CN101081837B - Method for synthesizing melamine cyanurate salt - Google Patents
Method for synthesizing melamine cyanurate salt Download PDFInfo
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- CN101081837B CN101081837B CN2006100837223A CN200610083722A CN101081837B CN 101081837 B CN101081837 B CN 101081837B CN 2006100837223 A CN2006100837223 A CN 2006100837223A CN 200610083722 A CN200610083722 A CN 200610083722A CN 101081837 B CN101081837 B CN 101081837B
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Abstract
The process of synthesizing melamine cyanurate includes the following steps: mixing urea, melamine and ammonium salt as dispersant in certain proportion to obtain mixture; pre-heating the reactor to 270-295 deg.c, starting the stirrer, leading nitrogen to the reactor, adding the mixture to the reactor, heating the material to 270-290 deg.c, and reacting for 60-70 min to obtain white powdered intermediate product; adding water in 14-18 times the weight of melamine to the intermediate product, heating to 100 deg.c, reacting for 10 hr, hot filtering, washing the filter cake with boiled water, stoving, and crushing to obtain melamine cyanurate product. The melamine cyanurate product of the process has purity of 99.5 % and yield up to 95.5 %, and is applied as fire retardant.
Description
Technical field
The present invention relates to a kind of synthetic method of environment-friendly type nitrogen flame retardant melamine cyanurate salt.
Background technology
In recent years; along with people to protecting the enhancing of ecological and Environmental awareness, be that the product that indicates arises at the historic moment with the green, traditional fire retardant material has been proposed challenge; particularly be the halogen flame of representative, because of toxicity and corrosion problems are subjected to severe challenge with the polybromodiphenyl ether.Show through a large amount of applied researcies that according to relevant document record halogen and phosphorus all can produce objectionable impurities in combustion processes.It is reported that melamine cyanurate salt (MCA is as follows) is the most representative up to now green fire retardant.MCA belongs to the nitrogen flame retardant, crystalloid is white in color, and have the powder of greasy feeling, and tasteless, nontoxic, proportion 1.5～1.6, be insoluble in water and other organic solvent, but can be scattered in preferably in the oils medium, in stable below 350 ℃, distillation more than 440 ℃, molecular weight is 255, and wherein nitrogen content is up to 49.41%.MCA not only has good flame retardant property as fire retardant, and the amount of being fuming is little, also as lubricant, is widely used in the materials such as polymeric amide, Resins, epoxy, resol, polyolefine in processing of high molecular material.In addition, MCA also can be used as additive, levelling agent, laking agent etc.At present, new purposes is also constantly being widened.MCA the more important thing is that to the fire-retardant physical action that not only has the heat absorption of distilling and quicken drippage of nylon it can change the thermal-oxidative degradation course of nylon, makes it fast charring formation and does not fire carbonaceous.These carbonaceous form one deck barrier layer because of the expanded foamed nylon base surface of covering, and have cut off contacting of nylon and air, thereby can stop the sustained combustion of nylon effectively.Simultaneously, decompose the non-flammable gas that produces and make the expanding layer of material expansion formation reduce heat conductivity greatly, help putting out certainly of material from fire.Therefore, MCA is fire-retardant to nylon, and existing physics fire retardation also has chemical fire retardation.When the superpolymer that contains this fire retardant is heated, can fast charring forms and do not fire barrier layer, can be heat insulation, oxygen barrier, press down cigarette, and can prevent molten drop, have good flame retardancy, advantages such as thermostability height, consistency are good, no transport phenomena.Adopted different routes to synthesize this product both at home and abroad, but number average adopts the synthetic MCA of liquid phase method mostly, its commodity mainly contain Melapur MC50, Melapur MC25, the Melapur MC XL of vapour Bagong department, the FYROL MC of AKZO NOBEL company, and the MCA of toray company.Domestic production producer mainly contains fine chemistry industry studying and designing institute, Sichuan, Shouguang WeiDong Chemical Co., Ltd., the smart chemical industry company limited that converges in Hefei, medium blue time chemical research institute.The synthetic method of MCA can be divided into