CN101717649B - Preparation method of enhanced magnesium-aluminum composite flame retardant - Google Patents

Preparation method of enhanced magnesium-aluminum composite flame retardant Download PDF

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CN101717649B
CN101717649B CN 200910218948 CN200910218948A CN101717649B CN 101717649 B CN101717649 B CN 101717649B CN 200910218948 CN200910218948 CN 200910218948 CN 200910218948 A CN200910218948 A CN 200910218948A CN 101717649 B CN101717649 B CN 101717649B
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magnesium
hydroxide
flame retardant
aluminum
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CN101717649A (en
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任庆利
罗强
李菲
王毓鹏
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Xidian University
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Abstract

The invention relates to a preparation method of enhanced magnesium-aluminum composite flame retardant, comprising the following steps of: 1. respectively preparing magnesium sulfate and crystallized magnesium chloride into 1000ml water solution, and mixing according to the mol concentration of 1: 1; 2. heating the mixed solution to 50 DEG C, adding calcium hydroxide power and preserving the temperature at 75 to 85 DEG C; 3. stopping heating when the solution becomes white suspended solution completely, putting into a baking oven after the suspended solution precipitates completely, and baking for 15 to 20 hours at 75 to 80 DEG C; 4. washing and filtering the precipitate to obtain basic magnesium chloride crystals; 5. adding the basic magnesium chloride into a sodium hydroxide and calcium hydroxide basic solution and soaking for 6 hours; 6. adding aluminum salts and sodium carbonate into reactant of the step 5 and preparing into 1000ml water solution; and 7. heating the mixed solution in the step 6 to 70 to 90 DEG C, stopping heating after 4 to 6 hours, putting into the baking oven after the suspended solution precipitates completely and baking for 3 to 6 hours, washing and filtering the precipitate to obtain the enhanced magnesium-aluminum composite flame retardant containing magnesium hydroxide and calcium carbonate.

Description

A kind of preparation method of enhanced magnesium-aluminum composite flame retardant
Technical field
The invention belongs to chemical material technical field, more particularly, the present invention relates to a kind of enhanced magnesium-aluminum composite flame retardant (fibrous crystals magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3) the preparation method, with the enhanced magnesium-aluminum composite flame retardant of this method preparation be used for the sheath of power cable, electronics, electrical equipment etc. or shell fire-retardant/toughener, and interior decoration with the occasions such as furred ceiling use fire-retardant/toughener.
Background technology
Fire preventing is a subject content of modern society's safety.Progress and development along with science and technology, the raising of people's living standard, the macromolecular materials such as plastics, rubber, synthon are applied to all respects such as building, communications and transportation, electrical material, aerospace, mining, household furniture and daily necessities widely.These macromolecule material products overwhelming majority has the characteristics such as inflammable or flammable, especially when they and electrical equipment are combined, more easily brings out fire, causes huge financial loss and loss of life and personal injury to society.Therefore it is very important these equipment being carried out fire-retardant finish.And the fire retardant that uses at present mostly is halogen containing flame-retardant, and as the cable sheath of traditional halogen containing flame-retardant, decomposition folds hydrogen halide when strongly being heated or burning, harm people's health, and also can produce corrosive nature to metal.Environmental protection is the theme of 21 century.Based on to the protection of environment and the concern of human health, develop nontoxic, as to hang down cigarette, Halogen inorganic anti-flaming material and become the Main Trends of The Development of fire retardant material.Particularly the RoHS instruction of European Union and WEEE instruction were promulgated in 2003, and in June, 2006 subsequently after some countries carry out, more and more stricter to the performance requriements of fire retardant, the research of fire retardant and fire retardant material must adapt to the requirement of International Environmental Protection rules.What replace will be the environment friendly flame retardant of safety non-toxic.Therefore the exploitation Showed Very Brisk of inorganic combustion inhibitor, the relevant scientific research institution in various countries has strengthened the research to inorganic combustion inhibitor, to obtain fire retardant with safety in utilization.
