CN106349506A - Preparation method of sodalite-red phosphorus synergistic flame retardant - Google Patents
Preparation method of sodalite-red phosphorus synergistic flame retardant Download PDFInfo
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- CN106349506A CN106349506A CN201610817042.3A CN201610817042A CN106349506A CN 106349506 A CN106349506 A CN 106349506A CN 201610817042 A CN201610817042 A CN 201610817042A CN 106349506 A CN106349506 A CN 106349506A
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- sodalite
- red phosphorus
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- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052665 sodalite Inorganic materials 0.000 claims abstract description 40
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010453 quartz Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 238000002955 isolation Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 6
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 231100000053 low toxicity Toxicity 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002079 cooperative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a preparation method of sodalite-red phosphorus synergistic flame retardant. The preparation method includes: mixing the sodalite with a certain amount of 0.1mol/L of a NiCl2 solution prior to filtering, cleaning, washing and placing in a quartz tube reactor after ion exchange under the temperature of 60DEG C for 30-150 minutes; feeding hydrogen under the temperature ranging from 400DEG C to 450DEG C for 20-90 minutes prior to feeding hydrogen phosphide under the temperature ranging from 410DEG C to 440DEG C for 2-10 minutes, and finally heating and warming the sample in an air-insulated reaction vessel under the temperature ranging from 260DEG C to 290DEG C for 10-60 minutes to obtain the sodalite-red phosphorus synergistic flame retardant loading 4%-30% of the red phosphorus by mass ratio in pore passages. The preparation method is simple in process, the shortcoming existing in independent use of the red phosphorus flame retardant is overcome, and the flame retardant is good in flame retardant performance.
Description
Technical field
The invention belongs to technical field of flame retardant is and in particular to a kind of preparation method of sodalite-red phosphorus synergistic fire retardant.
Background technology
With the enhancing of health of people environmental consciousness, seek environmental protection, low toxicity, efficient, multi-functional fire retardant have become resistance
The inexorable trend of combustion agent industry.The fire-retardant new technique such as super-refinement technology, microencapsulation technology, compounded technology, crosslinking technological is
Constantly develop.
In modern flame-retarded technology, the compounding of fire retardant is extremely important one side.Compounding is exactly to utilize fire retardant
Between interaction, to improve fire resistance, i.e. the cooperative effect of fire retardant.There is the fire-retardant effect of flame-retardant system of cooperative effect
Really good, fire resistance strengthens, not only can be fire-retardant but also can press down cigarette, also has some special functions, applied range, cost
Low, economic benefit can be significantly improved, be to realize one of non-halogen effective way of fire retardant.Red phosphorus is used in combination with other fire retardants
When, there is significant fire-resistant synergistic effect.
Inorganic combustion inhibitor has that good stability, nontoxic or low toxicity, corrosivity are little, lower-price characteristic, but its fire-retardant effect
Rate is low, it usually needs a large amount of interpolations just can have preferable flame retardant effect.Therefore, while improving fire block articles performance, it adds
Work degradation, mechanical property declines to a great extent, and has a strong impact on the quality of product.Research shows: the granularity of fire retardant is less, in base
In material, dispersion is bigger, and flame retardant effect is better.In recent years, Nano-technology Development is rapid, and nano material is used widely, now
Typically in micron order, if being reduced to nanoscale, flame retardant effect will significantly improve the fire retardant particle diameter using, the interpolation of fire retardant
Amount will be greatly lowered, it is possible to resolve the contradiction between Flame Retardancy energy and mechanical property.
