CN106279930B - 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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- CN106279930B CN106279930B CN201610817141.1A CN201610817141A CN106279930B CN 106279930 B CN106279930 B CN 106279930B CN 201610817141 A CN201610817141 A CN 201610817141A CN 106279930 B CN106279930 B CN 106279930B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000011068 loading method Methods 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- 235000003283 Pachira macrocarpa Nutrition 0.000 claims description 4
- 235000014364 Trapa natans Nutrition 0.000 claims description 4
- 235000009165 saligot Nutrition 0.000 claims description 4
- 241001083492 Trapa Species 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 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
- 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 abstract description 23
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 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
- 238000009413 insulation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 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
- 229920001200 poly(ethylene-vinyl acetate) Polymers 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
- 239000002245 particle Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 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 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 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
- 239000000047 product Substances 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
- 240000001085 Trapa natans Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease 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
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental 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
- 238000004079 fireproofing Methods 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
- 239000004615 ingredient Substances 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
- 231100001231 less toxic Toxicity 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
- 238000002156 mixing Methods 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
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 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
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of chabasie red phosphorus synergistic fire retardant, the method is by the NiCl of chabasie and a certain amount of 0.1mol/L2Solution mixes, at 60 DEG C after 30 120min of ion exchange, it is filtered, washed, dries, then it is placed in quartz tube reactor, 30 90min of hydrogen is passed through at 400 450 DEG C, 2 10h of hydrogen phosphide is passed through at 410 440 DEG C later, finally by sample in the reaction vessel of isolation air 10 60min of heating and thermal insulation at 260 290 DEG C, obtain load 4 32% in the duct in（Mass ratio）The chabasie red phosphorus synergistic fire retardant of red phosphorus.Preparation process of the present invention is simpler, solves and deficiency existing for red phosphorus combustion inhibitor is used alone, and the fire retardant of preparation has good flame retardant property.
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of preparation method of chabasie-red phosphorus synergistic fire retardant.
Background technology
With the enhancing of health of people environmental consciousness, seeks environmentally friendly, less toxic, efficient, multi-functional fire retardant and have become resistance
Fire the inexorable trend of agent industry.The fire-retardant new technology such as fine technology, microencapsulation technology, compounded technology, crosslinking technological is
It continues to 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 flame retardant property, the i.e. synergistic effect of fire retardant.The fire-retardant effect of flame-retardant system with synergistic effect
Fruit is good, and flame retardant property enhancing not only can be fire-retardant but also can press down cigarette, also have the function of that some are special, have a wide range of application, cost
It is low, economic benefit can be significantly improved, is one of the effective way for realizing that fire retardant is non-halogen.Red phosphorus is used in combination with other fire retardants
When, there is significant fire-resistant synergistic effect.
Inorganic combustion inhibitor has that stability is good, non-toxic or low-toxic, corrosivity is small, lower-price characteristic, but its fire-retardant effect
Rate is low, it usually needs a large amount of additions can just have preferable flame retardant effect.Therefore, while improving fire block articles performance, add
Work degradation, mechanical property decline to a great extent, and seriously affect the quality of product.Research shows that：The granularity of fire retardant is smaller, in base
Dispersion degree is bigger in material, and flame retardant effect is better.In recent years, Nano-technology Development is rapid, and nano material is used widely, now
Generally in the micron-scale, if being reduced to nanoscale, flame retardant effect will significantly improve the fire retardant grain size used, the addition of fire retardant
Amount will be greatly lowered, and can solve the contradiction between Flame Retardancy energy and mechanical property.
For phosphorus flame retardant since it is efficient, low toxicity, low cigarette are as the active material of fire retardant, especially red phosphorus is a kind of excellent
Fire retardant, fire retardant mechanism is：It is thermally decomposed, the metaphosphoric acid with extremely strong dehydration property is formed, to make the polymer of burning
On the one hand superficial charring, charring layer can reduce the releasing of fuel gas, on the other hand also have heat-absorbing action；In addition, red phosphorus with
After oxygen formation PO free radicals enter gas phase, a large amount of H, HO free radicals can be captured.But red phosphorus is when in use, is asked there are following
Topic：Inflammable, explosive can release hypertoxic PH with air Long Term Contact3Gas；This easily makes color articles as red；It is easy to 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 of the red phosphorus in storing, production, process：Second is that can be white
Degreeization widens the application range of red phosphorus to desalinate the color of red phosphorus；Third, the compatibility with base material can be improved, reduce to base material
The influence of physical and mechanical property；Fourth, the compounding of a variety of ignition-proof elements (fire retardant) can be realized by the selection to capsule material, improve
Flame-retardant smoke inhibition efficiency.Du Long is superfine to have studied the cooperative flame retardant of hydrotalcite and red phosphorus microcapsule 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 process is more complex, fire retardant
Granular size is not easy to control, limits its extensive use.
