CN101774974A - A process for the preparation of melamine cyanurate - Google Patents
A process for the preparation of melamine cyanurate Download PDFInfo
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- CN101774974A CN101774974A CN 201010001502 CN201010001502A CN101774974A CN 101774974 A CN101774974 A CN 101774974A CN 201010001502 CN201010001502 CN 201010001502 CN 201010001502 A CN201010001502 A CN 201010001502A CN 101774974 A CN101774974 A CN 101774974A
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- melamine cyanurate
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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Abstract
The invention relates to a process for the preparation of melamine cyanurate. A process, which comprises reacting melamine and cyanuric acid in an aqueous medium to form melamine cyanurate, removing the product slurry from the reaction vessel in the presence of a volatile base, spray drying said product slurry and collecting melamine cyanurate in the form of a dry powder. A method for granulating a powder of melamine cyanurate, and the product obtained therefrom are also provided.
Description
It is on March 5th, 2006 that the present patent application is based on the applying date, and application number is 200680000045.2 (international application no is PCT/IL2006/000298), and denomination of invention is divided an application for the patent application of " method for preparing melamine cyanurate ".
Melamine cyanurate (melamine cyanurate) be melamine (2,4,6-triamino-1,3,5-three azines (2,4,6-triamino-1,3,5-triazine)) and cyanuric acid (2,4,6-trihydroxy--1,3,5-three azines (2,4,6-trihydroxy-1,3,5-triazine) or its tautomeric ketone form (tautomeric keto form)) reaction product.Below, term " cyanuric acid " and " (different) cyanuric acid " but mutual alternative ground is used to represent enol (enol) and ketone (keto) tautomer.
Melamine cyanurate especially is mainly used in various thermoplastic compounds as flame-retardant additive (flame retardant additive), especially for polymeric amide, also has other purposes, for example as lubricant and plant nutrient.
In its most common form, the synthetic method that is used for preparing melamine cyanurate relates to the reaction at aqueous medium of melamine and cyanuric acid.Also propose in this area, by the pH of conditioned reaction mixture improves this general reaction process to wherein adding acidity or alkaline reagents.
In this can be at US 4,256, find general instruction in 591.According to the explanation of this patent, melamine and (different) cyanuric acid are scattered in the water, and preferred under 50 ℃～100 ℃ temperature, in the presence of mineral acid or organic acid, perhaps replacedly, in the presence of the alkaline reagents that is selected from caustic alkali, amine or ammonia, react, reaction neutralizes after finishing.
EP 507677 discloses a kind of method for preparing melamine cyanurate, and this method is included in the aqueous medium, in the presence of strong acid, under less than 1 pH melamine and cyanuric acid are reacted.
JP 56-032470 discloses a kind of by making melamine and cyanuric acid react the method for preparing melamine cyanurate in aqueous solvent, being higher than under 7.0 the pH.According to embodiment included in the disclosure text, melamine and cyanuric acid are in water, react in the presence of yellow soda ash.After reaction is finished, hydrochloric acid added make its neutralization in the reaction mixture, and by filtering the separate solid product.Dry and the grinding with the melamine cyanurate of gained at last.
In nearest open text CN 1506356, suggestion is in containing the water of ammoniacal liquor that concentration is 2～14% (weight %), react melamine and cyanuric acid under 100 ℃～200 ℃ temperature, and wherein said cyanuric acid is excessive existence.Product by filtering to come out from liquid phase separation, carry out drying then, thereby the granularity of obtaining (particle size) is about the product of 5～55 μ m.
Aforesaid method obtains pulverous melamine cyanurate.Though use as powder mass usually when melamine cyanurate is used for polymeric amide as flame-retardant additive, but make great efforts to provide the granular melamine cyanurate in the art, because granulated material than powder-product processing and transportation aspect favourable, this is to understand easily, certainly, prerequisite is finally will satisfy necessary requirement (for example, acceptable incendivity test, mechanical property, outward appearance) by the polymkeric substance that described granulated material is made flame retardant resistance.
A kind of method that obtains the granular melamine cyanurate of reporting in this field relates to uses various additives and tackiness agent (binding agent).For example, EP 666259 discloses a kind of method, wherein, and preparation melamine cyanurate in the presence of the metal oxide nanoparticles water-sol (metal oxide nano-particles hydrosol).Nearest open source literature WO 2003/35736 has obtained containing the granular melamine cyanurate of polyvinyl alcohol.
It is the solid fire line coacervate (agglomerate) of 0.1～5mm that DE 4040276 and similar EP 487974 have described mean particle size, its mean particle size is 0.1～5mm, this coacervate is to be that 0.1～10 micron basic granules (primary particle) makes by wet granulation from particle diameter, carries out drying then.
It is the particle of 100～2000 μ m that JP 07-149739 discloses median size (average grain diameter), and describing it is that the coacervate of the fine granular of 0.1～1 μ m is formed by median size.Seem that forming particle according to the disclosure text comprises and make water.
Method and thus obtained product that a kind of preparation does not contain the granular melamine cyanurate of tackiness agent are also disclosed in this area.EP 601542 discloses a kind of method for preparing melamine cyanurate, and this method comprises and not existing basically under any liquid medium situation, at 250～500 ℃ of heating melamine powder and cyanuric acid powder.When heating behind the mixture pelleting to described powder, can obtain the granulous melamine cyanurate.
