CN104387889A - Preparation method of silicon-dioxide particle acrylonitrile silicone copolymerized resin coating - Google Patents
Preparation method of silicon-dioxide particle acrylonitrile silicone copolymerized resin coating Download PDFInfo
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- CN104387889A CN104387889A CN201410662403.2A CN201410662403A CN104387889A CN 104387889 A CN104387889 A CN 104387889A CN 201410662403 A CN201410662403 A CN 201410662403A CN 104387889 A CN104387889 A CN 104387889A
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- dioxide granule
- silica dioxide
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- vinyl cyanide
- copolymer resins
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Abstract
The invention discloses a preparation method of a silicon-dioxide particle acrylonitrile silicone copolymerized resin coating, and particularly relates to a method for preparing a waterproof coating capable of reducing the surface friction force by utilizing a polymer copolymerizing technology and a nano-particle composite technology. The preparation method comprises four steps: substrate treatment, modification of silicon-dioxide nano particles, preparation of silicon-dioxide particle acrylonitrile silicone copolymerized resin and preparation of the silicon-dioxide particle acrylonitrile silicone composite coating. By adoption of the coating prepared by the invention, the surface friction force and the surface adhesive force can be reduced. The coating has the advantages that the water-proof property and the anti-corrosive property are good, and the service life of the surface of the material under the extreme condition can be effectively prolonged.
Description
Technical field
The present invention relates to process for modifying surface, be specifically related to the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating.
Background technology
Vinyl cyanide is a kind of synthesis, hemicrystalline organic polymer resin monomer.It is a kind of multi-functional polymkeric substance, is used for producing various product, comprises the textiles of ultra-filtration membrane, tubular fibre reverse osmosis membrane and fiber.At present, vinyl cyanide is applied to the common articles for daily use such as fishing rod, tennis racket and yacht.By the toughness of acrylonitrile based resins film or coating can be improved with the copolymerization of the materials such as silicone, and the surface wettability of material itself can be improved.Nano-composite coating is a kind of novel organic polymer compound coating grown up nearly ten years, nano particle high molecular polymer compound coating as mechanics of surface material modified and extremely people pay close attention to.The resource reserve of China's silicon-dioxide mineral products is large, and Functionality, quality and appealing design, output and outlet occupy first place in the world.But the deep process technology level comparatively backwardness of relevant silicon-dioxide, therefore also have industrial application all to have great importance for silica modified and its applied research, especially the application of nano SiO 2 particle matrix material in the high-technology field such as Aeronautics and Astronautics, automobile has important scientific meaning and practical significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of the superior silica dioxide granule vinyl cyanide silicone copolymer resins coating of a kind of tribological property, this coating have super-hydrophobic, resistance to abrasion good, preparation low cost, the simple feature of technique.
Following technical scheme is adopted for solving the problems of the technologies described above the present invention:
The preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating, comprises the following steps:
<1> base treatment: clean and dry substrate surface, substrate is metallic substance or semiconductor material; When wherein substrate is metallic substance, then use normal hexane and pentamethylene cleaning substrate surface respectively, and high temperature drying; When wherein substrate is semiconductor material, then use acetone and ethanol purge substrate surface respectively, then nitrogen dries up; Again plasma oxygen process is carried out to substrate surface;
The modification of <2> nano SiO 2 particle: nano SiO 2 particle is scattered in ultrasonic cleaning in acetone, and then be placed in the ethanol ultrasonic cleaning that purity is 95%, after filtering also vacuum-drying, nano SiO 2 particle is placed in the environment that relative humidity is 90%-100%RH, temperature is 70-90 DEG C and keeps 1-3 hour, carry out hydroxylation process; To be cooled after room temperature, hydroxylation silica dioxide granule is placed in the acetone soln that volumetric molar concentration is the triethoxyl silane of 1-100mM, is mixed with the suspension that mass body volume concentrations is 0.001-1g/L, then magnetic agitation, modification is carried out to silica dioxide granule; Modified silica dioxide granule is filtered, uses deionized water and alcohol flushing respectively, vacuum-drying;
The preparation of <3> silica dioxide granule vinyl cyanide silicone copolymer resins: acrylate is dissolved in dimethyl formamide and forms acrylonitrile solution, mass concentration is 0.001-1g/L; Mixed with mass ratio 1 ︰ 1-100 with this acrylonitrile solution by 3-trichlorine oxygen silicon Succinic anhydried, the modified silica particles adding step <2> gained by massfraction 0.5-10%wt in mixing solutions is prepared into silicon-dioxide vinyl cyanide silicone copolymer resins solution;
Prepared by <4> silica dioxide granule vinyl cyanide silicone compound coating: substrate surface silicon-dioxide third rare nitrile silicone copolymer resins solution of step <3> gained being evenly coated to step <1> gained by the method for dip-coating, spin coating or spraying, forms silica dioxide granule vinyl cyanide silicone compound resin coating; Substrate is dried, naturally cooling.
