polyvinyl alcohol be 1:(0.5~5), urea and isophthalic two
The mass ratio of phenol is 1:The ratio of (0.5~5) is formulated by urea, polyvinyl alcohol, resorcinol, i.e. urea, polyethylene
The mass ratio of alcohol and resorcinol is followed successively by 1:(0.5~5):(0.5~5).
Preferably, the addition of conditioner is 1%~6% of melamine quality in melamine resin solution in step 2；
More preferably, the addition of conditioner is 1.5%~4% of melamine quality in melamine resin solution；Preferred aspect, conditioner
Addition be 2% of melamine quality in melamine resin solution.
Further, initiator described in step 3 is with containing 1~3 by the phosphoric acid that mass fraction is 90%~110%
The aliphatic alcohol of carbon atom is formulated.Specifically, the mass ratio of phosphoric acid and aliphatic alcohol is 1:(1~3).More specifically, institute
The aliphatic alcohol stated is one or more mixtures in methanol, ethyl alcohol, propyl alcohol, when for a variety of mixtures when, with arbitrary
Than mixing.
Further, the processing mode Wei ﹕ dried wet stock in step 3 are 60~180 at a temperature of 70~140 DEG C
Minute.
Specifically, the bag that the pre-treatment ammonium polyphosphate solidliquid mixture obtained in step 3 by step 1 is obtained with step 2
The mass ratio for covering treatment fluid is the ratio of 1 ﹕ (1~5), and pre-treatment ammonium polyphosphate solidliquid mixture is mixed with cladding treatment fluid
It is even to obtain mixed liquor.More particularly, the bag that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
The mass ratio for covering treatment fluid is the ratio of 1 ﹕ (1.5~2.5).Again particularly, the pre-treatment ammonium polyphosphate obtained by step 1
The ratio that the mass ratio for the cladding treatment fluid that solidliquid mixture and step 2 obtain is 1 ﹕ 2.
Preferably, the pH value of cladding system is adjusted in step 3 to 3.5~5.5；More preferably, the pH value of cladding system is adjusted
To 4.0~5.0；Optimally, the pH value of cladding system is adjusted to 4.0~5.0.
Preferably, the addition of initiator described in step 3 is coat treatment fluid quality 10~20%；More preferably, institute
The addition for stating initiator is coat treatment fluid quality 15%.
A kind of preparation method of melamine resin coated ammonium polyphosphate having excellent water-resistance provided by the invention, in a creative way pin
To the ammonium polyphosphate of common quality, coating modification processing is carried out to it using melamine resin, by simple to operation
Stepwise reaction technique, the good melamine resin coated ammonium polyphosphate of water resistance, normal-temperature dissolution degree ＜ 0.8g/ is prepared
100mL water realizes the effect that comprehensive water resistance is substantially improved after common quality ammonium polyphosphate raw material coats, is common quality
The more feasible method of ammonium polyphosphate coating modification.
The present invention has melamine resin cladding polyphosphoric acid simple beneficial to Xiao Guo ﹕ preparation processes below, easy to operate, prepared
Ammonium product has good water resistance.The water solubility of ammonium polyphosphate can be effectively reduced after coated, promotes its water resistance.Through
Test, it is molten in normal-temperature dissolution degree, room temperature water resistance and hot water with the coated ammonium polyphosphate sample that the process of the present invention obtains
The water resistance for being much better than raw material is all shown in the three kinds of tests of solution degree.Pass through cladding, common quality ammonium polyphosphate raw material normal-temperature water
Solubility can be reduced greatly.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that
Described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, those of ordinary skill in the art's all other embodiments obtained without creative efforts, belongs to
The scope of protection of the invention.
