CN1166749C - Super-fine high smoke-suppressing flame retardant and preparing method thereof - Google Patents
Super-fine high smoke-suppressing flame retardant and preparing method thereof Download PDFInfo
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- CN1166749C CN1166749C CNB021008000A CN02100800A CN1166749C CN 1166749 C CN1166749 C CN 1166749C CN B021008000 A CNB021008000 A CN B021008000A CN 02100800 A CN02100800 A CN 02100800A CN 1166749 C CN1166749 C CN 1166749C
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- fire retardant
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
Abstract
The present invention relates to a super-fine high smoke-suppressing type inorganic flame retardant and a preparing method thereof. A full-back-mixing liquid membrane reactor for liquid-liquid two-phase coprecipitation reaction is used for a coprecipitation reaction so as to isolate nucleation and crystallization, and thus, crystal nucleation and growth conditions are respectively controlled. As a result, super-fine flame retardant powder with uniform granularity distribution is prepared. The flame retardant of the present invention can be used for thermoplastic resin and thermosetting resin and can be directly mixed with resin as well as mixed with the modified resin. Besides, the flame retardant has double functions of flame retardation and smoke suppression.
Description
Technical field:
The present invention relates to a kind of super-fine high smoke-suppressing flame retardant and preparation method thereof.
Background technology:
In recent years, synthetic material industry develops rapidly, and macromolecular material is widely-used in fields such as national defence, building, traffic, aviation, electrical equipment, household furniture.Yet macromolecular material generally is flammable, and the harm of fire has become an important social issue.Thereby the macromolecular material that uses under many circumstances need have flame retardancy.Usually adopt the method for adding fire retardant to realize fire-retardant purpose.The development of sound along with flame retardant area rules, establishment of standard in flame-retarded technology, more and more higher to the requirement of fire retardant, the demand of fire retardant is also increasing.
At present, halogen containing polymers such as widely used macromolecular material or PVC add halogen containing flame-retardant therein and can obtain flame retardant resistance.In the fire, these halogenous fire retardants can produce Cl or Br, and the active H reaction of active Cl or Br and superpolymer pyrolysated generates stable compound H Cl, and the incendiary chain reaction is suppressed, and burning is blocked.Regrettably, though this class material has good flame-retardant effect, but can discharge a large amount of smog and hydrogen chloride gas, these smog and hydrogen chloride gas stimulate eye and respiratory system, hinder people and flee the scene, and hinder fire extinguishing and rescue, according to expert statistics, because of the dead philtrum of fire, be more than 90% in the world because the smog and the poisonous gas that give out in the macromolecular material burning are choked to death the people, the expensive equipment of hydrogen chloride gas corrosion.Therefore, the harm that dense smoke, hydrogen halide cause during burning has caused people's great attention.Along with the development of Highrise buildings, subway industry, fire-dense smoke is also increasing to the potential hazard of people's life, and the low cigarette of development, low toxicity, halogen-free flame retardants are imperative.
The inorganic filler type fire retardant toxic low, do not produce corrosive gases, Heat stability is good, can not produce secondary pollution, advantage such as cheap, therefore, inorganic combustion inhibitor is called as nuisanceless fire retardant, comes into one's own day by day, becomes a kind of development trend.The inorganic filler type fire retardant mainly comprises weisspiessglanz, phosphoric acid salt, zinc borate, aluminium hydroxide, magnesium hydroxide etc., wherein the consumption maximum of aluminium hydroxide.Because the addition of inorganic combustion inhibitor in macromolecular material is big, sometimes unexpectedly up to 100-120phr (each hundred parts of resin content), and the surface properties of inorganic filler and polymer nature differ greatly, the two consistency is relatively poor, easily causes the processing characteristics of macromolecular material and physicals sharply to descend.Though reach flame retardant effect preferably, and nontoxic, because the specific surface area of magnesium hydroxide for fire retardant is very little, usually less than 20m
2/ g, it is little to be adsorbed with the poisonous gas ability, and smoke suppressing effect is not obvious, and processing characteristics and physicals in order to keep macromolecular material as far as possible, also needs to carry out complex surfaces to inorganic combustion inhibitor and handles, to improve the consistency with macromolecular material.
