CN103803516A - Method for micron-scale aluminum hypophosphite by virtue of alcohol-water method - Google Patents
Method for micron-scale aluminum hypophosphite by virtue of alcohol-water method Download PDFInfo
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Abstract
The invention relates to a method for micron-scale aluminum hypophosphite by virtue of an alcohol-water method and belongs to the manufacturing field of polymer-material fire retardants. The method comprises the following steps: firstly, adding a surfactant into a prepared alcohol-water mixed solution, and dissolving the surfactant at 70 DEG C while stirring; adding sodium hypophosphite monohydrate and soluble aluminum salt into the alcohol-water mixed solution, and uniformly mixing; carrying out stirring backflow for 0.5-4 hours at a reaction temperature of 40-100 DEG C; after the reaction, carrying out cooling, filtering, washing and drying, so as to obtain the micron-scale aluminum hypophosphite. The method has the beneficial effects that the grain size of the prepared aluminum hypophosphite is smaller than 5 microns, the shape of the aluminum hypophosphite is regular, the initial thermal decomposition temperature is 288 DEG C, the heat stability is good, and the aluminum hypophosphite is applied to the flame-retardant modification of various engineering plastics such as polyester, polyamide and the like.
Description
Technical field
The present invention relates to a kind of alcohol water law and prepare the method for micron order hypo-aluminum orthophosphate, belong to the manufacture manufacture field of macromolecular material fire retardant.
Background technology
Hypo-aluminum orthophosphate combustion inhibitor phosphorus content is high, Heat stability is good, flame retarding efficiency are high, work in-process does not cause the decomposition of polymkeric substance, non-volatile under preparation and fabrication thermoplastic polymer's usual conditions, make its application product there is higher thermostability, in the course of processing, there is good mechanical property and anti-marquis's property, be widely used in the engineering plastics such as polyester, polymeric amide flame-retardant modified.Li Qifei (Li Qifei. the synthetic and fire-retardant Nylon 6 research of hypophosphite fire retardant, Northeast Forestry University, master thesis, 2011), use hypo-aluminum orthophosphate flame-proof PA 6, when addition is 18wt%, oxygen index reaches 25,3.2mm vertical combustion batten can reach UL94V-0 level, can find out that hypo-aluminum orthophosphate has good flame retardant effect to PA6, and fire-retardant batten has good mechanical property.
CN102786041 discloses a kind of preparation method of hypo-aluminum orthophosphate, prepares sodium hypophosphite solution and alum liquor by dissolving, after adjusting pH value, presses certain mol proportion, is directly mixed with hypo-aluminum orthophosphate.Invention disclosed patent CN103145110 has announced again and has replaced Tai-Ace S 150 obtain solution using aluminum nitrate as aluminium salt after a while, and step is identical with CN102786041.In two patents, all adopt the method for first preparing aluminum salt solution, the method of then directly mixing with sodium hypophosphite solution is prepared hypo-aluminum orthophosphate, conventional aluminium salt is 18 water Tai-Ace S 150 and nine water aluminum nitrates, but still need rising temperature for dissolving aluminum nitrate and Tai-Ace S 150 before this mode of production reaction, prepare soluble aluminum salts solution, and aluminum nitrate and Tai-Ace S 150 dissolution rate are slower, not only consuming time and increased energy consumption; Secondly sodium hypophosphite solution is directly mixed with Tai-Ace S 150 or aluminum nitrate solution, tank solution adds fast, in reaction process, in reactor, easily produce gel, gel cementing covered section material, be unfavorable for that material fully mixes, impact reacts completely and carries out, and a large amount of gel cementings also bring impact to safety in production in time at the bottom of still, on still wall and stirring rake, due to the limitation of this method, and be unfavorable for direct suitability for industrialized production; And the hypo-aluminum orthophosphate particle diameter of preparation is only for being less than 50 microns, particle is larger, easily assemble, dispersed bad, still differ larger with conventional engineering plastics with 2000～3000 orders (5～6.5 microns) of fire retardant particle diameter, the application of impact in plastic flame modification, need to carry out mechanical disintegration and just can better in modifying plastics, bring into play flame retardant effect, by mechanical disintegration, hypo-aluminum orthophosphate is crushed in ultrafine powder process and easily produces a large amount of ultrafine dusts, also safety in production is brought to threat.
