CN101195749A - Novel La/ZSM-5 modified phosphor nitrogen series flame-proof material - Google Patents
Novel La/ZSM-5 modified phosphor nitrogen series flame-proof material Download PDFInfo
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- CN101195749A CN101195749A CNA2007101735857A CN200710173585A CN101195749A CN 101195749 A CN101195749 A CN 101195749A CN A2007101735857 A CNA2007101735857 A CN A2007101735857A CN 200710173585 A CN200710173585 A CN 200710173585A CN 101195749 A CN101195749 A CN 101195749A
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Abstract
The invention discloses novel La/ZSM-5 modified phosphorus-nitrogen flame retardant material, which is characterized in that the invention is composed of phosphorus-nitrogen intumescent flame retardant, a lanthana-loaded molecular sieve, and flame retardant organic polymer. The invention adopts the lanthana-loaded molecular sieve and the phosphorus-nitrogen intumescent flame retardant which are combined to be used, to ensure the decomposition temperature of the flame retardant organic polymer of the phosphorus-nitrogen intumescent flame retardant to be enhanced, thereby the stability is improved, and simultaneously the flame retardant performance can be also improved to a large extent.
Description
Technical field
The present invention relates to the method that a kind of heat resistanceheat resistant of organic fire-resisting material of La/ZSM-5 modification is decomposed, 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 lanthanum oxide-carrying and fire-retardant organic polymer thereof, and the weight ratio of the molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and lanthanum oxide-carrying is 20～100: 0.1～10; Preferred mass ratio is 0.5～1.5: 20;
The molecular sieve content of lanthanum oxide-carrying can not contact fully with fire retardant very little; The molecular sieve content of lanthanum oxide-carrying 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 lanthanum oxide-carrying 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 lanthanum oxide-carrying 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 lanthanum oxide-carrying 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 lanthanum trioxide amount is 0.1～10wt% in the molecular sieve in the molecular sieve of said lanthanum oxide-carrying, 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 lanthanum oxide-carrying, 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 0.31M of 100mL LaNO
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 lanthanum trioxide 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%La of 0.5g
2O
3-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%La
2O
3When 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 33% and 35%, did not add 5%La
2O
3The 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%La
2O
3-ZSM-5 molecular sieve content can improve thermostability and the flame retardant properties of fire-retardant PP.
The 5%La of table 1 different content
2O
3-ZSM-5 molecular sieve is to the thermal weight loss of fire-retardant PP and the influence of flame retardant properties
| 5％La 2O 3-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 | 414 470 | 415 474 | 416 475 | 419 479 | 422 481 |
| Limiting oxygen index(LOI) (%) | 28 | 33 | 35 | 35 | 33 | 33 |
Embodiment 2
Press the prepared 5%La of example 1 method
2O
3-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%La of table 2 different content
2O
3-ZSM-5 molecular sieve is to the thermal weight loss of fire-retardant PP and the influence of flame retardant properties
| 5％La 2O 3-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 | 392 31 | 398 32 | 400 32 | 416 31 | 420 30 |
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 phosphorus-nitrogen series anti-flaming material of a novel La/ZSM-5 modification is made of the molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and lanthanum oxide-carrying 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 lanthanum oxide-carrying is: 20～100: 0.1～10; The molecular sieve of phosphorus nitrogen expansion type combustion inhibitor and lanthanum oxide-carrying 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 lanthanum oxide-carrying, 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 lanthanum oxide-carrying, said lanthanum trioxide 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 lanthanum oxide-carrying, the mode of loading of lanthanum trioxide are the method that molecular sieve floods in the salts solution of lanthanum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101735857A CN101195749A (en) | 2007-12-28 | 2007-12-28 | Novel La/ZSM-5 modified phosphor nitrogen series flame-proof material |
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| CNA2007101735857A CN101195749A (en) | 2007-12-28 | 2007-12-28 | Novel La/ZSM-5 modified phosphor nitrogen series flame-proof material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475706B (en) * | 2009-01-22 | 2011-06-08 | 广东华南精细化工研究院有限公司 | Rear earth organic phosphonate flame retardant, synthesizing method and use thereof |
| CN112850740A (en) * | 2021-02-23 | 2021-05-28 | 浙江浙能技术研究院有限公司 | Synthesis method of sheet MFI topological structure molecular sieve |
-
2007
- 2007-12-28 CN CNA2007101735857A patent/CN101195749A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475706B (en) * | 2009-01-22 | 2011-06-08 | 广东华南精细化工研究院有限公司 | Rear earth organic phosphonate flame retardant, synthesizing method and use thereof |
| CN112850740A (en) * | 2021-02-23 | 2021-05-28 | 浙江浙能技术研究院有限公司 | Synthesis method of sheet MFI topological structure molecular sieve |
| CN112850740B (en) * | 2021-02-23 | 2022-03-08 | 浙江浙能技术研究院有限公司 | Synthesis method of sheet MFI topological structure molecular sieve |
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Open date: 20080611 |