CN102225751B - Synthetic method of aluminium zinc phosphate nanocrystal - Google Patents
Synthetic method of aluminium zinc phosphate nanocrystal Download PDFInfo
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Abstract
A synthetic method of an aluminium zinc phosphate nanocrystal adopts a direct synthetic method of low-heating solid-state chemical reaction, uses zinc salt powder, aluminium salt powder, and phosphate powder as raw materials, and comprises the following steps: adding a template, mixing and grinding under a condition with room temperature and normal pressure, allowing the reaction mixture to standat a temperature from room temperature to 90 DEG C, washing the reaction mixture with water to remove by products of soluble inorganic salts, filtering, drying the filter cake at 100 DEG C to obtain a product of a zinc phosphate nanocrystal with a microcrystal particle size of 35 nm. Compared with the prior art, the aluminium zinc phosphate product obtained by the method of the invention has better corrosion inhibition performance than traditional zinc phosphate or aluminium phosphate products, and is a antirust material with excellent performance. Additionally, the method has the advantages of no solvent required, mild reaction conditions, easy control, simple process, extensive raw material sources, etc.
Description
Technical field
The present invention relates to the synthetic method of phosphoric acid zinc-aluminium crystalline material, specifically a kind of synthetic method of aluminium zinc phosphate nanocrystal.
Background technology
Zinc phosphate is a kind of well-known rust-stabilising pigment, and its advantage mainly contains: better performances, and nontoxic, white or light, specific refractory power is low, therefore as easy as rolling off a log toning; Can be dispersed in the various base-materials such as oleoresin type and water-based; Coating with its preparation has good workability, and can film with metal substrate or with finish paint and have stronger sticking power; Raw material is easy to get, and is moderate etc.Therefore it is used as a kind of selectable pigment and is applied.But the antirust activity of standard zinc phosphate is not enough, and this mainly is because the solubleness of this pigment is low and water-disintegrable poor.Therefore, it is difficult comprehensively replacing traditional poisonous rust-stabilising pigment with the standard zinc phosphate, particularly in aqueous priming paint, does not only reach the purpose that substitutes zinc chromate with the identical PVC of zinc chromate the time, and excess adds and also is difficult to the purpose that reaches alternative.Another shortcoming of standard zinc phosphate is the produce effects time-delay, and the speed that namely forms effective protective membrane is too slow, therefore can not be used for the various maintenance priming paint of provisional protective cover.Facts have proved, adopt separately the standard zinc phosphate in the aqueous priming paint of meta-alkalescence, can not overcome so-called " dodging rust " problem.Therefore, it must cooperate with chromic salt and could be used for electrophoretic primer.
The crystal particle diameter of common zinc orthophosphate below 5 μ m, (be generally 0.5～4 μ m) [Yang Zongzhi. the development of low/mon poisionous Zinc phosphate series anticorrosive pigments. domestic and international coatings industry, 2001, (6): 38-40,46.], but because easily assembling, the pigment particle size that really embodies is much bigger, have in addition reach 12 μ m-20 μ m or larger, and size-grade distribution is very wide.Like this, little not good with dispersiveness because of specific surface area, antirust activity naturally just can be high.
In order to reach comprehensive purpose that tradition contains the heavy metal rust-stabilising pigment that replaces, must carry out modification to it, developing zinc phosphate of new generation is active rust-stabilising pigment.Therefore, work out that granularity is little, the modified zinc phosphate crystal of narrowly distributing is the key that improves zinc phosphate series pigments product performance and broadened application scope.
