CN100487065C - Red phosphorus double-layer covered with both organic and inorganic material and its preparation process - Google Patents
Red phosphorus double-layer covered with both organic and inorganic material and its preparation process Download PDFInfo
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- CN100487065C CN100487065C CNB021484880A CN02148488A CN100487065C CN 100487065 C CN100487065 C CN 100487065C CN B021484880 A CNB021484880 A CN B021484880A CN 02148488 A CN02148488 A CN 02148488A CN 100487065 C CN100487065 C CN 100487065C
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Abstract
The preparation process of red phosphorus double-layer covered with both o and inorganic material includes ball milling water dispersion containing coarse red phosphorus in 20-40 wt%, mixing with metal halide or sulfate and urea in stoichiometric amount inside a reflux condensating reactor for reaction at 90-120 deg.c for 4-6 hr, cooling, filtering, water washing and vacuum drying of filter cake, compounding into water suspension of 20-40 wt% concentration; adding water soluble resin, regulating pH to 3-4, heating, stirring, cooling, filtering, water washing, vacuum drying, or adding liposoluble resin diluted with acetone, xylene or gasoline to the filter cake via stirring, and vacuum drying to obtain the covered red phosphorus grain product of 2-10 micron size and with compactly covering hydroxide of 10-50 nm size on the surface and organic covering layer of 2-10 nm thickness to cover the inorganic covering layer.
Description
Technical field:
The invention belongs to the fire retardant technical field, particularly relate to inorganic-organic bilayer encapsulated red phosphorus and preparation method thereof.
Background technology:
Red phosphorus is as a kind of highly effective inorganic flame-proof agent, have that the amount of being fuming is low, nontoxic, advantage such as good weatherability, use range are wide, but in storage process and actual the use, red phosphorus exist low, the easy moisture absorption of point of ignition to be oxidized to acid and discharge poisonous gas phosphuret-(t)ed hydrogen, with defective such as resin compatible difference, limited the use of red phosphorus, therefore, must coat processing to red phosphorus.United States Patent (USP) 4; 853; 288 disclosed a kind of inorganic-the organic bilayer encapsulated red phosphorus; the weight of its inorganic coating layer and organic coating layer accounts for 0.1-5% and 1-20% of red phosphorus weight respectively; its preparation method is: add water-soluble metal salt in the red phosphorus aqeous suspension, the pH value with sodium hydroxide solution conditioned reaction system adds water-soluble trimeric cyanamide-formaldehyde resin performed polymer then; stirring reaction for some time is dry under nitrogen protection with product then at a certain temperature.The defective of this method is: though the precipitation agent hydroxide ion is constantly to join in the solution slowly under the stirring condition, but owing to have little time diffusion, cause in two kinds of solution blended places, the concentration height of elsewhere in the concentration ratio solution of precipitation agent, the phenomenon of this local overrich makes the relative degree of supersaturation of this part solution become very big, cause the precipitation of hydroxide short texture that generates, absorption impurity is many, and the inorganic coating layer compactness of formation is poor; Because inorganic coating layer compactness is poor, in order to improve the stability of double-coated red phosphorus, cause the content of organic coating layer of using to increase, cost is higher.
Technology contents:
The invention provides a kind of inorganic-organic bilayer encapsulated red phosphorus and preparation method thereof, to overcome the above-mentioned defective of prior art.
Of the present invention inorganic-preparation method of organic bilayer encapsulated red phosphorus, be characterised in that raw material and the weight proportion scope thereof that comprises following composition that adopt:
Red phosphorus 10-15%
Metal halide or vitriol 5-10%
Urea 10-15%
Water 50-70%
Resin 1-5%
Described metal halide or vitriol comprise crystallization magnesium chloride, crystal aluminum chloride, anhydrous magnesium sulfate, crystalline sulfuric acid aluminium; Described resin comprises water miscible trimeric cyanamide-formaldehyde resin or urea-formaldehyde resin, or oil-soluble resol or Resins, epoxy;
Its preparation process is:
(1) thick red phosphorus is washed with distilled water to neutrality, be made into the water dispersion of 20%-40% weight ratio, put into ball grinder, ground 30-60 minutes with 120-180 rev/mins of rotating speeds, adding has in the reaction vessel of reflux condensate device, under agitation slowly adds metal halide or vitriol and urea, be heated to 90-120 ℃, reacted 4.0-6.0 hours, and be cooled to room temperature, filter; Filter cake with distilled water wash after 70-90 ℃ of vacuum-dryings 6-10 hours, obtain the red phosphorus that oxyhydroxide coats;
(2) red phosphorus that above-mentioned oxyhydroxide is coated with water soluble resin or oil-soluble resin carries out the secondary coating:
For water soluble resin, to be made into the aqeous suspension of 20-40% weight ratio through the red phosphorus that above-mentioned oxyhydroxide coats, regulate pH value to 3-4, be heated to 60-90 ℃, stirred 1-2 hours, and be cooled to room temperature then, filter, filter cake with distilled water wash after, 70-90 ℃ of vacuum-dryings 6-10 hours;
For oil-soluble resin, with 5.0-10.0 times acetone or dimethylbenzene or gasoline resin is diluted, mix with the red phosphorus that coats of the oxyhydroxide that obtains in the step (1) then, stir, 70-90 ℃ of vacuum-dryings 2-5 hours.