" a kind of preparation method of aluminum hydroxide and magnesium hydroxide composite fire retardant " fire retardant patent application case (application number: 200710179627.8 of Chinese Aluminium Co., Ltd, the applying date: 2007.12.17), relate to the surface chemical modification treatment process as the aluminium hydroxide powder of fire retardant.It is characterized in that its preparation process is the acid magnesium salt solution to be added in active ultrafine aluminium hydroxide nucleus and the mother liquor in sodium hydroxide or aluminum oxide production process react, after surface of aluminum hydroxide forms the magnesium hydroxide coating layer, then through liquid-solid separation, washing, drying, break up and obtain the aluminum magnesium hydroxide composite granule.The aluminium hydroxide of the inventive method preparation is by depositing magnesium hydroxide in the ultrafine aluminium hydroxide surface chemistry, make surface of aluminum hydroxide coat the magnesium hydroxide of one deck densification, the composite flame-retardant agent median size that obtains (d50＜2.5 μ m), initial heat decomposition temperature＞255 ℃, temperature of initial decomposition higher than 220 ℃, pure cerium hydroxide aluminium, effectively improve the processing characteristics of aluminium hydroxide, widen its range of application.But the shortcoming of the method: the one, prepare " active ultrafine aluminium hydroxide nucleus ", and want " liquid-solid separation, washing, drying, break up " etc., technological operation requires harsh.The 2nd, there is no the control to " crystal habit ".
Another of Chinese Aluminium Co., Ltd " a kind of chemical method prepares the method for aluminium hydroxide, magnesium hydroxide composite fire retardant " patent application case (application number: 200610080470.9, the applying date: 2006.05.17), relate to a kind of preparation method for the plastic flame additive.The Al that the method is used 2O 3Concentration is 100～200g/L, α kBe in 1.40～1.65 sodium aluminate solution, add with sodium aluminate solution in the mol ratio of caustic alkali be the magnesium salts (MgSO of 1: 1.5 to 1: 10 4And MgCl 2Mixing solutions), at 20～80 ℃ of temperature, stirring reaction added the flocculation dewatering agent after 10～60 minutes, filtered to obtain solid materials; Add again dispersion agent, obtain powdery aluminium hydroxide, magnesium hydroxide composite fire retardant through making beating filtration, washing, oven dry.The heat-resisting decomposition temperature of the composite flame-retardant agent that method of the present invention is prepared obviously improves, reach more than 250 ℃, granularity and dispersed aspect all be improved.The weak point of the method is not have " crystal habit " to control, and will add " flocculation dewatering agent and dispersion agent " in preparation process, makes technique become complicated.
The patent application of Southeast China University " the compound fire retardant of a kind of organic-inorganic " (application number: 200410044838.7, the applying date: 2004.05.31), relate to a kind of cigarette and flame retardant properties of pressing down that have, good with the organic materials consistency, the composite flame-retardant agent that organic materials is had strengthening action, its chemical constitution is: [M 2+ 1-xM 3+ x(OH) 2] x+A n- x/nYH 2O is wherein: M 2+Mg 2+, Ca 2+, Mn 2+, Fe 2+, Co 2+, Ni 2+, Cu 2+, Zn 2+Deng one of divalent metal; M 3+Al 3+, Fe 3+, Cr 3+, Co 3+Deng one of trivalent metal cation; A n-Be that average valence is the inorganic or organic mixed anion with flame retardant properties or assistance flame retardant properties of n, the span of n is 1≤n≤6; The span of x is 0.1＜x＜0.5; The value of y is relevant with preparation condition, and scope is 0≤3y≤5 usually; Has laminate structure, by M 2+And M 3+Hydroxide layer and interlayer anion A n-Consist of.The deficiency of the method is not have " crystal habit " to control.
