CN104059388A - Double-coated microencapsulated red phosphorus and preparation method thereof - Google Patents
Double-coated microencapsulated red phosphorus and preparation method thereof Download PDFInfo
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- CN104059388A CN104059388A CN201410298045.1A CN201410298045A CN104059388A CN 104059388 A CN104059388 A CN 104059388A CN 201410298045 A CN201410298045 A CN 201410298045A CN 104059388 A CN104059388 A CN 104059388A
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Abstract
The invention discloses double-coated microencapsulated red phosphorus and a preparation method thereof. The preparation method comprises the following steps: preparing superfine red phosphorus; preparing a melamine-formaldehyde resin prepolymer solution; adding superfine red phosphorus, water with weight being 20-40 times that of red phosphorus, a dispersant with weight being 0.01-0.03 times that of red phosphorus and a stabilizer with weight being 0.005-0.01 time that of red phosphorus into a reactor, stirring to be uniform and heating, adding a catalyst and a metal salt solution into a system, adjusting the pH value by using ammonia water, performing heat preservation stirring, adding the melamine-formaldehyde resin prepolymer solution, adjusting the pH value to be 3-5 by using the ammonia water, and performing heat-preservation stirring for 1-3 hours; after the reaction is finished, cooling the solution, filtering, washing, and drying to obtain inorganic-organic double-coated microencapsulated red phosphorus. According to the preparation method, persulfate is used as a catalyst, organic clay is used as a stabilizer, the ignition point of prepared microencapsulated red phosphorus exceeds 440 DEG C, the PH3 release quantity and the hygroscopicity are remarkably reduced; and as a flame retardant for high molecular material, the double-coated microencapsulated red phosphorus is capable of reducing the influence on the mechanical property of the high molecular materials.
Description
Technical field
The present invention relates to microcapsule red phosphorus and preparation thereof.Particularly microcapsule red phosphorus of a kind of double-coated and preparation method thereof.
Background technology
The research tendency of current flame retardant area is exploitation halogen-free flame retardants, to replace gradually halogen flame.Microcapsule red phosphorus (MRP) is as a kind of efficient, low toxicity, press down the fire retardant of cigarette and good stability, be characterized in that inorganics or macromolecule resin film " are packed " closely continuously by the particulate of each red phosphorus one deck, so that red phosphorus and isolation, core is protected by wall material, this can overcome common red phosphorus and do the defect of fire retardant, there is efficient flame retardant resistance, applicability widely, safety non-toxic, little on base material physics and mechanical property impact, and can be compound by the selection of capsule material being realized to the compatibility of multiple ignition-proof element (fire retardant), meet the development trend of the low cigarette of fire retardant efficient halogen-free low toxicity.
According to the material of encapsulated red phosphorus (capsule material), the treatment process of micro encapsulation red phosphorus is divided into three kinds: inorganic coating method, and organic coating method, inorganic-organic hybrid is coated method.In view of inorganic or organic coating red phosphorus cut both ways, some leading companys in Japan, West Europe have proposed inorganic-organic hybrid method for coating in succession.Be similar to individual layer coated, compound coating material is generally selected Al (OH)
3, Zn (OH)
2deng being inorganic layer, resol, melamine-formaldehyde resin or epoxy resin are organic layer.For example, Al (OH) advocates first to use in the phosphorus chemistry industrial of Japan
3or Zn (OH)
2make the first layer coated, it is coated that reusable heat thermosetting resin is made the second layer, and Japan Chemical Industry company proposes to adopt Al (OH)
3, three layers of encapsulated red phosphorus etc. are made in other metal hydroxidess and organic coating agent.One section of European patent of 1986 is with the Al (OH) of 6 parts
3after adjusting all with the aqueous solution of 3% melamine formaldehyde resin, after the red phosphorus of coated 10-40 μ m, after measured in the water of 80 DEG C, every gram of PH per hour
3burst size is 1.27 × 10
-3mg, only through Al (OH)
3the pH of coated red phosphorus
3burst size 4.68 × l0
-3mg is low.