Summary of the invention:
Purpose of the present invention: a kind of inorganic type super-fine high smoke-suppressing fire retardant and preparation method thereof is provided, and make it have following feature: particle size distribution is narrow, and decomposes product specific surface area is big and show alkalescence, very easily is adsorbed with poisonous gas, particularly acid toxic gas; Have simultaneously fire-retardant, press down the cigarette double effects; Directly mix and to reach consistency and flame retardant effect preferably with superpolymer.
The invention main points:
A kind of super-fine high smoke-suppressing fire retardant, its chemical constitution and structure are:
[Mg
2+ 1-xAl
3+ x(OH)
2] (CO
3)
2- X/2MH
2O, wherein 0.2＜(x/1-x)＜0.5, m=1-3x/2, it is a laminate structure, laminate is Mg
2+And Al
3+Oxyhydroxide, interlayer is (CO
3)
2-Particle is of a size of 0.04-0.40 μ m, and preferably size of particles is 0.06-0.12 μ m.
The preparation method of above-mentioned super-fine high smoke-suppressing fire retardant, liquid-liquid two-phase coprecipitation reaction that employing is carried out in full back-mixing liquid film reactor, said full back-mixing liquid film reactor, by one the sealing casing as stator, one rotatable cone-shaped rotor is arranged in the stator, the tapering α of rotor (angle on hypotenuse and base on the longitudinal cross-section) is the 50-70 degree, the inner chamber of stator is identical with the rotor tapering cone-shaped, the outside surface of rotor and inner surface of stator have groove respectively, the groove of stator inner surface is shape in the shape of a spiral, the groove of rotor outer surface and the groove shapes of stator, number is identical, but be rightabout spirrillum, the groove width of groove is 1-5 with the groove depth ratio: 1, and the number of supratrochlear depression groove is 2-3 with the ratio of the cms of the maximum diameter of rotor: 1; The long-pending little end of rotor cross-section has liquid distributor, stator is provided with raw material fluid inlet and discharge port, fluid inlet is positioned at the long-pending little end of rotor cross-section, discharge port is positioned at the long-pending big end of rotor cross-section, leave the slit that can regulate size between stator inner surface and the rotor outer surface, gap size can be by variation modulation between the 1-20 micron of rotor and stator relative position.
Concrete reactions steps is as follows:
A: with soluble M g
2+Inorganic salt and solubility Al
3-Inorganic salt are mixed with mixing salt solution, Mg
2+With Al
3+Mol ratio be 1-4.5, Mg
2+Volumetric molar concentration be 0.2-2.5M, Al
3+Volumetric molar concentration be 0.1-1.25M; Yellow soda ash or sodium hydroxide and yellow soda ash are mixed with alkaline solution.
B: mixing salt solution in the steps A and alkaline solution are added respectively in the full back-mixing liquid film reactor simultaneously, and after liquid distributor disperseed, place, the slit thorough mixing between rotor and stator was discharged to crystallizing kettle through discharge port; The rotating speed of control rotor is 1000-8000rpm, and the flow of discharge port is 100-1000kg/h, the consumption of alkaline solution with salt solution mix after pH at 8.5-13 for suitable;
C: the mixed serum that step B is obtained places crystallizing kettle, under 70-180 ℃, stir, crystallization 2-24h, with the material after the crystallization after filtration, wash, be drying to obtain the super-fine high smoke-suppressing fire retardant.
Among the above-mentioned preparation method, said soluble M g in the steps A
2+Inorganic salt are Mg
2+With Cl
-NO
3 -SO
4 2-Any in the soluble salt of forming, the solubility trivalent metal salt is Al
3+With Cl
-NO
3 -SO
4 2-Any in the soluble salt of forming; The mol ratio of its sodium hydroxide of the alkaline solution among the step B and yellow soda ash is 0.5-4.
In full back-mixing liquid film reactor, adopt and force the microcosmic hybrid technology, nucleation and crystallization are separated, make reactant rapid thorough mixing in reactor, reaction back material hightails reactor, nucleation, synchronous growth when realizing particle, thus make material have the characteristic that size of particles is little and be evenly distributed, the size of particle can reach 0.04-0.40 μ m, is preferably 0.06-0.12 μ m; Particle size distribution is narrow, concentrates distribution range less than 0.02 μ m.
