CN106397836B - The preparation method of nano-beta molecular sieve-red phosphorus synergistic fire retardant - Google Patents
The preparation method of nano-beta molecular sieve-red phosphorus synergistic fire retardant Download PDFInfo
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- 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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Abstract
The present invention relates to a kind of preparation method of nano-beta molecular sieve red phosphorus synergistic fire retardant, the method is by beta-molecular sieve and the NiCl of a certain amount of 0.1mol/L2Solution mixes, at 60 DEG C after 20 90min of ion exchange, it is filtered, washed, dries, then it is placed in quartz tube reactor, 10 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 7 37% in the duct in（Mass ratio）The beta-molecular sieve 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 of nano-beta molecular sieve-red phosphorus synergistic fire retardant
Method.
Background technology
With the enhancing of health of people environmental consciousness, seeking environmentally friendly, less toxic, efficient, multi-functional fire retardant has 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 the synergistic effect of flame retardant property, i.e. 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 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 is with stability is good, nontoxic or less 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 fire block articles performance is improved, 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, so as 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；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 of the red phosphorus in storing, production, process：It second is that can be white
Degreeization to desalinate the color of red phosphorus, widens the application range 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 complicated, fire retardant
Granular size is difficult to control, and 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.At present, some existing researchers have 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 when being 2%, 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.）.
Beta-molecular sieve is the porous material for having tetragonal structure regular pore canal structure, and structure composition is (Nan[AlnSi64- nO128, n<7), aperture is about 0.6-0.8 nm, and skeleton is made of the polymorph mixing both with 12 rings.In duct
Metal ion has ion-exchange capacity, also has certain flame retardant property as inorganic material.
The purpose of the present invention is exactly by red phosphorus flame-retardant performance is good, the advantage of nano-beta molecular sieve material and the compounding of fire retardant
Synergy concentrates on one, and it is insufficient not only to have solved to be used alone several respects existing for red phosphorus combustion inhibitor, but also can to prepare particle big
It is small for nanoscale, uniform particle sizes fire retardant.The fire retardant remains the advantages of efficient red phosphorus combustion inhibitor, low cigarette, low toxicity, and sends out
Chemiluminescence of the beta-molecular sieve material to red phosphorus flame-retardant is waved, moreover it is possible to effectively control fire-retardant particles size, nano-meter flame retardants
The compatibility with organic material can also be improved, help to improve the mechanical property and thermal stability of flame retardant composite material.This hair
Ultra-fine dose of the nano-beta molecular sieve load red phosphorus of bright preparation has wide in organic coating and high molecular film material flame retardant area
Application prospect.
Invention content
The technical solution adopted by the present invention is：A kind of preparation method of nano-beta molecular sieve-red phosphorus synergistic fire retardant, this hair
It is bright using nano-beta molecular sieve, hydrogen phosphide as primary raw material, first Ni is loaded in beta-molecular sieve duct, then make hydrogen phosphide in beta molecule
Generation yellow phosphorus is catalytically decomposed by Ni in sieve pore road, yellow phosphorus is then converted to red phosphorus, you can nano-beta molecular sieve-red phosphorus collaboration resistance is made
Fire agent.Include the following steps：
（1）By beta-molecular sieve and the NiCl of 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+Beta-molecular sieve；
（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 beta-molecular sieve of load Ni in duct；
（3）It will（2）The beta-molecular sieve of the load Ni of preparation is passed through hydrogen phosphide at a certain temperature in quartz tube reactor
Certain time makes hydrogen phosphide be decomposed into yellow phosphorus in beta-molecular sieve 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 loading beta-molecular sieve-red phosphorus synergistic fire retardant of red phosphorus in duct.
In a preferred embodiment, the beta-molecular sieve grain size is 80-100nm.
In a preferred embodiment, the NiCl of the beta-molecular sieve and 0.1mol/L2Solution mixes, and ion is handed at 60 DEG C
The time changed is 20-90min.
In a preferred embodiment, the Ni loaded in the beta-molecular sieve duct2+The temperature restored in hydrogen is 400-
450 DEG C, time 10-90min.
In a preferred embodiment, the temperature that the hydrogen phosphide decomposes in beta-molecular sieve duct is 410-440 DEG C, the time
For 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 7-37%（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
Nano-scale, the fire retardant of uniform particle sizes.The fire retardant remains the advantages of efficient red phosphorus combustion inhibitor, low cigarette, low toxicity, and plays
Chemiluminescence of the beta-molecular sieve to red phosphorus flame-retardant, moreover it is possible to which effectively control fire-retardant particles size, nano-meter flame retardants can be with
Improve the compatibility with organic material, help to improve the mechanical property and thermal stability of flame retardant composite material.It is prepared by the present invention
Technology can effectively control phosphine gas to be decomposed in beta-molecular sieve duct, can control highly effective flame-retardant ingredient red phosphorus only into β points
Inside sub- sieve pore road, without being deposited in molecular sieve surface, preparation process 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
By the NiCl of beta-molecular sieve and 500mL 0.1mol/L that 10g medians are 80nm2Solution mixes, at 60 DEG C
90min is stirred, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 90min is passed through at 450 DEG C, at 440 DEG C
Hydrogen phosphide is passed through, reacts 10h, after cooling, sample in the reaction vessel of isolation air is heated to 290 DEG C, keeps the temperature 60min,
Obtain loading the fire retardant of red phosphorus, the resistance which is mixed with polyethylene in the beta-molecular sieve duct that red phosphorus content is 37%
The oxygen index (OI) of combustible material is 33.8.
