CN102134447B - Methyl-terminated acryloyloxy silsesquioxane/titanium dioxide nano anticorrosion protective film - Google Patents
Methyl-terminated acryloyloxy silsesquioxane/titanium dioxide nano anticorrosion protective film Download PDFInfo
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- CN102134447B CN102134447B CN 201010100510 CN201010100510A CN102134447B CN 102134447 B CN102134447 B CN 102134447B CN 201010100510 CN201010100510 CN 201010100510 CN 201010100510 A CN201010100510 A CN 201010100510A CN 102134447 B CN102134447 B CN 102134447B
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Abstract
The invention relates to an organic-inorganic hybrid nano anticorrosion protective film which is prepared by the following steps: 1. carrying out hydrolytic condensation on 3-(methylacryloyloxy)propyl-trimethoxysilane and a mixture of tetrabutyl titanate and tetraethyl orthosilicate by a sol-gel method to obtain silsesquioxane (SSO) containing titanium dioxide and silicon dioxide TiO2-SiO2-SSO, wherein ethanol is used as a diluter, the ratio of ethanol to mixture is (1.6-3):1, HCOOH and H2O are used as catalysts, the ratio of HCOOH to Si is (0.001-0.01):1, the ratio of H2O to Si is (1-3):1, and the synthesis temperature is 25-70 DEG C; and 2. adding the diluter ethanol into the product TiO2-SiO2-SSO solution (the ratio of ethanol to TiO2-SiO2-SSO is (3-6):1), adding benzoyl peroxide (BPO) (the mol ratio of TiO2-SiO2-SSO to BPO is 2:1), carrying out dip coating, spray coating or brushing coating according to the size of the film-applied object, and curing to form a reticular protective film. The organic-inorganic hybrid nano anticorrosion protective film has the function of resisting acid, alkali, salt, water, smoke, electro-chemical corrosion and the like, and performs the actions of corrosion prevention, protection and decoration on surfaces of metal, art ware, high-grade furniture and the like.
Description
Technical field: the present invention relates to a kind of inorganic-organic hybridization nano preservative protective film that is mainly used in metallic surface, artwork and top-grade furniture surface, belonging to fourth field.
Background technology: in recent years, organic-inorganic hybrid nanomaterials has begun to become focus and the advanced subject of domestic and international matrix material research field.This material is called the leading material of a new generation abroad.The process of tradition preparation nano composite material is as follows: at first utilize sol-gel method to prepare the nanogel particle, then with gel drying, sintering, pulverize, use at last the method for machinery or physics that nano particle (powder) is blended in the body, form composite nano materials.This synthesis technique not only process is complicated, and nano particle has agglomeration in system, and dispersity is relatively poor to be waited not enoughly, causes the protective membrane antiseptic property of being made by this material relatively poor.
Summary of the invention: the objective of the invention is to prevent that for existing protective membrane all kinds of corrosive natures are relatively poor and not enough, provide the protective membrane that a kind of performance is good, manufacture craft simple, have the functions such as super acid-proof, alkali, salt, water, smog, galvanic corrosion to people.Can be applicable to military-civil space flight navigation precision equipment, instrument, instrument, automobile case, historical relic, senior artwork, top-grade furniture etc.
The inorganic-organic hybridization nano preservative protective film mainly is to make according to following proportioning raw materials and method: the first step; utilize the mixture of sol-gel method hydrolytic condensation 3-(methacryloxypropyl) propyl trimethoxy silicane and tetrabutyl titanate/tetraethyl orthosilicate (wherein; tetrabutyl titanate accounts for 5～30% mixture weight per-cent; tetraethyl orthosilicate accounts for 15% mixture weight per-cent), the silsesquioxane TiO that contains titania/silica of synthesizing stable
2-SiO
2-SSO.This goes on foot synthesis condition: diluting solvent is ethanol, and Dilution ratio is ethanol: mixture=1.6～3: 1; Catalyzer formic acid HCOOH and water H
2O, HCOOH: Si=0.001～0.01: 1, H
2O: Si=1～3: 1; Synthesis temperature is 25～70 ℃; In the reaction time-continuing process, survey its molecular-weight average with gel chromatography, to determine to have generated TiO
2-SiO
2-SSO.Second step is to TiO
2-SiO
2Add diluting solvent ethanol in the-SSO solution system, Dilution ratio is ethanol: TiO
2-SiO
2-SSO=3～6: 1 adds initiator benzoyl peroxide BPO again, and mol ratio is TiO
2-SiO
2-SSO: BPO=2: 1; Adopt the coating method of dip-coating, spraying or brushing according to the size shape of membrane attached matter.Behind the film under 80～150 ℃ of temperature condition, solidified 1～24 hour, can the webbed inorganic-organic hybridization nano preservative protective film of shape.
Characteristics of the present invention are the scientific formulation of this protective membrane, and synthetic method is simple, have good anticorrosion, protection and decoration function, applicable to multinomial fields such as the army and the people, high-tech, utilize the existing construction equipment of oversimplifying to go into operation, and cost is low, is easy to promote.
Embodiment:
Embodiment 1: be applicable to small-sized object, adopt dip coating.
