CN112778228B - Preparation method of melamine cyanurate with large particle size and good crystal form - Google Patents
Preparation method of melamine cyanurate with large particle size and good crystal form Download PDFInfo
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- CN112778228B CN112778228B CN202110146609.XA CN202110146609A CN112778228B CN 112778228 B CN112778228 B CN 112778228B CN 202110146609 A CN202110146609 A CN 202110146609A CN 112778228 B CN112778228 B CN 112778228B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D251/30—Only oxygen atoms
- C07D251/32—Cyanuric acid; Isocyanuric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention provides a preparation method of crystalline melamine cyanurate with larger particle size and better crystal shape, which comprises the steps of sequentially adding a certain amount of solvent, catalyst, melamine and cyanuric acid into a reaction kettle according to a proportion, reacting at a certain pressure and a certain temperature, and cooling and filtering after the reaction is finished; the catalyst is one or two of hydrobromic acid and hydrochloric acid, the melamine cyanurate obtained by the preparation method has a large particle size, and meanwhile, the melamine cyanurate has a good crystal form and a small specific surface area, and is used as a flame retardant, so that the flame retardant is good in flame retardance and also has excellent fluidity and dispersibility.
Description
Technical Field
The invention belongs to the technical field of preparation of halogen-free flame retardant materials, and particularly relates to a preparation method of melamine cyanurate with large particle size and good crystal form.
Background
Melamine cyanurate, abbreviated as MCA, is a typical nitrogen-based flame retardant, has high nitrogen content, MCA has various advantages of extremely low application cost, excellent electrical properties, mechanical properties, colorability and the like, and meanwhile, MCA has the advantage of easy processing due to excellent balance between good thermal stability and efficient flame retardance when being used as a mixed additive to manufacture a flame-retardant master batch. Can be used in various thermoplastics, including Polyamide (PA), glass fiber reinforced polyamide, PBT, glass fiber reinforced PBT, PP, PS/HIPS, TPU, PET/PBT, textile and the like, and heat-solid resins, including epoxy resin, PU foam and unsaturated polyester. The flame retardant is used together with halogen series, antimony series and phosphorus series flame retardants, particularly is used together with APP as an intumescent flame retardant, and has good synergistic effect.
In view of the advantages of MCA, the MCA can be widely applied in processing, and can be used as a halogen-free flame retardant in polyamide, polyester, polyformaldehyde, polyurethane, synthetic rubber and plastic products, a solid lubricating additive added in lubricating oil, grease and paste, a flame retardant and delustering auxiliary agent added in fireproof paint, and a lubricant added in cosmetics. The flame retardant is applied to the flame retardance of polymers such as epoxy resin and the like, is particularly suitable for two pure nylons, namely nylon 6 and nylon 66, and can easily achieve the flame retardant effect of UL 94V-0 level; the MCA flame-retardant nylon has the comprehensive performance better than Decabromodiphenylethane (DBP), and especially the electrical performance CTI of MCA is greatly better than that of DBP. However, MCA is directly sublimed and decomposed by heat without melting, and MCA is dispersed in a resin matrix in a rigid particle state during melt blending with a polymer, and the dispersion state of MCA has great dependence on the initial particle size of the flame retardant particles.
The patent document CN102585290A of Jinan Taxing fine chemical industry Co., ltd discloses a preparation method of melamine cyanurate with large particle size and wide distribution, MCA products prepared by the method have large particle size (15-100 microns), although the particle size is large, the wide crystal form of the MCA products is not good, the dispersion in a base material is poor, and the flame retardant property is influenced.
The patent document CN104311500B of Jinan Thai Limited company discloses a method for preparing melamine cyanurate by a sol modification method, wherein the nano MCA (300 nm-500 nm) prepared by the method has improved flame retardance and mechanical properties, but has small crystal form and large specific surface area, thereby influencing the processing flowability and dispersibility.
