CN101230275A - High thermal-stability bittern-free phosphorous-nitrogen system flame-proof material - Google Patents
High thermal-stability bittern-free phosphorous-nitrogen system flame-proof material Download PDFInfo
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- CN101230275A CN101230275A CNA2007101735838A CN200710173583A CN101230275A CN 101230275 A CN101230275 A CN 101230275A CN A2007101735838 A CNA2007101735838 A CN A2007101735838A CN 200710173583 A CN200710173583 A CN 200710173583A CN 101230275 A CN101230275 A CN 101230275A
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- molecular sieve
- cerium oxide
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Abstract
The invention discloses a high thermal-stability halogen-free phosphorus nitrogen system flame retarding material, which is characterized in that the material is formed by phosphorus nitrogen expansion type flame retardant, the molecular sieve carrying cerium oxide, and the flame retarding organic polymer. The invention adopts compatibility usage of the molecular sieve carrying cerium oxide and the phosphorus nitrogen expansion type flame retardant, increases the decomposition temperature of the flame retarding organic polymer of the phosphorus nitrogen expansion type flame retardant, and then improves the stability of the flame retarding organic polymer, and improves the flame retarding performance to a great degree.
Description
Technical field
The present invention relates to a kind of method of heat resistanceheat resistant decomposition of organic fire-resisting material, relate in particular to the phosphorus nitrogen series expansion type anti-flaming material.
Background technology
Phosphorus nitrogen series expansion type anti-flaming material (IFR) is a main component with phosphorus, nitrogen, and is not halogen-containing, and it is as a kind of novel flame redundant material that grows up on the basis of anti-flaming dope, is the disclosed fire retardant material of CN 1446844A as publication number.When the poly-material of height that contains IFR was heated burning, the surface generated one deck carbonaceous foam layer, can be heat insulation, oxygen barrier, press down cigarette, and can prevent the molten drop behavior, long-time or repeated exposure are had good resistivity in flame.
IFR is a kind of very rising BACN, more and more is subject to people's attention.As tetramethylolmethane kind phosphate ester, dipentaerythritol phosphoric acid ester and tripentaerythritol phosphoric acid ester, Pentaerythritols phosphorous acid ester and corresponding melamine salt thereof etc.
But described IFR exists and is easy to the thermolysis defective, is used for polyolefinic fire-retardantly, directly influences thermostability, use properties and the processing characteristics of material.Therefore, how improving the thermostability to described material, prepare nanometer organic double compound etc. as adding laminated clay, is the very problem of concern of relevant personnel institute.
Summary of the invention
The technical issues that need to address of the present invention are the phosphorus nitrogen series expansion type anti-flaming materials that disclose a kind of high thermal stability, to overcome defective in the prior art.
The phosphorus nitrogen series expansion type anti-flaming material of high thermal stability of the present invention is made of the molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and load cerium oxide and fire-retardant organic polymer thereof, and the weight ratio of the molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and load cerium oxide is 20～100: 0.1～10; Preferred mass ratio is 0.5～1.5: 20;
The molecular sieve content of load cerium oxide can not contact fully with fire retardant very little; The molecular sieve content of load cerium oxide is too many, and the cost of fire retardant rises, and the performance of fire retardant changes.
Said organic polymer can be polypropylene (PP), polyethylene (PE), ethylene vinyl acetate copolymer.The molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and load cerium oxide and the ratio of organic polymer are: 10～30: 50～100, and preferential mass ratio is 15～20: 80～100.The molecular sieve content of phosphorus nitrogen expansion type combustion inhibitor and load cerium oxide is too high, influences the mechanical property and the processing characteristics of organic polymer; Content is too low, and flame retardant properties descends.
Said phosphorus nitrogen expansion type combustion inhibitor can be that its structure is at the dipentaerythritol phosphate ester melamine salt of the open method preparation of Chinese invention patent CN 1446844A:
Said phosphorus nitrogen expansion type combustion inhibitor also can be commercially available polyphosphoric acid by (APP) or trimeric cyanamide phosphoric acid ester (MPP) compound system with tetramethylolmethane.
The preparation method of the molecular sieve of said load cerium oxide adopts usually said pickling process.Wherein molecular sieve is the ZSM-5 of Hydrogen, and the Si/Al ratio is 20～100, and preferred Si/Al ratio is 35～80.Si/Al is than too little, and the acid amount is too big, causes the decomposition of organic polymer.
The cerium oxide amount is 0.1～10wt% in the molecular sieve in the molecular sieve of said load cerium oxide, and preferred charge capacity is 3～5%.
