CN110256877A - 一种多官能团嘌呤类化合物修饰的超疏水纳米材料及其修饰方法 - Google Patents
一种多官能团嘌呤类化合物修饰的超疏水纳米材料及其修饰方法 Download PDFInfo
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Abstract
一种多官能团嘌呤类化合物修饰超疏水纳米材料的方法,包括如下步骤:1)将纳米材料分散于溶剂中形成分散系,所述纳米材料在所述分散系的质量占比为1%‑50%;2)向所述分散系中加入催化剂,所述催化剂添加量为所述分散系的0.01%‑5%;3)向所述分散系中加入多官能团嘌呤类化合物,所述多官能团嘌呤类化合物在所述分散系的质量占比为0.1‑5%;所述多官能团嘌呤类化合物上带有嘌呤基团、羟基、氨基、羧基和酯基;通过本方法值得的超疏水纳米材料具有很好的耐久性和附着力。
Description
技术领域
本发明涉及精细化学品领域,具体涉及一种多官能团嘌呤类化合物修饰的超疏水纳米材料及其修饰方法。
背景技术
超疏水是指材料的表面与水之间的接触角>150°,这种材料具有良好的疏水能力,可以实现防污自洁、防水等多种功能,是近十几年来学术研究和产业化应用的热点之一。通过对荷叶、蝴蝶、壁虎等具有超疏水本领的植物和动物的超疏水部位进行研究,逐渐归纳出具有超疏水特性的表面所应该具备的两个重要条件:一是表面必须具备有粗糙的微纳结构;二是表面必须要有低表面能物质的修饰。
就人工合成的超疏水材料而言,一般用纳米或微米的材料构建粗糙的微纳结构,而表面能修饰材料多选用低表面能的蜡、硅油或氟化物等。目前超疏水材料虽然在理论研究上取得了重大进展,但是在实际应用方面仍然面临着附着力差和耐久性不好的问题。附着力差主要是因为微纳米材料与基底的结合力弱导致的,而耐久性不好主要是在户外使用紫外线照射导致的有机修饰材料分解所致。
发明内容
为解决上述问题本发明提供一种多官能团嘌呤类化合物修饰超疏水纳米材料的方法,通过该方法制备的超疏水纳米材料上带有嘌呤基团,该嘌呤基团可以吸收90%以上的紫外光,吸收紫外线的波长为250-385nm,被吸收的紫外光以热的形式辐射掉,进而保护了超疏水纳米材料的其他基团,提高了超疏水纳米材料的耐久性;另外,该超疏水纳米材料上还带多种其他基团,这些基团能够和基底材料上的基团进行缩合反应,有效拓宽本超疏水纳米材料的使用范围,同时也提升了其与基底材料之间的附着力。
一种多官能团嘌呤类化合物修饰超疏水纳米材料的方法,包括如下步骤:
1)将纳米材料分散于溶剂中形成分散系,纳米材料在分散系的质量占比为1%-50%;
2)向分散系中加入催化剂,催化剂添加质量为分散系质量的0.01%-5%;
3)向分散系中加入多官能团嘌呤类化合物,多官能团嘌呤类化合物在分散系的质量占比为0.1-5%,多官能团嘌呤类化合物上带有嘌呤基团、羟基、氨基、羧基和酯基。
通过本方法得到的超疏水纳米材料,由于其上带有嘌呤基团,嘌呤基团可以有效吸收90%以上的紫外线,可吸收紫外线波长为250-385nm,被嘌呤基团吸收的紫外光以热的形式辐射掉,进而达到保护超疏水纳米材料的其他有机基团不受紫外线破坏,有助于提高超疏水纳米材料的耐久性。同时,通过本方法得到的超疏水纳米材料上带有多种官能团,如羟基、氨基、羧基和酯基,可以与多种基底材料上的基团进行缩合形成连接键,提升了超疏水纳米材料的附着力,也扩宽了超疏水纳米材料的适用范围。
优选的,纳米材料为氧化硅、氧化钛、氧化铁和氧化锌中的任何一种;
优选的,溶剂为水、乙醇、丙醇、石油醚和酯类溶剂中的任何一种。
进一步,催化剂呈酸性或者碱性。
更为优选的,催化剂为盐酸、醋酸、硫酸、硝酸、氨水和氢氧化物中的任何一种。
进一步,多官能团嘌呤类化合物的化学结构式如式I所示:
其中,R1、R2和R3均选自-H和C1-C6的烷基,R4选自-H和-F,n=0-100。
该多官能团嘌呤类化合物上带有多种官能团,包括羟基、氨基、羧基和酯基,其中羟基与超疏水纳米材料上纳米氧化物的羟基结合,其余基团不变,因此经过其修饰的超疏水纳米材料上也带有羟基、氨基、羧基和酯基,又由于不同的基底材料含有不同的活性基团,因此其余基团的保留,拓宽了超疏水纳米材料的应用范围。
