CN102936429A - Preparation method of melamine-formaldehyde resin microencapsulated ammonium polyphosphate (APP) - Google Patents
Preparation method of melamine-formaldehyde resin microencapsulated ammonium polyphosphate (APP) Download PDFInfo
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- CN102936429A CN102936429A CN2012104189583A CN201210418958A CN102936429A CN 102936429 A CN102936429 A CN 102936429A CN 2012104189583 A CN2012104189583 A CN 2012104189583A CN 201210418958 A CN201210418958 A CN 201210418958A CN 102936429 A CN102936429 A CN 102936429A
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Abstract
The invention discloses a preparation method of melamine-formaldehyde resin microencapsulated ammonium polyphosphate (APP), which comprises the following steps: adding a solvent and a melamine-formaldehyde resin prepolymer into a reaction kettle provided with a stirring paddle and a reflux unit, heating to 60-80 DEG C while stirring, adding APP, stirring for 15-30 minutes, adding a curing agent, reacting for 30-120 minutes, heating to 70-150 DEG C, and reacting for 60-180 minutes; and after the reaction finishes, cooling to 55-60 DEG C, adding a formaldehyde catching agent, continuing stirring for 10-30 minutes, filtering, washing, and carrying out aging and drying with a rake-type drier at 120-160 DEG C for 8-48 hours while introducing ammonia gas, thereby obtaining the microencapsulated APP powder. The infrared spectrogram comparison on the microencapsulated APP prepared by the method disclosed by the invention indicates that the microencapsulated APP is free of hydroxymethyl peaks; the scanning electron microscope observation indicates that the coating film on the microencapsulated APP surface is compact and uniform and has uniform particle size; and the microencapsulated product has the advantages of favorable free-running property, complete encapsulation, high polymerization degree and low free formaldehyde.
Description
Technical field
The present invention relates to a kind of preparation method of melamine-formaldehyde resin microencapsulated ammonium polyphosphate.
Background technology
Ammonium polyphosphate (ammonium polyphosphate is hereinafter to be referred as APP) has following structural formula:
(n is the mean polymerisation degree of APP, n＞20)
As everyone knows, APP is a kind of fire retardant of excellent property.It has higher phosphorus content and nitrogen content, there is again the P-N synergistic effect between them, thereby has a high flame-retarded efficiency, again because it can carry out its flame retardant resistance of composite raising and implementation with many other fire retardants, the amount of being fuming is little, little (the LD50＞10g/kg), thereby person is arranged, and it is " environmental protection fire retarding agent " of toxicity.
Yet owing to himself chemical structure, there is following intrinsic defective in it.
(1) water absorbability is large.There is the oxygen key on its chemical structure, and oxygen key outside surface alignment often, cause it easily to absorb water molecules.Because it is unfavorable for long-term storage water absorbability, has also reduced in addition its chemical property, has limited its application on electrical equipment industry.
(2) with consistency and the bad dispersibility of base material.According to the similar compatibility principle, plastic rubber substrate is generally organic polymer material, and APP is inorganics, and consistency is poor between them, and APP is difficult for disperseing in base material.The result of mechanical dispersion is, the APP powder easily forms agglomerate at the local place of material, and the material wood property is descended, and since between them without avidity, fire retardant easily migrates to the surface from material internal, causes that the surface separates out " bloom ", flame retardant properties descends gradually.
(3) durability of fire-retardant is bad.APP meets water or acid-alkali medium, occur gradually small molecules after degraded and the degraded often soluble in water in, cause fire retardant to run off gradually, flame retardant properties also disappears thereupon.
(4) thermostability of APP is relatively poor.The initial decomposition temperature of general APP is about 250 ℃, although the temperature of setting in the PP course of processing can meet the demands, because the shearing of screw rod has the higher problem of local temperature, at this moment APP just can thermolysis discharge small molecules (NH in the course of processing
3), cause the degradation of product.
So, both at home and abroad a large amount of patents and document description the modification of APP, fall the fire retardation that above shortcoming is better brought into play APP in order to overcome.Adopting melamine-formaldehyde resin to carry out encapsulation is wherein commonly use the most a kind of.
DE2,949,537, DE3,005,252 and DE3,316,880 disclose with melamine-formaldehyde resin or phenol-formaldehyde resin and wrapped up, and preparation has resistant to hydrolysis performance, APP powder and the method for excellent in stability.Compare with the APP without parcel, the water-soluble obvious reduction of the APP behind the parcel, thermostability improves.But adopt disclosed method to wrap up when processing, the reactor inwall has resin knot wall, causes the reactor heat transfer conditions to worsen.In addition, the coating APP that adopts these class methods to obtain, the obvious chap of median size, even have the caking thing to form, and need carry out pulverization process in use, so just can destroy the integrity of APP parcel, cause the APP core partly exposed or fully exposed, stability decreases.