Tradition liquid phase is synthetic is one of main method of preparing superfine powder, but also exist particle size distribution wide, be difficult to control, reunite serious, the problem that monodispersity is poor.As improvement, alcohol water law becomes prepares preparation method conventional in superfine powder in recent years, and due to its advantage aspect distinctive particle diameter control and anti-reunion in superfine powder preparation, the product particle particle diameter of preparation is little, narrow diameter distribution.CN102267702 discloses a kind of method that alcohol water law is prepared sub-micron zinc borate, said method comprising the steps of: 1) the alcohol water mixed solution of preparation glycerol and water; 2) in described alcohol water mixed solution, add boric acid and zinc oxide, mix; 3) add crystal seed, stirring and refluxing; 4) product filtered while hot or the centrifugal settling of step 3 gained, wash through alcohol solution again, filter or centrifugal settling, dry, obtain sub-micron zinc borate powder, zinc borate, is also divided into compared with multiple types containing crystal water different amts according to wherein, thereby in preparation, also need to add different crystal seeds according to product is different, prepared be uniformly dispersed, zinc borate power that particle diameter is less than 1 micron.CN101880048 discloses the technique that a kind of alcohol water law is prepared houghite particle, and it is by Mg (NO
3)
2and Al (NO
3)
3, under nitrogen protection, be dissolved in alcohol solution, be made into mother liquor; By ammoniacal liquor and NaNO
3be dissolved in alcohol solution, be made into precipitation agent; Under strong stirring, precipitation agent is evenly added drop-wise in mother liquor, until pH value is to 9.0-10.0, dropwise, continue at normal temperatures to stir 1-3 hour, filter, wash with alcohol solution, make houghite particle, having made pattern rule, good dispersity, particle diameter is the houghite particle of 60nm left and right.But most of alcohol water law need be used acid or alkali as precipitation agent while preparing sample, regulate pH value, and by complete reactant solubilizing reaction, increased energy consumption and reaction process.
In the preparation technology of micron order hypo-aluminum orthophosphate, because the aluminium such as Tai-Ace S 150, aluminum nitrate salt is insoluble to the restriction of the low-carbon alcohol such as ethanol, methyl alcohol, ethylene glycol, glycerol and reaction conditions, have no the report that alcohol water law is prepared hypo-aluminum orthophosphate.
Summary of the invention
The technical problem to be solved in the present invention is: for the drawback existing in prior art, the invention provides a kind of alcohol water law and prepare the method for micron order hypo-aluminum orthophosphate, the hypo-aluminum orthophosphate particle prepared by the method is less, good dispersity, narrow diameter distribution, particle shape rule.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of alcohol water law of the present invention is prepared the method for micron order hypo-aluminum orthophosphate, specifically comprises the following steps:
1) the alcohol water mixed solution of 1:2～11 preparations alcohol and water by volume, is the tensio-active agent of alcohol water mixed solution total mass 0.1～2% to adding quality in alcohol water mixed solution, under 70 ℃ of agitation conditions, dissolves, and obtains solution A;
2) be 1:1～5 by a hydration sodium hypophosphite and aluminum soluble salt total mass and described alcohol water mixed solution mass ratio, in above-mentioned solution A, add a hydration sodium hypophosphite, under agitation condition, dissolve, obtain solution B; In above-mentioned solution B, add aluminum soluble salt again, mix, wherein a hydration sodium hypophosphite and aluminum soluble salt mass ratio are 1:0.5～5;
3) by the 2nd) mixing solutions that obtains of step stirring reaction 0.5～6 hour at the temperature of 40～100 ℃;
4) reaction is cooled to room temperature after finishing, and filters, and washing, dries, and obtains object product.
Alcohol of the present invention is one or more mixture of methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, propyl carbinol, isopropylcarbinol, ethylene glycol, glycerol, is preferably one or the mixture of methyl alcohol, ethanol, propyl alcohol, ethylene glycol.
Tensio-active agent of the present invention is one or more the mixture in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyvinylpyrrolidone, polyvinyl alcohol;
Aluminum soluble salt of the present invention is one or more the mixture in Tai-Ace S 150, aluminum nitrate, aluminum chloride, 18 water Tai-Ace S 150, nine water aluminum nitrates, Aluminum Chloride Hexahydrate.
