CN111285817A - Melamine polyphosphate and application thereof - Google Patents
Melamine polyphosphate and application thereof Download PDFInfo
- Publication number
- CN111285817A CN111285817A CN202010264460.0A CN202010264460A CN111285817A CN 111285817 A CN111285817 A CN 111285817A CN 202010264460 A CN202010264460 A CN 202010264460A CN 111285817 A CN111285817 A CN 111285817A
- Authority
- CN
- China
- Prior art keywords
- melamine polyphosphate
- melamine
- temperature
- pyrophosphate
- heat treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses melamine polyphosphate, which is prepared by mixing dimelamine pyrophosphate and an ammonia source and then carrying out high-temperature heat treatment. The invention also discloses a scheme for preparing the intermediate of dimelamine pyrophosphate from melamine, sodium pyrophosphate and inorganic acid, and drying and roasting the intermediate to obtain melamine polyphosphate. The invention also discloses application of the melamine polyphosphate in flame-retardant modified products. The melamine polyphosphate has the characteristics of high thermal stability, low water solubility and excellent flame retardant property, and the flame retardant modified product prepared by the melamine polyphosphate has excellent ageing resistance; the production process of the melamine polyphosphate has the advantages of simple steps, mild reaction conditions, stable and controllable reaction process, low energy consumption and little environmental pollution.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and particularly relates to melamine polyphosphate and application thereof.
Background
With the wide application of polymer materials to various aspects of life, the flammability problem of polymer materials is gradually exposed and causes national economic loss, the flame retardant is more and more paid attention to people, and the environmental-friendly halogen-free flame retardant especially draws attention. The melamine polyphosphate is an environment-friendly and efficient nitrogen-phosphorus flame retardant, and is suitable for engineering plastics such as PA66 and PBT with higher processing temperature.
At present, the preparation of melamine polyphosphate is mainly a two-step method, melamine and phosphoric acid are firstly mixed according to a certain proportion to obtain a melamine phosphate intermediate, and then the melamine polyphosphate is obtained through high-temperature heat treatment. However, the melamine polyphosphate prepared by the method has the problem that melamine phosphate and other substances do not completely react, and when the melamine polyphosphate and the flame-retardant synergist are compounded to cooperate with flame-retardant PA66 and PBT, the flame-retardant modified product has poor anti-aging effect, and the application range of the melamine polyphosphate is limited.
Disclosure of Invention
The invention aims to provide melamine polyphosphate and application thereof, aiming at solving the problems, so that the heat stability is improved, the water solubility of the melamine polyphosphate is reduced, and the anti-aging effect of the melamine polyphosphate in the application of a flame retardant is improved.
The technical content of the invention is as follows:
the melamine polyphosphate is prepared by mixing dimelamine pyrophosphate and an ammonia source and then carrying out high-temperature heat treatment.
Further, the melamine polyphosphate is prepared by the following steps:
(1) dissolving melamine, sodium pyrophosphate and inorganic acid in water, stirring and reacting at a certain reaction temperature, filtering, washing and drying a reaction mixture to obtain dimelamine pyrophosphate;
(2) mixing the dimelamine pyrophosphate obtained in the step (1) with an ammonia source, and then carrying out high-temperature heat treatment to obtain melamine polyphosphate.
In the step (1), the molar ratio of melamine, sodium pyrophosphate and inorganic acid is 1.9-2.1: 1: 4.
further, the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid.
Further, in the step (1), the stirring reaction time is 1.5-2.5 hours, and the reaction temperature is 80-95 ℃.
Further, in the step (1), the adding amount of water accounts for at least 60% of the total adding amount of the raw materials in mass fraction.
Further, in the step (2), the weight ratio of the dimelamine pyrophosphate to the ammonia source is 1: 0.02-0.05.
Further, the ammonia source is one or more of urea, melamine, dicyandiamide, ammonium carbonate and ammonium bicarbonate.
Further, in the step (2), the high-temperature heat treatment includes heating in two temperature ranges of a first temperature range and a second temperature range, the first temperature range is 170-200 ℃, the reaction time is 1-2 hours, the second temperature range is 300-350 ℃, and the reaction time is 2-3 hours.
The invention also comprises the application of the melamine polyphosphate prepared in the way of the invention in flame-retardant modified products.
