CN103964455A - Preparation method of zinc borate 3.5-hydrate - Google Patents
Preparation method of zinc borate 3.5-hydrate Download PDFInfo
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- CN103964455A CN103964455A CN201410239889.9A CN201410239889A CN103964455A CN 103964455 A CN103964455 A CN 103964455A CN 201410239889 A CN201410239889 A CN 201410239889A CN 103964455 A CN103964455 A CN 103964455A
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- boric acid
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Abstract
The invention belongs to the field of inorganic materials and in particular relates to a preparation method of zinc borate 3.5-hydrate. The method comprises the following steps: dissolving boric acid in water to prepare a boric acid solution; adding borax into the boric acid solution, stirring for dissolving, adding zinc nitrate, stirring at a speed of 100rpm, and performing heat preservation reaction to obtain zinc borate 3.5-hydrate, wherein the weight ratio of boric acid to water to borax to zinc nitrate is (12-22) : (180-200) : (95-113) : (97-110). The preparation method provided by the invention is simple in process, quick and stable in reaction, short in reaction time and low in energy consumption, and the production cost is reduced.
Description
Technical field
The invention belongs to field of inorganic materials, be specifically related to a kind of preparation method of 3.5 hydrate zinc borates.
Background technology
Zinc borate is a kind of efficient inorganic synergistic flame retardant, nano-zinc borate particle has Heat stability is good, fine size, proportion is little, easily disperse, the advantage such as nontoxic, and there is cooperative flame retardant effect between the flame-retardant additive such as ammonium polyphosphate, magnesium hydroxide, aluminium hydroxide, can greatly reduce inorganic addition, the own mechanical property of polymer materials that makes to add after fire retardant is improved.Inorganic nano zinc borate is widely used in the products such as all kinds of cable plastics sheaths, electrical equipment plastics and anti-flaming dope.
Zinc borate mainly contains 3 kinds of synthetic routes in industrial production: 1. zinc hydroxide-borate method, and the shortcoming of this method is that required zinc hydroxide needs in situ preparation, and the technique that this method is produced is loaded down with trivial details, and production cost is higher; 2. zinc oxide-borate method, this method technique is simple, suitable small serial production, but the price of the boric acid of this method and zinc oxide is all higher, so cost compare, cost is higher; 3. borate-zincate process, this method borax, zinc salt raw material are easy to get, and cost is lower, has certain advantage in granularity control; It is harsher that but the shortcoming of this method is reaction conditions.Borax is strong base-weak acid salt, makes the aobvious alkalescence of system solution, and zinc exists with zinc hydroxide micro-soluble material form, and replacement(metathesis)reaction speed is slowed down, and the reaction times extends, and has increased to a certain extent energy consumption, has improved product cost.
Patent CN102417189A discloses a kind of synthetic method of columnar zinc borate, and its product preparing is 2ZnO3B
2o
37H
2o, what borax accounted for strength of solution is 2.92%～5.28%, and reaction solution concentration is quite low, and energy consumption is high, and after reaction, needs room temperature to leave standstill, and the cycle is long.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of preparation method of 3.5 hydrate zinc borates, technique is simple, reaction fast and stable, the reaction times is short, and energy consumption is low, has reduced production cost.
The preparation method of 3.5 hydrate zinc borates of the present invention, comprises the following steps:
(1) first boric acid is dissolved in the water and is made into boric acid solution;
(2) in boric acid solution, add borax stirring and dissolving, add zinc nitrate to stir, insulation reaction, obtains product.
Wherein: in step (1), the temperature of water is 80-90 degree.
Step (2), for boric acid solution is warming up to 80-90 degree, adds borax stirring and dissolving in boric acid solution, adds zinc nitrate to stir, insulation reaction, temperature is 85-95 DEG C, the reaction times is 5-7 hour, filtered while hot after completion of the reaction, washing, dries to obtain product.
In step (2), add zinc nitrate to stir, stirring velocity is 100rpm.Owing to adopting this stirring velocity to stir, agitating vane strengthens the shearing force of crystal, easily forms tiny crystal.When high temperature filtration, filtration velocity is fast, can make solution and crystal sharp separation, and the impurity in solution can not gather in crystal, so gained zinc borate whiteness and purity all increase, whiteness reaches more than 98.5, granularity 2-6 micron.