The smoke-inhibiting flame retardant effect of super-fine high smoke-suppressing fire retardant of the present invention is mainly reflected in the decomposes process, being divided into two stages carries out, and the decomposition temperature of fs is 50-250 ℃, mainly is to lose crystal water, the decomposition temperature of subordinate phase is 200-400 ℃, mainly carries out interlayer anion CO
3 2-Removing of decomposition and laminate hydroxyl; Absorb a large amount of heats in the decomposition course, reduced the surface temperature of material, the thermolysis of superpolymer and rate of combustion are reduced greatly; The water vapour of emitting during decomposition has diluted inflammable gas simultaneously, also plays fire retardation; In addition, the carbonizing production of frosting combined and forms protective membrane when the Mg-Al composite oxide of generation was with burning after decomposing, and cut off the intrusion of heat energy and oxygen, also reached flame retardant effect; The most important thing is that the Mg-Al composite oxide surface is strong or weakly alkaline, can absorb or adsorb the sour gas that the superpolymer burning is emitted,, thereby have smoke suppressing effect as hydrogenchloride.
Fire retardant of the present invention can directly mix use with thermoplastic resins such as PVC, also can mix use with thermosetting resins such as Resins, epoxy.
Fire retardant of the present invention has good flame-retardant effect to soft pvc etc., and oxygen index shows the flame-proof PVC that adds fire retardant of the present invention under identical or close addition situation, and its flame retardant effect is better than adding the situation of aluminium hydroxide and magnesium hydroxide.Simultaneously, it is more obvious that its smoke suppressing effect shows, and the smoke density test result shows that fire retardant of the present invention is the good fumicants that presses down of soft pvc.Only add 20-40phr (every-hundred parts by weight resin are added the parts by weight of fire retardant) fire retardant of the present invention, just can make the product cigarette speed of soft pvc and maximum smoke density descend about 40%.
Fire retardant of the present invention mixes use with Resins, epoxy, smoke suppressing effect is remarkable under the flameless combustion condition, and is better with the Resins, epoxy mixed effect again after the modification.
Description of drawings:
Fig. 1: the structural representation of the used full back-mixing liquid film reactor of the present invention
Fig. 2: liquid distributor A-A sectional view
Fig. 3: rotor plane is launched synoptic diagram
Fig. 1 is the structural representation of the used full back-mixing liquid film reactor of the present invention, rotor 4 is one to be installed in the cone on the motor shaft 7, tapering α is the 50-70 degree, among Fig. 1 60 degree, its outside surface has helical groove, Fig. 1 further groove cross section is a rectangle, and groove width is 1-5 with the groove depth ratio: 1, and be 4: 1 among Fig. 1; The spiral fluted number is 2-3 with the ratio of the cms of the large section one end diameter of rotor: 1, and be 3: 1 among Fig. 1.Stator 3 is a right cylinder that inner chamber is a cone, and its internal surface has and the reciprocal helical groove of rotor, and the number of groove, shape are identical with rotor.As can be seen from Figure 1 stator 3 is by the slit between screw thread 5 adjustings and the rotor, and the adjustable extent in slit is the 1-20 micron.As can be seen from Figure 2 liquid distributor is the disk that has 4 rectangular paddle 8, is connected with rotor by pin 9.
Mixed salts solution with alkaline solution respectively by two opening for feeds on the stator 3 behind liquid distributor 2, thorough mixing is located in the slit between rotor 4 and stator 3, is discharged to crystallizing kettle through discharge port 6.
Embodiment:
Embodiment 1:
Choose 1.6 mole of magnesium chloride and 0.4 mol sulfuric acid aluminium is made into 1 liter of solution, get 3.8 moles of NaOH and 1.6 moles of Na
2CO
3Be made into 1 liter solution, two solution are mixed reactor slit 11 μ m in full back-mixing liquid film reactor, rotor speed is 3000rpm, and discharge port place liquid flow rate is 500kg/h, mixed serum pH=11.0, mix rear slurry in 100 ℃ of crystallization 6 hours, filtration, washing, drying.
The product crystal phase structure is good, average particle diameter 0.1 μ m, particle distribution D
90(90% particle) is less than 0.12 μ m.
20 parts the above-mentioned fire retardants that make are directly mixed with 100 parts of soft pvcs, the oxygen index LOI that measures the gained matrix material by GB/T 2406-93 and ASTM D 2863-91 is 28.7, carry out the smoke density experiment by ASTM E662-95, the product cigarette speed, maximum smoke density and the smog shading index that are obtained by the smoke density curve can provide the product smoke performance of sample under test condition respectively from different perspectives, and concrete outcome sees Table 1.