In alcohol solution of the present invention, the volume ratio of alcohol and water is preferably 1:2～7.
Dosage of surfactant of the present invention is preferably 0.1～1% of alcohol water mixed solution total mass.
Temperature of reaction in step 3) of the present invention is preferably 70～90 ℃, and the reaction times is preferably 2～4 hours.
The temperature of the drying course in step 4) of the present invention is preferably 50～130 ℃, more preferably 60～100 ℃.
Beneficial effect:
(1) the micron order hypo-aluminum orthophosphate diameter < 5 μ m that adopt alcohol water law to prepare, particle morphology rule, using alcohol water mixed solvent as reaction solvent, greatly reduce the solvability of hypo-aluminum orthophosphate, thereby reduce the polymolecularity of particle, obtained the narrower hypo-aluminum orthophosphate powder of size distribution; Ultra-fine hypo-aluminum orthophosphate powder is more conducive to the dispersion in macromolecule matrix material, reduces consumption, improves the interface binding power between fire retardant and macromolecular material;
(2) in reaction, aluminium salt, without dissolving, directly adds in reactor after crushed, has avoided the energy consumption in dissolution process, has shortened reaction process, has improved production efficiency;
(3) good thermal stability, 288 ℃ of the initial heat decomposition temperatures of this product (weightless 1%), higher than the processing temperature of existing most of engineering plastics, 600 ℃ time, carbon residue amount is 76.4wt%, thermostability is better than existing bibliographical information, can meet the various engineering such as polyester, polymeric amide flame retardant of plastic modification processing.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the micron order hypo-aluminum orthophosphate that obtains of embodiment 1;
Fig. 2 is the micron order hypo-aluminum orthophosphate thermogravimetric analysis figure that embodiment 1 obtains.
Embodiment
Below in conjunction with drawings and Examples, content of the present invention is described further.
Embodiment 1
In there-necked flask, add 3000ml water and 600ml ethanol configuration alcohol water mixed solution, dissolve to adding under 70 ℃ of agitation conditions of 5.4g polyvinylpyrrolidone in above-mentioned alcohol water mixed solution, obtain solution A; In solution A, add 900g mono-hydration sodium hypophosphite, under agitation condition, dissolve, obtain solution B; In above-mentioned solution B, add 1800g 18 water Tai-Ace S 150 again, mix, 80 ℃ of stirring reactions 2 hours, are cooled to room temperature after reaction finishes, and filter, and washing, dries to obtain micron order hypo-aluminum orthophosphate 930g for 80 ℃, and products obtained therefrom purity reaches 99.3%.
Scanning electron microscope (SEM) photograph as shown in Figure 1 shows the hypo-aluminum orthophosphate uniform particles making, and particle diameter is 3 microns of left and right.
Thermogravimetric analysis figure as shown in Figure 2 shows that the initial heat decomposition temperature of the hypo-aluminum orthophosphate making (weightless 1%) is 288 ℃, good thermal stability.
Embodiment 2
In there-necked flask, add 3000ml water and 800ml methyl alcohol configuration alcohol water mixed solution, in above-mentioned alcohol water mixed solution, add 15g Sodium dodecylbenzene sulfonate, under 70 ℃ of agitation conditions, dissolve, obtain solution A; In solution A, add 1500g mono-hydration sodium hypophosphite, under agitation condition, dissolve, obtain solution B; In above-mentioned solution B, add 1600g nine water aluminum nitrates again, mix, 75 ℃ of stirring reactions 1.5 hours, after reaction finishes, be cooled to room temperature, filter, washing, dry to obtain micron order hypo-aluminum orthophosphate 893g for 90 ℃, products obtained therefrom purity reaches 99.1%, 5 microns of particle diameter <.
Embodiment 3
In there-necked flask, add 2000ml water and 900ml methyl alcohol configuration alcohol water mixed solution, in above-mentioned alcohol water mixed solution, add 6g polyvinyl alcohol, under 70 ℃ of agitation conditions, dissolve, obtain solution A; In solution A, add 1100g mono-hydration sodium hypophosphite, under agitation condition, dissolve, obtain solution B; In above-mentioned solution B, add 800g Aluminum Chloride Hexahydrate again, mix, 80 ℃ of stirring reactions 3 hours, after reaction finishes, be cooled to room temperature, filter, washing, dry to obtain micron order hypo-aluminum orthophosphate 710g for 80 ℃, products obtained therefrom purity reaches 99.3%, 5 microns of particle diameter <.
