CN101519540B - Nanometer biological composite inhibitive phosphate pigment and preparation method thereof - Google Patents

Nanometer biological composite inhibitive phosphate pigment and preparation method thereof Download PDF

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CN101519540B
CN101519540B CN2009100740715A CN200910074071A CN101519540B CN 101519540 B CN101519540 B CN 101519540B CN 2009100740715 A CN2009100740715 A CN 2009100740715A CN 200910074071 A CN200910074071 A CN 200910074071A CN 101519540 B CN101519540 B CN 101519540B
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white
pigment
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alh
phosphate
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CN101519540A (en
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代威
刘晓
宋健龙
陆微微
丁士文
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Hebei University
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Abstract

The present invention provides a nanometer biological composite antirust phosphate pigment which comprises AlH2P3O10, Zn3(PO4)2 and Zn2B6O11 in the mol ratio of 2 to (1 to 3) to (0.01 to 0.1). The preparation process comprises the following steps: firstly, preparing a trimeric aluminium dihydrogen phosphate precursor and mixing with a suitable amount of boric acid; secondly, adding the mixture to an emulsion containing zinc oxide under a certain condition; and utilizing residual phosphoric acid and boric acid in the trimeric aluminium dihydrogen phosphate precursor to react with the zinc oxide in the emul containing zinc oxide under a certain condition; and thirdly, utilizing residual phosphoric acid and boric acid in the trimeric aluminium dihydrogen phosphate precursor to react with the zinc oxide in the emulsion so as to prepare the novel high-efficiency composite biological nanometer-stage antirust phosphate pigment. The nanometer biological composite antirust phosphate pigment of the present invention uses low-price organic salt as a raw material and adopts an innovative preparation method, namely a polymerization-ultrasound chemical precipitation method, to compound trimeric aluminium dihydrogen phosphate, zinc phosphate and zinc borate so as to generate the synergic action in the antirust process and improve the antirust performance in short, medium and long terms.