Embodiment 2:
Choose 1.6 mol sulfuric acid magnesium and 0.2 mol sulfuric acid aluminium, get 4.2 moles of NaOH and 1.6 moles of Na
2CO
3Be made into 1 liter of solution, two solution are mixed reactor slit 8 μ m in full back-mixing liquid film reactor, rotor speed 1500rpm, discharge port place liquid flow rate is 200kg/h, mixed serum pH=10.5, mixed serum filters 100 ℃ of crystallization 4 hours, washing, drying.
The product crystal phase structure is good, average particle diameter 0.08 μ m, particle distribution D
90Less than 0.1 μ m.
Respectively 60 parts of above-mentioned fire retardants that make are directly mixed with 100 parts of soft pvcs, the oxygen index LOI that measures the gained matrix material by GB/T 2406-93 and ASTM D 2863-91 is 28.4; Carry out the smoke density experiment by ASTME662-95, concrete outcome sees Table 1.
Embodiment 3:
Choose 1.2 molar nitric acid magnesium and 0.2 mol sulfuric acid aluminium is made into 1 liter of solution, get 4.5 moles of NaOH and 2.0 moles of Na
2CO
3Be made into 1 liter of solution, two solution are mixed reactor slit 12 μ m in full back-mixing liquid film reactor, rotor speed is 3500rpm, the liquid flow rate 450kg/h of discharge port place, mixed serum pH=10.5, mixed serum filters 100 ℃ of crystallization 5 hours, washing, drying.
The product crystal phase structure is good, average particle diameter 0.09 μ m, particle distribution D
90Less than 0.11 μ m.
40 parts of fire retardants of the present invention directly mix with 100 parts of soft pvcs, and oxygen index LOI is 28.8, carry out the smoke density experiment by ASTME662-95, and concrete outcome sees Table 1.
The comparative example 1
45 parts of commercially available technical grade fire retardant ultrafine aluminium hydroxides, 50 parts of DOP (dioctyl phthalate (DOP)), 100 parts of soft pvcs, the oxygen index LOI that measures the gained matrix material is 26.0.
The comparative example 2
40 parts of commercially available technical grade fire retardant ultrafine aluminium hydroxides, 30 parts of TOTM (trioctyl trimellitate), 100 parts of soft pvcs, the oxygen index LOI that measures the gained matrix material is 27.0.
The comparative example 3
45 parts of magnesium hydroxides, 50 parts of DOP, 100 parts of soft pvcs, the oxygen index LOI that measures the gained matrix material is 26.0.
Embodiment 4:
Choose 1.6 mole of magnesium chloride and 0.4 mol sulfuric acid aluminium is made into 1 liter of solution, get 3.8 moles of NaOH and 1.6 moles of Na
2CO
3Be made into 1 liter solution, two solution are mixed reactor slit 11 μ m in full back-mixing liquid film reactor, rotor speed is 3000rpm, and discharge port place liquid flow rate is 500kg/h, mixed serum pH=11.0, mix rear slurry in 100 ℃ of crystallization 6 hours, filtration, washing, drying.
The product crystal phase structure is good, average particle diameter 0.1 μ m, particle distribution D
90(90% particle) is less than 0.12 μ m.
20 parts of fire retardants that said process makes, 100 parts of Resins, epoxy directly mix, and make matrix material.Carry out the smoke density experiment by ASTM E662-95, the product cigarette speed, maximum smoke density and the smog shading index that are obtained by the smoke density curve can provide the product smoke performance of sample under test condition respectively from different perspectives, and concrete outcome sees Table 2.
Embodiment 5:
Choose 1.6 mole of magnesium chloride and 0.4 molar nitric acid aluminium is made into 1 liter of solution, get 3.8 moles of NaOH and 1.6 moles of Na
2CO
3Be made into 1 liter solution, two solution are mixed reactor slit 11 μ m in full back-mixing liquid film reactor, rotor speed is 3000rpm, and discharge port place liquid flow rate is 500kg/h, mixed serum pH=11.0, mix rear slurry in 100 ℃ of crystallization 6 hours, filtration, washing, drying.
The product crystal phase structure is good, average particle diameter 0.1 μ m, particle distribution D
90(90% particle) is less than 0.12 μ m.
40 parts of fire retardants that said process makes, 100 parts of Resins, epoxy, other is with embodiment 4.Concrete outcome sees Table 2.