In view of low, the easy spontaneous combustion of red phosphorus point of ignition, explosive, the easy moisture absorption of dust be disproportionated into acid and emit hypertoxic inflammable gas phosphuret-(t)ed hydrogen, with the problem such as the consistency of resin is poor, sharpest edges of the present invention are to use persulphate for catalyzer, taking the inorganic clay such as attapulgite, polynite as solution stabilizer, adopt inorganic hydroxide, organic melamine formaldehyde resin encapsulated red phosphorus to prepare microcapsule red phosphorus, this product has that thermostability is high, good dispersity, uniform particles, water absorbability and PH
3the advantage such as low.
Summary of the invention
The object of the invention is to propose that a kind of preparation technology is simple, Halogen, low toxicity, water absorbability and PH
3low microcapsule red phosphorus and preparation method thereof.
The technical solution that realizes the object of the invention is: microcapsule red phosphorus of a kind of double-coated and preparation method thereof, first carrying out the first layer with inorganic hydroxide is coated, carry out with melamine formaldehyde resin that the second layer is coated obtains product, the mass ratio of its component is as follows again:
Constituent mass ratio
Red phosphorus 1
Water 5-20
Dispersion agent 0.01-0.03
Stablizer 0.005-0.01
Catalyzer 0.005-0.25
Metal-salt 0.18-0.66
Melamine formaldehyde resin 0.22-0.56
Above proportioning is all taking red phosphorus quality as benchmark
Microcapsule red phosphorus of the double-coated that the present invention proposes and preparation method thereof, concrete steps are as follows:
(1) preparation of ultra-fine red phosphorus: (adopt Institutes Of Technology Of Nanjing's water ball grinding technique self-control, ﹥ 800 orders) boil 5 hours with the hydrochloric acid of 5% sulphuric acid soln and 5%, filter, wash 3 times, to remove iron and the copper impurity of trace in raw material, 80 DEG C of vacuum are dried 24 hours, are cooled to room temperature, cross 800 mesh sieves and are stored in dry wide-necked bottle.
(2) preparation of melamine formaldehyde resin performed polymer: add respectively trimeric cyanamide, 37% formaldehyde solution and methyl alcohol in reactor, wherein, the mass ratio of trimeric cyanamide, formaldehyde and methyl alcohol is 5:(10-30): 1, temperature control is to 70-90 DEG C, the ammoniacal liquor regulation system pH to 8-10 that is 25% with massfraction, reaction 20-35 minute, obtains melamine formaldehyde resin performed polymer.
(3) inorganic-organic double-coated: the ultra-fine red phosphorus that step (1) is obtained, the water of 20-40 times red phosphorus amount, the dispersion agent of 0.01-0.03 times red phosphorus amount and the stablizer of 0.005-0.01 times of red phosphorus amount join and stir in reactor and be warming up to 65-85 DEG C, then in system, add the metal salt solution that catalyzer, Theoretical Calculation amount mass concentration are 10%, make the quality of catalyzer, metal-salt be respectively 0.005-0.25 times, 0.18-0.66 times of red phosphorus amount; The pH to 8-10 of the ammoniacal liquor regulation system with 25%, insulated and stirred 0.5-2 hour, the melamine formaldehyde resin prepolymer solution that then adds Theoretical Calculation amount step (2) to obtain, make resin content in solution be red phosphorus quality 0.22-0.56 doubly.In this process, by the pH value of the HCL regulation system of 0.1mol/L to 3-5, insulated and stirred 1-3 hour.After reaction finishes, solution is cooling, to filter, washing, is dried, and obtains the microcapsule red phosphorus of inorganic-organic double-coated.
In the present invention, the described dispersion agent of step (3) be in Sodium dodecylbenzene sulfonate, polyvinyl alcohol or sodium stearate any.
In the present invention, the described stablizer of step (3) is any in polynite or attapulgite.
In the present invention, the described catalyzer of step (3) is any in Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
In the present invention, the described metal-salt of step (3) is any in anhydrous slufuric acid aluminium, anhydrous magnesium sulfate or zinc chloride.
The invention has the advantages that:
(1) utilize persulphate catalyzer to improve the surfactivity of red phosphorus, be conducive to be coated, make the microcapsule red phosphorus point of ignition of preparation reach 440 DEG C, water absorbability and PH
3be low to moderate respectively 1%, below 2ppm;
(2) organic clay (attapulgite, polynite) can improve the stablizer of solution, and contributes to control dispersiveness and the dimensional homogeneity of microcapsule red phosphorus;
(3) there is the iris action of layer chain structure due to organic clay, microencapsulated red phosphorus flame retardant thermostability is improved, and less on material mechanical performance impact while utilizing this fire retardant superpolymer.
