CN103804959A - Preparation method and application of modified silica sol - Google Patents
Preparation method and application of modified silica sol Download PDFInfo
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- CN103804959A CN103804959A CN201310720151.XA CN201310720151A CN103804959A CN 103804959 A CN103804959 A CN 103804959A CN 201310720151 A CN201310720151 A CN 201310720151A CN 103804959 A CN103804959 A CN 103804959A
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Abstract
The invention relates to the field of non-stick coatings. In order to solve the problem that existing non-stick coatings are low in surface energy and the hardness and wear resistance cannot satisfy the requirements, the invention provides a modified silica sol and a preparation method thereof. The modified silica sol is prepared by the following steps: adding fluorosilane and titanium tetrabutoxide into the silica sol; then, adjusting the pH to 4-5; stirring at 20-60 DEG C; and maintaining for 1-8 hours to obtain the modified silica sol. According to the modified silica sol, the surface energy of the silica sol can be effectively reduced. The modified silica sol provided by the invention applied to non-stick coatings has the advantages of wear resistance, high hardness, good non-stick property and the like.
Description
Technical field
The present invention relates to non-viscous paint field, relate in particular to a kind of modified silicasol and preparation method thereof and the coating that wear resistance is strong, hardness is high of preparing with this silicon sol.
Background technology
Silicon sol is the stable colloid dispersion forming in water or alcohol equal solvent that is scattered in of nano-silicon dioxide particle, has another name called silicic acid sol, or silica hydrosol.
The oh group of silica particle surface has stronger activity, utilizes some materials to react the surface chemistry that can change silicon dioxide granule with the oh group of silica particle surface.For example patent CN 101338082A discloses a kind of silane coupler modified silicon dioxide gel and its preparation method and application, but this patent adds organosilane, be mainly used in polishing fluid, for the desired surface of non-viscous paint can be low, hardness is high, wear-resisting strong feature can not meet; Patent CN 101240068A discloses the organosilane-modified silicon sol of a kind of use and in the application of preparing in water-borne coatings, but the wear resistance of coating is not embodied.
Non-viscous paint be a kind of coatingsurface be difficult for being adhered to by other viscous substances or adhere after the speciality coating that is easily removed.This kind of coating can extremely low, the non-stick property feature such as frictional coefficient is little, easy slip because of the surface of its coating that forms, and is widely used in the industries such as household electrical appliance, cooking utensils, automobile, machinery, chemical industry.For example CN 102643582 A disclose a kind of non-viscous paint, be made up of, but this coating exist the feature wearing no resistance in this non-viscous paint main film forming fluoro-resin, ACRYLIC EMULSION and water.
Summary of the invention
Have for solving current non-viscous paint the problem that surface energy is low, hardness and wear resistance can not meet the demands, the present invention proposes a kind of modified silicasol and preparation method thereof, the silicon sol after modification can reduce the surface energy of silicon sol effectively.
The invention allows for the application of modified silicasol on non-viscous paint, there is wear-resisting, the advantage such as hardness is high, viscosity is not good.
The present invention is achieved by the following scheme: a kind of preparation method of modified silicasol, described preparation method is following steps: in silicon sol, add fluoro silane and tetrabutyl titanate, then regulate pH to 4～5,20～60 ℃ of stirrings, keep obtaining modified silicasol after 1～8h.As preferably, adopt 10% aqueous acetic acid to regulate pH value.
Fluoro silane is selected from ten difluoro heptyl propyl trimethoxy silicanes, fluoro octyl triethoxyl silane, triethoxy-1H, 1H, 2H, a kind of in 2H-13 fluoro n-octyl silane, trimethylammonium pentafluorophenyl group silane, 13 fluoro octyl triethoxyl silanes or two kinds, consumption is 0.005～0.1% of reactant gross weight.
Described tetrabutyl titanate consumption is 0.1～2% of reactant gross weight.
In modified silicasol of the present invention, can also contain tensio-active agent.Tensio-active agent can be anion surfactant: as Sodium dodecylbenzene sulfonate, can be cats product: as palmityl trimethyl ammonium chloride, can be nonionogenic tenside: as polysorbate, can be also zwitterionics: as cocamidopropyl betaine.The consumption of tensio-active agent is 0.005～1.2% of reactant total mass.
The weight that above-mentioned reactant gross weight is fluoro silane, tetrabutyl titanate, silicon sol and.
This silicon sol combines the advantage of fluoro silane and titanium, and after fluoro silane, tetrabutyl titanate and silicon dioxide gel are mixed, carrying out modified-reaction can obtain.In modified silicasol, silica particle surface has been adhered in fluoro silane and silicon sol and has been contained titanium, has improved on the one hand the surface energy of silicon dioxide granule, has improved on the other hand the hardness of silicon dioxide granule.
Based on the improvement of above two kinds of performances, the application of the prepared modified silicasol of the preparation method of described modified silicasol on non-viscous paint.The non-viscous paint that adopts modified silicasol of the present invention to prepare, has improved the wear resistance of coating, therefore described non-viscous paint have lower surface can, wear resistance, hardness are high preferably.
Described non-viscous paint is made up of following component, and the weight percent of each component is:
Modified silicasol 8 ~ 60%,
Silane 10 ~ 46%,
Nano filling 2 ~ 38%,
Pigment 2 ~ 31%,
Water 18 ~ 41%,
PH adjusting agent 0.1 ~ 8%,
Polyaluminocarbosilane 0.2 ~ 6%,
Each component sum is 100%.
Described silane is selected from one or more in γ-aminopropyltrimethoxysilane, methyltrimethoxy silane, gamma-mercaptopropyltriethoxysilane, ethyl triethoxysilane, γ-aminopropyl triethoxysilane, tri isopropyl silane, phenyltrimethoxysila,e, ethyl trimethoxy silane and propyl trimethoxy silicane, and weight percent is 18 ~ 30%.
Described Nano filling is selected from one or more in nanometer potasium titanate, nano barium titanate aluminium, nanometer Calucium Silicate powder, silicon whisker, nano-cellulose, nano aluminium oxide, nano zirconium dioxide, nano-nickel oxide, nano silicon oxide, nano zine oxide, titanium nitride.
Described pigment is selected from that phosphoric acid cobalt violet, titanium dioxide, Pigment Yellow 73 183, carbon black, molybdate yellow, Red copper oxide, graphite, high titanium ash, titanium nickel yellow, cobalt titanate green, ferrimanganic are black, one or more in cobalt blue, copper-chrome black.
Described wet concentration is from pure water or deionized water.
Described pH adjusting agent is selected from one or more in the 5.5% sodium pyrosulfate aqueous solution, 2% oxalic acid aqueous solution, 10% aqueous hydrochloric acid, 5% aqueous nitric acid, 15% aqueous sulfuric acid, 20% phosphate aqueous solution, 20% aqueous acetic acid, 10% alcohol benzoate solution, 2% aqueous citric acid solution, acetic acid-sodium-acetate buffer, citric acid-sodium citrate buffer.
Described polyaluminocarbosilane is prepared by the following method: polydimethylsiloxane is put into reaction vessel, and under protection of inert gas, 300 ~ 500 ℃ of cracking, the liquid obtaining through prolong is poly-silicon-carbon silane; To gather silicon-carbon silane and mix with aluminium acetylacetonate, under protection of inert gas, be warming up to 400 ~ 550 ℃, be incubated 3 ~ 8 hours; after finishing, reaction is cooled to room temperature; with Virahol dissolving, to filter, filtrate obtains weak yellow liquid through 83 ~ 95 ℃ of distillation processing and is polyaluminocarbosilane.Described rare gas element is nitrogen, argon gas one wherein; Described aluminium acetylacetonate and poly-silicon-carbon silane quality proportioning are 2 ~ 20:100.
The preparation method of described non-viscous paint is following steps: in modified silicasol, add Nano filling, pigment, disperse to add again water after 5 ~ 9 hours, stir after 5 ~ 30 minutes, add again silane, polyaluminocarbosilane and pH adjusting agent, stir 3 ~ 9 hours, filter and obtain the non-viscous paint of modified silicasol.
In non-viscous paint of the present invention, can also contain other auxiliary agents such as flow agent, defoamer and dispersion agent.Described flow agent is selected from organic modified polyorganosiloxane class flow agent, as EFKA-3772, BYK-345, consumption be each component weight and 0.1 ~ 2.0%; ; Described defoamer is selected from silicone based defoamer, as SILCO AF-115, TEGO-3062, consumption be each component weight and 0.5 ~ 1.5%; ; Described dispersion agent is selected from polyacrylate(s) dispersion agent, as AFCONA ?4560, BEVALOID DP 270, consumption be each component weight and 0.2 ~ 1.8%.
The present invention is containing in the non-viscous paint of modified silicasol, and silica particle surface has been adhered to fluoro silane and contained titanium, has improved on the one hand the surface energy of silicon dioxide granule, has improved on the other hand the hardness of silicon dioxide granule.Adding of polyaluminocarbosilane, makes polyaluminocarbosilane and silane concerted reaction form fine and close Al-O-Si-C and Si-Al-Si-O reticulated structure in film coated surface, thereby has improved heat resistance, snappiness and the hardness of film.
Compared with prior art, the invention has the beneficial effects as follows:
(1) silicon sol after modification can reduce the surface energy of silicon sol effectively.
(2) non-viscous paint of described modified silicasol configuration has lower surface energy, good wear resistance, the feature that hardness is high.
Embodiment
Below specific embodiments of the invention, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is made following examples, all still belong within the scope of technical solution of the present invention.
In following examples, each component percentage composition, except special instruction, all refers to weight percent, and each component is all commercially available, and wherein in embodiment, in silicon sol, application examples, polyaluminocarbosilane also can be made by oneself.
Testing method described in test case is:
1* resistance toheat: test piece is toasted after 2 h in 180 ℃, put into the Ovenized electric furnace that potentiometer is checked, by 5 ℃/min rising temperature, start timing with furnace temperature to requirement of experiment temperature, sample, after continuous high temperature, takes out, be chilled to room temperature (25 ℃), observe coatingsurface situation with magnifying glass, as without be full of cracks, obscission, illustrate that coating heat resistance can be good.
Not viscosity test of 2*: will spray cated cooker, and be heated to 90 ℃, and directly place a raw egg of peeling off on its surface; Keep heating always, until the complete fry cooked of egg, promote gently egg with wooden scoop, as egg peels off naturally, being stained with property is not excellent; Slightly adhere to (adhered area is less than 30%), being stained with property is not for general; Adhere to serious (adhered area is greater than 60%), even can not peel off, being stained with property is not for poor.
3* water boiling resistance performance: after 180 ℃ of baking 2 h, cool to room temperature, is then positioned over test piece in the distilled water of 100 ℃ by test piece, is heated to paint film and destroys, occurs as bubbles, loss of gloss, variable color, the phenomenons such as be full of cracks.
4* acid resistance test: test piece is put into 5% hydrochloric acid and soak 24h, observe the variation that test piece rises.
5* alkali resistance test: test piece is put into 5%Na
2cO
3soak 24h, observe the variation that test piece rises.
Synthesis example 1: the preparation of silicon sol
In 86.08% distilled water, add 12.92% silica flour, make it to activate 10min, then continue to add 1.0% water glass, violent stirring 8h at 90 ℃ is then cooled to below 50 ℃ under the condition stirring, and carries out decompress filter after leaving standstill liquid, obtains SiO
2particle diameter is 10.5nm, SiO
2solid content is 24%.
Synthesis example 2: the preparation of polyaluminocarbosilane
500g polydimethylsiloxane is put into reaction vessel, and under nitrogen protection, 400 ℃ of cracking, the liquid obtaining through prolong is poly-silicon-carbon silane; 100g is gathered to silicon-carbon silane and mix with 5.5g aluminium acetylacetonate, be warming up to 500 ℃ under nitrogen protection, be incubated 5 hours, after reaction finishes, be cooled to room temperature, with Virahol dissolving, filter, filtrate obtains weak yellow liquid through 90 ℃ of distillation processing and is polyaluminocarbosilane.
Embodiment 1
Silicon sol (24% solid content prepared by synthesis example 1, particle diameter 10.5nm) 93.1%, ten difluoro heptyl propyl trimethoxy silicanes 0.09%, tetrabutyl titanate 0.8%, 10% acetum 2.3%, distilled water 3.71%, at 25 ℃, stirring reaction 24 hours, can obtain modified silicasol 1(10.5nm).
Embodiment 2
Silicon sol (24% solid content prepared by synthesis example 1, particle diameter 10.5nm) 93.1%, 13 fluoro octyl triethoxyl silanes 0.09%, tetrabutyl titanate 0.8%, 10% acetum 2.3%, distilled water 3.71%, at 25 ℃, stirring reaction 48 hours, can obtain modified silicasol 2(10.5nm).
Embodiment 3
Silicon sol (24% solid content prepared by synthesis example 1, particle diameter 10.5nm) 93.1%, 13 fluoro octyl triethoxyl silanes 0.09%, tetrabutyl titanate 1.6%, palmityl trimethyl ammonium chloride 0.22%, 10% acetum 2.3%, distilled water 3.49%, at 25 ℃, stirring reaction 48 hours, can obtain modified silicasol 3(10.5nm).
Embodiment 4
Silicon sol (24% solid content prepared by synthesis example 1, particle diameter 10.5nm) 93.1%, fluoro octyl triethoxyl silane 0.09%, tetrabutyl titanate 0.8%, polysorbate 0.3%, 10% acetum 2.3%, distilled water 3.41%, at 25 ℃, stirring reaction 48 hours, can obtain modified silicasol 4(10.5nm).
Embodiment 5
Silicon sol (24% solid content prepared by synthesis example 1, particle diameter 10.5nm) 93.1%, triethoxy-1H, 1H, 2H, 2H-13 fluoro n-octyl silane 0.09%, tetrabutyl titanate 0.8%, cocamidopropyl betaine 0.12%, 10% acetum 2.3%, distilled water 3.59%, at 25 ℃, stirring reaction 48 hours, can obtain modified silicasol 5(10.5nm).
Embodiment 6
Silicon sol (24% solid content prepared by synthesis example 1, particle diameter 10.5nm) 93.1%, trimethylammonium pentafluorophenyl group silane 0.09%, tetrabutyl titanate 0.8%, Sodium dodecylbenzene sulfonate 0.12%, 10% acetum 2.3%, distilled water 3.59%, at 25 ℃, stirring reaction 48 hours, can obtain modified silicasol 6(10.5nm).
Application examples 1
Modified silicasol 1:17.8%; Silane: methyltrimethoxy silane 16.9%; Nano filling: nano barium titanate aluminium 11.3%, titanium nitride 4%; Pigment: carbon black 11.3%; Water: 38.15%; PH adjusting agent: 10% aqueous hydrochloric acid 0.1%, 5% aqueous nitric acid 0.05%, polyaluminocarbosilane 0.4%.
In modified silicasol 1, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of methyltrimethoxy silane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 1.
Test case 1
Non-viscous paint 1 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 1:
Table 1
Application examples 2
Modified silicasol 2:29.3%; Silane: γ-aminopropyl triethoxysilane 16.8%; Nano filling: nano aluminium oxide 3.6%, nano zirconium dioxide 3.7%, titanium nitride 0.9%; Pigment: carbon black 9%; Deionized water: 34%; PH adjusting agent: 20% aqueous acetic acid 1.2%, polyaluminocarbosilane 1.5%.
In modified silicasol 2, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of γ-aminopropyl triethoxysilane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 2.
Test case 2
Non-viscous paint 2 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 2:
Table 2
Application examples 3
Modified silicasol 4:21.4%; Silane: phenyltrimethoxysila,e 16.5%, propyl trimethoxy silicane 11.1%; Nano filling: nanometer potasium titanate 5.1%, silicon whisker 3.1%, nano barium titanate aluminium 1.2%, nano-nickel oxide 3.2%, nano silicon oxide 3.1%, nano zine oxide 2.4%, titanium nitride 1.2%; Pigment: graphite 6%, carbon black 2.6%; Pure water: 19.7%; PH adjusting agent: 20% phosphate aqueous solution 0.7%, 2% aqueous citric acid solution 0.4%, polyaluminocarbosilane 2.3%.
