CN102936429B - 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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- CN102936429B CN102936429B CN201210418958.3A CN201210418958A CN102936429B CN 102936429 B CN102936429 B CN 102936429B CN 201210418958 A CN201210418958 A CN 201210418958A CN 102936429 B CN102936429 B CN 102936429B
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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, hereinafter to be referred as APP) has following structural formula:
(mean polymerisation degree that n is APP, n > 20)
As everyone knows, APP is a kind of fire retardant of excellent property.It has higher phosphorus content and nitrogen content, between them, there is again P-N synergistic effect, thereby there is 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, toxicity little (LD50 > 10g/kg), thereby it is " environmental protection fire retarding agent " person.
Yet due to himself chemical structure, there is following intrinsic defect in it.
(1) water absorbability is large.In its chemical structure, there is oxygen key, and oxygen key outside surface alignment often, cause it easily to absorb water molecules.Due to water absorbability, it is unfavorable for long-term storage, has also reduced in addition its chemical property, has limited its application in electrical equipment industry.
(2) with consistency and the bad dispersibility of base material.According to similar compatibility principle, plastic rubber substrate is generally organic polymer material, and APP is inorganics, and between them, consistency is poor, and APP is difficult for disperseing in base material.The result of mechanical dispersion is, APP powder easily forms agglomerate at the local place of material, not only makes material wood property decline, and due between them without avidity, fire retardant easily migrates to surface from material internal, causes that surface separates out " bloom ", flame retardant properties declines gradually.
(3) durability of fire-retardant is bad.APP meets water or acid-alkali medium, occur gradually small molecules after degraded and degraded often soluble in water in, cause fire retardant to run off gradually, flame retardant properties also disappears thereupon.
(4) thermostability of APP is poor.The initial decomposition temperature of general APP is 250 ℃ of left and right, although the temperature of setting in the PP course of processing can meet the demands, the shearing due to screw rod in the course of processing has the higher problem of local temperature, and at this moment APP just can thermolysis discharge small molecules (NH
3), cause the degradation of product.
So, both at home and abroad a large amount of patents and document description the modification of APP, to overcome, fall the fire retardation that above shortcoming is better brought into play APP.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 APP after parcel, thermostability improves.But adopt disclosed method to wrap up while processing, reactor inwall has resin knot wall, causes reactor heat transfer conditions to worsen.In addition the coated APP that adopts these class methods to obtain, the obvious chap of median size,, even there is caking thing to form, need in use to carry out pulverization process, so just can destroy the integrity of APP parcel, cause APP core part exposed or completely exposed, stability decreases.
EP0 in addition, 180,795 disclose two kinds prepares the method that melamine-formaldehyde resin wraps up, and a kind ofly for adopting, does not add solidifying agent and does not react under the reaction conditions of high temperature and pressurization, and the another kind of method that reduces temperature for using solidifying agent to reach is reacted.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 swelling clustering phenomena in water time in disperseing, and this phenomenon is because parcel surface 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, first use melamine and formaldehyde under alkaline condition, generate performed polymer; 2, APP is dispersed in and in solvent, adds the performed polymer obtaining in 1, then add solidifying agent reaction to obtain product; This kind of method operation is comparatively complicated, suitability for industrialized production inconvenient operation.
In above patent and document, except having the above-mentioned shortcoming of talking about, all ignored following 2 points:
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.The later stage of traditional technology dries and has ignored following problem: the powder after 1, drying must have dissolvent residual at integument internal surface, has solvent and go out from integument inside in drying course, causes 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, lack the protection to APP core, cause wrapping up incomplete APP and decompose under hyperthermia drying, the polymerization degree declines, and forms small molecules.
Summary of the invention
The preparation method who the object 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 preparation method for melamine-formaldehyde resin microencapsulated ammonium polyphosphate, comprises the following 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, then add solidifying agent, reaction 30 ~ 120min, be warming up to 70 ℃ ~ 150 ℃, reaction 60 ~ 180min, 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 the dry 8 ~ 48h of slaking, 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 fatty alcohol, the boiling point of 70 ℃ ~ 150 ℃ is the aliphatic ketone of 70 ℃ ~ 150 ℃.
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: microcapsule-coated ammonium polyphosphate prepared by the present invention is compared with not coated ammonium polyphosphate, the free-running property of particle is better, water-soluble reduction greatly in water, water-soluble in the water of 70 ℃ also greatly reduces and can stablize, obviously improve with the consistency of organic solvent, electric property has clear improvement.There is parcel closely knit, high-polymerization degree, consistency is good, water-soluble low, water-soluble lower and stable in the hot water of 70 ℃, the feature of electrical property excellence.It can be used for the macromolecular materials such as polyolefine, also can application and fabric, epoxy and coating in.
