CN104311500B - Sol-gel modified method prepares the method for melamine cyanurate - Google Patents
Sol-gel modified method prepares the method for melamine cyanurate Download PDFInfo
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- CN104311500B CN104311500B CN201410515675.XA CN201410515675A CN104311500B CN 104311500 B CN104311500 B CN 104311500B CN 201410515675 A CN201410515675 A CN 201410515675A CN 104311500 B CN104311500 B CN 104311500B
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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
- C07D251/56—Preparation of melamine
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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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Abstract
The invention discloses a kind of method that sol-gel modified method prepares melamine cyanurate, belong to halogen-free flame retardants preparation field.This preparation method comprises the steps: in aqueous solvent, with tripolycyanamide and cyanuric acid for raw material, by adding sol system in building-up process, to reach to control the purpose of particle diameter.In MCA course of reaction, add specific sol system, then heat to reaction a period of time under uniform temperature, obtain white slurry, obtain final products through sucking filtration, drying.Melamine cyanurate powder prepared by this method, uniform particle sizes is controlled, good dispersion, and cheaper starting materials, preparation technology are simply controlled, high financial profit.
Description
Technical field
The invention belongs to bittern-free flame-proof material preparation field, particularly relate to halogen-free flame retardants and modifiy and preparation field, the method that specifically sol-gel modified method prepares melamine cyanurate.
Background technology
Melamine cyanurate is called for short MCA, is a kind of high nitrogen-containing fire retardant developed by Japan at first the eighties in last century, is very suitable for nylon, polyamide-based fire-retardant.Its advantage with Halogen, low toxicity, environmental protection.
The industrial making method of MCA mainly has two kinds.One is cyanuric acid method, with tripolycyanamide (MA) and cyanuric acid (CA) for raw material, and stoichiometric number hour at 90 DEG C-98 DEG C, then through sucking filtration, dry, broken obtain finished product.Another kind is urea method, and using carbamide, tripolycyanamide is raw material, obtains cyanuric acid by urea pyrolysis, boiling through peracid, washes, dry obtains finished product.But, in the use procedure of MCA product, owing to MCA does not have molten condition, it is difficult in the substrate be uniformly dispersed, has had a strong impact on its fire resistance.It is thus desirable to its initial particle and crystal morphology are controlled by, to improve its fire resistance.
Jinan Taixing Fine Chemicals Co., ltd discloses " preparation method of a kind of big particle diameter width distribution melamine cyanurate " at patent documentation CN102585290A, the MCA product cut size that the method prepares relatively big (15-100 micron), dispersibility is poor in the substrate, and fire resistance is affected.
In academic dissertation " synthesis of modified melamine cyanurate and the research of Flameproof polyamide 6 thereof ", the MCA product that a kind of Firebrake ZB crystallite of author investigation is modified.The method, by generating the enclosed environment of " isolation of Firebrake ZB crystallite " at MCA in reacting, obtains super-refinement and homodisperse MCA product.But in the method, the joining day of Firebrake ZB presoma there is is strict demand, otherwise can have a strong impact on the productivity of MCA.Actual production is difficult to control to.
Academic dissertation " in the preparation of nylon 6/ modified MC A bittern-free flame-proof material, structure and performance study ", the MCA product that author investigation a kind of graphite oxide (alkene) is sol-gel modified.The method realizes the regulation and control to the original hydrogen bond structure of MCA by adding GO/OGO colloidal sol, obtains super-refinement and homodisperse MCA product.But in the method, GO/OGO is expensive, and economic profit is difficult to ensure that in the industrial production.
Summary of the invention
MCA microcrystalline growth in the building-up process of melamine cyanurate, is regulated and controled by the present invention by sol system.Utilizing the characteristic of colloidal sol itself, in the growth course of MCA crystallite, form the enclosed environment of relative insulation, thus regulating and controlling MCA product cut size and dispersibility, reaching to control the purpose of particle diameter.Product cut size prepared by the present invention is little, even particle size distribution, good dispersion, improve the compatibility of fire retardant and matrix material, not easily precipitate out, stable performance, and the dispersed particle in sol system is dispersed with MCA as fire retarding synergist, not only act as the purpose controlling particle diameter, and can be fire-retardant with MCA synergistic, improve the fire resistance of product.The method preparation process is simple, easily operates, and low in raw material price, less costly applicable large-scale production.