Embodiment 6:
Choose 1.6 mole of magnesium chloride and 0.4 mol sulfuric acid aluminium is made into 1 liter of solution, get 3.8 moles of NaOH and 1.6 moles of Na
2CO
3Be made into 1 liter solution, two solution are mixed reactor slit 11 μ m in full back-mixing liquid film reactor, rotor speed is 3000rpm, and discharge port place liquid flow rate is 500kg/h, mixed serum pH=11.0, mix rear slurry in 100 ℃ of crystallization 6 hours, filtration, washing, drying.
The product crystal phase structure is good, average particle diameter 0.1 μ m, particle distribution D
90(90% particle) is less than 0.12 μ m.
60 parts of fire retardants that said process makes, 100 parts of Resins, epoxy, other is with embodiment 4.Concrete outcome sees Table 2.
Embodiment 7:
Choose 1.6 mole of magnesium chloride and 0.4 mol sulfuric acid aluminium is made into 1 liter of solution, get 3.8 moles of NaOH and 1.6 moles of Na
2CO
3Be made into 1 liter solution, two solution are mixed reactor slit 11 μ m in full back-mixing liquid film reactor, rotor speed is 3000rpm, and discharge port place liquid flow rate is 500kg/h, mixed serum pH=11.0, mix rear slurry in 100 ℃ of crystallization 6 hours, filtration, washing, drying.
The product crystal phase structure is good, average particle diameter 0.1 μ m, particle distribution D
90(90% particle) is less than 0.12 μ m.
Fire retardant of the present invention after 20 parts of modifications, 100 parts of Resins, epoxy, other is with embodiment 4.Concrete outcome sees Table 2.
Show that by embodiment and test result fire retardant of the present invention is the good fumicants that presses down of soft pvc.Only add 20-40phr fire retardant of the present invention, just can make the product cigarette speed of soft pvc and maximum smoke density descend about 40%.The invention fire retardant mixes use with Resins, epoxy, smoke suppressing effect is remarkable under the flameless combustion condition.
Table 1
| Sample | PVC | Embodiment 1 | | Embodiment 2 |
| Fire retardant/phr of the present invention | 0 | 20 | 40 | 60 |
| Flameless combustion: | ||||
| Produce cigarette speed R | 67.4 | 63.9 | 38.7 | 43.8 |
| Maximum smoke density Dm | 479.9 | 455.0 | 275.6 | 312.2 |
| Smog shading index SOI | 571 | 210 | 183 | 155 |
| Flaming combustion: | ||||
| Produce cigarette speed R | 88.0 | 54.3 | 56.8 | 59.0 |
| Maximum smoke density Dm | 626.1 | 386.6 | 404.7 | 419.9 |
| Smog shading index SOI | 2220 | 911 | 727 | 782 |
| Oxygen index LOI | 28.7 | 28.8 | 28.4 | |
Table 2
| Sample | Resins, epoxy | Embodiment 4 | Embodiment 5 | | |
| Sample thickness/mm | 3.8 | 3.8 | 3.9 | 4.0 | 4.0 |
| Flameless combustion: | |||||
| Produce cigarette speed R | 113 | 74.0 | 75.6 | 51.4 | 62.4 |
| t 16/min | 2.8 | 2.4 | 2.7 | 4.3 | 3.7 |
| Maximum smoke density Dm | 805.9 | 524.7 | 537.2 | 363.4 | 443.1 |
| Smog shading index SOI | 326 | 166 | 150 | 43.6 | 74.7 |
Claims (4)
1. super-fine high smoke-suppressing fire retardant, its chemical constitution and structure are:
[Mg
2+ 1-xAl
3+ x(OH)
2] (CO
3)
2- X/2MH
2O, wherein 0.2＜(x/1-x)＜0.5, m=1-3x/2, it is a laminate structure, laminate is Mg
2+And Al
3+Oxyhydroxide, interlayer is (CO
3)
2-, particle is of a size of 0.04-0.40 μ m.
2. according to the super-fine high smoke-suppressing fire retardant of claim 1, it is characterized in that: size of particles is 0.06-0.12 μ m.