Find now, in water, react in the soup compound that the back forms at melamine and cyanuric acid and to have volatile alkali, ammonia/ammonium hydroxide particularly, help from liquid phase, easily to isolate the melamine cyanurate product, thereby the Powdered melamine cyanurate with advantageous property is provided by the described soup compound of spraying drying.For for simplicity, in whole specification sheets, existing species when term " ammonium hydroxide " collectivity is represented in the solution of ammonia in water balance.
Also find, can carry out non-slurry pelletizing (dry granulation) subsequently according to the Powdered melamine cyanurate that method mentioned above obtains, preferably undertaken by rolling (roller compaction), thereby obtain free-pouring melamine cyanurate saccharoid, this saccharoid is easy to be dispersed in the polymeric amide, therefore is particularly suitable for preparing fire-retardant polyamide thermoplastic compositions.
Therefore, a first aspect of the present invention provides a kind of method, this method comprises: melamine and cyanuric acid react in aqueous medium and form melamine cyanurate, most preferably be in the presence of the volatile alkali of ammonium hydroxide, (product slurry) removes from reaction vessel with the product slurry, the described product slurry of spraying drying, and collect dry powdered melamine cyanurate.
Particularly, the present invention includes following aspect:
1) a kind of method, this method comprises: reaction melamine and cyanuric acid form melamine cyanurate in aqueous medium, in the presence of volatile alkali, the product slurry are removed from reaction vessel, the described product slurry of spraying drying, and collect dry powdered melamine cyanurate.
2) according to the method for item 1, wherein said alkali is ammonium hydroxide, and it is before reaction beginning or react and carry out adding in the reaction vessel in the process.
3) according to the method for item 1 or 2, wherein concentration of reactants is the 5-40% of reaction mixture gross weight, and the ammonium hydroxide that is dissolved in the aqueous reaction mixture is 0.05-1% with respect to the weight concentration of the amount of water.
4) according to the method for item 3, the weight concentration that wherein is dissolved in the ammonium hydroxide in the reaction mixture is 0.1～0.4%.
5) according to each method among the item 2-4, this method comprises: add entry, melamine and ammonium hydroxide in reaction vessel, subsequently gradually to wherein adding cyanuric acid.
6) according to each method among the item 1-5, under 20～75 ℃ temperature, carry out.
7) according to the method for item 6, under 35～55 ℃ temperature, carry out.
8) according to each method among the item 1-7, wherein in the presence of excessive melamine, carry out this reaction.
9) according to the method for item 1, wherein said alkali is ammonium hydroxide, when wherein the reaction between melamine and cyanuric acid closes to an end described ammonium hydroxide is added in the reaction vessel, thus the viscosity of reduction product slurry.
10) according to the method for item 1, the melamine cyanurate powder that is wherein obtained is the coacervate form, its mean diameter is 10～50 μ m, and bulk density is 0.20～0.35g/ml, and described coacervate is the granulometric composition of 0.5～4 μ m by the mean sizes of measuring as laser diffraction.
11) a kind of method, this method comprise the non-slurry pelletizing of powder melamine cyanurate, thereby obtain the granular melamine cyanurate.
12) according to the method for item 11, wherein said non-slurry pelletizing comprises the melamine cyanurate that rolls with the formation compacting.
13) according to the method for item 11, wherein said non-slurry pelletizing is included in the pressing machine the melamine cyanurate of powder melamine cyanurate squeezing with the formation compacting.
14) according to the method for item 12 or 13, this method also comprises grinds the melamine cyanurate of compacting and randomly screening, is the saccharoid of 0.1～10mm to obtain diameter.
15) according to the method for item 14, wherein the diameter of saccharoid is 0.2～2mm, and described saccharoid is to be the granulometric composition of 0.3～12 μ m by mean sizes, measures as laser diffraction, and the bulk density of wherein said saccharoid is not less than 0.60g/ml.
16) according to the method for item 11, wherein provide Powdered melamine cyanurate with mixture, described mixture contains one or more solid fireproof additives.
17) according to each method among the item 11-16, wherein Powdered melamine cyanurate parent material is to obtain by each method among the item 1-10.
18) a kind of method, this method comprise that Powdered melamine cyanurate that will obtain by each method among the 1-10 or the granular melamine cyanurate that obtains by each method among the 11-17 add in the polymkeric substance.
19) according to the method for item 18, wherein this polymkeric substance is a polymeric amide.
20) polymer composition that obtains by 18 or 19 method.
21) melamine cyanurate of non-slurry pelletizing.
22) according to the melamine cyanurate of item 21, it is the granular melamine cyanurate that rolls.
23) melamine cyanurate saccharoid, this saccharoid are to be the granulometric composition of 0.3～12 μ m by the mean diameter of measuring as laser diffraction, and wherein particle size distribution parameter is d
50＜5 μ m and d
98＜100 μ m, and the bulk density of wherein said saccharoid is not less than 0.60g/ml.
24) according to the melamine cyanurate saccharoid of item 23, wherein this saccharoid is of a size of 0.1～10mm, and wherein said saccharoid is to be the granulometric composition of 0.5～4 μ m by the mean diameter of measuring as laser diffraction.
25) according to the melamine cyanurate saccharoid of item 24, the particulate mean diameter of wherein forming this saccharoid is 1～3 μ m.
26) melamine cyanurate of non-slurry pelletizing, it is according to each particulate form among the item 23-25.
