CN101139454B - Non-bittern swelling flame-proof polypropylene containing porous nickel phosphate and preparation method thereof - Google Patents
Non-bittern swelling flame-proof polypropylene containing porous nickel phosphate and preparation method thereof Download PDFInfo
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- CN101139454B CN101139454B CN2007100260973A CN200710026097A CN101139454B CN 101139454 B CN101139454 B CN 101139454B CN 2007100260973 A CN2007100260973 A CN 2007100260973A CN 200710026097 A CN200710026097 A CN 200710026097A CN 101139454 B CN101139454 B CN 101139454B
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Abstract
The invention provides a halogen-free expanding flame-retarded polypropylene containing porous nickel phosphate and a preparing way for the polypropylene, which is characterized in that, the invention contains expanding fire retardant complexed by tetramethylolmethane: ammonium polyphosphate by mass 5.3 swung dash 8.2%:10.7 swung dash 16.3% or tetramethylolmethane: melamine ammonium polyphosphateby mass 5.3 swung dash 8.2%:10.7 swung dash 16.3%, also contains porous nickel phosphate. The total mass of each component is: polypropylene 75-80%, complexed expanding fire retardant 16-24.5%, porous nickel phosphate 0.5-4%, which is a porous structure in hole diameter 8-13. As containing porous nickel phosphate, the expanding fire retardant can greatly reduce the addition of the expanding fireretardant, and reduce the influence from the expanding fire retardant on the mechanical properties such as tensile and fracture strength, etc. of materials, improve obviously the fire resistance of polypropylene, solve the molten drop of polypropylene when it is burning; and the production and the use of the polypropylene are very convenient.
Description
Technical field:
The invention belongs to halogen-free expansion type flame-proof polypropylene technology field, particularly contain polypropylene of expansion type flame retardant and porous calcium phosphate nickel and preparation method thereof simultaneously.
Background technology:
According to " modified polypropene novel material " (Zhao Min, high pretty firm etc. writing, chemistry press, in September, 2002) introduce, itself belongs to inflammable material polypropylene, its oxygen index only 17.0～18.0%, and charring rate is low, produces molten drop during burning, so all require to carry out flame-retardant modified to it in a lot of application scenarios.Polypropylene fire retardant is mainly adopted the interpolation fire retardant both at home and abroad at present.According to " applied surface science " (Applied Surface Science, 120:14,1997) and " combustion science " (J Fire Flam 2:97,1971) introduce, with and can be used in the Halogen additive flame retardant of polypropylene flame redardant, be expansion type flame retardant with what have future in engineering applications most for the people is good.Expansion type flame retardant is phosphorous, organic compounds containing nitrogen mostly, mainly plays fire retardation by forming porous foam charcoal layer at condensed phase.Usually adopt synergist such as zinc borate, zeolite and organo montmorillonite etc. and expansion type flame retardant synergistic polypropylene flame redardant at present.According to " advanced polymer processing technology " (Polymers For Advanced Technologies 14:3-11,2003) introduce, when zinc borate accounts for system total mass per-cent is 2% and expansion type flame retardant when accounting for system total mass per-cent and being 25%, the oxygen index of the polypropylene flame redardant that makes is than high 5 units of oxygen index that add the polypropylene flame redardant that 25% expansion type flame retardant makes separately, even but the polypropylene flame redardant that expansion type flame retardant and zinc borate synergistic system make still can't pass UL-94 V0 rank." polymer degradation is with stable " (Polymer Degradation and Stability 89:478-483,2005) introduced zeolite synergistic polypropylene flame redardant, the oxygen index that accounts for the polypropylene flame redardant that makes when system total mass 5% and expansion type flame retardant account for system total mass 25% when zeolite is than high 7 units of oxygen index that add the polypropylene flame redardant that 30% expansion type flame retardant makes separately, but because the total addition level of fire retardant and synergist is bigger, make the mechanical property such as the tensile strength of material, breaking tenacity descends.According to " polymer science magazine " (Journal of Polymer Science:part A:Ploymer chemistry 42:6163-6173,2004) introduce, organo montmorillonite and expansion type flame retardant synergistic polypropylene flame redardant can obviously reduce heat release rate, but the organo montmorillonite addition was above 4% o'clock, can agglomerated aggravate, flame retardant effect descends on the contrary.