The active material that phosphorus flame retardant is efficient due to it, low toxicity, low cigarette become fire retardant, especially red phosphorus are a kind of excellent
Fire retardant, its fire retardant mechanism is: decomposes, is formed and has the Metaphosphoric acid of extremely strong dehydration property, so that the polymer of burning
Superficial charring, charring layer one side can reduce the releasing of fuel gas, on the other hand also has heat-absorbing action；In addition, red phosphorus with
After oxygen forms po free radical entrance gas phase, a large amount of h, ho free radicals can be caught.But when using, there is following asking in red phosphorus
Topic: inflammable, explosive, hypertoxic ph can be released with air Long Term Contact3Gas；This easily makes color articles as redness；Easily inhale
Water, with polymer poor compatibility.Disadvantages mentioned above seriously limits the direct application of red phosphorus.By red phosphorus through microencapsulation technology at
Reason, can overcome the disadvantages mentioned above in red phosphorus performance, eliminate hidden danger in storing, production, the course of processing for the red phosphorus: two is can be white
Degreeization, to desalinate the color of red phosphorus, widens the range of application of red phosphorus；Three is the compatibility that can improve with base material, reduces to base material
The impact of physical and mechanical property；Four is can be realized the compounding of multiple ignition-proof elements (fire retardant), improved by the selection to capsule material
Flame-retardant smoke inhibition efficiency.Du Long is superfine to have studied the brucite and red phosphorus microcapsule cooperative flame retardant to ethylene-vinyl acetate copolymer
Effect (longchao du, baojun qu and zhenjin xu. flammability characteristics and
synergistic effect of hydrotalcite with microencapsulated red phosphorus in
halogen-free flame retardant eva composite. polymer degradation and stability
91 (2006) 995-1001.).Although the flame retardant effect of red phosphorus microcapsule is pretty good, its preparation technology is more complicated, fire retardant
Granular size is wayward, limits it and widely uses.
Porous material may apply to improve the performance of fire retardant in fire retardant, especially to macromolecular material heat stability
Raising particularly evident.At present, some researchers existing have carried out the research to such flame retardant performance.Ye Lei etc. studies
The multi-walled carbon nano-tubes and magnesium hydroxide cooperative flame retardant effect to ethylene-vinyl acetate copolymer, works as multi-walled carbon nano-tubes
Addition be 2% when, can substantially reduce the HRR of ethylene-vinyl acetate copolymer, mass loss rate reaches
50%-60%, makes the oxygen index (OI) of fire retardant improve 5%(lei ye, qianghua wu and baojun qu. synergistic
effects and mechanism of multiwalled carbon nanotubes with magnesium
hydroxide in halogen-free flame retardant eva/mh/mwnt nanocomposites. polymer
Degradation and stability 94 (2009) 751 756.).
The chemical formula of sodalite is na8(alsio4)6cl2, the sodalite cage (sod cage) that its structure arranges for body-centered cubic
It is formed by connecting by single four or single hexatomic rings, a sod cage is made up of six four-membered rings and eight hexatomic rings, the duct of sodalite
Window is hexatomic ring, and the metal ion in sodalite duct has ion-exchange capacity, also has as inorganic material certain
Fire resistance.
The purpose of the present invention is exactly to increase good for the red phosphorus flame-retardant performance, advantage of ultra-fine sodalite and the compounding collaborative of fire retardant
Effect concentrates on one, and the several respects both solving to be used alone red phosphorus combustion inhibitor presence are not enough, and can prepare granular size is Asia again
Micron, the fire retardant of uniform particle sizes.This fire retardant remains that red phosphorus combustion inhibitor is efficient, the advantage of low cigarette, low toxicity, has played side again
To the chemiluminescence of red phosphorus flame-retardant moreover it is possible to effective control fire-retardant particles size, micro-denier flame resistant agent can also improve sodium stone
With the compatibility of organic material, it is favorably improved mechanical property and the heat stability of flame-proof composite material.The side of present invention preparation
The load red phosphorus micro-denier flame resistant agent of sodium stone has broad application prospects in organic coating and high molecular film material flame retardant area.
Content of the invention
The technical solution used in the present invention is: a kind of preparation method of ultra-fine sodalite-red phosphorus synergistic fire retardant, the present invention
With submicron sodalite, hydrogen phosphide as primary raw material, first in sodalite duct, load ni, then make hydrogen phosphide in sodalite hole
In road, yellow phosphorus is generated by ni catalytic decomposition, yellow phosphorus is then converted to red phosphorus, you can ultra-fine sodalite-red phosphorus synergistic fire retardant is obtained.
Comprise the following steps:
(1) by the nicl of sodalite and a certain amount of 0.1mol/l2Solution mixes, after ion exchange certain time at 60 DEG C, mistake
Filter, wash, be dried, obtain loading ni in duct2+Sodalite；
(2) sample preparing (1) is placed in quartz tube reactor, is passed through hydrogen reducing certain time at a certain temperature, obtains
The sodalite of ni is loaded in duct；
(3) sodalite of the load ni preparing (2), in quartz tube reactor, is passed through hydrogen phosphide one timing at a certain temperature
Between, make hydrogen phosphide be decomposed into yellow phosphorus in sodalite duct；
(4) sample prepared by (3) is heated to uniform temperature in the reaction vessel of isolation air, held for some time, by Huang
Phosphorus is converted to red phosphorus, obtains loading the sodalite-red phosphorus synergistic fire retardant of red phosphorus in duct.