In modified silicasol 4, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of phenyltrimethoxysila,e, propyl trimethoxy silicane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 4.
Test case 3
Non-viscous paint 4 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 3:
Table 3
Application examples 4
Modified silicasol 3:25%; Silane: ethyl triethoxysilane 12%, tri isopropyl silane 7%; Nano filling: nano silicon 5%, silicon whisker 3.7%, nano-cellulose 8%, titanium nitride 1.3%; Pigment: high titanium ash 3%, titanium nickel yellow 1%, titanium dioxide 0.5%; Water: 27.8%; PH adjusting agent: acetic acid-sodium-acetate buffer 1.7%, polyaluminocarbosilane 4%.
In modified silicasol 3, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of ethyl triethoxysilane, tri isopropyl silane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 4.
Test case 4
Non-viscous paint 4 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 4:
Table 4
Application examples 5
Modified silicasol 5:21.2%; Silane: methyltrimethoxy silane 12%, phenyltrimethoxysila,e 9.5%, tri isopropyl silane 0.7%; Nano filling: potassium titanate 3%, silicon whisker 3%, Mierocrystalline cellulose 3.5%, titanium nitride 1.3%; Pigment: cobalt titanate green 15.2%; Water: 25.5%; PH adjusting agent: 15% aqueous sulfuric acid 1.8%, polyaluminocarbosilane 3.3%.
In modified silicasol 5, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of methyltrimethoxy silane, phenyltrimethoxysila,e, tri isopropyl silane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 5.
Test case 5
Non-viscous paint 5 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 5:
Table 5
Application examples 6
Modified silicasol 6:23%; Silane: propyl trimethoxy silicane 11.5%, γ-aminopropyl triethoxysilane 6%; Nano filling: nano aluminium oxide 10%, silicon whisker 5%, titanium nitride 2.1%; Pigment: ferrimanganic is black 3.3%, carbon black 4%, titanium dioxide 0.7%, Pigment Yellow 73 183 1%; Pure water: 26.3%; PH adjusting agent: 5% oxalic acid aqueous solution 0.2%, the 5.5% sodium pyrosulfate aqueous solution 0.5%, 15% aqueous sulfuric acid 0.1%, 20% phosphate aqueous solution 0.3%, polyaluminocarbosilane 6%.
In modified silicasol 6, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of propyl trimethoxy silicane, γ-aminopropyl triethoxysilane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 6.
Test case 6
Non-viscous paint 6 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 6:
Table 6
Application examples 7
Modified silicasol 5:21%; Silane: methyltrimethoxy silane 15%, propyl trimethoxy silicane 4%, γ-aminopropyltrimethoxysilane 2%; Nano filling: nano aluminium oxide 9.9%, titanium nitride 0.9%; Pigment: titanium dioxide 2.5%, cobalt blue 2.5%; Water: 35%; PH adjusting agent: citric acid-sodium citrate buffer 2.1%, polyaluminocarbosilane 5.1%.
In modified silicasol 5, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of methyltrimethoxy silane, propyl trimethoxy silicane, γ-aminopropyltrimethoxysilane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 7.
Test case 7
Non-viscous paint 7 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 7:
Table 7
Application examples 8
Modified silicasol 1:18.2%; Silane: γ-aminopropyl triethoxysilane 13%, tri isopropyl silane 10%; Nano filling: nano-cellulose 3%, nanometer Calucium Silicate powder 12%, titanium nitride 2%; Pigment: cobalt blue 10%, molybdate yellow 2%; Water: 28%; PH adjusting agent: 20% phosphate aqueous solution 0.4%, 20% aqueous acetic acid 0.2%, polyaluminocarbosilane 1.2%.
In modified silicasol 1, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of γ-aminopropyl triethoxysilane, tri isopropyl silane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 8.
