CN101429291B - Method for coating syndiotactic polystyrene poly-ammonium phosphate with microcapsule - Google Patents
Method for coating syndiotactic polystyrene poly-ammonium phosphate with microcapsule Download PDFInfo
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- CN101429291B CN101429291B CN2008101478829A CN200810147882A CN101429291B CN 101429291 B CN101429291 B CN 101429291B CN 2008101478829 A CN2008101478829 A CN 2008101478829A CN 200810147882 A CN200810147882 A CN 200810147882A CN 101429291 B CN101429291 B CN 101429291B
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- syndiotactic polystyrene
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- ammonium polyphosphate
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Abstract
The invention relates to a method for coating a syndiotactic polystyrene resin microcapsule on ammonium polyphosphate, which is characterized in that 10 weight portions of ammonium polyphosphate, 0.5 to 4 weight portions of syndiotactic polystyrene resin and 50 to 600 weight portions of dispersant are added into a reaction kettle which is provided with a stirrer, a thermometer and a reflux condenser, subjected to stirring and reflux for 30 minutes at a temperature of between 40 and 200 DEG C until the syndiotactic polystyrene resin is completely dissolved, continuously stirred and dispersed for 10 to 120 minutes, and continuously stirred after heating is stopped; the solution is slowly cooled to the room temperature and stands; suspension is delaminated, and a supernatant liquor is removed; and deposit is washed by an organic solvent, and subjected to suction filtration, drying and grinding to obtain microcapsule-coated ammonium polyphosphate powder. Compared with uncoated ammonium polyphosphate, the microcapsule-coated ammonium polyphosphate has good particle fluidity, compact and uniform coating, and improved dialysis resistance, fire resistance and thermal stability, and is used as a fire retardant of polymer materials such as polyolefin, polyurethane and so on.
Description
Technical field
The present invention relates to a kind of method, belong to polymkeric substance halogen-free flame retardants preparation field with coating syndiotactic polystyrene poly-ammonium phosphate with microcapsule.
Background technology
Ammonium polyphosphate (ammonium polyphosphate is hereinafter to be referred as APP) has following general structure:
(NH
4)
N+2P
nO
3n+1(n in the formula＞10 are integer)
A kind of powdery object of good fluidity normally, whiteness is higher, and potential of hydrogen is near neutral, and chemical stability is good, and is safe in utilization, is insoluble in most of polar organic solvent, is difficult for taking place chemical transformation; Heat stability is good, phosphorus content and nitrogen content are all very high, have phosphorus-nitrogen cooperative flame retardant effect between them, have high flame-retarded efficiency, are widely used in substituting halogen flame, are applied to rubber, plastics, coating, paper fire-retardant.
Yet, there is phosphorus oxygen key on its chemical structure, absorb water molecules easily, so its water absorbability causes the reduction of flame-proofed polymer material electrical property than the organic fire-retardant height, limited the application of goods in electrical equipment industry; And because it is an inorganics, relatively poor with organic consistency, therefore can increase in time and reduce with fire-retardant its flame retardant resistance of polymer materials of APP, the phenomenon of " anti-frost " takes place in the surface that goods are moved in the dialysis of APP meeting simultaneously.Therefore be the method used always of scholar in recent years to the micro encapsulation modification of APP.
JP9227110, US5534291 disclose the method with trimeric cyanamide micro encapsulation APP; DE2949537, EP0180795 disclose the method with terpolycyantoamino-formaldehyde resin micro encapsulation APP; US 6291068, CN 1229399 have proposed with the method for thermoplastic polyolefin resin monomer at APP surface aggregate formation microcapsule; US 5109037 has proposed also to have obtained progress preferably with the multipolymer micro encapsulation APP of alpha-olefin and vinyl Pyrrolidine in addition, proves that this method can obviously improve the water resistance of APP; CA 1255448, CA 1258009, CA 1258010 have proposed the method with polyurethane polymer micro encapsulation APP.These methods all are based on reducing the water absorbability of APP, improve its water tolerance, improve its thermostability and improve its flame retardant resistance.But the reaction environment of above micro encapsulation APP is the aqueous solution, and very easily hydrolysis of APP, its polymerization degree can reduce in the microcapsule process, and flame retardant properties descends, and the water tolerance of APP also can descend along with the decline of the polymerization degree; And as thermoplastic resin, removing the involved aqueous environment of many patents can cause outside the APP hydrolysis, the temperature resistant grade of most of thermoplastic resin is not high enough, and Vicat softening point is on the low side, and the microcapsule that cause this method to coat can not be applied to the higher polymer materials of processing environment.
