CN1539888A - Organic and non-organic hybrid, preservative, protective film - Google Patents

Organic and non-organic hybrid, preservative, protective film Download PDF

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CN1539888A
CN1539888A CN 03134157 CN03134157A CN1539888A CN 1539888 A CN1539888 A CN 1539888A CN 03134157 CN03134157 CN 03134157 CN 03134157 A CN03134157 A CN 03134157A CN 1539888 A CN1539888 A CN 1539888A
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CN1249178C (en )
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胡立江
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胡立江
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Abstract

An anticorrosion nano-class protecting film for metal, artwork and high-grade furniture is prepared through synthesizing stable sesquisiloxane of SiO2 from the mixture of trimethoxy silane and tetraethyl silicate through hydrolysis and condensation by sol-gel method at 25-70 deg.C under existance of tetrahydrofuran or alcohol as diluent and catalyst (HCOOH and H2O), and adding active cross-linking agent ortrigger.

Description

一种有机—无机杂化纳米防腐保护膜 An organic - inorganic hybrid nano-film corrosion protection

技术领域 FIELD

:本发明涉及一种主要用于金属表面、工艺品及高档家具表面的有机—无机杂化纳米防腐保护膜,属于化工领域。 : The present invention relates to a major surface of a metal, organic products and high-end surface of the furniture - inorganic hybrid nano-film corrosion protection, chemical industry belongs.

背景技术 Background technique

:近年来,有机—无机杂化纳米材料已开始成为国内外复合材料研究领域的热点和前沿课题。 : In recent years, organic - inorganic hybrid nano-material and has started to become a hot topic in the forefront of Composites study. 该材料被国外称为新一代主导材料。 This material is known as a new generation of leading foreign material. 传统制备纳米复合材料的过程如下:首先利用溶胶—凝胶法制备纳米凝胶颗粒,然后将凝胶干燥、烧结、研磨成粉,最后用机械或物理的方法将纳米颗粒(粉末)掺混到本体中,形成复合纳米材料。 Preparation of nanocomposite conventional process is as follows: First, by the sol - gel Preparation of Nano gel particles, the gel is then dried, sintered, pulverized, and finally with a mechanical or physical methods nanoparticles (powder) blended into the body, formed nanocomposite. 这种合成工艺不仅过程复杂,而且纳米颗粒在体系中有团聚现象,分散度较差等不足,致使由该材料制成的保护膜防腐性能较差。 This synthesis process is not only complicated, but there nanoparticle agglomeration in the system, such as poor dispersion is insufficient, resulting in poor corrosion resistance of the protective film made from the material.

发明内容 SUMMARY

:本发明的目的是针对现有保护膜防指各类腐蚀性能较差和不足,向人们提供一种性能好、制作工艺简单、具有超防酸、碱、盐、水、烟雾、电化学腐蚀等功能的保护膜。 : Object of the present invention is directed to preventing means all types of conventional protective film, and poor corrosion resistance is insufficient, it is good to provide one property, simple production process, a super anti-acid, alkali, salt, water, smoke, electrochemical corrosion protective film function. 可应用于军民用航天航海精密设备、仪器、仪表、汽车外壳、文物、高级艺术品、高档家具等。 It can be used in military and civilian space navigation precision equipment, instruments, meters, car shell, artifacts, artwork advanced, high-end furniture.