Test case 8
Non-viscous paint 8 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 8:
Table 8
Application examples 9
Modified silicasol 6:21.1%; Silane: ethyl trimethoxy silane 11%, ethyl triethoxysilane 4%, γ-aminopropyl triethoxysilane 3%, tri isopropyl silane 2%, gamma-mercaptopropyltriethoxysilane 1.5%; Nano filling: silicon whisker 2%, titanium nitride 1.5%; Pigment: titanium dioxide 11.0%, copper-chrome black 1.5%, carbon black 3.1%, Red copper oxide 0.5%; Water: 31.5%; PH adjusting agent: 10% alcohol benzoate solution 1.1%; Polyaluminocarbosilane 2.2%, flow agent: EFKA-3772 1.1%; Defoamer: SILCO AF-115 0.9%; Dispersion agent: AFCONA ?4,560 1.0%.
In modified silicasol, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of ethyl trimethoxy silane, ethyl triethoxysilane, γ-aminopropyl triethoxysilane, tri isopropyl silane, gamma-mercaptopropyltriethoxysilane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 9.
Test case 9
Non-viscous paint 9 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 9:
Table 9
Application examples 10
Modified silicasol 6:23%; Silane: methyltrimethoxy silane 20.6%; Nano filling: nano aluminium oxide 14.0%, silicon-dioxide 3.7%, silicon whisker 1%, titanium nitride 2.3%; Pigment: carbon black 4.2%, phosphoric acid cobalt violet 0.9%; Water: 24.7%; PH adjusting agent: acetic acid-sodium-acetate buffer 1.5%; Polyaluminocarbosilane 0.9%, flow agent: BYK-345 1.0%; Defoamer: TEGO-3062 0.8%; Dispersion agent: BEVALOID DP 270 1.4%.
In modified silicasol, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of methyltrimethoxy silane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 10.
Test case 10
Non-viscous paint 10 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 10:
Table 10
Application examples 11
Modified silicasol 6:26.8%; Silane: gamma-mercaptopropyltriethoxysilane 18.5%; Nano filling: nano aluminium oxide 6.1%, silicon-dioxide 8.7%, silicon whisker 2%, titanium nitride 4%; Pigment: carbon black 4.1%, phosphoric acid cobalt violet 0.9%; Water: 23.5%; PH adjusting agent: acetic acid-sodium-acetate buffer 0.5%; Polyaluminocarbosilane 1.2%, flow agent: BYK-345 1.5%; Defoamer: TEGO-3062 0.9%; Dispersion agent: BEVALOID DP 270 1.3%.
In modified silicasol 6, add Nano filling, pigment and titanium nitride to disperse 6 hours in dispersion machine high speed, add again distilled water, high-speed stirring 10 minutes, add the mixture of gamma-mercaptopropyltriethoxysilane and polyaluminocarbosilane, add again pH adjusting agent, high-speed stirring 4 hours, 400 orders filter, and obtain non-viscous paint 11.
Test case 11
Non-viscous paint 11 is sprayed on the aluminium sheet of sandblast, in 180 ℃ of baking ovens, dry 10 minutes, obtain the film that thickness is 35 μ m.Detect to such an extent that the performance of film is as shown in table 11:
Table 11
Claims (9)
1. a preparation method for modified silicasol, is characterized in that, described preparation method is following steps: in silicon sol, add fluoro silane and tetrabutyl titanate, then regulate pH to 4～5,20～60 ℃ of stirrings, keep obtaining modified silicasol after 1～8h.
2. the preparation method of a kind of modified silicasol according to claim 1, it is characterized in that, fluoro silane is selected from ten difluoro heptyl propyl trimethoxy silicanes, fluoro octyl triethoxyl silane, triethoxy-1H, 1H, 2H, a kind of in 2H-13 fluoro n-octyl silane, trimethylammonium pentafluorophenyl group silane, 13 fluoro octyl triethoxyl silanes or two kinds, consumption is 0.005～0.1% of reactant gross weight, described tetrabutyl titanate consumption be reactant gross weight be 0.1～2%.
