CN108148011A - High melamine polyphosphate of a kind of thermal stability and preparation method thereof - Google Patents
High melamine polyphosphate of a kind of thermal stability and preparation method thereof Download PDFInfo
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- CN108148011A CN108148011A CN201810048963.7A CN201810048963A CN108148011A CN 108148011 A CN108148011 A CN 108148011A CN 201810048963 A CN201810048963 A CN 201810048963A CN 108148011 A CN108148011 A CN 108148011A
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- melamine
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- melamine polyphosphate
- thermal stability
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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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- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of preparation methods of the high melamine polyphosphate of thermal stability, include the following steps：A. water is added in melamine, opens stirring, continue to react 1h after instilling phosphoric acid up to melamine phosphate；B. the obtained melamine phosphates of step a and inorganic agent are uniformly mixed to obtain homomixture, the inorganic agent is selected from one or more of urea, ammonium hydrogen carbonate or biuret；C. the homomixture that step b is obtained is heat-treated at 180 260 DEG C, heat treatment completes postcooling to get to the high melamine polyphosphate of heretofore described thermal stability.The degree of polymerization of melamine polyphosphate that is finally obtained according to preparation method provided by the invention is higher, water-soluble reduction, excellent heat stability, also be not in color change, compared to the prior art the temperature being heat-treated in preparation method provided by the invention significantly reduces, energy consumption is reduced, there is extremely wide application prospect.
Description
Technical field
The present invention relates to the preparations of melamine polyphosphate, are related specifically to a kind of high melamine of thermal stability and gather
Phosphate and preparation method thereof.
Background technology
With attention of the extensive use and people of fire proofing to environmental protection, the exploitation of environment friendly flame retardant
It is increasingly concerned, as the representative of halogen-free environment-friendly type flame-proof agent, melamine polyphosphate（MPP）People are also become to grind
The hot spot studied carefully and developed, the fire retardant may be used with nearly all plastics, be particularly suitable for the higher engineering plastics resistance of processing temperature
Combustion, such as fiberglass reinforced type nylon, polyester high molecular material.
At present, the method for preparing melamine polyphosphate is commonly divided into one-step method and two-step method.One-step method uses three
Poly cyanamid and polyphosphoric acid react one-step synthesis under certain condition, but this method is by the strong absorptive of polyphosphoric acid and water-disintegrable
It influences so that its operating condition is harsh, and target product complicated component, product purity is relatively low, and the melamine being prepared gathers
Phosphate is with obvious effects to be inferior to two-step method.Two-step method is first melamine and phosphatase reaction synthetic intermediate, then using heat
Melamine polyphosphate is made in processing.According to practical production experience, it is necessary to by intermediate product at 320 DEG C or more of high warm
After managing a period of time, can just produce the higher melamine polyphosphate of thermal stability, and at such high temperatures into
The defects of row heat treatment, is also more apparent, first, by be heat-treated under high temperature band final product melamine polyphosphate
Although thermal stability have raising to a certain extent relative to intermediate product, after thermogravimetry is tested, find
During weightlessness 1%, decomposition temperature is less than 360 DEG C, and thermal stability, which still needs, to be further improved；Secondly, temperature is excessively high to be caused most
There is khaki in the color of the melamine polyphosphate obtained eventually, limits its application in light plastics；In addition, high temperature
It is lower to be heat-treated the waste that also lead to the energy, increase production cost.
Invention content
The technical problem to be solved in the present invention is to provide a kind of preparation of the high melamine polyphosphate of thermal stability
Method can effectively reduce energy consumption using the preparation method, save production cost.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：A kind of high melamine of thermal stability
The preparation method of Quadrafos, includes the following steps：
A. water is added in melamine, opens stirring, continue to react 1h after instilling phosphoric acid up to melamine phosphate；
B. the obtained melamine phosphates of step a and inorganic agent are uniformly mixed to obtain homomixture, the inorganic agent is selected from urine
One or more of element, ammonium hydrogen carbonate or biuret；
C. the homomixture that step b is obtained is heat-treated at 180-260 DEG C, heat treatment completes postcooling to get to this hair
The high melamine polyphosphate of thermal stability described in bright.
Preferably, the mass ratio of melamine and phosphoric acid described in step a is 5:2-5:4.
Preferably, step a is filtered, washed after instilling phosphatase reaction 1h, is dried.
It is highly preferred that the drying carries out under vacuum, drying temperature is 130 DEG C -140 DEG C, drying time 2h-
3h。
Preferably, the mass ratio described in step b between melamine phosphate and the inorganic agent is 1:0.01-1:
0.30。
Preferably, the temperature being heat-treated described in step c is 180 DEG C -230 DEG C.