Therefore need to seek a kind of micro encapsulation material and method for coating thereof, improve the performance of APP material.This microencapsulation material should have following characteristics: 1) can be dissolved in organic solvent, because APP is insoluble to most of organic solvent, can prevent the influence of aqueous solvent to APP with organic solvent as dispersion agent during coating; 2) thermotolerance height, and have certain flame retardant resistance or can with the APP cooperative flame retardant; 3) consistency with polymer materials is good, can be used as the bridge that connects APP and polymeric matrix, reaches the purpose that reduces the APP dialysis.
Syndiotactic polystyrene (syndiotactic polystyrene, hereinafter to be referred as SPS) be a kind of crystallinity engineering plastics, (GPPS) compares with general purpose polystyrene, although the two starting material is identical, but since SPS in phenyl ring in molecular chain planar both sides cross-distribution, advise ordered arrangement between formation, regularity is good, thereby performance improves significantly.The SPS water tolerance is very good, has higher Vicat softening point: 254 ℃, melt temperature is at 270 ℃, under comparatively high temps, can keep its fundamental property constant, SPS is a kind of superpolymer that contains a large amount of phenyl ring in addition, and benzene ring structure carbon content height is easy to be dehydrated into carbon by ammonium polyphosphate.Therefore as can be seen, SPS is an ammonium polyphosphate microcapsule capsule wall material that meets above-mentioned requirements.SPS has the characteristic that is dissolved in the chloro organic solvent when heating in addition, and its character also determines method for coating of the present invention for " fusing disperses condensation method
The major technique characteristics of " fusing disperses condensation method " are: the waxy substance that is used as the wall material melts when being heated, and capsule-core is distributed in this liquid wall material, the dispersion liquid cooling that forms, form microcapsule structure then thereby the wall material is solidified and be coated on the capsule-core surface.
Summary of the invention
The objective of the invention is to provide a kind of method of coating syndiotactic polystyrene poly-ammonium phosphate with microcapsule, reach its anti-dialysis of raising thereby be characterized in utilizing syndiotactic polystyrene to be coated on the ammonium polyphosphate surface as the capsule material with excellent water tolerance and anti-dialysis at the deficiencies in the prior art; As the syndiotactic polystyrene resin of coating layer, the higher phenyl ring of carbon content can react fast rapid-result carbon with ammonium polyphosphate in its molecular structure in addition, and forms one deck adiabatic charcoal layer on its surface, reaches to stop the ammonium polyphosphate thermolysis and improve its thermotolerance; Utilize the syndiotactic polystyrene resin when heating up, can be dissolved in part chloro organic solvent, and the characteristics of separating out after the cooling use the method for " fusing disperses condensation " to prepare micro encapsulation ammonium polyphosphate material.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The method of syndiotactic polystyrene microcapsule-coated ammonium polyphosphate may further comprise the steps:
The syndiotactic polystyrene resin of 10 weight part ammonium polyphosphates and 0.5-4 weight part and the dispersion agent adding of 50-600 weight part are had agitator, temperature is taken into account in the reactor of condensation reflux unit, in temperature 40-200 ℃, stirring and refluxing 30 minutes, dissolve fully until the syndiotactic polystyrene resin, continued dispersed with stirring 10-120 minute, stop heating, continue to stir, make solution slowly cool to room temperature, leave standstill and make the suspension layering, remove supernatant liquid, with the throw out organic solvent washing, suction filtration, oven dry, grind, obtain the ammonium polyphosphate powder that microcapsule coat.
In the present invention, dispersant dosage is low excessively, and the dispersion effect of APP is not good enough, may form coacervate, influences final covered effect; Dispersant dosage is too high, and dispersion and the energy consumption that reclaims are too high, and be uneconomical from cost.The SPS quantity not sufficient can cause the coating of APP particle not exclusively, has the part particle exposed, and the purpose of coating does not reach; The consumption of SPS is too high, and the coating layer of APP particle surface is blocked up, and cost improves, and uses inconvenience, and influential to flame retardant resistance.
Wherein, ammonium polyphosphate is a white powder, and median size is 5-20 μ m, the II N-type waferN, and the polymerization degree is 500-1200; Syndiotactic polystyrene interlaminar resin normality is 50-90%, and density is 1.02g/cm
3, water-intake rate does not contain filler and auxiliary agent less than 0.04%.