Other EP0,180,795 disclose two kinds prepares the method that melamine-formaldehyde resin wraps up, and does not a kind ofly add solidifying agent and does not react under the reaction conditions of high temperature and pressurization for adopting, and another kind ofly reacts for using solidifying agent to reach the method that reduces temperature.The feeding mode of the one kettle way that these two kinds of methods all adopt, easy to operate.The powder free-running property that adopts these two kinds of methods to obtain is better, water-soluble also lower, but has the swelling clustering phenomena in the water time in disperseing, and this phenomenon is because parcel is surperficial not exclusively causes.
And the method for the melamine-formaldehyde resin of mentioning at present domestic most of document parcel ammonium polyphosphate, what all adopt is that two-step approach operates: 1, use first melamine and formaldehyde under the condition of alkalescence, generate performed polymer; 2, APP is dispersed in the performed polymer that obtains in the adding 1 in the solvent, adds again the solidifying agent reaction and obtain product; The operation of this kind method is comparatively complicated, the suitability for industrialized production inconvenient operation.
Except having the above-mentioned shortcoming of talking about, all ignored following 2 points in above patent and the document:
The first, melamine-formaldehyde resin is at the compatibility problem of organic solvent.Melamine-formaldehyde resin contains a large amount of methylols, polarity is stronger, bad with the consistency of organic oil-based solvent, ammonium polyphosphate surface after its parcel still has a large amount of methylols and exists, so also will inevitably cause the consistency of APP in organic oil-based solvent bad, viscosity is too large, has limited its application in fabric, epoxy and coating.
The second, the later stage hyperthermia drying problem of melamine-formaldehyde resin.Following problem has been ignored in the later stage oven dry of traditional technology: the powder after 1, drying must have dissolvent residual at the integument internal surface, has solvent and go out from integument inside in drying course, causes the surface to have Small Holes to exist, and causes parcel not exclusively; 2, the surfaces externally and internally of integument still has residual free formaldehyde absorption, and temperature is bad control, and free formaldehyde can be residual more, causes formaldehyde content higher; 3, shortage causes wrapping up incomplete APP and decomposes the protection of APP core under the hyperthermia drying, and the polymerization degree descends, and forms small molecules.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate.
The technical solution used in the present invention is:
A kind of preparation method of melamine-formaldehyde resin microencapsulated ammonium polyphosphate may further comprise the steps:
In the reactor with stirring rake and reflux, add solvent and melamine-formaldehyde resin performed polymer, stir, be warming up to 60 ℃ ~ 80 ℃, add again ammonium polyphosphate, then stir 15 ~ 30min, add again solidifying agent, reaction 30 ~ 120min, be warming up to 70 ℃ ~ 150 ℃, reaction 60 ~ 180min is after reaction finishes again, be cooled to 55 ~ 60 ℃, add formaldehyde-trapping agent, continue to stir 10 ~ 30min, filter, wash, adopt rake type dryer at 120 ~ 160 ℃, and pass into ammonia and carry out slaking drying 8 ~ 48h, obtain the ammonium polyphosphate powder of encapsulation.
The mass ratio of ammonium polyphosphate and solvent is 1:1.5 ~ 3.0.
The mass ratio of ammonium polyphosphate and melamine-formaldehyde resin performed polymer is 1:0.05 ~ 0.4.
The feeding quantity of solidifying agent is 0.5% ~ 10% of resin quality.
The addition of formaldehyde-trapping agent is 0.1% ~ 5.0% of solid reactant total mass.
Described solvent is the solvent of boiling point between 70 ℃ ~ 150 ℃.
The solvent of described boiling point between 70 ℃ ~ 150 ℃ comprises that water, boiling point are that 70 ℃ ~ 150 ℃ fatty alcohol, boiling point is 70 ℃ ~ 150 ℃ aliphatic ketone.
Described solidifying agent comprises ammonium chloride, Secondary ammonium phosphate, ammonium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate acid salt, citric acid, acetic acid.
Described formaldehyde-trapping agent comprises ammonium chloride, urea, ethylene urea, sodium bisulfite, 2-hydroxyethyl urea.
The invention has the beneficial effects as follows: the microcapsule-coated ammonium polyphosphate of the present invention's preparation is compared with the ammonium polyphosphate that does not coat, the free-running property of particle is better, water-soluble greatly reduction in water, water-soluble in 70 ℃ water also greatly reduces and can stablize, obviously improve with the consistency of organic solvent, electric property has clear improvement.It is closely knit to have parcel, high-polymerization degree, and consistency is good, and is water-soluble low, water-soluble lower and stable in 70 ℃ the hot water, the characteristics of electrical property excellence.It can be used for the macromolecular materials such as polyolefine, also can application and fabric, epoxy and coating in.
