CN102976300A - Method for preparing crystal II type ammonium polyphosphate by using polyphosphoric acid - Google Patents
Method for preparing crystal II type ammonium polyphosphate by using polyphosphoric acid Download PDFInfo
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- CN102976300A CN102976300A CN2012103023434A CN201210302343A CN102976300A CN 102976300 A CN102976300 A CN 102976300A CN 2012103023434 A CN2012103023434 A CN 2012103023434A CN 201210302343 A CN201210302343 A CN 201210302343A CN 102976300 A CN102976300 A CN 102976300A
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Abstract
The invention provides a method for preparing crystal II type ammonium polyphosphate by using polyphosphoric acid, and relates to the technical field of ammonium polyphosphate preparation. The technical scheme comprises: a, adopting polyphosphoric acid, ammonium phosphate and urea as reaction raw materials, measuring, adding the reaction raw materials to a reactor with a stirring paddle and jacket temperature control, carrying out stirring temperature control to completely melt the material, adding a measured reaction promoting agent and a crystal form conversion agent, completely melting, and carrying out continuous thermal insulation stirring ripening for 30 min; and b, transferring the material from the step a to another reactor with a double-roller grinding pressing wheel and jacket heat conducting oil heating, carrying out a reaction, then carrying out pressure maintaining cooling, and crushing to obtain the crystal II type ammonium polyphosphate. According to the present invention, the polyphosphoric acid raw material is adopted as the starting raw material, the polyphosphoric acid, the ammonium phosphate and the urea are subjected to a reaction, the reaction promoting agent and the crystal form conversion agent are added, melt mixing is performed, and the polymerization and crystal phase transformation reaction is performed to obtain the crystal II type ammonium polyphosphate product having stable quality so as to enrich a raw material synthesis route of the crystal II type ammonium polyphosphate product.
Description
Technical field
The present invention relates to the ammonium polyphosphate preparing technical field, specifically, is a kind of brand-new method by polyphosphoric acid raw material route to prepare crystal II-type ammonium polyphosphate.
Background technology
Ammonium polyphosphate (English name Ammonium Polyphosphate) is called for short APP, it is the good phosphorous flame-retardant material of a kind of flame retardant properties, nontoxic, tasteless with it, the characteristics that do not produce toxic and harmful, excellent property are widely used in the every field of fire retardant material, have obtained in recent years great development as important environment friendly flame retardant.
Known APP has 5 kinds of crystalline structure, be respectively I～V type, wherein the crystal I-type product is the porous particles material, and the surface has erratic composition, the polymerization degree is low, water-soluble large, easily the moisture absorption is poor with the polymer intermiscibility, dialysis is run off easily, cause flame retardant properties to reduce, its application is subject to larger restriction, is mainly used in the fire-retardant finish of paper, timber, fiber, coating etc.; Crystallization II-type APP is rhombic form, close structure, and particle surface is round and smooth, and the polymerization degree is large, be insoluble in water, be difficult for occuring the moisture absorption and degraded, decomposition temperature is high, Heat stability is good, good with the high molecular polymer intermiscibility, have preferably flame retardant effect, be the developing direction of following APP product.
Report in recent years morely about the production method of crystal II-type ammonium polyphosphate, also have and much carried out patent and declare.
Such as patent disclosure CN1629070A, select equimolar Vanadium Pentoxide in FLAKES and Secondary ammonium phosphate under 150-350 ℃, adding ammonium sulfate, trimeric cyanamide or volatile salt is condensing agent, makes crystal II-type ammonium polyphosphate through mixing, melting, crystallization, pulverizing under ammonia atmosphere.
Patent disclosure CN101254908B selects Vanadium Pentoxide in FLAKES, Secondary ammonium phosphate and urea soln to divide five step control conditions to generate the high heat-resistant crystallization II type ammonium polyphosphate product.
Patent disclosure CN101439851A adopts Vanadium Pentoxide in FLAKES, Secondary ammonium phosphate and urea to react under the ammonia environment and obtains the crystal I-type product, adds entry again in system, turns the crystallization processing and obtains the crystal II-type ammonium polyphosphate product.
Patent disclosure CN101597044A, at first select equimolar Vanadium Pentoxide in FLAKES and Secondary ammonium phosphate under atmosphere of inert gases, to react, alternately utilize again ammonia environment and add surface treatment agent to be divided into the crystal II-type ammonium polyphosphate product that six steps make the high-polymerization degree narrow molecular-weight.
Patent disclosure CN101538029A, select Secondary ammonium phosphate, urea and trimeric cyanamide as reaction raw materials, adding successively above three kinds of raw materials in reactor reacts, pass into afterwards ammonia and carry out ammonification and slaking crystallization, discharging cooling, pulverizing obtain the high-polymerization degree crystallization type II branched-chain poly-ammonium phosphate.
