CN106397835A - Preparation method of superfine A type molecular sieve-red phosphorus synergistic flame retardant - Google Patents
Preparation method of superfine A type molecular sieve-red phosphorus synergistic flame retardant Download PDFInfo
- Publication number
- CN106397835A CN106397835A CN201610817028.3A CN201610817028A CN106397835A CN 106397835 A CN106397835 A CN 106397835A CN 201610817028 A CN201610817028 A CN 201610817028A CN 106397835 A CN106397835 A CN 106397835A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- type molecular
- red phosphorus
- temperature
- duct
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to a preparation method of a superfine A type molecular sieve-red phosphorus synergistic flame retardant; the method comprises the steps: mixing an A type molecular sieve with a certain amount of a 0.1 mol/L NiCl2 solution, carrying out ion exchange for 10-120 min at the temperature of 60 DEG C, filtering, washing, drying, then placing in a quartz tube reactor, introducing hydrogen gas for 10-90 min at the temperature of 400-450 DEG, then introducing hydrogen phosphide for 2-10 h at the temperature of 410-440 DEG C, and finally carrying out heating heat preservation of the sample for 10-60 min at the temperature of 260-290 DEG C in an air isolated reaction vessel, to obtain the A type molecular sieve-red phosphorus synergistic flame retardant loaded with 5-35 mass% of red phosphorus in pore passages. The preparation process is relatively simple, the deficiency of single use of a red phosphorus flame retardant is solved, and the prepared flame retardant has good flame retardant property.
Description
Technical field
The invention belongs to technical field of flame retardant is and in particular to a kind of system of ultra-fine A type molecular sieve-red phosphorus synergistic fire retardant
Preparation 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 technology such as fine 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 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 less, in base
In material, decentralization 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：Thermally decomposed, formed 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, process 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 hydrotalcite 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 endurance
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.）.
A type molecular sieve is the porous material with regular pore canal structure, and the pore volume of the A type molecular sieve of submicron order is 2-
10cm3/ g, the metal ion in duct has ion-exchange capacity, also has certain fire resistance as inorganic material.
The purpose of the present invention is exactly answering the advantage of good, ultra-fine for red phosphorus flame-retardant performance A type molecular sieve material and fire retardant
Join Synergistic and concentrate on one, the several respects both solving to be used alone red phosphorus combustion inhibitor presence are not enough, can prepare particle again
Size is sub-micron, the fire retardant of uniform particle sizes.This fire retardant remains that red phosphorus combustion inhibitor is efficient, the advantage of low cigarette, low toxicity, and
Play A type molecular sieve material to the chemiluminescence of red phosphorus flame-retardant moreover it is possible to effective control fire-retardant particles size, ultra-fine resistance
Combustion agent can also improve the compatibility with organic material, is favorably improved mechanical property and the heat endurance of flame-proof composite material.
The ultra-fine A type molecular sieve load red phosphorus combustion inhibitor of present invention preparation has in organic coating and high molecular film material flame retardant area
Wide application prospect.
Content of the invention
The technical solution used in the present invention is：A kind of preparation method of ultra-fine A type molecular sieve-red phosphorus synergistic fire retardant, this
Invention, with sub-micron A type molecular sieve, hydrogen phosphide as primary raw material, first loads Ni in A type molecular sieve duct, then makes hydrogen phosphide
In A type molecular sieve duct, yellow phosphorus is generated by Ni catalytic decomposition, yellow phosphorus is then converted to red phosphorus, you can prepared ultra-fine A type molecular sieve-
Red phosphorus synergistic fire retardant.Comprise the following steps：
（1）NiCl by A type molecular sieve and a certain amount of 0.1mol/L2Solution mixes, after ion exchange certain time at 60 DEG C,
Filter, wash, be dried, obtain loading Ni in duct2+A type 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 A type molecular sieve of Ni is loaded in duct；
（3）Will（2）The A type molecular sieve of the load Ni of preparation, in quartz tube reactor, is passed through hydrogen phosphide one at a certain temperature
Fix time, make hydrogen phosphide be decomposed into yellow phosphorus in A type 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 A type molecular sieve-red phosphorus synergistic fire retardant of red phosphorus in duct.
In a preferred embodiment, described A type molecular sieve can be 3A, 4A or 5A type, and its particle diameter is 100-400nm.