有机—无机杂化纳米防腐保护膜主要是按照下述原料配比及方法制得:第一步,利用溶胶—凝胶法水解缩合三甲氧基硅烷类[例如:3-(2,3-环氧丙氧)丙基三甲氧基硅烷,3-(甲基丙烯酰氧)丙基三甲氧基硅烷,乙稀基三甲氧基硅烷等]与正硅酸四乙脂(占5~30%的重量百分比)的混合物,合成稳定的含有二氧化硅的倍半氧硅烷(SiO2-SSO)。 The organic - inorganic hybrid nano corrosion protective film is mainly according to the following raw material ratio and the method: the first step, by the sol - gel method trimethoxy silane hydrolyzed condensate [for example: 3- (2,3- oxo propoxy) propyl trimethoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane, ethylene trimethoxy silane, etc.] and the aliphatic tetraethyl orthosilicate (from 5 to 30% weight percent) was synthesized stable silica-containing silsesquioxane (SiO2-SSO). 此步合成条件:稀释溶剂为四氢呋喃或醇,稀释比例为3-6∶1;催化剂用甲酸(HCOOH)和水(H2O),HCOOH∶Si=3~6,H2O∶Si=0.16~3;合成温度为25~70℃;反应持续过程中,用凝胶色谱测其平均分子量,以确定生成了含有SiO2-SSO。 This step synthesis conditions: the solvent is tetrahydrofuran or an alcohol is diluted, the dilution ratio is 3-6:1; catalyst with formic acid (HCOOH) and water (H2O), HCOOH:Si = 3 ~ 6, H2O:Si = 0.16 ~ 3; Synthesis temperature is 25 ~ 70 ℃; duration of the reaction, the average molecular weight measured by gel permeation chromatography, to determine the producer containing SiO2-SSO. 第二步,向SiO2-SSO体系中加入稀释溶剂(四氢呋喃或醇),稀释比例为3~6∶1,再加入活性交联剂已二胺(EDA)或引发剂过氧化苯甲酰(BPO);根据着膜物的大小形状可采用不同种的涂膜法,如浸膜、喷涂、刷涂等。 The second step, addition of dilution solvent (tetrahydrofuran or an alcohol) to the SiO2-SSO system, the dilution ratio is 3 to 6:1, activated crosslinking agent is added diamine (EDA) or initiator benzoyl peroxide (BPO ); according to the size and shape of the membrane material may employ different kinds of coating method such as dip film, spraying, brushing and the like. 着膜后在80~150℃温度条件下,固化1~24小时,即可形成网状的有机—无机杂化纳米防腐保护膜。 After the film at a temperature of 80 ~ 150 ℃ cured for 1 to 24 hours to form a network of organic - inorganic hybrid nano corrosion protective film.

本发明的特点在于该保护膜的配方科学,合成方法简单,具有良好的防腐、保护及装饰作用,可适用于军民、高科技等多项领域,利用现有简单化工设备即可投产,成本低,易于推广。 Feature of the invention that the protective film formulation science, simple synthesis method, having good corrosion protective and decorative effect, is applicable to a number of military and civilian field, high technology, the use of conventional chemical equipment can be put into a simple, low cost , easy to spread.

具体实施例:实施例1:适用于小型物体,采用浸涂法。 Specific examples: Example 1: for small objects, a dip coating method.

第一步,把3-(2,3-环氧丙氧)丙基三甲氧基硅烷与正硅酸四乙脂(占20%的重量百分比)的混合物,用四氢呋喃稀释,稀释比例为3∶1;加催化剂甲酸(HCOOH)和水(H2O),HCOOH∶Si=3,H2O∶Si=3;合成温度在30℃;反应持续过程中,用凝胶色谱测其平均分子量达到1338左右,停止反应。 The first step, the 3- (2,3-glycidoxypropyl) trimethoxysilane and tetraethyl orthosilicate fat (by weight percentage 20%) was diluted with tetrahydrofuran, the dilution ratio is 3: 1; plus HCOOH (HCOOH) and water (H2O), HCOOH:Si = 3, H2O:Si = 3; synthesis temperature at 30 deg.] C; duration of the reaction, the average molecular weight measured by gel permeation chromatography reach about 1338, stop reaction. 此时合成了含有二氧化硅的3-(2,3-环氧丙氧)丙基倍半硅氧烷(SiO2-SSO)粘稠液,以上过程为溶胶-凝胶水解缩合法。 At this time, the synthesis of 3- (2,3-epoxy propoxy) containing silica propyl silsesquioxane (SiO2-SSO) viscous liquid, the above process is a sol - gel hydrolysis condensation.