Embodiment 4
In there-necked flask, add 2500ml water and 500ml ethylene glycol configuration alcohol water mixed solution, in above-mentioned alcohol water mixed solution, add 10g sodium lauryl sulphate, under 70 ℃ of agitation conditions, dissolve, obtain solution A; In solution A, add 1000g mono-hydration sodium hypophosphite, under agitation condition, dissolve, obtain solution B; In above-mentioned solution B, add 1100g Tai-Ace S 150 again, mix, 80 ℃ of stirring reactions 1 hour, after reaction finishes, be cooled to room temperature, filter, washing, dry to obtain micron order hypo-aluminum orthophosphate 682g for 80 ℃, products obtained therefrom purity reaches 99.1%, 5 microns of particle diameter <.
Embodiment 5
In there-necked flask, add 2000ml water and 700ml propyl alcohol configuration alcohol water mixed solution, in above-mentioned alcohol water mixed solution, add 8g polyvinylpyrrolidone, under 70 ℃ of agitation conditions, dissolve, obtain solution A; In solution A, add 700g mono-hydration sodium hypophosphite, under agitation condition, dissolve, obtain solution B; In above-mentioned solution B, add 750g Tai-Ace S 150 again, mix, 85 ℃ of stirring reactions 1.5 hours, after reaction finishes, be cooled to room temperature, filter, washing, dry to obtain micron order hypo-aluminum orthophosphate 446g for 90 ℃, products obtained therefrom purity reaches 99.2%, 5 microns of particle diameter <.
Claims (7)
1. alcohol water law is prepared a method for micron order hypo-aluminum orthophosphate, it is characterized in that: specifically comprise the following steps:
1) the alcohol water mixed solution of 1:2～11 preparations alcohol and water by volume, is the tensio-active agent of alcohol water mixed solution total mass 0.1～2% to adding quality in alcohol water mixed solution, under 70 ℃ of agitation conditions, dissolves, and obtains solution A;
2) be 1:1～5 by a hydration sodium hypophosphite and aluminum soluble salt total mass and described alcohol water mixed solution mass ratio, in above-mentioned solution A, add a hydration sodium hypophosphite, under agitation condition, dissolve, obtain solution B; In above-mentioned solution B, add aluminum soluble salt again, mix, wherein a hydration sodium hypophosphite and aluminum soluble salt mass ratio are 1:0.5～5;
3) by the 2nd) mixing solutions that obtains of step stirring reaction 0.5～6 hour at the temperature of 40～100 ℃;
4) reaction is cooled to room temperature after finishing, and filters, and washing, dries, and obtains object product;
Described alcohol is one or more mixture of methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, propyl carbinol, isopropylcarbinol, ethylene glycol, glycerol;
Described tensio-active agent is one or more the mixture in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, polyvinylpyrrolidone, polyvinyl alcohol;
Described aluminum soluble salt is one or more the mixture in Tai-Ace S 150, aluminum nitrate, aluminum chloride, 18 water Tai-Ace S 150, nine water aluminum nitrates, Aluminum Chloride Hexahydrate.
2. a kind of alcohol water law as claimed in claim 1 is prepared the method for micron order hypo-aluminum orthophosphate, it is characterized in that: described alcohol is one or the mixture of methyl alcohol, ethanol, propyl alcohol, ethylene glycol.
3. a kind of alcohol water law as claimed in claim 1 is prepared the method for micron order hypo-aluminum orthophosphate, it is characterized in that: in described alcohol solution, the volume ratio of alcohol and water is 1:2～7.
4. a kind of alcohol water law as claimed in claim 1 is prepared the method for micron order hypo-aluminum orthophosphate, it is characterized in that: described dosage of surfactant is 0.1～1% of alcohol water mixed solution total mass.
5. a kind of alcohol water law as claimed in claim 1 is prepared the method for micron order hypo-aluminum orthophosphate, it is characterized in that: the temperature of reaction in described step 3) is 70～90 ℃, and the reaction times is 2～4 hours.
