CN106809885B - 一种纳米钴蓝颜料的制备方法 - Google Patents
一种纳米钴蓝颜料的制备方法 Download PDFInfo
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- CN106809885B CN106809885B CN201710018496.9A CN201710018496A CN106809885B CN 106809885 B CN106809885 B CN 106809885B CN 201710018496 A CN201710018496 A CN 201710018496A CN 106809885 B CN106809885 B CN 106809885B
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- Prior art keywords
- cobalt
- aluminium
- salt
- acid
- cobalt blue
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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Abstract
本发明提供了一种纳米钴蓝颜料的制备方法，以钴盐、铝盐、带功能基团有机大分子、pH调节剂、溶剂和助剂为原料，利用带功能基团有机大分子对钴、铝的分子识别及诱导作用进行有机‑无机纳米自组装，再通过共沉淀反应，制备有机‑无机纳米复合沉淀，将沉淀分离、洗涤、煅烧、研磨、分散，得到纳米钴蓝颜料。该制备工艺流程简单、可控，重复性好，成本相对低廉，绿色环保，制备得到的纳米钴蓝颜料颜色鲜艳、着色性好。
Description
技术领域
本发明属于化工颜料技术领域，尤其涉及一种纳米钴蓝颜料的制备方法。
背景技术
钴蓝是金属氧化物混相颜料的一种，其颜色饱和度高，透明度、折射率等性能也较优异，因此可用于喷墨、涂料、陶瓷、塑料的着色，另外其显著优势是化学性质十分稳定，耐候性、耐热性、耐酸碱性都非常优异，在苛求环境也可达到满意的效果，且无毒环保，这些都使其拥有极大的应用空间，尤其是其在超耐久型涂层以及一些特种材料上的应用，拥有无可比拟的优势。
目前常用的制备钴蓝颜料的方法有固相法、液相法、气相法等方法。传统工业生产上制备钴蓝方法多用固相法，将金属盐或金属氧化物通过搅拌等方式使其机械混合，烘干后研磨成细小颗粒，在高温下烧结得到钴蓝颜料，这类方法有一定缺陷，在生产过程中，需要较高煅烧温度增加能耗，得到的最后产物大小不均匀，色泽较暗，化学稳定性较差。
气相法制备钴蓝是在高温下使固态原料通过蒸发为蒸汽或直接使用气态原材料，通过化学反应使得固态原料凝聚成固态颗粒，可得到纳米钴蓝产物，产物粒度小纯度高，但设备成本太过昂贵。
液相法制备钴蓝是通过使物料在液相时混合均匀，反应充分后再经过煅烧得到产物，产物粒度较小且纯度高，且煅烧温度要比固相法容易控制，但目前的缺点是成本比较高，工业规模化难推广。常见的液相法包括沉淀法、溶胶凝胶法、溶剂蒸发法、微乳液法、水热法等。中国专利CN105199435报道利用NaOH为沉淀剂，添加无机粘土矿物为填料，通过沉淀法得到杂化颜料前驱体，煅烧得到钴蓝颜料。Kurajica等以仲丁醇铝、仲丁醇、乙酰乙酸乙酯、硝酸钴为原料，通过溶胶-凝胶法制备前驱体，经过2天凝胶干燥后700-900℃煅烧得到钴蓝晶体(Materials Chemistry and Physics.2012,135(2-3):587-593)。中国专利CN101575465报道用溶剂蒸发法制备钴蓝，使用氮气喷枪使金属盐溶液分散在液氮中，冷冻干燥使溶质析出，煅烧后得到鲜亮的纳米级钴蓝粉体。中国专利CN102241528报道以硝酸钴、硝酸铝为原料，加入改性剂，在250℃、30Mpa条件下利用水热合成法，直接得到10-15nm疏水钴蓝纳米颗粒。从上面实例可以看出，通过液相法可以得到较为均匀、鲜艳的钴蓝颜料，但多用于实验室制备，在推广至大范围工业生产上仍有一定困难。
