CN114940781A - Composite coated red phosphorus flame retardant and preparation method thereof - Google Patents
Composite coated red phosphorus flame retardant and preparation method thereof Download PDFInfo
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- CN114940781A CN114940781A CN202210796182.2A CN202210796182A CN114940781A CN 114940781 A CN114940781 A CN 114940781A CN 202210796182 A CN202210796182 A CN 202210796182A CN 114940781 A CN114940781 A CN 114940781A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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Abstract
The invention provides a preparation method of a composite coated red phosphorus flame retardant, which comprises the following steps: (1) dispersing red phosphorus and a dispersing agent in water, adding melamine and cyanuric acid, and reacting for 0.5-3 h; (2) adding soluble zinc salt and 2-methylimidazole, reacting for 5-30 h, and dehydrating and drying the precipitate to obtain the composite coated red phosphorus flame retardant taking melamine cyanurate and ZIF-8 as capsule wall materials. The composite coated red phosphorus flame retardant provided by the invention has the characteristics of high whiteness, good oxidation resistance and high flame retardant efficiency.
Description
Technical Field
The invention relates to the field of flame retardant materials, and particularly relates to a composite coated red phosphorus flame retardant and a preparation method thereof.
Background
Compared with other halogen-free flame retardants, the red phosphorus flame retardant has the advantages of high flame retardant efficiency, small using amount and the like, and is widely applied to the fields of rubber, nylon, polyester, epoxy resin, polyurethane and the like. However, pure red phosphorus has the defects of easy moisture absorption, unstable property, poor compatibility with high polymer materials, easy coloring and the like. After the red phosphorus is coated, the stability is improved, and the compatibility with a high polymer material is better. In addition, after the purple red of the red phosphorus is covered by the capsule material, the color and luster of the coated red phosphorus are relatively light, and the red phosphorus can be used for processing light-colored high polymer material products. Therefore, the coated red phosphorus serving as a flame retardant is added into a high polymer material, so that the defect of direct use of the red phosphorus can be overcome, and a considerable or even better flame retardant effect can be achieved.
At present, the mature red phosphorus coated product in the market is melamine resin coated red phosphorus, which takes melamine resin as a capsule wall material, has the characteristics of good oxidation resistance, low moisture absorption rate and good compatibility with high polymer materials, and is widely applied to processing of nylon, PET, PP and the like (pandeming, university of China and south, doctor thesis, 2004). However, melamine resin is transparent polymer resin, has poor covering property on red phosphorus color, has dark color, and cannot be used for processing light-colored polymer material products. In addition, the patent reports that the red phosphorus flame retardant coated by the zeolite imidazole ester framework material and the preparation method (CN 202011228743.6) thereof, and the ZIF-8 can be uniformly coated on the surface of the red phosphorus, so that the prepared ZIF-8 coated red phosphorus has better whiteness, oxidation resistance and flame retardant property. However, compared with common inorganic coating materials such as melamine resin, aluminum hydroxide and the like, the raw material cost of the ZIF-8 is high, and the large-scale application of the ZIF-8 coated red phosphorus is influenced. Therefore, the ZIF-8 and the cheap material are explored to clad the red phosphorus in a composite mode so as to reduce the production cost, further improve the whiteness and the flame retardant property of the red phosphorus flame retardant, and still have important significance for expanding the application range of the red phosphorus flame retardant.
Disclosure of Invention
The invention aims to provide a preparation method of a composite coated red phosphorus flame retardant, and the composite coated red phosphorus flame retardant obtained by the method has the advantages of high whiteness, good oxidation resistance, high flame retardant efficiency, lower cost and the like.
The invention provides a preparation method of a composite coated red phosphorus flame retardant, which comprises the following steps:
(1) dispersing red phosphorus and a dispersing agent in water, adding melamine and cyanuric acid, and reacting for 0.5-3 h;
(2) adding soluble zinc salt and 2-methylimidazole, reacting for 5-30 h, and dehydrating and drying the precipitate to obtain the composite coated red phosphorus flame retardant taking ZIF-8 and melamine cyanurate as capsule wall materials.