The encapsulation APP preparing by the inventive method, by analyzing infrared spectrum, the APP after encapsulation does not contain methylol peak; With the electron microscopic observation of scanning, the APP surface wrap film after parcel is fine and close and even, and granular size is average; The product free-running property of parcel is good, and completely, the polymerization degree is high for parcel, and free formaldehyde is low.
Accompanying drawing explanation
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
Below in conjunction with specific embodiment, the present invention is described further:
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 ℃, at this temperature, add 20kg ammonium polyphosphate, then stir 20min, then add 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 ℃, at this temperature, add 20kg ammonium polyphosphate, then stir 15min, add again 0.2kg Glacial acetic acid, reaction 60min, then be warming up to 120 ℃, reaction 120min, after reaction finishes, is cooled to 60 ℃, 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 ℃, at this temperature, add 50kg ammonium polyphosphate, then stir 20min, add again 0.75kg Glacial acetic acid, reaction 30min, then be warming up to 125 ℃, reaction 150min, after reaction finishes, is cooled to 60 ℃, 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 ℃, at this temperature, add 50kg ammonium polyphosphate, then stir 20min, add again 0.19kg ammonium chloride, reaction 60min, then be warming up to 130 ℃, reaction 90min, after reaction finishes, is cooled to 60 ℃, add 3.0% the urea that accounts for 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 ℃, at this temperature, add 50kg ammonium polyphosphate, then stir 20min, add again 0.5kg ammonium chloride, reaction 120min, then be warming up to 135 ℃, reaction 180min, after reaction finishes, is cooled to 60 ℃, 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 100ml distilled water, and at 25 ℃ and 70 ℃, constant temperature stirs 20min, then uses the centrifugal 30min of whizzer.Make not molten APP all fall to bottom.Get upper strata stillness of night 7ml, join in the 100ml small beaker of known quality, dry at 130 ℃, the residual quality of weighing, from residual quantity, calculate water soluble fraction, obtain water soluble fraction massfraction (being the mass percent of water soluble fraction in the supernatant liquid taking out);
The performance test data obtaining is as table 1:
test case 2: water resistance test
Getting 50g APP is placed in 1L beaker and adds 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 table refer to according to the result of measuring and are converted into the quality of dissolving in the APP in 100g water), the result obtaining is as following table 2:
Fig. 1,2,3 is respectively infared spectrum, nuclear magnetic spectrum, the SEM figure of embodiment 1 product, from these figure, can find out, the APP after encapsulation does not contain methylol peak; APP surface wrap film after parcel is fine and close and even, and granular size is average.
Claims (1)
1. a preparation method for melamine-formaldehyde resin microencapsulated ammonium polyphosphate, is characterized in that: comprise the following 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, then add solidifying agent, reaction 30 ~ 120min, be warming up to 70 ℃ ~ 150 ℃, reaction 60 ~ 180min, 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 the dry 8 ~ 48h of slaking, 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 fatty alcohol, the boiling point of 70 ℃ ~ 150 ℃ is the aliphatic ketone of 70 ℃ ~ 150 ℃; 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.
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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 |
| 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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| DE2949537A1 (en) * | 1979-12-08 | 1981-06-11 | Hoechst Ag, 6000 Frankfurt | PARTICULATE AGENT FOR PREVENTING THE FLAMMABILITY OF FLAMMABLE SUBSTANCES |
| DE3005252A1 (en) * | 1980-02-13 | 1981-08-20 | Hoechst Ag, 6000 Frankfurt | PARTICULATE AGENT FOR PREVENTING THE COMBUSTIBILITY OF COMBUSTIBLE SUBSTANCES |
| DE3316880A1 (en) * | 1983-05-07 | 1984-11-08 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING HYDROLYSIS-STABLE POWDER-SHAPED AMMONIUM POLYPHOSPHATES |
| DE3531500A1 (en) * | 1984-10-26 | 1986-05-07 | Hoechst Ag, 6230 Frankfurt | METHOD FOR THE PRODUCTION OF HYDROLYSIS-STABLE, FINE-PARTICLE FLAME-PROTECTING AGENTS BASED ON AMMONIUM POLYPHOSPHATE |
| CN1216679C (en) * | 2003-04-10 | 2005-08-31 | 上海化工研究院 | Method for making ammonium polyphosphate clad by microcapsules |
| CN101659823B (en) * | 2009-09-27 | 2012-09-19 | 中国科学技术大学 | Expanded type fireproof coating and preparation method thereof |
| CN102093300B (en) * | 2010-12-31 | 2012-08-08 | 普塞呋（清远）磷化学有限公司 | Preparation method of high-flowing property high-purity crystallization flaky melamine cyanurate |
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