Embodiment 2
By the NiCl of beta-molecular sieve and 500mL 0.1mol/L that 10g medians are 100nm2Solution mixes, at 60 DEG C
Lower stirring 20min after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 10min is passed through at 400 DEG C, 410 DEG C
Under be passed through hydrogen phosphide, react 2h, after cooling, sample in the reaction vessel of isolation air be heated to 260 DEG C, keeps the temperature 10min,
Obtain loading the fire retardant of red phosphorus, the resistance which is mixed with polyethylene in the beta-molecular sieve duct that red phosphorus content is 7%
The oxygen index (OI) of combustible material is 28.2.
Embodiment 3
By the NiCl of beta-molecular sieve and 500mL 0.1mol/L that 10g medians are 90nm2Solution mixes, at 60 DEG C
55min is stirred, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 50min is passed through at 425 DEG C, at 425 DEG C
Hydrogen phosphide is passed through, reacts 6h, after cooling, sample in the reaction vessel of isolation air is heated to 275 DEG C, 35min is kept the temperature, obtains
The fire retardant of red phosphorus is loaded in the beta-molecular sieve duct that red phosphorus content is 22%, which is mixed with fire-retardant with polyethylene
The oxygen index (OI) of material is 32.7.
Embodiment 4
By the NiCl of beta-molecular sieve and 500mL 0.1mol/L that 10g medians are 80nm2Solution mixes, at 60 DEG C
90min is stirred, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 10min is passed through at 450 DEG C, at 440 DEG C
Hydrogen phosphide is passed through, reacts 10h, after cooling, sample in the reaction vessel of isolation air is heated to 290 DEG C, keeps the temperature 60min,
Obtain loading the fire retardant of red phosphorus, the resistance which is mixed with polyethylene in the beta-molecular sieve duct that red phosphorus content is 12%
The oxygen index (OI) of combustible material is 30.1.
Embodiment 5
By the NiCl of beta-molecular sieve and 500mL 0.1mol/L that 10g medians are 80nm2Solution mixes, at 60 DEG C
90min is stirred, after being filtered, washed, drying, is placed in quartz tube reactor, after hydrogen 90min is passed through at 450 DEG C, at 440 DEG C
Hydrogen phosphide is passed through, reacts 6h, after cooling, sample in the reaction vessel of isolation air is heated to 290 DEG C, 60min is kept the temperature, obtains
The fire retardant of red phosphorus is loaded in the beta-molecular sieve duct that red phosphorus content is 34%, which is mixed with fire-retardant with polyethylene
The oxygen index (OI) of material is 33.2.
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. the preparation method of a kind of nano-beta molecular sieve-red phosphorus synergistic fire retardant, which is characterized in that include the following steps：With nanometer
Beta-molecular sieve, hydrogen phosphide are primary raw material, by beta-molecular sieve and the NiCl of a certain amount of 0.1mol/L2Solution mix, at 60 DEG C from
Son exchanges after a certain period of time, is filtered, washed, dries, and obtains 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, obtains loading the beta-molecular sieve of Ni in duct, is passed through phosphatization at a certain temperature later
Hydrogen makes hydrogen phosphide be decomposed into yellow phosphorus in beta-molecular sieve duct, will be heated to a constant temperature in its reaction vessel in isolation air
Degree, red phosphorus is converted to by yellow phosphorus, obtains loading beta-molecular sieve-red phosphorus synergistic fire retardant of red phosphorus in duct；The grain size of beta-molecular sieve
For 80-100nm；Beta-molecular sieve and NiCl2The time that solion exchanges is 20-90min；The Ni loaded in beta-molecular sieve duct2+
The temperature restored in hydrogen is 400-450 DEG C, time 10-90min；Hydrogen phosphide decomposition temperature in beta-molecular sieve duct is
410-440 DEG C, time 2-10h；The heating temperature that yellow phosphorus is converted to red phosphorus is 260-290 DEG C, time 10-60min；It prepares
Fire retardant red phosphorus content be 7-37wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6033206A (en) * | 1983-07-29 | 1985-02-20 | Nippon Chem Ind Co Ltd:The | Phosphorus-zeolite composite, its manufacture, and flame retardant |
| JP3409800B2 (en) * | 1992-11-19 | 2003-05-26 | 日本化学工業株式会社 | Stabilized red phosphorus composition and flame retardant polymer material |
| US8288455B1 (en) * | 2011-12-06 | 2012-10-16 | Empire Technology Development, Llc | 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 |
| CN103506146B (en) * | 2013-10-09 | 2015-03-04 | 周口师范学院 | Catalyst for decomposing hydrogen phosphide gas as well as preparation method and application thereof |
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