CN1915828A - Method for preparing superfine aluminium hydroxide in flame retardant grade with high initial dehydration temperature - Google Patents
Method for preparing superfine aluminium hydroxide in flame retardant grade with high initial dehydration temperature Download PDFInfo
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- CN1915828A CN1915828A CN 200610127176 CN200610127176A CN1915828A CN 1915828 A CN1915828 A CN 1915828A CN 200610127176 CN200610127176 CN 200610127176 CN 200610127176 A CN200610127176 A CN 200610127176A CN 1915828 A CN1915828 A CN 1915828A
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 title claims abstract description 79
- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910021502 aluminium hydroxide Inorganic materials 0.000 title claims description 65
- 230000018044 dehydration Effects 0.000 title claims description 38
- 238000006297 dehydration reaction Methods 0.000 title claims description 38
- 239000013078 crystal Substances 0.000 claims abstract description 23
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 22
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 21
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229910001679 gibbsite Inorganic materials 0.000 claims description 7
- 230000009257 reactivity Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229940037003 alum Drugs 0.000 claims description 4
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 abstract 3
- 235000019837 monoammonium phosphate Nutrition 0.000 abstract 3
- 239000006012 monoammonium phosphate Substances 0.000 abstract 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 3
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 6
- 239000003595 mist Substances 0.000 description 6
- 238000001757 thermogravimetry curve Methods 0.000 description 5
- 238000001149 thermolysis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical group OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004347 surface barrier Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Fireproofing Substances (AREA)
Abstract
This invention relates to a method for preparing flame-retardant-grde ultrafine aluminum oxide and increasing its original water-loss temperature of heat decomposition. The flame-retardant-grde ultrafine aluminum oxide is prepared from purified sodium aluminate solution by two or more stages. The crystal seeds for aluminum hydroxide ultrafine powder are prepared by reacting aluminum salt with ammonium salt, or reacting sodium aluminate solution with carbonate. The modifier for increasing the original water-loss temperature of ultrafine aluminum oxide heat decomposition is one of monoammonium phosphate, monoammonium phosphate/glycerol and monoammonium phosphate/oxalic acid. The modified aluminum oxide has the original water-loss temperature higher than 205 deg.C, thus can be used as a flame retardant. The method has simple process and is suitable for mass production.
Description
Technical field
A kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature relates to a kind of preparation method who is used for flame retardant plastics, rubber preparation process flame-retardant additive aluminium hydroxide.
Background technology
The dehydration thermo-negative reaction can take place in aluminium hydroxide when being heated, and decompose the oxide compound fusing point height that the back produces, thermally-stabilised good, be covered in thermal conduction of combustionmaterial surface barrier and thermal radiation, thereby it has obtained more and more wide application in the fire-retardant field of needs such as plastics, rubber.Although its flame retardant properties is outstanding, and raw material sources are abundant, cheap, but it still exists some urgent problems during as fire retardant, mainly show as: 1. for to make material reach certain fire-retardant rank, the addition that needs is bigger, thereby cause the physicals severe exacerbation of material, production cost increases; 2. the initial dehydration temperaturre of aluminium hydroxide is lower, and generally between 180-200 ℃, this has seriously limited its application category.So the comprehensive flame retardant properties that improves flame retardant grade aluminium hydroxide is significant.
Super-refinement is effective measure that improve the aluminium hydroxide flame-retardant performance.Super-refinement aluminium hydroxide has the following advantages: 1. the ultra-fine inorganic rigid particles can play toughness reinforcing reinforced effects to macromolecular material, and therefore ultra-fine ATH particle not only makes the system flame retardant properties improve, and also can solve its this difficult problem that affects the mechanical properties; 2. the aluminium hydroxide of ultra-fine granularity also can increase and the flame-retardant polymer matrix between contact area, strengthen the ability of both interfacial interactions, thereby can more effectively improve both consistencies and the mechanical property of blend composition; 3. behind the ATH particulate super-refinement, same usage quantity because the specific surface area of ATH increases substantially, is that the particle surface steam partial pressure descends, so can improve flame retardant effect to a certain extent.When being 5 μ m as the ATH median size, oxygen index is 28, and when median size was 1 μ m, oxygen index was 33; 4. behind the super-refinement, might improve the resistance toheat of ATH.5. ATH particulate super-refinement also helps the improvement of the raising of synthetic materials finished product slickness and other mechanics, electric property, and this is particularly important in cable sheath and electric switch shell product.
