CN117964947A - Preparation of nano silicon dioxide limited zinc phosphate composite inorganic filler and application of nano silicon dioxide limited zinc phosphate composite inorganic filler in epoxy resin system - Google Patents
Preparation of nano silicon dioxide limited zinc phosphate composite inorganic filler and application of nano silicon dioxide limited zinc phosphate composite inorganic filler in epoxy resin system Download PDFInfo
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- CN117964947A CN117964947A CN202311786515.4A CN202311786515A CN117964947A CN 117964947 A CN117964947 A CN 117964947A CN 202311786515 A CN202311786515 A CN 202311786515A CN 117964947 A CN117964947 A CN 117964947A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 title claims abstract description 80
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000011256 inorganic filler Substances 0.000 title claims abstract description 43
- 229910003475 inorganic filler Inorganic materials 0.000 title claims abstract description 43
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 31
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001868 water Inorganic materials 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 31
- 239000000945 filler Substances 0.000 claims abstract description 29
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- -1 aluminum ions Chemical class 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 229920006334 epoxy coating Polymers 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229910018557 Si O Inorganic materials 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a preparation method of nano silicon dioxide limited zinc phosphate composite inorganic filler and application thereof in an epoxy resin system, wherein the preparation method of the nano silicon dioxide limited zinc phosphate composite inorganic filler comprises the following steps: mixing zinc oxide with water to obtain zinc oxide slurry; preparing an aluminum dihydrogen phosphate solution; mixing an aluminum dihydrogen phosphate solution with zinc oxide slurry to prepare zinc phosphate filler with aluminum ions introduced; mixing the zinc phosphate filler with aluminum ions introduced with KH560, stirring at room temperature, and standing; and dissolving KH570 modified nano-silica and surface modified zinc phosphate in an ethanol solution, stirring and drying to obtain the nano-silica limited-domain zinc phosphate composite inorganic filler. According to the invention, the zinc phosphate is used for preparing the composite inorganic filler with excellent performance after the nano silicon dioxide is subjected to gel-method limited-domain activation, and the inorganic filler can obviously improve the corrosion resistance, cathode stripping resistance and mechanical performance of the epoxy coating.
Description
Technical Field
The invention relates to the field of inorganic blending materials, in particular to preparation of a nano silicon dioxide finite field zinc phosphate composite inorganic filler and application thereof in an epoxy resin system.
Background
Inorganic fillers have been widely used as extenders in an effort to reduce manufacturing costs while improving certain properties, and epoxy resins can be modified by blending of the inorganic fillers to improve mechanical, thermal or electrical properties, particularly to reduce shrinkage.
Zinc phosphate is a nontoxic green inorganic filler, has a molecular formula of Zn 3(PO4)2, belongs to orthorhombic flaky crystals, and has corrosiveness and deliquescence. Dissolving in inorganic acid, ammonia water and ammonium salt solution; is insoluble in ethanol; is hardly soluble in water and its solubility in water decreases with an increase in temperature. Usually in the form of di-, tetra-, di-and tetra-water mixtures. When heated to a temperature of more than 100 ℃, a dihydrate is formed, when heated to 190 ℃, a monohydrate is formed, and when the temperature is about 250 ℃, crystal water is lost to form an anhydrous substance. The zinc phosphate has the advantages that the thickness and the strength of the coating are increased, the shielding effect of the coating can be improved, but the zinc phosphate has less help to the corrosion inhibition performance of the coating, the zinc phosphate filler is added, and meanwhile, the metal is added to partially modify anions and cations, so that the corrosion inhibition performance of the coating is greatly enhanced, the adhesive force is effectively increased, and the sensitivity to cathode stripping is reduced. Meanwhile, phenolic epoxy resin can be used as an additive for adding and blending modification to introduce a high benzene ring structure and a polyepoxy resin to improve the crosslinking density, tg, hardness and permeation resistance of the resin, so that the cathode stripping resistance of the epoxy resin coating is improved.