Wyler's process and cyanuric acid method by raw materials used difference.Wyler's process is divided into two-step approach and single stage method again, it is that raw material is through the synthetic MCA of two-step approach that Mr. Liu Kaiyu of chemical institute of China Central South University adopts urea, at first melt and dissolved by urea, curing, sour boiling get cyanuric acid, make MCA by cyanuric acid and trimeric cyanamide reaction again.In addition, the preparation of novel nitrogen flame retardant [J]. chemistry world, 2001, (4), 184～186 have announced with urea to be raw material, have synthesized MCA through two-step approach, at first with urea and ammonium chloride through melt and dissolved, solidify and make the cyanuric acid crude product, again through washing, the refining cyanuric acid that obtains; By cyanuric acid and trimeric cyanamide with 115～120 ℃ of reactions 10～12 hours, make white crystalline powder MCA through press filtration, washing, oven dry, pulverizing again, product yield is 95%, and technology is than urea single stage method complexity.The clear 54-125690 of Japan's publication has reported the method with urea and directly synthetic MCA of one step of trimeric cyanamide, its process is that urea and trimeric cyanamide are 3～10 ratio in molar ratio, adds in the reactor, while stirring heating, when temperature reaches 140～200 ℃, reactant becomes white solution; When temperature surpasses 200 ℃, become thickly, continue heating and become pressed powder, reach 350 ℃ at last.This handicraft product yield is about 91%, and product purity is 99.5%.Product yield is on the low side.The patent documentation report of the synthetic MCA of cyanuric acid method is many, and once adopt in organic polar solvents such as tetrahydrofuran (THF) and reacted the sixties in 20th century, but because, problems such as solvent recuperation are later on except just seldom having this class report for the needs of studying.Industrial extensive employing at present be to be the synthetic route of solvent with water because cyanuric acid and trimeric cyanamide solubleness in water are very little, therefore synthetic MCA need carry out in big water gaging.The pertinent literature report has: the preparation of MCA-flame-resistant lubricant and application, chemistry world, 1990 (7), 14-16; Flame-resistant lubricant melamine cyanurate synthetic, 219-223, Hebei Academy of Sciences journal, in November, 2000; The patent US5202438 of France Elf Atochem company, be PH less than 1 strongly acidic aqueous solution in the patented technology of synthetic MCA; The patent JP93 310716.1993 of Japan Nissan Chemical company is synthetic MCA in the presence of polyvinyl alcohol; European patent EP 666259.1994 adds silica gel in the process of synthetic MCA, 85 ℃ of reactions obtained in 2 hours soup compound spray again oven dry dry the MCA finished product.The drawback that adopts the synthetic MCA of liquid phase method to exist mainly is that water consumption is big, and the resultant granularity is thinner in addition, and filtration efficiency is poor, thereby influences the raising of whole flow process productivity, and to adopt the cyanuric acid of high price be the synthetic MCA of raw material, and raw materials cost is higher relatively.
Summary of the invention
It is the method for raw material one-step synthesis MCA that the object of the invention is to provide with urea and trimeric cyanamide, is stablizing the highly purified while of MCA, and its yield can be significantly improved.
The objective of the invention is to realize with following technical scheme:
A kind of synthetic method of melamine cyanurate salt is characterized in that:
Take by weighing raw material urea, trimeric cyanamide and ammonium salt class dispersion agent, wherein the mol ratio of urea and trimeric cyanamide is 3: 0.7～1.0, described ammonium salt class dispersion agent is 20～22% of a trimeric cyanamide weight, and above-mentioned raw material and dispersant are evenly obtained mixture, and is standby;
Reactor is preheated to 270～295 ℃, the more above-mentioned mixture that makes is added in the described reactor after, start and stir, feed nitrogen, temperature of charge rises to 270～290 ℃ in the question response device, and reinforced certainly beginning reaction obtained the white powder intermediate product after 60～70 minutes; Then, described intermediate product is cooled to≤100 ℃, adding its weight in this intermediate product is 14～18 times water of trimeric cyanamide weight; Be warming up to 100 ℃ again, and reaction 10 hours under this temperature, stop to stir, filtered while hot, its filter cake through the boiling water washing to neutral, oven dry, pulverize and make melamine cyanurate salt.