Embodiment 1
A kind of preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance, is realized by following steps：
Step 1: Li ﹕ are by the mass ratio of absolute methanol and neopelex activating agent at the Qian of ammonium polyphosphate
Absolute methanol with neopelex activating agent is uniformly mixed, pretreatment solution is obtained, by pre-treatment by the ratio of 25 ﹕ 1
Solution is added in the reaction kettle with heating stirring；Ammonium polyphosphate is added in pretreatment solution, at 35~55 DEG C
It under reaction temperature, is stirred to react 20 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, wherein, the addition of ammonium polyphosphate
For the 50% of pretreatment solution quality；
Step 2: coat Bei ﹕ a processed for the treatment of fluid, according to technical grade melamine, 37% (quality) formalin and water
Mass ratio is followed successively by 1:2:Melamine, formalin and water are mixed to obtain mixed liquor, adjust the pH value of mixed liquor by 45 ratio
To 8.5~9.0, then at a temperature of 80 DEG C, persistently it is stirred to react 60 minutes, obtains melamine resin solution；B, a steps are obtained
To melamine resin solution be cooled to 40~65 DEG C after, then add in conditioner thereto, insulated and stirred reaction 30min must be coated
Treatment fluid；Wherein, the addition of conditioner is 0.5% of melamine quality in melamine resin solution, and conditioner is by mass ratio
It is followed successively by 1:2:2 urea, polyvinyl alcohol and resorcinol is formulated；
Step 3: the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Mass ratio be 1 ﹕ 2.5 ratio, by pre-treatment ammonium polyphosphate solidliquid mixture with coat treatment fluid be uniformly mixed to obtain mixed liquor,
Adding in 10% initiator of cladding treatment fluid quality into mixed liquor again, (initiator is 90% (mass fraction) phosphoric acid and ethyl alcohol by matter
Measure ratio 1:1 mixture), cladding system is obtained, the pH value of cladding system is adjusted to 5.0~5.5, then at a temperature of 70 DEG C
Reaction 120 minutes, obtains reaction system, then reaction system filtered to obtain wet stock, then by wet stock at a temperature of 110 DEG C
It is 60 minutes dry, melamine resin coated ammonium polyphosphate is obtained, completes the preparation method of melamine resin coated ammonium polyphosphate.
Embodiment 2
A kind of preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance, is realized by following steps：
Step 1: it is 14 ﹕ that Li ﹕, which press absolute methanol and the mass ratio of lauryl sodium sulfate activating agent, at the Qian of ammonium polyphosphate
Absolute methanol with lauryl sodium sulfate activating agent is uniformly mixed, obtains pretreatment solution by 1 ratio, by pretreatment solution plus
Enter to having the function of in the reaction kettle of heating stirring；Ammonium polyphosphate is added in pretreatment solution, in 35~55 DEG C of reaction temperature
It under degree, is stirred to react 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, wherein, the addition of ammonium polyphosphate is preceding place
Manage the 60% of solution quality；
Step 2: coat Bei ﹕ a processed for the treatment of fluid, according to technical grade melamine, 37% (quality) formalin and water
Mass ratio is followed successively by 1:3:Melamine, formalin and water are mixed to obtain mixed liquor, adjust the pH value of mixed liquor by 60 ratio
To 7.5~8.0, then at a temperature of 90 DEG C, persistently it is stirred to react 120 minutes, obtains melamine resin solution；B, by a steps
After obtained melamine resin solution is cooled to 40~65 DEG C, then conditioner is added in thereto, insulated and stirred reaction 20min must be wrapped
Cover treatment fluid；Wherein, the addition of conditioner is 1% of melamine quality in melamine resin solution, and conditioner is by mass ratio
It is followed successively by 1:2:2 urea, polyvinyl alcohol and resorcinol is formulated；
Step 3: the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Mass ratio be 1 ﹕ 2 ratio, by pre-treatment ammonium polyphosphate solidliquid mixture with coat treatment fluid be uniformly mixed to obtain mixed liquor, then
15% initiator of cladding treatment fluid quality is added in into mixed liquor, and (initiator is 95% (mass fraction) phosphoric acid and ethyl alcohol by quality
Than 1:1.5 mixture), cladding system is obtained, the pH value of cladding system is adjusted to 4.5~5.0, then at a temperature of 85 DEG C
Reaction 180 minutes, obtains reaction system, then reaction system filtered to obtain wet stock, then by wet stock at a temperature of 110 DEG C
It is 60 minutes dry, melamine resin coated ammonium polyphosphate is obtained, completes the preparation method of melamine resin coated ammonium polyphosphate.