Disclosure of Invention
In order to solve the problems in the prior art and further optimize the prior process, the invention provides a preparation method of melamine cyanurate with large particle size and good crystal form, so as to achieve the purpose of improving the flame retardance, the fluidity and the dispersibility of melamine cyanurate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of melamine cyanurate with large particle size and good crystal form is characterized in that the preparation method comprises the steps of sequentially adding a certain amount of solvent, catalyst, melamine and cyanuric acid into a reaction kettle according to a proportion, reacting at a certain pressure and a certain temperature, cooling and filtering after the reaction is finished;
the catalyst is one or two of hydrobromic acid and hydrochloric acid;
the adding amount of the catalyst is 0.1-10% of the total mass of the melamine and the cyanuric acid;
preferably, the adding amount of the catalyst is 5-10% of the total mass of the melamine and the cyanuric acid;
the molar ratio of the melamine to the cyanuric acid is 1-1.05:1;
preferably, the molar ratio of melamine to cyanuric acid is 1:1;
the concentration of the hydrobromic acid is more than or equal to 48wt%; the concentration of the hydrochloric acid is more than or equal to 31wt%;
preferably, the hydrobromic acid concentration is 48wt%; the concentration of the hydrochloric acid is 31wt%;
the reaction pressure is 3-5 atmospheric pressures, and the reaction temperature is 120-150 ℃;
the solvent is water, and the addition amount of the solvent is 4-10 times of the total mass of the melamine and the cyanuric acid;
the reaction time is 1-10h;
the D50 of the melamine cyanurate is 5.0-20.1 μm.
By adopting the technical scheme, the invention has the beneficial effects that:
1. by adopting the preparation method, the D50 of the prepared melamine cyanurate can reach 5.0-20.1 μm and has larger grain diameter; meanwhile, the melamine cyanurate has good crystal form and small specific surface area;
2. the melamine cyanurate prepared by the preparation method has good flame retardance, MCA/nylon 6 flame retardant material prepared by adding MCA prepared by the invention into nylon 6 has flame retardance grade of 3.2mm reaching V0-V1 grade;
3. the melamine cyanurate prepared by the preparation method has excellent fluidity and dispersibility, the melt flow rate is obviously improved, the mechanical property of the product is excellent, and the flame retardant effect is better.
The attached drawings of the specification:
figure 1 a 3000-fold enlarged crystal form pattern of the conventional MCA prepared in comparative example 1;
FIG. 2A 500-fold magnification of the crystal form of MCA obtained in example 6 according to the invention;
FIG. 3 particle size distribution of MCA obtained in example 6 of the present invention
The specific implementation mode is as follows:
the invention is further illustrated below with reference to specific examples.
Example 1:
adding 1230g of water and 15g of hydrochloric acid with the content of 31 percent into a reaction kettle, then adding 126.15g of melamine and 129.07g of cyanuric acid, uniformly stirring, pressurizing to 3 atmospheric pressures, heating to 120 ℃, reacting for 2h, cooling to 70 ℃ after the reaction is finished, decompressing, filtering, and drying to obtain an MCA product, wherein the detected D50=5 microns, the crystal is oval, and the specific surface area is 1246.92m 2 /m 3 。
Example 2:
adding 1230g of water and 20g of hydrochloric acid with the content of 31 percent into a reaction kettle, then adding 126.15g of melamine and 129.07g of cyanuric acid, uniformly stirring, pressurizing to 3 atmospheric pressures, heating to 120 ℃, reacting for 4h, cooling to 70 ℃ after the reaction is finished, decompressing, filtering, and drying to obtain an MCA product, wherein the detected MCA product has the advantages of D50=8 microns, elliptic crystals and 1035.82m specific surface area 2 /m 3 。
Example 3:
adding 1230g of water and 25g of hydrochloric acid with the content of 31 percent into a reaction kettle, then adding 126.15g of melamine and 129.07g of cyanuric acid, uniformly stirring, pressurizing to 5 atmospheric pressures, heating to 150 ℃, reacting for 10h, cooling to 70 ℃ after the reaction is finished, decompressing, filtering, and drying to obtain an MCA product, wherein the detected D50=20 microns, the crystal is oval, and the specific surface area is 622.13m 2 /m 3 。
Example 4:
adding 1230g of water and 15g of hydrobromic acid with the content of 48% into a reaction kettle, then adding 126.15g of melamine and 129.07g of cyanuric acid, uniformly stirring, pressurizing to 3 atmospheres, heating to 120 ℃, reacting for 2h, cooling to 70 ℃ after the reaction is finished, decompressing, filtering, and drying to obtain an MCA product, wherein the detected D50=5.5 microns, the crystal is oval, and the specific surface area is 1225.20m 2 /m 3 。
