CN109370354B - 一种水性丙烯酸酯改性乳液涂料的制备方法 - Google Patents
一种水性丙烯酸酯改性乳液涂料的制备方法 Download PDFInfo
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Abstract
本发明公开一种水性丙烯酸酯改性乳液涂料的制备方法，其特征在于，包括如下步骤：将复合纳米丙烯酸酯乳液、2去离子水、钛白粉、短链改性的CaCO3/XH‑9纳米材料、乙二醇、三乙基己基磷酸混合，高速搅拌分散10min，混合均匀，即得到水性丙烯酸酯改性乳液涂料。
Description
技术领域
本发明涉及一种耐水性丙烯酸酯改性乳液涂料的制备方法。
背景技术
聚丙烯酸酯乳液以其优异的性能在油漆、涂料、胶粘剂、织物整理剂、皮革涂饰及油墨等行业得到十分广泛的应用。但是，大部分聚丙烯酸酯乳液为普通乳液，其粒径较大，多数是粒径在0.1～1μm的白色不透明低粘度胶体分散液。
由于纳米材料的表面效应、小尺寸效应、量子尺寸效应等性质，所以纳米聚合物粒子具有纳米粒子具有高表面能量和低的成膜温度，可以在同样的成膜温度下获得更高玻璃化温度的漆膜，从而具有更好的耐候性和耐污染性能。一般聚合物乳液的胶粒直径大于100nm，而兴起于80年代初的微乳液聚合可直接制备粒径在10-50nm的纳米级聚合物胶粒，这类纳米胶乳可有效的提高乳液的成膜性能、膜致密度、光洁度等性质。随着微乳液聚合制备技术的完善，用该种纳米聚合物胶乳来制备水性涂料已经成为可能。
发明内容
本发明公开了一种水性丙烯酸酯改性乳液涂料的制备方法，制备的丙烯酸酯乳液具有优异的物理性能。
一种水性丙烯酸酯改性乳液涂料的制备方法， 80份复合纳米丙烯酸酯乳液、25份去离子水、20份钛白粉、10份短链改性的CaCO3/ XH-9滤纳米材料、5份乙二醇、1份三乙基己基磷酸，高速搅拌分散10min，混合均匀，即得到水性丙烯酸酯改性乳液涂料。
复合纳米丙烯酸酯乳液制备方法如下：
在乳化釜内加入0.30份聚氧乙烯辛基苯酚醚-10、十二烷基硫酸钠0.3份、过硫酸铵0.15份，然后加入去离子水20份，开动搅拌使之全部溶解，在预乳化釜内依次加入丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸，搅拌乳化15min得到单体的预乳化液，
在装有搅拌、回流冷凝管的聚合釜内依次加入碳酸氢钠0.2份和去离子水30份，开动搅拌使之溶解并置于50℃水浴中，
然后装好恒压滴液漏斗，称取制好的单体预乳化液5份并加入到聚合釜内，加入0.3份改性纳米羟基磷灰石材料，称取过硫酸铵0.3份并溶于5份水中，缓慢加入到聚合釜内，同时调整水浴温度为82℃缓慢升温，待温度升为82℃后，缓慢滴加单体预乳化液，滴完后取5份水冲洗预乳化釜并滴加入聚合釜内，用氨水调 pH 值为8，得到复合纳米丙烯酸酯乳液。
改性纳米羟基磷灰石材料制备方法如下：20份直径40nm纳米羟基磷灰石粉末分散到200份水中，用盐酸调节pH到5，然后将5份环氧氯丙烷滴加到上述溶液中，25℃反应6h，过滤除去未参与反应的环氧氯丙烷，得到环氧氯丙烷改性纳米羟基磷灰石；将2份的4wt％超支化聚酰胺胺酸性溶液加入到20份的环氧氯丙烷改性纳米羟基磷灰石中，然后加入200份4％NaOH溶液，40℃搅拌2h，然后将纳米羟基磷灰石抽滤，水洗至中性放入烘箱内烘干，得到改性超支化聚酰胺纳米羟基磷灰石。
所述的短链改性的CaCO3/ XH-9滤纳米材料制备方法如下：