Embodiment 3
A kind of preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance, is realized by following steps：
Step 1: it is 10 ﹕ that Li ﹕, which press absolute ethyl alcohol and the mass ratio of dodecyl sodium sulfate activating agent, at the Qian of ammonium polyphosphate
Absolute ethyl alcohol with dodecyl sodium sulfate activating agent is uniformly mixed, obtains pretreatment solution by 1 ratio, by pretreatment solution plus
Enter to having the function of in the reaction kettle of heating stirring；Ammonium polyphosphate is added in pretreatment solution, in 35~55 DEG C of reaction temperature
It under degree, is stirred to react 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture, wherein, the addition of ammonium polyphosphate is preceding place
Manage the 60% of solution quality；
Step 2: coat Bei ﹕ a processed for the treatment of fluid, according to technical grade melamine, 37% (quality) formalin and water
Mass ratio is followed successively by 1:4:Melamine, formalin and water are mixed to obtain mixed liquor, adjust the pH value of mixed liquor by 50 ratio
To 8.0~8.5, then at a temperature of 85 DEG C, persistently it is stirred to react 80 minutes, obtains melamine resin solution；B, a steps are obtained
To melamine resin solution be cooled to 40~65 DEG C after, then add in conditioner thereto, insulated and stirred reaction 30min must be coated
Treatment fluid；Wherein, the addition of conditioner is 1.5% of melamine quality in melamine resin solution, and conditioner is by mass ratio
It is followed successively by 1:5:5 urea, polyvinyl alcohol and resorcinol is formulated；
Step 3: the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Mass ratio be 1 ﹕ 2 ratio, pre-treatment ammonium polyphosphate solidliquid mixture is mixed with cladding treatment fluid stirring after ten minutes equal
It is even to obtain mixed liquor, then (initiator is 95% (mass fraction) phosphorus to 15% initiator of addition cladding treatment fluid quality into mixed liquor
Acid and ethyl alcohol in mass ratio 1:2 mixture), cladding system is obtained, the pH value of cladding system is adjusted to 4.0~4.5, then 80
It is reacted 120 minutes at a temperature of DEG C, obtains reaction system, then reaction system filtered to obtain wet stock, then by wet stock at 110 DEG C
At a temperature of dry 180 minutes, obtain melamine resin coated ammonium polyphosphate, complete the preparation side of melamine resin coated ammonium polyphosphate
Method.
Embodiment 4
A kind of preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance, is realized by following steps：
Step 1: Li ﹕ are by absolute ethyl alcohol and activating agent (neopelex and dodecyl at the Qian of ammonium polyphosphate
Sodium sulfate quality is than the mixture for 1 ﹕ 1) mass ratio be 50 ﹕ 1 ratio, absolute ethyl alcohol with activating agent is uniformly mixed, is obtained
Pretreatment solution is added in the reaction kettle with heating stirring by pretreatment solution；Ammonium polyphosphate is added in into pre-treatment
In solution, under 35~55 DEG C of reaction temperature, it is stirred to react 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture,
In, the addition of ammonium polyphosphate is the 60% of pretreatment solution quality；
Step 2: coat Bei ﹕ a processed for the treatment of fluid, according to technical grade melamine, 37% (quality) formalin and water
Mass ratio is followed successively by 1:5:Melamine, formalin and water are mixed to obtain mixed liquor, adjust the pH value of mixed liquor by 60 ratio
To 8.0~8.5, then at a temperature of 85 DEG C, persistently it is stirred to react 120 minutes, obtains melamine resin solution；B, by a steps
After obtained melamine resin solution is cooled to 40~65 DEG C, then conditioner is added in thereto, insulated and stirred reaction 30min must be wrapped
Cover treatment fluid；Wherein, the addition of conditioner is 2% of melamine quality in melamine resin solution, and conditioner is by mass ratio
It is followed successively by 1:3:5 urea, polyvinyl alcohol and resorcinol is formulated；
Step 3: the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Mass ratio be 1 ﹕ 1.7 ratio, by pre-treatment ammonium polyphosphate solidliquid mixture with cladding treatment fluid stir mix after ten minutes
It is uniform to obtain mixed liquor, then (initiator is 110% (mass fraction) to 15% initiator of addition cladding treatment fluid quality into mixed liquor
Phosphoric acid and methanol in mass ratio 1:3 mixture), it obtains cladding system, adjusts the pH value of cladding system to 4.0~4.5, Ran Hou
It is reacted 180 minutes at a temperature of 85 DEG C, obtains reaction system, then reaction system filtered to obtain wet stock, then by wet stock 90
It is 180 minutes dry at a temperature of DEG C, melamine resin coated ammonium polyphosphate is obtained, completes the preparation of melamine resin coated ammonium polyphosphate
Method.