Example 5:
1230g of water and 20g of hydrobromic acid with the content of 48 percent are added into a reaction kettle, 126.15g of melamine and 129.07g of cyanuric acid are added into the reaction kettle, and the mixture is stirredStirring, pressurizing to 3 atmospheric pressure, heating to 120 deg.C, reacting for 4h, cooling to 70 deg.C, relieving pressure, vacuum filtering, and drying to obtain MCA product with D50=8.3 μm, elliptic crystal, and specific surface area of 1023.04m 2 /m 3 。
Example 6:
1230g of water and 25g of hydrobromic acid with the content of 48% are added into a reaction kettle, 126.15g of melamine and 129.07g of cyanuric acid are added, the materials are uniformly stirred, the pressure is increased to 5 atmospheres, the temperature is increased to 150 ℃, the reaction is carried out for 10 hours, the temperature is reduced to 70 ℃ after the reaction is finished, the pressure is relieved, the MCA product is obtained after suction filtration and drying, the detection D50=21.3 micrometers, the crystal is oval, and the specific surface area is 594.67m 2 /m 3 。
Example 7:
adding 1230g of water, 12g of hydrobromic acid with the content of 48% and 12g of hydrochloric acid with the content of 31% into a reaction kettle, then adding 126.15g of melamine and 129.07g of cyanuric acid, uniformly stirring, pressurizing to 5 atmospheric pressure, raising the temperature to 150 ℃, reacting for 10h, cooling to 70 ℃ after the reaction is finished, decompressing, carrying out suction filtration and drying to obtain an MCA product, detecting that D50=20.1 microns, wherein the crystal is oval, and the specific surface area is 625.33m 2 /m 3 。
Comparative example 1:
adding 1230g of water into a reaction kettle, then adding 126.15g of melamine and 129.07g of cyanuric acid, stirring uniformly, heating to 90 ℃ to react for 2h, stopping the reaction, performing suction filtration and drying to obtain an MCA product, wherein the detected D50=1.6 microns, the crystals are columnar, and the specific surface area is 5964.56m 2 /m 3 。
The application tests were as follows:
1. an extrusion method is adopted, 10kg of MCA prepared by the invention is added into 100kg of nylon 6 to prepare MCA/nylon 6 flame-retardant material, and the relevant properties of the material are shown in a table 1:
2. after 16kg of MCA, 100kg of nylon 66 and 0.2kg of antioxidant are uniformly mixed, the mixture is transferred into a double-screw extruder and extruded and injected at 220 ℃ to prepare the product with the properties shown in the table 2:
experimental data show that the MCA product prepared by the method has excellent fluidity and dispersibility, the melt flow rate is remarkably improved, the flame retardant effect is better, the mechanical property of the product is excellent, and the MCA product has uniform particle size, small addition amount, small influence on the performance of a base material and excellent mechanical property.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A process for preparing melamine cyanurate with large particle size and good crystal form,
the preparation method comprises the following steps: adding 1230g of water and 25g of hydrobromic acid with the content of 48% into a reaction kettle, then adding 126.15g of melamine and 129.07g of cyanuric acid, uniformly stirring, pressurizing to 5 atmospheric pressure, heating to 150 ℃, reacting for 10 hours, cooling to 70 ℃ after the reaction is finished, decompressing, filtering, and drying to obtain the MCA product.
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| CN202110146609.XA CN112778228B (en) | 2021-02-03 | 2021-02-03 | Preparation method of melamine cyanurate with large particle size and good crystal form |
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| CN202110146609.XA CN112778228B (en) | 2021-02-03 | 2021-02-03 | Preparation method of melamine cyanurate with large particle size and good crystal form |
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| CN112778228B true CN112778228B (en) | 2022-11-25 |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2674852B1 (en) * | 1991-04-04 | 1993-07-02 | Atochem | PROCESS FOR THE SYNTHESIS OF MELAMINE CYANURATE. |
| CN101633843A (en) * | 2009-07-04 | 2010-01-27 | 山东兄弟科技股份有限公司 | Preparation method of bromine nitrogen series composite flame retardant |
| CN102585290B (en) * | 2012-03-14 | 2013-04-17 | 济南泰星精细化工有限公司 | Method for preparing melamine cyanurate with large particle size and wide distribution |
| CN106588799A (en) * | 2016-11-15 | 2017-04-26 | 广东聚航新材料研究院有限公司 | Acid-type efficient preparation method of melamine cyanurate |
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