Due to the adoption of the technical scheme, the invention has the advantages that: the melamine polyphosphate has the characteristics of high thermal stability, low water solubility and excellent flame retardant property, and the application of the melamine polyphosphate in flame retardant modified products is provided, so that the flame retardant modified products have excellent anti-aging property; the production process of the melamine polyphosphate has the advantages of simple steps, mild reaction conditions, stable and controllable reaction process, low energy consumption and little environmental pollution.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
In one embodiment of the present invention, a melamine polyphosphate is provided, prepared by mixing dimelamine pyrophosphate with an ammonia source and then subjecting the mixture to a high temperature heat treatment. The dimelamine pyrophosphate can be prepared by a purchased finished product or a preparation method in the prior art, such as synthesizing a dimelamine pyrophosphate intermediate by taking phosphorus pentoxide and melamine as raw materials.
In one embodiment of the present invention, there is provided a melamine polyphosphate comprising a melamine polyphosphate made by:
(1) dissolving melamine, sodium pyrophosphate and inorganic acid in water, stirring and reacting at a certain reaction temperature, filtering, washing and drying a reaction mixture to obtain dimelamine pyrophosphate;
(2) mixing the dimelamine pyrophosphate obtained in the step (1) with an ammonia source, and then carrying out high-temperature heat treatment to obtain melamine polyphosphate.
In the embodiment, the intermediate obtained by synthesizing the dimelamine pyrophosphate by using sodium pyrophosphate, hydrochloric acid and melamine or by using phosphorus pentoxide, 85% phosphoric acid and melamine as raw materials exists in the form of melamine phosphate dimer, and compared with melamine phosphate, the intermediate has the characteristics of low solubility and high thermal stability, and the melamine phosphate compound which does not completely react is prevented from existing in the subsequent high-temperature polymerization process so as to influence the thermal stability and the solubility of the product.
In the step (1), the molar ratio of melamine, sodium pyrophosphate and inorganic acid is preferably 1.9-2.1: 1: 4. the amount of water added is at least 60% of the total amount of raw materials added in mass fraction. In this example and the following specific examples, the total amount of raw materials added refers to the total mass including melamine, sodium pyrophosphate, inorganic acid and water. The addition amount of water can be adjusted according to the solubility of other raw materials in water and the viscosity of the mixed solution. The inorganic acid can be one or more selected from hydrochloric acid, sulfuric acid and nitric acid, and is used as a catalyst and a stabilizer during reaction. Preferably, the reaction time is 1.5-2.5 hours, the reaction temperature is 80-95 ℃, and the raw materials are fully reacted.
In step (2), the weight ratio of dimelamine pyrophosphate to ammonia source is 1: 0.02-0.05. The ammonia source can be one or more of urea, melamine, dicyandiamide, ammonium carbonate and ammonium bicarbonate. The ammonia source mainly has the following functions: and an ammonia gas atmosphere is provided in the high-temperature heat treatment process, so that the influence on the quality of melamine polyphosphate caused by the thermal decomposition of the melamine structure in the intermediate structure in the high-temperature process is reduced. The source of ammonia may also include other compounds that can be decomposed by heat and can produce ammonia gas.
In the embodiment of the present invention, the high temperature heat treatment is preferably performed by heating in at least two temperature intervals.
More preferably, the high-temperature heat treatment comprises a first temperature zone and a second temperature zone, wherein the first temperature zone is 170-200 ℃, the reaction time is 1-2 hours, the second temperature zone is 300-350 ℃, and the reaction time is 2-3 hours. By adopting a sectional heating mode, the problems that the temperature is increased too fast in one section, the dimer melamine pyrophosphate intermediate is dehydrated quickly, the intermediate is likely to be heated unevenly to cause agglomeration, and the material reaction is not thorough are prevented.
The synthesis method of melamine polyphosphate with high thermal stability of the invention is further illustrated by the following specific examples.
Example 1
A preparation method of melamine polyphosphate with high thermal stability comprises the following steps:
(1) mixing melamine, sodium pyrophosphate and hydrochloric acid according to a molar ratio of 2: 1: 4 weighing the materials, adding the materials into an enamel reaction kettle filled with distilled water in advance under the stirring condition, wherein the mass of the distilled water in the reaction kettle accounts for 60 percent of the total amount of the added raw materials, reacting the mixed liquid at 85 ℃ for 2.0h, and centrifuging, washing and drying at 100 ℃ for 48h to obtain an intermediate;
(2) and (2) fully mixing the intermediate in the step (1) with urea according to the weight ratio of 1:0.05, carrying out heat treatment at 170 ℃ for 1.0 hour, then heating to 340 ℃ for heat treatment for 2.0 hours, cooling and crushing to obtain the melamine polyphosphate.