Dispersion agent is to contain-fatty compounds of Cl group or contain-Cl group aromatics, fatty compounds is at least a in monochloro methane, methylene dichloride, trichloromethane, monochlorethane, 11-ethylene dichloride, 12-ethylene dichloride and the trichloroethane, and aromatics is at least a in mono chloro benzene, 12-dichlorobenzene, 14-dichlorobenzene and the 124-trichlorobenzene.
The organic solvent of washing precipitate is any in monochloro methane, methylene dichloride, trichloromethane, monochlorethane, 11-ethylene dichloride, 12-ethylene dichloride or the trichloroethane.
Performance test data is to record by the following method:
1 granularity, particle size analysis, structure and microscopic pattern analysis: adopt the JSM-5900LV type scanning electron microscope of Japanese JEOL company, observation analysis under 200-10000x;
80 parts of 2 dialysis mensuration: 20 parts of APP before and after microcapsule are coated and polypropylene are pressed into test piece (100mm * 100mm * 1.6mm) with vulcanizing press behind the blend 5min in Banbury mixer.Test piece is soaked 4h in 95 ℃ of hot water, measure the surface resistivity of hot-water soak front and back, characterizes the quality of its anti-dialysis with the variation of surface resistivity;
3 thermogravimetric analysiss: adopt the SDT/Q600 thermogravimetric analyzer test of U.S. TA company, 10 ℃/min of temperature rise rate, nitrogen atmosphere, feeding amount 100ml/min;
4 flame retardant propertiess are measured: the oxygen index test, and APP, tetramethylolmethane, PP are injected into standard test specimen by 24: 6: 70 quality after than twin screw blend extruding pelletization test its oxygen index, press the GB2406 standard.
The result shows: the microcapsule that make with the inventive method coat APP, with uncoated APP relatively, colourity does not change, median size does not obviously increase, the particulate good fluidity.See for details shown in Fig. 1-6 stereoscan photograph, the APP surface forms uniform SPS coating film, and it is exposed to find no individual particle.Detailed being shown in Table 1 contrasts with not coating the fire-retardant PP of preceding APP, the anti-dialysis raising of the ammonium polyphosphate that the syndiotactic polystyrene resin microcapsule coats, and heat resisting temperature improves, and flame retardant properties also increases.Can be according to the product that present method makes as the fire retardant of macromolecular materials such as polyolefine.
The present invention has the following advantages:
The anti-dialysis of 1 material is significantly improved, and rate of release obviously reduces under the high humidity hot environment;
The thermostable type of 2 materials is significantly improved, and its main thermal weight loss step temperature increases substantially under nitrogen atmosphere, and the ammonium polyphosphate after the syndiotactic polystyrene resin microcapsule coats is used for the higher macromolecular material of processing temperature;
3 flame retardant resistances are improved, and the syndiotactic polystyrene capsule material on ammonium polyphosphate surface can be fire-retardant with the ammonium polyphosphate synergistic;
4 whole coating processes do not have chemical reaction, do not produce objectionable impurities, and the gained waste liquid can be reused after reclaiming purification, does not influence the effect that microcapsule coat.
Description of drawings
Fig. 1 is the sem photograph of the syndiotactic polystyrene resin-coated ammonium polyphosphate microcapsule of embodiment 1 gained
Fig. 2 is the sem photograph of the syndiotactic polystyrene resin-coated ammonium polyphosphate microcapsule of embodiment 2 gained
Fig. 3 is the sem photograph of the syndiotactic polystyrene resin-coated ammonium polyphosphate microcapsule of embodiment 3 gained
Fig. 4 is the sem photograph of the syndiotactic polystyrene resin-coated ammonium polyphosphate microcapsule of embodiment 4 gained
Fig. 5 is the sem photograph of the syndiotactic polystyrene resin-coated ammonium polyphosphate microcapsule of embodiment 5 gained
Fig. 6 is the sem photograph of the syndiotactic polystyrene resin-coated ammonium polyphosphate microcapsule of embodiment 6 gained
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this; present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
Normality 50% between inciting somebody to action, density 1.02g/cm
3Water-intake rate less than 0.04% SPS 0.5g and methylene dichloride 50ml join have agitator, temperature is taken into account in the reactor of reflux exchanger, in 40 ℃ of constant temperature stirring reactions of temperature 30 minutes, treat that SPS dissolves fully after, add particle diameter 5 μ m, the polymerization degree is 500, the APP 10g of II N-type waferN continued the constant temperature stir about 120 minutes, and APP is uniformly dispersed, stop heating and continue to stir, be cooled to room temperature until solution.With the solution left standstill layering, remove supernatant liquid, with throw out washed with dichloromethane, suction filtration, oven dry, grinding, the microcapsule that obtain good fluidity coat APP10.3g.
