CN106279930A - The preparation method of chabasie red phosphorus synergistic fire retardant - Google Patents
The preparation method of chabasie red phosphorus synergistic fire retardant Download PDFInfo
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- CN106279930A CN106279930A CN201610817141.1A CN201610817141A CN106279930A CN 106279930 A CN106279930 A CN 106279930A CN 201610817141 A CN201610817141 A CN 201610817141A CN 106279930 A CN106279930 A CN 106279930A
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- chabasie
- red phosphorus
- fire retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 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
- 238000002955 isolation Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- 239000003112 inhibitor Substances 0.000 abstract description 6
- 238000005342 ion exchange Methods 0.000 abstract description 4
- 230000007812 deficiency Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- 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 description 16
- 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
- -1 polyethylene Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 231100000053 low toxicity Toxicity 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 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
- 239000007789 gas Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000004079 fireproofing Methods 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 238000011161 development Methods 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
- 238000002156 mixing Methods 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
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052788 barium Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 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
- 238000000151 deposition 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
- 238000002050 diffraction method Methods 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
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052759 nickel Inorganic materials 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
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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 present invention relates to the preparation method of a kind of chabasie red phosphorus synergistic fire retardant, described method is by the NiCl of chabasie Yu a certain amount of 0.1mol/L2Solution mixes, after at 60 DEG C, ion exchanges 30 120min, filter, wash, be dried, then it is placed in quartz tube reactor, hydrogen 30 90min it is passed through at 400 450 DEG C, at 410 440 DEG C, be passed through hydrogen phosphide 2 10h afterwards, finally by sample in the reaction vessel of isolation air at 260 290 DEG C heating and thermal insulation 10 60min, obtain load 4 32%(mass ratioes in duct) the chabasie red phosphorus synergistic fire retardant of red phosphorus.Preparation technology of the present invention is relatively simple, solves and is used alone the deficiency that red phosphorus combustion inhibitor exists, and the fire retardant of preparation has good fire resistance.
Description
Technical field
The invention belongs to technical field of flame retardant, be specifically related to the preparation method of a kind of chabasie-red phosphorus synergistic fire retardant.
Background technology
Along with the enhancing of health of people environmental consciousness, seek environmental protection, low toxicity, fire retardant efficient, multi-functional have become resistance
The inexorable trend of combustion agent industry.The fire-retardant new techniques such as super-refinement technology, microencapsulation technology, compounded technology, crosslinking technological are
Development.
In modern flame-retarded technology, the compounding of fire retardant is an extremely important aspect.Compound and utilize fire retardant exactly
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
The best, 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 and other fire retardants are also used
Time, there is significant fire-resistant synergistic effect.
Inorganic combustion inhibitor has that good stability, nontoxic or low toxicity, corrosivity is 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 the least, at base
In material, dispersion is the biggest, and flame retardant effect is the best.In recent years, Nano-technology Development is rapid, and nano material is used widely, now
The fire retardant particle diameter used is typically at micron order, if being reduced to nanoscale, flame retardant effect will significantly improve, the interpolation of fire retardant
Amount will be greatly lowered, it is possible to resolve the contradiction between Flame Retardancy energy and mechanical property.
Phosphorus flame retardant is a kind of excellent due to the active material that it is efficient, low toxicity, low cigarette become fire retardant, especially red phosphorus
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, on the one hand charring layer can reduce the releasing of fuel gas, on the other hand also have heat-absorbing action；It addition, red phosphorus with
After oxygen forms PO free radical entrance gas phase, a large amount of H, HO free radical can be caught.But red phosphorus is in use, there is following asking
Topic: inflammable, explosive, severe toxicity 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 at microencapsulation technology
Reason, can overcome the disadvantages mentioned above in red phosphorus performance, eliminates red phosphorus hidden danger in storing, production, the course of processing: two is can be white
Degreeization, to desalinate the color of red phosphorus, widens the range of application of red phosphorus；Three is to improve the compatibility with base material, reduces base material
The impact of physical and mechanical property；Four is can be by the selection to capsule material, it is achieved compounding of multiple ignition-proof element (fire retardant), improves
Flame-retardant smoke inhibition usefulness.Du Long is superfine have studied brucite and the 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, but its preparation technology is more complicated, fire retardant
Granular size is wayward, limits it and uses widely.
Porous material may apply to improve in fire retardant the performance of fire retardant, especially to macromolecular material heat stability
Raising particularly evident.At present, more existing researchers have carried out the research to such flame retardant performance.Ye Lei etc. study
Multi-walled carbon nano-tubes and the magnesium hydroxide cooperative flame retardant effect to ethylene-vinyl acetate copolymer, work as multi-walled carbon nano-tubes
Addition when being 2%, 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.).