In step (2), bake out temperature is 98-110 DEG C.
Boric acid: water: borax: the weight ratio that feeds intake of zinc nitrate is 12-22:180-200:95-113:97-110.Be the 22-26% that borax accounts for reaction solution concentration, preferably 23%-25%: zinc nitrate accounts for the 22-27% of reaction solution concentration, preferably 24%-26%.Reaction solution is in the time of reaction, and the pH value of feed liquid is at 5-7.
Preferred a kind of technical scheme is:
In the first water that boric acid is dissolved in to 80-90 DEG C, be made into boric acid solution, boric acid concentration is 7-11%.Boric acid solution is warming up to 80-90 DEG C, add borax to stir, dissolve, temperature is elevated to 90 DEG C, add zinc nitrate, violent stirring, stirring velocity 100rpm, insulation reaction temperature is 85-95 DEG C, reaction times is 5-7 hour, reacting liquor while hot is filtered, and washes three times for 40-60 DEG C, dries for 98-110 DEG C and pulverizes and obtain product.
The zinc borate product microscopic appearance that the present invention prepares is better, analyzes through volumetry and burning decrement method, and the molecular formula of product is 2ZnO3B
2o
33.5H
2o, product purity is high, whiteness reaches more than 98.5, granularity 2-6 micron, the zinc borate fine size, the volume mass that adopt method of the present invention to make be little, easily disperse, and improves with the consistency of macromolecular material, zinc borate and macromolecular compound combine more closely, the every mechanical mechanics property that has further improved material, has reduced usage quantity, reduces product cost.
In sum, the present invention has the following advantages:
(1) temperature of reaction is low, and reaction time is short, and energy consumption is low;
(2) do not need to add zinc oxide and crystal seed, technique is simple;
(3) the zinc borate fineness that adopts method of the present invention to make is low, without pulverizing, can obtain the zinc borate of small particle size again, and good dispersity is good with macromolecular material consistency.Mother liquor can recycle, and produces environmental protection and energy saving without the three wastes;
(4) technique is simple, reaction fast and stable, and the reaction times is short, and energy consumption is low, has reduced production cost.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
In the first 190g water that 18g boric acid is dissolved in to 85 DEG C, be made into boric acid solution.Boric acid solution is warming up to 90 DEG C, add 100g borax to stir, dissolve, temperature is elevated to 90 DEG C, add 100g zinc nitrate, violent stirring, stirring velocity 100rpm, insulation reaction temperature is 90 DEG C, reaction times is 6 hours, reacting liquor while hot is filtered, and washes three times for 50 DEG C, dries for 105 DEG C and pulverizes and obtain product.Mother liquor and water lotion are collected, and replace water for reaction next time.Gained zinc borate whiteness is that 99.0, D50 is 3.89 μ m after testing.
Embodiment 2
In the first 180g water that 12g boric acid is dissolved in to 80 DEG C, be made into boric acid solution.Boric acid solution is warming up to 85 DEG C, add 95g borax to stir, dissolve, temperature is elevated to 90 DEG C, add 97g zinc nitrate, violent stirring, stirring velocity 100rpm, insulation reaction temperature is 85 DEG C, reaction times is 7 hours, reacting liquor while hot is filtered, and washes three times for 60 DEG C, dries for 110 DEG C and pulverizes and obtain product.Gained zinc borate whiteness is that 98.9, D50 is 4.54 μ m after testing.
Embodiment 3
In the first 200g water that 22g boric acid is dissolved in to 85 DEG C, be made into boric acid solution.Boric acid solution is warming up to 88 DEG C, add 113g borax to stir, dissolve, temperature is elevated to 90 DEG C, add 110g zinc nitrate, violent stirring, stirring velocity 100rpm, insulation reaction temperature is 95 DEG C, reaction times is 5 hours, reacting liquor while hot is filtered, and washes three times for 40 DEG C, dries for 98 DEG C and pulverizes and obtain product.Gained zinc borate whiteness is that 99.7, D50 is 3.86 μ m after testing.
