CN102775814A - Method for preparing micro-encapsulation red phosphorus - Google Patents
Method for preparing micro-encapsulation red phosphorus Download PDFInfo
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- CN102775814A CN102775814A CN201210282927XA CN201210282927A CN102775814A CN 102775814 A CN102775814 A CN 102775814A CN 201210282927X A CN201210282927X A CN 201210282927XA CN 201210282927 A CN201210282927 A CN 201210282927A CN 102775814 A CN102775814 A CN 102775814A
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Abstract
The invention discloses a method for preparing micro-encapsulation red phosphorus. The method comprises the steps of a, preparing melamine and formaldehyde into transparent melamine-formaldehyde glue for standby application; b, performing azeotropy of superfine red phosphorus and a fire retardant to obtain a stable flocculent system containing red phosphorus; c, slowly injecting the melamine-formaldehyde glue prepared in the step a into the stable flocculent system obtained in the step b to obtain turbid liquid; and d, adding acid into the turbid liquid obtained in the step c to perform constant temperature stirring, placing solid substance obtained through filtration after reaction is finished into a drying oven to perform constant temperature drying, and finally grinding the solid substance to obtain micro-encapsulation red phosphorus powder. The method for preparing the micro-encapsulation red phosphorus is especially used for preparation of whitened micro-encapsulation red phosphorus.
Description
Technical field
The present invention relates to a kind of method for preparing micro encapsulation red phosphorus, and process the purposes of micro encapsulation red phosphorus through this technology.
Background technology
In non-halogen flame retardant, red phosphorus is a kind of fire retardant preferably, has that addition is few, the high and low cigarette of flame retarding efficiency, low toxicity, an advantage such as of many uses.Non-halogen fire retardants such as compound phosphorus/magnesium, phosphorus/aluminium, phosphorus/graphite are processed in the composite uses of inorganic combustion inhibitor such as red phosphorus and white lake, expansile graphite, can use flame retardant amount significantly to reduce, thereby improve the processing characteristics and the physical and mechanical properties of plastics.But common red phosphorus is prone to oxidation, moisture absorption in air, cause dust explosion easily, hard transportation, and with defective such as macromolecular material intermiscibility difference, range of application is restricted.
For remedying this respect deficiency, to enlarge the red phosphorus range of application, people have adopted the microcapsule cladding process, make it to become micro encapsulation red phosphorus.Micro encapsulation red phosphorus and has efficient, low cigarette except that having overcome red phosphorus inherent drawback, work in-process does not produce toxic gas, and its dispersiveness, physics, mechanical property, thermostability and flame retardant properties are improved and improve.Micro encapsulation red phosphorus is widely used in thermoplastic's resins such as PET, PC, PBT, PA, PE, EVA, also can be used for the fire-retardant of thermosetting resins such as epoxy, phenolic aldehyde, unsaturated polyester and cis-1,4-polybutadiene rubber, ethylene-propylene rubber(EPR), scrim.(can be used for material fire-retardant that PET, PC, PBT etc. are rich in oxygen element separately; If be used for material fire-retardant that general-purpose plastics, rubber, Vilaterm, Vestolen PP 7052 etc. lack oxygen element, need and Marinco H, the composite use of white lake).Be specially adapted to the place that a small amount of fire retardant can meet the demands.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of micro encapsulation red phosphorus, it is realized through following technical scheme:
A kind of method that is used to prepare micro encapsulation red phosphorus comprises the steps:
A. it is subsequent use under alkaline condition, trimeric cyanamide and formaldehyde to be modulated into transparent melamino-formaldehyde glue;
B. with ultra-fine red phosphorus and a kind of fire retardant azeotropic, obtain containing the cotton-shaped system of stable state of red phosphorus;
C. in the cotton-shaped system of the slow implantation step b of melamino-formaldehyde glue gained stable state with step a preparation, obtain suspension liquid;
D. add sour back constant temperature to step c gained suspension liquid and stir, after reaction finishes filtration is obtained solid matter and put into the baking oven freeze-day with constant temperature, after grinding makes micro encapsulation red phosphorus powder.
In the present invention, regulating the acidic substance that the system acid-basicity is adopted in each step can be mineral acid or organic acid, includes but not limited to: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methyl siliconic acid, acetate, oxalic acid etc.; The alkaline matter that adopts can be that mineral alkali or organic bases or this area act on the material that alkali uses usually, includes but not limited to: sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, ammoniacal liquor, yellow soda ash, sodium hydrogencarbonate etc.