Chabasie is a kind of silicate, and molecular formula is (Ca, Na, K)4(Al4Si8O24)·12H2O.The crystal tool of chabasie
Having the eight yuan of pore canal system of three-dimensional along crystallography a axle, b axle and c-axis, pore size is 0.38 nm × 0.38 nm.Chabasie
The bonding force between cation and Si-Al such as Na, K, Ca in structure is weak, can by cation replacements such as Mg, Sr, Ba, Cu, Zn, Ni,
There is stronger ion-exchange capacity, also there is as inorganic material certain fire resistance.
The purpose of the present invention is exactly the compounding collaborative increasing of red phosphorus flame-retardant performance is good, the advantage of ultra-fine chabasie and fire retardant
Effect concentrates on one, both solves to be used alone several respects deficiency that red phosphorus combustion inhibitor exists, can prepare again granular size for Asia
Micron, the fire retardant of uniform particle sizes.This fire retardant remains red phosphorus combustion inhibitor cigarette efficient, low, the advantage of low toxicity, has played again Pedicellus et Pericarpium Trapae
The zeolite chemiluminescence to red phosphorus flame-retardant, moreover it is possible to effectively controlling fire-retardant particles size, micro-denier flame resistant agent can also improve
With the compatibility of organic material, it is favorably improved mechanical property and the heat stability of flame-proof composite material.Pedicellus et Pericarpium Trapae prepared by the present invention
Zeolite-loaded red phosphorus micro-denier flame resistant agent has broad application prospects at organic coating and high molecular film material flame retardant area.
Summary of the invention
The technical solution used in the present invention is: the preparation method of a kind of chabasie-red phosphorus synergistic fire retardant, and the present invention is with super
Thin chabasie, hydrogen phosphide are primary raw material, first load Ni in chabasie duct, then make hydrogen phosphide quilt in chabasie duct
Ni catalytic decomposition generates yellow phosphorus, and yellow phosphorus is then converted to red phosphorus, can be prepared by ultra-fine chabasie-red phosphorus synergistic fire retardant.Including with
Lower step:
(1) by the NiCl of chabasie Yu a certain amount of 0.1mol/L2Solution mixes, at 60 DEG C after ion exchange certain time, and mistake
Filter, wash, be dried, in obtaining duct, load Ni2+Chabasie；
(2) sample prepared by (1) is placed in quartz tube reactor, is passed through hydrogen reducing certain time at a certain temperature,
The chabasie of Ni is loaded in duct；
(3) chabasie of the load Ni (2) prepared, 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 chabasie duct；
(4) sample (3) prepared is heated to uniform temperature in the reaction vessel of isolation air, and held for some time, by Huang
Phosphorus is converted to red phosphorus, loads the chabasie-red phosphorus synergistic fire retardant of red phosphorus in obtaining duct.
In a preferred embodiment, described chabasie particle diameter is 0.4-0.8 μm.
In a preferred embodiment, described chabasie and the NiCl of 0.1mol/L2Solution mixes, ion exchange at 60 DEG C
Time be 30-120min.
In a preferred embodiment, the Ni of load in described chabasie duct2+In hydrogen, the temperature of reduction is 400-450
DEG C, the time is 30-90min.
In a preferred embodiment, the temperature that described hydrogen phosphide decomposes in chabasie duct is 410-440 DEG C, and the time is
2-10h。
In a preferred embodiment, described yellow phosphorus is converted to the heating-up temperature of red phosphorus and is 260-290 DEG C, and the time is 10-
60min。
Product red phosphorus content prepared by the present invention is 4-32%(mass ratio).
The advantage of fire retardant prepared by the present invention is to solve to be used alone the deficiency that red phosphorus combustion inhibitor exists, and can prepare
Submicron-scale, the fire retardant of uniform particle sizes.This fire retardant remains red phosphorus combustion inhibitor cigarette efficient, low, the advantage of low toxicity, sends out again
Wave the chabasie chemiluminescence to red phosphorus flame-retardant, moreover it is possible to effectively controlling 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 effectively control phosphine gas and decompose in chabasie duct, it is possible to controls highly effective flame-retardant composition red phosphorus and only enters Pedicellus et Pericarpium Trapae
Inside zeolite cavity, without depositing at zeolite surface, preparation technology is simpler.The present invention is also sodium hypophosphite industry byproduct
The recycling of phosphine gas provides new way.
Detailed description of the invention
Embodiment 1
By the NiCl that 20g median is 0.4 μm chabasie and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
120min, filters, washs, after drying, is placed in quartz tube reactor, after being passed through hydrogen 90min, is passed through at 440 DEG C at 450 DEG C
Hydrogen phosphide, reacts 10h, after cooling, in the reaction vessel of isolation air, sample is heated to 290 DEG C, is incubated 60min, obtains
Red phosphorus content be 32% chabasie 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 33.3.
Embodiment 2
By the NiCl that 20g median is 0.8 μm chabasie and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
30min, filters, washs, after drying, is placed in quartz tube reactor, after being passed through hydrogen 30min, is passed through at 410 DEG C at 400 DEG C
Hydrogen phosphide, reacts 2h, after cooling, in the reaction vessel of isolation air, sample is heated to 260 DEG C, is incubated 10min, obtains red
Phosphorus content be 4% chabasie duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) is 28.6.