In order to improve the antiseptic property of zinc phosphate series pigments, it is that rust-stabilising pigment carries out the surface-coating processing and carries out the bulk doped processing that the effort that people do comprises zinc phosphate, to increase new positively charged ion or to increase new negatively charged ion or increase simultaneously new positively charged ion and new negatively charged ion, in order to reach its antirust activity of raising and the purpose of broadened application scope.Wherein, mix aluminum ion and can greatly improve its antirust activity in zinc phosphate, this introducing that is attributed to an amount of aluminium can be regulated the solvability of zinc phosphate and at the sticking power of metallic surface.Mix in zinc phosphate aspect aluminium synthetic, the synthetic method of at present domestic open report mainly contains:
Ding Shiwen etc. have delivered the article about " the synthetic and sign of tripolyphosphate zinc-aluminium ", this article with zinc oxide and aluminium hydroxide as zinc source and aluminium source, phosphoric acid is as the phosphorus source, at first 100-150 ℃ of lower dissolving, again the viscous fluid that obtains is aggregated into the tripolyphosphate zinc-aluminium under 250～400 ℃, the rustless property of products obtained therefrom surpasses 4 times of national standard, illustrate that aluminum ions existence played collaborative rot-resistant effect (" University Of Hebei's journal (natural science edition) " 1992,12 (4): 47-50).Its shortcoming is that preparation technology is complicated, is difficult for carrying out scale operation.
Yellow wind China waits the article of having delivered about " the synthetic and sign of Zinc Aluminophosphate Molecular Sieve ZAPO-5 Crystal ", this article prepares phosphoric acid zinc-aluminium through 48h～96h crystallization by hydrothermal method to visit aluminium stone, phosphoric acid, zinc acetate, organic formwork agent as raw material under 160 ℃～200 ℃.When template is trolamine, synthesized P: Al: Zn=12: 11: 1 ZAPO-5 crystallite; In the fluorion system, then obtained molecular sieve ZAPO one 5 large single crystals (" synthetic chemistry " 2005,13 (3): 304-306) of length 178 μ m when being template with diethylaminoethanol.But there are no the relevant report as rust-stabilising pigment of the phosphoric acid zinc-aluminium of this composition.
Chinese patent 200810063893.9 has been introduced " fibre reinforcing zinc aluminum phosphate based composite material and preparation method thereof ", and the preparation fibre reinforcing zinc aluminum phosphate based composite material is to be made by fiber reinforced material and zinc phosphate aluminium glue gel material; Its preparation method is as follows: under 200～600 ℃ of conditions, with fiber reinforced material thermal treatment 10min～1h; Then prepare fibre reinforcing zinc aluminum phosphate based composite material according to die press technology for forming, its processing parameter is: molding temperature is 85～300 ℃, and molding pressure is 2～15MPa, and clamp time is 6～35 hours.
In the method for the synthetic phosphoric acid zinc-aluminium of above report, as zinc source and aluminium source, phosphoric acid is higher as the liquid phase reaction method cost in phosphorus source with zinc oxide and aluminium hydroxide, and the granularity of product is easy-regulating not; Though hydrothermal synthesis method can obtain the phosphoric acid zinc-aluminium of crystallite, processing condition are harsh, are difficult for realizing scale production; Sol-gel method prepares the phosphoric acid zinc-aluminium and also exists processing condition harsh, is difficult for realizing the shortcoming of scale production.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation technology simple, be easy to suitability for industrialized production, the synthetic method of gained zinc phosphate aluminum nanocrystalline good dispersity, aluminium zinc phosphate nanocrystal that corrosion inhibition is higher.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of synthetic method of phosphoric acid zinc-aluminium crystal, it adopts the rare earth chemical reaction method directly synthetic, concrete technology is, take zinc salt powder, aluminium salt powder, phosphate powder as raw material, its proportioning raw materials is: zinc salt: aluminium salt: phosphatic material mass ratio is 0.05～0.95: 0.05～0.95: 2.0～3.0, add template, template accounts for 0.1～10% of whole reactant weight; Grind 10～120min after under the condition of room temperature, normal pressure, mixing, then allow reaction mixture under room temperature～90 ℃, leave standstill 1～5 hour, then wash the inorganic salt by-product of solubility in the dereaction mixture with water, filter, filter cake 100 ℃ of lower oven dry, is obtained zinc phosphate aluminum nanocrystalline product.
Above-mentioned zinc salt is selected from a kind of or several combination in compatible situation in zinc chloride, zinc sulfate, zinc nitrate, the zinc acetate.
