CN105670485A - 一种纳米Al2O3改性聚氨酯树脂涂料及其制备方法 - Google Patents
一种纳米Al2O3改性聚氨酯树脂涂料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种纳米Al2O3改性的聚氨酯树脂涂料，所述涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、己二酸4-8份、醇酸树脂1-5份、环氧树脂2-4份、丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份、醋酸乙酯5-10份，磷酸0.5-1份，去离子水10-30份；以及纳米Al2O3浆料2-8份，本发明主要是在制备聚氨酯树脂涂料过程中添加改性的Al2O3纳米粉，实现采用硬脂酸钠对Al2O3纳米粉进行表面亲油化处理，进而形成有效的防腐蚀复合涂层，具有耐油性、耐海水、耐磨损和耐冲击等优良性能。
Description
技术领域
本发明涉及一种纳米Al2O3改性聚氨酯树脂涂料及其制备方法，属于材料涂层涂装技术领域。
背景技术
聚氨酯树脂(PolyurethaneResin)作为一种具有高强度、抗撕裂、耐磨等特性的高分子材料，在日常生活、工农业生产、医学等领域广泛应用。此外聚氨酯还可制成乳液、磁性材料等。聚氨酯树脂涂料具有明显优于其他涂料的特点，聚氨酯涂料的优点是漆膜耐磨性强，装饰性能好，涂膜附着力强，涂膜弹性高，涂膜耐腐蚀性能强，烘干温度范围宽，耐高温低温性能突出，绝缘性能优异，花色品种多，但其也有明显的缺点，例如保光保色性差，树脂乳液稳定性差，容易损坏涂层，施工要求高。
纳米微粒凭借其独特的小尺寸效应和表面效应，与聚氨酯树脂发生物理或化学结合的可能性大，能够增强粒子与基体的界面结合，从而提高聚氨酯树脂涂料产品的悬浮稳定性、流变性、附着力、光洁度、抗老化性和涂膜的表面硬度等。纳米微粒改性聚氨酯树脂的制备与性能评价，成为防腐涂料领域的研究热点之一。纳米Al2O3是亲水性的惰性粉体，并且粒子微细化增大了表面能，增大了纳米微粒附聚生成二次结构的可能性，进而增大了纳米Al2O3在聚氨酯树脂涂料中分散难度。因此要想把纳米Al2O3纳米粉应用到聚氨酯树脂涂料上，有必要对其进行表面亲油化改性处理，削弱或者消除团聚现象，确保其在有机介质中能够分散良好。
发明内容
本发明的目的在于提供一种纳米Al2O3改性的聚氨酯树脂涂料，主要是在制备聚氨酯树脂涂料过程中添加改性的Al2O3纳米粉，实现采用硬脂酸钠对Al2O3纳米粉进行表面亲油化处理，进而制备Al2O3改性耐腐蚀聚氨酯树脂涂料，本发明选择成本低廉的硬脂酸钠作为表面改性材料，SASS分子中具有类似偶联剂的亲水和疏水基团，实验验证发现，硬脂酸钠参与对Al2O3颗粒的表面改性反应，两者之间既发生化学吸附，又发生物理吸附，对Al2O3粉体具有良好的包覆作用，使得聚氨酯树脂涂料形成有效的防腐蚀复合涂层，具有耐油性、耐海水、耐磨损和耐冲击等优良性能。
本发明的技术方案为：
纳米Al2O3改性的聚氨酯树脂涂料的制备方法，包括如下步骤：
1)将定量的硬脂酸钠溶解于适量的乙醇和丙酮混合液中，配成初级混合溶液；
2)称取Al2O3纳米粉20重量份，添加到三口容器中，向三口容器内加入适量200-300重量份的上述硬脂酸钠混合溶液，形成悬浮溶液；
3)将该悬浮液在磁力搅拌下于50-60℃温度下加热1-2h，然后进行抽滤操作，所得产物于50℃干燥18-24h，得到改性的Al2O3纳米粉；
4)称取0.5-1重量份的改性Al2O3纳米粉，加入到20-40份的含有分散剂的二甲苯、乙二醇和丁醇混合溶液中，在直流搅拌机3000r/min速度下搅拌分散45min得到纳米Al2O3浆料；
5)按制备聚氨酯树脂涂料配比要求进行配置，具体是将甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、醋酸乙酯5-10份加入反应釜，使用搅拌机进行充分搅拌，升温至90-100℃，缓慢加入己二酸4-8份；继续加入醇酸树脂1-5份，环氧树脂2-4份，充分搅拌1h以上，然后加入扩链剂、活化剂以及催化剂：按照均分四次间隔30min加入丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份，磷酸0.5-1份；最后加入纳米Al2O3浆料2-8份和适量去离子水置于40℃温度下采用直流搅拌机以3000r/min速度下搅拌分散60min而成。