In described step <1>, high temperature drying temperature controls at 120 degree.
Plasma oxygen processing power in described step <1> is 50W, and processing the time length when substrate is semiconductor material is 1 minute, and processing the time length when substrate is metallic substance is 10 minutes.
The particle size range of described nano SiO 2 particle is 5nm-5um.
In described step <2>, nano SiO 2 particle to be scattered in acetone ultrasonic cleaning 10 minutes, and ultrasonic cleaning 10 minutes in the ethanol of purity 95%, ultrasonic power is 200W.
Hydroxylation treatment process in described step <2> is: be evenly laid in by silica dioxide granule in glass surface ware, temperature and humidity control box watch-glass being placed in relative humidity 90%-100%RH keeps temperature to be 70-90 DEG C, continue 1-3 hour, carry out hydroxylation process.
In described step <2>, the described magnetic agitation time is 12-24 hour.
In described step <2>, repeatedly rinse three times with deionized water and ethanol respectively.
Substrate being dried in described step <4> is that temperature is 90-140 DEG C, and baking time is 1-6 hour by base coating horizontal positioned in an oven.
Compared with prior art, the invention has the advantages that:
1, can in complex construction large-area preparation on the surface;
2, technique is simple, and raw material is easy to get, with low cost; ;
3, the coating of preparation has good hydrophobic, antifog, snow defence absorption property and has excellent abrasive resistance.
Embodiment:
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1:
The preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating is used for semiconductor monocrystal silicon face, acetone and ethanol is used to carry out cleaning 10 minutes successively to silicon substrate surface, nitrogen dries up again, then plasma oxygen process is carried out to silicon substrate surface, discharge power is 50W, 1 minute time length.
Be that the nano SiO 2 particle of 5nm-50nm to be scattered in acetone ultrasonic cleaning after 10 minutes by particle diameter, then ultrasonic cleaning 10 minutes in the ethanol of purity 95%, ultrasonic power is 200W; After filtering also vacuum-drying, nano SiO 2 particle is evenly laid in glass surface ware, and temperature and humidity control box watch-glass being placed in relative humidity 90%RH keeps temperature to be 70 DEG C, continues 3 hours, carries out hydroxylation process.To be cooled after room temperature, hydroxylation silica dioxide granule is placed in the acetone soln that volumetric molar concentration is 1mM triethoxyl silane, is mixed with the suspension that mass body volume concentrations is 0.001g/L, and magnetic agitation 12 hours, modification is carried out to silica dioxide granule.Modified silica dioxide granule is filtered, and repeatedly rinses three times with deionized water and ethanol respectively; Stand-by after vacuum-drying.
Acrylate is dissolved in dimethyl formamide and forms acrylonitrile solution, mass concentration is 0.001g/L; Be that 1 ︰ 100 mix with aforesaid propylene nitrile solution with mass ratio by 3-trichlorine oxygen silicon Succinic anhydried, the silica dioxide granule adding above-mentioned modification by massfraction 0.5%wt in mixing solutions is prepared into silicon-dioxide third rare nitrile silicone copolymer resins solution.