As preferably, the ratio of trimeric cyanamide and formaldehyde is 1:1～5 among the step a, more preferably 1:3～5.
In the present invention, the described fire retardant of step b is preferably the fire retardant of nitrogen phosphorus series, trimeric cyanamide cyanurate (MCA) more preferably wherein, and the especially preferred trade mark is the fire retardant of MAC-033.
In step b, particularly be that red phosphorus is mixed with a kind of fire retardant, add and carry out extra-fine grinding after water is modulated into the cake shape, obtain containing the cotton-shaped system of stable state of red phosphorus, isothermal reaction forms first parcel then.Wherein, red phosphorus can change according to the demand of the finished product with the ratio of fire retardant, preferred 1:0.1～4, more preferably 1:0.5～2.The temperature of isothermal reaction is controlled to be 30-110 ℃, and preferred 85-110 ℃, more preferably 95-100 ℃.
In step c, the melamino-formaldehyde glue of adding is the 1-50% of butt ratio in the suspension liquid, preferred 5-20%, more preferably 8-12%.
In steps d, the pH value that adds the sour hierarchy of control between 1-7, preferred 2-5.Thermostatically controlled temp is 30 ℃-90 ℃, preferred 85 ℃.
Another object of the present invention provides a kind of by the prepared micro encapsulation red phosphorus that obtains of aforesaid method.
Another object of the present invention provides a kind of by the purposes of the prepared micro encapsulation red phosphorus that obtains of aforesaid method in the preparation fire retardant.
In sum; Owing to adopted technique scheme; The invention has the beneficial effects as follows: the present invention selects for use multiple fire-retardant capsule material that red phosphorus is wrapped up; The micro encapsulation red phosphorus that makes not only flame retardant properties is excellent, and appearance color is particularly useful for the preparation of whiteness microcapsules red phosphorus by the purplish red pearl that changes into.Encapsulated red phosphorus adopts the multilayer parcel, and its product appearance whiteness and flame retardant properties obviously are superior to only adopting single MCA (trimeric cyanamide cyanurate) parcel.With the whiteness is example; Be 50% red phosphorus content equally; Only adopt the product of MCA (trimeric cyanamide cyanurate) parcel to measure with blue light measuring brightness appearance: whiteness is 33-35; And the present invention adopts 50% micro encapsulation red phosphorus of multilayer parcel, and product is measured with blue light measuring brightness appearance: whiteness is 45-52.
Embodiment
Disclosed all characteristics in this specification sheets, or the step in disclosed all methods or the process except mutually exclusive characteristic and/or the step, all can make up by any way.
Disclosed arbitrary characteristic in this specification sheets (comprising any accessory claim, summary) is only if special narration all can be replaced by other equivalences or the alternative features with similar purpose.That is, only if special narration, each characteristic is an example in a series of equivalences or the similar characteristics.
Embodiment 1:
100 ml water are poured in the 200ml there-necked flask, stir to be added 0.8g sodium hydroxide, successively add 18.7g trimeric cyanamide and 36.3g formaldehyde after being warming up to 85 ℃, the constant temperature stirring promptly obtained transparent melamino-formaldehyde glue with subsequent use after 40 minutes.Again 156g red phosphorus is mixed with the MCA-033 fire retardant of 146.2g respectively; Add and carry out extra-fine grinding after water 600ml is modulated into the cake shape, obtain containing the cotton-shaped system of stable state of red phosphorus, pour into then in the there-necked flask of 2000ml; Add 800ml water and be heated to 95 ℃; Constant temperature injects this cotton-shaped system system with the melamino-formaldehyde glue of preparation before after 1 hour again, adds technical hydrochloric acid 40ml, and the constant temperature stirring is the end reaction after 1 hour; Filtration is obtained solid matter puts as going into freeze-day with constant temperature in the baking oven, after grinding makes 310g micro encapsulation red phosphorus powder.