Description

Nanometer biological composite inhibitive phosphate pigment and preparation method
Technical field
The present invention relates to a kind of nanometer biological composite inhibitive phosphate pigment, belong to inorganic compounding phosphate pigment or coating preparing technical field.
Background technology
The pollution that the organic volatile material (VOC) that conventional solvent type coating is discharged in production and use produces is come after the automobile at present, classifies the primary pollution source in city as.As solvent based coating substitute water-borne coatings, be subjected to the attention of countries in the world.For a long time, that coatings industry uses is leaded, chromium (VI) is though the rustless property that waits the rust-stabilising pigment of toxic heavy metal to have excellence, but its toxicity is big, color is dark, the gas that distributes when welding is with cutting behind the dust that produces in the three wastes that production process produces, system lacquer process, the metallized paint and the poisonous paint film behind the coating damage or the like all can cause serious harm and pollution to human body and environment, therefore, the production of this class pigment progressively is restricted with use.All occupy bigger advantage with series of phosphate pigment with regard to the research on its kind, performance and the use range, thereby make it become the non-poisonous antirust pigment of consumption maximum.But there is some defective again in single phosphoric acid salt rust-stabilising pigment.Such as the particle of present commercially available zinc phosphate big (10～15 μ m); specific surface area is less; bad dispersibility; and its solubleness is low and water-disintegrable poor; the antirust activity deficiency, the speed that forms effective protective membrane is too slow, can not overcome so-called " dodging rust " problem; its rustless property does not reach the level of traditional zinc-chrome yellow, is difficult to replace traditional poisonous rust-stabilising pigment comprehensively.Aluminium dihydrogen tripolyphosphate is then owing to reasons such as acidity, water solubilities, and is not suitable for directly using as rust resisting pigment, and in addition modification makes it have suitable pH value, dissolubility, dispersiveness etc., just can become the available active rust resisting pigment of a kind of reality.Zinc borate then belongs to reactive pigment, and it but is not fine that the later stage rustless property of this pigment goes.
Summary of the invention
The object of the present invention is to provide a kind of nanometer biological composite inhibitive phosphate pigment and preparation method, carry out aluminium dihydrogen tripolyphosphate, zinc phosphate and zinc borate compound, make it in antirust process, produce synergy, introduce nano material simultaneously with over-all propertieies such as the ageing resistance that improves pigment, erosion resistance, radioresistances.
The object of the present invention is achieved like this: this nanometer biological composite inhibitive phosphate pigment, its composition comprises AlH 2P 3O 10, Zn 3(PO 4) 2, and Zn 2B 6O 11
AlH in the described nanometer biological composite inhibitive phosphate pigment 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11Mol ratio is 2: 1～3: 0.1～1.
The preparation method of described nanometer biological composite inhibitive phosphate pigment comprises the steps:
A, according to Al: the P mol ratio is that 1: 4～6 ratio takes by weighing Al (OH) 3In beaker, be dissolved in 85% strong phosphoric acid;
B, beaker is put into heating jacket, add thermal agitation at 80 ℃ and dissolve the Al (H that generates transparent thickness fully 2PO 4) 3The aqueous solution;
C, with step B gained Al (H 2PO 4) 3The aqueous solution changes evaporating dish over to, puts into muffle furnace at 280～330 ℃ of lower heating 3～6h, aggregates into the hard aluminium dihydrogen tripolyphosphate AlH of white 2P 3O 10Solid;
D, with step C gained AlH 2P 3O 10Solid takes out from muffle furnace, and after the room temperature to be naturally cooled to, the water that adds 2～3 times of product gross weights makes it expanded, the white slurry that gets;
E, with in the step D gained white soup compound according to Al: the B mol ratio is that 1: 0.03～0.3 ratio adds boric acid, stir evenly white soup compound;
F, in addition according to Al: the Zn mol ratio is that 1: 1.6～5.5 ratio takes by weighing zinc oxide in beaker, adds the water of 5～6 times of zinc oxide total amounts simultaneously, and the back that the stirs 30～60min that vibrates in ultrasonic wave obtains white soup compound;
G, the white slurry that obtains in the white slurry of step e gained and the step F evenly slowly mixed under hyperacoustic vibration and constantly stir, after about one hour mixing complete, obtain white paste mixture;
H, with step G gained white paste mixture at 60～100 ℃ of heated and stirred and the 1～3h that refluxes, outward appearance still is white soup compound;
I, step H gained white slurry is obtained white filter cake with the Buchner funnel suction filtration, place 100 ℃ drying box to dry filter cake, pulverizing obtains containing AlH 2P 3O 10, Zn 3(PO 4) 2, and Zn 2B 6O 11White nanometer biological composite inhibitive phosphate pigment, AlH wherein 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 1～3: 0.1～1.
The present invention is raw material with the inexpensive inorganic salt, adopt the preparation method's one polymerization-sonochemistry precipitator method of innovation to carry out aluminium dihydrogen tripolyphosphate, zinc phosphate and zinc borate compound, make it in antirust process, produce synergy, improve simultaneously short, in, secular antiseptic property; The present invention at first prepares the aluminium dihydrogen tripolyphosphate precursor in preparation process, mix with an amount of boric acid again, then under certain conditions its adding is contained in the emulsion of zinc oxide, utilize the reaction of the zinc oxide in the remaining phosphoric acid and boric acid and emulsion in the aluminium dihydrogen tripolyphosphate precursor, thereby prepare a kind of novel, complex ecological efficiently, nano level phosphoric acid salt rust-stabilising pigment.Not only solved the problem of environmental pollution of excess phosphoric acid in the simple aluminium dihydrogen tripolyphosphate production process, and the water-based anticorrosive paint for preparing with rust resisting pigment of the present invention can improve resistance to ag(e)ing, corrosion resistance, radiation resistance, can also further improve adhesive force, intensity, hardness, wearability and the salt spray resistance etc. of coating, have excellent weak point, in, long-term rustless property.