Above-mentioned synthetic method, its raw material urea and trimeric cyanamide mol ratio are 3: 0.85.
Above-mentioned synthetic method, the add-on of its water are 16 times of trimeric cyanamide weight.
Above-mentioned synthetic method, its described ammonium salt class dispersion agent is ammonium nitrate, ammonium chloride or ammonium sulfate.
Above-mentioned synthetic method, the nitrogen that feeds in reactor, its flow are 40～60ml/min.
Can obtain weight percentage by technique scheme is 99.5% melamine cyanurate salt, and its yield is up to 95.5%, has improved 4.5% than prior art, has positive effect.
Embodiment
Embodiment 1:
At first weighing urea 48 restrains, trimeric cyanamide 28.56 restrains, dispersion agent NH
4NO
36 grams are put into mixing machine and are mixed, and obtain mixture.The 1000mL four-hole bottle that to be furnished with electric mantle, agitator, thermometer, condenser, ammonia absorption system is preheated to 270 ℃, the mixture that adds above-mentioned mixing, after starting agitator, feed nitrogen, start above-mentioned ammonia absorption system and reclaim to take away the ammonia of generation; Material becomes thick when temperature reaches 200 ℃, continue to be warming up to 270 ℃, then material solidifies and becomes the white powder intermediate product, keep reaction 1 hour from the reinforced beginning, then this intermediate product is cooled to below 100 ℃ after (≤100 ℃, as follows), adds 456 gram water, be warming up to 100 ℃ again, and under this temperature, keep reaction 10 hours.And then filtered while hot, to neutral, the filter cake drying that obtains makes MCA finished product 54.3 grams to water-content≤0.2% (weight, as follows) with 800 gram boiling water washings, and yield is 94.0%, and purity is 99.5%.
Embodiment 2:
At first weighing urea 48 grams, trimeric cyanamide 30.24 grams, dispersion agent ammonium chloride 6 grams are put into mixing machine and are mixed, and obtain mixture.The 1000mL four-hole bottle that to be furnished with electric mantle, agitator, thermometer, condenser, ammonia absorption system is heated to 280 ℃, add above-mentioned mixture, start agitator, feed nitrogen, start described ammonia absorption system and reclaim to take away the ammonia of generation.Become thickly when temperature reaches 200 ℃, continue to be warming up to 280 ℃, then material solidifies and becomes the white powder intermediate product, keep reaction after 1 hour intermediate product to be cooled to below 100 ℃ from the reinforced beginning, add 456 gram water, be warming up to 100 ℃ again, keeping reaction after 10 hours under this temperature, filtered while hot, to neutral, its filter cake drying is dry to water-content≤0.2% with 800 gram boiling water washings, obtains MCA finished product 57.83 grams, yield is 94.5%, and purity is 99.5%.
Embodiment 3:
At first weighing urea 48 grams, trimeric cyanamide 28.56 grams, dispersion agent ammonium chloride 6 grams are put into mixing machine and are mixed, and obtain mixture.The 1000mL four-hole bottle that to be furnished with electric mantle, agitator, thermometer, condenser, ammonia recovery system is preheated to 290 ℃, the mixture that adds above-mentioned mixing, after starting agitator, feed chlorine, start above-mentioned ammonia absorption system and absorb to take away the ammonia of generation; Material becomes thick when temperature reaches 200 ℃, continue to be warming up to 290 ℃, then material solidifies and becomes the white powder intermediate product, keep reaction after 1 hour from the reinforced beginning, this intermediate product is cooled to (≤100 ℃, as follows) below 100 ℃, adds 514 gram water, be warming up to 100 ℃ again, and under this temperature, keep reaction 10 hours.And then filtered while hot, to neutral, its filter cake drying makes MCA finished product 55.2 grams to water-content≤0.2% with 800 gram boiling water washings, and yield is 95.5%, and purity is 99.8%.