The present invention is to the phosphorus nitrogen series expansion type anti-flaming material, compound system as many tetramethylolmethanes kind phosphate ester melamine salt or polyphosphoric acid amine (APP) or trimeric cyanamide phosphoric acid ester (MPP) and tetramethylolmethane, adopt molecular sieve compatibility use with the load cerium oxide, the decomposition temperature of phosphorus nitrogen series expansion type anti-flaming material is improved greatly, its flame retardant properties also greatly improves, thereby improved the thermostability of phosphorus nitrogen series expansion type anti-flaming material in organic polymer, what obtain is fire-retardant organic poly-good with the thing thermal stability, the flame retardant resistance height, low cigarette, nontoxic, non-corrosiveness, environmentally friendly.
Embodiment
Embodiment 1
At the 0.35MCe of 100mL (NO
3)
3In the aqueous solution, add 95g ZSM-5 molecular sieve (Si/Al=38) and carry out incipient impregnation, stir 1h, place 24h in air at room temperature, at 110 ℃ of dry 12h, 550 ℃ of roasting 4h in retort furnace again.The charge capacity that obtains cerium oxide through atomic absorption spectrochemical analysis is 5%.
By the prepared dipentaerythritol phosphate ester melamine salt powder of the method for mentioning among the Chinese invention patent CN 1446844A (particle mean size is 10 μ m) 25g, 26g, 26.5g, 27g, 27.5g respectively with 3g, 2g, 1.5g, 1g, the above-mentioned prepared 5%CeO of 0.5g
2-ZSM-5 molecular sieve mixes, and this mixture and 80g polypropylene are joined in the twin-roll plastic mixing mill, and 185 ℃ of mixing 10min mix it, 185 ℃ of shaped by fluid pressures on vulcanizer, and omnipotent sampling machine sample preparation, sample size is 100 * 100 * 3mm.Adopt oxygen index instrument JF-3,, measure the flame retardant properties of material according to the ASTME-1354 standard.Test its thermal weight loss simultaneously, test result is seen accompanying drawing 1.Work as 5%CeO
2When the content of-ZSM-5 molecular sieve was 0.5wt% and 1wt%, the limiting oxygen index(LOI) of fire-retardant PP increased, and was respectively 32% and 34%, did not add 5%CeO
2The limiting oxygen index(LOI) of fire-retardant PP is 28% during-ZSM-5 molecular sieve.The thermogravimetric data are summarised in table 1, as can be seen, and suitable 5%CeO
2-ZSM-5 molecular sieve content can improve thermostability and the flame retardant properties of fire-retardant PP.
The 5%CeO of table 1 different content
2-ZSM-5 molecular sieve is to the thermal weight loss of fire-retardant PP and the influence of flame retardant properties
| 5％CeO 2-ZSM-5 molecular sieve content (%) | 0 | 0.5 | 1.0 | 1.5 | 2.0 | 3.0 |
| 20% weightless temperature (℃) weightless temperature of (nitrogen) 80% (℃) (nitrogen) | 356 439 | 416 477 | 417 478 | 41 8 479 | 420 480 | 422 482 |
| Limiting oxygen index(LOI) (%) | 28 | 32 | 34 | 34 | 33 | 33 |
Embodiment 2
Press the prepared 5%CeO of example 1 method
2-ZSM-5 molecular sieve (Si/Al=50) 3g, 2g, 1.5g, 1g, 0.5g mix with the mixture (polyphosphoric acid amine and tetramethylolmethane ratio are 2: 1 weight ratios) of 25g, 26g, 26.5g, 27g, 27.5g polyphosphoric acid amine and tetramethylolmethane respectively, and this mixture and 80g polypropylene are joined in the twin-roll plastic mixing mill.Press the method sample preparation of embodiment 1, test its thermal weight loss and flame retardant properties, the results are shown in Table 2.
The 5%CeO of table 2 different content
2-ZSM-5 molecular sieve is to the thermal weight loss of fire-retardant PP and the influence of flame retardant properties
| 5％CeO 2-ZSM-5 molecular sieve content (%) | 0 | 0.5 | 1.0 | 1.5 | 2.0 | 3.0 |
| 20% weightless temperature (℃) (nitrogen) limiting oxygen index(LOI) (%) | 385 28 | 395 32 | 400 33 | 410 33 | 430 34 | 430 33 |
Embodiment 3
Si/Al is mixed with the mixture (melamine phosphate and tetramethylolmethane ratio are 2: 1 weight ratios) of 25g, 26g, 26.5g, 27g, 27.5g melamine phosphate and tetramethylolmethane respectively, and this mixture and 80g polypropylene are joined in the twin-roll plastic mixing mill than ZSM-5 molecular sieve (Si/Al=80) 3g, 2g, 1.5g, 1g, the 0.5g that are 80.Press the method sample preparation of embodiment 1, test its thermal weight loss, the results are shown in accompanying drawing 2 and table 3.The ZSM-5 of different content no matter be nitrogen atmosphere or oxygen atmosphere, can make the fire-retardant PP material thermostability of mixture of melamine phosphate and tetramethylolmethane be greatly improved as can be seen.From limiting oxygen index(LOI) as can be seen, the adding of ZSM-5 molecular sieve, flame retardant properties slightly descends with the increase of add-on.
