CN102134409A - Anti-corrosion protective nano-film containing epoxy-terminated silsesquioxane/titanium dioxide - Google Patents

Abstract

An organic-inorganic hybrid nano-anticorrosion protective film is prepared according to the following raw material ratio and method: 1. Utilize the sol-gel method to hydrolyze and condense 3-(2,3-epoxypropoxy)propyltrimethoxy A mixture of silane, tetrabutyl titanate and tetraethyl orthosilicate to synthesize a stable silsesquioxane TiO ₂ -SiO ₂ -SSO containing titanium dioxide and silicon dioxide. Synthesis conditions: the diluent is ethanol, the dilution ratio is ethanol: mixture = 1.6 ~ 3: 1, the catalyst uses HCOOH and H ₂ O, HCOOH: Si = 0.001 ~ 0.01: 1, H ₂ O: Si = 1 ~ 3 : 1, the synthesis temperature is 25～70°C; 2. Add diluent ethanol to the product TiO ₂ -SiO ₂ -SSO solution, the dilution ratio is ethanol:TiO ₂ -SiO ₂ -SSO=3～6:1, then add EDA, the molar ratio is TiO ₂ -SiO ₂ -SSO:EDA=2:1, according to the size of the film, it can be dipped, sprayed, brushed, and can form a network protective film after curing. It has super anti-acid, alkali, salt, water, smog, electrochemical corrosion and other functions. It is used on the surface of metals, handicrafts and high-end furniture to play anti-corrosion, protection and decoration functions.

Description

A kind of epoxy-terminated silsesquioxane/titanium dioxide nano-anticorrosion protective film

Technical field: The present invention relates to an organic-inorganic hybrid nano-anti-corrosion protective film mainly used on metal surfaces, handicrafts and high-grade furniture surfaces, belonging to the field of chemical industry.

Background technology: In recent years, organic-inorganic hybrid nanomaterials have become a hot and frontier topic in the field of composite material research at home and abroad. The material is known as a new generation of leading materials abroad. The traditional process of preparing nanocomposites is as follows: firstly, the sol-gel method is used to prepare nanogel particles, then the gel is dried, sintered, and ground into powder, and finally the nanoparticles (powder) are blended into the powder by mechanical or physical methods. In the bulk, a composite nanomaterial is formed. This synthesis process is not only complicated, but also has problems such as agglomeration and poor dispersion of nanoparticles in the system, resulting in poor anticorrosion performance of the protective film made of this material.

Summary of the invention: The purpose of the present invention is to provide people with a protective film with good performance, simple manufacturing process, super anti-acid, alkali, salt, water, smog, electrochemical Protective film for corrosion and other functions. It can be applied to military and civilian aerospace and navigation precision equipment, instruments, meters, automobile casings, cultural relics, high-end artworks, high-end furniture, etc.

The organic-inorganic hybrid nano-anticorrosion protective film is mainly prepared according to the following raw material ratio and method: the first step is to use the sol-gel method to hydrolyze and condense 3-(2,3-epoxypropoxy)propyltrimethoxy A mixture of base silane and tetrabutyl titanate/tetraethyl orthosilicate (wherein, tetrabutyl titanate accounts for 5 to 30% by weight of the mixture, and tetraethyl orthosilicate accounts for 15% by weight of the mixture), Synthesis of stable titania/silica-containing silsesquioxane TiO ₂ -SiO ₂ -SSO. The synthesis conditions of this step: the dilution solvent is ethanol, the dilution ratio is ethanol: mixture = 1.6 ~ 3: 1; the catalyst uses formic acid HCOOH and water H ₂ O, HCOOH: Si = 0.001 ~ 0.01: 1, H ₂ O: Si = 1 ～3:1; the synthesis temperature is 25～70°C; during the continuation of the reaction, the average molecular weight is measured by gel chromatography to confirm the formation of TiO ₂ -SiO ₂ -SSO. In the second step, add the diluting solvent ethanol to the TiO ₂ -SiO ₂ -SSO solution system, the dilution ratio is ethanol:TiO ₂ -SiO ₂ -SSO=3~6:1, and then add the active crosslinking agent hexamethylenediamine EDA, The molar ratio is TiO ₂ -SiO ₂ -SSO:EDA=2:1; the coating method of dipping, spraying or brushing is adopted according to the size and shape of the coating. After the film is applied, it is cured for 1 to 24 hours at a temperature of 80-150°C to form a network-shaped organic-inorganic hybrid nano-anti-corrosion protective film.