" method for preparing nano inorganic compound flame retardant with transfer method " (application number: 200510008695.9 of Beijing University of Chemical Technology, the applying date: 2005.03.04), be a kind ofly to utilize in the composite flame-retardant agent raw material micron order magnesium hydroxide macrobead to make carrier composite nanometer flame retardant to be carried out the method for surface modification treatment.nano inorganic compound flame retardant is comprised of nano grade inorganic fire retardant and micron order magnesium hydroxide and auxiliary flame retardant, the nano grade inorganic fire retardant is nano-aluminum hydroxide or nano-sized magnesium hydroxide, the median size of nano grade inorganic fire retardant≤100 nanometers, the median size of micron order magnesium hydroxide is at 1～10 micron, first surface-modifying agent is mixed with micron order magnesium hydroxide high-speed stirring, then adding the nano grade inorganic fire retardant to continue high-speed stirring mixes, add again at last the auxiliary flame retardant high-speed stirring to mix, finally obtain the nano inorganic compound flame retardant that the surface is coated with surface-modifying agent.Nano inorganic compound flame retardant with the present invention's preparation is used for flame-proof composite material, can obviously improve the tensile strength of flame-proof composite material.The shortcoming 1 of the method: nano-aluminum hydroxide, nanostructure modified aluminium hydroxide or nano-sized magnesium hydroxide and micron order magnesium hydroxide and auxiliary flame retardant are made respectively, and machinery mixes, and do not have " crystal habit " to control.Shortcoming 2: how to solve " the nanometer agglomeration problem " of inorganic nanoparticles in organic polymer; The inorganic nanoparticles of different-grain diameter is carrying out compound tense with organic polymer, and poly-agglomerating " segregation " problem of inorganic nanoparticles always occurs.Cause the severe exacerbations such as inorganic/organic fire-resisting matrix material machinery, electrical property, and can't use.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of inorganic enhanced magnesium-aluminum composite flame retardant (fibrous crystals magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3) the preparation method, solving the existing existing defective of inorganic combustion inhibitor technology, good with the enhanced magnesium-aluminum composite flame retardant crystal habit of the present invention's preparation, purity is high, and is remarkable as its flame retardant effect of fire retardant.
Enhanced magnesium-aluminum composite flame retardant provided by the invention (fibrous crystals magnesium aluminum-hydrotalcite Mg6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3) the preparation method, as follows by mole concentration proportioning for the preparation of component sal epsom+crystallization magnesium chloride, aluminium salt, sodium hydroxide, sodium carbonate and the calcium hydroxide of fire retardant:
Sal epsom+crystallization magnesium chloride 1.82mol/L～3.1mol/L
Aluminium salt 0.608mol/L～1.067mol/L
Sodium hydroxide 9.1mol/L～10.21mol/L
Sodium carbonate 2.84mol/L～3.11mol/L
Calcium hydroxide 0.03mol/L--2.1mol/L.
Wherein, solubility sal epsom and crystallization magnesium chloride jointly provide and generate the required magnesium ion of fire retardant; Calcium hydroxide promotes whisker growth and provides to generate the required calcium ion of calcium carbonate; Calcium hydroxide and sodium hydroxide also are used for adjusting the pH value; Sodium carbonate provides and generates the required carbanion of calcium carbonate; Aluminium salt provides the aluminum ion in the magnesium aluminum-hydrotalcite component.
In above-mentioned enhanced magnesium-aluminum composite flame retardant prepares component, the preferred sodium aluminate of aluminium salt, crystal aluminum chloride or aluminium carbonate.
Experiment of the present invention shows, along with magnesium source (sal epsom (MgSO 4)+crystallization magnesium chloride (MgCl 26H 2O)) raising of concentration, the pH value of reaction system descends significantly.Do not have whisker to occur when magnesium source concentration lower (0.5mol/L), from X diffraction result, product is the very high magnesium hydroxide of purity; After concentration brought up to 1.5, a part of whisker had appearred.Although X diffraction result is still magnesium hydroxide, resultant is needle-like crystal.After magnesium source concentration reaches 1.82mol/L, can observe a large amount of whiskers and generate.From X diffraction result, the resultant major part is basic magnesium chloride (Mg 3(OH) 5Cl4H 2O).When concentration continues to bring up to 3.1, just react to change towards contrary direction.
