CN109267052B - 一种基于树枝状大分子的无铬钝化液 - Google Patents

一种基于树枝状大分子的无铬钝化液 Download PDF

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CN109267052B
CN109267052B CN201811493837.9A CN201811493837A CN109267052B CN 109267052 B CN109267052 B CN 109267052B CN 201811493837 A CN201811493837 A CN 201811493837A CN 109267052 B CN109267052 B CN 109267052B
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passivation solution
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silane
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蒋文彬
叶凯
冯泽
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Quaker Chemical China Co Ltd
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Abstract

本发明公开了一种基于树枝状大分子的无铬钝化液，包括以下重量百分比含量的组分:至少一种有且仅含有环氧功能团的硅烷0.2～15％；过渡金属化合物0.1～5％；至少一种树枝状大分子0.1～5％；磷酸和/或磷酸盐0.1～20％；余量为水。本发明的基于树枝状大分子的无铬钝化液，是一种不含铬、具有极高存储稳定性、高固含量和低温成膜性的节能环保型钝化液，解决传统钝化液的相关缺陷和应用限制，尤其是在高温、高湿度、高盐度、长距离等运输过程中的稳定性问题。

Description

一种基于树枝状大分子的无铬钝化液
技术领域
本发明涉及一种基于树枝状大分子的无铬钝化液。
背景技术
现今金属表面钝化技术，包括铬酸盐钝化技术和无铬钝化技术两类，无铬技术是发展趋势，并在逐步取代铬酸盐钝化技术。目前市场上主流的无铬钝化技术，基于硅烷的技术，通常含有一定量的金属盐，高分子树脂，成膜助剂等，产品的缺点主要有两个方面：
第一个方面是存储时间短，通常不超过3～6个月，在夏季高温下甚至不超过一个月。原因在于：1.硅烷具有自缩合和交叉缩合性质，会随着时间的增加逐步形成沉淀或者凝胶，尤其是多种硅烷复配的情况下更加严重；2.金属盐会对硅烷的缩合反应进行催化，进一步降低稳定性；3.当配方中含有树脂，那么硅烷、金属盐和树脂三者分别会进行相互反应，进一步影响稳定性。
第二个方面是固含量通常不超过30％，浓度高的情况下，硅烷的自缩合和交叉缩合反应会大大加速，使产品迅速凝胶。这导致产品中含有70％以上的水，不仅会大大提高运输成本，也对钝化液烘干温度有较高要求，通常需要80-100℃高温烘烤才能有效烘干。
发明内容
本发明的目的是克服现有技术的缺陷，提供一种基于树枝状大分子的无铬钝化液，是一种不含铬、具有极高存储稳定性、高固含量和低温成膜性的节能环保型钝化液，解决传统钝化液的相关缺陷和应用限制，尤其是在高温、高湿度、高盐度、长距离等运输过程中的稳定性问题。
实现上述目的的技术方案是：一种基于树枝状大分子的无铬钝化液，包括以下重量百分比含量的组分:
Figure GDA0002480383170000021
余量为水。
上述的一种基于树枝状大分子的无铬钝化液，其中，所述无铬钝化液不包括含有氨功能团的硅烷和含有铬元素的物质。
上述的一种基于树枝状大分子的无铬钝化液，其中，所述有且仅含有环氧功能团的硅烷不包括不含有环氧功能团的硅烷；也不包括同时具有环氧功能团和其他功能团的硅烷。
上述的一种基于树枝状大分子的无铬钝化液，其中，所述过渡金属化合物为Zr、Ti、Mn、V、Co、Ni、Ce、Mo、W、H2ZrF6、H2TiF6、Zr(Ar)4、Zr-Ac、TiO2、ZrO2、V2O5和Ce(NO3)3中的一种或者几种。
上述的一种基于树枝状大分子的无铬钝化液，其中，所述树枝状大分子采用聚酰胺-胺型树枝状高分子，结构通式如下所示：
Figure GDA0002480383170000022
上述的一种基于树枝状大分子的无铬钝化液，其中，所述磷酸和/或磷酸盐为H3PO4、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、NaH2PO4、(Na)2HPO4、(Na)3PO4、NaNH4HPO4、(Na)2NH4HPO4、Na(NH4)2HPO4和有机磷酸中的一种或者几种。
本发明的基于树枝状大分子的无铬钝化液，与现有技术相比的主要优点是：