However, the common zinc phosphate has a large particle size, generally 15-45 μm, a small specific surface area, low solubility in water, poor hydrolyzability and low speed of forming a passivation protection film in the early stage of corrosion, so that the overall rust resistance of the paint is affected, and therefore, the paint is difficult to comprehensively replace a toxic rust-proof pigment and needs to be modified. The common zinc phosphate has the advantages of small specific surface area, low solubility, poor hydrolyzability, insufficient rust-preventing activity and slower speed of forming an effective protective film, and can not overcome the problem of 'flash rust' in the slightly alkaline water-based primer, the rust-preventing performance can not reach the level of the traditional zinc chrome yellow, and the traditional toxic rust-preventing pigment is difficult to replace comprehensively. It is therefore desirable to provide a modification that increases the activity of zinc phosphate while increasing its dispersibility in resin systems.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a preparation method of nano silicon dioxide limited zinc phosphate composite inorganic filler and application thereof in an epoxy resin system
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a nano silicon dioxide limited zinc phosphate composite inorganic filler, which comprises the following steps:
(1) Mixing zinc oxide with water to obtain zinc oxide slurry; mixing and stirring phosphoric acid, water and aluminum hydroxide, heating to above 120 ℃ to generate aluminum dihydrogen phosphate, and adding water for dilution to obtain aluminum dihydrogen phosphate solution; slowly adding the aluminum dihydrogen phosphate solution into partial zinc oxide slurry, heating to 80-90 ℃, maintaining the temperature and stirring, adding the rest zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction; filtering, drying and crushing to obtain zinc phosphate filler with aluminum ions introduced;
(2) Mixing the zinc phosphate filler with the aluminum ions introduced with KH560, stirring at room temperature, and standing;
(3) And (3) dissolving KH570 modified nano-silica and the surface modified zinc phosphate obtained in the step (2) into an ethanol solution, stirring at room temperature, and vacuum drying to remove the solvent, thereby obtaining the nano-silica limited-domain zinc phosphate composite inorganic filler.
The KH570 modified nano-silica (SiO 2 -KH 570) in the invention is KH570 surface modified nano-silica, the specific source and preparation process of SiO 2 -KH570 are not limited in the invention, and commercial KH570 surface modified nano-silica can be adopted.
In the invention, under the condition of alkali catalytic solution and especially when the water addition amount is high, the Si-O chains are not easy to intertwine, so that a discrete cluster structure with longer Si-O chains is easy to form. Along with the reduction of the water addition amount, the silane coupling agent KH570 is modified in such a way that the three-dimensional network gel structure is formed by gelation through being connected with the silicon dioxide chains of clusters, and the nano SiO 2 inorganic finite field with Si-O on the surface is introduced with the zinc phosphate filler of aluminum ions to prepare the composite antirust pigment filler serving as an epoxy resin system. The nano silicon dioxide gel inside and outside the composite filler can be well dispersed inside a resin system to participate in the formation of a cross-linked network, and the zinc phosphate can form a passivation film with the surface of a matrix to prevent the transmission of corrosion factors, so that the corrosion resistance and cathodic disbonding resistance of the resin are greatly improved. In addition, the research shows that the composite filler has better improving effect on mechanical properties of an epoxy resin system, such as adhesive force, dimensional stability and the like.
Preferably, in the step (1), the dosage mass ratio of the zinc oxide, the phosphoric acid and the aluminum hydroxide is 1:1.03:0.28.
Preferably, in the step (1), the time of heat preservation and stirring is 2-4h.
Preferably, in the step (1), the aluminum dihydrogen phosphate solution is slowly added into 88-92% zinc oxide slurry, heated to 80-90 ℃ and stirred at a constant temperature, and then the rest zinc oxide slurry is added.
Preferably, in the step (2), the mass ratio of the zinc phosphate filler into which aluminum ions are introduced to KH560 is (1.5-3.5): 1, a step of; further preferably, the mass ratio of the zinc phosphate filler into which aluminum ions are introduced to KH560 is (2-3): 1.
Preferably, in the step (2), the stirring time is 0.5-1.5h, and the stirring speed is 200-300r/min; the standing time is 0.5-1.5h, and the stirring and standing steps are repeated for 2-4 times.
Preferably, in the step (3), the mass ratio of the KH570 modified nano silica to the surface modified zinc phosphate obtained in the step (2) is 1: (7.5-15).
Preferably, in the step (3), the stirring time is 1-3h, and the stirring speed is 250-350r/min.
Preferably, in the step (3), the temperature of the vacuum drying is 40-85 ℃ and the drying time is 5-13h.