Preferably, the time being heat-treated described in step c is 1h-5h.
A kind of high melamine polyphosphate of thermal stability, is prepared by above-mentioned preparation method.
Compared to the prior art, the invention has the advantages that：The present invention is first by by melamine and phosphoric acid
Melamine phosphate is obtained by the reaction, then adds in specific inorganic agent to melamine phosphate（Urea, ammonium hydrogen carbonate or contracting
One or more of two ureas）, and be heat-treated in specific 180 DEG C -260 DEG C of temperature range, the trimerization finally obtained
The degree of polymerization of cyanamide Quadrafos is higher, water-soluble reduction, excellent heat stability, the melamine finally obtained is found after detection
The temperature of amine Quadrafos weightlessness 1% is more than 380 DEG C, due to carrying out hot place to intermediate product melamine phosphate in the present invention
The temperature of reason is very low, not only prevents final product melamine polyphosphate and becomes khaki since temperature is excessively high, and drop
Low energy consumption, has saved cost, has extremely wide application prospect.
Specific embodiment
Embodiment is given below so that the present invention to be specifically described, it is necessary to which indicated herein is following embodiment
It is used to further illustrate the present invention, it is impossible to be interpreted as limiting the scope of the invention, the ordinary skill in the field
Personnel still fall within protection scope of the present invention to the nonessential improvement of some made of the invention or adjustment according to this embodiment.
Embodiment 1
A kind of preparation method of the high melamine polyphosphate of thermal stability, includes the following steps：
A. 25.2g melamines are weighed, tetra- mouthfuls of the 1000mL equipped with electric mixer, thermometer, constant pressure funnel is placed in and burns
In bottle, distilled water 600mL is added in into four-hole boiling flask, and stir, at normal temperatures, be slowly dropped by constant pressure funnel
23.1g mass concentrations are 85% phosphoric acid solution, are added dropwise to complete within about 1 hour, treat that phosphoric acid solution is added dropwise to complete, and it is 1 small that the reaction was continued
When, it filters, washing is dried in vacuo 3 hours at 130 DEG C, obtains 43.5g melamine phosphates；
B. melamine phosphate step a obtained crushes, and adds in 4 g of urea and is uniformly mixed and obtains homomixture；
C. the homomixture that step b is obtained at 260 DEG C is heat-treated 1 hour, cooled down to get to product melamine polyphosphate
38.2 g。
Embodiment 2
A kind of preparation method of the high melamine polyphosphate of thermal stability, includes the following steps：
A. 25.2g melamines are weighed, are placed in tetra- mouthfuls of burnings of 1000mL equipped with electric mixer, thermometer and constant pressure funnel
In bottle, 600mL water is added in into four-hole boiling flask and is stirred, at normal temperatures, 18.4g mass is slowly dropped by constant pressure funnel
A concentration of 85% phosphoric acid solution, treats that phosphoric acid solution is added dropwise to complete, and treats that phosphoric acid solution is added dropwise to complete, and the reaction was continued 1 hour, filtering,
Washing, is dried in vacuo 2 hours at 130 DEG C, obtains 40.9g melamine phosphates；
B. melamine phosphate step a obtained crushes, and adds in ammonium hydrogen carbonate 5.3g and is uniformly mixed and obtains homomixture；
C. the homomixture that step b is obtained at 180 DEG C is heat-treated 5 hours, cooled down to get to product melamine polyphosphate
32.1g。
Embodiment 3
A kind of preparation method of the high melamine polyphosphate of thermal stability, includes the following steps：
A. 25.2g melamines are weighed, are placed in tetra- mouthfuls of burnings of 1000mL equipped with electric mixer, thermometer and constant pressure funnel
In bottle, 600mL water is added in into four-hole boiling flask and is stirred, at normal temperatures, 13.8g mass is slowly dropped by constant pressure funnel
A concentration of 85% phosphoric acid solution treats that phosphoric acid solution is added dropwise to complete, and the reaction was continued 1 hour, filters, washing, the vacuum at 130 DEG C
It is 2 hours dry, obtain 35.4g melamine phosphates；
B. melamine phosphate step a obtained crushes, and adds in biuret 6.0g and is uniformly mixed and obtains homomixture；
C. the homomixture that step b is obtained at 230 DEG C is heat-treated 3 hours, cooled down to get to product melamine polyphosphate
25.6 g。
Comparative example 1
A kind of preparation method of the high melamine polyphosphate of thermal stability is compared with embodiment 1, is uniquely distinguished as eliminating
The melamine phosphate obtained in step a is directly carried out the heat treatment in step c, cooled down up to product trimerization by step b
Cyanamide Quadrafos.