Brief description of the drawings
Fig. 1 is preparation technology's schema of the microcapsule red phosphorus of a kind of double-coated of the present invention.
Embodiment
Embodiment 1:
(1) preparation of ultra-fine red phosphorus: (adopt Institutes Of Technology Of Nanjing's water ball grinding technique self-control, ﹥ 800 orders) boil 5 hours with the hydrochloric acid of 5% sulphuric acid soln and 5%, filter, wash 3 times, to remove iron and the copper impurity of trace in raw material, 80 DEG C of vacuum are dried 24 hours, are cooled to room temperature, cross 800 mesh sieves and are stored in dry wide-necked bottle.
(2) preparation of melamine formaldehyde resin performed polymer: add respectively 6.67 grams of trimeric cyanamides, 13.33 gram of 37% formaldehyde solution and 1.33 grams of methyl alcohol in reactor, temperature control to 70 DEG C, the ammoniacal liquor regulation system pH to 8-9 that is 25% with massfraction, react 20 minutes, obtain melamine formaldehyde resin performed polymer.
(3) inorganic-organic double-coated: 20 grams of ultra-fine red phosphorus that step (1) is obtained, 100 ml waters, 0.2 gram of Sodium dodecylbenzene sulfonate and 0.1 polynite join and stir in reactor and be warming up to 65 DEG C, then to the alum liquor that adds 0.1 gram of Sodium Persulfate, 132 gram mass concentration 10% in system, the pH to 9-10 of the ammoniacal liquor regulation system with 25%, insulated and stirred 0.5 hour, then the melamine formaldehyde resin prepolymer solution that adds step (2) to obtain, by the pH value of the HCL regulation system of 0.1mol/L to 4-5, insulated and stirred 1 hour.After reaction finishes, solution is cooling, to filter, washing, is dried, and obtains the microcapsule red phosphorus of inorganic-organic double-coated.Its performance index are as shown in table 1.
Embodiment 2:
(1) preparation of ultra-fine red phosphorus: (adopt Institutes Of Technology Of Nanjing's water ball grinding technique self-control, ﹥ 800 orders) boil 5 hours with the hydrochloric acid of 5% sulphuric acid soln and 5%, filter, wash 3 times, to remove iron and the copper impurity of trace in raw material, 80 DEG C of vacuum are dried 24 hours, are cooled to room temperature, cross 800 mesh sieves and are stored in dry wide-necked bottle.
(2) preparation of melamine formaldehyde resin performed polymer: add respectively 2.86 grams of trimeric cyanamides, 17.14 gram of 37% formaldehyde solution and 0.57 gram of methyl alcohol in reactor, temperature control to 90 DEG C, the ammoniacal liquor regulation system pH to 9-10 that is 25% with massfraction, react 35 minutes, obtain melamine formaldehyde resin performed polymer.
(3) inorganic-organic double-coated: 20 grams of ultra-fine red phosphorus that step (1) is obtained, 400 ml waters, 0.6 gram of sodium stearate and 0.2 gram of polynite join and stir in reactor and be warming up to 85 DEG C, then to the liquor zinci chloridi that adds 5 grams of ammonium persulphates, 36 gram mass concentration 10% in system, the pH to 8-9 of the ammoniacal liquor regulation system with 25%, insulated and stirred 2 hours, then the melamine formaldehyde resin prepolymer solution that adds step (2) to obtain, by the pH value of the HCL regulation system of 0.1mol/L to 3-4, insulated and stirred 3 hours.After reaction finishes, solution is cooling, to filter, washing, is dried, and obtains the microcapsule red phosphorus of inorganic-organic double-coated.Its performance index are as shown in table 1.
Embodiment 3:
(1) preparation of ultra-fine red phosphorus: (adopt Institutes Of Technology Of Nanjing's water ball grinding technique self-control, ﹥ 800 orders) boil 5 hours with the hydrochloric acid of 5% sulphuric acid soln and 5%, filter, wash 3 times, to remove iron and the copper impurity of trace in raw material, 80 DEG C of vacuum are dried 24 hours, are cooled to room temperature, cross 800 mesh sieves and are stored in dry wide-necked bottle.