第二步,涂膜时向SiO2-SSO溶液体系中加入四氢呋喃稀释溶剂,稀释比例为3∶1,再加入己二胺(EDA)固化剂,摩尔比为SiO2-SSO∶EDA=2∶1;把小型物体浸入SiO2-SSO/EDA溶液体系进行成膜(浸涂法),浸入/浸出速度为27cm/min;加温固化,固化温度和时间:80℃固化4小时,120℃固化2小时,150℃固化1小时固化后即可形成网状的有机-无机杂化纳米防腐保护膜。 The second step, when the coating solution is added to the system SiO2-SSO tetrahydrofuran diluting solvent dilution ratio of 3:1, was added hexamethylene diamine (EDA) a curing agent, a molar ratio of SiO2-SSO:EDA = 2:1; the small objects immersed SiO2-SSO / EDA solution film formation system (dip coating method), immersion / leaching speed of 27cm / min; heat curing, curing temperature and time: four hours of curing 80 ℃, 120 deg.] C cured for 2 hours, organic mesh can be formed after curing cured for 1 hour 150 ℃ - inorganic hybrid nano corrosion protective film.

实施例2:适用于大型物体,采用喷涂法。 Example 2: For large objects, using the spray coating method.

第一步;把3-(甲基丙烯酰氧)丙基三甲氧基硅烷与正硅酸四乙脂(占15%的重量百分比)的混合物,用乙醇稀释,稀释比例为3∶1;加催化剂甲酸(HCOOH)和水(H2O),HCOOH∶Si=3,H2O∶Si=0.16;合成温度在40℃;反应持续过程中,用凝胶色谱测其平均分子量达到1421左右,停止反应。 The first step; mixture of 3- (methacryloxypropyl) trimethoxysilane and tetraethyl orthosilicate ester (accounting for 15% by weight percent), was diluted with ethanol, dilution ratio 3:1; plus HCOOH (HCOOH) and water (H2O), HCOOH:Si = 3, H2O:Si = 0.16; synthesis temperature at 40 ℃; duration of the reaction, the average molecular weight measured by gel permeation chromatography reach about 1421, the reaction was stopped. 此时合成了含有二氧化硅的3-(甲基丙烯酰氧)丙基倍半氧硅烷(SiO2-SSO)粘稠液。 At this time, a synthesized silica containing 3- (methacryloyloxy) propyl silsesquioxane (SiO2-SSO) viscous solution.

第二步,喷膜时,向SiO2-SSO溶液体系中加入稀释剂乙醇,稀释比例为6∶1,再加过氧化苯甲酰(BPO),摩尔比为SiO2-SSO∶BPO=2∶1;第一次喷涂后,室温固化4小时;第二次喷涂后加温固化,固化温度和时间:80℃固化12小时,120℃固化1小时,固化后即可形成网状的有机-无机杂化纳米防腐保护膜。 The second step, when the spray film, the solution was added to the system SiO2-SSO ethanol diluent, the dilution ratio 6:1, combined with benzoyl peroxide (the BPO), molar ratio of SiO2-SSO:BPO = 2:1 ; after the first spraying, cured 4 hours at room temperature; after the second spray heat curing, curing temperature and time: curing 80 ℃ 12 hours curing 120 ℃ 1 hour to form a network of post-curing the organic - inorganic hybrid nano corrosion protective film.

实施例3:适用于中型物体,采用刷涂法。 Example 3: for medium-sized objects, using the brush method.

第一步:把乙稀基三甲氧基硅烷与正硅酸四乙脂(占15%的重量百分比)的混合物,用乙醇稀释,稀释比例为3∶1;加催化剂甲酸(HCOOH)和水(H2O),HCOOH∶Si=3,H2O∶Si=0.16;合成温度在40℃;反应持续过程中,用凝胶色谱测其平均分子量达到710左右,停止反应。 Step: The mixture of ethylene trimethoxysilane and tetraethyl orthosilicate ester (accounting for 15% by weight percent), was diluted with ethanol, dilution ratio 3:1; plus HCOOH (HCOOH) and water ( H2O), HCOOH:Si = 3, H2O:Si = 0.16; synthesis temperature at 40 ℃; duration of the reaction, the average molecular weight measured by gel permeation chromatography reach about 710, the reaction was stopped. 此时合成了含有二氧化硅的乙稀基倍半氧硅烷(SiO2-SSO)粘稠液。 At this time, the synthesized silsesquioxane ethylene group (SiO2-SSO) viscous solution containing silica.

第二步,刷涂时,向SiO2-SSO溶液体系中加稀释剂乙醇,稀释比例为4∶1,再加BPO,摩尔比为SiO2-SSO∶BPO=2∶1;刷涂后加温固化,固化温度和时间:80℃固化12小时,120℃固化1小时,固化后即可形成网状的有机-无机杂化纳米防腐保护膜。 The second step, brushing, was added to the system SiO2-SSO ethanol diluent, the dilution ratio was 4 to 1 plus the BPO, molar ratio of SiO2-SSO:BPO = 2:1; heat curing after brushing , curing temperature and time: 80 ℃ cured for 12 hours, and 120 deg.] C the organic cured for 1 hour, the mesh can be formed after curing - inorganic hybrid nano corrosion protective film.

Claims (4)