Patent disclosure CN101428780A, adopt 85% phosphoric acid as reaction raw materials, at first phosphoric acid is dewatered, then add the first condensing agent, such as urea, add again the second condensing agent, such as trimeric cyanamide, pass into again the ammonia ammonification after 20～40 minutes, at last slaking 1～3 hour under ammonia environment, the discharging cooling obtains the crystallization type II branched-chain poly-ammonium phosphate product behind the comminution by gas stream.
Patent disclosure CN101830450A, select one or more mixture in phosphoric acid, monoammonium phosphate or the diammonium phosphate as reaction raw materials, react in two steps as polycondensation agent with one or both mixture of urea, trimeric cyanamide, especially pass into wet ammonia gas in the second step, cooling discharging, pulverizing can obtain crystal II-type ammonium polyphosphate after 0.5-4 hour.
Patent disclosure CN101891168A, a certain amount of ammonium phosphate salt and polyphosphoric acid melamine salt are mixed at normal temperatures, be warmed up to 120～320 ℃ and pass into wet ammonia, reacted 30～120 minutes, continue to be warmed up to 180～380 ℃ and pass into wet ammonia, reacted 1～5 hour, and through curing, broken, cooling, obtained crystal II-type ammonium polyphosphate afterwards.
The invention provides a kind of new synthetic route, is that raw material sets out and makes the method for crystal II-type ammonium polyphosphate by polyphosphoric acid namely.
Summary of the invention
The object of the invention is to enrich the raw material route of crystal II-type ammonium polyphosphate preparation, a kind of brand-new being set out by the polyphosphoric acid raw material is provided, preparation crystal II-type ammonium polyphosphate method.
The method that employing polyphosphoric acid of the present invention prepares crystal II-type ammonium polyphosphate is achieved through the following technical solutions:
A. add after adopting polyphosphoric acid, ammonium phosphate salt, urea as the reaction raw materials metering in the reactor with stirring arm and chuck temperature control, continue to stir temperature control to 50～150 ℃, material is melted fully, and then adding reaction promotor and compound modifying agent after metering, and make it to melt fully, continue insulated and stirred slaking 30 minutes;
B. the material that step a is stirred is transferred in another reactor with roller-crushing mill pinch roller and chuck heat-conducting oil heating, band roller-crushing mill pinch roller can make material continue mixing, fragmentation in reaction process, temperature keeps 150～250 ℃, pass into ammonia, and to keep that ammonia presses be 0.01～0.1MPa, polyreaction is kept ammonia and is pressed after 10～30 minutes, transformation of crystal ℃ was carried out 1～4 hour in rising temperature to 250～350, and the pressurize cooling obtains crystal II-type ammonium polyphosphate by pulverizing;
Polyphosphoric acid concentration is 114-118%, and the add-on of polyphosphoric acid is in 100 parts;
Ammonium phosphate salt refers to a kind of in monoammonium phosphate or the diammonium phosphate, and add-on is 20～35 parts;
The add-on of urea is 10～35 parts;
Described reaction promotor is a kind of in trimeric cyanamide, melam or the melem, and add-on is 1～5 part;
Described compound modifying agent is a kind of in cobalt oxide, ferric oxide, zinc oxide and the magnesium oxide, and add-on is 0.1～0.5 part.
The preferred trimeric cyanamide of described reaction promotor.
Described compound modifying agent preferential oxidation magnesium.
Enforcement by the technical program, namely set out by the polyphosphoric acid raw material, adopt polyphosphoric acid and ammonium phosphate salt and urea reaction, and interpolation reaction promotor and compound modifying agent, melt-blended by polymerization and turn crystallization and obtain stay-in-grade crystal II-type ammonium polyphosphate product, enriched the raw material synthetic route of crystal II-type ammonium polyphosphate product.
Description of drawings
Fig. 1 is the X-ray diffractogram of the crystal II-type ammonium polyphosphate for preparing of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but they are not limitation of the invention.
Embodiment 1
Take by weighing 100 parts of 116% polyphosphoric acids and add reactor, open stirring, keep 80 ℃ of temperature, in reactor, add 35 parts of monoammonium phosphates, 35 parts in urea, continue in system, to add 0.1 part in 1 part of trimeric cyanamide and magnesium oxide after the fusing fully, melt complete follow-up continuation of insurance temperature and stir 30min, discharging to temperature is in another reactor of 200 ℃, and pass into ammonia and keep ammonia and press 0.08MPa, polyreaction 30min keeps ammonia and presses and continue rising temperature to 300 and ℃ turn crystallization, pressurize is cooled to 150 ℃ after 3 hours, the pressure release discharging obtains the crystal II-type ammonium polyphosphate product after the pulverizing, the polymerization degree equals 1645, solubleness is 0.24g/100ml water, and 0.5% heat decomposition temperature is greater than 275 ℃.