The technical scheme is that
Sol-gel modified method prepares the method for melamine cyanurate, it is characterized in that, comprises the following steps:
In a kettle., add the water of 70-90 part, temperature is raised to 70-75 DEG C, add tripolycyanamide and cyanuric acid that mass ratio is 0.9-1.1:1, it is stirring evenly and then adding into 10-30 part colloidal sol, after continuing stirring 10-30min, temperature is raised to 85-98 DEG C, stopped reaction after reaction 1-5h, sucking filtration, dry, obtain melamine cyanurate powder.
Preferably, described colloidal sol is the one in aluminum hydroxide sol, magnesium hydroxide colloidal sol, phosphate sol.
The preparation method of described colloidal sol is:
With solvable aluminium salt and ammonia for raw material, add the dispersant of 1 ‰-5 ‰, react 1-2h at 80-120 DEG C, colloidal sol can be obtained；
With solvable aluminium salt and phosphoric acid for raw material, it is neutral for regulating PH with ammonia, adds the dispersant of 1 ‰-5 ‰, temperature is increased to 80-120 DEG C of reaction 1-2h, can obtain colloidal sol；
The preparation method of above-mentioned four kinds of colloidal sols can also adopt preparation method generally in the art to prepare.
Wherein, the dispersant described in the preparation method of above-mentioned colloidal sol is one or more in polyethylene glycol 200, PEG400, cetyl trimethylammonium bromide, sodium dodecylbenzenesulfonate etc..
Preferably, described colloidal sol is the one in aluminum hydroxide sol, phosphate sol.
Preferably, in described colloidal sol, the concentration of dispersed phase particles is 0.1-0.5mol/L.
Preferably, in described colloidal sol, the concentration of dispersed phase particles is 0.15～0.3mol/L.
Dispersion phase, also referred to as dispersate, is meant to dispersed material.For colloidal dispersion system, the dispersed phase particles that diameter is 1-100nm is disperseed in disperse medium, and between dispersed phase particles and disperse medium, have obvious physical interface face.
Preferably, described melamine cyanurate powder diameter ranges for 300nm-500nm.
In the present invention, utilize the crystallite of corresponding sol system to limit growth and the dispersion of melamine cyanurate (MCA) crystal.In sol system, the growth of MCA is subject to sterically hindered effect；Part sol system dispersed particle surface has hydrogen bond simultaneously, it is possible to control the direction of growth of MCA crystallite.
The invention have the benefit that
(1) the melamine cyanurate size tunable that prepared by the present invention (by controlling the pore size of sol templates, the component of colloidal sol and concentration, reaches to control the purpose of particle diameter；The colloidal sol that concentration is more big, porosity is more little, but the words that concentration is too big are susceptible to coagulation, when there is not coagulation, the hole of the big then colloidal sol of concentration is more little, and product is more thin, additionally, the component of colloidal sol also affects the fineness of product) and be evenly distributed, for 300-500nm, good dispersion, it is possible to be well applicable to downstream product.
(2) the modified melamine cyanurate excellent fireproof performance that the present invention relates to, not easily precipitates out in the matrix materials such as nylon, and improves the mechanical property of matrix material.
(3) low in raw material price used in the present invention, the simple controlled easy operation of preparation technology, have good economic benefit and using value.
Detailed description of the invention
In order to be more fully understood that the present invention, being further elucidated with present disclosure below in conjunction with embodiment, but present disclosure is not limited solely to the following examples, embodiment is not construed as limiting the scope of the present invention.
Embodiment 1
1. add 65g aluminum nitrate and 1L water, after stirring, be warmed up to 80 DEG C, add the ammonia of 600mL1mol/L and the polyethylene glycol 200 of 1g afterwards, after stirring 1h, obtain aluminum hydroxide sol.
2. in reactor, add 70g water, it is subsequently adding tripolycyanamide 8.6g and cyanuric acid 8.5g, it is stirring evenly and then adding into the 30mL aluminum hydroxide sol prepared, after continuing stirring 10min, is warmed up to stopped reaction after 90 DEG C of reaction 3h, sucking filtration, obtain the MCA product that mean diameter is 300nm after drying.
Embodiment 2
1. add 45g magnesium nitrate and 1L water, after stirring, be warmed up to 80 DEG C, be sequentially added into the PEG400 of the ammonia of 400mL1mol/L, 1.2g, after stirring 1h, obtain magnesium hydroxide colloidal sol.