With the encapsulation APP of the inventive method preparation, by analyzing infrared spectrum, the APP behind the encapsulation does not contain the methylol peak; With the electron microscopic observation of scanning, the APP surface wrap film behind the parcel is fine and close and even, and granular size is average; The product free-running property of parcel is good, and parcel is complete, and the polymerization degree is high, and free formaldehyde is low.
Description of drawings
Fig. 1 is the infared spectrum of product of the present invention.
Fig. 2 is the hydrogen nuclear magnetic spectrum of product of the present invention.
Fig. 3 is the SEM figure of product of the present invention.
Embodiment
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1:
In the 200L reactor with stirring rake and reflux, add 30kg water and 1kg
Melamine-formaldehyde resin CS-303Stir, be warming up to 65 ℃, under this temperature, add the 20kg ammonium polyphosphate, then stir 20min, add again the 0.1kg Glacial acetic acid, reaction 30min; Be warming up to again 90 ℃, reaction 60min, after reaction finishes, be cooled to 60 ℃, the urea that adds solid reaction weight 0.5% continues to stir 20min, filters, washs, adopts rake type dryer at 140 ℃, and pass into ammonia and carry out the dry 16h of slaking, obtain the ammonium polyphosphate powder 19.95kg of microcapsule coated.
Embodiment 2:
In the 200L reactor with stirring rake and reflux, add mixed solvent (mass ratio of ethanol and ethylene glycol is 1:5) and the 2kg of 36kg ethanol and ethylene glycol
Melamine-formaldehyde resin 5830, stir, be warming up to 65 ℃, under this temperature, add the 20kg ammonium polyphosphate, then stir 15min, add the 0.2kg Glacial acetic acid, reaction 60min is warming up to 120 ℃ more again, reaction 120min, reaction is cooled to 60 ℃ after finishing, the urea that adds solid reaction weight 1.0% continues to stir 20min, filters, washs, adopts rake type dryer at 140 ℃, and pass into ammonia and carry out the dry 24h of slaking, obtain the ammonium polyphosphate powder 19.21kg of microcapsule coated.
Embodiment 3:
In the 500L reactor with stirring rake and reflux, add mixed solvent (mass ratio of ethanol and glycerol is 1:4.5) and the 10kg of 150kg ethanol and glycerol
Melamine-formaldehyde resin TP 582-2, stir, be warming up to 75 ℃, under this temperature, add the 50kg ammonium polyphosphate, then stir 20min, add the 0.75kg Glacial acetic acid, reaction 30min is warming up to 125 ℃ more again, reaction 150min, reaction is cooled to 60 ℃ after finishing, add the urea that accounts for solid reactant total mass 2.0%, continue to stir 20min, filter, wash, adopt rake type dryer at 140 ℃, and pass into ammonia and carry out the dry 16h of slaking, obtain the ammonium polyphosphate powder 46.23kg of microcapsule coated.
Embodiment 4:
In the 500L reactor with stirring rake and reflux, add mixed solvent (mass ratio of methyl alcohol and ethylene glycol is 1:4) and the 3.75kg of 150kg methyl alcohol and ethylene glycol
Melamine-formaldehyde resin 5830, stir, be warming up to 75 ℃, under this temperature, add the 50kg ammonium polyphosphate, then stir 20min, add 0.19kg ammonium chloride, reaction 60min is warming up to 130 ℃ more again, reaction 90min, reaction is cooled to 60 ℃ after finishing, add 3.0% the urea account for the solid reactant total mass, continue to stir 20min, filter, washing, adopt rake type dryer at 150 ℃, and pass into ammonia and carry out the dry 24h of slaking, obtain the ammonium polyphosphate powder 48.39g of microcapsule coated.
Embodiment 5:
In the 500L reactor with stirring rake and reflux, add mixed solvent (mass ratio of Virahol and pimelinketone is 1:4) and the 5kg of 125kg Virahol and pimelinketone
Melamine-formaldehyde resin CS-303, stir, be warming up to 80 ℃, under this temperature, add the 50kg ammonium polyphosphate, then stir 20min, add 0.5kg ammonium chloride, reaction 120min is warming up to 135 ℃ more again, reaction 180min, reaction is cooled to 60 ℃ after finishing, the urea that adds solid reactant total mass 5.0% continues to stir 20min, filters, washs, adopts rake type dryer at 150 ℃, and pass into ammonia and carry out the dry 8h of slaking, obtain the ammonium polyphosphate powder 52.25kg of microcapsule coated.