(1)传统的无铬钝化液存储时间短，通常不超过3～6个月，在夏季高温下甚至不超过一个月；本发明通过引入树枝状大分子，即可以和硅烷分子形成氢键相互作用，有效抑制硅烷的自缩合和交叉缩合反应；也可以和金属离子形成络合物，有效抑制金属离子和硅烷，树脂，磷酸根离子等的相互反应。从而大大提高钝化液的稳定性，存储达3年以上；
(2)传统的无铬钝化液的固含量通常不超过30％，浓度高的情况下，硅烷的自缩合和交叉缩合反应会大大加速，使产品迅速凝胶。这导致产品中含有70％以上的水，不仅会大大提高运输成本，也对钝化液烘干温度有较高要求，通常需要80-100℃高温烘烤才能有效烘干；本发明通过树枝状大分子对硅烷缩合反应的抑制，有效防止高浓度下硅烷的缩合反应，因而可以将产品做成固含量达到60％的浓缩液，提高运输效率降低运输成本，同时，烘烤温度只需30-40℃，更加节能环保。
总的来说，本发明的基于树枝状大分子的无铬钝化液，是一种不含铬、具有极高存储稳定性、高固含量和低温成膜性的节能环保型钝化液，解决传统钝化液的相关缺陷和应用限制，尤其是在高温、高湿度、高盐度、长距离等运输过程中的稳定性问题，进一步满足现代金属防腐蚀行业的生产要求，同时符合成本节约、经济环保的发展理念。
具体实施方式
为了使本技术领域的技术人员能更好地理解本发明的技术方案，下面对其具体实施方式进行详细地说明：
实施例1
一种基于树枝状大分子的无铬钝化液，按照表1的配方组成:
组分 含量(重量％)
环氧硅烷 5.1
Zr化合物 2.2
聚酰胺-胺型树枝状高分子 0.15
H<sub>3</sub>PO<sub>4</sub> 3.3
水 89.25
表1
实施例2
一种基于树枝状大分子的无铬钝化液，按照表2的配方组成:
组分 含量(重量％)
环氧硅烷 4.1
Ce化合物 3.1
聚酰胺-胺型树枝状高分子 0.20
(NH<sub>4</sub>)<sub>2</sub>HPO<sub>4</sub> 5.5
水 87.10
表2
实施例3
一种基于树枝状大分子的无铬钝化液，按照表3的配方组成:
组分 含量(重量％)
环氧硅烷 6.1
V<sub>2</sub>O<sub>3</sub>化合物 1.8
聚酰胺-胺型树枝状高分子 0.15
(NH<sub>4</sub>)<sub>2</sub>HPO<sub>4</sub> 6.1
水 85.85
表3
实施例4
一种基于树枝状大分子的无铬钝化液，按照表4的配方组成:
组分 含量(重量％)
环氧硅烷 5.5
H<sub>2</sub>TiF<sub>6</sub>化合物 1.5
聚酰胺-胺型树枝状高分子 0.25
(NH<sub>4</sub>)<sub>2</sub>HPO<sub>4</sub> 5.4
水 87.35
表4
实施例5
一种基于树枝状大分子的无铬钝化液，按照表5的配方组成:
组分 含量(重量％)
环氧硅烷 4.5
H2TiF6化合物 2.1
聚酰胺-胺型树枝状高分子 0.30
羟基乙叉二膦酸 3.6
水 89.50
表5
本发明的基于树枝状大分子的无铬钝化液，不包括含有氨功能团的硅烷和含有铬元素的物质。
有且仅含有环氧功能团的硅烷不包括不含有环氧功能团的硅烷，比如不包括硅酸乙酯，氨基硅烷，乙烯基硅烷，巯基硅烷等；也不包括同时具有环氧功能团和其他功能团的硅烷。如此设计的主要目的是含有非环氧功能团的硅烷在本文所述的钝化剂体系中稳定性差，使用仅含有环氧基功能团的硅烷能够最大程度的保证钝化剂的存储稳定性。
树枝状大分子采用聚酰胺-胺型树枝状高分子，结构通式如下所示：
Figure GDA0002480383170000061
选择市面上有售的钝化液与申本发明的一种基于树枝状大分子的无铬钝化液进行比较(产品使用对象一致)。目前市面上对无铬钝化液的性能评价主要有以下几种，通过以下检测项目可以表明本发明(包含本发明中的所有实施例)与现有技术相比所具有的优点或积极效果。
稳定性试验
将配制后的样品分别储存于25℃室温，进行长期稳定性试验，每天记录样品状态，结果见表6所示：
Figure GDA0002480383170000062
表6
从表6中可以看出，与市售样相比，本发明的基于树枝状大分子的无铬钝化液有着超长的稳定性。本发明通过引入树枝状大分子，即可以和硅烷分子形成氢键相互作用，有效抑制硅烷的自缩合和交叉缩合反应；也可以和金属离子形成络合物，有效抑制金属离子和硅烷，树脂，磷酸根离子等的相互反应。从而大大提高钝化液的稳定性，存储达3年以上。
成膜温度试验
先在待测基板背面贴上测温纸，用涂敷法在基板上涂上钝化液，然后将其放入自动烘箱烘烤，检测其最低的成膜温度，结果见表7所示：
样品名称 成膜温度(℃)
市售样 80-100
本发明 30-40
表7
从表7可以看出：与市售样相比，本发明的基于树枝状大分子的无铬钝化液有着非常低的成膜温度，可以大大降低能耗消耗及提高从业人员的安全性，更加节能环保。本发明通过树枝状大分子对硅烷缩合反应的抑制，有效防止高浓度下硅烷的缩合反应，因而可以将产品做成固含量达到60％的浓缩液，提高运输效率降低运输成本，同时，烘烤温度只需30-40℃，更加节能环保。