With expansion type flame retardant or expansion type flame retardant and synergist such as zinc borate, polypropylene after zeolite and organo montmorillonite etc. are handled, though have characteristics such as LSZH and certain anti-molten, but flame retardant effect is still not ideal enough, anti-molten property is still waiting to improve, and because the addition of required fire retardant is bigger, can make the mechanical property such as the tensile strength of material, breaking tenacity descends.
Introduce according to " American Chemical Society's magazine " (J.Am.Chem.Soc.125:1309,2003), porous calcium phosphate nickel is the good molecular screen material of a class, contains NiO
6Octahedron and PO
4Tetrahedroid becomes skeleton structure, has 24 membered ring channel structures, and the aperture is
Its stability better, and nickel itself is exactly good catalyzer, the researchist mainly notes its application prospect aspect absorption, ion-exchange especially catalysis at present, but porous calcium phosphate nickel does not appear in the newspapers so far in the research aspect fire-retardant.
Summary of the invention:
The purpose of this invention is to provide a kind of halogen-free expansion type flame-proof polypropylene that contains porous calcium phosphate nickel and preparation method thereof, the addition and the anti-molten property that can reduce fire retardant when guaranteeing flame retardant effect are good.
The halogen-free expansion type flame-proof polypropylene that contains porous calcium phosphate nickel of the present invention is characterized in that each component by accounting for system total mass percentage score is not: polypropylene 75～80%, expansion type flame retardant 16～24.5%, porous calcium phosphate nickel 0.5～4%; This porous calcium phosphate nickel has the aperture
Pore passage structure.
The polyacrylic preparation method of halogen-free expansion type flame-proof who contains porous calcium phosphate nickel of the present invention, elder generation is NiCl in molar ratio
26H
2O: H
3PO
4: NH
4F: NH
4OH: H
2O was dissolved in six water nickelous chlorides in the water in 1.0: 1.0～1.5: 1.0～1.6: 0.8～1.0: 40.0, stir and add phosphoric acid and Neutral ammonium fluoride down successively, transferring the pH value of system with ammoniacal liquor again is 1.8～2.5, then mixture is sealed in the reactor, 160～190 ℃ of crystallization 3～7 days; Product takes out after-filtration, washes after drying with water, promptly obtains porous calcium phosphate nickel; It is characterized in that: polypropylene 75～80%, expansion type flame retardant 16～24.5% and the above-mentioned porous calcium phosphate nickel 0.5～4% that makes are put into Banbury mixer by accounting for system total mass per-cent, controlled temperature is at 160～190 ℃, rotating speed is 20～100 rev/mins, melt blending 5～30 minutes.
Expansion type flame retardant in above-mentioned halogen-free expansion type flame-proof polypropylene that contains porous calcium phosphate nickel and preparation method thereof is by mass percentage by tetramethylolmethane (I): ammonium polyphosphate (II) is by 5.3～8.2%: 10.7～16.3%; Or by tetramethylolmethane (I): trimeric cyanamide ammonium polyphosphate (III) is by 5.3～8.2%: 10.7～16.3% composite forming;
N 〉=30 wherein, m 〉=40.
When not adding porous calcium phosphate nickel, by accounting for system total mass per-cent, the polypropylene flame redardant when containing 25% expansion type flame retardant just can reach UL-94 V0 rank; And the halogen-free expansion type flame-proof polypropylene that contains porous calcium phosphate nickel of the present invention, owing to also contain porous calcium phosphate nickel in the system, polypropylene flame redardant when containing 16% expansion type flame retardant just can reach the UL-94V0 rank, has overcome shortcomings such as the big and flame retarding efficiency of existing polypropylene flame redardant fire retardant addition is low; With the expansion type flame-retarding agent content is 18% to be that 2% synergistic flame-retarded technology, expansion type flame-retarding agent content are 18% be 2% synergistic flame-retarded technology with the expansion type flame-retarding agent content with zinc borate content to be 18% to be that 2% synergistic flame-retarded technology is compared with polynite content with zeolite content, and the halogen-free expansion type flame-proof polypropylene that only contains 2% porous calcium phosphate nickel and 18% expansion type flame retardant reaches UL-94 V-0 rank; Adopt porous calcium phosphate nickel and expansion type flame retardant synergistic polypropylene flame redardant not only to improve the oxygen index flame retardant properties of polypropylene material greatly, also obviously improved the vertical combustion that embodies dripping property of refractory, production and use are all very convenient.