Embodiment 5
A kind of preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance, is realized by following steps：
Step 1: Li ﹕ are by absolute ethyl alcohol and activating agent (neopelex and dodecyl at the Qian of ammonium polyphosphate
Sodium sulfonate mass ratio is the mixture of 1 ﹕ 1) mass ratio be 80 ﹕ 1 ratio, absolute ethyl alcohol with activating agent is uniformly mixed, is obtained
Pretreatment solution is added in the reaction kettle with heating stirring by pretreatment solution；Ammonium polyphosphate is added in into pre-treatment
In solution, under 35~55 DEG C of reaction temperature, it is stirred to react 30 minutes, obtains pre-treatment ammonium polyphosphate solidliquid mixture,
In, the addition of ammonium polyphosphate is the 55% of pretreatment solution quality；
Step 2: coat Bei ﹕ a processed for the treatment of fluid, according to technical grade melamine, 37% (quality) formalin and water
Mass ratio is followed successively by 1:3:Melamine, formalin and water are mixed to obtain mixed liquor, adjust the pH value of mixed liquor by 45 ratio
To 8.0~8.5, then at a temperature of 80 DEG C, persistently it is stirred to react 100 minutes, obtains melamine resin solution；B, by a steps
After obtained melamine resin solution is cooled to 40~65 DEG C, then conditioner is added in thereto, insulated and stirred reaction 25min must be wrapped
Cover treatment fluid；Wherein, the addition of conditioner is 1% of melamine quality in melamine resin solution, and conditioner is by mass ratio
It is followed successively by 1:4:4 urea, polyvinyl alcohol and resorcinol is formulated；
Step 3: the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Mass ratio be 1 ﹕ 2 ratio, pre-treatment ammonium polyphosphate solidliquid mixture is mixed with cladding treatment fluid stirring after ten minutes equal
It is even to obtain mixed liquor, then (initiator is 100% (mass fraction) phosphorus to 15% initiator of addition cladding treatment fluid quality into mixed liquor
Acid and methanol in mass ratio 1:2.5 mixture), it obtains cladding system, adjusts the pH value of cladding system to 4.0~4.5, Ran Hou
It is reacted 120 minutes at a temperature of 80 DEG C, obtains reaction system, then reaction system filtered to obtain wet stock, then by wet stock 90
It is 120 minutes dry at a temperature of DEG C, melamine resin coated ammonium polyphosphate is obtained, completes the preparation of melamine resin coated ammonium polyphosphate
Method.