耐腐蚀性试验
根据美国ASTM B117所述标准方法进行测试。盐雾量1-2mL/h,氯化钠盐水的浓度5％，pH＝6.8-7.2。一般工业标准中的要求是放置72小时后产生的锈蚀小于5％，结果见表8所示：
样品名称 耐腐蚀性(ASTM B117)*(小时)
市售样 72-96
本发明 120-144
表8
从表8可以看出：与市售样相比，本发明的基于树枝状大分子的无铬钝化液有着更加优异的耐腐蚀性。
本发明的基于树枝状大分子的无铬钝化液还可以满足其它的性能测试：耐湿度，耐碱，耐溶剂和耐高温实验。
制剂(无铬钝化液)经受耐溶剂、耐高温、耐碱和湿度测试。该测试在具有约0.5～2.0mm厚度的镀锌钢面板上进行。颜色变化dE*在每个测试前后测量。这些测试的普通需求为dE*<3.0。国际照明技术委员会(CIE)使用间隔亮度ΔE*(也称为dE*、dE或“Delta E”)以表示色差。该值基于亮度、色调和饱和度的差表示。由CIE推荐，ΔE*ab的测定通过相应设备测试的准确的图形来表示
L*a*b色彩空间包括全部可感知的颜色。L*、a*和b*值通常是绝对的，具有预限定的范围。亮度L*在L*＝0时代表最暗的黑色，和在L*＝100时代表最亮的白色。颜色通道a*和b*在a*＝0和b*＝0时代表真实中性灰度值。红/绿对比色沿着a*轴表示，绿色在负a*值和红色在正a*值。黄/蓝对比色沿着b*轴表示，蓝色在负b*值和黄色在正b*值。不含Cr的钝化面板的中国市场需求为ΔE*<3.0。
耐湿度试验：
(1)测试在测试之前面板的L*a*b值；
(2)设置湿度箱：50℃，100％RH；
(3)将面板堆共同或单独放置在湿度箱中120h；
(4)测试在测试之后面板的L*a*b值并获得ΔE*。
耐碱试验：
(1)测试在测试之前面板的L*a*b值；
(2)用碱性清洁剂制备碱性溶液(pH9-10)并加热到50℃；
(3)将面板放置在溶液中3分钟；
(4)测试在测试之后面板的L*a*b值并获得ΔE*。
耐溶剂试验：
(1)测试在测试之前面板的L*a*b值；
(2)将面板固定在测试台上；
(3)按需求设置擦拭时间、擦拭负荷和擦拭速度；
(4)将擦拭纱布球用所需的溶剂浸渍；
(5)开启HunterLab的ColorFlex EZ并开始测试；
(6)测试在测试之后面板的L*a*b值并获得ΔE*。
耐高温试验：
(1)测试在测试之前面板的L*a*b值；
(2)将面板放置在240℃的烘箱内20分钟；
(3)20分钟之后，从烘箱移除面板并冷却至室温；
(4)测试在循环1测试之后面板的L*a*b*值并获得ΔE*1；
(5)将面板放置在240℃的烘箱内并再加热另外20分钟，冷却至室温，测试并获得循环2测试的ΔE*2；
(6)重复步骤5以获得ΔE*3和ΔE*4。
耐湿度，耐碱，耐溶剂和耐高温实验结果如表9所示：
Figure GDA0002480383170000091
表9
从表9可以看出：本发明的无铬钝化液耐湿度、耐碱、耐溶剂和耐高温。
综上所述，本发明的基于树枝状大分子的无铬钝化液，是一种不含铬、具有极高存储稳定性、高固含量和低温成膜性的节能环保型钝化液，解决传统钝化液的相关缺陷和应用限制，尤其是在高温、高湿度、高盐度、长距离等运输过程中的稳定性问题，进一步满足现代金属防腐蚀行业的生产要求，同时符合成本节约、经济环保的发展理念。
本技术领域中的普通技术人员应当认识到，以上的实施例仅是用来说明本发明，而并非用作为对本发明的限定，只要在本发明的实质精神范围内，对以上所述实施例的变化、变型都将落在本发明的权利要求书范围内。

Claims (2)

1.一种基于树枝状大分子的无铬钝化液，其特征在于，包括以下重量百分比含量的组分:
Figure FDA0002480383160000011
余量为水；
所述过渡金属化合物为H2ZrF6、H2TiF6、Zr(Ar)4、Zr-Ac、TiO2、ZrO2、V2O5和Ce(NO3)3中的一种或者几种；
所述树枝状大分子采用聚酰胺-胺型树枝状高分子，结构通式如下所示：
Figure FDA0002480383160000012
所述无铬钝化液不包括含有氨功能团的硅烷和含有铬元素的物质；
所述有且仅含有环氧功能团的硅烷不包括不含有环氧功能团的硅烷；也不包括同时具有环氧功能团和其他功能团的硅烷。
2.根据权利要求1所述的一种基于树枝状大分子的无铬钝化液，其特征在于，所述磷酸和/或磷酸盐为H3PO4、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4、NaH2PO4、(Na)2HPO4、(Na)3PO4、NaNH4HPO4、(Na)2NH4HPO4、Na(NH4)2HPO4和有机磷酸中的一种或者几种。
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