In a preferred embodiment, the NiCl of described A type molecular sieve and 0.1mol/L2Solution mixes, ion at 60 DEG C
The time exchanging is 10-120min.
In a preferred embodiment, the Ni loading in described A type 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 A type molecular sieve duct is 410-440 DEG C, when
Between be 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 5-35%（Mass ratio）.
The advantage of fire retardant prepared by the present invention is to solve the deficiency being used alone red phosphorus combustion inhibitor presence, can prepare
Submicron-scale, the fire retardant of uniform particle sizes.This fire retardant remains that red phosphorus combustion inhibitor is efficient, the advantage of low cigarette, low toxicity, sends out again
, moreover it is possible to effective control fire-retardant particles size, micro-denier flame resistant agent is also for the chemiluminescence having waved A type molecular sieve to red phosphorus flame-retardant
The compatibility with organic material can be improved, be favorably improved mechanical property and the heat endurance of flame-proof composite material.The present invention
Technology of preparing can be decomposed effective control phosphine gas in A type molecular sieve duct, only can control highly effective flame-retardant composition red phosphorus
Enter inside A type molecular sieve duct, without depositing in molecular sieve surface, preparation technology is simpler.The present invention is also hypophosphorous acid
The recycling of sodium industry byproduct phosphine gas provides new way.
Specific embodiment
Embodiment 1
NiCl by the A type molecular sieve of 10g median 100nm and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
Mix 120min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 90min at 450 DEG C, logical 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, is incubated 60min, obtains
The fire retardant of red phosphorus, the resistance that this fire retardant and polyethylene are mixed with is loaded in the A type molecular sieve duct being 35% to red phosphorus content
The oxygen index (OI) of combustible material is 33.1.
Embodiment 2
NiCl by the A type molecular sieve of 10g median 400nm and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
Mix 10min, 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 5% A type molecular sieve duct in load red phosphorus fire retardant, it is fire-retardant that this fire retardant and polyethylene are mixed with
The oxygen index (OI) of material is 27.9.
Embodiment 3
NiCl by the A type molecular sieve of 10g median 250nm and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
Mix 65min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 50min at 425 DEG C, logical 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, is incubated 35min, obtains
Red phosphorus content be 20% A type molecular sieve duct in load red phosphorus fire retardant, it is fire-retardant that this fire retardant and polyethylene are mixed with
The oxygen index (OI) of material is 31.5.
Embodiment 4
NiCl by the A type molecular sieve of 10g median 100nm and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
Mix 120min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 10min at 450 DEG C, logical 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, is incubated 60min, obtains
The fire retardant of red phosphorus, the resistance that this fire retardant and polyethylene are mixed with is loaded in the A type molecular sieve duct being 10% to red phosphorus content
The oxygen index (OI) of combustible material is 30.0.
Embodiment 5
NiCl by the A type molecular sieve of 10g median 100nm and 500mL 0.1mol/L2Solution mixes, and stirs at 60 DEG C
Mix 120min, filter, washing, be dried after, be placed in quartz tube reactor, after being passed through hydrogen 90min at 450 DEG C, logical 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, is incubated 60min, obtains
Red phosphorus content be 31% A type molecular sieve duct in load red phosphorus fire retardant, it is fire-retardant that this fire retardant and polyethylene are mixed with
The oxygen index (OI) of material is 32.6.