步骤1、将0.2kg干燥的CaCO3和0.5kg XH-9纳米材料,在500℃下活化,分散到的10L乙醇中,球磨之后将复合物和乙醇的混合物转移到装有3L氨水的的三口烧瓶中,将温度升高到60℃,加热1h,然后加入的1L的TEOS，继续搅拌，将得到的浆料过滤,用乙醇洗涤,最后得到短链改性的CaCO3/ XH-9滤纳米材料。
有益效果：纳米羟基磷灰石表面羰基上的氧原子可以与单体预乳化液的羧基或羟基结合形成氢键，并在微球表面形成一个聚合物层，降低纳米物质团聚现象，增强了乳液流变性，经过改性超支化聚酰胺后的纳米羟基磷灰石具有小尺寸效应,可以填充到乳液覆膜,有效地增强乳液涂层的物理隔绝作用。此外, 纳米羟基磷灰石表面原位聚合生成聚酰胺,添加到乳液中,使涂层的机械性能提高,在其孔道内的超支化聚酰胺延伸到孔口处与基体胶乳产生新键,增加了体系的交联密度，进而使涂膜的拉伸强度和断裂伸长率成倍增加，短链改性的CaCO3/ XH-9滤纳米材料在成膜时可以水解缩合，形成的网状结构，提高了膜的交联度，并且具有特定微观结构的粗糙度，获得显著的静态疏水性，从而提高了膜的耐水性、硬度等性能以及存储期。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1
一种水性丙烯酸酯改性乳液涂料的制备方法， 80份复合纳米丙烯酸酯乳液、25份去离子水、20份钛白粉、10份短链改性的CaCO3/ XH-9纳米材料、5份乙二醇、1份三乙基己基磷酸，高速搅拌分散10min，混合均匀，即得到水性丙烯酸酯改性乳液涂料。
复合纳米丙烯酸酯乳液制备方法如下：
在乳化釜内加入0.30份聚氧乙烯辛基苯酚醚-10、十二烷基硫酸钠0.3份、过硫酸铵0.15份，然后加入去离子水20份，开动搅拌使之全部溶解，在预乳化釜内依次加入丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸，搅拌乳化15min得到单体的预乳化液，
在装有搅拌、回流冷凝管的聚合釜内依次加入碳酸氢钠0.2份和去离子水30份，开动搅拌使之溶解并置于50℃水浴中，
然后装好恒压滴液漏斗，称取制好的单体预乳化液5份并加入到聚合釜内，加入0.3份改性纳米羟基磷灰石材料，称取过硫酸铵0.3份并溶于5份水中，缓慢加入到聚合釜内，同时调整水浴温度为82℃缓慢升温，待温度升为82℃后，缓慢滴加单体预乳化液，滴完后取5份水冲洗预乳化釜并滴加入聚合釜内，用氨水调 pH 值为8，得到复合纳米丙烯酸酯乳液。
改性纳米羟基磷灰石材料制备方法如下：20份直径40nm纳米羟基磷灰石粉末分散到200份水中，用盐酸调节pH到5，然后将5份环氧氯丙烷滴加到上述溶液中，25℃反应6h，过滤除去未参与反应的环氧氯丙烷，得到环氧氯丙烷改性纳米羟基磷灰石；将2份的4wt％超支化聚酰胺胺酸性溶液加入到20份的环氧氯丙烷改性纳米羟基磷灰石中，然后加入200份4％NaOH溶液，40℃搅拌2h，然后将纳米羟基磷灰石抽滤，水洗至中性放入烘箱内烘干，得到改性超支化聚酰胺纳米羟基磷灰石。
所述的短链改性的CaCO3/ XH-9滤纳米材料制备方法如下：
步骤1、将0.2kg干燥的CaCO3和0.5kg XH-9纳米材料,在500℃下活化,分散到的10L乙醇中,球磨之后将复合物和乙醇的混合物转移到装有3L氨水的的三口烧瓶中,将温度升高到60℃,加热1h,然后加入的1L的TEOS，继续搅拌，将得到的浆料过滤,用乙醇洗涤,最后得到短链改性的CaCO3/ XH-9滤纳米材料。
实施例2
与实施例1不同在于，
80份复合纳米丙烯酸酯乳液、15份去离子水、10份钛白粉、10份短链改性的CaCO3/XH-9滤纳米材料、5份乙二醇、1份三乙基己基磷酸，高速搅拌分散10min，混合均匀，即得到水性丙烯酸酯改性乳液涂料。
实施例3
与实施例1不同在于，
