CN116082847B - 一种用于超疏水改性的硅橡胶微球及其制备方法 - Google Patents
一种用于超疏水改性的硅橡胶微球及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于超疏水改性的硅橡胶微球及其制备方法。是由乙烯基聚硅氧烷、含氢聚硅氧烷、氟硅油、氟醚油、疏水纳米二氧化硅、乳化剂、铂金催化剂混合均匀后,在水中分散成乳液,并进一步交联成粒径为0.1~50μm的硅橡胶微球。与现有技术相比,本发明中,所述的氟硅油和氟醚油在包裹在硅橡胶微球内,不参与硅橡胶交联,随时间缓释到微球表面,起到疏水疏油的作用。硅橡胶微球按照1~10wt%添加到涂料或树脂中,在表面形成半球型微纳突起,实现超疏水的性能。
Description
技术领域
本发明属于功能材料领域,具体涉及一种用于超疏水改性的硅橡胶微球及其制备方法。
背景技术
超疏水材料一般定义为在材料表面稳定接触角θ>150°,滚动接触角α<10°时的材料,其在油水分离、生物医学、自清洁、纺织品、防腐蚀、文物保护等方面有广泛的应用。目前的超疏水材料多用含氟聚合物进行制备,而含氟聚合物比较昂贵,使得由含氟聚合物制备出的超疏水材料成本更高,大多只在实验室中进行制备,难以在市场上流通。于是,用价格相对低廉的硅酮胶等材料制备超疏水材料成为一个较好的选择。表面平整的硅橡胶、有机硅涂层等的接触角一般为100°左右,要达到超疏水的要求,必须在表面形成微纳级的粗糙结构。目前制备超疏水材料的主要有两个途径:(1)在粗糙结构表面修饰低表面能物质;(2)在具有低表面能材料的表面构成适当的粗糙结构。常用的方法有相分离法、模板法、电化学沉积法、溶胶—凝胶法、喷涂法、刻蚀法、自组装等方法。这些方法工艺复杂、制备条件苛刻、设备昂贵,难以规模化应用。
具有疏水功能的硅橡胶微球可以加入到涂料或者树脂中,表面形成微纳尺寸的半球突起,同时实现了粗糙结构和疏水两个要素,达到超疏水的目的。这种方法简便易行,适用性广。专利ZL 108129671 B提供了一种基于硅橡胶微球制备具有超疏水性的微纳小球的方法,在表面含有Si-H键的硅橡胶微球表面包覆经硅烷偶联剂和聚硅氧烷处理后的纳米级二氧化硅,从而获得超疏水的微纳小球。然而制备方法涉及到含Si-H键硅橡胶微球的制备、纳米二氧化硅表面处理、硅球表面包覆等步骤,工艺繁琐,且涉及硅胶球和纳米二氧化硅分离等难题,可行性较低。
发明内容
基于现有技术中硅橡胶微球存在的制备工艺繁琐、分离困难的问题,本发明提供一种用于超疏水改性的硅橡胶微球及其制备方法。本发明提供的硅橡胶微球中含有游离的氟硅油或者氟醚油,可以缓释到硅橡胶微球表面,配合微纳级球状结构,起到超疏水的目的。
本发明的目的可以通过以下技术方案来实现:
本发明提供一种用于超疏水材料的硅橡胶微球,是由以下质量份的物质制备:
且氟硅油与氟醚油不同时为0。
在本发明的一个实施方式中,用于超疏水材料的硅橡胶微球,是由以下质量份的物质制备:
或,由以下质量份的物质制备:
在本发明的一个实施方式中,所述乙烯基聚硅氧烷为乙烯基封端的聚二甲基硅氧烷,侧链有少量乙烯基或者不含乙烯基,乙烯基含量为(5~30)×10-5mol/g,黏度为100~1000mPa·s。
在本发明的一个实施方式中,所述含氢聚硅氧烷为含有Si-H键的聚二甲基硅氧烷,硅氢的含量为(5~60)×10-5mol/g,黏度为100~1000mPa·s。
在本发明的一个实施方式中,所述氟硅油具有如下的分子结构:
R[OSi(CH3)2]x[OSi(CH3)(CH2CH2CF3)]y R
其中,R为-OH、-OCH3、-Si(CH3)2C5H6、-Si(CH3)3、优选-Si(CH3)3;x为0~100的整数,y为3~100的整数。