In addition, raising aluminium hydroxide thermostability is also significant.Present industrial employing coupling agents etc. carry out surface coating modification to aluminium hydroxide powder to be handled, this can only improve aluminium hydroxide surface properties, improve the processing characteristics of itself and organic polymer material, and can not improve the thermostability of aluminium hydroxide, and production cost height.
Summary of the invention
The objective of the invention is the deficiency that exists at above-mentioned prior art, a kind of method that can effectively produce the high superfine aluminium hydroxide in flame retardant grade of preparation initial dehydration temperature that flame retardant grade ultrafine aluminium hydroxide and efficiency improve aluminium hydroxide thermolysis initial dehydration temperature is provided.
The objective of the invention is to be achieved through the following technical solutions.
A kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature, preparation process are that sodium aluminate solution carries out that two-stage or two-stage are above plants after branchs process obtains kind of a branch and finish, natural subsidence, filtration, and dry the washing back, obtains d
50In 0.5-5 μ m, crystalline form is the superfine aluminium hydroxide in flame retardant grade of gibbsite; Again aluminium hydroxide being carried out modification with the properties-correcting agent of phosphoric acid ammonium dihydrogen handles.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that alumina concentration is 80-160g/L in the used sodium aluminate solution of preparation process, and causticity compares α
kScope is 1.5-1.7.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that the crystal seed seed ratio that preparation process one-level kind is divided is 0.02-0.12, and planting the branch temperature is 40-60 ℃, and it is 2-10h that kind is divided the time; The timesharing of secondary kind, with the one-level kind divide rear slurry to be added to be equipped with the secondary decomposer of one-level decomposer with volume sodium aluminate dilute solution in, the secondary kind divides the temperature of decomposer to be controlled at 40-60 ℃, plants and divides a time 10-20h.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high, it is characterized in that preparation process carries out three grades of kind timesharing, with the secondary kind divide rear slurry to be added to be equipped with the three grade decomposers of secondary decomposer with volume sodium aluminate dilute solution in, the temperature that three grades of kinds are divided decomposer divides the time to be controlled at 40-60 ℃ and 10-20h respectively with planting.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that preparation process carries out multistage kind of timesharing, divide back liquid with the upper level kind and mix with volume sodium aluminate dilute solution after carry out kind of a branch.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that each grade of preparation process kind branch all adds the PEG-1000 of 0.2-0.5 ‰.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high, it is characterized in that preparation process kind branch is finished after, natural subsidence, filter after, wash 2-5 time and then obtains d 100-120 ℃ of oven dry
50In 0.5-5 μ m, crystalline form is the superfine aluminium hydroxide in flame retardant grade of gibbsite.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that crystal seed that preparation process adds is by being 1.5-1.7, Al to α k
2O
3Concentration is in the sodium aluminate solution of 40-60g/L, adds the reaction of sodium bicarbonate 6-8h of 0.5-2mol/L, and temperature of reaction is controlled at 25-40 ℃, and the terminal point pH value of reaction is controlled at 9.5～10, obtains the ultra-fine crystal seed of high reactivity after filtering this reaction solution.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high, it is characterized in that crystal seed that preparation process adds is by dripping to the volatile salt of the 1.0-2.0mol/L alum liquor toward 0.2-0.8mol/L, the limit edged stirs fast, temperature of reaction system is controlled at 40-60 ℃, the terminal point pH value is controlled at 7-8, filters the ultra-fine crystal seed of the high reactivity that obtains after this reaction system.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that the properties-correcting agent that preparation process adopts is primary ammonium phosphate.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that the properties-correcting agent that preparation process adopts is primary ammonium phosphate+glycerine, and wherein glycerine shared weight ratio in properties-correcting agent is 10%-30%.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high is characterized in that the properties-correcting agent that preparation process adopts is primary ammonium phosphate+oxalic acid, and its mesoxalic acid shared weight ratio in properties-correcting agent is 10%-30%.