27) melamine cyanurate that rolls, it is according to each particulate form among the item 23-25.
Term " volatile alkali " is meant that boiling point is lower than the alkaline reagents of the used temperature of spray-drying stage, and purpose is in order to remove described alkali from the melamine cyanurate product.According to the present invention, preferred volatile alkali, ammonium hydroxide can be before reaction beginning, reaction is carried out in the process or add in the reaction vessel preferred especially first kind and second kind of selection to after just having finished reacting.Operable other possible volatile alkalis are that boiling point is lower than 200 ℃ according to the present invention, preferably are lower than 100 ℃ organic amine, for example methylamine or ethamine.
The used parent material according to the present invention, melamine and cyanuric acid can commercially availablely be buied, and perhaps can make by method well-known in the art.
Comprehensive, most preferably contain water and the ammonium hydroxide that is dissolved in wherein according to reaction medium of the present invention, wherein melamine and cyanuric acid parent material are suspended in the described aqueous medium, the weight concentration that makes described solid reactant account for the reaction mixture gross weight is preferably 5～40%, more preferably 10～25%, most preferably be 15～20%.The ammonium hydroxide that is dissolved in this reaction mixture is preferably 0.05～1% with respect to the weight concentration (in ammonia) of water, and more preferably 0.1～0.4%.Most convenient be that ammonium hydroxide provides with aqueous solution form, is dissolved in NH wherein
3Representative concentration be about 25～28% (W/W), make this solution of appropriate amount can be poured in the water as reaction medium of the present invention.Perhaps, gaseous ammonia directly bubbling go in the water-based reaction medium.
It should be noted, melamine and the mol ratio between the cyanuric acid total amount that can carry out the present invention reaction be preferably 0.98: 1～and 1.02: 1, more preferably 0.995: 1～1.005: 1.But, have been found that in the presence of excessive melamine and can particularly advantageously react, even react completely that the cyanuric acid residual volume that makes the residual volume of melamine in the aqueous medium be higher than to exist in this medium is 0.2% (molar percentage) at the most in order to make.Under these conditions, formed soup compound has low relatively viscosity.Therefore, in view of above aspect, though can water, ammonium hydroxide and two kinds of solid reactants be added in the reaction zone according to any desirable order, but it is preferred by in water, melamine powder and the solution of ammonium hydroxide adding reaction zone with appropriate amount, carry out this process to wherein adding cyanuric acid gradually subsequently, guarantee thus under the excessive situation of melamine, to carry out this reaction.Adding cyanuric acid in reaction zone gradually can carry out continuously, perhaps more preferably carry out, make in about 30～120 minutes that every about 5～30 minutes roughly the described cyanuric acid of equivalent adds in the reaction mixture in proper order with intermittent mode (in a portion-wise manner).
Find,, in reaction mixture, exist a spot of ammonium hydroxide to make reaction even also can effectively carry out being lower than under 75 ℃ the temperature as what the preferred embodiment of the invention provided.Therefore, according to the preferred embodiments of the invention, reaction is at 20～75 ℃, more preferably carries out under 35～55 ℃ temperature.It should be noted that this reaction can be carried out in two or more different sub-range scopes of said temperature scope.Therefore, the particularly preferred embodiment according to the present invention add cyanuric acid in the reaction mixture that contains water, ammonium hydroxide and melamine before, is heated to this reaction mixture 38～42 ℃ first temperature earlier.In the process that adds cyanuric acid gradually, the temperature maintenance of system is in the scope of above-mentioned sub-range.Add cyanuric acid in this reaction mixture after, the reaction soup compound can be further heated second temperature to 48～52 ℃ of sub-range scopes, guarantees that therefore reaction finishes sooner.Under said temperature control situation, reaction lasts 1～4 hour.
The existence of ammonium hydroxide has significantly reduced the viscosity of this reaction soup compound in reaction zone, make be equipped with turbine stirrer (turbine agitator) even the standard reaction device in also can effectively react at high relatively solid reaction substrate concentration (for example about 20 weight %).Be about 170s in shearing rate
-1The time soup compound viscosity be preferably 50～350cP (for above-described solids concn), wherein temperature is not higher than 75 ℃.More preferably, the viscosity of product slurry is lower than 150cP under these conditions.
Although preferably in the presence of ammonium hydroxide, carry out the reaction of melamine and cyanuric acid, but according to replaceable embodiment of the present invention, described parent material is reacted under the situation that does not have ammonium hydroxide,, described reagent is added in the product slurry will finish the time or reaction when finishing basically in reaction then.Find that when adding ammonium hydroxide, the mobile of product slurry significantly increases, and makes that product is easy to remove from reaction vessel.
The product slurry can be taken a sample when reaction is finished, and makes the melamine of residual volume or cyanuric acid to neutralize by opposite reactant, thereby guarantees that the melamine cyanurate product satisfies necessary purity requirement.
After reaction is finished, the melamine cyanurate soup compound of gained is removed from reaction vessel and spraying drying.Spraying drying can use the NIRO spray-dryer suitably to carry out, and uses standard technique to collect product from moisture eliminator then.Common spraying drying parameter illustrates in following examples.Generally speaking, inlet temperature is 200～600 ℃, is preferably 300～450 ℃.Temperature out is 100～160 ℃, more preferably 130～150 ℃.