Embodiment 2:
100 ml water are poured in the 200ml there-necked flask, stir to be added 0.8g sodium hydroxide, successively add 18.7g trimeric cyanamide and 36.3g formaldehyde after being warming up to 85 ℃, the constant temperature stirring promptly obtained transparent melamino-formaldehyde glue with subsequent use after 40 minutes.Again 156g red phosphorus is mixed with the fire retardant of 146.2 g MCA-033 respectively; Add and carry out extra-fine grinding after water 600ml is modulated into the cake shape, obtain containing the cotton-shaped system of stable state of red phosphorus, pour into then in the there-necked flask of 2000ml; Add 800ml water and be heated to 95 ℃; Constant temperature injects this cotton-shaped system system with the melamino-formaldehyde glue of preparation before after 1 hour again, adds methyl siliconic acid 60 g, and the constant temperature stirring is the end reaction after 1 hour; Filtration is obtained solid matter puts as going into freeze-day with constant temperature in the baking oven, after grinding makes 304g micro encapsulation red phosphorus powder.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination that discloses in this manual, and the arbitrary new method that discloses or step or any new combination of process.
Claims (9)
1. a method for preparing micro encapsulation red phosphorus comprises the steps:
A. it is subsequent use under alkaline condition, trimeric cyanamide and formaldehyde to be modulated into transparent melamino-formaldehyde glue;
B. with ultra-fine red phosphorus and a kind of fire retardant azeotropic, obtain containing the cotton-shaped system of stable state of red phosphorus;
C. in the cotton-shaped system of the slow implantation step b of melamino-formaldehyde glue gained stable state with step a preparation, obtain suspension liquid;
D. add sour back constant temperature to step c gained suspension liquid and stir, after reaction finishes filtration is obtained solid matter and put into the baking oven freeze-day with constant temperature, after grinding makes micro encapsulation red phosphorus powder.
2. the method for claim 1, wherein regulating the acidic substance that the system acid-basicity is adopted in each step can be mineral acid or organic acid, preferred hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, methyl siliconic acid, acetate, oxalic acid; The alkaline matter that adopts can be that mineral alkali or organic bases or this area act on the material that alkali uses, preferred sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, ammoniacal liquor, yellow soda ash, sodium hydrogencarbonate usually.
3. according to claim 1 or claim 2 method, wherein the ratio of trimeric cyanamide and formaldehyde is 1:1～5 among the step a, more preferably 1:3～5.
4. like each described method of claim 1-3, wherein the described fire retardant of step b is preferably the fire retardant of nitrogen phosphorus series, trimeric cyanamide cyanurate (MCA) more preferably, and the especially preferred trade mark is the fire retardant of MAC-033.
5. like each described method of claim 1-3, wherein step b mixes red phosphorus with a kind of fire retardant, adds to carry out extra-fine grinding after water is modulated into the cake shape, obtains containing the cotton-shaped system of stable state of red phosphorus, and isothermal reaction forms first parcel then; Wherein, the preferred 1:0.1 of ratio～4 of red phosphorus and fire retardant, more preferably 1:0.5～2; The temperature of isothermal reaction is controlled to be 30-110 ℃, and preferred 85-110 ℃, more preferably 95-100 ℃.
6. like each described method of claim 1-5, in step c, the melamino-formaldehyde glue of adding is the 1-50% of butt ratio in the suspension liquid, preferred 5-20%, more preferably 8-12%.
7. like each described method of claim 1-6, in steps d, the pH value that adds the sour hierarchy of control between 1-7, preferred 2-5; Thermostatically controlled temp is 30 ℃-90 ℃, preferred 85 ℃.
8. the micro encapsulation red phosphorus for preparing like each said method of claim 1-7.
9. the purposes of micro encapsulation red phosphorus in the preparation fire retardant for preparing like each said method of claim 1-7.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254655A (en) * | 2013-05-14 | 2013-08-21 | 同济大学 | Preparation method of melamine/formaldehyde resin-coating melamine cyanurate (MCA) nano capsule |
| CN104325768A (en) * | 2014-10-20 | 2015-02-04 | 金宝丽科技（苏州）有限公司 | Preparation method of APET film with fluorescent effect |
| CN104325769A (en) * | 2014-10-21 | 2015-02-04 | 金宝丽科技（苏州）有限公司 | Preparation method of flame-retardant APET composite film |
| 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254655A (en) * | 2013-05-14 | 2013-08-21 | 同济大学 | Preparation method of melamine/formaldehyde resin-coating melamine cyanurate (MCA) nano capsule |
| CN104325768A (en) * | 2014-10-20 | 2015-02-04 | 金宝丽科技（苏州）有限公司 | Preparation method of APET film with fluorescent effect |
| CN104325769A (en) * | 2014-10-21 | 2015-02-04 | 金宝丽科技（苏州）有限公司 | Preparation method of flame-retardant APET composite film |
| 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 |
| 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 |
| 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 |
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| CN102775814B (en) | 2014-03-19 |
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