CN114410170B - 一种节能保温材料及其制备方法 - Google Patents

一种节能保温材料及其制备方法 Download PDF

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CN114410170B
CN114410170B CN202111624734.3A CN202111624734A CN114410170B CN 114410170 B CN114410170 B CN 114410170B CN 202111624734 A CN202111624734 A CN 202111624734A CN 114410170 B CN114410170 B CN 114410170B
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汤寅寅
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Tangshan Siyuan Paint Co ltd
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Abstract

本发明涉及一种保温涂层复合材料，所述涂层复合材料包括如下重量份数的组成：改性丙烯酸乳液50‑80份、隔热填料8‑15份、纳米二氧化钛15‑25份、纳米三氧化二铝7‑13份、分散剂1‑5份、成膜助剂1‑3份、耐沾污剂0.5‑3份、去离子水15‑32份、硅烷偶联剂2‑5份；所述改性丙烯酸乳液为甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2‑全氟辛基乙基甲基丙烯酸酯、1‑乙烯基‑3‑辛基咪唑溴盐按摩尔比1∶1∶1∶1∶1共聚得到。对丙烯酸乳液的单体结构进行改性，首次获得离子型的丙烯酸乳液；改性丙烯酸乳液与纳米隔热填料间的相溶性大幅增大，提升了纳米填料的分散性能，颗粒沉降时间大幅延长，施工效果更好。

Description

一种节能保温材料及其制备方法
技术领域
本发明属于建筑材料技术领域，具体涉及一种节能保温涂层材料及其制备方法。
背景技术
发展绿色建筑已经成为当前建筑节能降耗工作的重点，而绿色建筑的发展离不开节能、环保、绿色产品的应用。近年来，建筑反射隔热涂料作为一种新的功能型建筑涂料，涂敷在建筑物外墙或屋面时，可以有效降低太阳辐射热在建筑物外墙或屋面的累积，减少夏季通过建筑墙体或屋面传入到室内的热量，从而降低空调能耗，改善室内环境舒适度。市场上，目前主要从反射隔热颜料、反射隔热乳液和反射隔热填料来提高反射隔热涂料效果。
反射隔热涂料是建筑节能的新材料，现在已经应用于实际建筑节能工程。如中国发明专利CN112341931A公开了一种水性反辐射隔热涂料及其制备方法，主要包括氟硅乳液、硅丙乳液、填料、纳米二氧化钛、成膜助剂、抑菌剂等组分。然而，现行反射型节能涂料大部分为丙烯酸涂料，随时间变化，丙烯酸涂料具有不耐沾污的缺点。一般而言，丙烯酸涂料会在3年内降低50％，在部分污染严重的城市，其反射效果的下降速度更快，通常不到2年其反射效果就会降低50％。为了提高涂层材料的耐沾污性能，通常要在配方体系中添加纳米填料体系以改变涂层材料的界面性能，进而提高其抗沾污性能；然而，纳米填料体系一般为无机金属氧化物，与有机丙烯酸乳液的相溶性较差，长期放置时将出现沉降现象，在加上纳米填料强的界面效应，沉降后将出现团聚，造成涂层材料的不可逆，影响了涂料的适用期和施工效果。因此，目前急需一种新型的耐沾污性好、耐候性更持久，适用期常的新型隔热涂层复合材料。