In whole specification sheets, term " powder melamine cyanurate " etc. is meant size less than 100 μ m, is preferably the granular melamine cyanurate of 1～50 μ m, and described saccharoid preferably is the granulometric composition of 0.5～6 μ m by median size.The bulk density of powder melamine cyanurate (bulk density) is generally 0.15～0.35g/ml.
The desciccate of collecting behind said process is an example of powder melamine cyanurate.This product normally is close to the spheric coacervate, and its diameter is 5～30 μ m, and bulk density is 0.20～0.35g/ml, measure as laser diffraction, described coacervate is to be 0.5～4 μ m by mean sizes, and 1～3 μ m more preferably is most preferably the granulometric composition of 2 μ m.It should be noted that described particle is to combine under without any the auxiliary binder situation and form the coacervate of above definition.
Find surprisingly now, promoted the formation of key between particle exerting pressure on the powder melamine cyanurate, thereby the formation saccharoid, the saccharoid of Xing Chenging is characterised in that good dispersiveness thus, as (following it is described in more detail) measured by laser diffraction analysis.Therefore, provide a kind of method on the other hand, comprised, thereby formed the granular melamine cyanurate the non-slurry pelletizing of powder melamine cyanurate.Used term " non-slurry pelletizing " is meant that applying pressure wherein forms the compacting process of saccharoid in the literary composition.
The drying-granulating of powder melamine cyanurate can use various conventional debulking methods to carry out, and includes but not limited to roll.Roll be make powder pass through two rotating rollers (rotating roller) thus between make the closely knit drying-granulating method of powder.Powder is about 1～10 ton/cm in the application of force usually, is more preferably under 3～7 tons/cm to roll.The linear velocity of milling roller is generally 3～50cm/s, is more preferably 7cm/s.
Subsequent grinding also sieves the material that rolled of gained, thereby isolates the saccharoid fraction with suitable size.For the ultimate production (total crop) that improves required fraction, size can be dropped on selected level saccharoid and fresh powder melamine cyanurate exceptionally and merge, and turn back in the rolling device.
Therefore, the particularly preferred embodiment according to the present invention, the powder melamine cyanurate that obtains after the spraying drying step is carried out non-slurry pelletizing by rolling, and grinds then and optional the screening.
Except rolling, can use other compacting equipments, for example hydropress (hydraulic press) is finished non-slurry pelletizing process of the present invention.In order to form closely knit compression, the pressure that is applied on the powdered material can be at 40～400kg/cm
2, preferably at 70～300kg/cm
2Change in the scope.Sheet of gained compacting (tablet) or ball shape (pellet) material are ground and are sieved subsequently, thereby reclaim required saccharoid fraction.
It should be noted, the parent material that is used for the drying-granulating process can be the mixture of powder melamine cyanurate or itself and one or more solid additive, especially flame-retardant additive, wherein the weight concentration of melamine cyanurate in described solid mixture preferably is not less than 60% (w/w), more preferably is not less than 90%.In whole the specification sheets, term " melamine cyanurate saccharoid ", " granular melamine cyanurate " etc. are meant melamine cyanurate or the mixture that contains it are carried out the melamine cyanurate product that obtains after the non-slurry pelletizing (use rolls or hydropress).
On the other hand, the invention provides the melamine cyanurate of non-slurry pelletizing, the melamine cyanurate saccharoid that rolls that does not contain tackiness agent more preferably is provided, preferably it is of a size of 0.1～10mm, more preferably 0.2～2mm.The present invention also provides the melamine cyanurate saccharoid that does not contain tackiness agent, measures as laser diffraction, and this saccharoid is to be 0.3～12 μ m by mean diameter, is preferably 0.5～4 μ m, 1～3 μ m more preferably, and the particle that is most preferably 2 μ m is formed.The size distribution parameter is d
50＜5 μ m and d
98＜100 μ m, more preferably d
50＜3 μ m and d
98＜25 μ m, wherein d
50Be median size (median size), d
98It is the particle diameter that has only 2% overall particle (volume ratio) to surpass.The bulk density that the present invention does not contain the saccharoid of tackiness agent preferably is not less than 0.60g/ml, more preferably is not less than 0.63g/ml.
In view of above aspect, be understandable that Powdered or granular melamine cyanurate provided by the present invention can be broken into the essentially identical particle of mean sizes, measures as laser diffraction, mean sizes most preferably is 1～3 μ m, and is most preferably 2 μ m.
Can use Powdered or granular melamine cyanurate provided by the present invention suitably, especially be used for various polymkeric substance as fire retardant, it comprises polymeric amide, polyester and polypropylene, special preferred polyamide 6 and polyamide 6,6.Find that surprisingly the polymkeric substance that is compounded with granular melamine cyanurate of the present invention satisfies required mechanical property, and satisfied the requirement of UL-94 incendivity test.Think melamine cyanurate saccharoid according to the present invention and polymkeric substance can be broken into enough little particle between recombination epoch, thereby described particle is evenly distributed in whole polymkeric substance basically.Therefore, the present invention provides a kind of method on the other hand, comprises Powdered or granular melamine cyanurate of the present invention is added in the polymkeric substance.It is well-known (for example, US 4,314,927, EP 418210 and US 4,298,518) that melamine cyanurate is introduced method in the nylon.The flame retardant compositions of gained and can constitute other aspects of the present invention by the profiled member (moldedpart) of its acquisition.