Embodiment 2
Take by weighing 100 parts of 115% polyphosphoric acids and add reactor, open stirring, keep 90 ℃ of temperature, in reactor, add 35 parts of monoammonium phosphates, 20 parts in urea, continue in system, to add 0.2 part in 3 parts of trimeric cyanamides and magnesium oxide after the fusing fully, melt complete follow-up continuation of insurance temperature and stir 30min, discharging to temperature is in another reactor of 250 ℃, and pass into ammonia and keep ammonia and press 0.1MPa, polyreaction 20min keeps ammonia and presses and continue rising temperature to 300 and ℃ turn crystallization, pressurize is cooled to 150 ℃ after 4 hours, the pressure release discharging obtains the crystal II-type ammonium polyphosphate product after the pulverizing, the polymerization degree equals 1178, solubleness is 0.35g/100ml water, and 0.5% heat decomposition temperature is greater than 275 ℃.
Embodiment 3
Take by weighing 100 parts of 114% polyphosphoric acids and add reactor, open stirring, keep 110 ℃ of temperature, in reactor, add 35 parts of monoammonium phosphates, 10 parts in urea, continue in system, to add 0.1 part of 5 parts of melams and ferric oxide after the fusing fully, melt complete follow-up continuation of insurance temperature and stir 30min, discharging to temperature is in another reactor of 250 ℃, and pass into ammonia and keep ammonia and press 0.1MPa, polyreaction 30min keeps ammonia and presses and continue rising temperature to 300 and ℃ turn crystallization, pressurize is cooled to 150 ℃ after 4 hours, the pressure release discharging obtains the crystal II-type ammonium polyphosphate product after the pulverizing, the polymerization degree equals 1245, solubleness is 0.13g/100ml water, and 0.5% heat decomposition temperature is greater than 275 ℃.
Embodiment 4
Take by weighing 100 parts of 118% polyphosphoric acids and add reactor, open stirring, keep 80 ℃ of temperature, in reactor, add 35 parts of monoammonium phosphates, 20 parts in urea, continue in system, to add 0.5 part in 2 parts of trimeric cyanamides and zinc oxide after the fusing fully, melt complete follow-up continuation of insurance temperature and stir 30min, discharging to temperature is in another reactor of 200 ℃, and pass into ammonia and keep ammonia and press 0.05MPa, polyreaction 20min keeps ammonia and presses and continue rising temperature to 280 and ℃ turn crystallization, pressurize is cooled to 150 ℃ after 4 hours, the pressure release discharging obtains the crystal II-type ammonium polyphosphate product after the pulverizing, the polymerization degree equals 1538, solubleness is 0.25g/100ml water, and 0.5% heat decomposition temperature is greater than 275 ℃.
Embodiment 5
Take by weighing 100 parts of 116% polyphosphoric acids and add reactor, open stirring, keep 100 ℃ of temperature, in reactor, add 30 parts of diammonium phosphate, 35 parts in urea, continue in system, to add 0.4 part of 5 parts of melems and cobalt oxide after the fusing fully, melt complete follow-up continuation of insurance temperature and stir 30min, discharging to temperature is in another reactor of 230 ℃, and pass into ammonia and keep ammonia and press 0.08MPa, polyreaction 30min keeps ammonia and presses and continue rising temperature to 340 and ℃ turn crystallization, pressurize is cooled to 150 ℃ after 2 hours, the pressure release discharging obtains the crystal II-type ammonium polyphosphate product after the pulverizing, the polymerization degree equals 1106, solubleness is 0.18g/100ml water, and 0.5% heat decomposition temperature is greater than 275 ℃.
Embodiment 6
10 parts in urea, 0.1 part of compound modifying agent selective oxidation iron, the remaining operation of base gets the crystal II-type ammonium polyphosphate product with embodiment 1 after the pulverizing, and the polymerization degree equals 1312, and solubleness is 0.20g/100ml water, and 0.5% heat decomposition temperature is greater than 275 ℃.