发明内容
为解决现有技术的不足，本发明提供一种保温涂层复合材料，所述涂料包括如下重量份数的组成：改性丙烯酸乳液50-80份、隔热填料8-15份、纳米二氧化钛15-25份、纳米三氧化二铝7-13份、分散剂1-5份、成膜助剂1-3份、耐沾污剂0.5-3份、去离子水15-32份、硅烷偶联剂2-5份；
所述改性丙烯酸乳液为甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2-全氟辛基乙基甲基丙烯酸酯、1-乙烯基-3-辛基咪唑溴盐按摩尔比1∶1∶1∶1∶1共聚得到；所述改性丙烯酸乳液共聚后含有如下结构单元：
Figure GDA0003795871290000021
所述结构单元仅为示意结构，其中各单体根据添加量和聚合过程随机排序；所述改性丙烯酸乳液一方面含有全氟烷基基团，可有效提高成膜后涂层材料的耐水性能；同时单体中还含有1-乙烯基-3-辛基咪唑溴盐离子型单体，共聚后得到的丙烯酸聚合物为离子型化合物，该化合物可有效提升乳液颗粒与无机纳米填料的相容性，提高了纳米填料颗粒的分散性能，有效避免了团聚现象，储存期更长；
所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶0.8-1.2；
所述分散剂为多聚磷酸钠盐分散剂；
所述纳米二氧化钛为金红石型钛白粉；
所述硅烷偶联剂为甲基三甲氧基硅烷、二甲基二甲氧基硅烷、正硅酸乙酯中的至少一种；
所述成膜助剂为醇酯十二；所述耐沾污剂为含氟表面活性剂Zonyl 8952；
本发明还提供一种所述保温涂层复合材料的制备方法，具体包括如下步骤：
(1)改性丙烯酸乳液的制备：取引发剂过硫酸铵用去离子水充分溶解得引发剂溶液；将甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2-全氟辛基乙基甲基丙烯酸酯、1-乙烯基-3-辛基咪唑溴盐、去离子水和十二烷基二苯醚二磺酸钠加入反应釜中，剧烈搅拌进行预乳化30min；在另一反应釜中加入一定量的去离子水和pH缓冲剂碳酸氢钠，升高温度到80℃后加入1/3的引发剂和10％的预乳化单体，保温反应至体系呈蓝色，得种子乳液；将剩余预乳化单体和引发剂溶液，逐滴加入到种子乳液中，滴加完毕后，升高温度到85-90℃，保温反应2-3h，反应完毕后降至室温，用氨水调节pH值为7-8，得改性丙烯酸乳液。
(2)将相应质量份数的去离子水、改性丙烯酸乳液、成膜助剂、耐沾污剂、分散剂、硅烷偶联剂依次加入反应釜中，剧烈搅拌获得基础浆料；
(3)向基础浆料中依次加入隔热填料、纳米二氧化钛、纳米三氧化二铝，升高温度到55-60℃，剧烈搅拌2-3h，然后加入氨水调节pH值到7-8，继续搅拌1-2h，降温出料得新型保温涂层复合材料；
本发明的有益效果在于，对丙烯酸乳液的单体结构进行改性，首次获得离子型的丙烯酸乳液；改性丙烯酸乳液与纳米隔热填料间的相溶性大幅增大，提升了纳米填料的分散性能，颗粒沉降时间大幅延长，施工效果更好。
附图说明
图1为实施例1放置60天后的施工效果图；其中a图为整体效果；b图为局部放大图；
图2为对比例1放置60天后的施工效果图；其中a图为整体效果；b图为表面孔洞的放大图；
具体实施方式
以下对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
实施例1.