In a preferred embodiment, described sodalite particle diameter is 300-800nm.
In a preferred embodiment, the nicl of described sodalite and 0.1mol/l2Solution mixes, ion exchange at 60 DEG C
Time be 30-150min.
In a preferred embodiment, the ni loading in described sodalite duct2+In hydrogen, the temperature of reduction is 400-450
DEG C, the time is 20-90min.
In a preferred embodiment, the temperature that described hydrogen phosphide decomposes in sodalite duct is 410-440 DEG C, and the time is
2-10h.
In a preferred embodiment, described yellow phosphorus be converted to red phosphorus heating-up temperature be 260-290 DEG C, the time be 10-
60min.
Product red phosphorus content prepared by the present invention is 4-30%(mass ratio).
The advantage of fire retardant prepared by the present invention is to solve the deficiency being used alone red phosphorus combustion inhibitor presence, can prepare
Submicron-scale, the fire retardant of uniform particle sizes.This fire retardant remains that red phosphorus combustion inhibitor is efficient, the advantage of low cigarette, low toxicity, sends out again
Wave sodalite to the chemiluminescence of red phosphorus flame-retardant moreover it is possible to effective control fire-retardant particles size, micro-denier flame resistant agent also may be used
To improve the compatibility with organic material, it is favorably improved mechanical property and the heat stability of flame-proof composite material.System of the present invention
Standby technology can be decomposed effective control phosphine gas in sodalite duct, can control the highly effective flame-retardant composition red phosphorus only side of entrance
Inside sodium stone duct, without in sodalite surface deposition, preparation technology is simpler.The present invention is also sodium hypophosphite industrial by-product
The recycling of product phosphine gas provides new way.
Specific embodiment
Embodiment 1
Nicl by the sodalite for 300nm for the 15g median and 500ml 0.1mol/l2Solution mixes, and stirs at 60 DEG C
150min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 90min at 450 DEG C, be passed through at 440 DEG C
Hydrogen phosphide, reacts 10h, after cooling, sample is heated to 290 DEG C in the reaction vessel of isolation air, is incubated 60min, obtains
Red phosphorus content be 30% sodalite duct in load red phosphorus fire retardant, the fire-retardant material that this fire retardant and polyethylene are mixed with
The oxygen index (OI) of material is 32.9.
Embodiment 2
Nicl by the sodalite for 800nm for the 15g median and 500ml 0.1mol/l2Solution mixes, and stirs at 60 DEG C
30min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 20min at 400 DEG C, be passed through at 410 DEG C
Hydrogen phosphide, reacts 2h, after cooling, sample is heated to 260 DEG C in the reaction vessel of isolation air, is incubated 10min, obtains red
Phosphorus content be 4% sodalite duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) is 27.2.
Embodiment 3
Nicl by the sodalite for 550nm for the 15g median and 500ml 0.1mol/l2Solution mixes, and stirs at 60 DEG C
90min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 55min at 425 DEG C, be passed through at 425 DEG C
Hydrogen phosphide, reacts 6h, after cooling, sample is heated to 275 DEG C in the reaction vessel of isolation air, is incubated 35min, obtains red
Phosphorus content be 19% sodalite duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) be 30.5.
Embodiment 4
Nicl by the sodalite for 300nm for the 15g median and 500ml 0.1mol/l2Solution mixes, and stirs at 60 DEG C
150min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 20min at 450 DEG C, be passed through at 440 DEG C
Hydrogen phosphide, reacts 10h, after cooling, sample is heated to 290 DEG C in the reaction vessel of isolation air, is incubated 60min, obtains
Red phosphorus content be 10% sodalite duct in load red phosphorus fire retardant, the fire-retardant material that this fire retardant and polyethylene are mixed with
The oxygen index (OI) of material is 28.6.
Embodiment 5
Nicl by the sodalite for 300nm for the 15g median and 500ml 0.1mol/l2Solution mixes, and stirs at 60 DEG C
150min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 90min at 450 DEG C, be passed through at 440 DEG C
Hydrogen phosphide, reacts 6h, after cooling, sample is heated to 290 DEG C in the reaction vessel of isolation air, is incubated 60min, obtains red
Phosphorus content be 26% sodalite duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) be 32.2.
