CN111057022A - Preparation process of Melamine Hydrobromide (MHB) and application of MHB in flame-retardant polypropylene - Google Patents
Preparation process of Melamine Hydrobromide (MHB) and application of MHB in flame-retardant polypropylene Download PDFInfo
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- CN111057022A CN111057022A CN201911348277.2A CN201911348277A CN111057022A CN 111057022 A CN111057022 A CN 111057022A CN 201911348277 A CN201911348277 A CN 201911348277A CN 111057022 A CN111057022 A CN 111057022A
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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
- 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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation process of Melamine Hydrobromide (MHB) and application thereof in flame-retardant polypropylene, belonging to the technical field of flame retardant production, and the preparation process of the melamine hydrobromide comprises the following steps: adding an alcohol solvent into a sealed container, slowly adding melamine into the container, stirring to completely dissolve the melamine in the solvent, slowly dropwise adding hydrobromic acid, controlling the reaction temperature in the container to be less than 40 ℃ in the dropwise adding process of the hydrobromic acid, measuring the change of the pH value in the container at any time until the pH value is 8, stopping dropwise adding the hydrobromic acid, and keeping the temperature for 30 min; filtering to obtain a filter cake, and drying to evaporate residual solvent in the filter cake to obtain the melamine hydrobromide. The MHB production process is simple, the MHB is applied to the flame-retardant polypropylene, the addition amount is small, and the flame-retardant polypropylene can pass UL94-V2 tests only by adding 0.8-1.5 wt%, so that the MHB produced by the invention has high-efficiency flame-retardant effect.
Description
Technical Field
The invention relates to the technical field of flame retardant production, in particular to a preparation process of Melamine Hydrobromide (MHB) and application thereof in flame-retardant polypropylene.
Background
Melamine flame retardants belong to the class of nitrogen flame retardants. Most of the nitrogen flame retardant is decomposed into NH by heating3、N2、NO2And the like, nontoxic and low-corrosion gas, and also has the functions of absorbing heat, reducing temperature and diluting combustible free radicals and gas.
Polypropylene (PP) is widely applied due to its excellent properties of high rigidity, high strength, good heat resistance, easy processing and the like, and is one of the fastest growing varieties of current general-purpose plastics. However, PP is flammable, has a high heat release, and generates a large amount of molten droplets to easily spread flames. Therefore, the research on the flame retardant PP is always paid attention at home and abroad. According to the requirement of flame retardant grade, in the prior art, the polypropylene material reaches UL94-VO grade mainly by adding more than 20% of halogen-free flame retardant, or reaches UL94-V2 grade by adding flame retardant of bromine antimony system or phosphorus-nitrogen system. Although the polypropylene high polymer material can achieve a good flame retardant effect by adding the flame retardant, the addition amount of the flame retardant is large, so that the cost of the flame retardant polypropylene is high, and the application field of the flame retardant is limited.
Disclosure of Invention
The invention provides a preparation process of Melamine Hydrobromide (MHB) and application of the MHB in flame-retardant polypropylene, the MHB production process is simple, the MHB is applied to the flame-retardant polypropylene, the addition amount is small, and the flame-retardant polypropylene can pass UL94-V2 tests only by adding 0.8-1.5 wt%, which shows that the MHB produced by the invention has high-efficiency flame-retardant effect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation process of melamine hydrobromide comprises the following steps:
(1) adding an alcohol solvent into a sealed container, slowly adding melamine into the container, stirring to completely dissolve the melamine in the solvent, slowly dropwise adding hydrobromic acid, controlling the reaction temperature in the container to be less than 40 ℃ in the dropwise adding process of the hydrobromic acid, measuring the change of the pH value in the container at any time until the pH value is 8, stopping dropwise adding the hydrobromic acid, and keeping the temperature for 30 min;
(2) filtering to obtain a filter cake, and drying to evaporate residual solvent in the filter cake to obtain the melamine hydrobromide.
Preferably, the alcohol solvent is any one of methanol and ethanol.
Preferably, the molar ratio of the alcohol solvent to the melamine to the hydrobromic acid is 2: 1: 0.5-2.5, and the concentration of the hydrobromic acid is 30-40%.
The MHB obtained by the preparation process of the Melamine Hydrobromide (MHB) is applied to flame-retardant polypropylene, and the addition amount of the MHB accounts for 0.8-1.5 wt% of polypropylene resin.