6. a kind of alcohol water law as claimed in claim 1 is prepared the method for micron order hypo-aluminum orthophosphate, it is characterized in that: the temperature of the drying course in described step 4) is 50～130 ℃.
7. a kind of alcohol water law as claimed in claim 1 is prepared the method for micron order hypo-aluminum orthophosphate, it is characterized in that: the temperature of the drying course in described step 4) is 60～100 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448948A (en) * | 2014-12-10 | 2015-03-25 | 山东川君化工股份有限公司 | Preparation method of modified aluminium hypophosphite |
| CN104860281A (en) * | 2015-06-01 | 2015-08-26 | 武汉理工大学 | Preparation method of aluminum hypophosphite |
| CN105199144A (en) * | 2015-09-10 | 2015-12-30 | 北京理工大学 | Submicron organic spiro aluminum phosphate flame retardant and preparation method thereof |
| CN107973281A (en) * | 2017-12-01 | 2018-05-01 | 合肥学院 | Anhydrous tubular metal hypophosphite and preparation method thereof |
| CN111410840A (en) * | 2020-05-15 | 2020-07-14 | 四川大学 | Halogen-free flame-retardant nylon low-dimensional product material and preparation method thereof |
| CN113308024A (en) * | 2021-05-27 | 2021-08-27 | 武汉工程大学 | Aluminum hypophosphite-polyphosphazene core-shell type flame retardant and preparation method thereof |
| CN113979412A (en) * | 2021-10-29 | 2022-01-28 | 湖北航天化学技术研究所 | Synthesis method of fine-particle-size low-cost aluminum hypophosphite flame retardant |
| CN114314538A (en) * | 2021-12-16 | 2022-04-12 | 湖北省兴发磷化工研究院有限公司 | Synthesis method of superfine aluminum hypophosphite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267702A (en) * | 2011-07-04 | 2011-12-07 | 北京石油化工学院 | Method for preparing sub-micron zinc borate by virtue of alcohol-water method |
| CN102786041A (en) * | 2012-08-24 | 2012-11-21 | 南京师范大学 | Method for preparing aluminum hypophosphite |
-
2014
- 2014-01-25 CN CN201410044439.4A patent/CN103803516A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267702A (en) * | 2011-07-04 | 2011-12-07 | 北京石油化工学院 | Method for preparing sub-micron zinc borate by virtue of alcohol-water method |
| CN102786041A (en) * | 2012-08-24 | 2012-11-21 | 南京师范大学 | Method for preparing aluminum hypophosphite |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448948A (en) * | 2014-12-10 | 2015-03-25 | 山东川君化工股份有限公司 | Preparation method of modified aluminium hypophosphite |
| CN104860281A (en) * | 2015-06-01 | 2015-08-26 | 武汉理工大学 | Preparation method of aluminum hypophosphite |
| CN105199144A (en) * | 2015-09-10 | 2015-12-30 | 北京理工大学 | Submicron organic spiro aluminum phosphate flame retardant and preparation method thereof |
| CN105199144B (en) * | 2015-09-10 | 2018-03-02 | 北京理工大学 | A kind of organic loop coil aluminum phosphate fire retardant of submicron order and preparation method thereof |
| CN107973281A (en) * | 2017-12-01 | 2018-05-01 | 合肥学院 | Anhydrous tubular metal hypophosphite and preparation method thereof |
| CN107973281B (en) * | 2017-12-01 | 2019-12-03 | 合肥学院 | Anhydrous tubular metal hypophosphite and preparation method thereof |
| CN111410840A (en) * | 2020-05-15 | 2020-07-14 | 四川大学 | Halogen-free flame-retardant nylon low-dimensional product material and preparation method thereof |
| CN113308024A (en) * | 2021-05-27 | 2021-08-27 | 武汉工程大学 | Aluminum hypophosphite-polyphosphazene core-shell type flame retardant and preparation method thereof |
| CN113979412A (en) * | 2021-10-29 | 2022-01-28 | 湖北航天化学技术研究所 | Synthesis method of fine-particle-size low-cost aluminum hypophosphite flame retardant |
| CN114314538A (en) * | 2021-12-16 | 2022-04-12 | 湖北省兴发磷化工研究院有限公司 | Synthesis method of superfine aluminum hypophosphite |
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Application publication date: 20140521 |