Oxygen index (OI) (fire resistance) test experiments:
By the fire retardant of above-described embodiment 1,2,3,4 and 5 preparation and polyethylene mixing (wherein fire retardant accounts for 30%), at 120 DEG C
Twin-roll mixing 10min, makes the laminar sample that thickness is 1mm.Oxygen index (OI) test is carried out according to gb/t2406 1993.
Claims (1)
1. a kind of preparation method of sodalite-red phosphorus synergistic fire retardant is it is characterised in that comprise the following steps: with submicron side
Sodium stone, hydrogen phosphide are primary raw material, by the nicl of sodalite and a certain amount of 0.1mol/l2Solution mixes, and at 60 DEG C, ion is handed over
After changing certain time, filter, wash, be dried, obtain loading ni in duct2+Sodalite, be then placed in quartz tube reactor,
It is passed through hydrogen at a certain temperature, obtain in duct, loading the sodalite of ni, be passed through hydrogen phosphide at a certain temperature afterwards, make phosphorus
Change hydrogen and be decomposed into yellow phosphorus in sodalite duct, it is heated to uniform temperature in the reaction vessel of isolation air, by yellow phosphorus
Be converted to red phosphorus, obtain in duct, loading the sodalite-red phosphorus synergistic fire retardant of red phosphorus；The particle diameter of sodalite is 300-800nm；
Sodalite and nicl2The time that solion exchanges is 30-150min；The ni of load in sodalite duct2+Hydrogen reduces
Temperature be 400-450 DEG C, the time be 20-90min；Hydrogen phosphide decomposition temperature in sodalite duct is 410-440 DEG C, the time
For 2-10h；The heating-up temperature that yellow phosphorus is converted to red phosphorus is 260-290 DEG C, and the time is 10-60min；The fire retardant red phosphorus of preparation contains
Measure as 4-30%(mass ratio).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033206A (en) * | 1983-07-29 | 1985-02-20 | Nippon Chem Ind Co Ltd:The | Phosphorus-zeolite composite, its manufacture, and flame retardant |
| JPH06157013A (en) * | 1992-11-19 | 1994-06-03 | Nippon Chem Ind Co Ltd | Stabilized red phosphorus composition and flame retardant polymeric material |
| CN102935371A (en) * | 2012-11-16 | 2013-02-20 | 南开大学 | Catalyst for preparing yellow phosphorus through catalytic decomposition of phosphine gas and preparation method thereof |
| CN103506146A (en) * | 2013-10-09 | 2014-01-15 | 周口师范学院 | Catalyst for decomposing hydrogen phosphide gas as well as preparation method and application thereof |
| CN103906825A (en) * | 2011-12-06 | 2014-07-02 | 英派尔科技开发有限公司 | Phosphorus loaded particles and methods for their preparation and use |
-
2016
- 2016-09-12 CN CN201610817042.3A patent/CN106349506B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033206A (en) * | 1983-07-29 | 1985-02-20 | Nippon Chem Ind Co Ltd:The | Phosphorus-zeolite composite, its manufacture, and flame retardant |
| JPH06157013A (en) * | 1992-11-19 | 1994-06-03 | Nippon Chem Ind Co Ltd | Stabilized red phosphorus composition and flame retardant polymeric material |
| CN103906825A (en) * | 2011-12-06 | 2014-07-02 | 英派尔科技开发有限公司 | Phosphorus loaded particles and methods for their preparation and use |
| CN102935371A (en) * | 2012-11-16 | 2013-02-20 | 南开大学 | Catalyst for preparing yellow phosphorus through catalytic decomposition of phosphine gas and preparation method thereof |
| CN103506146A (en) * | 2013-10-09 | 2014-01-15 | 周口师范学院 | Catalyst for decomposing hydrogen phosphide gas as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| JORGE BALLESTER,ET AL.: "A copper-catalyzed variant of the Michaelis-Arbuzov reaction", 《CHEMCATCHEM》 * |
| 张延武等: "浅色水滑石/红磷复合阻燃剂的制备及性能", 《热固性树脂》 * |
| 石斌等: "氢气高温还原制备的负载型镍基催化剂用于苯酚加氢的性能", 《化工进展》 * |
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