Above-mentioned aluminium salt comprises a kind of or several combination in compatible situation in aluminum chloride, aluminum nitrate, the Tai-Ace S 150;
Above-mentioned phosphoric acid salt is selected from a kind of or several combination in compatible situation in sodium phosphate, sodium hydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, the potassiumphosphate;
Have the two or more crystal water that contain in above-mentioned zinc salt, aluminium salt and the phosphoric acid salt at least;
It can be nonionic surface active agent that above-mentioned template is selected from above-described template, the combination in a kind of or compatible situation in the protonated organic amine; Nonionic surface active agent in the template is Oleum Cocois alkylamide, tween series, OP is serial, polyoxyethylene glycol is serial, a kind of in the polyether series, Sorbic Acid glyceryl ester or several combination in compatible situation; Protonated organic amine be a kind of in alkane amine series, alkene amine series, the aromatic hydrocarbons amine series or after several combinations in the compatible situation with mineral acid or the formed salt of organic acid.Carry out fully in order to guarantee reaction, before three kinds of inorganic salt hybrid reactions, template must be pre-mixed evenly with mixture or the phosphate powder that zinc salt powder, aluminium salt powder form, template is premixed in the mixture that zinc salt powder, aluminium salt powder form, perhaps template is premixed in the phosphate powder, perhaps template is sneaked in the powder of three kinds of salt respectively in advance.
The method of above-mentioned synthetic zinc phosphate aluminum nanocrystalline, before zinc salt, aluminium salt and phosphate powder hybrid reaction, template elder generation is pre-mixed evenly with mix powder or the phosphate powder of zinc salt, aluminium salt, perhaps template is premixed in the phosphate powder, perhaps template is sneaked in the powder of three kinds of salt respectively in advance.
The process of above-described synthetic zinc phosphate aluminum nanocrystalline, the inorganic salt by-product that washes solubility in the dereaction mixture with water can reclaim and be used, be about to it concentrated, can make other byproduct, such as materials such as sodium sulfate, vitriolate of tartar, ammonium sulfate, sodium-chlor, Repone K, sodium-acetate, SODIUMNITRATE, saltpetre, when obtaining these byproducts, can avoid again because directly discharging the pollution that environment causes.
With the zinc phosphate aluminum nanocrystalline that above-mentioned synthetic method obtains, productive rate has realized that more than 95% the reaction process step is few, does not need solvent, and productive rate is high, and reaction conditions is gentle, easy to control.Adopt product that method of the present invention obtains that the corrosion inhibition of carbon steel is better than traditional zinc phosphate or aluminum phosphate.
The present invention mainly adopts the low fever solid phase reaction synthesis method, under the condition of room temperature, normal pressure, in the crystal water medium under the inducing of template, in constrained, orderly microencapsulation, carry out the metathesis conversion reaction by zinc salt powder, aluminium salt powder, phosphate powder.Reaction generates the binary metal phosphoric acid salt of insoluble and the inorganic salt by-product of solubility, discharge simultaneously the crystal water in the reaction raw materials, then the inorganic salt of solubility are because of supersaturation, form crystallization with crystal, the binary metal phosphoric acid salt that perhaps generates generates crystal water in conjunction with free-water, and these processes produce a strong convergent force.Do in template under the inducing of template, the powerful internal pressure that above-mentioned convergent force forms is ordered about the also syncrystallization of corresponding insoluble metal phosphoric acid salt indissoluble and that be difficult to crystallization around the inorganic salt.Because of the difficultly-soluble phosphates of respective metal through being scattered in equably after the reaction around the inorganic salt of solubility, and do not have that the difference because of different metal indissoluble thing solubility product produces the fractional precipitation problem in the liquid phase method, so can mix equably with the yardstick of molecular level between the phosphoric acid salt of different metal, make the interionic that forms the phosphoric acid zinc-aluminium realize self-assembly, and in-situ transesterification change into zinc phosphate aluminium crystal.