发明内容
为解决上述问题，本发明提供了一种粒径可控的纳米钴蓝颜料的制备方法，该制备工艺流程简单、可控，重复性好，成本相对低廉，绿色环保，制备得到的纳米钴蓝颜料颜色鲜艳、着色性好。
本发明的目的是通过以下技术方案实现的：
一种纳米钴蓝颜料的制备方法，包括如下步骤：1)、钴蓝前驱体的制备：以钴盐、铝盐、带功能基团有机大分子、pH调节剂、溶剂和助剂为原料，带功能基团有机大分子上的功能基团通过络合、配位、静电等作用与钴离子、铝离子结合，使有机大分子官能团位点表面的钴、铝离子浓度大幅度升高，利用带功能基团有机大分子作为沉淀剂，通过共沉淀反应，快速成核形成钴蓝颜料前驱体，并利用带功能基团有机大分子的诱导作用(静电、结构及立体化学匹配)及空间位阻作用对晶体生长进行调控和限制，有机-无机纳米自组装制备有机-无机纳米复合沉淀，将沉淀分离、洗涤后制得钴蓝前驱体；2)将制得的钴蓝前驱体经煅烧、研磨、分散，得到原始粒径小于100nm的纳米钴蓝颜料；
其中钴盐、铝盐的摩尔投料比为3:1-1:3，钴盐用量占原料总重的1-20wt％，铝盐用量占原料总重的1-20wt％，带功能基团有机大分子用量占原料总重的1-15wt％，助剂用量占原材料总量的0-20wt％，溶剂用量占原料总重的40-96.9wt％，pH调节剂用量占原料总重的0.1-5wt％；
所述带功能基团有机大分子为分子量为1000-10000的壳聚糖或聚乳酸。
进一步地，上述钴蓝前驱体的制备方法包括以下步骤：a)向带功能基团有机大分子、助剂和溶剂的混合液中搅拌加入钴盐、铝盐，使铝盐、钴盐溶解；b)之后加入pH调节剂，调节溶液pH在1-14，在5-180℃搅拌0.1-100小时得到产物悬浮液；c)将产物悬浮液离心分离，并洗涤沉淀物，制得钴蓝前驱体。
进一步地，钴盐、铝盐摩尔投料比为2:1-1:2。
进一步地，所述钴盐选自无机钴盐、碱式钴盐、酸式钴盐、有机钴盐、螯合钴盐中的1至3种。优选地，所述钴盐选自硝酸钴、亚硝酸钴、硫酸钴、碱式硫酸钴、酸式硫酸钴、氯化钴、醋酸钴、甲酸钴、丙二醇钴、异丙醇钴、赖氨酸钴、甘氨酸钴、丙氨酸钴、亮氨酸钴、六氨合钴酸钾、六氨合钴酸钠、乙二酸四乙酸螯合钴、环烷酸钴、异辛酸钴中的1至3种。
进一步地，所述铝盐选自无机铝盐、碱式铝盐、酸式铝盐、有机铝盐、螯合铝盐中的1至3种。优选地，所述铝盐选自硝酸铝、亚硝酸铝、硫酸铝、碱式硫酸铝、酸式硫酸铝、氯化铝、醋酸铝、甲酸铝、丙二醇铝、异丙醇铝、赖氨酸铝、甘氨酸铝、丙氨酸铝、亮氨酸铝、铝氨酸钾、乙二酸四乙酸螯合铝、环烷酸铝、异辛酸铝中的1至3种。
进一步地，所述助剂选自共沉淀剂、分散剂、消泡剂的一种或几种。其中，所述共沉淀剂是向液相中加入的试剂，与被沉淀物具有弱相互作用(如静电作用、氢键作用、正负电荷作用等)，能与沉淀剂协同作用使沉淀产生，优先选自8-羟基喹啉、乙二酸四乙酸二钠、抗坏血酸钠、柠檬酸钠、聚丙烯酰胺、聚合氯化铝、草酸、氨基酸的一种或几种。
所述分散剂是在分子内同时具有亲油性和亲水性两种相反性质的界面活性剂，可采用油墨、涂料、胶黏剂生产中常规分散剂。
所述消泡剂可采用颜料、油墨、涂料、胶黏剂生产中常规消泡剂。
进一步地，所述溶剂为水，或水和亲水性有机溶剂的混合溶剂。优选地，所述亲水性有机溶剂选自醇、吡咯烷酮、醇醚、醇醚酯中的1-2种。更优选地，所述亲水性有机溶剂选自乙醇、异丙醇、1，3-丙二醇、乙二醇、丙三醇、季戊四醇、N-甲基吡咯烷酮、聚乙烯吡咯烷酮、乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、丙二醇乙醚醋酸酯、丙二醇丁醚醋酸酯、乙二醇丁醚醋酸酯的1-2种。