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 ultra-fine A type molecular sieve-red phosphorus synergistic fire retardant is it is characterised in that comprise the following steps：With Asia
Micron A type molecular sieve, hydrogen phosphide are primary raw material, by the NiCl of A type molecular sieve and a certain amount of 0.1mol/L2Solution mixes,
After ion exchange certain time at 60 DEG C, filter, wash, be dried, obtain loading Ni in duct2+A type molecular sieve, be then placed on
In quartz tube reactor, it is passed through hydrogen at a certain temperature, obtain loading the A type molecular sieve of Ni in duct, afterwards in a constant temperature
It is passed through hydrogen phosphide under degree, makes hydrogen phosphide be decomposed into yellow phosphorus in A type molecular sieve duct, by it in the reaction vessel of isolation air
It is heated to uniform temperature, yellow phosphorus is converted to red phosphorus, obtain in duct, loading the A type molecular sieve-red phosphorus synergistic fire retardant of red phosphorus；
A type molecular sieve can be 3A, 4A or 5A type, and its particle diameter is 100-400nm；A type molecular sieve and NiCl2Solion exchange when
Between be 10-120min；The Ni of load in A type 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 A type molecular sieve duct is 410-440 DEG C, and the time is 2-10h；Yellow phosphorus is converted to red phosphorus
Heating-up temperature is 260-290 DEG C, and the time is 10-60min；The fire retardant red phosphorus content of preparation is 5-35%（Mass ratio）.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817028.3A CN106397835B (en) | 2016-09-12 | 2016-09-12 | The preparation method of ultra-fine A type molecular sieve-red phosphorus synergistic fire retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817028.3A CN106397835B (en) | 2016-09-12 | 2016-09-12 | The preparation method of ultra-fine A type molecular sieve-red phosphorus synergistic fire retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106397835A true CN106397835A (en) | 2017-02-15 |
| CN106397835B CN106397835B (en) | 2018-07-06 |
Family
ID=57999680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610817028.3A Active CN106397835B (en) | 2016-09-12 | 2016-09-12 | The preparation method of ultra-fine A type molecular sieve-red phosphorus synergistic fire retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397835B (en) |
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 CN201610817028.3A patent/CN106397835B/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》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106397835B (en) | 2018-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | The synergistic effect of layered double hydroxides with other flame retardant additives for polymer nanocomposites: a critical review | |
| Liu et al. | Preparation of ammonium polyphosphate and dye co-intercalated LDH/polypropylene composites with enhanced flame retardant and UV resistance properties | |
| CN104072805B (en) | A kind of preparation method of composite flame-retardant agent based on Vermiculitum | |
| Li et al. | Mitigation the release of toxic PH3 and the fire hazard of PA6/AHP composite by MOFs | |
| CN103087360B (en) | Micro encapsulation expandable flame retardant natural rubber and preparation method thereof is covered in double-contracting | |
| CN111004414B (en) | Two-component intercalated hydrotalcite-like additive and application thereof in polypropylene plastics | |
| Wang et al. | Nanoengineering core/shell structured brucite@ polyphosphate@ amine hybrid system for enhanced flame retardant properties | |
| CN110003575A (en) | A kind of ethylene propylene diene rubber of halogen-free flameproof | |
| Liu et al. | Activated carbon spheres (ACS)@ SnO2@ NiO with a 3D nanospherical structure and its synergistic effect with AHP on improving the flame retardancy of epoxy resin | |
| Chen et al. | Improving fire resistance of epoxy resin using electrolytic manganese residue-based zeolites modified with metal–organic framework ligands | |
| CN103788459B (en) | The preparation method of nanometer hydrogen-oxygen oxygen bismuth/polyethylene fire retardant composite material | |
| Liu et al. | A novel ternary inorganic–organic hybrid flame retardant containing biomass and MOFs for high-performance rigid polyurethane foam | |
| CN106317459B (en) | A kind of preparation method of cancrinite-red phosphorus synergistic fire retardant | |
| CN106397837B (en) | The preparation method of ultra-fine ZSM-5 molecular sieve-red phosphorus synergistic fire retardant | |
| CN117026638A (en) | Paste composite flame retardant | |
| CN106397835A (en) | Preparation method of superfine A type molecular sieve-red phosphorus synergistic flame retardant | |
| CN106366347B (en) | The preparation method of ultra-fine X-type molecular sieve-red phosphorus synergistic fire retardant | |
| CN106366346B (en) | A kind of preparation method of superfine Y-type molecular sieve-red phosphorus synergistic fire retardant | |
| CN106349506B (en) | A kind of preparation method of sodalite-red phosphorus synergistic fire retardant | |
| CN106397836B (en) | The preparation method of nano-beta molecular sieve-red phosphorus synergistic fire retardant | |
| Song et al. | Coordination bond cleavage of metal–organic frameworks and application to flame-retardant polymeric materials | |
| CN106279930B (en) | The preparation method of chabasie-red phosphorus synergistic fire retardant | |
| CN106317460B (en) | A kind of preparation method of p-zeolite-red phosphorus synergistic fire retardant | |
| CN107674303B (en) | Modified kaolin flame-retardant synergist and preparation method and application thereof | |
| CN106349507B (en) | A kind of preparation method of modenite-red phosphorus synergistic fire retardant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |