CN106276838A - A kind of preparation method and application of antirust filler calcium hydroxy phosphate - Google Patents
A kind of preparation method and application of antirust filler calcium hydroxy phosphate Download PDFInfo
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- CN106276838A CN106276838A CN201610682004.1A CN201610682004A CN106276838A CN 106276838 A CN106276838 A CN 106276838A CN 201610682004 A CN201610682004 A CN 201610682004A CN 106276838 A CN106276838 A CN 106276838A
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- Prior art keywords
- calcium
- hydroxy phosphate
- phosphoric acid
- phosphate
- calcium hydroxy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
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Abstract
The present invention relates to the preparation method and application of a kind of antirust filler calcium hydroxy phosphate, a calcium oxide and phosphoric acid are raw material, by raw material simple and easy to get, and the equal avirulence of all raw materials, for environment without any pollution；Without the need for the separation of intermediate product, reaction time is short, simple for process, low cost, and cost performance is high, and the product Heat stability is good obtained has good application prospect；Prepared calcium hydroxy phosphate is applied in corrosion-resistant epoxy paint, has exceeded commercially available common zinc phosphate, thus reached novel antirust filler low cost, nontoxic and efficient target in terms of antirust ability.
Description
Technical field
The present invention relates to Inorganic synthese technical field, the preparation method of a kind of antirust filler calcium hydroxy phosphate
And application.
Background technology
Calcium hydroxy phosphate is as the main component of hydroxyapatite, and it is made pottery as skeleton embedded material and tooth processed for a long time
Porcelain, illustrates that the acid resistance of calcium hydroxy phosphate and Saline alkali tolerance are the best, and it will not occur biodegradation simultaneously.Phosphate
The rust-proof mechanism of antirust filler be phosphate radical in wet condition with metal reaction, generate a kind of passivating film, thus stop outside
To corrosion of metal.So, calcium hydroxy phosphate can also be applied as antirust filler, and, according to calcium hydroxy phosphate itself
Character, the resistance to corrosion ratio in theory of its made antirusting paint be all phosphatic zinc phosphate or trimerization
Aluminum phosphate is eager to excel.
At present the preparation method of calcium hydroxy phosphate mainly has following several: (1) sedimentation method, and this is to prepare calcium hydroxy phosphate
One of conventional method, this method is simple to operate, convenient and practical, if the strict rate of addition controlling reaction, the pH of reflection
Value, reacts initial calcium-phosphorus ratio, it is possible to obtain the calcium phosphate phase of different calcium-phosphorus ratio.(2) Hydrolyze method, this method is to utilize one
The hydrolysis in aqueous such as a little material such as DCPD generates calcium phosphate.(3) sol-gel method, this method is with phosphate
Under alcohol environment, form gel with calcium salt, and interpolation organic acid regulates course of reaction in colloidal sol, thus obtain more stable
Colloidal sol, finally utilize deflagrate method to obtain calcium phosphate powder.(4) solid reaction process, solid state reaction is also the earliest for making
One of method of standby calcium phosphate, course of reaction is exactly that the P source compound of solid-state and the calcium source compound of solid-state are evenly mixed in
Together, react at 1000 DEG C.Solid phase method can be prepared and meet stoichiometric proportion or the various crystallne phosphoric acids of crystalline phase composition
Calcium material.But the method requires high temperature and longer response time, and the sinterability of powder is the most very poor, and range of application is the most more come
The least.
Japan Patent JP61-151009 proposes in a nitrogen atmosphere, under conditions of temperature is 50～70 DEG C of PH=10,
Use CaHPO4·2H2O Yu CaO (or Ca (OH)2) react synthesis of hydroxy calcium phosphate.Environment and PH are had very by this test method
High requirement.In patent No. JP61-168364, disclose the preparation method of a kind of calcium hydroxy phosphate, it be by calcium hydroxide and
Phosphoric acid reacts generation in the solution, its synthesis calcium hydroxy phosphate and mixture drying of unreacted reactant, be dehydrated, pulverize and get final product
To the calcium hydroxy phosphate that noncrystalline is porous prilled, dry at 190 DEG C and obtain drying solid in 24 hours.
Chinese patent CN 102849700A, in the presence of hydrolytic collagen, obtains hydroxyl phosphorus by chemical precipitation method
Lime stone, the prices of raw materials needed for this method are higher, are not suitable for the synthesis of coating calcium hydroxy phosphate.
CN101297978 discloses a kind of method using phase transfer method to prepare nanometer hydroxyapatite, but this method is used
Solvent be organic solvent, a lot of unfavorable factors can be brought, such as environmental conservation etc..
Summary of the invention
The invention aims to provide the preparation method and application of a kind of antirust filler calcium hydroxy phosphate, by dissociating
The phosphate anion gone out and iron ion generation complexation, make substrate surface form one layer of fine and close passivating film, stop corrosive medium
Penetrate into, thus improve adhesive strength and the rustless property of coating.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
The preparation method of a kind of antirust filler calcium hydroxy phosphate, comprises the following steps:
Step one: take calcium oxide, adds water and is sufficiently stirred for so that it is be dispersed, obtain calcium oxide dispersion, standby, resultant bulk
In system, the substance withdrawl syndrome of calcium oxide is 3～5mol/ L；
Step 2: take strong phosphoric acid, adds water and is diluted, and obtains phosphoric acid,diluted, standby, the substance withdrawl syndrome of gained phosphoric acid,diluted be 1～
3mol/ L；
Step 3: step 2 gained phosphoric acid,diluted is slowly dropped in step one gained system, control reaction temperature be 25 DEG C～
50 DEG C, after completion of dropwise addition, stir reaction 2 ~ 3h, course of reaction keeps calcium oxide be in excess state, it is to avoid calcium phosphate by-product
Produce；
Step 4: step 3 gained reactant liquor is carried out filtration under diminished pressure, takes filter cake and dries in 100 DEG C of air dry ovens to permanent
Weight, obtains calcium hydroxy phosphate.
In described step 3, the amount of calcium oxide and the material of phosphoric acid is than for 3:5～2:3.
In described step 2, strong phosphoric acid is the strong phosphoric acid of 85%.
The application of antirust filler calcium hydroxy phosphate prepared by a kind of method as above, makees the calcium hydroxy phosphate of gained
For antirust applying filler in corrosion-resistant epoxy paint, wherein calcium hydroxy phosphate shared mass fraction in epoxy coating formula is 5%
~ 10%, and this paint brush is applied on the steel plate of low prepared surface, to improve adhesive strength and the antiseptic property of coating.
Beneficial effects of the present invention:
The preparation method of the antirust filler calcium hydroxy phosphate that the present invention provides, by raw material simple and easy to get, and also all former
Expect equal avirulence, for environment without any pollution；Without the need for the separation of intermediate product, reaction time is short, and technique is the easiest
OK, low cost, cost performance is high, and the product Heat stability is good obtained has good application prospect；Prepared calcium hydroxy phosphate
It is applied in corrosion-resistant epoxy paint, in terms of antirust ability, has exceeded commercially available common zinc phosphate, thus reached novel antirust and filled out
Material low cost, nontoxic and efficient target.
Accompanying drawing explanation
Fig. 1 product XRD of the present invention spectrum and standard spectrum comparison diagram；
The electrochemical impedance figure of two kinds of coating immersion 60d on Fig. 2 band rust steel plate.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further elaborated.
The preparation method of a kind of antirust filler calcium hydroxy phosphate, comprises the following steps:
Step one: take calcium oxide, adds water and is sufficiently stirred for so that it is be dispersed, obtain calcium oxide dispersion, standby, resultant bulk
In system, the substance withdrawl syndrome of calcium oxide is 3～5mol/ L；
Step 2: take strong phosphoric acid, adds water and is diluted, and obtains phosphoric acid,diluted, standby, the substance withdrawl syndrome of gained phosphoric acid,diluted be 1～
3mol/ L；
Step 3: step 2 gained phosphoric acid,diluted is slowly dropped in step one gained system, control reaction temperature be 25 DEG C～
50 DEG C, after completion of dropwise addition, stir reaction 2 ~ 3h, course of reaction keeps calcium oxide be in excess state, it is to avoid calcium phosphate by-product
Produce；
Step 4: step 3 gained reactant liquor is carried out filtration under diminished pressure, takes filter cake and dries in 100 DEG C of air dry ovens to permanent
Weight, obtains calcium hydroxy phosphate.
The application of antirust filler calcium hydroxy phosphate prepared by a kind of method as above, makees the calcium hydroxy phosphate of gained
For antirust applying filler in corrosion-resistant epoxy paint, wherein calcium hydroxy phosphate shared mass fraction in epoxy coating formula is 5%
~ 10%, and this paint brush is applied on the steel plate of low prepared surface, to improve adhesive strength and the antiseptic property of coating.
Embodiment 1
In the there-necked flask of the 250ml with stirring, adding the calcium oxide of 0.03mol, the deionized water adding 10mL fills
Divide stirring, make dispersed；Measure 5.76g 85% strong phosphoric acid (amount of the material of phosphoric acid is 0.05mol), and add 50mL
Deionized water be diluted, then use constant pressure addition funnel will dilution after phosphoric acid in 30min, be slowly dropped to three mouthfuls
In flask, completion of dropwise addition stirring reaction 3h, then the emulsion of gained is carried out filtration under diminished pressure, place into 100 DEG C of forced air dryings
Case is dried to constant weight, obtain calcium hydroxy phosphate.
Embodiment 2:
In the there-necked flask of the 250ml with stirring, adding the calcium oxide of 0.05mol, the deionized water adding 10mL fills
Divide stirring, make dispersed；Measure 9.6g 85% strong phosphoric acid (amount of the material of phosphoric acid is 0.083mol), and add 83mL
Deionized water be diluted, then use constant pressure addition funnel will dilution after phosphoric acid in 30min, be slowly dropped to three mouthfuls
In flask, completion of dropwise addition stirring reaction 3h, then the emulsion of gained is carried out filtration under diminished pressure, place into 100 DEG C of forced air dryings
Case is dried to constant weight, obtain calcium hydroxy phosphate.
Embodiment 3:
In the there-necked flask of the 250ml with stirring, adding the calcium oxide of 0.03mol, the deionized water adding 10mL fills
Divide stirring, make dispersed；Measure 5.1g 85% strong phosphoric acid (amount of the material of phosphoric acid is 0.045mol), and add 15mL
Deionized water be diluted, then use constant pressure addition funnel will dilution after phosphoric acid in 60min, be slowly dropped to three mouthfuls
In flask, completion of dropwise addition stirring reaction 2h, then the emulsion of gained is carried out filtration under diminished pressure, place into 100 DEG C of forced air dryings
Case is dried to constant weight, obtain calcium hydroxy phosphate.
Embodiment 4:
In the reactor of the 10L with stirring, adding the calcium oxide of 0.3mol under room temperature, the deionized water adding 1L is abundant
Stirring, makes dispersed；Measure 57.6g 85% strong phosphoric acid (amount of the material of phosphoric acid is 0.5mol), and add going of 5L
Ionized water is diluted, and then uses constant pressure addition funnel to be slowly dropped in 30min in system by the phosphoric acid after dilution, drips
Add end stirring reaction 2h, then the emulsion of gained is carried out filtration under diminished pressure, place in 100 DEG C of air dry ovens and dry
To constant weight, obtain calcium hydroxy phosphate.
Prepared calcium hydroxy phosphate carries out XRD spectra analysis, and the standard spectrogram (such as Fig. 1) in contrast XRD spectra understands,
The product of the proof present invention is calcium hydroxy phosphate.
Using obtain calcium hydroxy phosphate as antirust applying filler in corrosion-resistant epoxy paint, it is at epoxy coating formula
Mass fraction shared by is 5%-10%, and is applied to by this paint brush on the band rust steel plate of low prepared surface, contrasts calcium hydroxy phosphate
Epoxy anticorrosive coating before and after interpolation band rust steel plate on adhesive strength and sea water immersion 60d latter two coating electrochemistry resistance
Anti-value (is shown in Table 1 and Fig. 2), and the interpolation of calcium hydroxy phosphate is remarkably improved adhesive strength and the antiseptic property of coating.
As seen from Figure 1, the XRD collection of illustrative plates of obtained calcium hydroxy phosphate sample and calcium hydroxy phosphate (Ca5(PO4)3OH)
Standard card peak value essentially identical, it may be determined that made calcium phosphate sample be mainly composed of calcium hydroxy phosphate.