In the accompanying drawings:
Fig. 1 a-1b is the scanning electronic microscope photograph of melamine cyanurate powder of the present invention.
Embodiment
Viscosity measurement
The viscosity of soup compound is to measure under 40 ℃ temperature by FANN viscometer (from Baroid).This device is made of two centered cylinder, rotor and stators.The speed of rotor is equivalent to 170～1000sec in 100～600rpm scope
-1Shearing rate.
Granule sieving (particle sizing) and dispersed test
Spray-dired melamine cyanurate powder and partical
Granule sievingBe to use laser diffraction system [Malvern (UK) Model Mastersizer 2000] to carry out according to the step of Mastersizer 2000 operational guidances.Dispersion medium is a Virahol.Pre-treatment is at the ultra sonic bath of 1 liter of volume [Cole Parmer (USA) Model 8890; 2L volume, output rating are 70 watts when 42KHz] in carry out.Working method is as follows:
In the 10ml Virahol in the 1g product adding bottle.Mixture was placed ultra sonic bath 1 minute.Then blend sample is added and be equipped with in the measuring cell (measurement cell) of Virahol.Add sample amount need obtain 10～20% light obscuration (obscuration).Inner ultrasonicly used 5 minutes in 60% maximum strength (maximum strength during nominal frequency at 40KHz is 27W) time.Detect data according to following model parameter:
Product specific refractory power (product refractive index): 1.52; Specific absorption (absorption) 0.1; The specific refractory power of Virahol: 1.39.Analytical model: general objects; Particle shape: irregular (default).
Mean particle size is defined as the mean value D[4 of volume weighted, 3].d
50Be volume median diameter, d
50Be top value of cutting (top cut), be defined as the particle diameter that only surpasses the overall 2 volume % of particle.
Residual water
Water residual in the product is measured by Karl Fisher volumetry.
Melamine and cyanuric acid remaining excessive
The 3g desciccate was mixed 1 hour with 22ml distilled water.Filtered sample then.Use post REGIS NH by the HPLC method
2Analyze the remaining excessive of the melamine of filtrate or cyanuric acid, wherein eluent is acetonitrile and cushions phosphoric acid salt.
End of processing
It is by the analysis meter (heating rate: 10 ℃/minute) that uses TA Instrument Model 2950 desciccate to be carried out thermogravimetric analysis (thermal gravimetric analysis) to measure that reaction finishes.Weight loss when reaction finishes to be characterised in that 290 ℃ is lower than 1%.
Incendivity test (UL-94V):
Incendivity testing vertical flammability (flammabilityvertical buring test) according to Underwriters Laboratories Inc..
Limit oxygen index (LOI):
According to ASTM D 2863-77, use Stanton Redcroft FTA Flammability Unit.
Notched izod is impacted (Notched Izod Impact):
According to ASTM D256, use Zwick 5102 pendulum impact test instruments (pendulum impacttester).
The tensile property of plastics (tensile property):
According to ASTM D638, Type I Dumbell, test speed are 5mm/ minute, use the Zwick1435 material testing machine.
Embodiment 1
In 3 liters of jacketed reactors (jacketed reactor) water (2530g) is housed; Contain 25%NH
3Solution of ammonium hydroxide (10.5g solution) and melamine (327.2g, 2.59 moles).This reactor content of mechanical stirring.Reactor mixture is heated to 40 ℃, and in reactor disposable adding cyanuric acid 97.5% (343.4g, 2.59 moles).Temperature of reaction remains on 40～45 ℃ and reaches 1 hour.The product slurry is at 1000s
-1And 170s
-1Shearing rate the time viscosity be respectively 13cP and 60cP.Product is dry in the Minor Unit of disk NIRO (Denmark).Temperature in: 400 ℃, temperature out: 120 ℃.Residual water in the product is 0.25% (w/w).
The quality of final product (reaction finish) is to be 0.6% to confirm by using thermogravimetric analysis 290 ℃ weight loss.Measure as laser diffraction, this product is the granulometric composition of 2.5 μ m by mean sizes, and the size distribution of this product is as follows: d
50=2.1 μ m, d
98=17 μ m.
Embodiment 2
Repeat the step of embodiment 1 about 70-75 ℃ temperature.Soup compound is at 1000s
-1And 170s
-1Shearing rate the time viscosity be respectively 80cP and 320cP.
Embodiment 3
181.6kg distilled water, 16.2kg melamine and 730g solution of ammonium hydroxide (25%NH are housed in 220 liters of reactors
3).Stir this mixture, and be heated to 40 ℃.Added four batches of 4.25kg cyanuric acids in 15 minutes at interval, reaction mixture remains on 40 ℃ during this period.Temperature is elevated to 50 ℃ then, and reaction mixture was kept 1 hour in this temperature.The product slurry is at 1000s
-1And 170s
-1Shearing rate the time viscosity be respectively 25cP and 100cP.With this soup compound pack into (NIRO, Denmark) in the spray-dryer.The spraying drying parameter is listed below:
Temperature in: 400 ℃
Temperature out: 130-150 ℃
Atomizer speed (atomizer speed): 24,000rpm
Soup compound feeding rate (feed rate): 20 liters/hour
Air velocity: 400kg/ hour
Residual water in the product is 0.15%.The quality of final product (reaction finish) is to be 0.5% to detect by using thermogravimetric analysis 290 ℃ weight loss.