(2) preparation of melamine formaldehyde resin performed polymer: add respectively 3.25 grams of trimeric cyanamides, 16.75 gram of 37% formaldehyde solution and 0.65 gram of methyl alcohol in reactor, temperature control to 80 DEG C, the ammoniacal liquor regulation system pH to 8-9 that is 25% with massfraction, react 30 minutes, obtain melamine formaldehyde resin performed polymer.
(3) inorganic-organic double-coated: 20 grams of ultra-fine red phosphorus that step (1) is obtained, 300 ml waters, 0.5 gram of polyvinyl alcohol and 0.16 gram of attapulgite join and stir in reactor and be warming up to 80 DEG C, then to the Adlerika that adds 0.4 gram of Potassium Persulphate, 50 gram mass concentration 10% in system, the pH to 8-9 of the ammoniacal liquor regulation system with 25%, insulated and stirred 2 hours, then the melamine formaldehyde resin prepolymer solution that adds step (2) to obtain, by the pH value of the HCL regulation system of 0.1mol/L to 3-4, insulated and stirred 3 hours.After reaction finishes, solution is cooling, to filter, washing, is dried, and obtains the microcapsule red phosphorus of inorganic-organic double-coated.Its performance index are as shown in table 1.
Embodiment 4:
(1) preparation of ultra-fine red phosphorus: (adopt Institutes Of Technology Of Nanjing's water ball grinding technique self-control, ﹥ 800 orders) boil 5 hours with the hydrochloric acid of 5% sulphuric acid soln and 5%, filter, wash 3 times, to remove iron and the copper impurity of trace in raw material, 80 DEG C of vacuum are dried 24 hours, are cooled to room temperature, cross 800 mesh sieves and are stored in dry wide-necked bottle.
(2) preparation of melamine formaldehyde resin performed polymer: add respectively 4.0 grams of trimeric cyanamides, 16.0 gram of 37% formaldehyde solution and 0.8 gram of methyl alcohol in reactor, temperature control to 70 DEG C, the ammoniacal liquor regulation system pH to 9-10 that is 25% with massfraction, react 25 minutes, obtain melamine formaldehyde resin performed polymer.
(3) inorganic-organic double-coated: 20 grams of ultra-fine red phosphorus that step (1) is obtained, 200 ml waters, 0.36 gram of polyvinyl alcohol and 0.2 gram of attapulgite join and stir in reactor and be warming up to 75 DEG C, then to the alum liquor that adds 0.3 gram of ammonium persulphate, 68 gram mass concentration 10% in system, the pH to 9-10 of the ammoniacal liquor regulation system with 25%, insulated and stirred 0.5 hour, then the melamine formaldehyde resin prepolymer solution that adds step (2) to obtain, by the pH value of the HCL regulation system of 0.1mol/L to 4-5, insulated and stirred 2 hours.After reaction finishes, solution is cooling, to filter, washing, is dried, and obtains the microcapsule red phosphorus of inorganic-organic double-coated.Its performance index are as shown in table 1.
The performance of micro encapsulation red phosphorus prepared by above-described embodiment detects as follows:
Point of ignition test: Shimadzu DTA-50, TGA-50 (Japan), 10 DEG C/min of temperature rise rates, air atmosphere, α-Al
2o
3for reference substance;
Wettability test: press GB/T16913.6 – 1997 standard testings, 80 DEG C, sample, places and measure moisture absorption weightening finish percentage ratio after 1 month;
PH
3test: take 40 grams of water, 20 grams of samples are put into 500 milliliters of Erlenmeyer flasks of band plug, shake up, and place 24 hours after sealing at 40 DEG C of temperature.With the phosphuret-(t)ed hydrogen (PH in ammonium molybdate colorimetric method for determining flask gas phase
3) burst size;
The above-mentioned performance perameter detected result of the microcapsule red phosphorus of being prepared by above-described embodiment is listed in table 1; The performance perameter detection method of encapsulated red phosphorus is not with embodiment 1-4, and the results are shown in Table 1.
The microcapsule red phosphorus the performance test results of table 1 double-coated
| Embodiment | Rate of moisture absorption/% | PH 3Burst size/ppm | Point of ignition/DEG C |
| Not encapsulated red phosphorus | 5.84 | 440 | 338 |
| Embodiment 1 | 0.23 | 2.89 | 392 |
| Embodiment 2 | 0.176 | 3.61 | 403 |
| Embodiment 3 | 0.065 | 0.375 | 440 |
| Embodiment 4 | 0.121 | 2.422 | 387 |
Correlation data by upper table can be found out: the point of ignition of the microcapsule red phosphorus of being prepared by the embodiment of the present invention, rate of moisture absorption, PH
3burst size is all better than the red phosphorus not being coated, and the present invention has obviously improved thermostability and the stability of red phosphorus.