Example 2
(1) Mixing melamine, sodium pyrophosphate and nitric acid according to a molar ratio of 2: 1: 4 weighing the materials, adding the materials into an enamel reaction kettle filled with distilled water in advance under the stirring condition, wherein the mass of the distilled water in the reaction kettle accounts for 65 percent of the total amount of the added raw materials, reacting the mixed liquid at 90 ℃ for 2.0h, and centrifuging, washing and drying at 100 ℃ for 48h to obtain an intermediate;
(2) and (2) fully mixing the intermediate in the step (1) with ammonium carbonate according to the weight ratio of 1:0.03, carrying out heat treatment at 180 ℃ for 1.5 hours, then heating to 330 ℃ for heat treatment for 2.0 hours, cooling and crushing to obtain the melamine polyphosphate.
Example 3
(1) Mixing melamine, sodium pyrophosphate and hydrochloric acid according to a molar ratio of 2: 1: 4 weighing the materials, adding the materials into an enamel reaction kettle filled with distilled water in advance under the stirring condition, wherein the mass of the distilled water in the reaction kettle accounts for 70 percent of the total amount of the added raw materials, reacting the mixed liquid at 80 ℃ for 2.0h, and centrifuging, washing and drying at 100 ℃ for 48h to obtain an intermediate;
(2) and (2) fully mixing the intermediate in the step (1) with ammonium bicarbonate according to the weight ratio of 1:0.05, carrying out heat treatment at 180 ℃ for 1.0 hour, then heating to 320 ℃ for 2.5 hours, cooling and crushing to obtain the melamine polyphosphate.
Example 4
(1) Mixing melamine, sodium pyrophosphate and nitric acid according to a molar ratio of 2: 1: 4 weighing the materials, adding the materials into an enamel reaction kettle filled with distilled water in advance under the stirring condition, wherein the mass of the distilled water in the reaction kettle accounts for 60 percent of the total amount of the added raw materials, reacting the mixed liquid at 95 ℃ for 2.0h, and centrifuging, washing and drying at 100 ℃ for 48h to obtain an intermediate;
(2) and (2) fully mixing the intermediate in the step (1) with dicyandiamide according to the weight ratio of 1:0.03, carrying out heat treatment at 200 ℃ for 1.0 hour, then heating to 350 ℃ for 3.0 hours, cooling and crushing to obtain the melamine polyphosphate.
Example 5
(1) Slowly dripping 85% phosphoric acid into a phosphorus pentoxide reactor with the same quantity, reacting for 1.5h at 200 ℃, cooling to 70 ℃, adding acetic acid with 6 times of weight ratio, fully stirring and dispersing, adding melamine with 2 times of mol of phosphorus element in batches, refluxing and reacting for 2.5h at 125 ℃, filtering, vacuumizing and drying to obtain an intermediate product;
(2) and (2) fully mixing the intermediate product obtained in the step (1) with dicyandiamide according to the weight ratio of 1:0.03, carrying out heat treatment at 200 ℃ for 1.0 hour, then heating to 350 ℃ for 3.0 hours, cooling and crushing to obtain the melamine polyphosphate.
Example 6
(1) Mixing melamine, sodium pyrophosphate and hydrochloric acid according to a molar ratio of 2: 1: 4 weighing the materials, adding the materials into an enamel reaction kettle filled with distilled water in advance under the stirring condition, wherein the mass of the distilled water in the reaction kettle accounts for 60 percent of the total amount of the added raw materials, reacting the mixed liquid at 85 ℃ for 2.0h, and centrifuging, washing and drying at 100 ℃ for 48h to obtain an intermediate;
(2) and (2) fully mixing the intermediate in the step (1) with urea according to the weight ratio of 1:0.05, heating to 340 ℃, carrying out heat treatment for 3.0 hours, cooling and crushing to obtain the melamine polyphosphate.