The invention provides a nano silicon dioxide domain-limited zinc phosphate composite inorganic filler, which is prepared by a preparation method of the nano silicon dioxide domain-limited zinc phosphate composite inorganic filler.
The third aspect of the invention provides application of the nano silicon dioxide limited zinc phosphate composite inorganic filler in an epoxy resin system.
Compared with the prior art, the invention has the beneficial effects that:
According to the method, the nano silicon dioxide is subjected to gel method limited domain activation zinc phosphate to prepare the composite inorganic filler with excellent performance, the composite inorganic filler adopts a metal cation doping mode to improve activity, nano silicon dioxide (KH 570 modified) limited domain is used for improving the dispersibility in a resin system, a silane coupling agent is used for introducing a composite material into the resin crosslinking system through surface modification, the dispersibility in the resin system is good, a passivation film can be formed on the surface of a substrate to prevent corrosion factor diffusion, so that the coating has excellent cathode stripping resistance, the bonding failure phenomenon of the epoxy coating in a high-humidity high-salt external cathode protection environment can be effectively reduced, and the inorganic filler can obviously improve the corrosion resistance, cathode stripping resistance and mechanical property of the epoxy coating.
According to the preparation method of the nano silicon dioxide limited zinc phosphate composite inorganic filler, provided by the invention, the water bath device, the reaction kettle and the overhead mechanical stirrer are used for heating and stirring the mixed materials to obtain the finished product material with uniform mixing of the materials, the equipment requirement of the whole process is low, the operation is simple, the preparation method is nontoxic and harmless, the preparation process condition is simple, the operation is easy, the cost is low, and the preparation method is suitable for small-batch sample preparation.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Example 1
The nano silicon dioxide limited zinc phosphate composite inorganic filler comprises the following preparation raw materials in parts by weight:
100 parts of zinc oxide, 103 parts of phosphoric acid, 28 parts of aluminum hydroxide, 5 parts of KH56023 parts of KH570 modified nano-silica (SiO 2 -KH 570) (specification: particle size 20 nm, purity 99wt%, manufacturer: jiangsu Xianfeng nm, product number: 100363).
The preparation method comprises the following steps:
S1: zinc oxide and a proper amount of water are mixed and stirred in a reaction kettle to obtain zinc oxide slurry. Adding phosphoric acid and water into another kettle, adding aluminum hydroxide under stirring, heating to above 120deg.C, dissolving aluminum hydroxide in phosphoric acid to obtain aluminum dihydrogen phosphate, and diluting with water under stirring to obtain aluminum dihydrogen phosphate solution. Slowly adding the aluminum dihydrogen phosphate solution into the 90% zinc oxide slurry under stirring, heating to 85 ℃, keeping the temperature, stirring for 2 hours, supplementing the 10% zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction. Filtering, drying at 120 ℃, crushing, detecting, metering and packaging to obtain the zinc phosphate filler introduced with aluminum ions.
S2: the zinc phosphate filler with aluminum ions is mixed with KH560 according to the mass ratio of 2:1, stirring for 1h at a speed of 300r/min at room temperature, standing for 1h, and repeating the steps three times.
S3: KH570 modified nano-silica and surface modified zinc phosphate were dissolved in ethanol solution, the mixture was stirred at room temperature for 2 hours, and then the solution was dried at 45℃under vacuum for 12 hours to remove the solvent.
Example 2
The nano silicon dioxide limited zinc phosphate composite inorganic filler comprises the following preparation raw materials in parts by weight:
100 parts of zinc oxide, 103 parts of phosphoric acid, 28 parts of aluminum hydroxide, 56023 parts of KH, and 5 parts of KH570 modified nano-silica.
The preparation method comprises the following steps:
S1: zinc oxide and a proper amount of water are mixed and stirred in a reaction kettle to obtain zinc oxide slurry. Adding phosphoric acid and water into another kettle, adding aluminum hydroxide under stirring, heating to above 120deg.C, dissolving aluminum hydroxide in phosphoric acid to obtain aluminum dihydrogen phosphate, and diluting with water under stirring to obtain aluminum dihydrogen phosphate solution. Slowly adding the aluminum dihydrogen phosphate solution into the 90% zinc oxide slurry under stirring, heating to 85 ℃, keeping the temperature, stirring for 2 hours, supplementing the 10% zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction. Filtering, drying at 120 ℃, crushing, detecting, metering and packaging to obtain the zinc phosphate filler introduced with aluminum ions.