Embodiment 4:
At first weighing urea 48 restrains, trimeric cyanamide 28.56 restrains, dispersion agent NH
4SO
46 grams are put into mixing machine and are mixed, and obtain mixture.The 1000mL four-hole bottle that to be furnished with electric mantle, agitator, thermometer, condenser, ammonia recovery system is preheated to 295 ℃, the mixture that adds above-mentioned mixing, after starting agitator, feed chlorine, start above-mentioned ammonia absorption system and absorb to take away the ammonia of generation; Material becomes thick when temperature reaches 200 ℃, continue to be warming up to 290 ℃, then material solidifies and becomes the white powder intermediate product, keep reaction after 1 hour from the reinforced beginning, this intermediate product is cooled to (≤100 ℃, as follows) below 100 ℃, adds 514 gram water, be warming up to 100 ℃ again, and under this temperature, keep reaction 10 hours.And then filtered while hot, to neutral, its filter cake drying makes MCA finished product 55.2 grams to water-content≤0.2% with 800 gram boiling water washings, and yield is 95.5%, and purity is 99.8%.
Test finds that when temperature was higher than 300 ℃, product colourity was bad.
The MCA that the present invention makes with technique scheme, its key technical indexes is:
Product purity 〉=99.5%
Product whiteness 〉=95%
Moisture content≤0.2%
Remaining trimeric cyanamide≤0.001%
Remaining cyanuric acid≤0.2%.
Embodiment 5 (comparative example):
At first weighing urea 48 restrains, trimeric cyanamide 28.56 restrains, dispersion agent NH
4Cl 6 grams, putting into mixing machine mixes, add and be furnished with electric mantle, agitator, thermometer, condenser, in the 1000mL four-hole bottle of ammonia recovery system, start and stir, feed nitrogen, slowly heat up, when temperature rose to 106 ℃, material all melted, and continued to heat up, when temperature reaches 200 ℃, become thick, during to 280 ℃, material solidifies and becomes the white powder intermediate product, is keeping reaction after 1 hour under this state, this intermediate product is cooled to below 100 ℃, add 456 gram water, be warming up to 100 ℃, keeping reaction after 10 hours under this temperature, filtered while hot, to neutral, its filter cake drying gets MCA finished product 52.60 grams with 800 gram boiling water wash agitation, yield is 91%, and purity is 98.5%.
From example 5 as seen, when reactor without preheating, be warming up to 106 ℃, 200 ℃, 280 ℃ slow temperature-rise period after reinforced gradually, generate the white powder intermediate product after, under this state, keep reaction 1 hour, its product purity is 98.5%, yield is 91%.Reactor of the present invention carries out preheating institute temperature in advance, and it is 60～70 minutes that the reinforced certainly beginning keeps the reaction times, and product purity is up to 99.8%, and product yield is up to 95.5%.This shows, reactor is preheated to temperature required earlier positively effect is arranged to improving product yield and quality product.
Analytical procedure that the present invention adopts is a liquid chromatography, and this is those of ordinary skills' technology in common knowledge.
Simply introduce the test of MCA flame retardant properties below: with the polyamide 66 is research object, and melamine cyanurate salt is carried out flame retardant properties and Mechanical Properties.Concrete prescription sees Table 1, and test result sees 2.
The basic recipe of table 1 polypropylene flame redardant
| Prescription | Ratio (wt%) |
| Polyamide 66 | 91.6 |
| Fire retardant MCA | 8.0 |
| Antioxidant 1010 | 0.2 |
| Oxidation inhibitor 168 | 0.2 |
Sample making course: fire retardant MCA and nylon 66 dryings, the prescription that provides by last table 1 more accurately takes by weighing fire retardant MCA, nylon 66 and various auxiliary agent that the present invention of requirement makes, is added to thorough mixing in the high-speed mixer; Each section of twin screw extruder temperature starts slow speed of revolution screw rod, the material that mixes after reaching technique initialization value (column data as follows) and stablizing half an hour; enter twin screw extruder through feeding machine (control feed rate), fully heating, mixing after, by die head extruded stock bar; after water cooling; send into dicing machine, evenly be cut into particle, again after the drying; by the relevant criterion injection moulding; obtain the standard batten, and carry out fire-retardant Mechanics Performance Testing according to standard, its test result sees the following form 2.
