CN106835100A - 一种聚苯胺‑环氧树脂耐蚀性复合钝化膜 - Google Patents
一种聚苯胺‑环氧树脂耐蚀性复合钝化膜 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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Abstract
本发明公开了一种聚苯胺‑环氧树脂耐蚀性复合钝化膜，由下列原料制备制成：甲基丙烯酸十二氟庚酯、甲基丙烯酸六氟丁酯、硅烷偶联剂KH560、偶氮二异丁腈、硅烷偶联剂KH570、硅烷偶联剂KH858适量、硅烷偶联剂KH550、三氟甲基三甲基硅烷、十二烷基硫酸钠、碳纳米管、苯胺、过硫酸铵、钼酸钠、磷酸、双氧水、硅溶胶、环氧树脂、固化剂、无水乙醇适量、四氢呋喃适量、稀硝酸适量、去离子水适量；本发明制备的钝化液制备方法简单，成本低，无毒环保，提供的钝化方法能够大幅度缩短处理时间，省去了涂油工艺，并且形成的钝化膜具有良好的耐磨、耐腐蚀、耐热和耐指纹性，减缓镀锌层的腐蚀，应用前景良好。
Description
技术领域
本发明涉及无铬钝化技术领域，尤其涉及一种聚苯胺-环氧树脂耐蚀性复合钝化膜。
背景技术
镀锌宽带钢板是指表面镀有一层锌的钢板，镀锌是为了防止钢板表面产生腐蚀，延长钢板使用寿命，镀锌宽带钢板与人们的生活日益密切，主要用于家电板、手机外壳、建筑用彩涂板和汽车板凳。由于锌很活泼，在大气中易受到酸、碱、氧气、二氧化碳和水蒸气等物质的腐蚀，因此需要对其进行钝化处理，镀锌板传统钝化方式普遍采用含有铬酸盐的钝化液，该方法具有成膜性能优良、成本低以及工艺简单等优点，但铬酸盐中含有的铬离子对人体具有致癌性，同时对环境也产生极大的危害。目前从事表面处理的专家及学者们对无铬钝化液的配制及其无铬钝化工艺的性能研究取得了一定的进展，主要集中在无机组分钝化、有机物钝化和无机有机复合钝化，这些新兴钝化产品基本满足无铬钝化要求，性能已接近或达到铬酸盐钝化水平。
但是在某些方面仍需要进一步研究，为克服无机组分钝化产生的耐蚀性和有机组分钝化附着性能差的问题，张振海在《镀锌宽带钢无机/有机复合钝化液的制备及抗腐蚀性能》一文中主要主要采用有机硅烷和无机缓蚀剂进行复配，通过调节各物质的用量及反应比例，研究钝化液的性能极其在工业生产中的应用情况。根据有机硅烷酸性条件下水解反应原理，采用硅烷偶联剂KH560和硅烷偶联剂KH602进行水解反应，添加一定量的无机缓蚀剂钒酸钠和硫酸钛，中试生产出无铬钝化产品，涂装成膜，对其钝化膜进行测试，膜层耐电化学性能良好，72H中性盐雾试验出现白锈的面积仅为4—6%，其耐蚀性能可接近铬酸盐钝化膜，附着力达到1级，表面结构均匀致密；针对耐指纹钝化产品，将钼酸钠溶解在水中，用有机酸调节pH至中性，天机一定量的改性纳米二氧化硅，配置成无机钝化液，硅烷偶联剂KH570和硅烷偶联剂KH858复配成有机硅烷化钝化液，将两种钝化液进一步复配，得到钼酸盐有机硅烷钝化液，膜层性能优良。该作者提供的无铬钝化液可以从根本上解决现有钝化液中有毒有害铬离子对人们毒害的问题，也能够真正替代含铬钝化液，实现对电镀锌宽带钢板的度化，但是该无铬钝化液形成的镀化膜在低摩擦、抗氧、耐腐蚀、自润滑、耐磨等性能上仍不能满足市场需求，需进一步改性提高应用领域，扩大应用前景。
发明内容
本发明目的就是为了弥补已有技术的缺陷，提供一种聚苯胺-环氧树脂耐蚀性复合钝化膜。
本发明是通过以下技术方案实现的：
一种聚苯胺-环氧树脂耐蚀性复合钝化膜，由下列重量份的原料制备制成：甲基丙烯酸十二氟庚酯4-4.6、甲基丙烯酸六氟丁酯5.2-5.6、硅烷偶联剂KH560 16-18、偶氮二异丁腈0.2-0.3、硅烷偶联剂KH570 90-100、硅烷偶联剂KH858适量、硅烷偶联剂KH550 3.5-4、三氟甲基三甲基硅烷1.1-1.5、十二烷基硫酸钠7.8-8.5、碳纳米管1.1-1.4、苯胺14-17、过硫酸铵0.05-0.15、钼酸钠30-33、磷酸26-28、双氧水50-60、硅溶胶11-13、环氧树脂33-35、固化剂3-5、无水乙醇适量、四氢呋喃适量、稀硝酸适量、去离子水适量。
所述一种聚苯胺-环氧树脂耐蚀性复合钝化膜，由下列具体步骤制备制成：
（1）将硅烷偶联剂KH550加到乙醇溶液中，在60℃恒温下磁力搅拌1-1.5h，再加入三氟甲基三甲基硅烷继续恒温磁力搅拌4-6h，反应结束后冷却至室温备用；
（2）将十二烷基硫酸钠加到1%（v/v）的盐酸溶液中，搅拌30-50min后形成质量浓度为1.5%的乳化剂溶液，将碳纳米管加到步骤（1）制备的混合溶液中超声震荡成0.8%的分散液，再将该分散液加到上述乳化剂溶液中超声震荡20min，震荡结束后以1d/min的速率滴加苯胺溶液，滴加结束后调节溶液的pH值为2-3，最后加入过硫酸铵于冰浴条件下反应4-6h，反应结束后得到混合液备用；
（3）将甲基丙烯酸十二氟庚酯、甲基丙烯酸六氟丁酯和硅烷偶联剂KH560混合加到15-17倍量的四氢呋喃中，搅拌至完全溶解后加入偶氮二异丁腈，以300-400r/min的转速搅拌，然后升高温度至65℃，恒温反应8-10h，反应结束后冷却至室温得到含氟硅烷聚合物溶液；
（4）在常温下依次将钼酸钠、磷酸、双氧水加到去离子水中，搅拌30min后得钼酸钠浓度为30g/L的无机盐钝化液，将硅烷偶联剂KH570和硅烷偶联剂KH858按照质量比2:1进行复合，然后溶解75%的无水乙醇中，制成总浓度为150g/L的硅烷溶液，静置反应2-3h后用稀硝酸溶液调节pH至4-5，得到有机硅烷复合钝化液；
（5）将步骤（4）制备的无机盐钝化液和有机硅烷复合钝化液混合，搅拌均匀后在常温下将硅溶胶、环氧树脂、步骤（2）制备的产物、步骤（3）制备的产物加到上述溶液中，搅拌3h后加入固化剂，继续搅拌3h后得到复合钝化液；将镀锌板放入钝化液中常温浸涂30S，烘干温度为160-180℃，烘干时间30S，自然条件下冷却即得钝化膜。
本发明的优点是：传统的钝化方法采用含有六价铬的钝化液，得到的钝化膜耐蚀性好，消耗成本低，但在实际工业生产上对人体和环境造成严重的危害，由于硅烷具有无毒、无味、耐腐蚀性能好及易水解及在基材表面成膜等优点，无机-有机复合钝化是近年来取代无铬钝化的主要研究方向，本发明采用硅烷偶联剂KH570和硅烷偶联剂KH858在弱酸性条件下水解形成有机硅烷钝化液，再辅以无机组分形成无机-有机硅烷复合钝化液，为提高钝化膜的极压磨损、耐腐蚀、耐热、自润滑等性能，本发明采用自由基溶液聚合法