Further, the dispersing agent is sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether or polyvinylpyrrolidone, and the mass ratio of the dispersing agent to red phosphorus is 0.5-2: 100.
further, the reaction temperature is 60-100 ℃.
Further, the mass ratio of the melamine to the red phosphorus is 0.25-1: 1.
further, the molar ratio of the melamine to the cyanuric acid is 0.95-1.05: 1.
further, the zinc salt is zinc acetate, zinc nitrate, zinc chloride or zinc sulfate.
Further, Zn in the zinc salt 2+ The molar ratio of the melamine to the melamine is 0.5-2: 1.
further, Zn is contained in the zinc salt 2+ The molar ratio to 2-methylimidazole is 1: 3 to 9.
The invention also provides a composite coated red phosphorus flame retardant, which is prepared by a self-assembly method of red phosphorus, melamine, cyanuric acid, zinc salt and 2-methylimidazole, and is characterized in that the red phosphorus is compositely coated by melamine cyanurate and ZIF-8.
The preparation method provided by the invention has the advantages that the process is simple, the red phosphorus surface is coated by the melamine cyanurate, and then the ZIF-8 shell layer is self-assembled on the outer layer of the red phosphorus surface, the coating is uniform, the color covering performance is better, and the prepared composite coated red phosphorus flame retardant has the characteristics of high whiteness and good oxidation resistance, so that the composite coated red phosphorus flame retardant can be applied to processing of light-color high polymer materials.
The melamine cyanurate is a high-efficiency nitrogen-containing flame retardant with good color and luster covering property and low cost; ZIF-8 is a novel capsule wall material which can be continuously self-assembled on the surface of a solid, can be uniformly coated on the surface of the solid, and has better synergistic flame retardant property. The melamine cyanurate and the ZIF-8 are used as composite capsule materials for coating red phosphorus, and the advantages of the melamine cyanurate and the ZIF-8 can be effectively combined, so that the whiteness and the flame retardant property of the prepared melamine cyanurate and ZIF-8 composite coated red phosphorus are superior to those of melamine cyanurate or ZIF-8 single coated red phosphorus. The melamine cyanurate and the ZIF-8 are used as the composite capsule wall material for coating red phosphorus, and have good synergistic effect.
Detailed Description
The following provides a more detailed description of the present invention. The above and other objects, features and advantages of the present invention will be apparent to those skilled in the art from the detailed description of the present invention.
Example 1
Dispersing 17 g of red phosphorus and 0.17 g of sodium dodecyl benzene sulfonate in 360 mL of water, adding 8.5 g of melamine and 8.5 g of cyanuric acid, and stirring and reacting for 2 hours at 80 ℃; and adding 12 g of zinc acetate and 33 g of 2-methylimidazole, continuously stirring for reacting for 10 hours, and dehydrating and drying the precipitate obtained by the reaction to obtain the composite coated red phosphorus flame retardant taking melamine cyanurate and ZIF-8 as capsule walls, wherein the content of red phosphorus is 38%.
Example 2
Dispersing 17 g of red phosphorus and 0.1 g of sodium dodecyl sulfate in 300 mL of water, adding 4.5 g of melamine and 4.3 g of cyanuric acid, and reacting for 3 hours at 60 ℃ with stirring; and adding 12.5 g of zinc nitrate and 40 g of 2-methylimidazole, continuously stirring for reacting for 20 hours, and dehydrating and drying the precipitate obtained by the reaction to obtain the composite coated red phosphorus flame retardant taking melamine cyanurate and ZIF-8 as capsule wall materials, wherein the content of red phosphorus is 45%.
Example 3
Dispersing 17 g of red phosphorus and 0.3 g of polyvinylpyrrolidone in 500 mL of water, adding 17 g of melamine and 17.5 g of cyanuric acid, and reacting for 0.5 h at 95 ℃ with stirring; and adding 11 g of zinc sulfate and 25 g of 2-methylimidazole, continuously stirring for reacting for 6 hours, and dehydrating and drying precipitates obtained by the reaction to obtain the composite coated red phosphorus flame retardant taking melamine cyanurate and ZIF-8 as capsule wall materials, wherein the content of red phosphorus is 26%.