The feature of the present invention is that the formula of the protective film is scientific, the synthesis method is simple, and it has good anti-corrosion, protection and decoration functions. It can be applied to many fields such as military and civilian, high-tech, etc. It can be put into production by using existing simple chemical equipment, and the cost is low. , easy to promote.

Detailed ways:

Embodiment 1: It is suitable for small objects and adopts the dip coating method.

The first step, the mixture of 3-(2,3-epoxypropoxy)propyltrimethoxysilane and tetrabutyl titanate/tetraethyl orthosilicate, the weight percent of tetrabutyl titanate in the mixture 5 to 30%, the weight percentage of tetraethyl orthosilicate is 15%, dilute with ethanol, the dilution ratio is ethanol: mixture = 3: 1; add catalyst HCOOH and H ₂ O, HCOOH: Si = 0.01: 1, H ₂ O:Si=3:1; the synthesis temperature was 30°C; during the continuous process of the reaction, the average molecular weight was measured by gel chromatography, and when it reached 1338, the reaction was stopped. At this time, 3-(2,3-epoxypropoxy)propylsilsesquioxane TiO ₂ -SiO ₂ -SSO viscous liquid containing titanium dioxide/silica was synthesized, and the above process was sol-gel hydrolysis and shrinkage legitimate;

In the second step, when coating the film, add ethanol dilution solvent to the TiO ₂ -SiO ₂ -SSO solution system, the dilution ratio is ethanol:TiO ₂ -SiO ₂ -SSO=3:1, and then add the curing agent EDA, the molar ratio is TiO ₂ -SiO ₂ -SSO:EDA=2:1; small objects are immersed in TiO ₂ -SiO ₂ -SSO/EDA solution system to form a film, the immersion/leaching speed is 27cm/min; heating and curing, curing temperature and time : First cured at 80°C for 4 hours, then cured at 120°C for 2 hours, and finally cured at 150°C for 1 hour. After curing, a network-shaped organic-inorganic hybrid nano-anti-corrosion protective film can be formed.

Embodiment 2: It is suitable for medium-sized objects and adopts the brushing method.

The first step is with embodiment 1;

The second step, when brushing, add diluent ethanol to the TiO ₂ -SiO ₂ -SSO solution system, the dilution ratio is ethanol:TiO ₂ -SiO ₂ -SSO=4:1, add EDA, the molar ratio is TiO ₂ -SiO ₂ -SSO:EDA=2:1; heat and cure after brushing, curing temperature and time: firstly cure at 80°C for 12 hours, then cure at 120°C for 1 hour, after curing, a network of organic-inorganic hybrids can be formed. Nano anti-corrosion protective film.

Embodiment 3: It is suitable for large objects and adopts spraying method.

The first step is with embodiment 1;

In the second step, when spraying the film, add diluent ethanol to the TiO ₂ -SiO ₂ -SSO solution system, the dilution ratio is ethanol:TiO ₂ -SiO ₂ -SSO=6:1, plus EDA, the molar ratio is TiO ₂ -SiO ₂ -SSO:EDA=2:1; after the first spraying, cure at room temperature for 4 hours; after the second spraying, heat curing, curing temperature and time: firstly cure at 80°C for 12 hours, then cure at 120°C for 1 hour , After curing, it can form a network-like organic-inorganic hybrid nano-anti-corrosion protective film.

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 sol-gel method hydrolytic condensation 3-(2; 3-epoxy third oxygen) mixture of propyl trimethoxy silicane and tetrabutyl titanate, positive tetraethyl orthosilicate; the weight percent of tetrabutyl titanate is 5～30% in the described mixture; the weight percent of positive 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 an ethanol, and Dilution ratio is an 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 are 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 system, Dilution ratio is ethanol: TiO ₂-SiO ₂-SSO=3～6: 1 adds active crosslinker hexanediamine EDA again, and mol ratio is TiO ₂-SiO ₂-SSO: EDA=2: 1; The coating method of film, spraying or brushing is soaked in size shape employing according to membrane attached matter; Behind the film under 80～150 ℃ of temperature condition, solidified 1～24 hour, can form netted inorganic-organic hybridization nano preservative protective film.

2. the novel method of preparation inorganic-organic hybridization nano preservative protective film according to claim 1, this protective membrane can be respectively applied for the dip-coating to small-sized object, the spread coating of medium-sized object, and the spraying of large-sized object.