在本发明的一个实施方式中,所述氟醚油是含有-CF2CF2O-结构的全氟醚油,黏度为20~500mPa·s。
在本发明的一个实施方式中,所述疏水纳米二氧化硅为用硅氮烷、羟基硅油或八甲基四硅氧烷处理的纳米二氧化硅,比表面积为150~400m2/g。
在本发明的一个实施方式中,所述乳化剂为聚醚硅油、吐温40、吐温60、吐温80、斯盘40、斯盘60、十二烷基苯磺酸钠、十二烷基硫酸钠、硬脂酸钠、OP-10中的一种或几种的组合。
在本发明的一个实施方式中,所述铂金催化剂为Karstedt型Pt催化剂,有效含量为1000~10000ppm。
在本发明的一个实施方式中,所述分散剂为聚乙烯醇、聚丙烯酸钠、明胶中的一种或几种的组合。
本发明还进一步提供用于超疏水改性的硅橡胶微球的制备方法,按照以下步骤制备:
(1)将乙烯基聚硅氧烷、含氢聚硅氧烷、氟硅油、氟醚油、疏水纳米二氧化硅和乳化剂在室温下搅拌10~30min直到混合均匀,加入铂金催化剂继续搅拌5~20min,得到液体硅橡胶;
(2)将分散剂溶于水中,加入到液体硅胶中,用匀质机乳化5~30min,得到液体硅橡胶乳液;
(3)改用分散机在10~60℃下继续搅拌1~24h,得到含微米和纳米尺寸的硅橡胶微球;
(4)通过过滤或离心分离硅橡胶微球,用水或乙醇清洗掉表面的乳化剂和分散剂,烘干得到内含氟硅或氟醚聚合物的硅橡胶微球。
按照本发明提供的用于超疏水材料的硅橡胶微球的制备方法,得到的硅橡胶微球的粒径为0.1~50μm,水接触角大于150°。优选地,用于超疏水材料的硅橡胶微球的粒径为10~30μm。
本发明还进一步提供用于超疏水材料的硅橡胶微球的应用。将用于超疏水材料的硅橡胶微球添加到涂料或树脂中,放置7天后,表面接触角大于120°;其中,用于超疏水材料的硅橡胶微球添加量为1~10wt%。优选地,放置7天后,表面接触角大于130°。
在本发明的一个实施方式中,所述涂料选择为液体硅橡胶、丙烯酸酯涂料或聚氨酯涂料。
在本发明的一个实施方式中,所述树脂选择为聚乙烯、聚丙烯、聚苯乙烯、聚酯、有机玻璃。
与现有技术相比,本发明具有以下优点及有益效果:
本发明制备的硅橡胶微球内含有与硅橡胶不完全相容的有机氟硅或者氟醚聚合物,它们不参与硅橡胶的交联,能随时间缓释迁移到硅球表面,起到疏水和疏油的作用。硅橡胶微球用于涂料或者树脂中时,涂料或树脂表面裸露出的硅橡胶半球形成微纳粗糙结构,进而构成了超疏水的两个必要条件,产生超疏水的效果。
附图说明
图1为实施例1制备的硅橡胶微球的显微镜照片,平均粒径为11μm。
图2为实施例2制备的硅橡胶微球的显微镜照片,平均粒径为25μm。
图3为实施例1中用硅橡胶微球改性的有机硅涂层放置7天后的水接触角,平均值为144.9°。
图4为实施例2中用硅橡胶微球改性的聚氨酯涂层放置7天后的水接触角,平均值为133.7°。
图5为实施例3中硅橡胶微球改性的聚丙烯薄片放置7天后的水接触角,平均值为151.6°。
图6为对比例1中有机硅涂层的水接触角,平均值为95.0°。
图7为对比例2中聚氨酯涂层的水接触角,平均值为89.2°。
图8为对比例3中聚丙烯薄片的水接触角,平均值为90.1°。
图9为对比例4中有机硅涂层的水接触角,平均值为111.2°。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将100g端乙烯基硅油(乙烯基含量10-4mol/g,黏度为600mPa·s)、100g含氢硅油(硅氢含量10-4mol/g,黏度为300mPa·s)、20g甲基封端氟硅油(黏度700mPa·s)、2.2g聚醚硅油(分子量,聚醚含量)和2.2g吐温60混合均匀,然后加入0.5g铂金催化剂(铂有效含量为4000ppm),搅拌10min。加入1000g 1%的聚乙烯醇溶液(PVA1799),用匀质机在20000r/min转速下乳化10min,然后用分散机在20℃下搅拌8h。离心分离出上层硅橡胶微球,用乙醇清洗2遍,干燥后得到约220g硅橡胶微粉。