Description of drawings:
Fig. 1 is at the X-ray diffractogram of the porous calcium phosphate nickel of 180 ℃ of crystallization 144 hours preparation among the embodiment 1;
Fig. 2 is the high-resolution electron microscopy figure of the porous calcium phosphate nickel of 180 ℃ of crystallization preparation in 144 hours.
Fig. 3 is at the X-ray diffractogram of the porous calcium phosphate nickel of 160 ℃ of crystallization 72 hours preparation among the embodiment 2.
Fig. 4 is at the high-resolution electron microscopy figure of the porous calcium phosphate nickel of 190 ℃ of crystallization 168 hours preparation among the embodiment 3.
Embodiment:
Further specify the present invention with embodiment below.
Embodiment 1:
Earlier by " micropore and mesopore material " (Microporous and Mesoporous Materials; 85 (3): 355-364,2005) method of being introduced prepares synthesizing porous nickelous phosphate: in being dissolved in the 106.5g Nickel dichloride hexahydrate in the 314ml deionized water, under agitation dropwise add 55.56g ortho-phosphoric acid; Add Neutral ammonium fluoride 16.68g then; Splash into ammoniacal liquor at last and regulate pH value to 2.5, stir after 0.5 hour, in the stainless steel synthesis reactor with this mixture immigration capacity teflon lined that is 500ml, it is 70% of synthesis reactor volume that mixture adds charge.180 ℃ and autogenous pressure lower seal crystallization 144 hours; Resulting yellow-green colour solid matter with deionized water washing 3 times earlier at air drying, is dried under 100 ℃ of conditions again, promptly obtains product porous calcium phosphate nickel, and is standby.
Above-mentioned products therefrom porous calcium phosphate nickel is carried out X-ray diffraction analysis and high-resolution electron microscopy analysis.Fig. 1 is at the diffractogram of the X ray of the porous calcium phosphate nickel of 180 ℃ of crystallization 144 hours preparation in the present embodiment, Fig. 2 is this porous calcium phosphate nickel high-resolution electron microscopy figure, with " American Chemical Society's magazine " (J.Am.Chem.Soc 125:1309,2003) and " micropore and mesopore material " (Microporous and Mesoporous Materials; 85 (3): 355-364,2005) X-ray diffractogram, the high resolution collection of illustrative plates unanimity of the porous calcium phosphate nickel of report in.This porous calcium phosphate nickel has pore passage structure, and the aperture is
The above-mentioned porous calcium phosphate nickel that will account for system total mass 2% by mass ratio with account for 75% polypropylene, 7.7% tetramethylolmethane and 15.3% ammonium polyphosphate and add in the Banbury mixer, melt blending is 10 minutes under 180 ℃ and 100 rev/mins of conditions of rotating speed, promptly obtains containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel.
With the dry rear fender of polypropylene flame redardant, cut into the standard batten of 130X13X3mm and 130X6.5X3mm, carry out the test of UL-94 vertical combustion by the test on CZF-3 type horizontal vertical burning determinator of ASTM D635-77 standard, its vertical combustion can reach UL-94 V-0 rank; Limiting oxygen index(LOI) is tested on HC-2 type oxygen index instrument by ASTM D2863-77 standard, and its limiting oxygen index(LOI) value reaches 35.5.
Comparative Examples 1:
To account for the polypropylene, 8.3% tetramethylolmethane of system total mass 75% and 16.7% ammonium polyphosphate adds in the Banbury mixer by mass ratio, melt blending is 10 minutes under 180 ℃ and 100 rev/mins of conditions of rotating speed, obtains polypropylene flame redardant.The laggard row of standard batten that cuts into 130X6.5X3mm and 130X13X3mm detects, and its limiting oxygen index(LOI) value reaches 28, and vertical combustion can reach UL-94 V-0 rank.
Keep under the 25% constant situation at expansion type flame retardant and porous calcium phosphate nickel total addition level as can be seen from embodiment 1 and Comparative Examples 1, the oxygen index of embodiment 1 will exceed 7 units than the oxygen index of Comparative Examples 1, illustrates that the present invention has obviously improved the flame retardant properties of polypropylene material.