By dip-coating, spin coating or spraying method silicon-dioxide vinyl cyanide silicone copolymer resins dissolution homogeneity is distributed on the substrate surface handled well, forms silica dioxide granule vinyl cyanide silicone copolymer resins coating.It is in 90 DEG C of baking ovens 6 hours that base coating after process lies in a horizontal plane in temperature, naturally cooling in moisture eliminator.
Embodiment 2:
The preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating is used for Semiconductor GaAs surface, acetone and ethanol is used to carry out cleaning 10 minutes successively to GaAs based basal surface, nitrogen dries up again, then plasma oxygen process is carried out to GaAs based basal surface, discharge power is 50W, 1 minute time length.
Be that the nano SiO 2 particle of 50nm-100nm to be scattered in acetone ultrasonic cleaning after 10 minutes by particle diameter, then ultrasonic cleaning 10 minutes in the ethanol of purity 95%, ultrasonic power is 200W; After filtering also vacuum-drying, nano SiO 2 particle is evenly laid in glass surface ware, and temperature and humidity control box watch-glass being placed in relative humidity 100%RH keeps temperature to be 80 DEG C, continues 2 hours, carries out hydroxylation process.To be cooled after room temperature, hydroxylation silica dioxide granule is placed in the acetone soln that volumetric molar concentration is 10mM triethoxyl silane, is mixed with the suspension that mass body volume concentrations is 0.05g/L, and magnetic agitation 16 hours, modification is carried out to silica dioxide granule.Modified silica dioxide granule is filtered, and repeatedly rinses three times with deionized water and ethanol respectively; Stand-by after vacuum-drying.
Acrylate is dissolved in dimethyl formamide and forms acrylonitrile solution, mass concentration is 0.05g/L; Be that 1 ︰ 50 mix with aforesaid propylene nitrile solution with mass ratio by 3-trichlorine oxygen silicon Succinic anhydried, the silica dioxide granule adding above-mentioned modification by massfraction 1.0%wt in mixing solutions is prepared into silicon-dioxide third rare nitrile silicone copolymer resins solution.
By dip-coating, spin coating or spraying method silicon-dioxide vinyl cyanide silicone copolymer resins dissolution homogeneity is distributed on the GaAs based basal surface handled well, forms silica dioxide granule vinyl cyanide silicone copolymer resins coating.It is in 110 DEG C of baking ovens 4 hours that base coating after process lies in a horizontal plane in temperature, naturally cooling in moisture eliminator.
Embodiment 3:
The preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating is used for aluminum alloy surface, uses normal hexane and pentamethylene to clean 10 minutes to aluminum alloy surface successively, and in 120 DEG C high temperature drying; And to the process of aluminum alloy surface plasma oxygen, discharge parameter is power 50W, 10 minutes time length.
Be that the nano SiO 2 particle of 100nm-500nm to be scattered in acetone ultrasonic cleaning after 10 minutes by particle diameter, be ultrasonic cleaning 10 minutes in the ethanol of 95% again in purity, ultrasonic power is 200W, after filtering also vacuum-drying, nano SiO 2 particle is evenly laid in glass surface ware, temperature and humidity control box watch-glass being placed in relative humidity 100%RH keeps temperature to be 90 DEG C, continues 1 hour, carries out hydroxylation process.To be cooled after room temperature, hydroxylation silica dioxide granule is placed in the acetone soln that volumetric molar concentration is 50mM triethoxyl silane, is mixed with the suspension that mass body volume concentrations is 0.5g/L, and magnetic agitation 20 hours, modification is carried out to silica dioxide granule.Modified silica dioxide granule is filtered, and repeatedly rinses three times with deionized water and ethanol respectively; Stand-by after vacuum-drying.