与现有技术相比，添加硬脂酸处理后的纳米Al2O3的聚氨酯树脂涂料，其附着力要明显优于添加未改性纳米微粒的聚氨酯树脂涂料，经过硬脂酸钠包覆处理后，纳米Al2O3与成膜物质的亲和性得以增强，与聚氨酯树脂成膜物质的界面结合力得以提高，同时可以阻止或减轻硬团聚体的形成，容易获得良好的分散性，进而增强了聚氨酯树脂涂料涂层的机械强度，附着力显著提高。此外，由于Al2O3纳米微粒表面吸附了改性剂，在粒子和基料界面间形成一层膜，它能在Al2O3和有机基料的界面间进行适度的应力转移，一定程度上提高了涂膜附着力和柔韧性。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
本发明的纳米Al2O3改性的聚氨酯树脂涂料的制备方法如下，首先将Al2O3纳米粉进行表面改性，方法如下：
1)将一定量的硬脂酸钠(StearicacidSodiumSalt，简称SASS)溶解于乙醇和丙酮混合液中，配成初级混合溶液；
2)称取定量Al2O3纳米粉，添加到三口容器中，向三口容器内加入适量的硬脂酸钠混合溶液，形成悬浮溶液；
3)将该悬浮液在磁力搅拌下，于50-60℃温度下加热一定时间，然后进行抽滤，所得产物于50℃干燥18-24h，得到改性的Al2O3纳米粉；
然后进行工艺条件的优化检测以得出最优的改性结果，制备纳米Al2O3浆料，具体为：
4)通过测定改性指数和沉降指数来优化上述改性工艺条件直至得到最优结果；
5)首先称取定量改性后的Al2O3纳米粉，加入到含有分散剂的二甲苯、乙二醇和丁醇混合溶液中，在直流搅拌机3000r/min速度下搅拌分散45min得到纳米Al2O3浆料；
最后，制备本发明的耐腐蚀聚氨酯树脂涂料，具体为：
6)按制备聚氨酯树脂涂料要求进行配置，具体是将甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、醋酸乙酯加入反应釜，使用搅拌机进行充分搅拌，升温至90-100℃，缓慢加入己二酸；继续加入醇酸树脂，环氧树脂，充分搅拌1h以上，然后加入扩链剂、活化剂以及催化剂：按照均分四次间隔30min加入丙二醇、甲基二乙醇胺、二酯酸二丁基锡和磷酸；最后加入纳米Al2O3浆料和适量去离子水置于40℃温度下采用直流搅拌机以3000r/min速度下搅拌分散60min而成。
上述通过测定改性指数和沉降指数来优化改性工艺条件，主要是针对不同的Al2O3纳米粉设置具体的改性配置参数以求得最优的改性效果，具体步骤如下：
4.1)称取1-1.5g上述改性的Al2O3纳米粉，置于盛有20-30mL工业用水的磨口量筒中，用直流电机搅拌15-30min，以使Al2O3纳米粉充分分散在水介质中，再将该悬浮液于20℃下静置24h，取出漂浮在水面上的纳米Al2O3，烘干称重；
4.2)按下式计算其改性指数，该改性指数＝(样品漂浮部分的质量/样品总质量)X100％；当改性指数大于90％时，说明改性条件最优设置；
之所以以改性指数为指标，是为了考察硬脂酸钠用量、硬脂酸钠浓度、改性温度和改性时间的影响，影响改性效果的因素主要有改性剂类型、改性剂用量、改性剂浓度、改性时间、改性温度、搅拌速度等。经试验验证可知，随着硬脂酸钠用量的增加，改性纳米Al2O3的改性指数先增大后减小。当硬脂酸钠用量为纳米Al2O3的5-6％时，改性指数最大达到90-96％。该结果说明，硬脂酸钠的用量对改性效果影响很大，用量过多或过少均达不到有效的改性效果。当硬脂酸钠用量不足时，对粉体的改性不完全，硬脂酸钠没有很好的包覆十粉体表面，未被改性的粉体不能漂浮十水面而沉淀下来；当改性剂用量过大时，搅拌的均匀性降低，将导致硬脂酸钠分子局部分布的不均匀，单个硬脂酸钠分子可能会联接多个纳米微粒而引起絮凝。
至于反应时间和反应温度，经试验实测可知，反应进行15min后，改性指数约为70％；随着时间的延长，改性指数逐渐上升，改性60min后，改性指数达到90-96％，改性反应基本完成；此后，再增加时间改性指数基本趋于稳定。因此，改性时间应以60min为最佳。
4.3)通过沉降实验衡量改性效果，称取1-1.5g上述改性的Al2O3纳米粉样品，置于带磨口的刻度量筒中，先加少量二甲苯将纳米Al2O3充分润湿后，再加二甲苯至20mL充分振动均匀，室温条件下静置不同时间，记录沉积物的质量，并将其换算成沉降指数；该沉降指数＝(样品沉淀部分的质量/样品总质量)X100％
经试验可知，未经过改性的纳米Al2O3在二甲苯中约4-6h就完全沉降下来，而经过硬脂酸钠包覆改性后，在二甲苯中经过24h仅有1-2％的沉淀，经过48h也只有约2-3％的沉淀。因此，改性后的纳米Al2O3在二甲苯中有较好的分散性能，改性效果较好。