The method of the superfine aluminium hydroxide in flame retardant grade that preparation initial dehydration temperature of the present invention is high, the preparation process of the modified aluminium hydroxide when it is characterized in that preparing is that the properties-correcting agent with respect to aluminium hydroxide dry mass 3%-10% is added in the aluminum hydroxide slime, suction filtration behind 60～95 ℃ of following stirring reaction 60-90min, with warm water washing 3-5 time, at 110-120 ℃ of dry 6-12h; Solid content in the aluminum hydroxide slime is 15-50%.
Adopt method of the present invention, used in the preparation of aluminium hydroxide process repeatedly to plant and divided, the crystal seed of taking passes through aluminium salt and ammonium salt or sodium aluminate solution and carbonate chemistry prepared in reaction; The properties-correcting agent that improves the employing of ultrafine aluminium hydroxide thermolysis initial dehydration temperature is biphosphate ammonium chemical feedstocks.The thermolysis initial dehydration temperature of preparation and superfine aluminium hydroxide in flame retardant grade micro mist can be greater than 205 ℃.
Description of drawings
The SEM electromicroscopic photograph of Fig. 1 embodiment of the invention 1 gained fine aluminum hydroxide powder;
The XRD curve of Fig. 2 embodiment of the invention 1 gained fine aluminum hydroxide powder;
The DSC-TGA curve of Fig. 3 embodiment of the invention 1 gained fine aluminum hydroxide powder;
The DSC-TGA curve of Fig. 4 embodiment of the invention 1 gained modified aluminium hydroxide micro mist;
The DSC-TGA curve of Fig. 5 embodiment of the invention 2 gained modified aluminium hydroxide micro mists.
Below in conjunction with example the present invention is elaborated, but be used for anything but limiting the scope of the invention.
Embodiment
A kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature, preparation process is sodium aluminate solution to be carried out two-stage or plant the branch process more than the two-stage, wherein the crystal seed seed of one-level kind branch is than being 0.02-0.12, and planting the branch temperature is 40-60 ℃, and planting the branch time is 2-10h; The timesharing of secondary kind, with the one-level kind divide rear slurry to be added to be equipped with the secondary decomposer of one-level decomposer with volume sodium aluminate dilute solution in, the secondary kind divides the temperature of decomposer to be controlled at 40-60 ℃, plants and divides a time 10-20h; Carry out multistage kind of timesharing, carry out kind of a branch after the upper level kind is divided back liquid and mixed with volume sodium aluminate dilute solution; After planting branch back natural subsidence, filtration, wash 2-5 back and obtain d 100-120 ℃ of oven dry
50In 0.5-5 μ m, crystalline form is the superfine aluminium hydroxide in flame retardant grade of gibbsite.Each grade of preparation process kind is divided the PEG-1000 that all adds 0.2-0.5 ‰.
The crystal seed that preparation process adds is by to α
kBe 1.5-1.7, Al
2O
3Concentration is in the sodium aluminate solution of 40-60g/L, the reaction of sodium bicarbonate 6-8h that adds 0.5-2mol/L, temperature of reaction is controlled at 25-40 ℃, the terminal point pH value of reaction is controlled at 9.5～10, filter and obtain the ultra-fine crystal seed of high reactivity behind this reaction solution or by dripping to the volatile salt of 1.0-2.0mol/L alum liquor toward 0.2-0.8mol/L, the limit edged stirs fast, temperature of reaction system is controlled at 40-60 ℃, the terminal point pH value is controlled at 7-8, filters the ultra-fine crystal seed of the high reactivity that obtains after this reaction system.