The experimental installation that the present invention prepares enhanced magnesium-aluminum composite flame retardant as shown in Figure 1.Reactor is a uncovered container 1, adopts electric furnace 3 heating; Agitator 4 carries out mechanical stirring, and stirring velocity is adjustable continuously in 50～3000r/min scope.
The present invention prepares the fibrous crystals magnesium-aluminum composite, and fire-retardant/toughener carries out according to the following steps:
The first step is mixed with crystallization magnesium chloride and sal epsom respectively the aqueous solution of 1000ml, and after once filtering, crystallization magnesium chloride and magnesium sulfate solution mixed in 1: 1 in molar ratio; Its volumetric molar concentration meets given proportioning;
Second step is heated to 50 ℃ with the magnesium solution that mixes, and then adds wherein the calcium hydroxide powder; In 75 ℃～85 ℃ scopes, selected constant temperature insulation, and constantly stir, constantly measure the pH value of solution therebetween, the pH value is controlled in 7.5～8 scopes;
In the 3rd step, after reaction solution became white suspension liquid fully, stopped heating, standing was put into baking oven after the suspension liquid precipitation is complete, carry out skillfully according to corresponding temperature and time;
Wherein: skilled temperature range is: 75 ℃～80 ℃.Skilled period, scope was: 15 hours～20 hours.
The 4th step, will precipitate and wash once, filter, obtain producing fibrous basic magnesium chloride crystal (Mg 3(OH) 5Cl4H 2O).
With above-mentioned component proportioning and the prepared basic magnesium chloride of processing method, through scanning electron microscope (SEM) observation, prepared Mg 3(OH) 5Cl4H 2The footpath of O: 1 micron～2 microns, long: as 10 microns～50 microns, to see Fig. 2～Fig. 3.Through the electron diffraction of transmission electron microscope, show that prepared basic magnesium chloride is single crystal, sees Fig. 4.Through the XRD test, its chemical constitution is Mg 3(OH) 5Cl4H 2O sees Fig. 5.
The 5th step added in the strong alkaline aqueous solution that sodium hydroxide and calcium hydroxide is made into (the pH value is controlled at 11) being prepared into basic magnesium chloride, soaked 6 hours;
The 6th step added aluminium salt and sodium carbonate in the reactant of the 5th step acquisition, be mixed with the aqueous solution of 1000ml by said ratio;
The 7th step was heated to 70 ℃～90 ℃ with this mixing solutions, and constantly stirred, and constantly measured the pH value of solution therebetween, and the pH value is controlled at 11;
In the 8th step, the reaction times is controlled at 4 hours to 6 hours, and then stopped heating, standing, put into baking oven after the suspension liquid precipitation is complete, carries out skillfully according to corresponding temperature and time;
Wherein: skilled temperature range is: 50 ℃～90 ℃.Skilled period, scope was: 3 days～6 days.
The 8th step, will precipitate washing once, filter, acquisition fibrous crystals magnesium-aluminum composite is fire-retardant/toughener (fibrous crystals magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3).
The equation of above-mentioned chemical reaction is:
1.MgCl 2+2MgSO 4+4H 2O+2Ca(OH) 2+NaOH→Mg 3(OH) 5Cl·4H 2O+2CaSO 4+NaCl
2. add aluminium salt:
A) when aluminium salt sodium aluminate, the equation of chemical reaction is:
Mg 3(OH) 5Cl·4H 2O+NaOH+NaAlO 2+Na 2CO 3+Ca(OH) 2
→Mg 6Al 2(OH) 16CO 3·4H 2O+NaCl+H 2O+CaCO 3+Mg(OH) 2
B) when aluminium salt crystal aluminum chloride, the equation of chemical reaction is:
Mg 3(OH) 5Cl·4H 2O+NaOH+AlCl 3·6H 2O+Na 2CO 3+Ca(OH) 2
→Mg 6Al 2(OH) 16CO 3·4H 2O+NaCl+H 2O+CaCO 3+Mg(OH) 2
C) when aluminium salt aluminium carbonate, the equation of chemical reaction is:
Mg 3(OH) 5Cl·4H 2O+NaOH+Al 2(CO 3) 3+Na 2CO 3+Ca(OH) 2
→Mg 6Al 2(OH) 16CO 3·4H 2O+NaCl+H 2O+CaCO 3+Mg(OH)2
With above-mentioned component proportioning and the prepared fibrous crystals enhanced magnesium-aluminum composite flame retardant of processing method, observe through scanning electron microscope (SEM), prepared fibrous footpath: 0.8 micron～5 microns, long: as 5 microns～45 microns, to see Fig. 6 (a)～Figure 10 (a).Through the XRD test, its chemical constitution is magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3Complex phase is seen Fig. 6 (b)～Figure 10 (b).