Embodiment 3
By the NiCl that 20g median is 0.6 μm chabasie and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
75min, filters, washs, after drying, is placed in quartz tube reactor, after being passed through hydrogen 60min, is passed through at 425 DEG C at 425 DEG C
Hydrogen phosphide, reacts 6h, after cooling, in the reaction vessel of isolation air, sample is heated to 275 DEG C, is incubated 35min, obtains red
Phosphorus content be 16% chabasie duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) be 31.0.
Embodiment 4
By the NiCl that 20g median is 0.4 μm chabasie and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
120min, filters, washs, after drying, is placed in quartz tube reactor, after being passed through hydrogen 30min, is passed through at 440 DEG C at 450 DEG C
Hydrogen phosphide, reacts 10h, after cooling, in the reaction vessel of isolation air, sample is heated to 290 DEG C, is incubated 60min, obtains
Red phosphorus content be 10% chabasie 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 29.5.
Embodiment 5
By the NiCl that 20g median is 0.4 μm chabasie and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
120min, filters, washs, after drying, is placed in quartz tube reactor, after being passed through hydrogen 90min, is passed through at 440 DEG C at 450 DEG C
Hydrogen phosphide, reacts 6h, after cooling, in the reaction vessel of isolation air, sample is heated to 290 DEG C, is incubated 60min, obtains red
Phosphorus content be 27% chabasie duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) be 32.8.
Oxygen index (OI) (fire resistance) test experiments:
The fire retardant prepared by above-described embodiment 1,2,3,4 and 5 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. the preparation method of chabasie-red phosphorus synergistic fire retardant, it is characterised in that comprise the following steps: with submicron Pedicellus et Pericarpium Trapae
Zeolite, hydrogen phosphide are primary raw material, by the NiCl of chabasie Yu 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, in obtaining duct, load Ni2+Chabasie, be then placed in quartz tube reactor,
It is passed through hydrogen at a certain temperature, loads the chabasie of Ni in obtaining duct, be passed through hydrogen phosphide the most at a certain temperature, make phosphorus
Change hydrogen and be decomposed into yellow phosphorus in chabasie duct, it is heated to uniform temperature, by yellow phosphorus in the reaction vessel of isolation air
Be converted to red phosphorus, in obtaining duct, load the chabasie-red phosphorus synergistic fire retardant of red phosphorus；The particle diameter of chabasie is 0.4-0.8 μm；
Chabasie and NiCl2The time of solion exchange is 30-120min；The Ni of load in chabasie duct2+Hydrogen reduces
Temperature be 400-450 DEG C, the time is 30-90min；Hydrogen phosphide decomposition temperature in chabasie duct is 410-440 DEG C, the time
For 2-10h；Yellow phosphorus is converted to the heating-up temperature of red phosphorus and is 260-290 DEG C, and the time is 10-60min；The fire retardant red phosphorus of preparation contains
Amount is 4-32%(mass ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817141.1A CN106279930B (en) | 2016-09-12 | 2016-09-12 | The preparation method of chabasie-red phosphorus synergistic fire retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817141.1A CN106279930B (en) | 2016-09-12 | 2016-09-12 | The preparation method of chabasie-red phosphorus synergistic fire retardant |
Publications (2)
| Publication Number | Publication Date |
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| CN106279930A true CN106279930A (en) | 2017-01-04 |
| CN106279930B CN106279930B (en) | 2018-07-17 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1669398A1 (en) * | 2003-09-10 | 2006-06-14 | Fuji Electric Holdings Co., Ltd. | Reactive flame retardant and flame-retardant processed resin obtained with the same |
| CN102172536A (en) * | 2011-03-16 | 2011-09-07 | 天津工业大学 | Method for preparing loaded phosphide catalyst by taking red phosphorus as phosphorus source |
| WO2012117915A1 (en) * | 2011-03-03 | 2012-09-07 | 株式会社カネカ | Novel insulating film and printed wiring board provided with insulating film |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1669398A1 (en) * | 2003-09-10 | 2006-06-14 | Fuji Electric Holdings Co., Ltd. | Reactive flame retardant and flame-retardant processed resin obtained with the same |
| WO2012117915A1 (en) * | 2011-03-03 | 2012-09-07 | 株式会社カネカ | Novel insulating film and printed wiring board provided with insulating film |
| CN102172536A (en) * | 2011-03-16 | 2011-09-07 | 天津工业大学 | Method for preparing loaded phosphide catalyst by taking red phosphorus as phosphorus source |
| 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 (2)
| Title |
|---|
| 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》 * |
| 汪艳等: "氢氧化铝及红磷协同阻燃热收缩材料的制备及性能", 《武汉工程大学学报》 * |
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| CN106279930B (en) | 2018-07-17 |
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