Test case 1: solubility property is measured
10g APP is scattered in the 100ml distilled water, at 25 ℃ and 70 ℃ of lower constant temperature stirring 20min, then uses the centrifugal 30min of whizzer.Make not molten APP all fall to the bottom.Get upper strata stillness of night 7ml, join in the 100ml small beaker of known quality, in 130 ℃ of lower dryings, the residual quality of weighing, calculate water soluble fraction from residual quantity, get water soluble fraction massfraction (being the mass percent of water soluble fraction in the supernatant liquid that takes out);
The performance test data such as the table 1 that obtain:
Test case 2: water resistance test
Getting 50g APP places the 1L beaker to add 500g water, cover lid is positioned in the water bath with thermostatic control heating unit that is set to 70 ℃, soak 168h, then test the water-soluble variation of its every day (specifically, data in the table refer to according to the result who measures and are converted into the quality of dissolving in the APP in the 100g water), the result who obtains such as following table 2:
Fig. 1,2,3 is respectively infared spectrum, nuclear magnetic spectrum, the SEM figure of embodiment 1 product, can find out that from these figure the APP behind the encapsulation does not contain the methylol peak; APP surface wrap film behind the parcel is fine and close and even, and granular size is average.
Claims (9)
1. the preparation method of a melamine-formaldehyde resin microencapsulated ammonium polyphosphate is characterized in that: may further comprise the steps:
In the reactor with stirring rake and reflux, add solvent and melamine-formaldehyde resin performed polymer, stir, be warming up to 60 ℃ ~ 80 ℃, add again ammonium polyphosphate, then stir 15 ~ 30min, add again solidifying agent, reaction 30 ~ 120min, be warming up to 70 ℃ ~ 150 ℃, reaction 60 ~ 180min is after reaction finishes again, be cooled to 55 ~ 60 ℃, add formaldehyde-trapping agent, continue to stir 10 ~ 30min, filter, wash, adopt rake type dryer at 120 ~ 160 ℃, and pass into ammonia and carry out slaking drying 8 ~ 48h, obtain the ammonium polyphosphate powder of encapsulation.
2. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1, it is characterized in that: the mass ratio of ammonium polyphosphate and solvent is 1:1.5 ~ 3.0.
3. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1, it is characterized in that: the mass ratio of ammonium polyphosphate and melamine-formaldehyde resin performed polymer is 1:0.05 ~ 0.4.
4. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1, it is characterized in that: the feeding quantity of solidifying agent is 0.5% ~ 10% of resin quality.
5. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1, it is characterized in that: the addition of formaldehyde-trapping agent is 0.1% ~ 5.0% of solid reactant total mass.
6. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1, it is characterized in that: described solvent is the solvent of boiling point between 70 ℃ ~ 150 ℃.
7. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1 is characterized in that: the solvent of described boiling point between 70 ℃ ~ 150 ℃ comprises that water, boiling point are that 70 ℃ ~ 150 ℃ fatty alcohol, boiling point is 70 ℃ ~ 150 ℃ aliphatic ketone.
8. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1, it is characterized in that: described solidifying agent comprises ammonium chloride, Secondary ammonium phosphate, ammonium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate acid salt, citric acid, acetic acid.
9. the preparation method of a kind of melamine-formaldehyde resin microencapsulated ammonium polyphosphate according to claim 1, it is characterized in that: described formaldehyde-trapping agent comprises ammonium chloride, urea, ethylene urea, sodium bisulfite, 2-hydroxyethyl urea.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483873A (en) * | 2013-09-27 | 2014-01-01 | 清远市普塞呋磷化学有限公司 | Preparation method of low-viscosity microcapsule-wrapped APP (ammonium polyphosphate) |
| CN103756292A (en) * | 2014-01-08 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Linear phenolic resin modified polyurethane composite flame-retardant foam and preparation method thereof |
| CN103980541A (en) * | 2014-05-23 | 2014-08-13 | 华东理工大学 | Coating modification method for melamine formaldehyde resin of ammonium polyphosphate |
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| CN103483873B (en) * | 2013-09-27 | 2015-06-17 | 清远市普塞呋磷化学有限公司 | Preparation method of low-viscosity microcapsule-wrapped APP (ammonium polyphosphate) |
| CN103756292A (en) * | 2014-01-08 | 2014-04-30 | 合肥杰事杰新材料股份有限公司 | Linear phenolic resin modified polyurethane composite flame-retardant foam and preparation method thereof |
| CN103980541A (en) * | 2014-05-23 | 2014-08-13 | 华东理工大学 | Coating modification method for melamine formaldehyde resin of ammonium polyphosphate |
| CN103980541B (en) * | 2014-05-23 | 2016-06-15 | 华东理工大学 | A kind of melamino-formaldehyde resin coating modification method of ammonium polyphosphate |
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