Embodiment 2
Normality 90% between inciting somebody to action, density 1.02g/cm
3The water rate less than 0.04% SPS 4g and 12-ethylene dichloride 600ml join have agitator, temperature is taken into account in the reactor of reflux exchanger, in 60 ℃ of constant temperature stirring reactions of temperature 30 minutes, treat that SPS dissolves fully after, add particle diameter 20 μ m, the polymerization degree is 1200, the APP 10g of II N-type waferN continued the constant temperature stir about 10 minutes, and APP is uniformly dispersed, stop heating and continue to stir, be cooled to room temperature until solution.With the solution left standstill layering, remove supernatant liquid, with throw out 12-ethylene dichloride washing, suction filtration, oven dry, grinding, the microcapsule that obtain good fluidity coat APP13.2g.
Embodiment 3
Normality 70% between inciting somebody to action, density 1.02g/cm
3The water rate less than 0.04% SPS 2g and 124-trichlorobenzene 200ml join have agitator, temperature is taken into account in the reactor of reflux exchanger, in 200 ℃ of constant temperature stirring reactions of temperature 30 minutes, treat that SPS dissolves fully after, add particle diameter 10 μ m, the polymerization degree is 1000, the APP 10g of II N-type waferN continued the constant temperature stir about 30 minutes, and APP is uniformly dispersed, stop heating and continue to stir, be cooled to room temperature until solution.With the solution left standstill layering, remove supernatant liquid, with trichloromethane washing, suction filtration, oven dry, grinding, the microcapsule that obtain good fluidity coat APP11.8g with throw out.
Embodiment 4
Normality 80% between inciting somebody to action, density 1.02g/cm
3The water rate is less than 0.04% SPS 2g and 1,2-dichlorobenzene 160ml join have agitator, temperature was taken into account in the reactor of reflux exchanger, in 180 ℃ of constant temperature stirring reactions of temperature 30 minutes, after treating that SPS dissolves fully, add particle diameter 15 μ m, the polymerization degree is 1000, the APP 10g of II N-type waferN, continued the constant temperature stir about 60 minutes, APP is uniformly dispersed, stops heating and continue to stir, be cooled to room temperature until solution.With the solution left standstill layering, remove supernatant liquid, with monochloro methane washing, suction filtration, oven dry, grinding, the microcapsule that obtain good fluidity coat APP11.7g with throw out.
Embodiment 5
Normality 60% between inciting somebody to action, density 1.02g/cm
3The water rate is less than 0.04% SPS 4g and 1,1-ethylene dichloride 160ml join have agitator, temperature was taken into account in the reactor of reflux exchanger, in 80 ℃ of constant temperature stirring reactions of temperature 30 minutes, after treating that SPS dissolves fully, add particle diameter 15 μ m, the polymerization degree is 1000, the APP 10g of II N-type waferN, continued the constant temperature stir about 100 minutes, APP is uniformly dispersed, stops heating and continue to stir, be cooled to room temperature until solution.With the solution left standstill layering, remove supernatant liquid, with trichloroethane washing, suction filtration, oven dry, grinding, the microcapsule that obtain good fluidity coat APP13.7g with throw out.
Embodiment 6
Normality 80% between inciting somebody to action, density 1.02g/cm
3The water rate less than 0.04% SPS 1.5g and trichloroethane 160ml join have agitator, temperature is taken into account in the reactor of reflux exchanger, in 75 ℃ of constant temperature stirring reactions of temperature 30 minutes, treat that SPS dissolves fully after, add particle diameter 15 μ m, the polymerization degree is 1000, the APP 10g of II N-type waferN continued the constant temperature stir about 90 minutes, and APP is uniformly dispersed, stop heating and continue to stir, be cooled to room temperature until solution.With the solution left standstill layering, remove supernatant liquid, with monochlorethane washing, suction filtration, oven dry, grinding, the microcapsule that obtain good fluidity coat APP11.0g with throw out.