Porous material can be applied in fire retardant the performance for improving fire retardant, especially to high molecular material thermal stability
Raising it is particularly evident.Currently, having some researchers has carried out the research to such flame retardant performance.The researchs such as Ye Lei
Multi-walled carbon nanotube and magnesium hydroxide work as multi-walled carbon nanotube to the cooperative flame retardant effect of ethylene-vinyl acetate copolymer
Additive amount be 2% when, the heat release rate of ethylene-vinyl acetate copolymer can be substantially reduced, 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 of chabasie has
It is the nm of 0.38 nm × 0.38 to have eight yuan of pore canal systems of three-dimensional along crystallography a axis, b axis and c-axis, pore size.Chabasie
Na, K, Ca in structure etc. cation Si-Al between bonding force it is weak, can by cation replacements such as Mg, Sr, Ba, Cu, Zn, Ni,
With stronger ion-exchange capacity, also there is certain flame retardant property as inorganic material.
The purpose of the present invention is exactly to increase the advantage of good, the ultra-fine chabasie of red phosphorus flame-retardant performance and the collaboration of the compounding of fire retardant
Effect concentrates on one, has not only solved to be used alone several respects deficiency existing for red phosphorus combustion inhibitor, but also it is Asia that can prepare granular size
Micron, uniform particle sizes fire retardant.The fire retardant remains the advantage of efficient red phosphorus combustion inhibitor, low cigarette, low toxicity, and has played water chestnut
Chemiluminescence of the zeolite to red phosphorus flame-retardant, moreover it is possible to which effectively control fire-retardant particles size, micro-denier flame resistant agent can also improve
With the compatibility of organic material, the mechanical property and thermal stability of flame retardant composite material are helped to improve.Water chestnut prepared by the present invention
Zeolite-loaded red phosphorus micro-denier flame resistant agent has broad application prospects in organic coating and high molecular film material flame retardant area.
Invention content
The technical solution adopted by the present invention is：A kind of preparation method of chabasie-red phosphorus synergistic fire retardant, 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 decompositions generate yellow phosphorus, and yellow phosphorus is then converted to red phosphorus, you can ultra-fine chabasie-red phosphorus synergistic fire retardant is made.Including with
Lower step：
（1）By the NiCl of chabasie and a certain amount of 0.1mol/L2Solution mixes, the ion exchange certain time at 60 DEG C
Afterwards, it is filtered, washed, dries, obtain loading Ni in duct2+Chabasie；
（2）It will（1）The sample of preparation is placed in quartz tube reactor, is passed through one timing of hydrogen reducing at a certain temperature
Between, obtain the chabasie that Ni is loaded in duct；
（3）It will（2）The chabasie of the load Ni of preparation is passed through hydrogen phosphide one at a certain temperature in quartz tube reactor
It fixes time, hydrogen phosphide is made to be decomposed into yellow phosphorus in chabasie duct；
（4）It will（3）The sample of preparation is heated to certain temperature in the reaction vessel of isolation air, held for some time,
Yellow phosphorus is converted into red phosphorus, obtains the chabasie-red phosphorus synergistic fire retardant for loading red phosphorus in duct.
In a preferred embodiment, the chabasie grain size is 0.4-0.8 μm.
In a preferred embodiment, the NiCl of the chabasie and 0.1mol/L2Solution mixes, the ion exchange at 60 DEG C
Time be 30-120min.
In a preferred embodiment, the Ni loaded in the chabasie duct2+The temperature restored in hydrogen is 400-450
DEG C, time 30-90min.
In a preferred embodiment, the temperature that the hydrogen phosphide decomposes in chabasie duct is 410-440 DEG C, and the time is
2-10h。
In a preferred embodiment, the heating temperature that the yellow phosphorus is converted to red phosphorus is 260-290 DEG C, time 10-
60min。
Product red phosphorus content prepared by the present invention is 4-32%（Mass ratio）.
It is to solve that deficiency existing for red phosphorus combustion inhibitor is used alone the advantages of fire retardant prepared by the present invention, can prepares
Submicron-scale, uniform particle sizes fire retardant.The fire retardant remains the advantage of efficient red phosphorus combustion inhibitor, low cigarette, low toxicity, and sends out
Chemiluminescence of the chabasie to red phosphorus flame-retardant is waved, moreover it is possible to which effectively control fire-retardant particles size, micro-denier flame resistant agent may be used also
To improve the compatibility with organic material, the mechanical property and thermal stability of flame retardant composite material are helped to improve.System of the present invention
Standby technology can effectively control phosphine gas and be decomposed in chabasie duct, can control highly effective flame-retardant ingredient red phosphorus and only enter water chestnut
Inside zeolite cavity, without being deposited in zeolite surface, preparation process is simpler.The present invention is also sodium hypophosphite industry byproduct
The recycling of phosphine gas provides new way.