Of the present invention inorganic-the organic bilayer encapsulated red phosphorus, it is characterized in that: particle diameter be the precipitation of hydroxide of 10-50 nanometers to be coated on particle diameter densely as inorganic coating layer be 2-10 microns red phosphorus particle surface, organic coating layer of 2-10 nanometer thickness is coated on the inorganic coating layer closely; Described inorganic coating layer material comprises magnesium hydroxide or aluminium hydroxide, and described organic coating layer material comprises trimeric cyanamide-formaldehyde resin or urea-formaldehyde resin or resol or Resins, epoxy.
Prepare in the method for inorganic-organic bilayer encapsulated red phosphorus in the present invention, precipitation of hydroxide is to be undertaken by following reaction:
CO(NH
2)
2+3?H
2O＝CO
2↑+2?NH
4 ++2?OH
-
Mg
2++2?OH
-＝Mg(OH)
2↓
Because the present invention adopts hydrolysis of urea to produce the precipitation agent hydroxide ion, hydroxide ion is separated out from solution lentamente, be evenly distributed in the solution, avoided local overrich phenomenon, the relative degree of supersaturation of solution is less all the time in precipitation process, sedimentary formation speed slowly and has evenly improved the compactness that generates coating layer at the red phosphorus particle surface, and absorption impurity is few; Since inorganic coating layer densification, the corresponding consumption that reduces its organic coating layer in outside; Gained is inorganic-the organic bilayer encapsulated red phosphorus in, inorganic coating layer and organic coating layer account for 10-15% and 4-8% of red phosphorus weight respectively, the content of organic coating layer is lower, has reduced cost.
Description of drawings:
Fig. 1 is for amplifying 50,000 times transmission electron microscope photo through grinding back red phosphorus particulate among the embodiment 1.
Fig. 2 is with the transmission electron microscope photo of magnesium hydroxide as 80,000 times of the amplifications of inorganic layer encapsulated red phosphorus among the embodiment 1.
Fig. 3 is the transmission electron microscope photo of 80,000 times of the amplifications of magnesium hydroxide among the embodiment 1-terpolycyantoamino-formaldehyde resin double-coated red phosphorus.
Embodiment:
Embodiment 1.
The thick red phosphorus of 12 grams is washed with water to neutrality, be made into aqeous suspension by 30% weight ratio, put into ball grinder, setting drum's speed of rotation is 150 rev/mins, ground 45 minutes, be transferred in 250 milliliters the reaction vessel that has reflux condensate device, under magnetic agitation, add 6.0 gram magnesium chlorides and 8.2 gram urea lentamente, be heated to 105 ℃ of reactions 5.0 hours, solution is cooled to room temperature, filter, filter cake with distilled water wash after, in vacuum drying oven,, obtain the red phosphorus that magnesium hydroxide coats in 80 ℃ of dryings 7.0 hours;
The red phosphorus of magnesium hydroxide coating is made into the aqeous suspension of 20% weight ratio, add 1.2 gram formaldehyde-melamine resins, with concentration is that 30% formic acid solution is transferred PH=3.0, is warming up to 90 ℃, stirring reaction 1.5 hours, cooling, filter, filter cake with distilled water wash after, be placed in the vacuum drying oven, 85 ℃ of dryings 7.0 hours, obtain the red phosphorus of magnesium hydroxide and trimeric cyanamide-formaldehyde resin double-coated.