Comparative example 2
The preparation method and embodiment 2 of a kind of high melamine polyphosphate of thermal stability compare, and are uniquely distinguished as eliminating step
The melamine phosphoric acid obtained in step a is directly carried out the heat treatment in step c, cooled down up to product melamine by rapid b
Quadrafos.
Comparative example 3
The preparation method and embodiment 3 of a kind of high melamine polyphosphate of thermal stability compare, and are uniquely distinguished as eliminating step
The melamine phosphoric acid obtained in step a is directly carried out the heat treatment in step c, cooled down up to product melamine by rapid b
Quadrafos.
Comparative example 4
The preparation method and embodiment 2 of a kind of high melamine polyphosphate of thermal stability compare, and are uniquely distinguished as step c
In heat treatment temperature be changed to 320 DEG C by 180 DEG C, other are consistent with embodiment 2.
Performance data test method
Heat stability testing：Using thermogravimetry, i.e., a small amount of trimerization for being obtained in Example 1-3 respectively and comparative example 1-4
Cyanamide phosphate and product melamine polyphosphate using thermobalance as test equipment, sample are heated, sample as sample
Weight change causes balance displacement to be converted to electromagnetic quantities after heated, this small electricity is sent into after amplifier amplifies
Recorder records, and the size of electricity is proportional to the weight change amount of sample.When weight occurs in heating process in measured matter
During variation, thermogravimetric curve will be declined, by analyzing thermogravimetric curve, it is possible to know sample in how many spend
Mostly heavy weight variation, the present invention in specific embodiment in test be example weight reduce 1% when temperature level.
Water solubility test：Using a small amount of product melamine polyphosphate in Example 1-3 and comparative example 1-4 as sample
Product add in weight to obtain the slurries of 2wt% in the water of 49 times of sample, then test melamine polyphosphate in the slurries
Solubility.
The performance parameter of melamine phosphate and product melamine polyphosphate in embodiment 1-3 and comparative example 1-4
Test result see the table below shown in 1.
As shown in Table 1, the melamine polyphosphate being prepared using method provided by the invention passes through thermogravimetric analysis
After method test, it is found that weightless 1% temperature of the melamine polyphosphate can reach 380 DEG C or more, solubility in water exists
0.016g/100mL is water-soluble hereinafter, the better heat stability of melamine polyphosphate being finally prepared in the present invention
Property is relatively low, and comparative example 1-3 before being heat-treated under the conditions of 180 DEG C -260 DEG C to melamine phosphate due to not adding in
Inorganic agent leads to weightless 1% temperature of the product being finally prepared melamine polyphosphate relative to three obtained in step a
Paracyanogen amine phosphate has no raising, and solubility is inferior to embodiment 1-3.
In addition caused most it is found that since the heat treatment temperature of comparative example 4 is excessively high by the comparative example 4 in table 1 and embodiment 2
There is khaki in the melamine polyphosphate obtained eventually, tests obtained thermal stability and water solubility is also inferior to embodiment
2。
Claims (8)
1. a kind of preparation method of the high melamine polyphosphate of thermal stability, it is characterised in that：Include the following steps：
A. water is added in melamine, opens stirring, continue to react 1h after instilling phosphoric acid up to melamine phosphate；
B. the obtained melamine phosphates of step a and inorganic agent are uniformly mixed to obtain homomixture, the inorganic agent is selected from urine
One or more of element, ammonium hydrogen carbonate or biuret；
C. the homomixture that step b is obtained is heat-treated at 180-260 DEG C, heat treatment completes postcooling to get to this hair
The high melamine polyphosphate of thermal stability described in bright.
2. according to the preparation method of the melamine polyphosphate described in claim 1, it is characterised in that：Described in step a
The mass ratio of melamine and phosphoric acid is 5:2-5:4.
3. according to the preparation method of the melamine polyphosphate described in claim 1, it is characterised in that：Step a instills phosphorus
It is filtered, washed, is dried after acid reaction 1h.
4. according to the preparation method of the melamine polyphosphate described in claim 3, it is characterised in that：The drying is true
It is carried out under empty condition, drying temperature is 130 DEG C -140 DEG C, drying time 2h-3h.
5. according to the preparation method of the melamine polyphosphate described in claim 1, it is characterised in that：Described in step b
Mass ratio between melamine phosphate and the inorganic agent is 1:0.01-1:0.30.
6. according to the preparation method of the melamine polyphosphate described in claim 1, it is characterised in that：Described in step c
The temperature of heat treatment is 180 DEG C -230 DEG C.