Method of the present invention compared with prior art, the advantage such as having reaction does not need solvent, and reaction conditions is gentle, easy to control, and technique is simple, raw material sources are wide.Both overcome when respective metal generates throw out in the liquid phase method fractional precipitation problem that the difference because of solubility product causes, overcome again the large shortcoming of the quantity discharged of waste water in the liquid phase method.This law is compared with high-temperature solid phase reaction method, high-energy ball milling method, can greatly reduce the formation temperature of phosphoric acid zinc-aluminium crystal.Characteristic of the present invention is to synthesize on demand the phosphoric acid zinc-aluminium product of required component, performance.
Description of drawings
Fig. 1 adopts the X-ray diffraction (XRD) of the product of the method for the invention acquisition to analyze collection of illustrative plates.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described.
Below be that the present invention utilizes the rare earth chemical reaction method to synthesize phosphoric acid zinc-aluminium Zn
(3-1.5x)Al
x(PO
4)
2Several embodiment of (0＜x＜2) crystal:
Embodiment 1
Preparation Zn
1.5Al
1.0(PO
4)
2
Get zinc sulfate ZnSO
47H
2O powder 15.0mol is 4313.3g, aluminum nitrate Al (NO
3)
39H
2O powder 10.0mol is 3751.3g, sodium phosphate Na
3PO
412H
2O powder 23.0mol is 8742.1g, and PEG-4000 is 258g.In an enamelled vessel, add sodium phosphate powder, then add PEG-4000 and mix for subsequent use, then under room temperature, normal pressure, under agitation in the sodium phosphate powder that mixes with PEG-4000, add above-mentioned zinc salt powder, aluminium salt powder, add to mix and fully grind 40min in the rear immigration grinding plant, at room temperature leave standstill 1.5h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution can't detect SO
4 2-Till, filtration under diminished pressure.At 100 ℃ of lower baking 2～4h, the filter cake grinds with oven dry obtains aluminium zinc phosphate nanocrystal with filter cake, take zinc salt as benchmark, and yield 〉=95%.
Embodiment 2
Preparation powder Zn
1.5Al
1.0(PO
4)
2
Get zinc sulfate ZnSO
47H
2O powder 15.0mol is 4313.3g, aluminum chloride AlCl
36H
2O powder 10.0mol is 2414.3g, sodium phosphate Na
3PO
412H
2O) powder 23.0mol is 8742.1g, and OP-10 is 338g.In an enamelled vessel, add sodium phosphate powder, then add OP-10 and ground and mixed evenly for subsequent use, then under room temperature, normal pressure, under agitation to the uniform sodium phosphate powder of OP-10 ground and mixed in add above-mentioned zinc salt powder, aluminium salt powder, add to mix and fully grind 50min in the rear immigration grinding plant, at room temperature leave standstill 1.5h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution can't detect SO
4 2-Till, filtration under diminished pressure.At 100 ℃ of lower baking 3～4h, the filter cake grinds with oven dry obtains aluminium zinc phosphate nanocrystal with filter cake, take zinc salt as benchmark, and yield 〉=95%.
Embodiment 3
Preparation Zn
1.5Al
1.0(PO
4)
2
Get zinc sulfate ZnSO
47H
2O powder 15.0mol is 4313.3g, aluminum nitrate Al (NO
3)
39H
2O powder 10.0mol is 3751.3g, sodium hydrogen phosphate Na
2HPO
412H
2O powder 25.0mol is 9628.5g, and tween-80 is 131g, triethanolamine hydrochloride 131g.In an enamelled vessel, add the sodium hydrogen phosphate powder, then add the tween-80 of half and the triethanolamine hydrochloride of half and mix, for subsequent use.In another enamelled vessel, zinc sulphate powder, aluminum nitrate powder are fully mixed, then add second half tween-80 and second half triethanolamine hydrochloride and mix, for subsequent use.Then under room temperature, normal pressure, under agitation in sodium hydrogen phosphate, add above-mentioned zinc salt powder, the mixture of aluminium salt powder, add to mix and fully grind 70min in the rear immigration grinding plant, at room temperature leave standstill 2h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution can't detect SO
4 2-Till, filtration under diminished pressure.At 100 ℃ of lower baking 3～4h, the filter cake grinds with oven dry obtains aluminium zinc phosphate nanocrystal with filter cake, take zinc salt as benchmark, and yield 〉=95%.