Performance to the inorganic-organic bilayer encapsulated red phosphorus of present embodiment preparation detects as follows:
1. oxidative stability:
Accurately taking by weighing 1.000 gram red phosphorus is suspended in the 100ml water, this suspension is heated to boiling 1.0 hours, filter, in filtrate, add 1.000 gram analytical pure sodium-chlor, dissolving back is with the oxygen acid that forms because of phosphorus oxidation in the sodium hydroxide solution titration filtrate of having demarcated, represents oxidative stability with the gram number of the sodium hydroxide of every gram red phosphorus consumption.
2. water absorbability:
Accurately take by weighing 5.000 gram red phosphorus, be dispersed in the watch-glass, watch-glass is put into 50 ℃ the close drying case that has saturated ammonium sulphate solution, place and weigh after 7 days, calculate the weight that red phosphorus increases, recently represent water absorbability with the weightening finish percentage of every gram red phosphorus average every day.
3. point of ignition:
Detect according to GB9343-88.
4. phosphuret-(t)ed hydrogen burst size:
Phosphuret-(t)ed hydrogen and HgCl
2Reaction generates insoluble P (HgCl)
3, P (HgCl)
3By the iodine oxidation, the Sulfothiorine titration of excessive iodine is represented with the amount that every gram red phosphorus discharges phosphuret-(t)ed hydrogen every day.
By the calculating of weighing, the inorganic-organic bilayer encapsulated red phosphorus of present embodiment preparation, the weight of its inorganic coating layer and organic coating layer accounts for 14.0% and 5.5% of red phosphorus weight respectively.Detection shows: the oxidative stability of the inorganic-organic bilayer encapsulated red phosphorus of present embodiment preparation is 0.26mg, NaOH/g, red phosphorus; Water absorbability is 0.054%; Point of ignition is 394 ℃; The phosphuret-(t)ed hydrogen burst size is 0.44 μ g/g24h.
List the magnesium hydroxide of present embodiment preparation and the above-mentioned performance perameter detected result of trimeric cyanamide-formaldehyde resin double-coated red phosphorus in table 1.
By calculating and learn that the red phosphorus particle grain size is not more than 1.0 millimeters through grinding transmission electron microscope photo Fig. 1 that back red phosphorus particulate amplifies 50,000 times.
By transmission electron microscope photo Fig. 2 of 80,000 times of the amplifications of the red phosphorus that only coats with magnesium hydroxide as can be seen the magnesium hydroxide particle densification be coated on red phosphorus particulate surface, magnesium hydroxide particle epigranular, median size are 12.5 nanometers.
By being coated on the inorganic coating layer of magnesium hydroxide of the organic as can be seen coating layer trimeric cyanamide of the transmission electron microscope photo Fig. 3-formaldehyde resin densification of 80,000 times of the amplifications of product magnesium hydroxide-terpolycyantoamino-formaldehyde resin double-coated red phosphorus, the thickness of the organic coating layer of trimeric cyanamide-formaldehyde resin is 2-10 nanometers.
Embodiment 2.
The thick red phosphorus of 120 grams is washed with water to neutrality, be made into aqeous suspension by 20% weight ratio, put into ball grinder, ground 60 minutes with 130 rev/mins of rotating speeds, be transferred to then in 2000 milliliters the reaction vessel that has reflux condensate device, under magnetic agitation, slowly add 40 gram sal epsom, add 60.0 gram urea again, be heated to 98 ℃ of reactions 6.0 hours, solution is cooled to room temperature, filter, filter cake with distilled water wash after in vacuum drying oven in 80 ℃ of dryings 8.0 hours, obtain the red phosphorus that magnesium hydroxide coats;
The red phosphorus of magnesium hydroxide coating is made into the aqeous suspension of weight ratio 30%, add 12 gram formaldehyde-urea resins, the pH=3.5 of regulator solution, be warming up to 65 ℃, reacted 1.5 hours, cooling, filter, filter cake is placed in the vacuum drying oven after with distilled water wash, in 85 ℃ of dryings 9.0 hours, obtains the red phosphorus of magnesium hydroxide and trimeric cyanamide-formaldehyde resin double-coated.
Calculate as can be known by weighing, the inorganic-organic bilayer encapsulated red phosphorus of present embodiment preparation, the weight of its inorganic coating layer and organic coating layer accounts for 14.2% and 5.5% of red phosphorus weight respectively.
List the performance perameter detected result of the inorganic-organic bilayer encapsulated red phosphorus of present embodiment preparation in table 1.
Embodiment 3.