Compared with prior art, the present invention has following characteristics:
(1) magnesium hydroxide that provides with method of the present invention is a kind of enhanced magnesium-aluminum composite flame retardant fire-retardant, smoke elimination performance brilliance that has.Single with regard to magnesium aluminum-hydrotalcite, is exactly a kind of Halogen, nontoxic, desirable fire retardant, can be fire-retardant at (gas phase, condensed phase), many-side such as smoke elimination, filling play the effect of prevention polymer combustion.Magnesium hydroxide and calcium carbonate have also been generated with method of the present invention when generating magnesium aluminum-hydrotalcite, so-called magnesium hydroxide itself is also a kind of Halogen of excellent property, nontoxic fire retardant and smoke suppressant, increase magnesium hydroxide like " alliance between giants; have complementary advantages " in magnesium aluminum-hydrotalcite, the magnesium aluminum-hydrotalcite performance of the good fire-proof smoke suppressor of script performance is optimized more.And calcium carbonate is the reinforcing inorganic filler that is widely used in plastics and rubber, that is: it is that a kind of skeleton supports, and plays booster action to consisting of crystal.Enhanced magnesium-aluminum composite flame retardant magnesium aluminum-hydrotalcite Mg of the present invention 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3Complex body generates by chemical reaction, and each component compatibility is good, and " nanometer agglomeration problem ", " segregation " problem of the composition appearance that mixes can not occur adding with physical mechanical method.
(2) magnesium aluminum-hydrotalcite Mg of the present invention 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3Preparation fibrous crystals magnesium aluminum-hydrotalcite Mg under normal pressure 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3, avoided in the hydrothermal method requirement to autoclave.
(3) technological process is simple, and resultant need to slaking in thick gravy, does not require specific installation, and raw materials used sufficient cheap, is suitable for industrialized production fully.
(4) observation from scanning electron microscope shows, fibrous crystals magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3The crystal habit homogeneity good; Show this fibrous crystals magnesium aluminum-hydrotalcite Mg through the XRD test 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3Phase composite is stable.
(4) dry front fibrous crystals magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3Good dispersity in the aqueous solution.
(5) fibrous crystals magnesium aluminum-hydrotalcite Mg of the present invention 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3, have Halogen, nontoxic, the characteristics that press down cigarette as fire retardant, be conducive to protection and the human health of environment, be a kind of efficient inorganic combustion inhibitor new variety of very promising enhancement type.It is further exploitation magnesium salt whisker/flame retardance of polymer enhanced type composite material, and basic substance and wide research and development spaces are provided.