进一步地，所述pH调节剂选自可溶于水的无机酸性化合物、有机酸性化合物、无机碱性化合物、有机碱性化合物中的1-3种。优选地，所述pH调节剂选自硫酸、盐酸、硝酸、醋酸、草酸、丁二酸、苹果酸、柠檬酸、氢氧化钠、氢氧化钾、氨水、尿素、碳酸钠、碳酸钾、醋酸钠、醋酸钾、草酸钾、草酸钠、二乙胺、三乙胺、二乙醇胺、三乙醇胺、氨基酸、六次甲基四胺、1-氨基-2-丙醇、三乙烯四胺、四乙烯五胺、甲基-氨基乙基咪唑、四甲基咪唑、吡啶、苯丙醇胺中的1-3种。
进一步地，煅烧温度为500-1500℃，煅烧时间为0.5-24小时。
本发明制备得到的纳米钴蓝颜料，可作为着色颜料应用。
本发明制备得到的纳米钴蓝颜料，可在油墨、涂层材料、塑料、陶瓷、搪瓷、玻璃、美术颜料、装饰领域应用。
本发明的有益效果在于：(1)利用带功能基团有机大分子上的功能基团，通过络合、配位、静电等作用与钴离子、铝离子结合，使有机大分子官能团位点表面的钴、铝离子浓度大幅度升高，通过共沉淀反应，快速成核形成钴蓝颜料前驱体，利用带功能基团有机大分子的诱导作用(静电、结构及立体化学匹配)及空间位阻作用对晶体生长进行调控和限制，有机-无机纳米自组装制备原始粒径小于100nm的纳米钴蓝颜料；
(2)在钴蓝前驱体的制备过程中加入带功能基团有机大分子，可以增加钴蓝颜料的孔隙率，使之易于研磨、粉碎、分散；
(3)通过控制加入带功能基团有机大分子种类及用量、钴/铝摩尔比，可以获得粒径可控、颜色鲜亮，着色力较好的不同色彩的钴蓝颜料，应用前景广阔；
(4)本发明提供的制备方法工艺简单、可控，重复性好，能耗小，成本相对低廉，绿色环保，工业上容易实现，有利于规模化生产。
附图说明
图1为本发明实施例4制备的钴蓝颜料红外光谱(FTIR)图，图中显示钴蓝颜料在557cm-1和645cm-1的特征吸收峰。
图2是本发明实施例4制备的钴蓝颜料X射线衍射分析(XRD)图，图中显示样品为钴蓝(CoAl2O4)结构。
图3是本发明实施例4制备的钴蓝颜料扫描电镜(SEM)照片，图中显示钴蓝晶体颗粒原始粒径为30-40nm。
图4是本发明实施例4制备的钴蓝粒径分布图，通过动态光散射(DLS)测定，平均粒径为282.7nm，峰值在275.3nm左右，分布范围较窄。
具体实施方式
下面结合具体实施例对本发明的构思和原理作进一步解释说明。
实施例1
在一个500毫升四颈烧瓶中，称取10克聚乙二醇、8克羧甲基纤维素、1克消泡剂，将其溶于80克去离子水、20克乙醇的混合溶剂中，超声分散10min，使体系分散均匀。再将4克硝酸钴、2克硝酸铝加入分散液中，在1500转/分速度下搅拌，常温搅拌2小时，加入40克10wt％草酸水溶液、20克1wt％六亚甲基四胺水溶液、15克1wt％氢氧化钠水溶液，将体系的pH值调节到3-5，缓慢沉淀，恒温搅拌24小时，取出产物，在3000转/分速度下离心分离10分钟，1:1水/乙醇混合溶液洗涤，至滤出液用pH试纸检验结果为中性，将沉淀放置在室温干燥，得到钴蓝前驱体。将钴蓝前驱体放在马弗炉中煅烧，以50℃/min的速度升温至1500℃，保温12h，得到钴蓝粉体。然后进行研磨、分散，制备出平均粒径440.6nm左右的纳米钴蓝颜料，颜料颜色偏绿。
实施例2