Comparative example 1
Dispersing 17 g of red phosphorus and 0.17 g of sodium dodecyl benzene sulfonate in 360 mL of water, adding 13.5 g of melamine and 13.5 g of cyanuric acid, stirring and reacting at 80 ℃ for 12 h, dehydrating and drying precipitates obtained by the reaction to obtain the single-coated red phosphorus flame retardant taking melamine cyanurate as a capsule wall material, wherein the content of red phosphorus is 38%.
Comparative example 2
Dispersing 17 g of red phosphorus and 0.17 g of sodium dodecyl benzene sulfonate in 360 mL of water, adding 27.5 g of zinc acetate and 75 g of 2-methylimidazole, stirring at 80 ℃ for reaction for 12 hours, dehydrating and drying a precipitate obtained by the reaction to obtain the single-coated red phosphorus flame retardant taking ZIF-8 as a capsule wall material, wherein the content of red phosphorus is 38%.
Performance test experiments:
the composite coated red phosphorus samples prepared in examples 1 to 3, the melamine cyanurate coated red phosphorus prepared in comparative example 1, and the ZIF-8 coated red phosphorus sample prepared in comparative example 2 were subjected to the following tests:
and (3) whiteness testing: weighing 10.00 g of sample, tabletting, placing in a sample box, and testing on a digital display whiteness instrument, wherein the results are shown in table 1;
and (3) oxidation resistance test: respectively weighing 10.00 g of sample in a three-neck flask containing 200 ml of distilled water, boiling the solution for 1 hour, filtering, removing initial filtrate, adding 10.00 g of analytically pure sodium chloride into 100 ml of the filtrate, titrating oxyacid formed by oxidation in the filtrate by using a standard sodium hydroxide solution after dissolution, and expressing the oxidation resistance of oxyacid by the milligrams of sodium hydroxide consumed by each gram of red phosphorus, wherein the results are shown in table 1;
limiting oxygen index test: the test was carried out according to the method of GB/T2406.2-2009, and the addition amount of the coated red phosphorus flame retardant was 8%, and the results are shown in Table 1.
From the test results of examples 1 to 3 in table 1, it can be seen that the melamine cyanurate and ZIF-8 composite coated red phosphorus flame retardant has high whiteness and flame retardant efficiency, and has good oxidation resistance. According to the test results of the example 1, the comparative example 1 and the comparative example 2, the flame retardant performance and the whiteness of the melamine cyanurate and the ZIF-8 composite coated red phosphorus are better than those of the melamine cyanurate or the ZIF-8 single coated red phosphorus. The results show that the melamine cyanurate and the ZIF-8 are used as the composite capsule wall material for coating red phosphorus, so that the advantages of the melamine cyanurate and the ZIF-8 can be effectively combined, and a good synergistic effect is achieved.
It should be understood that although the present invention has been clearly illustrated by the foregoing examples, various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention, and it is intended to cover all such changes and modifications as fall within the scope of the appended claims.
Claims (9)
1. The preparation method of the composite coated red phosphorus flame retardant is characterized by comprising the following steps:
(1) dispersing red phosphorus and a dispersing agent in water, adding melamine and cyanuric acid, and reacting for 0.5-3 h;
(2) adding soluble zinc salt and 2-methylimidazole, reacting for 5-30 h, and dehydrating and drying the precipitate to obtain the composite coated red phosphorus flame retardant taking melamine cyanurate and ZIF-8 as capsule wall materials.
2. The preparation method of the composite coated red phosphorus flame retardant of claim 1, wherein the dispersing agent is sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether or polyvinylpyrrolidone, and the mass ratio of the dispersing agent to red phosphorus is 0.5-2: 100.
3. the preparation method of the composite coated red phosphorus flame retardant of claim 1, wherein the reaction temperature is 60-100 ℃.