Embodiment 2:
In being dissolved in the 106.5g Nickel dichloride hexahydrate in the 314ml deionized water, under agitation dropwise add 83.34g ortho-phosphoric acid; Add Neutral ammonium fluoride 26.69g then; Splash into ammoniacal liquor at last and regulate pH value to 1.8, stirs mixing in 0.5 hour after, in the stainless steel synthesis reactor with this mixture immigration capacity teflon lined that is 500ml, it is 70% of synthesis reactor volume that mixture adds charge.160 ℃ and autogenous pressure lower seal crystallization 72 hours; Resulting yellow-green colour solid matter with deionized water is washed 3 times, and is first at air drying, again dry for standby under 100 ℃ of conditions.Products therefrom is carried out X-ray diffraction analysis.Fig. 2 is at the diffractogram of the X ray of the porous calcium phosphate nickel of 160 ℃ of crystallization 72 hours preparation in the present embodiment, identical with embodiment Fig. 1, with " American Chemical Society's magazine " (J.Am.Chem.Soc 125:1309,2003) and " micropore and mesopore material " (Microporous and Mesoporous Materials; 85 (3): 355-364,2005) the X-ray diffractogram unanimity of the porous calcium phosphate nickel of report in.
The porous calcium phosphate nickel that will account for above-mentioned preparation in the present embodiment of system total mass 1% by mass ratio with account for 75% polypropylene, 8% tetramethylolmethane and 16% ammonium polyphosphate and add in the Banbury mixer, melt blending is 5 minutes under 190 ℃ and 20 rev/mins of conditions of rotating speed, promptly obtains containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel.
With the dry rear fender of polypropylene flame redardant, the standard batten that cuts into 130X6.5X3mm and 130X13X3mm detects, and its limiting oxygen index(LOI) value reaches 32, and vertical combustion can reach UL-94 V-0 rank.
Embodiment 3:
In being dissolved in the 106.5g Nickel dichloride hexahydrate in the 314ml deionized water, under agitation dropwise add 55.56g ortho-phosphoric acid; Add Neutral ammonium fluoride 16.68g then; Splash into ammoniacal liquor at last and regulate pH value to 2.5, stir after 0.5 hour, in the stainless steel synthesis reactor with this mixture immigration capacity teflon lined that is 500ml, it is 70% of synthesis reactor volume that mixture adds charge.190 ℃ and autogenous pressure lower seal crystallization 168 hours; Resulting yellow-green colour solid matter with deionized water is washed 3 times, and is first at air drying, again dry for standby under 100 ℃ of conditions.Fig. 4 is at the high-resolution electron microscopy figure of the porous calcium phosphate nickel of 190 ℃ of crystallization 168 hours preparation, with " micropore and mesopore material " (Microporous and Mesoporous Materials in the present embodiment; 85 (3): 355-364,2005) the high-resolution electron microscopy figure unanimity of the porous calcium phosphate nickel of report in.
The porous calcium phosphate nickel that will account for above-mentioned preparation in the present embodiment of system total mass 3% by mass ratio with account for 75% polypropylene, 7.3% tetramethylolmethane and 14.7% ammonium polyphosphate and add in the Banbury mixer, melt blending is 5 minutes under 160 ℃ and 20 rev/mins of conditions of rotating speed, promptly obtains containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel.With the dry rear fender of this polypropylene flame redardant, the standard batten that cuts into 130X6.5X3mm and 130X13X3mm detects, and its limiting oxygen index(LOI) value reaches 31.5, and vertical combustion can reach UL-94 V-0 rank.
Embodiment 4:
Porous calcium phosphate nickel makes by embodiment 1 method.The porous calcium phosphate nickel that will account for system total mass 4% by mass ratio with account for 75% polypropylene, 7% tetramethylolmethane and 14% ammonium polyphosphate and add in the Banbury mixer, melt blending is 30 minutes under 160 ℃ and 100 rev/mins of conditions of rotating speed, promptly obtains containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel.Dry rear fender, the standard batten that cuts into 130X13X3mm detects, and vertical combustion can reach UL-94 V-0 rank.
Embodiment 5:
Porous calcium phosphate nickel makes by embodiment 2 methods.The porous calcium phosphate nickel that will account for system total mass 2% by mass ratio with account for 80% polypropylene, 6% tetramethylolmethane and 12% ammonium polyphosphate and add in the Banbury mixer, melt blending is 10 minutes under 180 ℃ and 50 rev/mins of conditions of rotating speed, promptly obtain containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel, vertical combustion can reach UL-94 V-0 rank.