The beneficial effects of the invention are as follows:
the process for producing MHB is simple, the danger coefficient of the used raw materials is lower, the alcohol solvent is adopted for dissolving instead of water, the absorption effect of the MHB is better than that of water, the purity is high, the solvent is low in price and easy to recover, and the reaction temperature needs to be controlled to be less than 40 ℃ to prevent the solvent from volatilizing because the reaction is exothermic; the reaction for producing MHB is carried out at normal temperature and normal pressure, and the exothermic reaction in the container can be carried out in a jacket cooling mode; the MHB produced by the invention is applied to flame-retardant polypropylene, the addition amount is small, the addition amount in homopolymerized PP is 0.8-1.5 wt%, the flame-retardant grade can REACH UL94-V2 grade, the obtained flame-retardant polypropylene does not contain organic bromine compounds, the flame-retardant polypropylene can completely pass SGS and REACH standard tests, in addition, the transparency of the polypropylene is not influenced, and the MHB can be used for transparent PP flame-retardant products and used for replacing PA6 and other raw materials at V2 flame retardant grade.
Detailed Description
To facilitate understanding of those skilled in the art, the present invention will be further described with reference to specific examples:
example 1:
a preparation process of melamine hydrobromide comprises the following steps:
(1) adding an alcohol solvent into a sealed container, slowly adding melamine into the container, stirring to completely dissolve the melamine in the solvent, slowly dropwise adding hydrobromic acid, controlling the reaction temperature in the container to be less than 40 ℃ in the dropwise adding process of the hydrobromic acid, measuring the change of the pH value in the container at any time until the pH value is 8, stopping dropwise adding the hydrobromic acid, and keeping the temperature for 30 min;
(2) filtering to obtain a filter cake, and drying to evaporate residual solvent in the filter cake to obtain the melamine hydrobromide.
The alcohol solvent is any one of methanol and ethanol. The molar ratio of the alcohol solvent to the melamine to the hydrobromic acid is 2: 1: 0.5, and the concentration of the hydrobromic acid is 30 percent.
Example 2:
a preparation process of melamine hydrobromide comprises the following steps:
(1) adding an alcohol solvent into a sealed container, slowly adding melamine into the container, stirring to completely dissolve the melamine in the solvent, slowly dropwise adding hydrobromic acid, controlling the reaction temperature in the container to be less than 40 ℃ in the dropwise adding process of the hydrobromic acid, measuring the change of the pH value in the container at any time until the pH value is 8, stopping dropwise adding the hydrobromic acid, and keeping the temperature for 30 min;
(2) filtering to obtain a filter cake, and drying to evaporate residual solvent in the filter cake to obtain the melamine hydrobromide.
The alcohol solvent is any one of methanol and ethanol. The molar ratio of the alcohol solvent to the melamine to the hydrobromic acid is 2: 1: 2.5, the concentration of the hydrobromic acid is 40 percent.
Example 3:
a preparation process of melamine hydrobromide comprises the following steps:
(1) adding an alcohol solvent into a sealed container, slowly adding melamine into the container, stirring to completely dissolve the melamine in the solvent, slowly dropwise adding hydrobromic acid, controlling the reaction temperature in the container to be less than 40 ℃ in the dropwise adding process of the hydrobromic acid, measuring the change of the pH value in the container at any time until the pH value is 8, stopping dropwise adding the hydrobromic acid, and keeping the temperature for 30 min;
(2) filtering to obtain a filter cake, and drying to evaporate residual solvent in the filter cake to obtain the melamine hydrobromide.
The alcohol solvent is any one of methanol and ethanol. The molar ratio of the alcohol solvent to the melamine to the hydrobromic acid is 2: 1: 1.5, the concentration of the hydrobromic acid is 35 percent.
And (3) performance testing:
firstly, the Melamine Hydrobromide (MHB) prepared in the above examples 1-3 was subjected to a performance test, and the performance indexes thereof are shown in Table 1:
TABLE 1
| Serial number | Appearance of the product | Melting Point | Purity of |
| Example 1 | White superfine powder | 260℃ | 97％ |
| Example 2 | White superfine powder | 270℃ | 98％ |
| Example 3 | White superfine powder | 268℃ | 99％ |
Secondly, the Melamine Hydrobromide (MHB) prepared in the above example 3 is applied to flame retardant polypropylene, and the specific method is as follows: respectively adding MHB with different contents into polypropylene resin, uniformly mixing the raw materials, extruding and granulating by a double screw at 170 ℃ to obtain flame-retardant polypropylene, carrying out injection molding on the material at 200 ℃, and finally carrying out injection molding in an injection molding machine to obtain standard sample strips, wherein the standard sample strips have the sizes of (3.2mm, 1.6mm and 0.8 mm). The flame retardant performance was tested based on the flame retardant standard method of UL94, and the flame retardant rating was evaluated, and the specific data and test results are shown in table 2.