  1. 1.一种有机一无机杂化纳米防腐保护膜,其特征在于:该保护膜是按照下述原料配比及方法制得:第一步,利用溶胶—凝胶法水解缩合三甲氧基硅烷类包括3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙稀基三甲氧基硅烷等与正硅酸四乙脂的混合物,合成稳定的含有二氧化硅的倍半氧硅烷;此步合成条件:稀释溶剂为四氢呋喃或醇,稀释比例为3~6∶1,催化剂用HCOOH和H2O,HCOOH∶Si=3~6,H2O∶Si=0.16~3,合成温度为25~70℃;反应持续过程中,用凝胶色谱测其平均分子量,以确定生成了含有二氧化硅的倍半硅氧烷,即SiO2-SSO;第二步,向SiO2-SSO体系中加入稀释剂四氢呋喃或醇,稀释比例为3~6∶1,再加入活性交联剂为EDA或引发剂为BPO;根据着膜物的大小形状可采用不同种的涂膜法,如浸膜、喷涂、刷涂等;着膜后在80~150 An organic-inorganic hybrid nano corrosion protective film, wherein: the protective film is obtained by the following methods and raw material ratio: The first step, by the sol - gel method trimethoxy silane hydrolyzed condensate It includes 3- (2,3-epoxypropoxy) propyl trimethoxysilane, 3- (methacryloxy) propyl trimethoxysilane, ethylene group trimethoxysilane and tetraethyl orthosilicate fat mixture, synthesis of stable silica-containing silsesquioxane; this step synthesis conditions: the solvent is tetrahydrofuran or an alcohol is diluted, the dilution ratio is 3 to 6:1, catalyst HCOOH and H2O, HCOOH:Si = 3 ~ 6, H2O:Si = 0.16 ~ 3, the synthesis temperature is 25 ~ 70 ℃; duration of the reaction, the average molecular weight measured by gel permeation chromatography, to determine the producer of a silsesquioxane containing silica, i.e. SiO2- the SSO; the second step was added to the system SiO2-SSO tetrahydrofuran or an alcohol diluent, the dilution ratio is 3 to 6:1, the crosslinking agent is added EDA activity or the BPO initiator; according to the size and shape of the membrane material may be different kinds of coating method such as dip film, spraying, brushing and the like; the film is 80 to 150 after 温度条件下,固化1~24小时,即可形成网状的有机—无机杂化纳米防腐保护膜。 Under a temperature condition, curing for 1 to 24 hours to form a network of organic - inorganic hybrid nano corrosion protective film.
  2. 2.根据权利要求1所述的一种有机—无机杂化纳米防腐保护膜,其特征在于,采用浸涂法制备防腐保护膜:第一步,把3-(2,3-环氧丙氧)丙基三甲氧基硅烷与正硅酸四乙脂-重量百分比占20%的混合物,用四氢呋喃稀释,稀释比例为3∶1,加催化剂HCOOH和H2O,HCOOH∶Si=3,H2O∶Si=3,合成温度在30℃;反应持续过程中,用凝胶色谱测其平均分子量达到1338左右,停止反应;此时合成了含有二氧化硅的3-(2,3-环氧丙氧)丙基倍半硅氧烷粘稠液;第二步,涂膜时向SiO2-SSO溶液体系中加入四氢呋喃稀释溶剂,稀释比例为3∶1,再加入EDA固化剂,摩尔比为SiO2-SSO∶EDA=2∶1;把小型物体浸入SiO2-SSO/EDA溶液体系进行成膜,浸入/浸出速度为27cm/min;加温固化,固化温度和时间:80℃固化4小时,120℃固化2小时,150℃固化1小时固化后即可形成网状的有机-无机杂化纳米防腐保护膜 The first step, the 3- (2,3-epoxypropoxy: inorganic hybrid nano-film corrosion protection, wherein, dip coating film prepared corrosion protection - An organic according to claim 1 ) propyl trimethoxysilane and tetraethyl orthosilicate lipid - 20% by weight of the mixture, diluted with tetrahydrofuran, 3:1 dilution ratio, the catalyst addition HCOOH and H2O, HCOOH:Si = 3, H2O:Si = 3, synthesis temperature at 30 deg.] C; duration of the reaction, the average molecular weight measured by gel permeation chromatography reach about 1338, the reaction was stopped; synthesized case of 3- (2,3-epoxy propoxy) propoxy containing silica silsesquioxane viscous liquid; the second step, when the coating solution is added to the system SiO2-SSO tetrahydrofuran diluting solvent dilution ratio of 3:1, EDA was further added a curing agent, a molar ratio of SiO2-SSO:EDA = 2/1; the small objects immersed SiO2-SSO / EDA solution deposition system was immersed / leaching speed of 27cm / min; heat curing, curing temperature and time: curing 80 ℃ 4 hours and cured 120 ℃ 2 hours. organic mesh can be formed after curing cured for 1 hour 150 ℃ - inorganic hybrid nano-film corrosion protection .
  3. 3.根据权利要求1所述的一种有机—无机杂化纳米防腐保护膜,其特征在于,采用喷涂法制备防腐保护膜:第一步,把3-(甲基丙烯酰氧)丙基三甲氧基硅烷与正硅酸四乙脂-重量百分比占15%的混合物,用乙醇稀释,稀释比例为3∶1,加催化剂HCOOH和H2O,HCOOH∶Si=3,H2O∶Si=0.16,合成温度在40℃,反应持续过程中,用凝胶色谱测其平均分子量达到1421左右,停止反应;此时合成了含有二氧化硅的3-(甲基丙烯酰氧)丙基倍半氧硅烷稠液;第二步,喷膜时,向SiO2-SSO体系中加入稀释剂乙醇,稀释比例为6∶1,再加BPO,摩尔比为SiO2-SSO∶BPO=2∶1;第一次喷涂后,室温固化4小时;第二次喷涂后加温固化,固化温度和时间:80℃固化12小时,120℃固化1小时,固化后即可形成网状的有机-无机杂化纳米防腐保护膜。 According to one of the claims 1 to organic - inorganic hybrid nano-film corrosion protection, wherein, spraying corrosion protective film prepared by: a first step, the 3- (methacryloyloxy) propyltrimethoxysilane silane and tetraethyl orthosilicate lipid - 15% by weight of the mixture, diluted with ethanol, diluted 3:1 ratio, the catalyst addition HCOOH and H2O, HCOOH:Si = 3, H2O:Si = 0.16, synthesis temperature at 40 ℃, the duration of the reaction, the average molecular weight measured by gel permeation chromatography reach about 1421, the reaction was stopped; case synthesized 3- (methacryloyloxy) propyl silica-containing liquid condensed silsesquioxane ; the second step, when the spray film is added to the system SiO2-SSO ethanol diluent, the dilution ratio 6:1, together with the BPO, molar ratio of SiO2-SSO:BPO = 2:1; after the first spraying, four hours of curing at room temperature; after the second spray heat curing, curing temperature and time: curing 80 ℃ 12 hours curing 120 ℃ 1 hour to form a network of post-curing the organic - inorganic hybrid nano corrosion protective film.
  4. 4.根据权利要求1所述的一种有机—无机杂化纳米防腐保护膜,其特征在于,采用刷涂法制备防腐保护膜:第一步,把乙稀基三甲氧基硅烷与正硅酸四乙脂-重量百分比占15%的混合物,用乙醇稀释,稀释比例为3∶1,加催化剂HCOOH和H2O,HCOOH∶Si=3,H2O∶Si=0.16;合成温度在40℃;反应持续过程中,用凝胶色谱测其平均分子量达到710左右,停止反应;此时合成了含有二氧化硅的乙稀基倍半氧硅烷粘稠液;第二步,刷涂时向SiO2-SSO溶液体系中加稀释剂乙醇,稀释比例为4∶1,再加BPO,摩尔比为SiO2-SSO∶BPO=2∶1;刷涂后加温固化,固化温度和时间:80℃固化12小时,120℃固化1小时,固化后即可形成网状的有机-无机杂化纳米防腐保护膜。 According to one of the claims 1 to organic - inorganic hybrid nano-film corrosion protection, wherein the corrosion protection applied by brush film prepared: a first step, the ethylene trimethoxysilane and tetraethyl orthosilicate tetraethyl lipid - 15% by weight of the mixture, diluted with ethanol, diluted 3:1 ratio, the catalyst addition HCOOH and H2O, HCOOH:Si = 3, H2O:Si = 0.16; synthesis temperature at 40 ℃; duration of the reaction , the measured gel chromatography average molecular weight of around 710, the reaction was stopped; in this case the synthesized silsesquioxane ethylene group viscous solution containing silica; the second step, when brushing the solution system SiO2-SSO ethanol was added diluent, the dilution ratio was 4 to 1 plus the BPO, molar ratio of SiO2-SSO:BPO = 2:1; brush after heat curing, curing temperature and time: 12 hours curing 80 ℃, 120 ℃ cured for 1 hour, the mesh can be formed after curing of the organic - inorganic hybrid nano corrosion protective film.
CN 03134157 2003-08-25 2003-08-25 Organic and inorganic hybrid antiseptic protective film CN1249178C (en)