Specific implementation mode
Embodiment 1
By the NiCl that 20g medians are 0.4 μm of chabasie and 500mL 0.1mol/L2Solution mixes, and is stirred at 60 DEG C
120min is mixed, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 90min is passed through at 450 DEG C, is led at 440 DEG C
Enter hydrogen phosphide, react 10h, after cooling, sample is heated to 290 DEG C in the reaction vessel of isolation air, 60min is kept the temperature, obtains
The fire retardant of red phosphorus is loaded in the chabasie duct for being 32% to red phosphorus content, which is mixed with fire-retardant with polyethylene
The oxygen index (OI) of material is 33.3.
Embodiment 2
By the NiCl that 20g medians are 0.8 μm of chabasie and 500mL 0.1mol/L2Solution mixes, and is stirred at 60 DEG C
30min is mixed, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 30min is passed through at 400 DEG C, is led at 410 DEG C
Enter hydrogen phosphide, react 2h, after cooling, sample is heated to 260 DEG C in the reaction vessel of isolation air, 10min is kept the temperature, obtains
The fire retardant of red phosphorus, the fire proofing which is mixed with polyethylene are loaded in the chabasie duct that red phosphorus content is 4%
Oxygen index (OI) be 28.6.
Embodiment 3
By the NiCl that 20g medians are 0.6 μm of chabasie and 500mL 0.1mol/L2Solution mixes, and is stirred at 60 DEG C
75min is mixed, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 60min is passed through at 425 DEG C, is led at 425 DEG C
Enter hydrogen phosphide, react 6h, after cooling, sample is heated to 275 DEG C in the reaction vessel of isolation air, 35min is kept the temperature, obtains
The fire retardant of red phosphorus, the fire-retardant material which is mixed with polyethylene are loaded in the chabasie duct that red phosphorus content is 16%
The oxygen index (OI) of material is 31.0.
Embodiment 4
By the NiCl that 20g medians are 0.4 μm of chabasie and 500mL 0.1mol/L2Solution mixes, and is stirred at 60 DEG C
120min is mixed, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 30min is passed through at 450 DEG C, is led at 440 DEG C
Enter hydrogen phosphide, react 10h, after cooling, sample is heated to 290 DEG C in the reaction vessel of isolation air, 60min is kept the temperature, obtains
The fire retardant of red phosphorus is loaded in the chabasie duct for being 10% to red phosphorus content, which is mixed with fire-retardant with polyethylene
The oxygen index (OI) of material is 29.5.
Embodiment 5
By the NiCl that 20g medians are 0.4 μm of chabasie and 500mL 0.1mol/L2Solution mixes, and is stirred at 60 DEG C
120min is mixed, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 90min is passed through at 450 DEG C, is led at 440 DEG C
Enter hydrogen phosphide, react 6h, after cooling, sample is heated to 290 DEG C in the reaction vessel of isolation air, 60min is kept the temperature, obtains
The fire retardant of red phosphorus, the fire-retardant material which is mixed with polyethylene are loaded in the chabasie duct that red phosphorus content is 27%
The oxygen index (OI) of material is 32.8.
Oxygen index (OI)（Flame retardant property）Test experiments：
Fire retardant and polyethylene prepared by above-described embodiment 1,2,3,4 and 5 mixes（Wherein fire retardant accounts for 30%）, 120
The laminar sample that thickness is 1mm is made in twin-roll mixing 10min at DEG C.Oxygen index (OI) test is carried out according to GB/T2406-1993.
Claims (1)
1. a kind of preparation method of chabasie-red phosphorus synergistic fire retardant, which is characterized in that include the following steps：With sub-micron water chestnut
Zeolite, hydrogen phosphide are primary raw material, by the NiCl of chabasie and a certain amount of 0.1mol/L2Solution mixes, and ion is handed at 60 DEG C
It changes after a certain period of time, is filtered, washed, dries, obtain loading Ni in duct2+Chabasie, be then placed in quartz tube reactor,
It is passed through hydrogen at a certain temperature, obtains the chabasie for loading Ni in duct, is passed through hydrogen phosphide at a certain temperature later, makes phosphorus
Change hydrogen and be decomposed into yellow phosphorus in chabasie duct, it is heated to certain temperature in the reaction vessel of isolation air, by yellow phosphorus
Red phosphorus is converted to, the chabasie-red phosphorus synergistic fire retardant for loading red phosphorus in duct is obtained；The grain size of chabasie is 0.4-0.8 μm；
Chabasie and NiCl2The time that solion exchanges is 30-120min；The Ni loaded in chabasie duct2+It is restored in hydrogen
Temperature be 400-450 DEG C, time 30-90min；Hydrogen phosphide decomposition temperature in chabasie duct is 410-440 DEG C, the time
For 2-10h；The heating temperature that yellow phosphorus is converted to red phosphorus is 260-290 DEG C, time 10-60min；The fire retardant red phosphorus of preparation contains
Amount is 4-32wt%.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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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| 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 |
| 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 |
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| 氢氧化铝及红磷协同阻燃热收缩材料的制备及性能;汪艳等;《武汉工程大学学报》;20121130;第50-54页 * |
| 浅色水滑石/红磷复合阻燃剂的制备及性能;张延武等;《热固性树脂》;20070531;第21-23页 * |
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