在一个500毫升四颈烧瓶中，称取8克聚甲基丙烯酸、2克壳聚糖、2.6克分散剂，将其溶于100克去离子水中，超声分散10min，使体系分散均匀。再将2克醋酸钴、2.4g碳酸钴、7克醋酸铝、8g碳酸铝加入上述分散液中，在500转/分速度下，60℃搅拌12小时，加入8克10wt％醋酸水溶液、20克1wt％碳酸钠水溶液、40克10wt％氨水溶液，将体系的pH值调节到4-6，缓慢沉淀，60℃搅拌12小时，取出产物，真空抽滤，用水反复洗涤，至滤出液用pH试纸检验结果为中性，将沉淀放置在60℃烘箱中烘干，得到钴蓝前驱体。将钴蓝前驱体放在马弗炉中煅烧，以30℃/min的速度升温至800℃，保温50小时，得到钴蓝粉体。然后进行研磨、分散，制备出平均粒径396.3nm左右的纳米钴蓝颜料，颜料颜色偏绿。
实施例3
在一个500毫升四颈烧瓶中，称取10克聚乙烯醇、9克聚乙醇胺、0.1克消泡剂，将其溶于80克去离子水、10克乙醇的混合溶剂中，超声分散10min，使体系分散均匀。再将10克乙二胺四乙酸二钴、12.2克硫酸钴、18.7克异丙醇铝加入分散液中，在3000转/分速度下搅拌，常温搅拌半小时，加入10克1wt％草酸钠水溶液、40克10wt％氢氧化钠水溶液，将体系的pH值调节到5-7，缓慢沉淀，在90℃条件下搅拌2小时，取出产物，滤网过滤，用水洗涤，至滤出液用pH试纸检验结果为中性，将沉淀放置在180℃烘箱中烘干，得到钴蓝前驱体。将钴蓝前驱体放在回转窑中煅烧，以20℃/min的速度升温至1200℃，保温5小时，得到钴蓝粉体。然后进行研磨、分散，制备出平均粒径445.5nm左右的纳米钴蓝颜料，颜料颜色偏紫。
实施例4
在一个500毫升四颈烧瓶中，称取10克羟甲基纤维素、5.3克聚乙烯吡咯烷酮、10克聚乳酸、0.2克8-羟基喹啉，将其溶于60克去离子水、30克丙二醇甲醚醋酸酯、10克丙二醇的混合溶剂中，超声分散50min，使体系分散均匀。再将2克氯化钴、4.5克三氯化铝加入分散液中，在2000转/分速度下，80℃搅拌5小时，加入18克10wt％苹果酸水溶液、20克1wt％赖氨酸溶液、30克10wt％氢氧化钠水溶液，将体系的pH值调节到8-10，缓慢沉淀，恒温搅拌24小时，取出产物，在5000转/分速度下离心分离5分钟，用乙醇洗涤，至滤出液为中性，将沉淀放置在100℃烘箱真空干燥，得到钴蓝前驱体。将钴蓝前驱体放在马弗炉中煅烧，以10℃/min的速度升温至700℃，保温50h，得到钴蓝粉体。然后进行研磨、分散，制备出平均粒径282.7nm左右的纳米钴蓝颜料，颜料颜色为鲜艳的蓝色。
对制备出的该纳米钴蓝颜料进行谱图表征，得到如图1-4所示结果，如图1中所示，557cm-1和645cm-1的红外特征吸收峰为钴蓝颜料的特征吸收峰，图2显示钴蓝颜料样品为CoAl2O4结构，图3显示钴蓝晶体颗粒原始粒径为30-40nm，图4的动态光散射测定钴蓝颜料样品平均粒径为282.7nm，峰值在275.3nm左右，分布范围较窄，存在一定的团聚现象。
实施例5
在一个500毫升四颈烧瓶中，称取4克聚丙二醇、4克聚乙烯醇，将其溶于80克去离子水、20克乙醇的混合溶剂中，超声分散10min，使体系分散均匀。再将20克硫酸钴、11.7克硫酸铝加入分散液中，在1500转/分速度下搅拌，常温搅拌2小时，加入10克10％四甲基咪唑溶液、20克1％精氨酸溶液、30克1％氢氧化钠水溶液、0.3克聚丙烯酰胺，将体系的pH值调节到5-7，缓慢沉淀，在40℃恒温搅拌24小时，取出产物，布袋过滤，用水反复洗涤，至滤出液用pH试纸检验结果为中性，将沉淀放置在真空烘箱中常温干燥，得到钴蓝前驱体。将钴蓝前驱体放在回转窑中煅烧，以40℃/min的速度升温至1000℃，保温12h，得到钴蓝粉体。然后进行研磨、分散，制备出平均粒径361.7nm左右的纳米钴蓝颜料，颜料颜色为蓝色。
Claims (13)
1.一种纳米钴蓝颜料的制备方法，包括如下步骤：1)钴蓝前驱体的制备：以钴盐、铝盐、带功能基团有机大分子、pH调节剂、溶剂和助剂为原料，通过共沉淀反应，将沉淀分离、洗涤后制得钴蓝前驱体；2)将制得的钴蓝前驱体经煅烧、研磨、分散，得到原始粒径小于100nm的纳米钴蓝颜料；