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Cited By (12)

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WO2010095146A1 (en) * 2009-02-18 2010-08-26 Tata Steel Limited Anti-corrosion sol-gel hybrid coating on zinc and zinc alloy steel sheets and preparing method thereof
CN102134447A (en) * 2010-01-25 2011-07-27 哈尔滨工业大学 Methyl-terminated acryloyloxy silsesquioxane/titanium dioxide nano anticorrosion protective film
CN102134409A (en) * 2010-01-25 2011-07-27 哈尔滨工业大学 Anti-corrosion protective nano-film containing epoxy-terminated silsesquioxane/titanium dioxide
CN102631884A (en) * 2012-04-12 2012-08-15 苏州大学 Closed mesoporous silicon oxide and preparation method of same
CN102858887A (en) * 2010-04-28 2013-01-02 3M创新有限公司 Articles including nanosilica-based primers for polymer coatings and methods
CN102873015A (en) * 2012-10-29 2013-01-16 南京信息工程大学 Method for treating metal surface
CN102134446B (en) 2010-01-25 2013-01-30 哈尔滨工业大学 Vinyl silsesquioxane/titanium dioxide nano anticorrosion protective film
CN102912345A (en) * 2012-10-29 2013-02-06 南京信息工程大学 Aluminium alloy surface corrosion control method
CN103980816A (en) * 2014-05-23 2014-08-13 泉州三欣新材料科技有限公司 Metal surface hybridization protection coating and preparation and application method and application thereof
CN103992668A (en) * 2014-05-28 2014-08-20 泉州三欣新材料科技有限公司 Aluminum alloy umbrella skeleton surface coating as well as preparation and application method thereof
CN104829863A (en) * 2015-03-31 2015-08-12 台州学院 Nanometer polyhedral oligomeric silsesquioxane fire retardant containing ionic liquid, and preparation method and application thereof
CN106336798A (en) * 2016-09-21 2017-01-18 东莞市联洲知识产权运营管理有限公司 Preparation method of titanium and zirconium-containing organic-inorganic hybrid protective film