如玻璃基底富含羟基,漆面富含酯基、氨基、羧基,一些织物表面也含有丰富的羟基等,本发明中的超疏水纳米材料上的羟基、羧基、氨基和酯基可以和玻璃的羟基、织物的羟基、漆面的酯基、氨基、羧基形成氢键,这些化学键的结合均能明显提升超疏水纳米材料在基底材料上的附着力;该化合物的结构中,R1、R2、R3为碳原子数小于6的烷烃或氢原子,此时均可以取得良好的疏水效果和附着力,R4为F原子或H原子,其中为F原子时,疏水性会好于H原子。
更为优选的,多官能团嘌呤类化合物的结构式中R1为甲基,R2为丙基,R3为己基,R4为F原子,n=0-10。
更为优选的,多官能团嘌呤类化合物的结构式中R1为丙基,R2为甲基,R3为丁基,R4为F原子,n=10-30。
更为优选的,多官能团嘌呤类化合物的结构式中R1为戊基,R2为己基,R3为甲基,R4为-H,n=30-60。
更为优选的,多官能团嘌呤类化合物的结构式中R1为己基,R2为己基,R3为甲基,R4为-H,n=60-100。
本发明的有益效果在于:
1.本发明的超疏水纳米材料的嘌呤基团时可吸收90%以上的紫外线,吸收紫外线的波长为250-385nm,被吸收的紫外光以热的形式辐射掉,进而保护超疏水材料的其他有机基团不受紫外光破坏,显著提高了超疏水材料的户外耐久性;
2.本发明的超疏水纳米材料还包括氨基、羧基、酯基和未参与缩合的羟基与基底材料的活性基团(如玻璃表面的羟基,漆面的酯基、氨基和羟基以及织物羟基等)结合形成氢键,进而提高纳米疏水材料的在基底材料上的附着力;
3.本发明的超疏水纳米材料上还具有烷基、-F或者-H,进一步提高了基底材料的疏水性。
附图说明
图1是本发明实施例一中超疏水纳米材料合成过程中的化学反应式。
图2是本发明实施例一中二氧化钛超疏水纳米材料的扫描电镜图。
图3是本发明实施例一中二氧化钛超疏水材料的接触角测试。
具体实施方式
下面结合具体实施例对本发明内容做进一步详细说明,但本发明保护范围不仅限于以下实施例,凡是属于本发明内容等同的技术方案,均属于本专利的保护范围。
实施例1
1)将二氧化钛纳米材料(本实施例中用的为P25纳米二氧化钛)分散于水中形成分散系,二氧化钛纳米材料在分散系的质量占比为1%;
2)向分散系中加入盐酸或醋酸,搅拌均匀,盐酸或醋酸添加量为分散系的0.01%;
3)室温下,向分散系中加入多官能团嘌呤类化合物,搅拌均匀静置,多官能团嘌呤类化合物在分散系的质量占比为0.1-5%。本实施例多官能团嘌呤类化合物的结构为:R1为甲基,R2为丙基,R3为己基,R4为F,n=0。
其中,多官能团嘌呤类化合物的化学式如式II所示,
多官能团嘌呤类化合物通过中间六元环上的羟基与二氧化钛纳米材料上的纳米氧化物的羟基进行缩合,步骤1)至步骤6)的具体缩合反应式,如反应式一。
通过电子显微镜(市面上购买的普通电子显微镜)扫描得到如图2所示的二氧化钛超疏水纳米材料的扫描电镜图。
采用百格实验法对上述二氧化钛超疏水纳米材料进行附着力测试,测试步骤如下:
1)将按照前述实施例1的步骤制得的二氧化钛超疏水纳米材料均匀的涂在玻璃上,厚度为10mm,待其干燥,制得试样板一(共计三块);同时取一用蜡修饰得到的二氧化硅超疏水纳米材料,按照同样方法均匀的涂在玻璃上,厚度为10mm,待其干燥,制得对照板一;
2)用百格刀在试样板一和对照板一的表面分别划10*10个(共计100个)1mm*1mm的小网格,每一条划线应深及涂料的底层,并用毛刷将测试区域的碎片刷干净,用3M600号胶纸粘住被测试小网格,并用橡皮檫用力擦拭胶带,然后用手抓住胶带一端,在垂直方向(90°)扯下胶纸;
3)测试涂料脱落数量,具体结果如下总表1。
接着,取一块新的试样板一,对其进行接触角测试,采用接触角测试仪(市面上购买的普通电子显微镜)对其进行接触角测试,测试结果如图3所示,接触角为158°,接触角大于150°,试样板一具有超疏水性。经过接触角测试,验证了本方法制得的二氧化钛超疏水纳米材料具有超疏水性。
最后,取一新的试样板一,对其进行耐久性测试。
实验仪器:ZN-P硫化橡胶人工气候老化箱(荧光紫外灯)(北京中科环试仪器有限公司);接触角测试仪(市面上购买的普通电子显微镜);SFL-I反射率测定仪(天津永利达材料试验机有限公司);
实验条件:
(1)ZN-P硫化橡胶人工气候老化箱(荧光紫外灯)的实验条件:
循环时间:8h紫外光暴露接着4h冷凝;
紫外光波长:250-385nm;
紫外光暴露温度:(50±3)℃;
冷凝温度:(50±3)℃;
试样板距离灯平面距离为100mm;
试样板评估间隔周期:20天,目测试样板表面是否有失光、粉化、开裂、脱落及斑点等现象;并用SFL-I反射率测定仪检测试样板的光泽度。
实验方法:在试样板一开始老化试验前,记录试样板一的状态;将试样板一放置在硫化橡胶人工气候老化箱内的样板支架上,然后将硫化橡胶人工气候老化箱的参数调至上述参数,对其进行老化试验,每隔20天对试样板一进行观察和测定,主要从两方面:(1)观察涂膜外观:查看脱落、粉化、起皱情况,(2)光泽度测试:用SFL-I反射率测定仪按国标《GB/T1743-79(89)》测定;同时记录SFL-I反射率测定仪的检测结果。
实验结果见下表1-2:
表1-2:试样板一进行老化试验数据记录
通过上表数据,可以分析出,按照实施例1的方法制作的二氧化硅超疏水材料,从80天开始才有脱落显现,因此本发明可耐紫外老化接近2000h,经过约2000h多个小时的试验,光泽度才从高光泽变成平光(高光泽-70%以上;平光-50%-70%;亚光-10%-50%;无光-10%以下)。
实施例2
1)将二氧化硅纳米材料分散于乙醇中形成分散系,二氧化硅纳米材料在分散系的质量占比为20%;
2)向分散系中加入氨水,搅拌均匀,氨水添加量为分散系的2%;
3)室温下,向分散系中加入多官能团嘌呤类化合物,搅拌均匀静置,多官能团嘌呤类化合物在分散系的质量占比为3%,其中,多官能团嘌呤类化合物的结构为:R1为丙基,R2为甲基,R3为丁基,R4为F,n=30
采用实施例1的喷涂方法将制得的二氧化硅超疏水纳米材料喷涂在汽车漆面,得到试样板二(共计3块),并按照实施例1中同样的方法对其依次进行百格实验法、接触角测试、以及耐久性试验。其中,接触角测试结果与实施例1中的结果相同,接触角大于150°,仍为超疏水纳米材料,百格实验法结果见下总表1,耐久性试验实验结果见下表2-2。
表2-2:试样板一进行老化试验数据记录
通过上表数据,可以分析出,按照实施例1的方法制作的二氧化硅超疏水材料,其在经过220天的老化实验后,才开始有脱落趋势,经过约4800h的试验,光泽度仍然为高光泽(高光泽-70%以上;平光-50%-70%;亚光-10%-50%;无光-10%以下),因此二氧化硅超疏水材料可耐紫外老化接近5000h。
实施例3
1)将氧化锌纳米材料分散于石油醚或醋酸乙酯中形成分散系,氧化锌纳米材料在分散系的质量占比为50%;
2)向分散系中加入硫酸或硝酸,搅拌均匀,硫酸或硝酸添加量为分散系的5%;
3)室温下,向分散系中加入多官能团嘌呤类化合物,搅拌均匀静置,多官能团嘌呤类化合物在分散系的质量占比为5%,其中,多官能团嘌呤类化合物的结构为:R1为己基,R2为己基,R3为甲基,R4为H,n=100。
采用实施例1的喷涂方法将制得的氧化锌超疏水纳米材料喷涂在布上,得到试样板三(共计3块),并按照实施例1中同样的方法对其依次进行百格实验法、接触角测试、以及耐久性试验。其中,接触角测试结果与实施例1中的结果相同,接触角大于150°,仍为超疏水纳米材料,百格实验法结果见下总表1,耐久性试验实验结果见下表3-2。
表3-2:试样板一进行老化试验数据记录
通过上表数据,可以分析出,按照实施例1的方法制作的氧化锌超疏水材料,经过180天的试验后,才开始有小块脱落,光泽度才从高光泽变为平光(高光泽-70%以上;平光-50%-70%;亚光-10%-50%;无光-10%以下),因此可耐紫外老化接近4000h。
实施例4
1)将氧化铁纳米材料分散于醋酸丁酯中形成分散系,氧化铁纳米材料在分散系的质量占比为50%;
2)向分散系中加入氢氧化钠,搅拌均匀,氢氧化钠添加量为分散系的2%;
3)室温下,向分散系中加入多官能团嘌呤类化合物,搅拌均匀静置,多官能团嘌呤类化合物在分散系的质量占比为3%,其中,多官能团嘌呤类化合物的结构为:R1为戊基,R2为己基,R3为甲基,R4为H,n=60。
采用实施例1的喷涂方法将制得的氧化铁超疏水纳米材料喷涂在外墙上,得到试样板四(3块),并按照实施例1中同样的方法对其依次进行百格实验法、接触角测试、以及耐久性试验。其中,接触角测试结果与实施例1中的结果相同,接触角大于150°,仍为超疏水纳米材料,百格实验法结果见总表1,耐久性试验实验结果见下表4-2。