3. the preparation method of a kind of modified silicasol according to claim 2, is characterized in that, reactant gross weight be fluoro silane, tetrabutyl titanate, silicon sol weight and.
4. the application of the prepared modified silicasol of the preparation method of a modified silicasol as claimed in claim 1 on non-viscous paint.
5. the application of a kind of modified silicasol according to claim 4, is characterized in that, described non-viscous paint is made up of following component, and the weight percent of each component is:
Modified silicasol 8 ~ 60%,
Silane 10 ~ 46%,
Nano filling 2 ~ 38%,
Pigment 2 ~ 31%,
Water 18 ~ 41%,
PH adjusting agent 0.1 ~ 8%,
Polyaluminocarbosilane 0.2 ~ 6%,
Each component sum is 100%.
6. according to the application of a kind of modified silicasol described in claim 4 or 5, it is characterized in that,
Described silane is selected from one or more in γ-aminopropyltrimethoxysilane, methyltrimethoxy silane, gamma-mercaptopropyltriethoxysilane, ethyl triethoxysilane, γ-aminopropyl triethoxysilane, tri isopropyl silane, phenyltrimethoxysila,e, ethyl trimethoxy silane and propyl trimethoxy silicane, and weight percent is 18 ~ 30%;
Described Nano filling is selected from one or more in nanometer potasium titanate, nano barium titanate aluminium, nanometer Calucium Silicate powder, silicon whisker, nano-cellulose, nano aluminium oxide, nano zirconium dioxide, nano-nickel oxide, nano silicon oxide, nano zine oxide, titanium nitride;
Described pigment is selected from that phosphoric acid cobalt violet, titanium dioxide, Pigment Yellow 73 183, carbon black, molybdate yellow, Red copper oxide, graphite, high titanium ash, titanium nickel yellow, cobalt titanate green, ferrimanganic are black, one or more in cobalt blue, copper-chrome black;
Described wet concentration is from pure water or deionized water;
Described pH adjusting agent is selected from one or more in the 5.5% sodium pyrosulfate aqueous solution, 2% oxalic acid aqueous solution, 10% aqueous hydrochloric acid, 5% aqueous nitric acid, 15% aqueous sulfuric acid, 20% phosphate aqueous solution, 20% aqueous acetic acid, 10% alcohol benzoate solution, 2% aqueous citric acid solution, acetic acid-sodium-acetate buffer, citric acid-sodium citrate buffer.
7. according to the application of a kind of modified silicasol described in claim 4 or 5, it is characterized in that, described polyaluminocarbosilane is prepared by the following method: polydimethylsiloxane is put into reaction vessel, under protection of inert gas, 300 ~ 500 ℃ of cracking, the liquid obtaining through prolong is poly-silicon-carbon silane; To gather silicon-carbon silane and mix with aluminium acetylacetonate, and be warming up to 400 ~ 550 ℃ under protection of inert gas, and be incubated 3 ~ 8 hours, and after reaction finishes, be cooled to room temperature, and with Virahol dissolving, filter, filtrate obtains polyaluminocarbosilane through 83 ~ 95 ℃ of distillations.
8. the application of a kind of modified silicasol according to claim 7, is characterized in that, described rare gas element is nitrogen, argon gas one wherein, and described aluminium acetylacetonate and poly-silicon-carbon silane quality proportioning are 2 ~ 20:100.
9. according to the application of a kind of modified silicasol described in claim 4 or 5, it is characterized in that, the preparation method of described non-viscous paint is following steps: in modified silicasol, add Nano filling, pigment, disperse to add again water after 5 ~ 9 hours, stir after 5 ~ 30 minutes, add again silane, polyaluminocarbosilane and pH adjusting agent, stir 3 ~ 9 hours, filter and obtain the non-viscous paint of modified silicasol.
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| CN111148345B (en) * | 2019-12-30 | 2022-10-11 | 中国科学院宁波材料技术与工程研究所 | Blue dielectric paste for thick film circuit, preparation method and application |
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| CN115260799B (en) * | 2022-07-25 | 2023-08-11 | 万华化学集团股份有限公司 | Anti-sticking coating material, coating method and application thereof |
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