CN106397836A - Preparation method of nano Beta molecular sieve and red phosphorus synergistic flame retardant - Google Patents
Preparation method of nano Beta molecular sieve and red phosphorus synergistic flame retardant Download PDFInfo
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- CN106397836A CN106397836A CN201610817137.5A CN201610817137A CN106397836A CN 106397836 A CN106397836 A CN 106397836A CN 201610817137 A CN201610817137 A CN 201610817137A CN 106397836 A CN106397836 A CN 106397836A
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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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention relates to a preparation method of nano Beta molecular sieve and red phosphorus synergistic flame retardant, comprising: mixing Beta molecular sieve and suitable NiCl2 solution having a concentration of 0.1 mol/L, allowing ion exchanging at 60 DEG C for 20-90 min, filtering, washing and drying, placing in a quartz tube reactor, introducing hydrogen at 400-450 DEG C for 10-90 min, introducing hydrogen phosphide at 410-440 DEG C for 2-10 h, heating the sample in an air isolated reaction vessel at 260-290 DEG C, and holding the temperature for 10-60 min to obtain the Beta molecular sieve and red phosphorus synergistic flame retardant with 7-37% (by mass) of red phosphorus loaded to ducts. The preparation process is simple, the defects of the sole use of red phosphorus flame retardant are overcome, and the prepared flame retardant has good flame retardance.
Description
Technical field
The invention belongs to technical field of flame retardant is and in particular to a kind of preparation of nano-beta molecular sieve-red phosphorus synergistic fire retardant
Method.
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, form the Metaphosphoric acid with 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.）.
Beta-molecular sieve is the porous material with tetragonal structure regular pore canal structure, and its structure composition is (Nan[AlnSi64- nO128, n<7), aperture is about 0.6-0.8 nm, and skeleton is mixed by the polymorph both with ten bicyclo- and forms.In duct
Metal ion has ion-exchange capacity, also has certain fire resistance as inorganic material.
The purpose of the present invention is exactly that good for the red phosphorus flame-retardant performance, advantage of nano-beta molecular sieve material and fire retardant is compounding
Synergistic concentrates on one, and the several respects both solving to be used alone red phosphorus combustion inhibitor presence are not enough, can prepare granule big again
The little fire retardant for nanoscale, 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 beta-molecular sieve material to the chemiluminescence of red phosphorus flame-retardant moreover it is possible to effective control fire-retardant particles size, nano-meter flame retardantses
The compatibility with organic material can also be improved, be favorably improved mechanical property and the heat stability of flame-proof composite material.This
Nano-beta molecular sieve ultra-fine dose of the red phosphorus of load of bright preparation has wide in organic coating and high molecular film material flame retardant area
Application prospect.
Content of the invention
The technical solution used in the present invention is：A kind of preparation method of nano-beta molecular sieve-red phosphorus synergistic fire retardant, this
Bright with nano-beta molecular sieve, hydrogen phosphide as primary raw material, first in beta-molecular sieve duct, load Ni, then make hydrogen phosphide in beta molecule
In sieve aperture road, yellow phosphorus is generated by Ni catalytic decomposition, yellow phosphorus is then converted to red phosphorus, you can prepared nano-beta molecular sieve-red phosphorus works in coordination with resistance
Combustion agent.Comprise the following steps：
（1）NiCl by beta-molecular sieve 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+Beta-molecular sieve；
（2）Will（1）The sample of preparation is placed in quartz tube reactor, is passed through hydrogen reducing certain time at a certain temperature, obtains
The beta-molecular sieve of Ni is loaded in duct；
（3）Will（2）The beta-molecular sieve of the load Ni of preparation, in quartz tube reactor, is passed through hydrogen phosphide certain at a certain temperature
Time, hydrogen phosphide is made to be decomposed into yellow phosphorus in beta-molecular sieve duct；
（4）Will（3）The sample of preparation 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, obtains loading the beta-molecular sieve-red phosphorus synergistic fire retardant of red phosphorus in duct.
In a preferred embodiment, described beta-molecular sieve particle diameter is 80-100nm.
In a preferred embodiment, the NiCl of described beta-molecular sieve and 0.1mol/L2Solution mixes, and at 60 DEG C, ion is handed over
The time changed is 20-90min.
In a preferred embodiment, the Ni loading in described beta-molecular sieve duct2+In hydrogen, the temperature of reduction is 400-
450 DEG C, the time is 10-90min.
In a preferred embodiment, the temperature that described hydrogen phosphide decomposes in beta-molecular sieve duct is 410-440 DEG C, the time
For 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 7-37%（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
Nano-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, plays again
, to the chemiluminescence of red phosphorus flame-retardant moreover it is possible to effective control fire-retardant particles size, nano-meter flame retardantses are acceptable for beta-molecular sieve
Improve the compatibility with organic material, be favorably improved mechanical property and the heat stability of flame-proof composite material.Prepared by the present invention
Technology can be decomposed effective control phosphine gas in beta-molecular sieve duct, highly effective flame-retardant composition red phosphorus can be controlled only to enter β and divide
Inside sub- sieve aperture road, without depositing in molecular sieve surface, 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 beta-molecular sieve for 80nm for the 10g 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 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 37% beta-molecular sieve 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 33.8.
Embodiment 2
NiCl by the beta-molecular sieve for 100nm for the 10g median and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
Mix 20min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 10min at 400 DEG C, logical 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, is incubated 10min, obtains
Red phosphorus content be 7% beta-molecular sieve 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 28.2.
Embodiment 3
NiCl by the beta-molecular sieve for 90nm for the 10g median and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
55min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 50min 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 22% beta-molecular sieve duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) be 32.7.
Embodiment 4
NiCl by the beta-molecular sieve for 80nm for the 10g 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 10min 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 12% beta-molecular sieve 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 30.1.
Embodiment 5
NiCl by the beta-molecular sieve for 80nm for the 10g 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 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 34% beta-molecular sieve duct in load red phosphorus fire retardant, the fire proofing that this fire retardant and polyethylene are mixed with
Oxygen index (OI) be 33.2.
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 nano-beta molecular sieve-red phosphorus synergistic fire retardant is it is characterised in that comprise the following steps：With nanometer
Beta-molecular sieve, hydrogen phosphide are primary raw material, by the NiCl of beta-molecular sieve and a certain amount of 0.1mol/L2Solution mix, at 60 DEG C from
After son exchanges certain time, filter, wash, be dried, obtain loading Ni in duct2+Beta-molecular sieve, be then placed on quartzy tube reaction
In device, it is passed through hydrogen at a certain temperature, obtain in duct, loading the beta-molecular sieve of Ni, be passed through phosphatization afterwards at a certain temperature
Hydrogen, makes hydrogen phosphide be decomposed into yellow phosphorus in beta-molecular sieve duct, and it is heated to a constant temperature in the reaction vessel of isolation air
Degree, yellow phosphorus is converted to red phosphorus, obtains loading the beta-molecular sieve-red phosphorus synergistic fire retardant of red phosphorus in duct；The particle diameter of beta-molecular sieve
For 80-100nm；Beta-molecular sieve and NiCl2The time that solion exchanges is 20-90min；The Ni of load in beta-molecular sieve duct2+
In hydrogen, the temperature of reduction is 400-450 DEG C, and the time is 10-90min；Hydrogen phosphide decomposition temperature in beta-molecular sieve duct is
410-440 DEG C, the time is 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；Preparation
Fire retardant red phosphorus content be 7-37%（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 CN201610817137.5A patent/CN106397836B/en active Active
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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