本实施例提供一种保温涂层复合材料，所述涂料包括如下重量份数的组成：改性丙烯酸乳液58份、隔热填料9份、纳米二氧化钛17份、纳米三氧化二铝10份、多聚磷酸钠盐分散剂2份、醇酯十二1份、含氟表面活性剂Zonyl 8952耐沾污剂1份、甲基三甲氧基硅烷2、去离子水20份；所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶1；
所述保温涂层复合材料的制备方法，包括如下步骤：
(1)改性丙烯酸乳液的制备：取引发剂过硫酸铵16g用去离子水184g充分溶解得引发剂溶液；将甲基丙烯酸甲酯100g、丙烯酸丁酯128g、甲基丙烯酸86g、2-全氟辛基乙基甲基丙烯酸酯532g、1-乙烯基-3-辛基咪唑溴盐287g、去离子水3400g和十二烷基二苯醚二磺酸钠48g加入反应釜中，剧烈搅拌进行预乳化30min；在另一反应釜中加入去离子水2266g和pH缓冲剂碳酸氢钠84g，升高温度到80℃后加入1/3的引发剂和10％的预乳化单体，保温反应至体系呈蓝色，得种子乳液；将剩余预乳化单体和引发剂溶液，逐滴加入到种子乳液中，滴加完毕后，升高温度到85-90℃，保温反应2-3h，反应完毕后降至室温，用氨水调节pH值为7-8，得改性丙烯酸乳液。
(2)将相应质量份数的去离子水200g、步骤(1)制备的改性丙烯酸乳液580g、醇酯十二10g、含氟表面活性剂Zonyl 8952耐沾污剂10g、多聚磷酸钠盐分散剂20g、甲基三甲氧基硅烷20g依次加入反应釜中，剧烈搅拌获得基础浆料；
(3)向基础浆料中依次加入隔热填料90g、纳米二氧化钛170g、纳米三氧化二铝100个，升高温度到55-60℃，剧烈搅拌2-3h，然后加入氨水调节pH值到7-8，继续搅拌1-2h，降温出料得新型保温涂层复合材料。
实施例2.
本实施例提供一种保温涂层复合材料，所述涂料包括如下重量份数的组成：改性丙烯酸乳液65份、隔热填料10份、纳米二氧化钛20份、纳米三氧化二铝10份、多聚磷酸钠盐分散剂3份、醇酯十二1份、含氟表面活性剂Zonyl 8952耐沾污剂2份、去离子水28份、二甲基二甲氧基硅烷3份；所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶1.2；
所述保温涂层复合材料的制备方法同实施例1。
实施例3.
本实施例提供一种保温涂层复合材料，所述涂料包括如下重量份数的组成：改性丙烯酸乳液75份、隔热填料14份、纳米二氧化钛23份、纳米三氧化二铝13份、多聚磷酸钠盐分散剂4份、醇酯十二2份、含氟表面活性剂Zonyl 8952耐沾污剂2份、去离子水32份、二甲基二甲氧基硅烷3份；所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶0.8；
所述保温涂层复合材料的制备方法同实施例1。
实施例4.
本实施例提供一种保温涂层复合材料，所述涂料包括如下重量份数的组成：改性丙烯酸乳液75份、隔热填料9份、纳米二氧化钛25份、纳米三氧化二铝10份、多聚磷酸钠盐分散剂2份、醇酯十二1份、含氟表面活性剂Zonyl 8952耐沾污剂1份、去离子水27份、正硅酸乙酯4份；所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶1；
所述保温涂层复合材料的制备方法同实施例1。
对比例1.
本对比例提供一种传统保温涂层复合材料，所述涂料包括如下重量份数的组成：丙烯酸乳液58份、隔热填料9份、纳米二氧化钛17份、纳米三氧化二铝10份、多聚磷酸钠盐分散剂2份、醇酯十二1份、含氟表面活性剂Zonyl 8952耐沾污剂1份、甲基三甲氧基硅烷2、去离子水20份；所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶1；
所述丙烯酸乳液的组成为甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2-全氟辛基乙基甲基丙烯酸酯按摩尔比1∶1∶1∶1共聚得到，制备方法同实施例1。
对比例2.