Comparative example 1
The melamine polyphosphate is prepared by performing liquid phase synthesis, centrifugal dehydration and drying on melamine and phosphoric acid according to the molar ratio of 1:1 to obtain a melamine phosphate intermediate, reacting the intermediate at a high temperature of 350 ℃ for a period of time, and crushing.
Comparative example 2
(1) Mixing melamine, sodium pyrophosphate and hydrochloric acid according to a molar ratio of 2: 1: 4 weighing the materials, adding the materials into an enamel reaction kettle filled with distilled water in advance under the stirring condition, wherein the mass of the distilled water in the reaction kettle accounts for 60 percent of the total amount of the added raw materials, reacting the mixed liquid at 85 ℃ for 2.0h, and centrifuging, washing and drying at 100 ℃ for 48h to obtain an intermediate;
(2) and (2) carrying out heat treatment on the intermediate in the step (1) at 170 ℃ for 1.0 hour, then heating to 340 ℃ for heat treatment for 2.0 hours, cooling and crushing to obtain the melamine polyphosphate.
Comparative example 3
(1) Mixing melamine, sodium pyrophosphate and hydrochloric acid according to a molar ratio of 2: 1: and 4, weighing the materials, adding the materials into an enamel reaction kettle filled with distilled water in advance under the stirring condition, wherein the mass of the distilled water in the reaction kettle accounts for 60 percent of the total amount of the added raw materials, reacting the mixed liquid at 80 ℃ for 2.5 hours, and centrifuging, washing and drying at 100 ℃ for 48 hours to obtain an intermediate.
The results of the performance parameter tests of the melamine polyphosphates of examples 1 to 6 and comparative examples 1 to 3 are shown in table 1 below.
Table 1 results of performance parameter test of each example and comparative example
As can be seen from Table 1, the melamine polyphosphate prepared by the method provided by the invention has good thermal stability and low water solubility.
The melamine polyphosphates of the examples and comparative examples were extruded and injection molded according to the following formulations. The extrusion molding formula comprises: 49.5wt% of PBT (Catharanthus roseus chemical 1100), 30wt% of glass fiber, 11.7wt% of high-heat-stability melamine polyphosphate, 8.6wt% of aluminum diethylphosphinate or zinc diethylphosphinate, 10100.1 wt% of antioxidant and 1680.1 wt% of antioxidant, wherein the flame-retardant and anti-aging properties of the obtained flame-retardant modified plastic product are shown in Table 2.
TABLE 2 flame retardance and aging Properties of examples and comparative examples
As can be seen from Table 2, the melamine polyphosphate with high thermal stability not only has good flame retardant property, but also has excellent aging resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The melamine polyphosphate is characterized by being prepared by mixing dimelamine pyrophosphate and an ammonia source and then carrying out high-temperature heat treatment.
2. Melamine polyphosphate according to claim 1, wherein said melamine polyphosphate is prepared by:
(1) dissolving melamine, sodium pyrophosphate and inorganic acid in water, stirring and reacting at a certain reaction temperature, filtering, washing and drying a reaction mixture to obtain dimelamine pyrophosphate;
(2) mixing the dimelamine pyrophosphate obtained in the step (1) with an ammonia source, and then carrying out high-temperature heat treatment to obtain melamine polyphosphate.
3. The method for synthesizing melamine polyphosphate according to claim 2, wherein in the step (1), the molar ratio of melamine, sodium pyrophosphate and inorganic acid is 1.9-2.1: 1: 4.
4. melamine polyphosphate according to claim 2, characterised in that the inorganic acid is selected from one or several of hydrochloric acid, sulphuric acid, nitric acid.
5. The melamine polyphosphate according to claim 2, wherein in the step (1), the stirring reaction time is 1.5-2.5 hours, and the reaction temperature is 80-95 ℃.
6. The melamine polyphosphate according to claim 2, wherein in step (1), the amount of water added is at least 60% by mass of the total amount of raw materials added.
7. The melamine polyphosphate according to claim 2, wherein in step (2), the weight ratio of dimelamine pyrophosphate to the ammonia source is from 1: 0.02-0.05.
8. The melamine polyphosphate according to any one of claims 1 to 7, wherein the ammonia source is one or more of urea, melamine, dicyandiamide, ammonium carbonate and ammonium bicarbonate.