其中钴盐、铝盐的摩尔投料比为3:1-1:3，钴盐用量占原料总重的1-20wt％，铝盐用量占原料总重的1-20wt％，带功能基团有机大分子用量占原料总重的1-15wt％，助剂用量占原材料总量的0-20wt％，溶剂用量占原料总重的40-96.9wt％，pH调节剂用量占原料总重的0.1-5wt％；
所述带功能基团有机大分子为同时带有氨基和羟基的分子量为1000-10000的壳聚糖；
所述助剂选自共沉淀剂、分散剂、消泡剂的一种或几种。
2.根据权利要求1所述的纳米钴蓝颜料的制备方法，其特征在于，步骤1)钴蓝前驱体的制备方法包括以下步骤：
a)向带功能基团有机大分子、助剂和溶剂的混合液中搅拌加入钴盐、铝盐，使铝盐、钴盐溶解；b)之后加入pH调节剂，调节溶液pH在1-14，在5-180℃搅拌0.1-100小时得到产物悬浮液；c)将产物悬浮液离心分离，并洗涤沉淀物，制得钴蓝前驱体。
3.根据权利要求1或2所述的纳米钴蓝颜料的制备方法，其特征在于，钴盐、铝盐摩尔投料比为2:1-1:2。
4.根据权利要求1或2所述的纳米钴蓝颜料的制备方法，其特征在于，所述钴盐选自无机钴盐、碱式钴盐、酸式钴盐、有机钴盐、螯合钴盐中的1至3种；所述铝盐选自无机铝盐、碱式铝盐、酸式铝盐、有机铝盐、螯合铝盐中的1至3种。
5.根据权利要求4所述的纳米钴蓝颜料的制备方法，其特征在于，所述钴盐选自硝酸钴、亚硝酸钴、硫酸钴、碱式硫酸钴、酸式硫酸钴、氯化钴、醋酸钴、甲酸钴、丙二醇钴、异丙醇钴、赖氨酸钴、甘氨酸钴、丙氨酸钴、亮氨酸钴、六氨合钴酸钾、六氨合钴酸钠、乙二酸四乙酸螯合钴、环烷酸钴、异辛酸钴中的1至3种。
6.根据权利要求4所述的纳米钴蓝颜料的制备方法，其特征在于，所述铝盐选自硝酸铝、亚硝酸铝、硫酸铝、碱式硫酸铝、酸式硫酸铝、氯化铝、醋酸铝、甲酸铝、丙二醇铝、异丙醇铝、赖氨酸铝、甘氨酸铝、丙氨酸铝、亮氨酸铝、铝氨酸钾、乙二酸四乙酸螯合铝、环烷酸铝、异辛酸铝中的1至3种。
7.根据权利要求1所述的纳米钴蓝颜料的制备方法，其特征在于，所述共沉淀剂选自8-羟基喹啉、乙二酸四乙酸二钠、抗坏血酸钠、柠檬酸钠、聚丙烯酰胺、聚合氯化铝、草酸、氨基酸的一种或几种。
8.根据权利要求1或2所述的纳米钴蓝颜料的制备方法，其特征在于，所述溶剂为水，或水和亲水性有机溶剂的混合溶剂。
9.根据权利要求8所述的纳米钴蓝颜料的制备方法，其特征在于，所述亲水性有机溶剂选自醇、吡咯烷酮、醇醚、醇醚酯中的1至2种。
10.根据权利要求9所述的纳米钴蓝颜料的制备方法，其特征在于，所述亲水性有机溶剂选自乙醇、异丙醇、1，3-丙二醇、乙二醇、丙三醇、季戊四醇、N-甲基吡咯烷酮、聚乙烯吡咯烷酮、乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、丙二醇乙醚醋酸酯、丙二醇丁醚醋酸酯、乙二醇丁醚醋酸酯的1至2种。
11.根据权利要求1或2所述的纳米钴蓝颜料的制备方法，其特征在于，所述pH调节剂选自可溶于水的无机酸性化合物、有机酸性化合物、无机碱性化合物、有机碱性化合物中的1至3种。
12.根据权利要求11所述的纳米钴蓝颜料的制备方法，其特征在于，所述pH调节剂选自硫酸、盐酸、硝酸、醋酸、草酸、丁二酸、苹果酸、柠檬酸、氢氧化钠、氢氧化钾、氨水、尿素、碳酸钠、碳酸钾、醋酸钠、醋酸钾、草酸钾、草酸钠、二乙胺、三乙胺、二乙醇胺、三乙醇胺、氨基酸、六次甲基四胺、1-氨基-2-丙醇、三乙烯四胺、四乙烯五胺、甲基-氨基乙基咪唑、四甲基咪唑、吡啶、苯丙醇胺中的1至3种。
13.根据权利要求1所述的纳米钴蓝颜料的制备方法，其特征在于，煅烧温度为500-1500℃，煅烧时间为0.5-24小时。
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