合成含氟硅烷聚合物溶液，其具有含氟基团，能够降低表面能，又含有硅烷基团，硅烷基团可以水解成羟基，能够与基底表面以共价键方式结合，促进成膜性，并且具有很高的结合强度，提高附着力，形成良好的疏水性、高耐热性等优点，聚苯胺具有合成原料成本低廉、优异的抗划伤、抗点蚀等优点，能够在钢铁和铝合金等的表面形成均匀致密的聚苯胺膜，起到良好的防腐防锈的作用，但是其在一般的有机溶剂中溶解性较差，因此需要对其进行掺杂改善其溶解性，本发明将有机硅单体进行水解后和有机氟单体共混改性形成有机氟硅水解液，将碳纳米管分散在该水解液中，然后利用原位生成的方法合成具有聚苯胺包覆碳纳米管的粒子，促进钝化液的成膜性，使其钝化膜具有良好的耐磨、耐腐蚀、耐热和耐指纹性，本发明制备的钝化液制备方法简单，成本低，无毒环保，提供的钝化方法能够大幅度缩短处理时间，省去了涂油工艺，并且形成的钝化膜具有良好的耐磨、耐腐蚀、耐热和耐指纹性，减缓镀锌层的腐蚀，应用前景良好。
具体实施方式
一种聚苯胺环氧树脂耐蚀性复合钝化膜，由下列重量份（公斤）的原料制备制成：甲基丙烯酸十二氟庚酯4、甲基丙烯酸六氟丁酯5.2、硅烷偶联剂KH560 16、偶氮二异丁腈0.2、硅烷偶联剂KH570 90、硅烷偶联剂KH858适量、硅烷偶联剂KH550 3.5、三氟甲基三甲基硅烷1.1、十二烷基硫酸钠7.8、碳纳米管1.1、苯胺14、过硫酸铵0.05、钼酸钠30、磷酸26、双氧水50、硅溶胶11、环氧树脂33、固化剂3、无水乙醇适量、四氢呋喃适量、稀硝酸适量、去离子水适量。
所述一种聚苯胺环氧树脂耐蚀性复合钝化膜，由下列具体步骤制备制成：
（1）将硅烷偶联剂KH550加到乙醇溶液中，在60℃恒温下磁力搅拌1h，再加入三氟甲基三甲基硅烷继续恒温磁力搅拌4h，反应结束后冷却至室温备用；
（2）将十二烷基硫酸钠加到1%（v/v）的盐酸溶液中，搅拌30min后形成质量浓度为1.5%的乳化剂溶液，将碳纳米管加到步骤（1）制备的混合溶液中超声震荡成0.8%的分散液，再将该分散液加到上述乳化剂溶液中超声震荡20min，震荡结束后以1d/min的速率滴加苯胺溶液，滴加结束后调节溶液的pH值为2，最后加入过硫酸铵于冰浴条件下反应4h，反应结束后得到混合液备用；
（3）将甲基丙烯酸十二氟庚酯、甲基丙烯酸六氟丁酯和硅烷偶联剂KH560混合加到15倍量的四氢呋喃中，搅拌至完全溶解后加入偶氮二异丁腈，以300r/min的转速搅拌，然后升高温度至65℃，恒温反应8h，反应结束后冷却至室温得到含氟硅烷聚合物溶液；
（4）在常温下依次将钼酸钠、磷酸、双氧水加到去离子水中，搅拌30min后得钼酸钠浓度为30g/L的无机盐钝化液，将硅烷偶联剂KH570和硅烷偶联剂KH858按照质量比2:1进行复合，然后溶解75%的无水乙醇中，制成总浓度为150g/L的硅烷溶液，静置反应2h后用稀硝酸溶液调节pH至4，得到有机硅烷复合钝化液；
（5）将步骤（4）制备的无机盐钝化液和有机硅烷复合钝化液混合，搅拌均匀后在常温下将硅溶胶、环氧树脂、步骤（2）制备的产物、步骤（3）制备的产物加到上述溶液中，搅拌3h后加入固化剂，继续搅拌3h后得到复合钝化液；将镀锌板放入钝化液中常温浸涂30S，烘干温度为160℃，烘干时间30S，自然条件下冷却即得钝化膜。