The first step, the mixture of 3-(methacryloxypropyl) propyl trimethoxy silicane and tetrabutyl titanate/tetraethyl orthosilicate, the weight percent of tetrabutyl titanate is 5～30% in the described mixture, the weight percent of tetraethyl orthosilicate is 15%, use alcohol dilution, Dilution ratio is ethanol: mixture=3: 1; Add catalyzer HCOOH and H
2O, HCOOH: Si=0.01: 1, H
2O: Si=3: 1; Synthesis temperature is at 30 ℃; In the reaction time-continuing process, survey its molecular-weight average with gel chromatography, reach at 1338 o'clock, stopped reaction.Synthesized 3-(methacryloxypropyl) the propyl trimethoxy silsesquioxane TiO that contains titania/silica this moment
2-SiO
2-SSO viscous fluid, above process are sol-gel hydrolytic condensation method;
Second step is when filming, to TiO
2-SiO
2Add the alcohol dilution solvent in the-SSO solution system, Dilution ratio is ethanol: TiO
2-SiO
2-SSO=3: 1, add again initiator B PO, mol ratio is TiO
2-SiO
2-SSO: BPO=2: 1; Small-sized object is immersed TiO
2-SiO
2-SSO/BPO solution system carries out film forming, and immersion/leaching velocity is 27cm/min; Heating cure, solidification value and time: at first 80 ℃ solidified 4 hours, and then 120 ℃ solidified 2 hours, and last 150 ℃ solidified 1 hour, can the webbed inorganic-organic hybridization nano preservative protective film of shape after the curing.
Embodiment 2: be applicable to medium-sized object, adopt spread coating.
The first step is with embodiment 1;
Second step is during brushing, to TiO
2-SiO
2Add diluent ethanol in the-SSO solution system, Dilution ratio is ethanol: TiO
2-SiO
2-SSO=4: 1, add again BPO, mol ratio is TiO
2-SiO
2-SSO: BPO=2: 1; Heating cure after brushing, solidification value and time: at first 80 ℃ solidified 12 hours, and then 120 ℃ solidified 1 hour, can the webbed inorganic-organic hybridization nano preservative protective film of shape after the curing.
Embodiment 3: be applicable to large-sized object, adopt spraying method.
The first step is with embodiment 1;
Second step is during the spray film, to TiO
2-SiO
2Add diluent ethanol in the-SSO solution system, Dilution ratio is ethanol: TiO
2-SiO
2-SSO=6: 1, add again BPO, mol ratio is TiO
2-SiO
2-SSO: BPO=2: 1; After spraying for the first time, self-vulcanizing 4 hours; For the second time heating cure after the spraying, solidification value and time: at first 80 ℃ solidified 12 hours, and then 120 ℃ solidified 1 hour, can the webbed inorganic-organic hybridization nano preservative protective film of shape after the curing.
Claims (2)
1. inorganic-organic hybridization nano preservative protective film; it is characterized in that: this protective membrane is to make according to following proportioning raw materials and method: the first step; utilize the mixture of sol-gel method hydrolytic condensation 3-(methacryloxypropyl) propyl trimethoxy silicane and tetrabutyl titanate, tetraethyl orthosilicate; the weight percent of tetrabutyl titanate is 5～30% in the described mixture; the weight percent of tetraethyl orthosilicate is 15%, the silsesquioxane TiO that contains titania/silica of synthesizing stable
2-SiO
2-SSO; This goes on foot synthesis condition: diluting solvent is ethanol, and Dilution ratio is ethanol: mixture=1.6～6: 1, and catalyzer formic acid HCOOH and water H
2O, HCOOH: Si=0.001～0.01: 1, H
2O: Si=1～3: 1; Synthesis temperature is 25～70 ℃, in the reaction time-continuing process, surveys its molecular-weight average with gel chromatography, to determine to have generated TiO
2-SiO
2-SSO; Second step is to TiO
2-SiO
2Add diluting solvent ethanol in the-SSO system, Dilution ratio is ethanol: TiO
2-SiO
2-SSO=3～6: 1 adds initiator benzoyl peroxide BPO again, and mol ratio is TiO
2-SiO
2-SSO: BPO=2: 1; Adopt the coating method of dip-coating, spraying or brushing according to the size shape of membrane attached matter; Behind the film under 80～150 ℃ of temperature condition, solidified 1～24 hour, can the webbed inorganic-organic hybridization nano preservative protective film of shape.
2. inorganic-organic hybridization nano preservative protective film according to claim 1, this protective membrane is respectively applied to the dip-coating to small-sized object, the brushing of medium-sized object, and the spraying of large-sized object.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010100510 CN102134447B (en) | 2010-01-25 | 2010-01-25 | Methyl-terminated acryloyloxy silsesquioxane/titanium dioxide nano anticorrosion protective film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010100510 CN102134447B (en) | 2010-01-25 | 2010-01-25 | Methyl-terminated acryloyloxy silsesquioxane/titanium dioxide nano anticorrosion protective film |
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|---|---|
| CN102134447A CN102134447A (en) | 2011-07-27 |
| CN102134447B true CN102134447B (en) | 2013-01-30 |
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|---|---|---|---|---|
| WO2013017132A1 (en) * | 2011-07-29 | 2013-02-07 | Inmold Biosystems A/S | Reactive silicon oxide precursor facilitated anti-corrosion treatment |
| CN113445303A (en) * | 2021-07-09 | 2021-09-28 | 广西五行材料科技有限公司 | Nano material for removing formaldehyde and sterilizing for leather and textiles and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265029B1 (en) * | 1995-05-04 | 2001-07-24 | William Lewis | Low-cost, user-friendly hardcoating solution, process and coating |
| CN1539888A (en) * | 2003-08-25 | 2004-10-27 | 胡立江 | Organic and non-organic hybrid, preservative, protective film |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6265029B1 (en) * | 1995-05-04 | 2001-07-24 | William Lewis | Low-cost, user-friendly hardcoating solution, process and coating |
| CN1539888A (en) * | 2003-08-25 | 2004-10-27 | 胡立江 | Organic and non-organic hybrid, preservative, protective film |
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| CN102134447A (en) | 2011-07-27 |
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