Table 3 ZSM-5 molecular sieve (Si/Al=80) addition is to the influence of fire retardant material PP heat decomposition temperature in nitrogen atmosphere
| Weightless (%) | Weightless temperature (℃) |
| Fire-retardant PP | The content of molecular sieve in fire-retardant PP | |||||
| 0.5 | 1.0 | 1.5 | 2.0 | 3.0 | ||
| 5 | 315 | 325 | 331 | 341 | 350 | 395 |
| 10 | 365 | 356 | 384 | 410 | 425 | 446 |
| 20 | 385 | 422 | 442 | 454 | 454 | 465 |
| 30 | 390 | 451 | 454 | 459 | 463 | 469 |
| 70 | 425 | 472 | 471 | 472 | 473 | 476 |
| Limiting oxygen index(LOI) (%) | 28 | 29 | 30 | 31 | 30 | 29 |
Claims (5)
1. the bittern-free phosphorous-nitrogen system flame-proof material of a high thermal stability is made of the molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and load cerium oxide and fire-retardant organic polymer thereof.
Said phosphorus nitrogen expansion type combustion inhibitor, can be in Chinese invention patent CN 1446844A, invented as tetramethylolmethane kind phosphate ester, dipentaerythritol phosphoric acid ester and tripentaerythritol phosphoric acid ester, Pentaerythritols phosphorous acid ester and corresponding melamine salt thereof, also can be commercially available polyphosphoric acid by (APP) or trimeric cyanamide phosphoric acid ester (MPP) compound system with tetramethylolmethane;
Said fire-retardant organic polymer can be polypropylene (PP), polyethylene (PE), ethylene vinyl acetate copolymer.
2. the weight ratio of the molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and load cerium oxide is: 20～100: 0.1～10; The molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and load cerium oxide and the ratio of organic polymer are: 10～30: 50～100.
3. the phosphorus nitrogen series expansion type anti-flaming material of high thermal stability according to claim 1 is characterized in that, the molecular sieve of load cerium oxide, said molecular sieve are Hydrogen ZSM-5, and the Si/Al ratio is 20～100, and preferred Si/Al ratio is 35～80.
4. the phosphorus nitrogen series expansion type anti-flaming material of high thermal stability according to claim 1 is characterized in that, the molecular sieve of load cerium oxide, said cerium oxide content in molecular sieve is 0.1～10wt%, and preferred charge capacity is 3～5wt%.
5. the phosphorus nitrogen series expansion type anti-flaming material of high thermal stability according to claim 1 is characterized in that, the molecular sieve of load cerium oxide, the mode of loading of cerium oxide are the method that molecular sieve floods in the salts solution of cerium.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101735838A CN101230275A (en) | 2007-12-28 | 2007-12-28 | High thermal-stability bittern-free phosphorous-nitrogen system flame-proof material |
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| CNA2007101735838A CN101230275A (en) | 2007-12-28 | 2007-12-28 | High thermal-stability bittern-free phosphorous-nitrogen system flame-proof material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964376A (en) * | 2012-11-29 | 2013-03-13 | 石家庄启宏橡塑制品有限公司 | Preparation method and application of halogen-free environment-friendly flame retardant |
| CN107163474A (en) * | 2017-06-01 | 2017-09-15 | 苏州蔻美新材料有限公司 | A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant |
| CN107501493A (en) * | 2017-08-10 | 2017-12-22 | 长春工业大学 | Phosphorus nitrogen expansion type combustion inhibitor and its production and use |
-
2007
- 2007-12-28 CN CNA2007101735838A patent/CN101230275A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964376A (en) * | 2012-11-29 | 2013-03-13 | 石家庄启宏橡塑制品有限公司 | Preparation method and application of halogen-free environment-friendly flame retardant |
| CN107163474A (en) * | 2017-06-01 | 2017-09-15 | 苏州蔻美新材料有限公司 | A kind of preparation method and applications of low smoke and zero halogen nitrogen phosphorus composite fire retardant |
| CN107501493A (en) * | 2017-08-10 | 2017-12-22 | 长春工业大学 | Phosphorus nitrogen expansion type combustion inhibitor and its production and use |
| CN107501493B (en) * | 2017-08-10 | 2019-06-07 | 长春工业大学 | Phosphorus nitrogen expansion type combustion inhibitor and its preparation method and application |
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Open date: 20080730 |