Embodiment 4
Preparation Zn
1.65Al
0.9(PO
4)
2
Get zinc nitrate Zn (NO
3)
26H
2O powder 16.5mol is 4908.4g, aluminum nitrate Al (NO
3)
39H
2O powder 9.0mol is 3376.2g, potassiumphosphate K
3PO
43H
2O powder 23.0mol is 6125.1g, and OP-10 is 223g.In an enamelled vessel, add the potassiumphosphate powder, then add OP-10 and mix, for subsequent use; In another enamelled vessel, zinc nitrate powder, aluminum nitrate powder are fully mixed, for subsequent use.Under room temperature, normal pressure, under agitation in the potassiumphosphate powder that mixes with OP-10, add above-mentioned zinc salt powder, the mixture of aluminium salt powder, add to mix and fully grind 40min in the rear immigration grinding plant, at room temperature leave standstill 1.5h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution can't detect SO
4 2-Till, filtration under diminished pressure.At 100 ℃ of lower baking 3～4h, the filter cake grinds with oven dry obtains aluminium zinc phosphate nanocrystal with filter cake, take zinc salt as benchmark, and yield 〉=95% ().
Embodiment 5
Preparation Zn
1.65Al
0.9(PO
4)
2
Get zinc chloride ZnCl
2Powder 16.5mol is 2248.8g, aluminum chloride AlCl
36H
2O powder 9.0mol is 2172.9g, ammonium phosphate (NH
4)
3PO
43H
2O powder 23.0mol is 4672.0g, and tween-80 is 133g.In an enamelled vessel, add the ammonium phosphate powder, then add tween-80 and mix, for subsequent use; In another enamelled vessel, zinc chloride powder, aluminum chloride powder are fully mixed, for subsequent use.Under room temperature, normal pressure, under agitation to the uniform ammonium phosphate powder of tween-80 ground and mixed in add above-mentioned zinc salt powder, the mixture of aluminium salt powder, add to mix and fully grind 60min in the rear immigration grinding plant, at room temperature leave standstill 2h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution can't detect SO
4 2-Till, filtration under diminished pressure.At 100 ℃ of lower baking 3～4h, the filter cake grinds with oven dry obtains aluminium zinc phosphate nanocrystal with filter cake, take zinc salt as benchmark, and yield 〉=95%.
Embodiment 6
Preparation Zn
1.65Al
0.9(PO
4)
2
Get zinc acetate Zn (CH
3COO)
22H
2O powder 16.5mol is 4908.4g, aluminum chloride AlCl
36H
2O powder 9.0mol is 2172.9g, sodium phosphate Na
3PO
412H
2O powder 23.0mol is 8742.8g, and tween-80 is 113g, ethylenediamine-hydrochloride 113g.In an enamelled vessel, add sodium phosphate powder, then add the tween-80 of half and the ethylenediamine-hydrochloride of half and mix, for subsequent use.In another enamelled vessel, zinc acetate powder, aluminum chloride powder are fully mixed, then add second half tween-80 and second half ethylenediamine-hydrochloride and mix, for subsequent use.Under room temperature, normal pressure, add above-mentioned zinc salt powder, the mixture of aluminium salt powder in the sodium phosphate powder that under agitation mixes to tween-80 and ethylenediamine-hydrochloride, add to mix and fully grind 60min in the rear immigration grinding plant, at room temperature leave standstill 2h, wash reaction mixture with water and to filtrate, use 0.5molL
-1BaCl
2Solution can't detect SO
4 2-Till, filtration under diminished pressure.At 100 ℃ of lower baking 3～4h, the filter cake grinds with oven dry obtains aluminium zinc phosphate nanocrystal with filter cake, take zinc salt as benchmark, and yield 〉=95%.