Description of drawings
Fig. 1 the present invention prepares basic magnesium chloride whisker experimental installation schematic diagram
The scanning electron microscope of Fig. 2 basic magnesium chloride whisker (SEM) photo (amplify 1500 times, the right scale is 10 microns)
The scanning electron microscope of Fig. 3 basic magnesium chloride whisker (SEM) photo (amplify 1500 times, the right scale is 10 microns)
The electron diffraction result of the transmission electron microscope of Fig. 4 basic magnesium chloride whisker
The XRD figure spectrum of the homemade basic magnesium chloride whisker of Fig. 5 shows that its chemical constitution is Mg 3(OH) 5Cl4H 2O
Fig. 6 (a) fibrous crystals magnesium-aluminum composite is fire-retardant/scanning electron microscope (SEM) photo (amplify 5000 times, middle scale is 5 microns) of toughener
Fig. 6 (b) fibrous crystals magnesium-aluminum composite is fire-retardant/the XRD figure spectrum of toughener, show that its chemical constitution is: magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3
Fig. 7 (a) fibrous crystals magnesium-aluminum composite is fire-retardant/scanning electron microscope (SEM) photo (amplify 1000 times, middle scale is 10 microns) of toughener
Fig. 7 (b) fibrous crystals magnesium-aluminum composite is fire-retardant/the XRD figure spectrum of toughener, show that its chemical constitution is: magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3
Fig. 8 (a) fibrous crystals magnesium-aluminum composite is fire-retardant/scanning electron microscope (SEM) photo (amplify 1000 times, middle scale is 10 microns) of toughener
Fig. 8 (b) fibrous crystals magnesium-aluminum composite is fire-retardant/the XRD figure spectrum of toughener, show that its chemical constitution is: magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3
Fig. 9 (a) fibrous crystals magnesium-aluminum composite is fire-retardant/scanning electron microscope (SEM) photo (amplify 2000 times, middle scale is 10 microns) of toughener
Fig. 9 (b) fibrous crystals magnesium-aluminum composite is fire-retardant/the XRD figure spectrum of toughener, show that its chemical constitution is: magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3
Figure 10 (a) fibrous crystals magnesium-aluminum composite is fire-retardant/scanning electron microscope (SEM) photo (amplify 2000 times, middle scale is 10 microns) of toughener
Figure 10 (b) fibrous crystals magnesium-aluminum composite is fire-retardant/the XRD figure spectrum of toughener, show that its chemical constitution is: magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3
Embodiment
Below in conjunction with preferred embodiment, content of the present invention is elaborated.
Embodiment 1
Getting the magnesium ion concentration that is mixed with by crystallization magnesium chloride and sal epsom (mixing in 1: 1 in molar ratio) is 1.82mol/L, NaAlO 2Be 0.608mol/L, NaOH is 9.1mol/L, Na 2CO 3Be 2.84mol/L, Ca (OH) 2Be 0.03mol/L, react according to above step.Wherein prepare producing fibrous basic magnesium chloride crystal (Mg 3(OH) 5Cl4H 2O) time: its temperature of reaction is that 75 ℃, reaction times are 3 hours, and skilled temperature subsequently is that 75 ℃, skilled period are 15 hours.And when preparing fibrous enhanced magnesium-aluminum composite flame retardant: its temperature of reaction is that 70 ℃, reaction times are 4 hours, and skilled temperature subsequently is that 60 ℃, skilled period are 3 days.Obtain the enhanced magnesium-aluminum composite flame retardant in approximately 5 microns～15 microns of length, approximately 0.8 micron～2 microns, footpath, see Fig. 6.
Embodiment 2
Getting the magnesium ion concentration that is mixed with by crystallization magnesium chloride and sal epsom (mixing in 1: 1 in molar ratio) is 3.1mol/L, NaAlO 2Be 1.067mol/L, NaOH is 10.21mol/L, Na 2CO 3Be 3.11mol/L, Ca (OH) 2Be 2.1mol/L, react according to above step.Wherein prepare producing fibrous basic magnesium chloride crystal (Mg 3(OH) 5Cl4H 2O) time: its temperature of reaction is that 85 ℃, reaction times are 4 hours, and skilled temperature subsequently is that 80 ℃, skilled period are 20 hours.And when preparing fibrous enhanced magnesium-aluminum composite flame retardant: its temperature of reaction is that 90 ℃, reaction times are 5 hours, and skilled temperature subsequently is that 85 ℃, skilled period are 6 days.Obtain the enhanced magnesium-aluminum composite flame retardant in approximately 8 microns～40 microns of length, approximately 0.8 micron～5 microns, footpath, see Fig. 7.