表4-2:试样板一进行老化试验数据记录
通过上表数据,可以分析出,按照实施例1的方法制作的氧化铁超疏水纳米材料,经过约160天试验,光泽度才从高光泽变成平光(高光泽-70%以上;平光-50%-70%;亚光-10%-50%;无光-10%以下),因此氧化铁超疏水纳米材料接近3000小时。
取用蜡修饰得到的二氧化钛超疏水纳米材料、二氧化硅超疏水纳米材料、氧化锌超疏水纳米材料、氧化铁超疏水纳米材料,分别记为对照组1、对照组2、对照组3、对照组4,其中,对照组1参见实施例1进行百格法平行实验,,对照组2参见实施例1进行百格法平行实验,对照组3参见实施例3进行百格法平行实验,对照组4参见实施例4进行百格法平行实验。
总表1:实施例1-4及对照组的百格法实验结果
ASTM等级:5B表示切口的边缘完全光滑,格子边缘没有任何脱落;
ASTM等级:4B表示在切口的相交处有小片剥落,划个区内实际破损≤5%;
ASTM等级:3B表示在切口的相交或边缘处有剥落,面积大约为5%-15%;
ASTM等级:0B表示在划线的边缘及交叉点处有成片的油漆脱落,面积大于65%;
通过上述总表1,可以看出,通过本实施例1-4的方法得到的超疏水纳米材料与基底材料的附着力远比一般修饰剂(如蜡)修饰得到的超疏水纳米材料强。
Claims (10)
1.一种多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:包括如下步骤:
1)将纳米材料分散于溶剂中形成分散系,所述纳米材料在所述分散系的质量占比为1%-50%;
2)向所述分散系中加入催化剂,所述催化剂添加质量为所述分散系质量的0.01%-5%;
3)向所述分散系中加入多官能团嘌呤类化合物,所述多官能团嘌呤类化合物在所述分散系的质量占比为0.1-5%;所述多官能团嘌呤类化合物上带有嘌呤基团、羟基、氨基、羧基和酯基。
2.如权利要求1所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述纳米材料为氧化硅、氧化钛、氧化铁和氧化锌中的任何一种。
3.如权利要求1所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述溶剂为水、乙醇、丙醇、石油醚和酯类溶剂中的任何一种。
4.如权利要求1所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述催化剂为盐酸、醋酸、硫酸、硝酸、氨水和氢氧化物中的任何一种。
5.如权利要求1-4任一项所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述多官能团嘌呤类化合物的化学结构式如式I所示:
其中,R1、R2和R3均选自-H和C1-C6的烷基,R4选自-H和-F,n=0-100。
6.如权利要求5所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述多官能团嘌呤类化合物的结构式中所述R1为甲基,R2为丙基,R3为己基,R4为F原子,n=0-10。
7.如权利要求5所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述多官能团嘌呤类化合物的结构式中所述R1为丙基,R2为甲基,R3为丁基,R4为F原子,n=10-30。
8.如权利要求5所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述多官能团嘌呤类化合物的结构式中所述R1为戊基,R2为己基,R3为甲基,R4为-H,n=30-60。
9.如权利要求5所述的多官能团嘌呤类化合物修饰超疏水纳米材料的方法,其特征在于:所述多官能团嘌呤类化合物的结构式中所述R1为己基,R2为己基,R3为甲基,R4为-H,n=60-100。
10.一种多官能团嘌呤类化合物修饰的超疏水纳米材料,其特征在于:所述超疏水纳米材料采用权利要求1-9任一项所述方法制备。
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