The preparation process of the modified aluminium hydroxide during preparation is that the properties-correcting agent with respect to aluminium hydroxide dry mass 3%-10% is added in the aluminum hydroxide slime, suction filtration behind 60～95 ℃ of following stirring reaction 60-90min, with warm water washing 3-5 time, at 110-120 ℃ of dry 6-12h; Solid content in the aluminum hydroxide slime is 15-50%.Properties-correcting agent is primary ammonium phosphate; Or in properties-correcting agent glycerine to account for weight ratio be 10%-30% primary ammonium phosphate+glycerine; Or be 10%-30% primary ammonium phosphate+oxalic acid in the weight ratio that the properties-correcting agent mesoxalic acid accounts for.
Embodiment 1
With sodium aluminate and sodium bicarbonate is the prepared crystal seed of raw material, carries out the two-stage kind and divides the preparation superfine aluminium hydroxide in flame retardant grade, and carry out modification with primary ammonium phosphate as properties-correcting agent.
The first step: the preparation of crystal seed.
Toward α
kBe 1.5, Al
2O
3Concentration is the reaction of sodium bicarbonate 8h that adds 1mol/L in the sodium aluminate solution of 40g/L, and temperature of reaction is controlled at 25～30 ℃, and the terminal point pH value of reaction is controlled at 9.5～10, filters the gained precipitation and is crystal seed;
Second step: the two-stage kind is divided the preparation ultrafine aluminium hydroxide.
The crystal seed seed ratio that first step kind is divided is 0.08, and planting the branch temperature is 60 ℃, and planting the branch time is 3h; The timesharing of secondary kind, with the one-level kind divide rear slurry to be added to be equipped with the secondary decomposer of one-level decomposer with volume sodium aluminate dilute solution in, the secondary kind divides the temperature of decomposer to be controlled at 45 ℃, plants and divides a time 18h; Each grade kind branch all adds 0.2 ‰ PEG-1000.Kind divide finish after, natural subsidence, filtration, and after washing 3 times 120 ℃ of oven dry, can obtain d
50In 1.57 μ m, crystalline form is the superfine aluminium hydroxide in flame retardant grade of gibbsite.
As can be seen from Figure 1, the granularity of present embodiment gained fine aluminum hydroxide powder is even substantially; As can be seen from Figure 2, present embodiment gained micro mist has typical gibbsite crystalline form.
The 3rd step: the modification of aluminium hydroxide is handled.
's 5: 1 slip with the second step gained filter cake with deionized water furnishing liquid-solid ratio, in this slip, add the primary ammonium phosphate that is equivalent to aluminium hydroxide dry mass 5% then, suction filtration behind 90 ℃ of following stirring reaction 60min, with warm water washing 3 times, at 120 ℃ of dry 12h, promptly get the modified aluminium hydroxide micro mist.The DSC-TGA curve of fine aluminum hydroxide powder before and after the respectively little present embodiment modification of Fig. 3 and Fig. 4, obviously, the thermostability improved micro mist is handled in the primary ammonium phosphate modification, and thermolysis initial dehydration temperature 195.11 ℃ before by modification have been brought up to 207.88 ℃ after the modification.
Embodiment 2
With volatile salt and Tai-Ace S 150 is the prepared crystal seed of raw material, carries out the two-stage kind and divides the preparation superfine aluminium hydroxide in flame retardant grade, and carry out modification with primary ammonium phosphate+glycerine as properties-correcting agent.
The first step: the preparation of crystal seed.
The volatile salt of the 1.0mol/L alum liquor toward 0.5mol/L is dripped, and the limit edged stirs fast, and temperature of reaction system is controlled at 50 ℃, and the terminal point pH value is controlled at 7.5, promptly gets the ultra-fine crystal seed of high reactivity after filtering this reaction system;
Second step: the two-stage kind is divided the preparation ultrafine aluminium hydroxide.
Step is with second step of embodiment 1.
The 3rd step: the modification of aluminium hydroxide is handled.
Basic step is with the 3rd step of embodiment 1, but the properties-correcting agent that is adopted is primary ammonium phosphate+glycerine, and the mass ratio of primary ammonium phosphate and glycerine is 8: 2.
Fig. 5 is the DSC-TGA curve of present embodiment gained modified aluminium hydroxide micro mist.Obviously, modification is handled the thermolysis initial dehydration temperature of back fine aluminum hydroxide powder greater than 205 ℃.