7. according to the preparation method of the melamine polyphosphate described in claim any one of 1-6, it is characterised in that：Step
The time being heat-treated described in c is 1h-5h.
8. the high melamine polyphosphate of a kind of thermal stability, which is characterized in that by claim 1-7 any one of them systems
Preparation Method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810048963.7A CN108148011A (en) | 2018-01-18 | 2018-01-18 | High melamine polyphosphate of a kind of thermal stability and preparation method thereof |
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|---|---|---|---|
| CN201810048963.7A CN108148011A (en) | 2018-01-18 | 2018-01-18 | High melamine polyphosphate of a kind of thermal stability and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285817A (en) * | 2020-04-07 | 2020-06-16 | 四川省精细化工研究设计院 | Melamine polyphosphate and application thereof |
| CN112431021A (en) * | 2020-11-24 | 2021-03-02 | 常州大学 | Preparation method of flame-retardant natural loofah sponge |
| RU2758253C1 (en) * | 2021-03-15 | 2021-10-27 | Федеральное государственное автономное образовательное учреждение высшего образования «Национальный исследовательский Томский государственный университет» | Method for obtaining melamine polyphosphate |
| CN117069948A (en) * | 2023-10-17 | 2023-11-17 | 四川省成都市福来隆科技有限公司 | Preparation method of melamine polyphosphate containing aldehyde functional group |
| CN117089079A (en) * | 2023-10-17 | 2023-11-21 | 四川省成都市福来隆科技有限公司 | Preparation method of melamine polyphosphate containing carboxyl functional groups |
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| PL249727A1 (en) * | 1984-09-21 | 1986-03-25 | Inst Chemii Nieorganicznej | Method of obtaining melamine polyphosphate |
| JPH11246778A (en) * | 1998-03-04 | 1999-09-14 | Unitika Ltd | Flame retardant resin composition |
| CN102127230A (en) * | 2010-01-19 | 2011-07-20 | 中化蓝天集团有限公司 | New process for preparing modified melamine polyphosphate |
| CN104513210A (en) * | 2013-09-29 | 2015-04-15 | 青岛市首胜实业有限公司 | Preparation method for intumescent flame retardant melamine phosphate |
| CN105504292A (en) * | 2015-12-24 | 2016-04-20 | 瓮福（集团）有限责任公司 | Preparation method of MPOP |
| CN105924651A (en) * | 2016-05-09 | 2016-09-07 | 东华大学 | Preparation method of high-polymerization-degree melamine polyphosphate |
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| PL249727A1 (en) * | 1984-09-21 | 1986-03-25 | Inst Chemii Nieorganicznej | Method of obtaining melamine polyphosphate |
| JPH11246778A (en) * | 1998-03-04 | 1999-09-14 | Unitika Ltd | Flame retardant resin composition |
| CN102127230A (en) * | 2010-01-19 | 2011-07-20 | 中化蓝天集团有限公司 | New process for preparing modified melamine polyphosphate |
| CN104513210A (en) * | 2013-09-29 | 2015-04-15 | 青岛市首胜实业有限公司 | Preparation method for intumescent flame retardant melamine phosphate |
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| CN105924651A (en) * | 2016-05-09 | 2016-09-07 | 东华大学 | Preparation method of high-polymerization-degree melamine polyphosphate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285817A (en) * | 2020-04-07 | 2020-06-16 | 四川省精细化工研究设计院 | Melamine polyphosphate and application thereof |
| CN112431021A (en) * | 2020-11-24 | 2021-03-02 | 常州大学 | Preparation method of flame-retardant natural loofah sponge |
| RU2758253C1 (en) * | 2021-03-15 | 2021-10-27 | Федеральное государственное автономное образовательное учреждение высшего образования «Национальный исследовательский Томский государственный университет» | Method for obtaining melamine polyphosphate |
| CN117069948A (en) * | 2023-10-17 | 2023-11-17 | 四川省成都市福来隆科技有限公司 | Preparation method of melamine polyphosphate containing aldehyde functional group |
| CN117089079A (en) * | 2023-10-17 | 2023-11-21 | 四川省成都市福来隆科技有限公司 | Preparation method of melamine polyphosphate containing carboxyl functional groups |
| CN117089079B (en) * | 2023-10-17 | 2023-12-26 | 四川省成都市福来隆科技有限公司 | Preparation method of melamine polyphosphate |
| CN117069948B (en) * | 2023-10-17 | 2024-01-02 | 四川省成都市福来隆科技有限公司 | Preparation method of melamine polyphosphate containing aldehyde functional group |
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