The thick red phosphorus of 10 grams is washed with water to neutrality, be made into aqeous suspension by 40% weight ratio, put into ball grinder, after 45 minutes, be transferred in 250.0 milliliters the reaction vessel that has reflux condensate device with 150 rev/mins of rotating speed mills, under magnetic agitation, slowly add 4.5 gram aluminum chloride and 8.0 gram urea, be heated to 115 ℃ of reactions 4.5 hours, solution is cooled to room temperature, filter, filter cake with distilled water wash after in vacuum drying oven in 80 ℃ of dryings 7.0 hours; The red phosphorus that aluminium hydroxide is coated joins with 0.5 of 5.0 gram acetone diluted and restrains in the Resins, epoxy, stir into the even attitude of pasty state, send in the drying plant that has solvent recovery unit, carried out drying 3.5 hours, obtain the red phosphorus of aluminium hydroxide and Resins, epoxy double-coated at 70 ℃.
Calculate as can be known by weighing, the inorganic-organic bilayer encapsulated red phosphorus of present embodiment preparation, the weight of its inorganic coating layer and organic coating layer accounts for 13.6% and 4.7% of red phosphorus weight respectively.
List the performance perameter detected result of the inorganic-organic bilayer encapsulated red phosphorus of present embodiment preparation in table 1.
The contrast experiment 4.
For embodying superiority of the present invention, carried out following experiment by the prior art scheme: the thick red phosphorus of 12 grams is washed with water to neutrality, be made into the aqeous suspension of 40% weight ratio, put into ball grinder, ground 40 minutes with 160 rev/mins of rotating speeds, be transferred to then in 250 milliliters the reaction vessel that has reflux condensate device, under magnetic agitation, add 2.5 Tai-Ace S 150, slowly add concentration and be 10% sodium hydroxide solution, the pH=5.5 of regulator solution adds 3.5 gram trimeric cyanamide-formaldehyde resin performed polymers again, with concentration the pH=5.0 of 10% formic acid regulator solution, be heated to 85 ℃ of insulation reaction 2 hours, and be cooled to room temperature then, filter, filter cake with distilled water wash after in vacuum drying oven 85 ℃ of dryings 7.0 hours, obtain the red phosphorus of aluminium hydroxide and trimeric cyanamide-formaldehyde resin double-coated.
By the calculating of weighing, the inorganic-organic bilayer encapsulated red phosphorus of Comparative Examples 4 preparations, the weight of its inorganic coating layer and organic coating layer accounts for 4.8% and 16.5% of red phosphorus weight respectively.
List the performance perameter detected result of the inorganic-organic bilayer encapsulated red phosphorus of Comparative Examples 4 preparation in table 1.
The performance perameter of inorganic in table 1. embodiment and the Comparative Examples-organic bilayer encapsulated red phosphorus
From the correlation data of last table, can be clear that, inorganic-its oxidative stability of organic bilayer encapsulated red phosphorus, point of ignition, water absorbability and the phosphuret-(t)ed hydrogen burst size of embodiment of the invention preparation all is better than the red phosphorus of inorganic-organic bilayer coating of prior art for preparing, and the present invention has significantly improved the stability of red phosphorus.
Claims (2)
1, a kind of inorganic-preparation method of organic bilayer encapsulated red phosphorus, it is characterized in that adopting the raw material and the weight proportion scope thereof that comprise following composition:
Red phosphorus 10-15%
Metal halide or vitriol 5-10%
Urea 10-15%
Water 50-70%
Resin 1-5%
Described metal halide or vitriol comprise crystallization magnesium chloride, crystal aluminum chloride, anhydrous magnesium sulfate, crystalline sulfuric acid aluminium; Described resin comprises water miscible trimeric cyanamide-formaldehyde resin or urea-formaldehyde resin, or oil-soluble resol or Resins, epoxy;
Its preparation process is:
(1) thick red phosphorus is washed with distilled water to neutrality, be made into the water dispersion of 20%-40% weight ratio, put into ball grinder, ground 30-60 minutes with 120-180 rev/mins rotating speeds, adding has in the reaction vessel of reflux condensate device, under agitation slowly adds metal halide or vitriol and urea, be heated to 90-120 ℃, reacted 4.0-6.0 hours, and be cooled to room temperature, filter; Filter cake with distilled water wash after 70-90 ℃ of vacuum-dryings 6-10 hours, obtain the red phosphorus that oxyhydroxide coats;
(2) red phosphorus that above-mentioned oxyhydroxide is coated with water soluble resin or oil-soluble resin carries out the secondary coating:
For water soluble resin, to be made into the aqeous suspension of 20-40% weight ratio through the red phosphorus that above-mentioned oxyhydroxide coats, regulate pH value to 3-4, be heated to 60-90 ℃, stirred 1-2 hours, and be cooled to room temperature then, filter, filter cake with distilled water wash after, 70-90 ℃ of vacuum-dryings 6-10 hours;
For oil-soluble resin, with 5.0-10.0 times acetone or dimethylbenzene or gasoline resin is diluted, mix with the red phosphorus that coats of the oxyhydroxide that obtains in the step (1) then, stir, 70-90 ℃ of vacuum-dryings 2-5 hours.