按照实施例提供的方法制备出钝化膜，对其进行性能测试，结果如下：
附着力性能：1级；硫酸铜点滴试验：180S；耐中性盐雾试验：168h；5%氯化钠浸泡试验：120h；耐指纹性：△E＜2，经手接触后表面指纹不可见。
Claims (2)
1.一种聚苯胺-环氧树脂耐蚀性复合钝化膜，其特征在于，由下列重量份的原料制备制成：甲基丙烯酸十二氟庚酯4-4.6、甲基丙烯酸六氟丁酯5.2-5.6、硅烷偶联剂KH560 16-18、偶氮二异丁腈0.2-0.3、硅烷偶联剂KH570 90-100、硅烷偶联剂KH858适量、硅烷偶联剂KH550 3.5-4、三氟甲基三甲基硅烷1.1-1.5、十二烷基硫酸钠7.8-8.5、碳纳米管1.1-1.4、苯胺14-17、过硫酸铵0.05-0.15、钼酸钠30-33、磷酸26-28、双氧水50-60、硅溶胶11-13、环氧树脂33-35、固化剂3-5、无水乙醇适量、四氢呋喃适量、稀硝酸适量、去离子水适量。
2.根据权利要求1所述一种聚苯胺-环氧树脂耐蚀性复合钝化膜，其特征在于，由下列具体步骤制备制成：
（1）将硅烷偶联剂KH550加到乙醇溶液中，在60℃恒温下磁力搅拌1-1.5h，再加入三氟甲基三甲基硅烷继续恒温磁力搅拌4-6h，反应结束后冷却至室温备用；
（2）将十二烷基硫酸钠加到1%（v/v）的盐酸溶液中，搅拌30-50min后形成质量浓度为1.5%的乳化剂溶液，将碳纳米管加到步骤（1）制备的混合溶液中超声震荡成0.8%的分散液，再将该分散液加到上述乳化剂溶液中超声震荡20min，震荡结束后以1d/min的速率滴加苯胺溶液，滴加结束后调节溶液的pH值为2-3，最后加入过硫酸铵于冰浴条件下反应4-6h，反应结束后得到混合液备用；
（3）将甲基丙烯酸十二氟庚酯、甲基丙烯酸六氟丁酯和硅烷偶联剂KH560混合加到15-17倍量的四氢呋喃中，搅拌至完全溶解后加入偶氮二异丁腈，以300-400r/min的转速搅拌，然后升高温度至65℃，恒温反应8-10h，反应结束后冷却至室温得到含氟硅烷聚合物溶液；
（4）在常温下依次将钼酸钠、磷酸、双氧水加到去离子水中，搅拌30min后得钼酸钠浓度为30g/L的无机盐钝化液，将硅烷偶联剂KH570和硅烷偶联剂KH858按照质量比2:1进行复合，然后溶解75%的无水乙醇中，制成总浓度为150g/L的硅烷溶液，静置反应2-3h后用稀硝酸溶液调节pH至4-5，得到有机硅烷复合钝化液；
（5）将步骤（4）制备的无机盐钝化液和有机硅烷复合钝化液混合，搅拌均匀后在常温下将硅溶胶、环氧树脂、步骤（2）制备的产物、步骤（3）制备的产物加到上述溶液中，搅拌3h后加入固化剂，继续搅拌3h后得到复合钝化液；将镀锌板放入钝化液中常温浸涂30S，烘干温度为160-180℃，烘干时间30S，自然条件下冷却即得钝化膜。
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| CN105937029A (zh) * | 2016-06-29 | 2016-09-14 | 无锡伊佩克科技有限公司 | 一种无机-有机复合钝化液的制备方法 |
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