利用显微镜测量硅橡胶微粉的粒径及其分布。将1g硅橡胶微粉加入到20g道康宁DC184灌封胶中,搅拌均匀,刮涂在玻璃片上固化成有机硅涂层。测试7天后的水接触角。
实施例2
将100g端乙烯基硅油(乙烯基含量1.5×10-4mol/g,黏度为400mPa·s)、80g含氢硅油(硅氢含量2×10-4mol/g,黏度为200mPa·s)、20g聚二甲基硅氧-b-甲基三氟丙基硅氧烷嵌段型氟硅油(黏度1000mPa·s,二甲基硅氧链段占50%)、10g疏水纳米二氧化硅R812,2g聚醚硅油(分子量,聚醚含量)和2g OP-10混合均匀,然后加入1g铂金催化剂(铂有效含量为2000ppm),搅拌10min。加入1000g 0.1%的聚丙烯酸钠溶液,用匀质机在10000r/min转速下乳化10min,然后用分散机在25℃下搅拌8h。离心分离出上层硅橡胶微球,用乙醇清洗2遍,干燥后得到210g左右硅橡胶微粉。
利用显微镜测量硅橡胶微粉的粒径及其分布。将1g硅橡胶微粉加入到25g威固KS-929C聚氨酯涂料中,搅拌均匀,刮涂在玻璃片上固化成聚氨酯涂层。测试7天后的水接触角。
实施例3
将100g端乙烯基硅油(乙烯基含量5×10-5mol/g,黏度为900mPa·s)、50g含氢硅油(硅氢含量10-4mol/g,黏度为300mPa·s)、10g全氟聚醚油(杜邦Krytox GPL105)、2g吐温40和2g吐温80混合均匀,然后加入0.3g铂金催化剂(铂有效含量为6000ppm),搅拌10min。加入2000g去离子水,用匀质机在20000r/min转速下乳化10min,然后用分散机在40℃下搅拌3h。离心分离出上层硅橡胶微球,用乙醇清洗2遍,干燥后得到约170g硅橡胶微粉。
利用显微镜测量硅橡胶微粉的粒径及其分布。将5g硅橡胶微粉与60g聚丙烯Y2600熔融共混,模压成片。测试7天后的水接触角。
对比例1
20g道康宁DC184灌封胶刮涂在玻璃片上固化成有机硅涂层。测试7天后的水接触角。
对比例2
25g威固KS-929C聚氨酯涂料涂在玻璃片上固化成聚氨酯涂层。测试7天后的水接触角。
对比例3
60g聚丙烯Y2600用高温压机模压成片,测试7天后的水接触角。
对比例4
将100g端乙烯基硅油(乙烯基含量10-4mol/g,黏度为600mPa·s)、100g含氢硅油(硅氢含量10-4mol/g,黏度为300mPa·s)、2.2g聚醚硅油(分子量,聚醚含量)和2.2g吐温60混合均匀,然后加入0.5g铂金催化剂(铂有效含量为4000ppm),搅拌10min。加入1000g 1%的聚乙烯醇溶液(PVA1799),用匀质机在20000r/min转速下乳化10min,然后用分散机在20℃下搅拌8h。离心分离出上层硅橡胶微球,用乙醇清洗2遍,干燥后得到约220g硅橡胶微粉。
利用显微镜测量硅橡胶微粉的粒径及其分布。将1g硅橡胶微粉加入到20g道康宁DC184灌封胶中,搅拌均匀,刮涂在玻璃片上固化成有机硅涂层。测试7天后的水接触角。
实施例和对比例得到如表1的数据。
表1实施例和对比例硅橡胶微球平均粒径以及样品7天后水接触角