Collected dried powder is made up of the intimate globular coacervate that is of a size of 10～30 μ m.Measure as laser diffraction, the particulate mean diameter of forming described coacervate is 1.5 μ m, and size-grade distribution is as follows: d
50=1.3 μ m, d
98=6 μ m.The bulk density of Powdered melamine cyanurate is 0.30g/ml.Fig. 1 a is the scanning electronic microscope photograph by the melamine cyanurate coacervate of the present invention's acquisition.Fig. 1 b is the scanning electronic microscope photograph of described coacervate, and it shows the particle of forming described coacervate.
Embodiment 4
Water (2671g) is housed in 3 liters of jacketed reactors; Ethylamine solution 70% (10.5g solution) and melamine (233.3g, 1.85 moles).This reactor content of mechanical stirring, and be heated to 40 ℃.Add 61.25g cyanuric acid 97.5% (245g, 1.85 moles) in four batches in this reactor, add every batch be spaced apart 15 minutes, reaction mixture remains on 40 ℃ during this period.Temperature is elevated to 50 ℃ then, and makes reaction mixture remain on this temperature to reach 1 hour.The product slurry is at 1000s
-1And 170s
-1Viscosity during shearing rate is respectively 4cP and 6cP.Product is dry in the Minor Unit of disk NIRO (Denmark).Residual water in the product is 0.25% (w/w).
The quality of final product (reaction finish) is to be 0.8% to detect by using thermogravimetric analysis 290 ℃ weight loss.Measure as laser diffraction, this product is the granulometric composition of 1.5 μ m by mean sizes, and this size-grade distribution is as follows: d
50=1.2 μ m, d
98=8 μ m.
Embodiment 5 (contrast)
Omit NH
4OH solution repeats the process of embodiment 1, and temperature remains on 50 ℃ and reaches 4 hours.According to after the drying to the X-ray diffraction analysis of final product, this reaction is not finished.
Embodiment 6 (contrast)
Omit NH
4OH solution, the process of repetition embodiment 2.Afterreaction was finished in 1 hour.The product slurry that is obtained is very sticking, to such an extent as to can not it be discharged by the bottom opening of this reaction vessel.
Embodiment 7
Repeat the process of embodiment 6, in the product slurry, add 52.5g NH then
4OH solution (25%NH
3) mixed 30 minutes at 75 ℃ then.The flowability of soup compound improves, and makes it be easy to discharge from the bottom opening of this reaction vessel.
Embodiment 8
Use rolls carries out non-slurry pelletizing to Powdered melamine cyanurate
Use double roll press (Hutt, Germany) to roll the 1000g powdered product of embodiment 3.The diameter of roller is 22cm, and its length is 6cm.Roll squeezer produces pillow formed body (pillow shaped body).Applied force is 6 tons/cm, and rotating speed is 6rpm.Material circulates twice in rolling machine, purpose is the intensity (strength) that rolls thing in order to increase.Material to compacting grinds then, and sieves by 1mm and 0.5mm sieve.Isolate the particle fraction (550g) that is of a size of 0.5～1mm.(+1mm, 50g) (0.5mm 350g) is considered as retained material with thin fraction with thick fraction.
Above-mentioned retained material (about 400g) and the fresh powder mixes of 600g, and repeat above-mentioned several times rolling/grind/sieve step, to obtain partical.The bulk density of this granular melamine cyanurate is 0.65g/ml.Measure as laser diffraction, this saccharoid is the granulometric composition of 2 μ m by mean sizes, and size-grade distribution is as follows: d
50=1.4 μ m, d
98=8.0 μ m.
Embodiment 9
Use rolls carries out non-slurry pelletizing to Powdered melamine cyanurate
Use the commercially available melamine cyanurate parent material of buying (the Melapur MC25 of CIBA, Switzerland) to repeat the granulation process of embodiment 8, measure as laser diffraction, the mean particle size of described parent material is 5.3 microns, and has following size-grade distribution: d
50=3.6 μ m, d
98=18 μ m.
The bulk density of thus obtained partical is 0.73g/ml.Measure as laser diffraction, this saccharoid is 10 microns a granulometric composition by mean sizes, and size-grade distribution is as follows: d
50=4.1 μ m, d
98=80 μ m.
Embodiment 10
Use hydropress that Powdered melamine cyanurate is carried out non-slurry pelletizing
Use the Powdered melamine cyanurate of hydropress compacting embodiment 3.At diameter is the flap of preparation 15gr in wolfram varbide (tungsten carbide) cylinder mold of 2.5cm.Applied pressure is 40～350kg/cm
2Measure the density of stampings by measurement volumes and weight.By standard compression experimental measurement crushing strength (crushing strength).Then this flap is ground, and sieve by 1mm and 0.5mm sieve.The particulate granularity that is obtained by the laser-diffractometer analysis.The result is illustrated in the following table 1.