2. in reactor, add 80g water, it is sequentially added into tripolycyanamide 10.6g, cyanuric acid 10g, it is stirring evenly and then adding into the aluminum hydroxide sol described in 20mL, after continuing stirring 20min, is warmed up to stopped reaction after 95 DEG C of reaction 2.5h, sucking filtration, obtain the MCA product that mean diameter is 350nm after drying.
Embodiment 3
1. add 40g aluminum chloride and 1L water, after stirring, be warmed up to 90 DEG C, add the phosphoric acid that 23g mass fraction is 85% and stir, add the ammonia of 600mL1mol/L, 1.8g cetyl trimethylammonium bromide afterwards, after stirring 2h, obtain aluminium phosphate sol.
2. in reactor, add 90g water, it is sequentially added into tripolycyanamide 9g, cyanuric acid 9g, it is stirring evenly and then adding into aluminium phosphate sol described in 10g, after continuing stirring 30min, is warmed up to stopped reaction after 98 DEG C of reaction 2h, sucking filtration, obtain the MCA product that mean diameter is 400nm after drying.
Embodiment 4
1. add 45g aluminum nitrate and 1L water, after stirring, be warmed up to 80 DEG C, add the ammonia of 400mL1mol/L and the polyethylene glycol 200 of 1g afterwards, after stirring 1h, obtain aluminum hydroxide sol.
2. in reactor, add 70g water, it is subsequently adding tripolycyanamide 8.6g and cyanuric acid 8.5g, it is stirring evenly and then adding into the 30mL aluminum hydroxide sol prepared, after continuing stirring 10min, is warmed up to stopped reaction after 90 DEG C of reaction 3h, sucking filtration, obtain the MCA product that mean diameter is 400nm after drying.
Embodiment 5
1. add 25g aluminum nitrate and 1L water, after stirring, be warmed up to 80 DEG C, add the ammonia of 200mL1mol/L and the polyethylene glycol 200 of 1g afterwards, after stirring 1h, obtain aluminum hydroxide sol.
2. in reactor, add 70g water, it is subsequently adding tripolycyanamide 8.6g and cyanuric acid 8.5g, it is stirring evenly and then adding into the 30mL aluminum hydroxide sol prepared, after continuing stirring 10min, is warmed up to stopped reaction after 90 DEG C of reaction 3h, sucking filtration, obtain the MCA product that mean diameter is 500nm after drying.
Application Example 1
By the MCA product 11kg obtained by embodiment 1, nylon-66 100kg, antioxidant 0.2kg, mix homogeneously, then material is proceeded to double screw extruder, in 220 DEG C of extrusions, injection moulding.Product fire resistance is tested up to UL-94-1.6mmV0 level.
Application example 2
After the MCA product 13kg prepared in example 2, nylon-66 100kg, antioxidant 0.2kg, mix homogeneously, then material is proceeded to double screw extruder, in 220 DEG C of extrusions, injection moulding.Product fire resistance is tested up to UL-94-1.6mmV0 level.
Application example 3
By the MCA product 14kg prepared in example 3, nylon-66 100kg, antioxidant 0.2kg, mix homogeneously, then material is proceeded to double screw extruder, in 220 DEG C of extrusions, injection moulding.Product fire resistance is tested up to UL-94-1.6mmV0 level.
Application Example 4
By the MCA product 14kg prepared in example 4, nylon-66 100kg, antioxidant 0.2kg, mix homogeneously, then material is proceeded to double screw extruder, in 220 DEG C of extrusions, injection moulding.Product fire resistance is tested up to UL-94-1.6mmV0 level.
Application Example 5
By the MCA product 16kg prepared in example 5, nylon-66 100kg, antioxidant 0.2kg, mix homogeneously, then material is proceeded to double screw extruder, in 220 DEG C of extrusions, injection moulding.Product fire resistance is tested up to UL-94-1.6mmV0 level.
Comparative example
The micron order MCA product 16kg that conventional method prepared, nylon66 fiber 100kg, antioxidant 0.2kg, after mix homogeneously, then proceed to double screw extruder by material, in 220 DEG C of extrusions, injection moulding.Product fire resistance is tested up to UL-94-1.6mmV2 level.