100份复合纳米丙烯酸酯乳液、20份去离子水、25份钛白粉、10份短链改性的CaCO3/ XH-9纳米材料、5份乙二醇、1份三乙基己基磷酸，高速搅拌分散10min，混合均匀，即得到水性丙烯酸酯改性乳液涂料。
对比例1
与实施例1不同在于，
不加入改性纳米羟基磷灰石材料。
对比例2
与实施例1不同在于，
纳米羟基磷灰石粉末不经过改性处理，为普通羟基磷灰石材料。
对比例3
与实施例1不同在于，
改性纳米羟基磷灰石材料为环氧氯丙烷改性纳米羟基磷灰石而不是改性超支化聚酰胺纳米羟基磷灰石。
对比例4
与实施例1不同在于，
不加入短链改性的CaCO3/ XH-9纳米材料。
对比例5
与实施例1不同在于，
普通CaCO3替代短链改性的CaCO3/ XH-9纳米材料。
下表中各实施例和对比例乳液成膜性能测试数据
| 水接触角 | 耐水性 | |
| 实施例1 | 131° | 无变化 |
| 实施例2 | 117° | 无变化 |
| 实施例3 | 121° | 无变化 |
| 对比例1 | 74° | 失光、略微起泡 |
| 对比例2 | 67° | 失光、略微起泡 |
| 对比例3 | 83° | 失光 |
| 对比例4 | 62° | 失光、略微起泡 |
| 对比例5 | 60° | 起泡、起皱 |
GB/T 1733-1993 漆膜耐水性测定法。
Claims (1)
1.一种水性丙烯酸酯改性乳液涂料的制备方法，其特征在于，将 80份复合纳米丙烯酸酯乳液、25份去离子水、20份钛白粉、10份短链改性的CaCO3/ XH-9纳米材料、5份乙二醇和1份三乙基己基磷酸，高速搅拌分散10min，混合均匀，即得到水性丙烯酸酯改性乳液涂料；
所述的复合纳米丙烯酸酯乳液制备方法如下：
在乳化釜内加入0.30份聚氧乙烯辛基苯酚醚-10、十二烷基硫酸钠0.3份、过硫酸铵0.15份，然后加入去离子水20份，开动搅拌使之全部溶解，在预乳化釜内依次加入丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸，搅拌乳化15min得到单体的预乳化液，
在装有搅拌、回流冷凝管的聚合釜内依次加入碳酸氢钠0.2份和去离子水30份，开动搅拌使之溶解并置于50℃水浴中，
然后装好恒压滴液漏斗，称取制好的单体预乳化液5份并加入到聚合釜内，加入0.3份改性超支化聚酰胺纳米羟基磷灰石，称取过硫酸铵0.3份并溶于5份水中，缓慢加入到聚合釜内，同时调整水浴温度为82℃缓慢升温，待温度升为82℃后，缓慢滴加单体预乳化液，滴完后取5份水冲洗预乳化釜并滴加入聚合釜内，用氨水调 pH 值为8，得到复合纳米丙烯酸酯乳液；
所述的改性超支化聚酰胺纳米羟基磷灰石制备方法如下：20份直径40nm纳米羟基磷灰石粉末分散到200份水中，用盐酸调节pH到5，然后将5份环氧氯丙烷滴加到上述溶液中，25℃反应6h，过滤除去未参与反应的环氧氯丙烷，得到环氧氯丙烷改性纳米羟基磷灰石；将2份的4wt％超支化聚酰胺酸性溶液加入到20份的环氧氯丙烷改性纳米羟基磷灰石中，然后加入200份4％NaOH溶液，40℃搅拌2h，然后将纳米羟基磷灰石抽滤，水洗至中性放入烘箱内烘干，得到改性超支化聚酰胺纳米羟基磷灰石；
所述的短链改性的CaCO3/ XH-9纳米材料制备方法如下：
步骤1、将0.2kg干燥的CaCO3和0.5kg XH-9纳米材料,在500℃下活化,分散到的10L乙醇中,球磨之后将复合物和乙醇的混合物转移到装有3L氨水的的三口烧瓶中,将温度升高到60℃,加热1h,然后加入的1L的TEOS，继续搅拌，将得到的浆料过滤,用乙醇洗涤,最后得到短链改性的CaCO3/ XH-9纳米材料。
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