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Publication number Priority date Publication date Assignee Title
WO2010095146A1 (en) * 2009-02-18 2010-08-26 Tata Steel Limited Anti-corrosion sol-gel hybrid coating on zinc and zinc alloy steel sheets and preparing method thereof
CN102134447B (en) 2010-01-25 2013-01-30 哈尔滨工业大学 Methyl-terminated acryloyloxy silsesquioxane/titanium dioxide nano anticorrosion protective film
CN102134447A (en) * 2010-01-25 2011-07-27 哈尔滨工业大学 Methyl-terminated acryloyloxy silsesquioxane/titanium dioxide nano anticorrosion protective film
CN102134409A (en) * 2010-01-25 2011-07-27 哈尔滨工业大学 Anti-corrosion protective nano-film containing epoxy-terminated silsesquioxane/titanium dioxide
CN102134446B (en) 2010-01-25 2013-01-30 哈尔滨工业大学 Vinyl silsesquioxane/titanium dioxide nano anticorrosion protective film
CN102858887B (en) * 2010-04-28 2018-02-13 3M创新有限公司 Articles and comprising a polymer coating of nano-silica based primer
CN102858887A (en) * 2010-04-28 2013-01-02 3M创新有限公司 Articles including nanosilica-based primers for polymer coatings and methods
US10066109B2 (en) 2010-04-28 2018-09-04 3M Innovative Properties Company Articles including nanosilica-based primers for polymer coatings and methods
CN102631884A (en) * 2012-04-12 2012-08-15 苏州大学 Closed mesoporous silicon oxide and preparation method of same
CN102912345A (en) * 2012-10-29 2013-02-06 南京信息工程大学 Aluminium alloy surface corrosion control method
CN102873015A (en) * 2012-10-29 2013-01-16 南京信息工程大学 Method for treating metal surface
CN102912345B (en) 2012-10-29 2014-10-22 南京信息工程大学 An aluminum surface corrosion Method
CN102873015B (en) 2012-10-29 2014-04-09 南京信息工程大学 Method for treating metal surface
CN103980816A (en) * 2014-05-23 2014-08-13 泉州三欣新材料科技有限公司 Metal surface hybridization protection coating and preparation and application method and application thereof
CN103980816B (en) * 2014-05-23 2016-09-07 泉州三欣新材料科技有限公司 Heteroaryl protective coating of a metal surface and its preparation method and application of use
CN103992668A (en) * 2014-05-28 2014-08-20 泉州三欣新材料科技有限公司 Aluminum alloy umbrella skeleton surface coating as well as preparation and application method thereof
CN104829863A (en) * 2015-03-31 2015-08-12 台州学院 Nanometer polyhedral oligomeric silsesquioxane fire retardant containing ionic liquid, and preparation method and application thereof
CN104829863B (en) * 2015-03-31 2017-08-25 台州学院 A nano-level cage polysilsesquioxane flame retardant and preparation method and use of ion-containing liquid
CN106336798A (en) * 2016-09-21 2017-01-18 东莞市联洲知识产权运营管理有限公司 Preparation method of titanium and zirconium-containing organic-inorganic hybrid protective film

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