Table 1 product of the present invention and contrast product performance comparison table
Application Example experimental data shows, sol-gel modified method MCA involved by this patent adds in PA66 base material, reach same flame retardant rating UL94V-0 level, the micron-sized MCA product that the addition of required fire retardant is prepared significantly lower than conventional method, and its particle diameter of MCA product that the present invention relates to is more slight, in matrix material, the amount of the required fire retardant added is more few.
The micron order MCA application experiment data that embodiment 1-5 produces with comparative example's conventional method show, this patent document relates to the addition of MCA product significantly lower than conventional MCA product, fire resistance is more excellent, and it is uniform to the present invention relates to product cut size, good dispersion, addition is few, and the performance impact of matrix material is little, excellent in mechanical performance.The present invention relates to the production method process of MCA simply controlled, less costly, it is suitable for industrialization large-scale production and application.
Claims (3)
1. the method that sol-gel modified method prepares melamine cyanurate, it is characterized in that, comprise the following steps: in a kettle., add the water of 70-90 part, temperature is raised to 70-75 DEG C, add tripolycyanamide and cyanuric acid that mass ratio is 0.9-1.1:1, it is stirring evenly and then adding into 10-30 part phosphate sol, after continuing stirring 10-30min, temperature is raised to 85-98 DEG C, stopped reaction after reaction 1-5h, sucking filtration, dry, obtain melamine cyanurate powder；In described phosphate sol, the concentration of dispersed phase particles is 0.1-0.5mol/L.
2. the method that sol-gel modified method according to claim 1 prepares melamine cyanurate, is characterized in that, in described phosphate sol, the concentration of dispersed phase particles is 0.15 ~ 0.3mol/L.
3. the method that sol-gel modified method according to claim 1 and 2 prepares melamine cyanurate, is characterized in that, described melamine cyanurate powder diameter ranges for 300nm-500nm.
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| CN201410515675.XA CN104311500B (en) | 2014-09-29 | 2014-09-29 | Sol-gel modified method prepares the method for melamine cyanurate |
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| CN201410515675.XA CN104311500B (en) | 2014-09-29 | 2014-09-29 | Sol-gel modified method prepares the method for melamine cyanurate |
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| CN104311500B true CN104311500B (en) | 2016-07-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109438379B (en) * | 2018-10-23 | 2022-04-01 | 湖南工业大学 | Preparation method of melamine cyanurate |
| CN115232388A (en) * | 2022-09-21 | 2022-10-25 | 江苏恒尚节能科技股份有限公司 | Heat-insulating refractory material for building curtain wall and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510059A (en) * | 1994-02-08 | 1996-04-23 | Nissan Chemical Industries, Ltd. | Surface-treated melamine cyanurate powder and process for its production |
| CN1364858A (en) * | 2002-02-07 | 2002-08-21 | 合肥精汇化工研究所 | Process for preparing flame-retarding lubricant MCA |
| CN1632058A (en) * | 2004-11-09 | 2005-06-29 | 四川大学 | Melamine cyanuric acid microcapsule inorganic frame retardant and its preparation method |
| CN101039923A (en) * | 2004-10-15 | 2007-09-19 | 西巴特殊化学品控股有限公司 | Melamine cyanurate in crystalline form |
-
2014
- 2014-09-29 CN CN201410515675.XA patent/CN104311500B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510059A (en) * | 1994-02-08 | 1996-04-23 | Nissan Chemical Industries, Ltd. | Surface-treated melamine cyanurate powder and process for its production |
| CN1364858A (en) * | 2002-02-07 | 2002-08-21 | 合肥精汇化工研究所 | Process for preparing flame-retarding lubricant MCA |
| CN101039923A (en) * | 2004-10-15 | 2007-09-19 | 西巴特殊化学品控股有限公司 | Melamine cyanurate in crystalline form |
| CN1632058A (en) * | 2004-11-09 | 2005-06-29 | 四川大学 | Melamine cyanuric acid microcapsule inorganic frame retardant and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 尼龙6/改性MCA复合材料的力学性能研究;魏珊珊等;《矿冶工程》;20090630;第29卷(第3期);第89页1.2、2.1 * |
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Address after: 250204 Luxi Luye Road, Diaozhen Chemical Park, Mingshui Economic and Technological Development Zone, Zhangqiu District, Jinan City, Shandong Province Patentee after: Shandong Taixing New Materials Co., Ltd. Address before: 250101 Building 3, North District, University Science Park, Jinan High-tech Zone, Shandong Province Patentee before: Jinan TaiXing Fine Chemical Co., Ltd. |