Claims (3)
1. a method that adopts polyphosphoric acid to prepare crystal II-type ammonium polyphosphate is characterized in that, the steps include:
A. add after adopting polyphosphoric acid, ammonium phosphate salt, urea as the reaction raw materials metering in the reactor with stirring arm and chuck temperature control, continue to stir temperature control to 50～150 ℃, material is melted fully, and then adding reaction promotor and compound modifying agent after metering, and make it to melt fully, continue insulated and stirred slaking 30 minutes;
B. the material that step a is stirred is transferred in another reactor with roller-crushing mill pinch roller and chuck heat-conducting oil heating, temperature keeps 150～250 ℃, pass into ammonia, and to keep that ammonia presses be 0.01～0.1MPa, polyreaction is kept ammonia and is pressed after 10～30 minutes, transformation of crystal ℃ was carried out 1～4 hour in rising temperature to 250～350, and the pressurize cooling obtains crystal II-type ammonium polyphosphate by pulverizing;
Polyphosphoric acid concentration is 114-118%, and the add-on of polyphosphoric acid is in 100 parts;
Ammonium phosphate salt refers to a kind of in monoammonium phosphate or the diammonium phosphate, and add-on is 20～35 parts;
The add-on of urea is 10～35 parts;
Described reaction promotor is a kind of in trimeric cyanamide, melam or the melem, and add-on is 1～5 part;
Described compound modifying agent is a kind of in cobalt oxide, ferric oxide, zinc oxide and the magnesium oxide, and add-on is 0.1～0.5 part.
2. employing polyphosphoric acid according to claim 1 prepares the method for crystal II-type ammonium polyphosphate, it is characterized in that, described reaction promotor trimeric cyanamide.
3. employing polyphosphoric acid according to claim 1 prepares the method for crystal II-type ammonium polyphosphate, it is characterized in that, described compound modifying agent magnesium oxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503276A (en) * | 2015-12-28 | 2016-04-20 | 川恒生态科技有限公司 | Preparation method of full water-soluble solid ammonium polyphosphate |
| CN106586997A (en) * | 2016-12-16 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of type II ammonium polyphosphate |
| CN106586998A (en) * | 2016-12-18 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of ammonium polyphosphate having high polymerization degree |
| CN110759324A (en) * | 2019-11-07 | 2020-02-07 | 中化重庆涪陵化工有限公司 | Method for producing ammonium polyphosphate by using phosphoric acid and urea |
| CN112875668A (en) * | 2021-03-17 | 2021-06-01 | 云南云天化股份有限公司 | Method for preparing water-soluble ammonium polyphosphate by two-step method |
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| US4687651A (en) * | 1985-10-15 | 1987-08-18 | Thermal Science, Inc. | Method for producing ammonium polyphosphate |
| JPH07315817A (en) * | 1994-05-23 | 1995-12-05 | Chisso Corp | Production of ii type polyphosphoric acid ammonium fine particle |
| CN1651488A (en) * | 2004-12-23 | 2005-08-10 | 云南省化工研究院 | Production method of poly ammonium phosphate |
| CN102190291A (en) * | 2011-03-22 | 2011-09-21 | 华东理工大学 | Method for preparing crystal II-type ammonium polyphosphate by crystal transformation method |
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| US4687651A (en) * | 1985-10-15 | 1987-08-18 | Thermal Science, Inc. | Method for producing ammonium polyphosphate |
| JPH07315817A (en) * | 1994-05-23 | 1995-12-05 | Chisso Corp | Production of ii type polyphosphoric acid ammonium fine particle |
| CN1651488A (en) * | 2004-12-23 | 2005-08-10 | 云南省化工研究院 | Production method of poly ammonium phosphate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503276A (en) * | 2015-12-28 | 2016-04-20 | 川恒生态科技有限公司 | Preparation method of full water-soluble solid ammonium polyphosphate |
| CN105503276B (en) * | 2015-12-28 | 2020-06-02 | 川恒生态科技有限公司 | Preparation method of full water-soluble solid ammonium polyphosphate |
| CN106586997A (en) * | 2016-12-16 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of type II ammonium polyphosphate |
| CN106586997B (en) * | 2016-12-16 | 2018-07-06 | 上海普信高分子材料有限公司 | A kind of preparation method of II type ammonium polyphosphate |
| CN106586998A (en) * | 2016-12-18 | 2017-04-26 | 衢州普信新材料有限公司 | Preparation method of ammonium polyphosphate having high polymerization degree |
| CN110759324A (en) * | 2019-11-07 | 2020-02-07 | 中化重庆涪陵化工有限公司 | Method for producing ammonium polyphosphate by using phosphoric acid and urea |
| CN110759324B (en) * | 2019-11-07 | 2023-03-21 | 中化重庆涪陵化工有限公司 | Method for producing ammonium polyphosphate by using phosphoric acid and urea |
| CN112875668A (en) * | 2021-03-17 | 2021-06-01 | 云南云天化股份有限公司 | Method for preparing water-soluble ammonium polyphosphate by two-step method |
| CN112875668B (en) * | 2021-03-17 | 2022-12-02 | 云南云天化股份有限公司 | Method for preparing water-soluble ammonium polyphosphate by two-step method |
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