S2: the zinc phosphate filler with aluminum ions is mixed with KH560 according to the mass ratio of 2:1, stirring for 0.5h at a speed of 300r/min at room temperature, standing for 0.5h, and repeating the steps three times.
S3: KH570 modified nano-silica and surface modified zinc phosphate were dissolved in ethanol solution, the mixture was stirred at room temperature for 2 hours, and then the solution was dried at 45℃under vacuum for 12 hours to remove the solvent.
Example 3
The nano silicon dioxide limited zinc phosphate composite inorganic filler comprises the following preparation raw materials in parts by weight:
100 parts of zinc oxide, 103 parts of phosphoric acid, 28 parts of aluminum hydroxide, 56023 parts of KH, and 5 parts of KH570 modified nano-silica.
The preparation method comprises the following steps:
S1: zinc oxide and a proper amount of water are mixed and stirred in a reaction kettle to obtain zinc oxide slurry. Adding phosphoric acid and water into another kettle, adding aluminum hydroxide under stirring, heating to above 120deg.C, dissolving aluminum hydroxide in phosphoric acid to obtain aluminum dihydrogen phosphate, and diluting with water under stirring to obtain aluminum dihydrogen phosphate solution. Slowly adding the aluminum dihydrogen phosphate solution into the 90% zinc oxide slurry under stirring, heating to 85 ℃, keeping the temperature, stirring for 2 hours, supplementing the 10% zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction. Filtering, drying at 120 ℃, crushing, detecting, metering and packaging to obtain the zinc phosphate filler introduced with aluminum ions.
S2: the zinc phosphate filler with aluminum ions is mixed with KH560 according to the mass ratio of 2:1, stirring for 1h at 200r/min at room temperature, standing for 1h, and repeating the steps three times.
S3: KH570 modified nano-silica and surface modified zinc phosphate were dissolved in ethanol solution, the mixture was stirred at room temperature for 2 hours, and then the solution was dried in vacuo at 80℃for 6 hours to remove the solvent.
Example 4
The nano silicon dioxide limited zinc phosphate composite inorganic filler comprises the following preparation raw materials in parts by weight:
100 parts of zinc oxide, 103 parts of phosphoric acid, 28 parts of aluminum hydroxide, 56016 parts of KH and 5 parts of KH570 modified nano-silica.
The method comprises the following steps:
S1: zinc oxide and a proper amount of water are mixed and stirred in a reaction kettle to obtain zinc oxide slurry. Adding phosphoric acid and water into another kettle, adding aluminum hydroxide under stirring, heating to above 120deg.C, dissolving aluminum hydroxide in phosphoric acid to obtain aluminum dihydrogen phosphate, and diluting with water under stirring to obtain aluminum dihydrogen phosphate solution. Slowly adding the aluminum dihydrogen phosphate solution into the 90% zinc oxide slurry under stirring, heating to 85 ℃, keeping the temperature, stirring for 2 hours, supplementing the 10% zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction. Filtering, drying at 120 ℃, crushing, detecting, metering and packaging to obtain the zinc phosphate filler introduced with aluminum ions.
S2: the zinc phosphate filler with aluminum ions is mixed with KH560 according to the mass ratio of 3:1, stirring for 1h at a speed of 300r/min at room temperature, standing for 1h, and repeating the steps three times.
S3: KH570 modified nano-silica and surface modified zinc phosphate were dissolved in ethanol solution, the mixture was stirred at room temperature for 2 hours, and then the solution was dried at 45℃under vacuum for 12 hours to remove the solvent.
Comparative example 1
The nano silicon dioxide limited zinc phosphate composite inorganic filler comprises the following preparation raw materials in parts by weight:
100 parts of zinc oxide, 103 parts of phosphoric acid, 28 parts of aluminum hydroxide and 5 parts of KH570 modified nano-silica.