3. the preparation method of claim 1 or 2 super-fine high smoke-suppressing fire retardant adopts the liquid-liquid two-phase coprecipitation reaction that carries out in full back-mixing liquid film reactor, and concrete reactions steps is as follows:
A: with soluble M g
2+Inorganic salt and solubility Al
3+Inorganic salt are mixed with mixing salt solution, Mg
2+With Al
3+Mol ratio be 1-4.5, Mg
2+Volumetric molar concentration be 0.2-2.5M, Al
3+Volumetric molar concentration be 0.1-1.25M; Yellow soda ash and sodium hydroxide are mixed with alkaline solution, wherein the consumption of alkaline solution with salt solution mix after pH at 8.5-13 for suitable;
B: mixing salt solution in the steps A and alkaline solution are added respectively in the full back-mixing liquid film reactor simultaneously, and after liquid distributor disperseed, place, the slit thorough mixing between rotor and stator was discharged to crystallizing kettle through discharge port; The rotating speed of control rotor is 1000-8000rpm, and the flow of discharge port is 100-1000kg/h, the consumption of alkaline solution with salt solution mix after pH at 8.5-13 for suitable;
C: the mixed serum that step B is obtained places crystallizing kettle, under 70-180 ℃, stir, crystallization 2-24h, with the material after the crystallization after filtration, wash, be drying to obtain the super-fine high smoke-suppressing fire retardant.
4. according to the preparation method of claim 3, it is characterized in that: the soluble M g in the steps A
2+Inorganic salt are muriate, nitrate or vitriol; Solubility Al
3+Inorganic salt are muriate, nitrate or vitriol; The mol ratio of the sodium hydroxide of alkaline solution and yellow soda ash is 0.5-4 among the step B.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021008000A CN1166749C (en) | 2002-01-29 | 2002-01-29 | Super-fine high smoke-suppressing flame retardant and preparing method thereof |
| AU2002344028A AU2002344028A1 (en) | 2002-01-29 | 2002-10-25 | A superfine flame retardant agent having smoke suppression and method of the same |
| PCT/CN2002/000758 WO2003091358A1 (en) | 2002-01-29 | 2002-10-25 | A superfine flame retardant agent having smoke suppression and method of the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021008000A CN1166749C (en) | 2002-01-29 | 2002-01-29 | Super-fine high smoke-suppressing flame retardant and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1435467A CN1435467A (en) | 2003-08-13 |
| CN1166749C true CN1166749C (en) | 2004-09-15 |
Family
ID=27627278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021008000A Expired - Fee Related CN1166749C (en) | 2002-01-29 | 2002-01-29 | Super-fine high smoke-suppressing flame retardant and preparing method thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1166749C (en) |
| AU (1) | AU2002344028A1 (en) |
| WO (1) | WO2003091358A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717649B (en) * | 2009-11-13 | 2013-06-12 | 西安电子科技大学 | Preparation method of enhanced magnesium-aluminum composite flame retardant |
| CN102585845B (en) * | 2010-12-31 | 2014-04-09 | 梁清源 | Inorganic mineral composite flame retardant and preparation method thereof |
| CN103046316A (en) * | 2012-12-07 | 2013-04-17 | 浙江理工大学 | Method for finishing environment-friendly flame-retardant waterproof coating fabric |
| CN103113623B (en) * | 2013-02-25 | 2014-06-25 | 合肥工业大学 | Preparation method of LDHs (Layered Double Hydroxides) composite flame retardant |
| CN114573011A (en) * | 2022-03-18 | 2022-06-03 | 北京化工大学 | Controllable preparation method of ultrathin composite metal hydroxides with different thicknesses |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5392855A (en) * | 1977-01-27 | 1978-08-15 | Kyowa Kagaku Kougiyou Kk | Noncombustible composition of thermoplastic resin |
| JP2585052B2 (en) * | 1988-03-14 | 1997-02-26 | 神島化学工業株式会社 | Manufacturing method of inorganic flame retardant for thermoplastic resin |
| CN1036593A (en) * | 1988-03-29 | 1989-10-25 | M&T化学有限公司 | Flame retardant polymer is formed |
| CN1144858C (en) * | 1997-12-24 | 2004-04-07 | 中国科学院近代物理研究所 | Process for preparing surface-active magnesium hydrooxide flame retardant |
-
2002
- 2002-01-29 CN CNB021008000A patent/CN1166749C/en not_active Expired - Fee Related
- 2002-10-25 AU AU2002344028A patent/AU2002344028A1/en not_active Abandoned
- 2002-10-25 WO PCT/CN2002/000758 patent/WO2003091358A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002344028A1 (en) | 2003-11-10 |
| CN1435467A (en) | 2003-08-13 |
| WO2003091358A1 (en) | 2003-11-06 |
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