Get the phosphoric acid zinc-aluminium crystal that above-mentioned arbitrary embodiment synthesizes, carry out XRD analysis, according to the Scherrer formula, the particle diameter that calculates zinc phosphate aluminium powder form crystallite is about 35nm.As scheme shown in the l, can find out from the XRD analysis collection of illustrative plates, adopting the synthetic phosphoric acid zinc-aluminium product of the method for the invention is a kind of crystalline compounds.
Claims (3)
1. the synthetic method of an aluminium zinc phosphate nanocrystal, it is characterized in that: it adopts the rare earth chemical reaction method directly synthetic, concrete technology is, take zinc salt powder, aluminium salt powder, phosphate powder as raw material, its proportioning raw materials is: zinc salt: aluminium salt: phosphatic material mass ratio is 0.05～0.95: 0.05～0.95:2.0～3.0, add template, template accounts for 0.1～10 % of whole reactant weight; Grind 10～120 min after under the condition of room temperature, normal pressure, mixing, then allow reaction mixture under room temperature～90 ℃, leave standstill 1～5 hour, then wash the inorganic salt by-product of solubility in the dereaction mixture with water, filter, with filter cake oven dry under 100 ℃, obtain the aluminium zinc phosphate nanocrystal product, its crystallite particle diameter is 35 nm
Above-mentioned zinc salt is selected from a kind of or several combination in compatible situation in zinc chloride, zinc sulfate, zinc nitrate, the zinc acetate;
Above-mentioned aluminium salt comprises a kind of or several combination in compatible situation in aluminum chloride, aluminum nitrate, the Tai-Ace S 150;
Above-mentioned phosphoric acid salt is selected from a kind of or several combination in compatible situation in sodium phosphate, sodium hydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, the potassiumphosphate;
Have the two or more crystal water that contain in above-mentioned zinc salt, aluminium salt and the phosphoric acid salt at least;
Above-mentioned template comprises that tween series, OP are serial, a kind of in the polyoxyethylene glycol or several combination in compatible situation; Perhaps template is the combination of ethylenediamine-hydrochloride and tween; Perhaps template is the combination of triethanolamine hydrochloride and tween.
2. the synthetic method of aluminium zinc phosphate nanocrystal according to claim 1, it is characterized in that: before zinc salt, aluminium salt and phosphate powder hybrid reaction, mix powder or phosphate powder with template and zinc salt, aluminium salt is pre-mixed evenly first, and perhaps template is sneaked in the powder of three kinds of salt respectively in advance.
3. the synthetic method of aluminium zinc phosphate nanocrystal according to claim 1, it is characterized in that: mix and add in the process of template in zinc salt powder, aluminium salt powder, phosphate powder, the mixture that zinc salt powder, aluminium salt powder are formed joins in the phosphate powder, perhaps phosphate powder is added in the mixture that zinc salt powder and aluminium salt powder form.
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| CN103881711B (en) * | 2014-03-24 | 2017-01-11 | 广西大学 | Method for preparing manganese doped lithium zinc phosphate yellow green fluorescent powder by adopting low heat solid-phase reaction |
| CN105206832B (en) * | 2015-08-27 | 2019-02-22 | 张家港智电芳华蓄电研究所有限公司 | A kind of sintering preparation method of zinc load material |
| CN106634373A (en) * | 2015-11-03 | 2017-05-10 | 无锡市太湖防腐材料有限公司 | Waterborne zinc aluminum phosphate anti-rusting primer and preparation method thereof |
| CN105694570B (en) * | 2016-03-04 | 2017-07-25 | 广西民族大学 | A kind of nanometer zinc phosphate rust resisting pigment continuous producing method and process units |
| CN110697672B (en) * | 2019-11-22 | 2021-05-11 | 浙江大学台州研究院 | Preparation method of zinc phosphate for water-based anticorrosive paint |
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