The main operational condition of forcing machine:
The thermometer 235-255 of heating zone ℃
235 ℃ of one section temperature
240 ℃ of two sections temperature
245 ℃ of three sections temperature
255 ℃ of four sections temperature
250 ℃ of five sections temperature
Rate of feeding 150-250kg/h
Screw speed 200-400rpm.
The performance test data table of table 2 polypropylene flame redardant
From the following table test result, when fire retardant consumption 10%, flame retardant rating reaches the UL94V-0 level, can satisfy the application performance requirement of flame-retardant PA 66.
| Project | PA66 (not adding fire retardant) | PA66+ MCA of the present invention | The method of inspection |
| Incendivity | Burning has cigarette, molten drop is arranged, afterflame | V-0 | The UL94 standard |
| Tensile strength (Mpa) | 76.5 | 76.0 | ASTMD638 |
| Flexural strength (Mpa) | 127.4 | 88.4 | ASTMD790 |
| Notched Izod impact strength (J/m -1) | 6700 | ASTMD256 | |
| Heat-drawn wire (1.86MPa)/℃ | 70 | 130 | ASTMD648 |
Claims (4)
1. the synthetic method of a melamine cyanurate salt is characterized in that:
Take by weighing raw material urea, trimeric cyanamide and dispersion agent, wherein the mol ratio of urea and trimeric cyanamide is 3: 0.7～1.0, and dispersion agent is 20～22% of a trimeric cyanamide weight, and above-mentioned raw material and dispersant are evenly obtained mixture, and is standby;
Dispersion agent is ammonium nitrate or ammonium sulfate;
Reactor is preheated to 270～295 ℃, be added to the mixture that makes in the described reactor again after, start to stir, feed nitrogen, temperature of charge rises to 270～290 ℃ in the question response device, and the reinforced certainly beginning obtains the white powder intermediate product after keeping 60～70 minutes reaction times;
Then, above-mentioned intermediate product is cooled to≤100 ℃ after, adding its weight in this intermediate product is 14～18 times water of trimeric cyanamide weight;
Be warming up to 100 ℃ again, and reaction 10 hours under this temperature, stop to stir, filtered while hot, its filter cake through the boiling water washing to neutral, oven dry is dry, pulverize and make melamine cyanurate salt.
2. the synthetic method of melamine cyanurate salt according to claim 1, it is characterized in that: urea and trimeric cyanamide mol ratio are 3: 0.85.
3. the synthetic method of melamine cyanurate salt according to claim 1, it is characterized in that: the add-on of water is 16 times of trimeric cyanamide weight.
4. the synthetic method of melamine cyanurate salt according to claim 1, it is characterized in that: the nitrogen that feeds in reactor, its flow are 40～60ml/min.
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| CN2006100837223A CN101081837B (en) | 2006-06-02 | 2006-06-02 | Method for synthesizing melamine cyanurate salt |
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| CN2006100837223A CN101081837B (en) | 2006-06-02 | 2006-06-02 | Method for synthesizing melamine cyanurate salt |
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| CN101081837B true CN101081837B (en) | 2010-07-28 |
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| CN101899354B (en) * | 2010-07-29 | 2012-12-05 | 济南泰星精细化工有限公司 | Method for producing high-purity flame-resistant lubricant by improved powder method |
| CN102174213B (en) * | 2011-01-27 | 2012-05-30 | 济南泰星精细化工有限公司 | Rodlike crystalline melamine cyanurate fire retardant and preparation method thereof |
| CN105259294B (en) * | 2015-11-16 | 2017-05-10 | 济南泰星精细化工有限公司 | Method for detecting residual quantity of melamine and cyanuric acid in melamine cyanurate |
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