可以看出,基于本发明实施例1、2、3制备的硅橡胶微球用于涂料或者树脂中时,涂料或树脂表面裸露出的硅橡胶半球形成微纳粗糙结构,进而构成了超疏水的两个必要条件,产生超疏水的效果。而对比例4中没有添加氟硅油或氟醚油,导致其硅橡胶微球平均粒径较小,且样品7天后水接触角较小。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.一种用于超疏水材料的硅橡胶微球,其特征在于,是由以下质量份的物质制备:
且氟硅油与氟醚油不同时为0。
2.根据权利要求1所述的一种用于超疏水材料的硅橡胶微球,其特征在于,是由以下质量份的物质制备:
或,由以下质量份的物质制备:
3.根据权利要求1或2所述的一种用于超疏水材料的硅橡胶微球,其特征在于,所述乙烯基聚硅氧烷为乙烯基封端的聚二甲基硅氧烷,侧链有少量乙烯基或者不含乙烯基,乙烯基含量为(5~30)×10-5mol/g,黏度为100~1000mPa·s。
4.根据权利要求1或2所述的一种用于超疏水材料的硅橡胶微球,其特征在于,所述含氢聚硅氧烷为含有Si-H键的聚二甲基硅氧烷,硅氢的含量为(5~60)×10-5mol/g,黏度为100~1000mPa·s。
5.根据权利要求1或2所述的一种用于超疏水材料的硅橡胶微球,其特征在于,所述氟硅油具有如下的分子结构:
R[OSi(CH3)2]x[OSi(CH3)(CH2CH2CF3)]y R
其中,R为-OH、-OCH3、-Si(CH3)2C5H6、-Si(CH3)3;x为0~100的整数,y为3~100的整数。
6.根据权利要求1或2所述的一种用于超疏水材料的硅橡胶微球,其特征在于,所述氟醚油是含有-CF2CF2O-结构的全氟醚油,黏度为20~500mPa·s。
7.根据权利要求1或2所述的一种用于超疏水材料的硅橡胶微球,其特征在于,所述疏水纳米二氧化硅为用硅氮烷、羟基硅油或八甲基四硅氧烷处理的纳米二氧化硅,比表面积为150~400m2/g;
所述乳化剂为聚醚硅油、吐温40、吐温60、吐温80、斯盘40、斯盘60、十二烷基苯磺酸钠、十二烷基硫酸钠、硬脂酸钠、OP-10中的一种或几种的组合;
所述铂金催化剂为Karstedt型Pt催化剂,有效含量为1000~10000ppm;
所述分散剂为聚乙烯醇、聚丙烯酸钠、明胶中的一种或几种的组合。
8.权利要求1或2所述用于超疏水改性的硅橡胶微球的制备方法,其特征在于,按照以下步骤制备:
(1)将乙烯基聚硅氧烷、含氢聚硅氧烷、氟硅油、氟醚油、疏水纳米二氧化硅和乳化剂在室温下搅拌10~30min直到混合均匀,加入铂金催化剂继续搅拌5~20min,得到液体硅橡胶;
(2)将分散剂溶于水中,加入到液体硅胶中,用匀质机乳化5~30min,得到液体硅橡胶乳液;
(3)改用分散机在10~60℃下继续搅拌1~24h,得到含微米和纳米尺寸的硅橡胶微球;
(4)通过过滤或离心分离硅橡胶微球,用水或乙醇清洗掉表面的乳化剂和分散剂,烘干得到内含氟硅或氟醚聚合物的硅橡胶微球。
9.权利要求1或2所述用于超疏水改性的硅橡胶微球的应用,其特征在于,将用于超疏水材料的硅橡胶微球添加到涂料或树脂中,其中,用于超疏水材料的硅橡胶微球添加量为1~10wt%。
10.根据权利要求9所述用于超疏水改性的硅橡胶微球的应用,其特征在于,所述涂料选择为液体硅橡胶、丙烯酸酯涂料或聚氨酯涂料;
所述树脂选择为聚乙烯、聚丙烯、聚苯乙烯、聚酯、有机玻璃。
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CN113337178A (zh) * | 2021-05-26 | 2021-09-03 | 复旦大学 | 一种多重响应的可控自修复超疏水/高疏水涂层材料及其制备方法 |
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