The adhesive strength measured value of two kinds of coatings on table 1 band rust steel plate
By table 1 and Fig. 2 it can be seen that the adhesive strength of interpolation calcium hydroxy phosphate epoxy coating and electrochemical impedance value significantly carry
Height, this is that the iron ion of phosphate radical and the base material dissociateed due to calcium hydroxy phosphate defines one layer of fine and close oxide-film, not only
Improve coating adhesive strength on band rust steel plate, strengthen the coating iris action to hydrone simultaneously, improve coating
Antiseptic property.
Claims (4)
1. the preparation method of an antirust filler calcium hydroxy phosphate, it is characterised in that comprise the following steps:
Step one: take calcium oxide, adds water and is sufficiently stirred for so that it is be dispersed, obtain calcium oxide dispersion, standby, resultant bulk
In system, the substance withdrawl syndrome of calcium oxide is 3～5mol/ L；
Step 2: take strong phosphoric acid, adds water and is diluted, and obtains phosphoric acid,diluted, standby, the substance withdrawl syndrome of gained phosphoric acid,diluted be 1～
3mol/ L；
Step 3: step 2 gained phosphoric acid,diluted is slowly dropped in step one gained system, control reaction temperature be 25 DEG C～
50 DEG C, after completion of dropwise addition, stir reaction 2 ~ 3h, course of reaction keeps calcium oxide be in excess state, it is to avoid calcium phosphate by-product
Produce；
Step 4: step 3 gained reactant liquor is carried out filtration under diminished pressure, takes filter cake and dries in 100 DEG C of air dry ovens to permanent
Weight, obtains calcium hydroxy phosphate.
The preparation method of antirust filler calcium hydroxy phosphate the most as claimed in claim 1, it is characterised in that: oxygen in described step 3
Change the amount of calcium and the material of phosphoric acid ratio for 3:5～2:3.
The preparation method of antirust filler calcium hydroxy phosphate the most as claimed in claim 1, it is characterised in that: dense in described step 2
Phosphoric acid is the strong phosphoric acid of 85%.
4. the application of antirust filler calcium hydroxy phosphate prepared by the method for claim 1, it is characterised in that: by institute
The calcium hydroxy phosphate obtained is as antirust applying filler in corrosion-resistant epoxy paint, and wherein calcium hydroxy phosphate is in epoxy coating formula
Shared mass fraction is 5% ~ 10%, and is applied on the steel plate of low prepared surface by this paint brush, to improve the adhesive strength of coating
And antiseptic property.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610682004.1A CN106276838A (en) | 2016-08-18 | 2016-08-18 | A kind of preparation method and application of antirust filler calcium hydroxy phosphate |
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| CN201610682004.1A CN106276838A (en) | 2016-08-18 | 2016-08-18 | A kind of preparation method and application of antirust filler calcium hydroxy phosphate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298903A (en) * | 2017-06-27 | 2017-10-27 | 天长市巨龙车船涂料有限公司 | A kind of antirust modified coating |
| CN108017994A (en) * | 2017-12-27 | 2018-05-11 | 安徽凤阳亚欧玻璃工艺品有限公司 | A kind of preparation method of the breakage-proof coating of glassware |
| CN112194456A (en) * | 2020-10-10 | 2021-01-08 | 云南莱德福科技有限公司 | Material containing calcium hydroxy phosphate, one-step synthesis and forming method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112837A (en) * | 2013-03-18 | 2013-05-22 | 厦门大学 | Preparation method of nano-hydroxyapatite |
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2016
- 2016-08-18 CN CN201610682004.1A patent/CN106276838A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112837A (en) * | 2013-03-18 | 2013-05-22 | 厦门大学 | Preparation method of nano-hydroxyapatite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298903A (en) * | 2017-06-27 | 2017-10-27 | 天长市巨龙车船涂料有限公司 | A kind of antirust modified coating |
| CN108017994A (en) * | 2017-12-27 | 2018-05-11 | 安徽凤阳亚欧玻璃工艺品有限公司 | A kind of preparation method of the breakage-proof coating of glassware |
| CN112194456A (en) * | 2020-10-10 | 2021-01-08 | 云南莱德福科技有限公司 | Material containing calcium hydroxy phosphate, one-step synthesis and forming method and application thereof |
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