Embodiment 4
In the first 200g water that 16g boric acid is dissolved in to 90 DEG C, be made into boric acid solution.Boric acid solution is warming up to 80 DEG C, add 108g borax to stir, dissolve, temperature is elevated to 90 DEG C, add 105g zinc nitrate, violent stirring, stirring velocity 100rpm, insulation reaction temperature is 88 DEG C, reaction times is 6 hours, reacting liquor while hot is filtered, and washes three times for 55 DEG C, dries for 102 DEG C and pulverizes and obtain product.Gained zinc borate whiteness is that 98.5, D50 is 4.59 μ m after testing.
One, product embodiment 1-4 being prepared does burning decrement test:
Adopt prior art, concrete test procedure is as follows:
Take 5g sample, be accurate to 0.0002g, be placed in High Temperature Furnaces Heating Apparatus, 450 DEG C of calcinations to the porcelain crucible of constant mass.
Burning decrement is with massfraction w
3meter, is calculated as follows:
In formula:
M
1---the numerical value of the quality of porcelain crucible and test portion before calcination, unit is gram (g);
M
2---the numerical value of the quality of porcelain crucible and test portion after calcination, unit is gram (g);
M---the numerical value of test portion quality, unit is gram (g).
The arithmetical av of the row measurement result of making even is measurement result, and the absolute difference of twice replicate(determination) result is not more than 0.02%.
Two, product embodiment 1-4 being prepared does titration test:
Adopt prior art, concrete test procedure is as follows:
Sample preparation: take 1.5g～2.0g sample, be accurate to 0.0002g, be placed in 250mL beaker, add 80mL water, 5mL hydrochloric acid soln (1:1), heating for dissolving, should avoid boiling, is cooled to room temperature, move in 250mL volumetric flask, be diluted with water to scale, shake up.
1. the mensuration of zinc oxide content
(1) agents useful for same:
Ammonia soln: 2+3.
Ammonia-chloride buffer solution first: pH ≈ 10.
Disodium ethylene diamine tetraacetate standard titration solution: c (EDTA) ≈ 0.05mo1/L.
Eriochrome black T indicating liquid: 5g/L.
(2) analytical procedure
Pipette 25mL testing liquid, be placed in 250mL Erlenmeyer flask, add water to 60mL, drip the pH ≈ 10 (with pH test paper inspection) of ammonia soln to solution, then ammonia-ammonia chloride the buffered soln, the 3d～5d eriochrome black T indicating liquid that add 10mL, become blueness with disodium ethylene diamine tetraacetate standardized solution volumetric soiutions from red-purple and be terminal.
Carry out blank test, blank test solution is except not adding sample simultaneously, and other operations are identical with testing liquid with the reagent adding.
The content of zinc oxide is with zinc oxide (ZnO) massfraction w
2meter, is calculated as follows:
In formula:
V
0---the numerical value of the volume of the disodium ethylene diamine tetraacetate standard titration solution that titration blank test solution consumes, unit is milliliter (mL);
V
1---the numerical value of the volume of the disodium ethylene diamine tetraacetate standard titration solution that burette test solution consumes, unit is milliliter (mL);
C---the accurate numerical value of disodium ethylene diamine tetraacetate standard titration solution concentration, unit is mole every liter (mol/L);
M---the numerical value of test portion quality, unit is gram (g);
The numerical value of M---zinc oxide (ZnO) molar mass, unit be gram every mole (g/mol) (M=81.38).
The arithmetical av of the row measurement result of making even is measurement result, and the absolute difference of twice replicate(determination) result is not more than 0.30%.
2, boron oxide content is measured:
Pipette testing liquid 25mL (6.3.1.3.1), be placed in 250mL Erlenmeyer flask, add Bromothymol blue indicating liquid 5d～8d, regulate near green with sodium hydroxide solution, use Standard Volumetric Solutions for Sodium Hydroxide instead and be neutralized into yellow-green colour, accurately add with drop-burette the identical disodium ethylene diamine tetraacetate titrand (allowing the excessive 0.1mL of being no more than) of disodium ethylene diamine tetraacetate standard titration solution volume numerical value consuming with mensuration zinc oxide again, be neutralized into yellow-green colour with Standard Volumetric Solutions for Sodium Hydroxide, add 3g N.F,USP MANNITOL, 5d～8d instructions phenolphthalein solution, be titrated to bluish voilet with Standard Volumetric Solutions for Sodium Hydroxide and be terminal.