Embodiment 6
A kind of preparation method for the melamine resin coated ammonium polyphosphate having excellent water-resistance, is realized by following steps：
Step 1: Li ﹕ are by absolute ethyl alcohol and activating agent (lauryl sodium sulfate, detergent alkylate at the Qian of ammonium polyphosphate
The mass ratio of sodium sulfonate and dodecyl sodium sulfate is the mixture of 1 ﹕, 1 ﹕ 1) mass ratio be 30 ﹕ 1 ratio, by absolute ethyl alcohol
It is uniformly mixed with activating agent, obtains pretreatment solution, pretreatment solution is added in the reaction kettle with heating stirring；It will
Ammonium polyphosphate is added in pretreatment solution, under 35~55 DEG C of reaction temperature, is stirred to react 30 minutes, is obtained the poly- phosphorus of pre-treatment
Sour ammonium solidliquid mixture, wherein, the addition of ammonium polyphosphate is the 60% of pretreatment solution quality；
Step 2: coat Bei ﹕ a processed for the treatment of fluid, according to technical grade melamine, 37% (quality) formalin and water
Mass ratio is followed successively by 1:2:Melamine, formalin and water are mixed to obtain mixed liquor, adjust the pH value of mixed liquor by 60 ratio
To 7.5~8.0, then at a temperature of 80 DEG C, persistently it is stirred to react 60 minutes, obtains melamine resin solution；B, a steps are obtained
To melamine resin solution be cooled to 40~65 DEG C after, then add in conditioner thereto, insulated and stirred reaction 30min must be coated
Treatment fluid；Wherein, the addition of conditioner is 2% of melamine quality in melamine resin solution, conditioner by mass ratio according to
Secondary is 1:0.5:1 urea, polyvinyl alcohol and resorcinol is formulated；
Step 3: the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Mass ratio be 1 ﹕ 2 ratio, pre-treatment ammonium polyphosphate solidliquid mixture is mixed with cladding treatment fluid stirring after ten minutes equal
It is even to obtain mixed liquor, then (initiator is 90% (mass fraction) phosphorus to 15% initiator of addition cladding treatment fluid quality into mixed liquor
Acid and ethyl alcohol in mass ratio 1:2 mixture), cladding system is obtained, the pH value of cladding system is adjusted to 3.5~4.0, then 80
It is reacted 180 minutes at a temperature of DEG C, obtains reaction system, then reaction system filtered to obtain wet stock, then by wet stock at 90 DEG C
At a temperature of dry 180 minutes, obtain melamine resin coated ammonium polyphosphate, complete the preparation side of melamine resin coated ammonium polyphosphate
Method.
The quality index of the ammonium polyphosphate used in the step of above-described embodiment 1 to implementation 6 one is as shown in table 1.
Table 1 is embodiment 1 to the quality index for the ammonium polyphosphate for implementing to use in step 1 in 6.
Table 1
The present invention coats embodiment 1 to the embodiment 6 ammonium polyphosphate raw material used and the melamine resin being prepared poly-
The water resistance of the coating modification product of ammonium phosphate is tested respectively, and the results are shown in Table 2.
Table 2 is that the ammonium polyphosphate raw material that embodiment 1 is used into embodiment 6 and the melamine resin being prepared coat poly- phosphorus
The water resistance test result of the coating modification product of sour ammonium.
Table 2
The method of water resistance test for example Xias ﹕ in the present invention
Normal-temperature dissolution degree Ce Shi ﹕ specific analytical methods are pressed《HG/T2770-2008 industry ammonium polyphosphate》Middle solubility test
Prescriptive procedure carry out.
Room temperature it is resistance to it is aqueous survey examination ﹕ continuously stirred unlike foregoing normal-temperature dissolution degree test method the time be changed to 8 it is small when,
Remaining operation is the same as normal-temperature dissolution degree test operation method.
85 DEG C of hot water are resistance to aqueous to survey that examination ﹕ claims sample in ratio as defined in normal-temperature dissolution degree test method and to configure sample water-soluble
Liquid, after stirring when holding 3 is small at a temperature of 85 DEG C, operating procedure is the same as normal-temperature dissolution degree test method afterwards.
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can readily occur in change or replacement, should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention described should be subject to the protection scope in claims.