Although with preferred embodiment in detail the present invention has been described in detail, but it is not intended to limit the present invention.Any those skilled in the art, without departing from the spirit and scope of the present invention, should make various amendments and change.Therefore protection scope of the present invention should be considered as appending claims limited range.
Claims (3)
1. a preparation method for the microcapsule red phosphorus of double-coated, is characterized in that described method comprises following preparation process:
(1) preparation of ultra-fine red phosphorus: (adopt Institutes Of Technology Of Nanjing's water ball grinding technique self-control, ﹥ 800 orders) boil 5 hours with the hydrochloric acid of 5% sulphuric acid soln and 5%, filter, wash 3 times, to remove iron and the copper impurity of trace in raw material, 80 DEG C of vacuum are dried 24 hours, are cooled to room temperature, cross 800 mesh sieves and are stored in dry wide-necked bottle;
(2) preparation of melamine formaldehyde resin performed polymer: add respectively according to a certain ratio trimeric cyanamide, 37% formaldehyde solution and methyl alcohol in reactor, temperature control is to 70-90 DEG C, the ammoniacal liquor regulation system pH to 8-10 that is 25% with massfraction, reaction 20-35 minute, obtains melamine formaldehyde resin performed polymer;
(3) inorganic-organic double-coated: ultra-fine red phosphorus, water, dispersion agent and the stablizer that step (1) is obtained joins and stir in reactor and be warming up to 65-85 DEG C, then in system, add catalyzer, metal salt solution, the pH to 8-10 of the ammoniacal liquor regulation system with 25%, insulated and stirred 0.5-2 hour, the melamine formaldehyde resin prepolymer solution that then adds step (2) to obtain;
In this process, by the pH value of the HCL regulation system of 0.1mol/L to 3-5, insulated and stirred 1-3 hour; After reaction finishes, solution is cooling, to filter, washing, is dried, and obtains the microcapsule red phosphorus of inorganic-organic double-coated.
2. the preparation method of the microcapsule red phosphorus of a kind of double-coated according to claim 1, is characterized in that the mass ratio of trimeric cyanamide, 37% formaldehyde solution and methyl alcohol in step (2) is 5:(10-30): 1.
3. the preparation method of the microcapsule red phosphorus of a kind of double-coated according to claim 1, it is characterized in that the stablizer described in step (3) be in attapulgite, polynite any, its quality be red phosphorus quality 0.005-0.01 doubly.
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| 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 |
| CN106995534A (en) * | 2017-05-16 | 2017-08-01 | 泸溪亿兴科技有限公司 | A kind of preparation method of red phosphorus combustion inhibitor |
| CN108469501A (en) * | 2018-06-14 | 2018-08-31 | 云南江磷集团股份有限公司 | The method for quickly measuring red phosphorus stability |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN106995534A (en) * | 2017-05-16 | 2017-08-01 | 泸溪亿兴科技有限公司 | A kind of preparation method of red phosphorus combustion inhibitor |
| CN108469501A (en) * | 2018-06-14 | 2018-08-31 | 云南江磷集团股份有限公司 | The method for quickly measuring red phosphorus stability |
| CN110452528A (en) * | 2019-07-15 | 2019-11-15 | 山东省科学院能源研究所 | Microcapsule coated infiltrative type red phosphorus flame-retardant nylon 6 and preparation method |
| CN110483989A (en) * | 2019-07-15 | 2019-11-22 | 山东省科学院能源研究所 | Microcapsule coated infiltrative type red phosphorus flame-retardant nylon66 fiber and preparation method |
| CN110452528B (en) * | 2019-07-15 | 2022-01-04 | 山东省科学院能源研究所 | Microcapsule coated and infiltrated red phosphorus flame-retardant nylon 6 and preparation method thereof |
| CN110483989B (en) * | 2019-07-15 | 2022-01-04 | 山东省科学院能源研究所 | Microcapsule coated and infiltrated red phosphorus flame-retardant nylon 66 and preparation method thereof |
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Application publication date: 20140924 |