综上所述，通常情况下，最佳改性工艺条件为：硬脂酸钠用量为Al2O3纳米粉质量的5％，改性温度60℃、改性时间60min，该工艺条件下改性指数为90％以上。
由此，根据本发明的一个方面，
本发明的纳米Al2O3改性的聚氨酯树脂涂料的制备方法，包括如下步骤：
1)将1重量份的硬脂酸钠溶解于适量的10-15重量份的乙醇和丙酮混合液中，配成初级混合溶液；
2)称取Al2O3纳米粉20重量份，添加到三口容器中，向三口容器内加入适量200-300重量份的上述硬脂酸钠混合溶液，形成悬浮溶液；
3)将该悬浮液在磁力搅拌下于50-60℃温度下加热1-2h，然后进行抽滤操作，所得产物于50℃干燥18-24h，得到改性的Al2O3纳米粉；
4)称取0.5-1重量份的改性Al2O3纳米粉，加入到20-40份的含有分散剂的二甲苯、乙二醇和丁醇混合溶液中，在直流搅拌机3000r/min速度下搅拌分散45min得到纳米Al2O3浆料；
5)按制备聚氨酯树脂涂料配比要求进行配置，具体是将甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、醋酸乙酯5-10份加入反应釜，使用搅拌机进行充分搅拌，升温至90-100℃，缓慢加入己二酸4-8份；继续加入醇酸树脂1-5份，环氧树脂2-4份，充分搅拌1h以上，然后加入扩链剂、活化剂以及催化剂：按照均分四次间隔30min加入丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份，磷酸0.5-1份；最后加入纳米Al2O3浆料2-8份和适量去离子水置于40℃温度下采用直流搅拌机以3000r/min速度下搅拌分散60min而成。
本发明采用硬脂酸钠对Al2O3纳米粉进行表面亲油化处理，进而制备了Al2O3改性耐腐蚀聚氨酯树脂涂料，本发明选择成本低廉的硬脂酸钠作为表面改性材料，SASS分子中具有类似偶联剂的亲水和疏水基团，实验验证发现，硬脂酸钠已经参与了对Al2O3颗粒的表面改性反应，两者之间既发生化学吸附，又发生物理吸附，对Al2O3粉体具有良好的包覆作用。
尽管上文对本发明的具体实施方式给予了详细描述和说明，但是应该指明的是，我们可以依据本发明的构想对上述实施方式进行各种等效改变和修改，其所产生的功能作用仍未超出说明书所涵盖的精神时，均应在本发明的保护范围之内。例如，重量份可以选择为克或其他重量单位。以上所述，仅为本发明的较佳实施例，并不用以限制本发明，凡是依据本发明的技术实质对以上实施例所作的任何细微修改、等同替换和改进，均应包含在本发明技术方案的保护范围之内。
Claims (2)
1.一种纳米Al2O3改性的聚氨酯树脂涂料，所述涂料由以下原料按照重量配比制成：甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、已二酸4-8份、醇酸树脂1-5份、环氧树脂2-4份、丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份、醋酸乙酯5-10份，磷酸0.5-1份，去离子水10-30份；以及纳米Al2O3浆料2-8份。
2.一种如权利要求1所述的纳米Al2O3改性的聚氨酯树脂涂料的制备方法，包括如下步骤：
1)将定量的硬脂酸钠溶解于适量的乙醇和丙酮混合液中，配成初级混合溶液；
2)称取Al2O3纳米粉20重量份，添加到三口容器中，向三口容器内加入适量200-300重量份的上述硬脂酸钠混合溶液，形成悬浮溶液；
3)将该悬浮液在磁力搅拌下于50-60℃温度下加热1-2h，然后进行抽滤操作，所得产物于50℃干燥18-24h，得到改性的Al2O3纳米粉；
4)称取0.5-1重量份的改性Al2O3纳米粉，加入到20-40重量份的含有分散剂的二甲苯、乙二醇和丁醇混合溶液中，在直流搅拌机3000r/min速度下搅拌分散45min得到纳米Al2O3浆料；
5)按制备聚氨酯树脂涂料配比要求进行配置，具体是将甲苯二异氰酸酯60-80份、二环己基甲烷二异氰酸酯5-10份、六亚甲基二异氰酸酯5-10份、醋酸乙酯5-10份加入反应釜，使用搅拌机进行充分搅拌，升温至90-100℃，缓慢加入已二酸4-8份；继续加入醇酸树脂1-5份，环氧树脂2-4份，充分搅拌1h以上，然后加入扩链剂、活化剂以及催化剂：按照均分四次间隔30min加入丙二醇1-3份、甲基二乙醇胺1-3份、二酯酸二丁基锡1-4份，磷酸0.5-1份；最后加入纳米Al2O3浆料2-8份和适量去离子水置于40℃温度下采用直流搅拌机以3000r/min速度下搅拌分散60min而成。
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