本对比例提供一种传统保温涂层复合材料，所述涂料包括如下重量份数的组成：丙烯酸乳液75份、隔热填料9份、纳米二氧化钛25份、纳米三氧化二铝10份、多聚磷酸钠盐分散剂2份、醇酯十二1份、含氟表面活性剂Zonyl 8952耐沾污剂1份、正硅酸乙酯4份、去离子水27份；所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶1；
所述丙烯酸乳液的组成为甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2-全氟辛基乙基甲基丙烯酸酯按摩尔比1∶1∶1∶1共聚得到，制备方法同实施例1。
对上述实施例和对比例制备的隔热涂层材料，分别静置30日、60日、90日观察涂层材料的防沉降性能，并对制备材料的工艺性能进行了比较，结果如下：
Figure GDA0003795871290000071
对实施例1和对比例1制备出的两种样品分别放置60天后进行进行施工，对制备出的涂层进行SEM分析，结果如图1、图2所示；其中图1本发明制备出的涂层表面规整，无孔洞，局部进一步放大后也没有看到明显缺陷；图2对比例制备出的涂层施工后表面有大量孔洞，对孔洞进一步放大发现孔洞处有颗粒的聚集现象，进一步证明本发明可有效抑制颗粒集聚现象。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种保温涂层复合材料，其特征在于，所述涂层复合材料包括如下重量份数的组成：改性丙烯酸乳液50-80份、隔热填料8-15份、纳米二氧化钛15-25份、纳米三氧化二铝7-13份、分散剂1-5份、成膜助剂1-3份、耐沾污剂0.5-3份、去离子水15-32份、硅烷偶联剂2-5份；
所述改性丙烯酸乳液为甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2-全氟辛基乙基甲基丙烯酸酯、1-乙烯基-3-辛基咪唑溴盐按摩尔比1∶1∶1∶1∶1共聚得到；
所述改性丙烯酸乳液的制备：取引发剂过硫酸铵用去离子水充分溶解得引发剂溶液；将甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2-全氟辛基乙基甲基丙烯酸酯、1-乙烯基-3-辛基咪唑溴盐、去离子水和十二烷基二苯醚二磺酸钠加入反应釜中，剧烈搅拌进行预乳化30min；在另一反应釜中加入一定量的去离子水和pH缓冲剂碳酸氢钠，升高温度到80℃后加入1/3的引发剂溶液和10％的预乳化单体，保温反应至体系呈蓝色，得种子乳液；将剩余预乳化单体和引发剂溶液，逐滴加入到种子乳液中，滴加完毕后，升高温度到85-90℃，保温反应2-3h，反应完毕后降至室温，用氨水调节pH值为7-8，得改性丙烯酸乳液。
2.根据权利要求1所述的一种保温涂层复合材料，其特征在于，所述隔热填料为空心玻璃微珠、纳米气凝胶微粉的组合物，二者质量比为1∶0.8-1.2。
3.根据权利要求1所述的一种保温涂层复合材料，其特征在于，所述分散剂为多聚磷酸钠盐分散剂；所述纳米二氧化钛为金红石型钛白粉；所述硅烷偶联剂为甲基三甲氧基硅烷、二甲基二甲氧基硅烷、正硅酸乙酯中的至少一种；所述成膜助剂为醇酯十二；所述耐沾污剂为含氟表面活性剂Zonyl 8952。
4.权利要求1-3中任一项所述的一种保温涂层复合材料的制备方法，其特征在于，具体包括如下步骤：
(1)改性丙烯酸乳液的制备：取引发剂过硫酸铵用去离子水充分溶解得引发剂溶液；将甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、2-全氟辛基乙基甲基丙烯酸酯、1-乙烯基-3-辛基咪唑溴盐、去离子水和十二烷基二苯醚二磺酸钠加入反应釜中，剧烈搅拌进行预乳化30min；在另一反应釜中加入一定量的去离子水和pH缓冲剂碳酸氢钠，升高温度到80℃后加入1/3的引发剂溶液和10％的预乳化单体，保温反应至体系呈蓝色，得种子乳液；将剩余预乳化单体和引发剂溶液，逐滴加入到种子乳液中，滴加完毕后，升高温度到85-90℃，保温反应2-3h，反应完毕后降至室温，用氨水调节pH值为7-8，得改性丙烯酸乳液；
(2)将相应质量份数的去离子水、改性丙烯酸乳液、成膜助剂、耐沾污剂、分散剂、硅烷偶联剂依次加入反应釜中，剧烈搅拌获得基础浆料；
(3)向基础浆料中依次加入隔热填料、纳米二氧化钛、纳米三氧化二铝，升高温度到55-60℃，剧烈搅拌2-3h，然后加入氨水调节pH值到7-8，继续搅拌1-2h，降温出料得保温涂层复合材料。
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