Embodiment 3
Getting the magnesium ion concentration that is mixed with by crystallization magnesium chloride and sal epsom (mixing in 1: 1 in molar ratio) is 2.4mol/L, NaAlO 2Be 0.826mol/L, NaOH is 10mol/L, Na 2CO 3Be 2.95mol/L, Ca (OH) 2Be 1.2mol/L, react according to above step.Wherein prepare producing fibrous basic magnesium chloride crystal (Mg 3(OH) 5Cl4H 2O) time: its temperature of reaction is that 80 ℃, reaction times are 4 hours, and skilled temperature subsequently is that 80 ℃, skilled period are 20 hours.And when preparing fibrous enhanced magnesium-aluminum composite flame retardant: its temperature of reaction is that 80 ℃, reaction times are 4 hours, and skilled temperature subsequently is that 90 ℃, skilled period are 5 days.Obtain the enhanced magnesium-aluminum composite flame retardant in approximately 15 microns～35 microns of length, approximately 1 micron～4 microns, footpath, see Fig. 8.
Embodiment 4
Getting the magnesium ion concentration that is mixed with by crystallization magnesium chloride and sal epsom (mixing in 1: 1 in molar ratio) is 2.6mol/L, AlCl 36H 2O is 0.912mol/L, and NaOH is 10mol/L, Na 2CO 3Be 2.97mol/L, Ca (OH) 2Be 1.3mol/L, react according to above step.Wherein prepare producing fibrous basic magnesium chloride crystal (Mg 3(OH) 5Cl4H 2O) time: its temperature of reaction is that 85 ℃, reaction times are 4 hours, and skilled temperature subsequently is that 80 ℃, skilled period are 16 hours.And when preparing fibrous enhanced magnesium-aluminum composite flame retardant: its temperature of reaction is that 85 ℃, reaction times are 5 hours, and skilled temperature subsequently is that 90 ℃, skilled period are 6 days.Obtain the enhanced magnesium-aluminum composite flame retardant in approximately 30 microns～45 microns of length, approximately 2 microns～5 microns, footpath, see Fig. 9.
Embodiment 5
Getting the magnesium ion concentration that is mixed with by crystallization magnesium chloride and sal epsom (mixing in 1: 1 in molar ratio) is 2.9mol/L, Al 2(CO 3) 3Be 0.98mol/L, NaOH is 10.2mol/L, Na 2CO 3Be 3.07mol/L, Ca (OH) 2Be 1.6mol/L, react according to above step.Wherein prepare producing fibrous basic magnesium chloride crystal (Mg 3(OH) 5Cl4H 2O) time: its temperature of reaction is that 80 ℃, reaction times are 5 hours, and skilled temperature subsequently is that 80 ℃, skilled period are 18 hours.And when preparing fibrous enhanced magnesium-aluminum composite flame retardant: its temperature of reaction is that 80 ℃, reaction times are 6 hours, and skilled temperature subsequently is that 50 ℃, skilled period are 6 days.Obtain the magnesium-aluminum composite flame retardant in approximately 8 microns～30 microns of length, approximately 1 micron～3 microns, footpath, see Figure 10.