Acrylate is dissolved in dimethyl formamide and forms acrylonitrile solution, mass concentration is 0.5g/L; Be that 1:10 mix with aforesaid propylene nitrile solution with mass ratio by 3-trichlorine oxygen silicon Succinic anhydried, the silica dioxide granule adding above-mentioned modification by massfraction 5.0%wt in mixing solutions is prepared into silicon-dioxide third rare nitrile silicone copolymer resins solution.
Silicon-dioxide vinyl cyanide silicone copolymer resins dissolution homogeneity is distributed to the aluminum alloy substrate handled well on the surface by dip-coating, spin coating or spraying method, forms silica dioxide granule vinyl cyanide silicone copolymer resins coating.It is in 130 DEG C of baking ovens 2 hours that base coating after process lies in a horizontal plane in temperature, naturally cooling in moisture eliminator.
Embodiment 4:
The preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating is used for stainless steel surface, uses normal hexane and pentamethylene to clean 10 minutes to stainless steel surface successively, and in 120 DEG C high temperature drying; And to the process of stainless steel surface plasma oxygen, discharge parameter is power 50W, 10 minutes time length.
Be that the nano SiO 2 particle of 500nm-5um to be scattered in acetone ultrasonic cleaning after 10 minutes by particle diameter, be ultrasonic cleaning 10 minutes in the ethanol of 95% again in purity, ultrasonic power is 200W, after filtering also vacuum-drying, silica dioxide granule is evenly laid in glass surface ware, temperature and humidity control box watch-glass being placed in relative humidity 100%RH keeps temperature to be 90 DEG C, continues 1 hour, carries out hydroxylation process.To be cooled after room temperature, hydroxylation silica dioxide granule is placed in the acetone soln that volumetric molar concentration is 100mM triethoxyl silane, is mixed with the suspension that mass body volume concentrations is 1g/L, and magnetic agitation 24 hours, modification is carried out to silica dioxide granule.Modified silica dioxide granule is filtered, and repeatedly rinses three times with deionized water and ethanol respectively; Stand-by after vacuum-drying.
Acrylate is dissolved in dimethyl formamide and forms acrylonitrile solution, mass concentration is 1g/L; Be that 1:1 mix with aforesaid propylene nitrile solution with mass ratio by 3-trichlorine oxygen silicon Succinic anhydried, the silica dioxide granule adding above-mentioned modification by massfraction 10%wt in mixing solutions is prepared into silicon-dioxide third rare nitrile silicone copolymer resins solution.
By dip-coating, spin coating or spraying method silicon-dioxide vinyl cyanide silicone copolymer resins dissolution homogeneity is distributed on the stainless steel-based basal surface handled well, forms silica dioxide granule vinyl cyanide silicone copolymer resins coating.It is in 140 DEG C of baking ovens 1 hour that base coating after process lies in a horizontal plane in temperature, naturally cooling in moisture eliminator.
Claims (9)
1. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating, is characterized in that, comprise the following steps:
<1> base treatment: clean and dry substrate surface, substrate is metallic substance or semiconductor material; When wherein substrate is metallic substance, then use normal hexane and pentamethylene cleaning substrate surface respectively, and high temperature drying; When wherein substrate is semiconductor material, then use acetone and ethanol purge substrate surface respectively, then nitrogen dries up; Again plasma oxygen process is carried out to substrate surface;
The modification of <2> nano SiO 2 particle: nano SiO 2 particle is scattered in ultrasonic cleaning in acetone, and then be placed in the ethanol ultrasonic cleaning that purity is 95%, after filtering also vacuum-drying, nano SiO 2 particle is placed in the environment that relative humidity is 90%-100%RH, temperature is 70-90 DEG C and keeps 1-3 hour, carry out hydroxylation process; To be cooled after room temperature, hydroxylation silica dioxide granule is placed in the acetone soln that volumetric molar concentration is the triethoxyl silane of 1-100mM, is mixed with the suspension that mass body volume concentrations is 0.001-1g/L, then magnetic agitation, modification is carried out to silica dioxide granule; Modified silica dioxide granule is filtered, uses deionized water and alcohol flushing respectively, vacuum-drying;
The preparation of <3> silica dioxide granule vinyl cyanide silicone copolymer resins: acrylate is dissolved in dimethyl formamide and forms acrylonitrile solution, mass concentration is 0.001-1g/L; Mixed with mass ratio 1 ︰ 1-100 with this acrylonitrile solution by 3-trichlorine oxygen silicon Succinic anhydried, the modified silica particles adding step <2> gained by massfraction 0.5-10%wt in mixing solutions is prepared into silicon-dioxide vinyl cyanide silicone copolymer resins solution;
Prepared by <4> silica dioxide granule vinyl cyanide silicone compound coating: substrate surface silicon-dioxide third rare nitrile silicone copolymer resins solution of step <3> gained being evenly coated to step <1> gained by the method for dip-coating, spin coating or spraying, forms silica dioxide granule vinyl cyanide silicone compound resin coating; Substrate is dried, naturally cooling.
2. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, it is characterized in that, in described step <1>, high temperature drying temperature controls at 120 degree.
3. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, it is characterized in that, plasma oxygen processing power in described step <1> is 50W, processing the time length when substrate is semiconductor material is 1 minute, and processing the time length when substrate is metallic substance is 10 minutes.
4. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, it is characterized in that, the particle size range of described nano SiO 2 particle is 5nm-5um.
5. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, it is characterized in that, in described step <2>, nano SiO 2 particle to be scattered in acetone ultrasonic cleaning 10 minutes, ultrasonic cleaning 10 minutes in the ethanol of purity 95%, ultrasonic power is 200W.
6. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, it is characterized in that, hydroxylation treatment process in described step <2> is: be evenly laid in by silica dioxide granule in glass surface ware, temperature and humidity control box watch-glass being placed in relative humidity 90%-100%RH keeps temperature to be 70-90 DEG C, continue 1-3 hour, carry out hydroxylation process.
7. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, it is characterized in that, in described step <2>, the described magnetic agitation time is 12-24 hour.
8. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, is characterized in that, in described step <2>, repeatedly rinses three times respectively with deionized water and ethanol.
9. the preparation method of silica dioxide granule vinyl cyanide silicone copolymer resins coating according to claim 1, it is characterized in that, substrate being dried in described step <4> is by base coating horizontal positioned in an oven, temperature is 90-140 DEG C, and baking time is 1-6 hour.
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Citations (4)
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| CN101544838A (en) * | 2009-05-07 | 2009-09-30 | 南京工业大学 | Ultra-hydrophobic nanometer SiO2/high polymer complex film and preparation method thereof |
| CN101838496A (en) * | 2010-04-09 | 2010-09-22 | 南京工业大学 | Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof |
| CN103224719A (en) * | 2013-02-04 | 2013-07-31 | 湖北大学 | Fluorosilicone material for super-hydrophobic coating and its preparation method and use method |
| CN103289031A (en) * | 2013-06-09 | 2013-09-11 | 河南大学 | High-transparency super-hydrophobicity coating material and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544838A (en) * | 2009-05-07 | 2009-09-30 | 南京工业大学 | Ultra-hydrophobic nanometer SiO2/high polymer complex film and preparation method thereof |
| CN101838496A (en) * | 2010-04-09 | 2010-09-22 | 南京工业大学 | Super-hydrophobic polyurethane/ oxide nano particle hybrid coating material and preparation method thereof |
| CN103224719A (en) * | 2013-02-04 | 2013-07-31 | 湖北大学 | Fluorosilicone material for super-hydrophobic coating and its preparation method and use method |
| CN103289031A (en) * | 2013-06-09 | 2013-09-11 | 河南大学 | High-transparency super-hydrophobicity coating material and application thereof |
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Inventor after: Lu Chaoxia Inventor after: Huang Xing Inventor before: Mo Yufei Inventor before: Lu Chaoxia |
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Application publication date: 20150304 |