Embodiment 6:
Porous calcium phosphate nickel makes by embodiment 3 methods.The porous calcium phosphate nickel that will account for system total mass 4% by mass ratio with account for 80% polypropylene, 5.3% tetramethylolmethane and 10.7% ammonium polyphosphate and add in the Banbury mixer, melt blending is 30 minutes under 190 ℃ and 20 rev/mins of conditions of rotating speed, promptly obtain containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel, vertical combustion can reach UL-94 V-0 rank.
Embodiment 7:
Porous calcium phosphate nickel makes by embodiment 3 methods.The porous calcium phosphate nickel that will account for system total mass 0.5% by mass ratio with account for 75% polypropylene, 8.2% tetramethylolmethane and 16.3% ammonium polyphosphate ammonium and add in the Banbury mixer, melt blending is 30 minutes under 160 ℃ and 100 rev/mins of conditions of rotating speed, promptly obtain containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel, vertical combustion can reach UL-94 V-0 rank.
Embodiment 8:
Porous calcium phosphate nickel makes by embodiment 1 method.The porous calcium phosphate nickel that will account for system total mass 2% by mass ratio with account for 80% polypropylene, 6% tetramethylolmethane and 12% trimeric cyanamide ammonium polyphosphate and add in the Banbury mixer, melt blending is 5 minutes under 180 ℃ and 50 rev/mins of conditions of rotating speed, promptly obtain containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel, vertical combustion can reach UL-94 V-0 rank.
Embodiment 9:
Porous calcium phosphate nickel makes by embodiment 2 methods.The porous calcium phosphate nickel that will account for system gross weight 0.5% by mass ratio with account for 75% polypropylene, 8.2% tetramethylolmethane and 16.3% trimeric cyanamide ammonium polyphosphate and add in the Banbury mixer, melt blending is 30 minutes under 190 ℃ and 100 rev/mins of conditions of rotating speed, promptly obtain containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel, vertical combustion can reach UL-94 V-0 rank.
Embodiment 10:
Porous calcium phosphate nickel makes by embodiment 3 methods.The porous calcium phosphate nickel that will account for system gross weight 4% by mass ratio with account for 80% polypropylene, 5.3% tetramethylolmethane and 10.7% trimeric cyanamide ammonium polyphosphate and add in the Banbury mixer, melt blending is 10 minutes under 170 ℃ and 50 rev/mins of conditions of rotating speed, promptly obtain containing the polypropylene flame redardant of the halogen-free expansible of porous calcium phosphate nickel, vertical combustion can reach UL-94 V-0 rank.
Comparative Examples 2:
By weight the polypropylene that will account for system total mass 80%, 6.7% tetramethylolmethane with account for 13.3% ammonium polyphosphate and add in the Banbury mixer, melt blending is 10 minutes under 160 ℃ and 50 rev/mins of conditions of rotating speed, promptly obtains the polypropylene flame redardant of halogen-free expansible.With the dry rear fender of polypropylene flame redardant, the standard batten that cuts into 130X13X3mm detects, and vertical combustion does not reach the UL-94 rank.
Comparative Examples 3:
Add in the Banbury mixer with accounting for 80% polypropylene, 6% tetramethylolmethane and account for 12% ammonium polyphosphate by weight the zeolite that will account for system total mass 2%, melt blending is 10 minutes under 180 ℃ and 50 rev/mins of conditions of rotating speed, promptly obtain the polypropylene flame redardant of halogen-free expansible, vertical combustion does not reach UL-94 V0 rank.
Comparative Examples 4:
Add in the Banbury mixer with accounting for 80% polypropylene, 6% tetramethylolmethane and account for 12% ammonium polyphosphate by weight the zinc borate that will account for system total mass 2%, melt blending is 10 minutes under 180 ℃ and 50 rev/mins of conditions of rotating speed, promptly obtain the polypropylene flame redardant of halogen-free expansible, vertical combustion does not reach UL-94 V0 rank.
Comparative Examples 5:
Add in the Banbury mixer with accounting for 80% polypropylene, 6% tetramethylolmethane and account for 12% ammonium polyphosphate by weight the organic modification montmonrillonite that will account for system total mass 2%, melt blending is 10 minutes under 180 ℃ and 50 rev/mins of conditions of rotating speed, promptly obtain the polypropylene flame redardant of halogen-free expansible, vertical combustion does not reach UL-94 V0 rank.