The main test result of table 1 embodiment 1-6
Claims (1)
1. the preparation method of a coating syndiotactic polystyrene poly-ammonium phosphate with microcapsule is characterized in that this method may further comprise the steps:
The syndiotactic polystyrene resin of 10 weight part ammonium polyphosphates and 0.5-4 weight part and the dispersion agent adding of 50-600 weight part are had agitator, temperature is taken into account in the reactor of condensation reflux unit, in temperature 40-200 ℃, stirring and refluxing 30 minutes, dissolve fully until the syndiotactic polystyrene resin, continued dispersed with stirring 10-120 minute, stop heating, continue to stir, make solution slowly cool to room temperature, leave standstill and make the suspension layering, remove supernatant liquid, with the throw out organic solvent washing, suction filtration, oven dry, grind, obtain the ammonium polyphosphate powder that microcapsule coat;
Wherein, ammonium polyphosphate: white powder, median size are 5-20 μ m, the II N-type waferN, and the polymerization degree is 500-1200; The syndiotactic polystyrene resin: a normality is 50-90%, and density is 1.02g/cm
3, water-intake rate is less than 0.04%;
Described dispersion agent is to contain-fatty compounds of Cl group or contain-Cl group aromatics: fatty compounds is methylene dichloride, trichloromethane, monochlorethane, 1,1-ethylene dichloride, 1, at least a in 2-ethylene dichloride and the trichloroethane; Aromatics is a mono chloro benzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene and 1,2, at least a in the 4-trichlorobenzene;
The organic solvent of described washing precipitate is methylene dichloride, trichloromethane, monochlorethane, 1,1-ethylene dichloride, 1, any in 2-ethylene dichloride or the trichloroethane.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101829527B (en) * | 2010-04-01 | 2011-12-28 | 河北大学 | Method for preparing microcapsule-coated ammonium polyphosphate |
| CN102850592B (en) * | 2012-08-30 | 2014-01-29 | 西南石油大学 | Preparation method for ammonium polyphosphate/polystyrene core-shell microspheres |
| CN103172908A (en) * | 2013-03-05 | 2013-06-26 | 云南磷化集团有限公司 | Method for coating ammonium polyphosphate by using binary composite coating agent |
| EP3326967A1 (en) | 2016-11-25 | 2018-05-30 | Leibniz-Institut für Polymerforschung Dresden e.V. | Modified multifunctional polyphosphate and method to prepare the multifunctional modified polyphosphates |
| US10377874B2 (en) | 2017-11-01 | 2019-08-13 | Shenyang Shunfeng New Material Co., Ltd. | Bio-based fire retardant derived from polyacrylamide grafted starch and use thereof |
| CN107955210A (en) * | 2017-12-01 | 2018-04-24 | 广东顺德同程新材料科技有限公司 | A kind of preparation method and microcapsule flame retardant of microcapsules hypo-aluminum orthophosphate combustion inhibitor |
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| US5109037A (en) * | 1990-06-15 | 1992-04-28 | Ppg Industries, Inc. | Surface-moldified ammonium polyphosphate |
| US5534291A (en) * | 1993-03-09 | 1996-07-09 | Chisso Corporation | Process for producing a melamine-coated ammonium polyphosphate |
| CN1229399A (en) * | 1997-06-26 | 1999-09-22 | 智索股份有限公司 | Thermoplastic resin coated ammonium polyphosphate and process for preparation thereof |
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2008
- 2008-12-16 CN CN2008101478829A patent/CN101429291B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5109037A (en) * | 1990-06-15 | 1992-04-28 | Ppg Industries, Inc. | Surface-moldified ammonium polyphosphate |
| US5534291A (en) * | 1993-03-09 | 1996-07-09 | Chisso Corporation | Process for producing a melamine-coated ammonium polyphosphate |
| CN1229399A (en) * | 1997-06-26 | 1999-09-22 | 智索股份有限公司 | Thermoplastic resin coated ammonium polyphosphate and process for preparation thereof |
| US6291068B1 (en) * | 1997-06-26 | 2001-09-18 | Chisso Corporation | Thermoplastic resin-coated ammonium polyphosphate and process for the preparation thereof |
Non-Patent Citations (1)
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| 谢吉星等.聚磷酸铵的微胶囊化与阻燃应用.《阻燃材料与技术》.2004,(第1期),1-2. * |
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