The method comprises the following steps:
S1: zinc oxide and a proper amount of water are mixed and stirred in a reaction kettle to obtain zinc oxide slurry. Adding phosphoric acid and water into another kettle, adding aluminum hydroxide under stirring, heating to above 120deg.C, dissolving aluminum hydroxide in phosphoric acid to obtain aluminum dihydrogen phosphate, and diluting with water under stirring to obtain aluminum dihydrogen phosphate solution. Slowly adding the aluminum dihydrogen phosphate solution into the 90% zinc oxide slurry under stirring, heating to 85 ℃, keeping the temperature, stirring for 2 hours, supplementing the 10% zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction. Filtering, drying at 120 ℃, crushing, detecting, metering and packaging to obtain the zinc phosphate filler introduced with aluminum ions.
S2: KH570 modified nano silica and zinc phosphate having aluminum ions introduced thereto were dissolved in an ethanol solution, the mixture was stirred at room temperature for 2 hours, and then the solution was dried at 45 ℃ in vacuo for 12 hours to remove the solvent.
Comparative example 2
The nano silicon dioxide limited zinc phosphate composite inorganic filler comprises the following preparation raw materials in parts by weight:
100 parts of zinc oxide, 103 parts of phosphoric acid, 28 parts of aluminum hydroxide, 56023 parts of KH, and 5 parts of KH570 modified nano-silica.
The method comprises the following steps:
S1: and mixing and stirring most of zinc oxide with a proper amount of water in a reaction kettle to obtain zinc oxide slurry. Adding phosphoric acid and water into another kettle, adding aluminum hydroxide under stirring, heating to above 120deg.C, dissolving aluminum hydroxide in phosphoric acid to obtain aluminum dihydrogen phosphate, and diluting with water under stirring to obtain aluminum dihydrogen phosphate solution. Slowly adding the aluminum dihydrogen phosphate solution into the zinc oxide slurry under stirring, heating to 85 ℃, keeping the temperature, stirring for 2 hours, adding a small amount of zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction. Filtering, drying at 120 ℃, crushing, detecting, metering and packaging to obtain the zinc phosphate filler introduced with aluminum ions.
S2: the zinc phosphate filler with aluminum ions is mixed with KH560 according to the mass ratio of 2:1, stirring for 1h at a speed of 300r/min at room temperature, standing for 1h, and repeating the steps three times.
S3: KH570 modified nano silica and surface modified zinc phosphate were dissolved in a sufficient amount of pure water, the mixture was stirred at room temperature for 2 hours, and then the solution was dried under vacuum at 45 ℃ for 12 hours to remove the solvent.
Application example 1
The nano silicon dioxide limited zinc phosphate composite inorganic filler is applied to an epoxy resin system.
The resin (epoxy resin E-51, 50phr; phenolic epoxy resin, 20 phr), pigment filler (carbon black/kaolin, 19 phr), reactive diluent (660A, 10 phr) and auxiliary agent (KH 560,1 phr) after blending are mechanically stirred at normal temperature for 400rpm and 1h, and the rotational speed is increased to 1200rpm after the components are basically mixed and stirred for 12h. The primer and the curing agent are mixed according to the mass ratio of (2-4): 1, after mixing, stirring thoroughly at 400rpm or by a manual medicine spoon, coating the thoroughly mixed primer curing agent on a test piece plate, curing for 90min at 80 ℃, and waiting for cooling to room temperature to obtain the epoxy coating.
Taking examples 1-5 and comparative examples 1-2 for performance testing; the materials were mixed into a resin system according to application example 1, and the adhesive force was measured according to ISO21809-3, the impact strength was measured according to ISO21809-3, and the cathodic disbonding was measured according to ISO21809-3, the test results are shown in Table 1 below.
TABLE 1
Analysis of results:
(1) The nano silicon dioxide limited zinc phosphate composite inorganic filler prepared in the embodiment 1-5 is used for successfully enhancing the cathode stripping resistance and mechanical property of the epoxy resin, has good adhesive force, and can not generate debonding phenomenon in 28 days under the cathode stripping condition of 23 ℃ and minus 1.5V.
(2) From the combination of the example 1 and the comparative example 1, the surface of the composite filler zinc phosphate and the nano silicon dioxide in the comparative example 1 is not modified by a coupling agent, the composite degree is poor, the compatibility with a resin system is poor, the adhesive force and the cathode stripping resistance are poor, and the composite filler zinc phosphate and the nano silicon dioxide are not suitable for the application of the epoxy paint under the environment of high-humidity high-salt external cathode protection.