4. The preparation method of the composite coated red phosphorus flame retardant according to claim 1, wherein the mass ratio of melamine to red phosphorus is 0.25-1: 1.
5. the preparation method of the composite coated red phosphorus flame retardant of claim 1, wherein the molar ratio of melamine to cyanuric acid is 0.95-1.05: 1.
6. the method for preparing the composite coated red phosphorus flame retardant of claim 1, wherein the zinc salt is zinc acetate, zinc nitrate, zinc chloride or zinc sulfate.
7. The method for preparing the composite coated red phosphorus flame retardant of claim 1, wherein Zn is contained in the zinc salt 2 + With melamineThe ratio is 0.5-2: 1.
8. the method for preparing the composite coated red phosphorus flame retardant of claim 1, wherein Zn is contained in the zinc salt 2 + The molar ratio to 2-methylimidazole is 1: 3 to 9.
9. A composite coated red phosphorus flame retardant prepared by the method of any one of claims 1 to 8, wherein the red phosphorus is compositely coated with melamine cyanurate and ZIF-8.
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Citations (8)
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|---|---|---|---|---|
| US4879067A (en) * | 1986-06-19 | 1989-11-07 | Rinkagaku Kogyo Co., Ltd. | Red phosphorus flame retardant and nonflammable resinous composition containing the same |
| CN1429251A (en) * | 2000-05-25 | 2003-07-09 | 日本化学工业株式会社 | Red phosphorus fire retardant for epoxy, red phosphorus fire retardant composition for epoxy, their mfg. method, epoxy composition for semiconductor sealing materials |
| CN1515615A (en) * | 2003-08-26 | 2004-07-28 | 四川大学 | Molecular composite trimeric cyanamide cyanurate fire retarder and its preparation method and application |
| CN1632057A (en) * | 2004-11-09 | 2005-06-29 | 四川大学 | Melamine cyanuric acid red phosphorous-based microcapsule and its preparation method and use |
| TWI292422B (en) * | 2000-12-18 | 2008-01-11 | Nippon Chemical Ind | |
| CN103665864A (en) * | 2012-09-21 | 2014-03-26 | 腾辉电子（苏州）有限公司 | Glue solution for copper-clad laminate and preparation method thereof |
| CN112409641A (en) * | 2020-11-06 | 2021-02-26 | 邵阳市富森阻燃材料有限公司 | Zeolite imidazole ester framework material coated red phosphorus flame retardant and preparation method thereof |
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-
2022
- 2022-07-07 CN CN202210796182.2A patent/CN114940781A/en active Pending
Patent Citations (8)
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|---|---|---|---|---|
| US4879067A (en) * | 1986-06-19 | 1989-11-07 | Rinkagaku Kogyo Co., Ltd. | Red phosphorus flame retardant and nonflammable resinous composition containing the same |
| CN1429251A (en) * | 2000-05-25 | 2003-07-09 | 日本化学工业株式会社 | Red phosphorus fire retardant for epoxy, red phosphorus fire retardant composition for epoxy, their mfg. method, epoxy composition for semiconductor sealing materials |
| TWI292422B (en) * | 2000-12-18 | 2008-01-11 | Nippon Chemical Ind | |
| CN1515615A (en) * | 2003-08-26 | 2004-07-28 | 四川大学 | Molecular composite trimeric cyanamide cyanurate fire retarder and its preparation method and application |
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| CN103665864A (en) * | 2012-09-21 | 2014-03-26 | 腾辉电子（苏州）有限公司 | Glue solution for copper-clad laminate and preparation method thereof |
| CN112409641A (en) * | 2020-11-06 | 2021-02-26 | 邵阳市富森阻燃材料有限公司 | Zeolite imidazole ester framework material coated red phosphorus flame retardant and preparation method thereof |
| CN114479286A (en) * | 2021-12-28 | 2022-05-13 | 武汉金发科技有限公司 | Low-smoke halogen-free flame-retardant polypropylene composition and preparation method and application thereof |
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