From the foregoing description as can be seen: the optimal components ratio scope that contains porous calcium phosphate nickel the halogen-free expansion type flame-proof polypropylene of porous calcium phosphate nickel is 1～4%, when the content of porous calcium phosphate nickel polypropylene fire retardant effect 2% time best.Keep under the 20% constant situation at expansion type flame retardant and fire retarding synergist total addition level as can be seen from embodiment 5,8 and Comparative Examples 3,4,5, the embodiment 5 and the embodiment 8 that have only added 2% porous calcium phosphate nickel can reach UL-94 V0 rank.From embodiment 6,10 and Comparative Examples 1,2 as can be seen when not containing porous calcium phosphate nickel, 25% expansion type flame retardant just can make polypropylene reach UL-94 V0 rank, yet add after the porous calcium phosphate nickel, 16% expansion type flame retardant just can make polypropylene reach the UL-94V0 rank.The flame retarding efficiency that porous calcium phosphate nickel is described is apparently higher than existing fire-retardant synergistic technology, and the halogen-free expansion type flame-proof technology that contains porous calcium phosphate nickel has obviously improved the flame retardant properties of polypropylene material.
Claims (2)
1. a halogen-free expansion type flame-proof polypropylene that contains porous calcium phosphate nickel is characterized in that each component by accounting for system total mass percentage score is not: polypropylene 75～80%, expansion type flame retardant 16～24.5%, porous calcium phosphate nickel 0.5～4%; This porous calcium phosphate nickel have the aperture be 8～
Pore passage structure; Wherein said expansion type flame retardant is by mass percentage by tetramethylolmethane (I): ammonium polyphosphate (II) is by 5.3～8.2%: 10.7～16.3%; Or by tetramethylolmethane (I): trimeric cyanamide ammonium polyphosphate (III) is by 5.3～8.2%: 10.7～16.3% composite forming;
N 〉=30 wherein, m 〉=40.
2. the described polyacrylic preparation method of halogen-free expansion type flame-proof who contains porous calcium phosphate nickel of claim 1, NiCl in molar ratio earlier
26H
2O: H
3PO
4: NH
4F: NH
4OH: H
2O was dissolved in six water nickelous chlorides in the water in 1.0: 1.0～1.5: 1.0～1.6: 0.8～1.0: 40.0, stir and add phosphoric acid and Neutral ammonium fluoride down successively, transferring the pH value of system with ammoniacal liquor again is 1.8～2.5, then mixture is sealed in the reactor, 160～190 ℃ of crystallization 3～7 days; Product takes out after-filtration, washes after drying with water, promptly obtains porous calcium phosphate nickel; It is characterized in that: polypropylene 75～80%, expansion type flame retardant 16～24.5% and the above-mentioned porous calcium phosphate nickel 0.5～4% that makes are put into Banbury mixer by accounting for system total mass per-cent, controlled temperature is at 160～190 ℃, rotating speed is 20～100 rev/mins, melt blending 5～30 minutes; Wherein said expansion type flame retardant is by mass percentage by tetramethylolmethane (I): ammonium polyphosphate (II) is by 5.3～8.2%: 10.7～16.3%; Or by tetramethylolmethane (I): trimeric cyanamide ammonium polyphosphate (III) is by 5.3～8.2%: 10.7～16.3% composite forming;
N 〉=30 wherein, m 〉=40.
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| CN101638583B (en) * | 2009-08-31 | 2012-07-11 | 中国科学技术大学 | Nitrogen-phosphorus expansion flame retardant containing flame retardant synergist and preparation method thereof |
| CN104773715B (en) * | 2015-04-03 | 2017-06-23 | 安徽理工大学 | A kind of mushroom porous calcium phosphate nickel and preparation method thereof |
| CN110527206A (en) * | 2019-08-15 | 2019-12-03 | 安徽壹石通材料科技股份有限公司 | A kind of preparation and its application of nitrogen-phosphorus-boron expansion type flame retardant |
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| CN1335332A (en) * | 2001-08-28 | 2002-02-13 | 巴陵石化岳阳石油化工总厂 | Expanding fire retardant composition without halide for polyolefine |
| CN1923882A (en) * | 2006-09-01 | 2007-03-07 | 西北师范大学 | Expansion type inflaming retarding polypropylene material |
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| CN1335332A (en) * | 2001-08-28 | 2002-02-13 | 巴陵石化岳阳石油化工总厂 | Expanding fire retardant composition without halide for polyolefine |
| CN1923882A (en) * | 2006-09-01 | 2007-03-07 | 西北师范大学 | Expansion type inflaming retarding polypropylene material |
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