The content of boron oxide is with boron oxide (B
2o
3) massfraction w1 meter, be calculated as follows:
In formula:
V
0---the numerical value of the volume of the Standard Volumetric Solutions for Sodium Hydroxide that titration blank test solution consumes, unit is milliliter (mL);
V---the numerical value of the volume of the Standard Volumetric Solutions for Sodium Hydroxide that burette test solution consumes, unit is milliliter (mL);
The accurate numerical value of the concentration of C---Standard Volumetric Solutions for Sodium Hydroxide, unit is mole every liter (mol/L);
The numerical value of the quality of M---test portion, unit is gram (g);
The arithmetical av of the row measurement result of making even is measurement result, and the absolute difference of twice replicate(determination) result is not more than 0.30%.
Test result is in table 1.
The product test result that table 1 embodiment 1-4 prepares
Can find by table 1, embodiment 1-4 crystal water is between 13-15%, and zinc oxide content is in 37.0 ± 1.5% scopes, and boron oxide content, in 48.0 ± 1.5% scopes, meets the feature of 3.5 hydrate zinc borates.
Claims (6)
1. a preparation method for 3.5 hydrate zinc borates, is characterized in that: comprise the following steps:
(1) first boric acid is dissolved in the water and is made into boric acid solution;
(2) in boric acid solution, add borax stirring and dissolving, add zinc nitrate to stir, insulation reaction, obtains product.
2. the preparation method of 3.5 hydrate zinc borates according to claim 1, is characterized in that: in step (1), the temperature of water is 80-90 degree.
3. the preparation method of 3.5 hydrate zinc borates according to claim 1, it is characterized in that: step (2) is for to be warming up to 80-90 degree by boric acid solution, in boric acid solution, add borax stirring and dissolving, add zinc nitrate to stir, insulation reaction, temperature is 85-95 DEG C, reaction times is 5-7 hour, filtered while hot after completion of the reaction, washing, dries to obtain product.
4. according to the preparation method of 3.5 hydrate zinc borates described in claim 1 or 3, it is characterized in that: in step (2), add zinc nitrate to stir, stirring velocity is 100rpm.
5. the preparation method of 3.5 hydrate zinc borates according to claim 3, is characterized in that: in step (2), bake out temperature is 98-110 DEG C.
6. the preparation method of 3.5 hydrate zinc borates according to claim 1, is characterized in that: boric acid: water: borax: the weight ratio that feeds intake of zinc nitrate is 12-22:180-200:95-113:97-110.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105372386A (en) * | 2015-12-25 | 2016-03-02 | 富耐克超硬材料股份有限公司 | Method for measuring content of free boron oxide in boron nitride |
| CN107673364A (en) * | 2017-10-13 | 2018-02-09 | 济南泰星精细化工有限公司 | A kind of preparation method of 2335 zinc borate flame retardant |
| CN109279618A (en) * | 2018-10-25 | 2019-01-29 | 青岛科技大学 | It is a kind of for repairing the reparation liquid and restorative procedure of 2335 type zinc borate defects |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105372386A (en) * | 2015-12-25 | 2016-03-02 | 富耐克超硬材料股份有限公司 | Method for measuring content of free boron oxide in boron nitride |
| CN107673364A (en) * | 2017-10-13 | 2018-02-09 | 济南泰星精细化工有限公司 | A kind of preparation method of 2335 zinc borate flame retardant |
| CN109279618A (en) * | 2018-10-25 | 2019-01-29 | 青岛科技大学 | It is a kind of for repairing the reparation liquid and restorative procedure of 2335 type zinc borate defects |
| CN109279618B (en) * | 2018-10-25 | 2022-01-28 | 青岛科技大学 | Repair liquid and repair method for repairing 2335 type zinc borate defects |
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