2, a kind of inorganic-the organic bilayer encapsulated red phosphorus, it is characterized in that: particle diameter is that the precipitation of hydroxide of 10-50 nanometers is coated on particle diameter densely as inorganic coating layer and is not more than 1.0 millimeters red phosphorus particle surface, and organic coating layer of 2-10 nanometer thickness is coated on the inorganic coating layer closely; Described inorganic coating layer material comprises magnesium hydroxide or aluminium hydroxide, and described organic coating layer material comprises trimeric cyanamide-formaldehyde resin or urea-formaldehyde resin or resol or Resins, epoxy.
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|---|---|---|---|
| CNB021484880A CN100487065C (en) | 2002-12-07 | 2002-12-07 | Red phosphorus double-layer covered with both organic and inorganic material and its preparation process |
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|---|---|---|---|
| CNB021484880A CN100487065C (en) | 2002-12-07 | 2002-12-07 | Red phosphorus double-layer covered with both organic and inorganic material and its preparation process |
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|---|---|
| CN1506408A CN1506408A (en) | 2004-06-23 |
| CN100487065C true CN100487065C (en) | 2009-05-13 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731888B (en) * | 2012-05-22 | 2014-06-18 | 宁波一舟塑胶有限公司 | Multilayer coated red phosphorus low-smoke halogen-free flame-retardant polyolefin cable sheath material and preparation method thereof |
| CN105602004A (en) * | 2016-01-20 | 2016-05-25 | 天津商业大学 | Double-wall microencapsulated red phosphorus and preparation method and waterborne polyurethane flame-retardant film thereof |
| CN106189049A (en) * | 2016-08-04 | 2016-12-07 | 浙江畅通科技有限公司 | A kind of lead-acid accumulator flame-retardant plastic-housing material |
| CN106854295B (en) * | 2016-12-05 | 2021-09-03 | 合肥杰事杰新材料股份有限公司 | Low-odor low-emission white red phosphorus flame-retardant master batch for white red phosphorus and nylon and preparation method thereof |
| CN109134939B (en) * | 2018-08-09 | 2019-12-31 | 福州大学 | Piperazine modified lignin/magnesium aluminum hydroxide double-coated red phosphorus flame retardant and application thereof in PP |
| CN109135478B (en) * | 2018-08-17 | 2021-04-30 | 河南省阳光防腐涂装有限公司 | Environment-friendly fireproof composite coating |
| CN111499922B (en) * | 2020-05-28 | 2022-03-08 | 杭州本松新材料技术股份有限公司 | Red phosphorus flame-retardant system, thermoplastic composition, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698215A (en) * | 1985-03-19 | 1987-10-06 | Saffa S.P.A. | Stabilized red phosphorus for use as flame-retardant, in particular for compositions on the basis of polymers |
| US5543444A (en) * | 1993-08-12 | 1996-08-06 | Rinkagaku Kogyo Co., Ltd. | Red phosphorus flame retardant and nonflammable resinous composition |
-
2002
- 2002-12-07 CN CNB021484880A patent/CN100487065C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698215A (en) * | 1985-03-19 | 1987-10-06 | Saffa S.P.A. | Stabilized red phosphorus for use as flame-retardant, in particular for compositions on the basis of polymers |
| US5543444A (en) * | 1993-08-12 | 1996-08-06 | Rinkagaku Kogyo Co., Ltd. | Red phosphorus flame retardant and nonflammable resinous composition |
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Assignee: ANHUI FEIJIAN ENERGY SAVING SCIENCE & TECHNOLOGY CO., LTD. Assignor: University of Science and Technology of China Contract fulfillment period: 2009.8.12 to 2014.8.12 contract change Contract record no.: 2009340000184 Denomination of invention: Red phosphorus double-layer covered with both organic and inorganic material and its prepn process Granted publication date: 20090513 License type: Exclusive license Record date: 2009.8.20 |
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