9. The melamine polyphosphate according to claim 2, wherein in the step (2), the high-temperature heat treatment comprises heating in two temperature ranges of a first temperature range and a second temperature range, wherein the first temperature range is 170-200 ℃ and the reaction time is 1-2 hours, the second temperature range is 300-350 ℃ and the reaction time is 2-3 hours.
10. Use of a melamine polyphosphate according to any one of claims 1 to 9 in a flame retardant modified article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010264460.0A CN111285817A (en) | 2020-04-07 | 2020-04-07 | Melamine polyphosphate and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010264460.0A CN111285817A (en) | 2020-04-07 | 2020-04-07 | Melamine polyphosphate and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111285817A true CN111285817A (en) | 2020-06-16 |
Family
ID=71018178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010264460.0A Pending CN111285817A (en) | 2020-04-07 | 2020-04-07 | Melamine polyphosphate and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111285817A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998008898A1 (en) * | 1996-08-29 | 1998-03-05 | E.I. Du Pont De Nemours And Company | Flame retardant composition |
| CN108148011A (en) * | 2018-01-18 | 2018-06-12 | 湖南工学院 | High melamine polyphosphate of a kind of thermal stability and preparation method thereof |
-
2020
- 2020-04-07 CN CN202010264460.0A patent/CN111285817A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998008898A1 (en) * | 1996-08-29 | 1998-03-05 | E.I. Du Pont De Nemours And Company | Flame retardant composition |
| CN108148011A (en) * | 2018-01-18 | 2018-06-12 | 湖南工学院 | High melamine polyphosphate of a kind of thermal stability and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李晓丽等: "焦磷酸蜜胺盐的合成与表征", 《化学与黏合》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110819009B (en) | High-melt-index halogen-free flame-retardant polypropylene material and preparation method thereof | |
| JP7258295B2 (en) | Crystalline aluminum phosphite and method for producing and using the same | |
| CN108264720B (en) | Precipitation-free halogen-free flame retardant composition | |
| CN114015115B (en) | Preparation method of intumescent flame retardant based on piperazine pyrophosphate/melamine cyanurate/ammonium polyphosphate | |
| CN109503860B (en) | Modified lignin for intumescent flame retardant and preparation method thereof, intumescent flame retardant and preparation method thereof | |
| CN109679138B (en) | Halogen-free flame retardant melamine polyphosphate borate salt and preparation method and application thereof | |
| CN103387666B (en) | A kind of preparation method of fire-retardant Nylon 66 material | |
| JP7402470B2 (en) | Condensates of poly/monophosphite and dihydrogen phosphite and their preparation and use | |
| CN108250646B (en) | Halogen-free flame retardant composition | |
| CN108129825B (en) | high-CTI high-heat-resistance halogen-free flame-retardant PC/ABS composition and preparation method thereof | |
| CN114015060A (en) | Ammonium polyphosphate flame retardant, and preparation method and application thereof | |
| CN103387665B (en) | A kind of preparation method of fire-retardant polyamide material | |
| CN111285817A (en) | Melamine polyphosphate and application thereof | |
| CN103408751B (en) | A kind of preparation method of MCA fire-retardant polyamide material | |
| CN114426678B (en) | Lignin-based flame-retardant charring agent and synthetic method and application thereof | |
| CN113580293A (en) | High-dispersion modified melamine polyphosphate flame retardant and preparation method and application thereof | |
| CN113980360A (en) | Bio-based flame retardant applied to polylactic acid film, and manufacturing method and application thereof | |
| CN112194833A (en) | Intumescent flame-retardant polyethylene containing organic metal complex and preparation method thereof | |
| CN104478817A (en) | Melamine salt and preparation method thereof | |
| CN117865905A (en) | Preparation method of melamine polyphosphate with high purity and high polymerization degree | |
| CN114409960B (en) | Flame-retardant/antioxidant synergistic auxiliary agent, synthesis method thereof and application thereof in PET recovery | |
| CN117624068A (en) | Precipitation-resistant modified melamine polyphosphate and preparation method and application thereof | |
| CN118027397A (en) | Preparation method of flame-retardant nylon 6 | |
| CN117551338B (en) | Flame-retardant cold-resistant and damp-heat-resistant polyester composition and preparation method thereof | |
| CN112143031B (en) | Preparation method of attapulgite doped ammonium polyphosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200616 |
|
| RJ01 | Rejection of invention patent application after publication |