(3) From the combination of the example 1 and the comparative example 2, the zinc phosphate composite filler of the comparative example 2 does not form a temperature limited composite structure with nano silicon dioxide, has obviously lower adhesive force and cathode stripping resistance than the examples 1-5, and is not suitable for the application of the epoxy paint under the environment of high-humidity high-salt external cathode protection.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (10)
1. The preparation method of the nano silicon dioxide limited zinc phosphate composite inorganic filler is characterized by comprising the following steps of:
(1) Mixing zinc oxide with water to obtain zinc oxide slurry; mixing and stirring phosphoric acid, water and aluminum hydroxide, heating to above 120 ℃ to generate aluminum dihydrogen phosphate, and adding water for dilution to obtain aluminum dihydrogen phosphate solution; slowly adding the aluminum dihydrogen phosphate solution into partial zinc oxide slurry, heating to 80-90 ℃, maintaining the temperature and stirring, adding the rest zinc oxide slurry, and heating to boiling to neutralize phosphoric acid of the reaction; filtering, drying and crushing to obtain zinc phosphate filler with aluminum ions introduced;
(2) Mixing the zinc phosphate filler with the aluminum ions introduced with KH560, stirring at room temperature, and standing;
(3) And (3) dissolving KH570 modified nano-silica and the surface modified zinc phosphate obtained in the step (2) into an ethanol solution, stirring at room temperature, and vacuum drying to remove the solvent, thereby obtaining the nano-silica limited-domain zinc phosphate composite inorganic filler.
2. The method for preparing nano-silica domain-limited zinc phosphate composite inorganic filler according to claim 1, wherein in the step (1), the dosage mass ratio of zinc oxide, phosphoric acid and aluminum hydroxide is 1:1.03:0.28.
3. The method for preparing nano-silica limited zinc phosphate composite inorganic filler according to claim 1, wherein in the step (1), the time of heat preservation and stirring is 2-4h.
4. The method for preparing nano-silica limited zinc phosphate composite inorganic filler according to claim 1, wherein in the step (2), the mass ratio of the zinc phosphate filler into which aluminum ions are introduced to KH560 is (1.5-3.5): 1.
5. The method for preparing nano-silica limited zinc phosphate composite inorganic filler according to claim 1, wherein in the step (2), the stirring time is 0.5-1.5h, and the stirring speed is 200-300r/min; the standing time is 0.5-1.5h, and the stirring and standing steps are repeated for 2-4 times.
6. The preparation method of the nano-silica domain-limited zinc phosphate composite inorganic filler according to claim 1, wherein in the step (3), the mass ratio of the KH570 modified nano-silica to the surface modified zinc phosphate obtained in the step (2) is 1: (7.5-15).
7. The method for preparing nano-silica limited zinc phosphate composite inorganic filler according to claim 1, wherein in the step (3), the stirring time is 1-3h, and the stirring speed is 250-350r/min.
8. The method for preparing nano-silica limited zinc phosphate composite inorganic filler according to claim 1, wherein in the step (3), the vacuum drying temperature is 40-85 ℃ and the drying time is 5-13h.
9. The nano silicon dioxide limited zinc phosphate composite inorganic filler is characterized by being prepared by the preparation method of the nano silicon dioxide limited zinc phosphate composite inorganic filler in any one of claims 1-8.
10. The use of the nano-silica limited zinc phosphate composite inorganic filler of claim 9 in an epoxy resin system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311786515.4A CN117964947A (en) | 2023-12-25 | 2023-12-25 | Preparation of nano silicon dioxide limited zinc phosphate composite inorganic filler and application of nano silicon dioxide limited zinc phosphate composite inorganic filler in epoxy resin system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311786515.4A CN117964947A (en) | 2023-12-25 | 2023-12-25 | Preparation of nano silicon dioxide limited zinc phosphate composite inorganic filler and application of nano silicon dioxide limited zinc phosphate composite inorganic filler in epoxy resin system |
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| CN117964947A true CN117964947A (en) | 2024-05-03 |
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| CN202311786515.4A Pending CN117964947A (en) | 2023-12-25 | 2023-12-25 | Preparation of nano silicon dioxide limited zinc phosphate composite inorganic filler and application of nano silicon dioxide limited zinc phosphate composite inorganic filler in epoxy resin system |
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| CN (1) | CN117964947A (en) |
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2023
- 2023-12-25 CN CN202311786515.4A patent/CN117964947A/en active Pending
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