Description of drawings
Fig. 1 is the TEM photo of gained sample after supersound process, illustrates that composite phosphate rust-stabilising pigment of the present invention is a nano level.
Embodiment
Embodiment 1, preparation AlH 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 1: 0.1 rust resisting pigment
(1) accurately takes by weighing 15.6g Al (OH) 3(0.2 mole) is in beaker and be dissolved in the strong phosphoric acid of 55ml (0.8 mole) 85% (Al and P mol ratio are 1: 4);
(2) beaker is put into heating jacket, heat and produce a large amount of bubbles when being stirred to 80 ℃, then bubble reduces solution clarification thickness gradually, and at this moment, reaction has been carried out fully;
(3) change the transparent viscous solution of gained over to furnace pot, put into muffle furnace, aggregate into white hard solid at 280 ℃ of following reacting by heating 6h.；
The white hard solid that (4) will aggregate into takes out, after waiting to naturally cool to room temperature, after adding 60ml water and making it expanded white soup compound;
(5) adding 3.7g (0.06 mole) boric acid in above-mentioned white slurry, stir evenly, still is white slurry;
(6) (in three-necked bottle, add simultaneously 145ml water, the 30min that vibrates in ultrasonic wave after stirring obtains white slurry accurately to take by weighing 25.9g (0.32 mole) ZnO;
(7) under hyperacoustic vibration, evenly slowly be added drop-wise to (5) step gained white slurry in the resulting white slurry of (6) step and constantly stir, mix completely behind the 1h, remain white slurry;
(8) with gained white soup compound at the 60 ℃ of heated and stirred and the 3h that refluxes, outward appearance still is white soup compound;
(9) gained white slurry is obtained white filter cake with the Buchner funnel suction filtration, place 100 ℃ drying box to dry filter cake, pulverize and obtain containing AlH 2P 3O 10, Zn 3(PO 4) 2, and Zn 2B 6O 11White nanometer biological composite inhibitive phosphate pigment, AlH wherein 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 1: 0.1.
Embodiment 2, preparation AlH 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 2: 0.2 rust resisting pigments
(1) accurately takes by weighing 15.6g Al (OH) 3 in beaker and be dissolved in the strong phosphoric acid of 69ml85% (Al is 1: 5 with the ratio of P).
(2) beaker is put into heating jacket, heat and produce a large amount of bubbles when being stirred to 80 ℃, then bubble reduces solution clarification thickness gradually, and at this moment, reaction has been carried out fully.
(3) change the transparent viscous solution of gained over to furnace pot, put into muffle furnace and heat 4h down, aggregate into white hard solid at 300 ℃.
The white hard solid that (4) will aggregate into takes out, after waiting to naturally cool to room temperature, after adding 100ml water and making it expanded white soup compound.
(5) adding 7.4g boric acid in above-mentioned white slurry, stir evenly, still is white slurry.
(6) accurately take by weighing 51.8g ZnO in three-necked bottle, add simultaneously 290ml water, the 30min that vibrates in ultrasonic wave after stirring obtains white slurry.
(7) under hyperacoustic vibration, evenly slowly be added drop-wise to (5) step gained white slurry in the resulting white slurry of (6) step and constantly stir, mix completely behind the 1h, remain white slurry.
(8) with gained white soup compound at the 85 ℃ of heated and stirred and the 2h that refluxes, outward appearance still is white soup compound.
(9) gained white slurry is obtained white filter cake with the Buchner funnel suction filtration, place 100 ℃ drying box to dry filter cake, pulverize and obtain containing AlH 2P 3O 10, Zn 3(PO 4) 2, and Zn 2B 6O 11White nanometer biological composite inhibitive phosphate pigment, wherein, AlH 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 2: 0.2 rust resisting pigments.
Embodiment 3, preparation AlH 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 3: 1 rust resisting pigments
(1) accurately takes by weighing 15.6g Al (OH) 3 in beaker and be dissolved in the strong phosphoric acid of 90ml85% (Al is 1: 6 with the ratio of P).
(2) beaker is put into heating jacket, heat and produce a large amount of bubbles when being stirred to 80 ℃, then bubble reduces solution clarification thickness gradually, and at this moment, reaction has been carried out fully.
(3) change the transparent viscous solution of gained over to furnace pot, put into muffle furnace and heat 3h down, aggregate into white hard solid at 330 ℃.
The white hard solid that (4) will aggregate into takes out, after waiting to naturally cool to room temperature, after adding 150ml water and making it expanded white soup compound.
(5) adding 37.1g boric acid in above-mentioned white slurry, stir evenly, still is white slurry.
(6) accurately take by weighing 89.1g ZnO in three-necked bottle, add simultaneously 500ml water, the 60min that vibrates in ultrasonic wave after stirring obtains white slurry.
(7) under hyperacoustic vibration, evenly slowly be added drop-wise to (5) step gained white slurry in the resulting white slurry of (6) step and constantly stir, mix completely behind the 1h, remain white slurry.
(8) with gained white soup compound at the 100 ℃ of heated and stirred and the 1h that refluxes, outward appearance still is white soup compound.
(9) gained white slurry is obtained white filter cake with the Buchner funnel suction filtration, place 100 ℃ drying box to dry filter cake, pulverize and obtain containing AlH 2P 3O 10, Zn 3(PO 4) 2, and Zn 2B 6O 11White nanometer biological composite inhibitive phosphate pigment, wherein, AlH 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 3: 1 rust resisting pigments.
Listed examples of the present invention is intended to further illustrate the preparation and the application direction of this nanometer biological composite inhibitive phosphate pigment, and protection scope of the present invention is not constituted any restriction.