Claims (2)

1. the preparation method of an enhanced magnesium-aluminum composite flame retardant, component sal epsom+crystallization magnesium chloride, aluminium salt, sodium hydroxide, sodium carbonate and the calcium hydroxide of preparation fire retardant are as follows by mole concentration proportioning:
Figure FSB00000997314600011
In above-mentioned enhanced magnesium-aluminum composite flame retardant prepared component, aluminium salt was sodium aluminate, crystal aluminum chloride or aluminium carbonate;
Its feature comprises the following steps:
The first step is mixed with sal epsom and crystallization magnesium chloride respectively the aqueous solution of 1000ml, and sal epsom and crystallization magnesium chloride are mixed by mole concentration ratio at 1: 1, and its volumetric molar concentration meets given proportioning;
Second step is heated to 50 ℃ with the mixing solutions of magnesium ion, then adds wherein the calcium hydroxide powder, constantly stirs, and in 75 ℃～85 ℃ insulations, constantly measures the pH value of solution therebetween, and the pH value is controlled in 7.5～8 scopes;
The 3rd step, after reaction solution becomes white suspension liquid fully, stopped heating, standing, put into baking oven until suspension liquid precipitation after fully and carry out skillfully, skillfully temperature is: 75 ℃～80 ℃, be skilled period: 15 hours～20 hours;
The 4th step, will precipitate washing filtering, obtain producing fibrous basic magnesium chloride crystal " Mg 3(OH) 5Cl4H 2O ";
The 5th step added the basic magnesium chloride of preparation in the strong alkaline aqueous solution that sodium hydroxide and calcium hydroxide is made into and soaked 6 hours, and the pH value is controlled at 11;
The 6th step added aluminium salt and sodium carbonate in the reactant of the 5th step acquisition, add the aqueous solution that water is mixed with 1000ml;
In the 7th step, the mixing solutions that the 6th step was made is heated to 70 ℃～90 ℃, and constantly stirs, and constantly measures the pH value of solution therebetween, and the pH value is controlled at 11;
The 8th step, stopped heating after mixing solutions 4～6 hours reaction, standing, put into baking oven until the suspension liquid precipitation after fully and carry out skillfully, skillfully temperature is: 50 ℃～90 ℃, be skilled period: 3 days～6 days;
The 9th step, will precipitate washing filtering, obtain to contain the enhanced magnesium-aluminum composite flame retardant " Mg of magnesium hydroxide and calcium carbonate 6Al 2(OH) 16CO 34H 2O/Mg (OH) 2/ CaCO 3".
2. the preparation method of enhanced magnesium-aluminum composite flame retardant according to claim 1, it is characterized in that: the component of prepared enhanced magnesium-aluminum composite flame retardant is magnesium aluminum-hydrotalcite Mg 6Al 2(OH) 16CO 34H 2O/ magnesium hydroxide Mg (OH) 2/ calcium carbonate CaCO 3Complex phase, its crystal habit is fibrous crystals, the footpath: 0.8 micron～5 microns, long: 5 microns～45 microns.
CN 200910218948 2009-11-13 2009-11-13 Preparation method of enhanced magnesium-aluminum composite flame retardant Expired - Fee Related CN101717649B (en)

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CN106049161B (en) * 2016-05-25 2017-10-24 西安电子科技大学 Calcium carbonate and magnalium nano composite fire retardant paper and preparation method thereof
CN106745609B (en) * 2016-12-29 2020-06-16 西安电子科技大学 Preparation method of enhanced aluminum calcium chloride crystal
CN108585001B (en) * 2018-03-30 2020-05-05 岭南师范学院 Layered double metal hydroxide LDH-CO3-SO42-Preparation method and application of whisker
CN108706620B (en) * 2018-05-29 2020-06-16 西北工业大学 Nano calcium hydroxide/magnesium aluminum carbonate nano hydrotalcite nano composite material and preparation method thereof
CN109516481B (en) * 2019-01-18 2020-10-27 安徽工业大学 Preparation method of magnesium-aluminum composite flame retardant
CN111793248B (en) * 2020-07-22 2021-10-08 江西广源化工有限责任公司 Talcum powder-magnesium hydroxide composite inorganic flame-retardant filler and preparation method thereof
CN112724465A (en) * 2020-12-29 2021-04-30 宁波艾克姆新材料有限公司 Flame-retardant silane crosslinked nano modified polyolefin pre-dispersed master batch auxiliary
CN114427173B (en) * 2022-01-17 2022-12-16 齐鲁工业大学 High-flame-retardancy magnesium hydroxide flame-retardant paper and in-situ synthesis method thereof
CN115724449B (en) * 2022-11-22 2023-12-12 浙大城市学院 Mixed salt nano aluminum adjuvant and preparation method and application thereof

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