Claims (13)
1. method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature, preparation process are sodium aluminate solution to be carried out two-stage or plant branchs process more than the two-stage, plant divide finish after, natural subsidence, filtration, dry the washing back, obtains d
50In 0.5-5 μ m, crystalline form is the superfine aluminium hydroxide in flame retardant grade of gibbsite; Again aluminium hydroxide being carried out modification with the properties-correcting agent of phosphoric acid ammonium dihydrogen handles.
2. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1 is characterized in that alumina concentration is 80-160g/L in the used sodium aluminate solution of preparation process, and causticity compares α
kScope is 1.5-1.7.
3. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1 is characterized in that the crystal seed seed ratio that preparation process one-level kind is divided is 0.02-0.12, and planting the branch temperature is 40-60 ℃, and it is 2-10h that kind is divided the time; The timesharing of secondary kind, with the one-level kind divide rear slurry to be added to be equipped with the secondary decomposer of one-level decomposer with volume sodium aluminate dilute solution in, the secondary kind divides the temperature of decomposer to be controlled at 40-60 ℃, plants and divides a time 10-20h.
4. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1, it is characterized in that preparation process carries out three grades of kind timesharing, with the secondary kind divide rear slurry to be added to be equipped with the three grade decomposers of secondary decomposer with volume sodium aluminate dilute solution in, the temperature that three grades of kinds are divided decomposer divides the time to be controlled at 40-60 ℃ and 10-20h respectively with planting.
5. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1 is characterized in that preparation process carries out multistage kind of timesharing, divide back liquid with the upper level kind and mix with volume sodium aluminate dilute solution after carry out kind of a branch.
6. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1 is characterized in that each grade of preparation process kind branch all adds the PEG-1000 of 0.2-0.5 ‰.
7. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1, it is characterized in that preparation process kind branch is finished after, natural subsidence, filter after, wash 2-5 time and then obtains d 100-120 ℃ of oven dry
50In 0.5-5 μ m, crystalline form is the superfine aluminium hydroxide in flame retardant grade of gibbsite.
8. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1 is characterized in that crystal seed that preparation process adds is by to α
kBe 1.5-1.7, Al
2O
3Concentration is in the sodium aluminate solution of 40-60g/L, adds the reaction of sodium bicarbonate 6-8h of 0.5-2mol/L, and temperature of reaction is controlled at 25-40 ℃, and the terminal point pH value of reaction is controlled at 9.5～10, obtains the ultra-fine crystal seed of high reactivity after filtering this reaction solution.
9. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1, it is characterized in that crystal seed that preparation process adds is by dripping to the volatile salt of the 1.0-2.0mol/L alum liquor toward 0.2-0.8mol/L, the limit edged stirs fast, temperature of reaction system is controlled at 40-60 ℃, the terminal point pH value is controlled at 7-8, filters the ultra-fine crystal seed of the high reactivity that obtains after this reaction system.
10. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1 is characterized in that the properties-correcting agent that preparation process adopts is primary ammonium phosphate.
11. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1, it is characterized in that the properties-correcting agent that preparation process adopts is primary ammonium phosphate+glycerine, wherein glycerine shared weight ratio in properties-correcting agent is 10%-30%.
12. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1, it is characterized in that the properties-correcting agent that preparation process adopts is primary ammonium phosphate+oxalic acid, its mesoxalic acid shared weight ratio in properties-correcting agent is 10%-30%.