Table 1
| Grinding pressure (kg/cm 2) | Density (g/cm 3) | Crushing strength (kg/cm 2) | Mean particle size (μ m) | ??d 50??(μm) | ??d 98??(μm) |
| ??40 | ??0.91 | ??0.9 | ??2.1 | ??1.8 | ??6.6 |
| ??100 | ??1.08 | ??2.5 | ??1.9 | ??1.4 | ??8.7 |
| ??200 | ??1.17 | ??3.1 | ??1.7 | ??1.3 | ??5.0 |
| ??350 | ??1.27 | ??4.2 | ??1.9 | ??1.4 | ??11.4 |
Embodiment 11 (contrast)
Powdered melamine cyanurate is carried out wet granulation
The 153gr melamine cyanurate powder that obtains among the embodiment 3 is mixed with 47g water, and to press opening be the sieve of 1.6mm.The product that is obtained is that the sieve of 0.5mm sieves by opening.The weight of thick fraction is 135gr, and thin level is divided into 60g.Product dried overnight in 110 ℃ stove of thick fraction reclaims the 105g partical.Measure as laser diffraction, this particle is the granulometric composition of 19.5 μ m by mean sizes, and size-grade distribution is as follows: d
50=2.3 μ m, d
98=160 μ m.
Embodiment 12 (contrast)
Powdered melamine cyanurate is carried out wet granulation
Following process is according to the work embodiment of JP 07-149739.With mean particle size 40 microns cyanuric acid 99% (310g; 2.38 mole) and mean particle size be 57 microns melamine (300g; 2.38 mole) put into the Henshel mixing machine.Stir this mixture, and heat the chuck of this mixing machine with 100 ℃ heating medium.Use peristaltic pump (peristaltic pump) then, during 30 minutes, slowly add 100g water.Restir half an hour under these conditions.Heating medium is heated to 120 ℃ then, and under this temperature, continues to stir 1 hour.
Obtain the granular melamine cyanurate.The mean sizes of this saccharoid is about 250 microns, and its moisture content is 0.2%.Detect reaction by X-ray diffraction and finish, the use thermogravimetric analysis is about 0.9% 290 ℃ weight loss.
Measure as laser diffraction, the particulate mean sizes of forming this saccharoid is about 55 μ m, and size-grade distribution is as follows: d
50=28 μ m, d
98=455 μ m.The submicron particle of measuring as scanning electronic microscope is of a size of 0.2～1 micron.
Embodiment 13
In open vent (open vent) temperature 260～270 ℃ moving twin screw extruder (co-rotating twin screw the extruder) (D=25mm of Berstorff ZE25 corotation, L/D=32) in, 88 parts of nylon 6,6 (Zytel EFE 1032 NC 10 ex.Du Pont) are compound with 12 parts of Powdered melamine cyanurate (product of embodiment 3).Use the gravity supply ex.K-tron of system.(strand) makes pellet with the compound thigh.The pellet that is produced is dried overnight in 80 ℃ vacuum oven (vacuum oven).
The pellet that is obtained is used for mould test sample (mold test specimen), and its thickness is 0.8 and 1.6mm, is used for the test of UL-94 incendivity, and thickness is other character that the test sample of 3.2mm is used to measure the melamine cyanurate that contains polymeric amide.The result is illustrated in the table 2.
Embodiment 14
Repeat the step of embodiment 13 with the granular melamine cyanurate that rolls that obtains among the embodiment 8.The result is illustrated in the table 2.
Table 2
Claims (16)
1. the melamine cyanurate that obtains of the non-slurry pelletizing by the powder melamine cyanurate.
2. according to the melamine cyanurate of claim 1, it obtains by rolling the powder melamine cyanurate.
3. melamine cyanurate saccharoid, this saccharoid are to be the granulometric composition of 0.3～12 μ m by the mean diameter of measuring as laser diffraction, and wherein said particle size distribution parameter is d
50＜5 μ m and d
98＜100 μ m.
4. according to the melamine cyanurate saccharoid of claim 3, the bulk density of wherein said saccharoid is not less than 0.60g/ml.
5. according to the melamine cyanurate saccharoid of claim 3 or 4, wherein this saccharoid is of a size of 0.1～10mm, and wherein said saccharoid is to be the granulometric composition of 0.5～4 μ m by the mean diameter of measuring as laser diffraction.
6. according to the melamine cyanurate saccharoid of claim 5, the particulate mean diameter of wherein forming this saccharoid is 1～3 μ m.
7. according to the melamine cyanurate of claim 1, it is according to each particulate form among the claim 3-6.
8. according to the melamine cyanurate of claim 2, it is according to each particulate form among the claim 3-6.
9. method for preparing melamine cyanurate, this method comprise the non-slurry pelletizing of powder melamine cyanurate, thereby obtain the granular melamine cyanurate.
10. according to the method for claim 9, wherein said non-slurry pelletizing comprises the melamine cyanurate that rolls with the formation compacting.
11. according to the method for claim 9, wherein said non-slurry pelletizing is included in the pressing machine the melamine cyanurate of powder melamine cyanurate squeezing with the formation compacting.
12. according to the method for claim 10 or 11, this method also comprises grinds the melamine cyanurate of compacting and randomly screening, is the saccharoid of 0.1～10mm to obtain diameter.
13. according to the method for claim 12, wherein the diameter of saccharoid is 0.2～2mm, described saccharoid is to be the granulometric composition of 0.3～12 μ m by mean sizes, measures as laser diffraction, and the bulk density of wherein said saccharoid is not less than 0.60g/ml.
14. according to each method among the claim 9-12, wherein provide the powder melamine cyanurate with mixture, described mixture contains one or more solid fireproof additives.
15. a method, it comprises that the granulous melamine cyanurate that will limit in each among the claim 1-8 is added into polymkeric substance.