Claims (3)

1. nanometer biological composite inhibitive phosphate pigment, its composition comprises AlH 2P 3O 10, Zn 3(PO 4) 2, and Zn 2B 6O 11
2. according to the described nanometer biological composite inhibitive phosphate pigment of claim 1, its feature comprises AlH in the rust resisting pigment 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11Mol ratio is 2: 1～3: 0.1～1.
3. according to the preparation method of the described nanometer biological composite inhibitive phosphate pigment of claim 1, its feature comprises the steps:
A, according to Al: the P mol ratio is that 1: 4～6 ratio takes by weighing Al (OH) 3In beaker, be dissolved in 85% strong phosphoric acid;
B, beaker is put into heating jacket, add thermal agitation at 80 ℃ and dissolve the Al (H that generates transparent thickness fully 2PO 4) 3The aqueous solution;
C, with step B gained Al (H 2PO 4) 3 aqueous solution change furnace pot over to, put into muffle furnace at 280～330 ℃ of heating 3～6h down, aggregate into the hard aluminium dihydrogen tripolyphosphate AlH of white 2P 3O 10Solid;
D, with step C gained AlH 2P 3O 10Solid takes out from muffle furnace, and after the room temperature to be naturally cooled to, the water that adds 2～3 times of product gross weights makes it expanded, the white slurry that gets;
E, with in the step D gained white soup compound according to Al: the B mol ratio is that 1: 0.03～0.3 ratio adds boric acid, stir evenly white soup compound;
F, in addition according to Al: the Zn mol ratio is that 1: 1.6～5.5 ratio takes by weighing zinc oxide in beaker, adds the water of 5～6 times of zinc oxide total amounts simultaneously, and the back that the stirs 30～60min that vibrates in ultrasonic wave obtains white soup compound;
G, the white slurry that obtains in the white slurry of step e gained and the step F evenly slowly mixed under hyperacoustic vibration and constantly stir, after one hour mixing complete, obtain white paste mixture;
H, with step G gained white paste mixture at 60～100 ℃ of heated and stirred and the 1～3h that refluxes, outward appearance still is white soup compound;
I, step H gained white slurry is obtained white filter cake with the Buchner funnel suction filtration, place 100 ℃ drying box to dry filter cake, pulverizing obtains containing AlH 2P 3O 10, Zn 3(PO 4) 2, and Zn 2B 6O 11White nanometer biological composite inhibitive phosphate pigment, AlH wherein 2P 3O 10: Zn 3(PO 4) 2: Zn 2B 6O 11=2: 1～3: 0.1～1.
CN2009100740715A 2009-04-03 2009-04-03 Nanometer biological composite inhibitive phosphate pigment and preparation method thereof Expired - Fee Related CN101519540B (en)

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CN103468048B (en) * 2013-09-25 2015-01-14 广西民族大学 High-cost performance modified aluminum tripolyphosphate anti-rust pigment and preparation method thereof
CN103497556B (en) * 2013-09-25 2015-07-01 广西民族大学 Modified aluminum tripolyphosphate anti-rust pigment for middle and low-end coatings and preparation method thereof
CN103569990B (en) * 2013-11-20 2015-06-24 苏州大学 Inorganic substrate phosphate pigment and preparation method and application of inorganic substrate phosphate pigment

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207301A (en) * 1978-03-14 1980-06-10 Alexeeva Olga V Process for producing zinc phosphate
CN1072655A (en) * 1991-11-22 1993-06-02 美国博克斯化学有限公司 Zinc borate
CN1099719A (en) * 1994-04-18 1995-03-08 郑州金岭化工有限公司 Method for preparing dihydrate tripolyphosphate aluminium dihydride

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207301A (en) * 1978-03-14 1980-06-10 Alexeeva Olga V Process for producing zinc phosphate
CN1072655A (en) * 1991-11-22 1993-06-02 美国博克斯化学有限公司 Zinc borate
CN1099719A (en) * 1994-04-18 1995-03-08 郑州金岭化工有限公司 Method for preparing dihydrate tripolyphosphate aluminium dihydride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP昭58-132048A 1983.08.06

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