TABLE 2
| The addition amount of | 0 | 0.8 | 1.0 | 1.2 | 1.5 |
| Flame retardant properties | Without hierarchy | UL94-V2 | UL94-V2 | UL94-V2 | UL94-V2 |
The tests show that the MHB produced by the invention is applied to the flame-retardant polypropylene, the addition amount is small, and the flame-retardant polypropylene can pass the UL94-V2 test only by adding 0.8-1.5 wt%, which shows that the MHB produced by the invention has high-efficiency flame-retardant effect.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (4)
1. A preparation process of melamine hydrobromide is characterized by comprising the following steps:
(1) adding an alcohol solvent into a sealed container, slowly adding melamine into the container, stirring to completely dissolve the melamine in the solvent, slowly dropwise adding hydrobromic acid, controlling the reaction temperature in the container to be less than 40 ℃ in the dropwise adding process of the hydrobromic acid, measuring the change of the pH value in the container at any time until the pH value is 8, stopping dropwise adding the hydrobromic acid, and keeping the temperature for 30 min;
(2) filtering to obtain a filter cake, and drying to evaporate residual solvent in the filter cake to obtain the melamine hydrobromide.
2. The process according to claim 1, wherein the alcoholic solvent is any one of methanol and ethanol.
3. The process according to claim 1, wherein the molar ratio of the alcohol solvent to the melamine to the hydrobromic acid is 2: 1: 0.5-2.5, and the concentration of the hydrobromic acid is 30-40%.
4. Use of a Melamine Hydrobromide (MHB) obtained by the process according to any of claims 1-3 in flame retardant polypropylene, wherein said MHB is added in an amount of 0.8-1.5 wt% based on the polypropylene resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911348277.2A CN111057022A (en) | 2019-12-24 | 2019-12-24 | Preparation process of Melamine Hydrobromide (MHB) and application of MHB in flame-retardant polypropylene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911348277.2A CN111057022A (en) | 2019-12-24 | 2019-12-24 | Preparation process of Melamine Hydrobromide (MHB) and application of MHB in flame-retardant polypropylene |
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| CN111057022A true CN111057022A (en) | 2020-04-24 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880420A (en) * | 2010-04-23 | 2010-11-10 | 上海美莱珀化工材料科技有限公司 | Surface precipitation-free flame-retardant polypropylene compound and preparation method thereof |
| CN102924752A (en) * | 2012-10-26 | 2013-02-13 | 清远市普塞呋磷化学有限公司 | Composition of fire retardant capable of enabling flame-retardant level of polypropylene to reach V2-level |
| CN104447595A (en) * | 2014-10-27 | 2015-03-25 | 武汉理工大学 | Preparation method of melamine hydrobromide flame retardant |
| CN105694221A (en) * | 2016-03-21 | 2016-06-22 | 中山康诺德新材料有限公司 | Efficient flame retardant polyolefin composition |
| CN110256764A (en) * | 2019-06-05 | 2019-09-20 | 江苏远祥新材料有限公司 | A kind of flame-retardant formulations and its manufacturing method of Polypropylene flame-retardant plastic template |
-
2019
- 2019-12-24 CN CN201911348277.2A patent/CN111057022A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880420A (en) * | 2010-04-23 | 2010-11-10 | 上海美莱珀化工材料科技有限公司 | Surface precipitation-free flame-retardant polypropylene compound and preparation method thereof |
| CN102924752A (en) * | 2012-10-26 | 2013-02-13 | 清远市普塞呋磷化学有限公司 | Composition of fire retardant capable of enabling flame-retardant level of polypropylene to reach V2-level |
| CN104447595A (en) * | 2014-10-27 | 2015-03-25 | 武汉理工大学 | Preparation method of melamine hydrobromide flame retardant |
| CN105694221A (en) * | 2016-03-21 | 2016-06-22 | 中山康诺德新材料有限公司 | Efficient flame retardant polyolefin composition |
| CN110256764A (en) * | 2019-06-05 | 2019-09-20 | 江苏远祥新材料有限公司 | A kind of flame-retardant formulations and its manufacturing method of Polypropylene flame-retardant plastic template |
Non-Patent Citations (1)
| Title |
|---|
| YILUN TAN，ET AL.: "Synthesis and characterization of melamine halogen acid salts and its application as flame retardant", 《ADVANCED MATERIALS RESEARCH》 * |
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