Claims (7)
1. a kind of preparation method , of melamine resin coated ammonium polyphosphate having excellent water-resistance Qi Te signs Yu ﹕ are by following step
Suddenly ﹕ are realized
Step 1: Li ﹕ are in the ratio that the mass ratio of alcohol and activating agent is 10~100 ﹕ 1 at the Qian of ammonium polyphosphate, by alcohol and activity
Agent mixes, and obtains pretreatment solution；Ammonium polyphosphate is added in pretreatment solution, under 35~55 DEG C of reaction temperature, stirring is anti-
Should, obtain pre-treatment ammonium polyphosphate solidliquid mixture, wherein, the addition of ammonium polyphosphate for pretreatment solution quality 20%~
60%, the C atomicities of alcohol are 1-5；The ammonium polyphosphate is average degree of polymerization ＜ 100, normal-temperature dissolution degree ＜ 5.0g/100mL water
Common ammonium polyphosphate；
Step 2: the Bei ﹕ processed of cladding treatment fluid add in conditioner in 40~65 DEG C of melamine resin solution, insulation reaction obtains
Coat treatment fluid；Wherein, the addition of conditioner is 0.5%~10% of melamine quality in melamine resin solution；It is described
Conditioner is formulated by urea, polyvinyl alcohol, resorcinol, and the mass ratio of urea and polyvinyl alcohol is 1:0.5~5,
The mass ratio of urea and resorcinol is 1:0.5~5；
Step 3: the matter for the cladding treatment fluid that the pre-treatment ammonium polyphosphate solidliquid mixture obtained by step 1 is obtained with step 2
Amount ratio is the ratio of 1 ﹕ 0.5~10, and pre-treatment ammonium polyphosphate solidliquid mixture is uniformly mixed to obtain mixed liquor with cladding treatment fluid,
Initiator is added in into mixed liquor again, obtains cladding system, the addition of the initiator be coat treatment fluid quality 5~
30%, the pH value of cladding system is adjusted to 2.5~5.5, is then reacted 30~180 minutes, is obtained instead at a temperature of 55~100 DEG C
System is answered, then is dried by the isolated wet stock of reaction system, then by wet stock, obtains melamine resin coated ammonium polyphosphate, it is complete
Into the preparation method of melamine resin coated ammonium polyphosphate.
2. a kind of preparation method of melamine resin coated ammonium polyphosphate having excellent water-resistance according to claim 1, special
Levy Yu ﹕ step 2 described in melamine resin solution with the following method Zhi for get Dao ﹕ according to melamine, formalin and water
Mass ratio be followed successively by 1:1~10:Melamine, formalin and water are mixed to obtain mixed liquor by 30~100 ratio, are adjusted
The pH value of mixed liquor is to 5.5~9.5, then at a temperature of 45~100 DEG C, is stirred to react 30~180 minutes, obtains melamine tree
Lipoprotein solution.
3. a kind of preparation method of melamine resin coated ammonium polyphosphate having excellent water-resistance according to claim 2, special
It levies Yu ﹕ and adjusts the pH value of mixed liquor to 7.5~9.0.
4. a kind of preparation method of melamine resin coated ammonium polyphosphate having excellent water-resistance according to claim 1,2 or 3,
Activating agent is selected from lauryl sodium sulfate, neopelex, dodecyl sodium sulfonate described in Qi Te sign Yu ﹕ step 1
One or more kinds of mixtures in sodium, when for a variety of mixtures when, with arbitrary than mixing.
5. a kind of preparation method of melamine resin coated ammonium polyphosphate having excellent water-resistance according to claim 1,2 or 3,
Its spy's sign is with containing 1~3 carbon atom by the phosphoric acid that mass fraction is 90%~100% in the initiator described in ﹕ step 3
Aliphatic alcohol be formulated.
6. a kind of preparation method of melamine resin coated ammonium polyphosphate having excellent water-resistance according to claim 5, special
The mass ratio for levying Yu ﹕ phosphoric acid and aliphatic alcohol is 1:1~3.
7. a kind of preparation method of melamine resin coated ammonium polyphosphate having excellent water-resistance according to claim 1,2 or 3,
In Qi Te sign Yu ﹕ step 3 by the processing mode Wei ﹕ of wet stock drying 60~180 minutes at a temperature of 70~140 DEG C.
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