13. a kind of method for preparing the high superfine aluminium hydroxide in flame retardant grade of initial dehydration temperature of stating according to claim 1, the preparation process of the modified aluminium hydroxide when it is characterized in that preparing is that the properties-correcting agent with respect to aluminium hydroxide dry mass 3%-10% is added in the aluminum hydroxide slime, suction filtration behind 60～95 ℃ of following stirring reaction 60-90min, with warm water washing 3-5 time, at 110-120 ℃ of dry 6-12h; Solid content in the aluminum hydroxide slime is 15%-50%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675926A (en) * | 2012-04-24 | 2012-09-19 | 中国铝业股份有限公司 | Method for raising thermal decomposition temperature of aluminum hydroxide |
| CN105601991A (en) * | 2015-12-30 | 2016-05-25 | 青岛科技大学 | Application of aluminate substances to flame-retardant thermoplastic plastic as flame retardant |
| CN105776269A (en) * | 2016-03-24 | 2016-07-20 | 中国铝业股份有限公司 | Micro-powder aluminum hydroxide preparation method and device and micro-powder aluminum hydroxide |
| CN106698484A (en) * | 2016-12-26 | 2017-05-24 | 荆门市格林美新材料有限公司 | Method for recycling aluminum and magnesium from different sludge to prepare high-purity composite flame retardants |
| CN109368674A (en) * | 2018-12-26 | 2019-02-22 | 贵州博汇联润铝业有限公司 | A kind of high temperature resistant low-sodium aluminum hydroxide micro mist preparation method |
| CN109422285A (en) * | 2017-08-30 | 2019-03-05 | 洛阳中超新材料股份有限公司 | Low oil factor aluminium hydroxide and its preparation method and application |
| CN111099645A (en) * | 2019-12-23 | 2020-05-05 | 山东泰星新材料股份有限公司 | Preparation method of flower-shaped aluminum hydroxide for pouring sealant |
| CN111320192A (en) * | 2020-04-23 | 2020-06-23 | 成都铬科高化工技术有限责任公司 | Method for preparing superfine aluminum hydroxide from chromium-containing aluminum mud |
| CN115676863A (en) * | 2022-09-13 | 2023-02-03 | 中南大学 | Equiaxial near-spherical superfine aluminum hydroxide and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675926A (en) * | 2012-04-24 | 2012-09-19 | 中国铝业股份有限公司 | Method for raising thermal decomposition temperature of aluminum hydroxide |
| CN105601991A (en) * | 2015-12-30 | 2016-05-25 | 青岛科技大学 | Application of aluminate substances to flame-retardant thermoplastic plastic as flame retardant |
| CN105601991B (en) * | 2015-12-30 | 2018-03-02 | 青岛科技大学 | Application of the aluminate material as fire retardant in flame retardant thermoplastic |
| CN105776269A (en) * | 2016-03-24 | 2016-07-20 | 中国铝业股份有限公司 | Micro-powder aluminum hydroxide preparation method and device and micro-powder aluminum hydroxide |
| CN106698484A (en) * | 2016-12-26 | 2017-05-24 | 荆门市格林美新材料有限公司 | Method for recycling aluminum and magnesium from different sludge to prepare high-purity composite flame retardants |
| CN106698484B (en) * | 2016-12-26 | 2017-11-10 | 荆门市格林美新材料有限公司 | The method that magnalium prepares high-purity composite flame-retardant agent is reclaimed from different sludge |
| CN109422285A (en) * | 2017-08-30 | 2019-03-05 | 洛阳中超新材料股份有限公司 | Low oil factor aluminium hydroxide and its preparation method and application |
| CN109368674A (en) * | 2018-12-26 | 2019-02-22 | 贵州博汇联润铝业有限公司 | A kind of high temperature resistant low-sodium aluminum hydroxide micro mist preparation method |
| CN111099645A (en) * | 2019-12-23 | 2020-05-05 | 山东泰星新材料股份有限公司 | Preparation method of flower-shaped aluminum hydroxide for pouring sealant |
| CN111099645B (en) * | 2019-12-23 | 2022-10-18 | 山东泰星新材料股份有限公司 | Preparation method of flower-shaped aluminum hydroxide for pouring sealant |
| CN111320192A (en) * | 2020-04-23 | 2020-06-23 | 成都铬科高化工技术有限责任公司 | Method for preparing superfine aluminum hydroxide from chromium-containing aluminum mud |
| CN115676863A (en) * | 2022-09-13 | 2023-02-03 | 中南大学 | Equiaxial near-spherical superfine aluminum hydroxide and preparation method thereof |
| CN115676863B (en) * | 2022-09-13 | 2024-03-26 | 中南大学 | Equiaxial nearly spherical superfine aluminum hydroxide and preparation method thereof |
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