16. according to the method for claim 15, wherein said polymkeric substance is a polymeric amide.
Applications Claiming Priority (2)
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| IL16727805 | 2005-03-07 | ||
| IL167278 | 2005-03-07 |
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| CN200680000045.2A Division CN1942452B (en) | 2005-03-07 | 2006-03-05 | A process for the preparation of melamine cyanurate |
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| CN 201010001502 Expired - Fee Related CN101774974B (en) | 2005-03-07 | 2006-03-05 | Process for preparation of melamine cyanurate |
| CN200680000045.2A Expired - Fee Related CN1942452B (en) | 2005-03-07 | 2006-03-05 | A process for the preparation of melamine cyanurate |
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| Country | Link |
|---|---|
| EP (1) | EP1856064A4 (en) |
| CN (2) | CN101774974B (en) |
| WO (1) | WO2006095337A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103732582A (en) * | 2011-07-07 | 2014-04-16 | 列夫·达维多维奇·拉斯涅特索夫 | Method for preparing melamine cyanurate |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7855244B2 (en) | 2007-08-06 | 2010-12-21 | E.I. Du Pont De Nemours And Company | Flame retardant polytrimethylene terephthalate composition |
| CN101863544B (en) * | 2010-06-29 | 2011-09-28 | 湖南科技大学 | Cyanuric acid-based heavy metal chelating flocculant and preparation method thereof |
| CA2821799C (en) | 2010-12-16 | 2020-01-14 | Merck Patent Gmbh | Dry granulated cell culture media |
| CN102898389A (en) * | 2012-10-16 | 2013-01-30 | 郑州大学 | Method for recycling melamine waste residue |
| CN103992287A (en) * | 2013-10-18 | 2014-08-20 | 上海美莱珀化工材料科技有限公司 | Preparation method of melamine cyanurate |
| CN110317181B (en) * | 2019-06-13 | 2022-04-08 | 山东泰星新材料股份有限公司 | Preparation method and application of melamine cyanurate nanosheet microspheres |
| RU2758252C1 (en) * | 2021-03-15 | 2021-10-27 | Федеральное государственное автономное образовательное учреждение высшего образования «Национальный исследовательский Томский государственный университет» | Method for obtaining melamine cyanurate |
| CN114751869B (en) * | 2022-04-21 | 2024-02-13 | 山东泰星新材料股份有限公司 | Preparation method of high-dispersion melamine cyanurate flame retardant |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298518A (en) | 1976-09-06 | 1981-11-03 | Mitsubishi Chemical Industries, Ltd. | Polyamide resin composition |
| JPS6033850B2 (en) * | 1977-01-17 | 1985-08-05 | 日産化学工業株式会社 | Flame retardant resin composition |
| JPS5826396B2 (en) * | 1978-08-24 | 1983-06-02 | 油化メラミン株式会社 | lubricant |
| EP0019768B1 (en) | 1979-06-02 | 1983-05-11 | BASF Aktiengesellschaft | Flameproof polyamide moulding compositions containing a filler |
| EP0418210A1 (en) | 1989-09-15 | 1991-03-20 | Monsanto Company | Flame retardant nylon moulding resins with improved physical properties |
| US5493023A (en) * | 1992-12-09 | 1996-02-20 | Mitsui Toatsu Chemicals, Inc. | Granular melamine cyanurate and preparation process thereof |
| JP2751815B2 (en) * | 1994-02-08 | 1998-05-18 | 日産化学工業株式会社 | Surface-treated melamine cyanurate powder and method for producing the same |
| AT400031B (en) * | 1994-02-08 | 1995-09-25 | Chemie Linz Gmbh | METHOD FOR PRODUCING MELAMINE CYANURATE |
| AU1894799A (en) * | 1998-09-08 | 2000-03-27 | Isle Firestop Ltd. | Combustion retardant for polymeric materials |
| TWI284126B (en) * | 2001-10-25 | 2007-07-21 | Ciba Sc Holding Ag | Free flowing melamine cyanurate agglomerate, method for producing same and use in flame retardant polymer compositions and polymer compositions containing melamine cyanurate |
| CN1253443C (en) * | 2002-12-12 | 2006-04-26 | 川化股份有限公司 | Prepn of high-purity melamine cyanuric acid |
| WO2006040289A1 (en) * | 2004-10-15 | 2006-04-20 | Ciba Specialty Chemicals Holding Inc. | Melamine cyanurate in crystalline form |
-
2006
- 2006-03-05 EP EP06711280A patent/EP1856064A4/en not_active Withdrawn
- 2006-03-05 WO PCT/IL2006/000298 patent/WO2006095337A2/en not_active Application Discontinuation
- 2006-03-05 CN CN 201010001502 patent/CN101774974B/en not_active Expired - Fee Related
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103732582A (en) * | 2011-07-07 | 2014-04-16 | 列夫·达维多维奇·拉斯涅特索夫 | Method for preparing melamine cyanurate |
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| Publication number | Publication date |
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| WO2006095337A2 (en) | 2006-09-14 |
| CN101774974B (en) | 2013-08-14 |
| CN1942452A (en) | 2007-04-04 |
| CN1942452B (en) | 2013-04-17 |
| WO2006095337A3 (en) | 2006-11-30 |
| EP1856064A4 (en) | 2010-08-04 |
| EP1856064A2 (en) | 2007-11-21 |
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