CN115160826A - 一种功能性纳米ZnO及其制备方法和用途 - Google Patents
一种功能性纳米ZnO及其制备方法和用途 Download PDFInfo
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- CN115160826A CN115160826A CN202210824281.7A CN202210824281A CN115160826A CN 115160826 A CN115160826 A CN 115160826A CN 202210824281 A CN202210824281 A CN 202210824281A CN 115160826 A CN115160826 A CN 115160826A
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Abstract
本发明涉及功能性纳米ZnO的合成技术领域,特别是将一种功能性纳米ZnO及其制备方法以及作为光敏剂和增强剂应用到水性聚氨酯丙烯酸酯复合材料中。本发明通过水热合成法制得可控形貌的纳米ZnO,采用KH570进行改性后加入到水性聚氨酯丙烯酸酯乳液中,制得复合乳液,将复合乳液通过成膜方式转移到聚四氟乙烯板上或者将织物基基材浸润在复合乳液中后取出,干燥后通过波长为365nm的紫外光下照射固化,最终干燥制得水性聚氨酯丙烯酸酯复合材料。KH570改性的纳米ZnO不仅实现了高效的紫外光引发,还增强了改性水性聚氨酯丙烯酸酯复合材料的紫外吸收能力,改善了织物基涂层的力学性能、界面性能和耐水性,并实现了织物基涂层界面上亲疏水性能的可调。
Description
技术领域
本发明涉及功能性纳米ZnO的合成技术领域,特别是一种功能性纳米ZnO及其制备方法以及作为光敏剂和增强剂应用到水性聚氨酯丙烯酸酯复合材料中。
背景技术
目前,小分子光敏剂已经得到广泛应用,这类光敏剂在光固化过程中,残留量和光解产物容易迁移至产品表面,产生一定的气味,甚至毒性,极大地限制了其在食品包装、医疗卫生等方面的应用。另外,小分子光敏剂还存在阻氧、黄化、与UV固化树脂相容性差等缺点。近年来,相应的有机大分子光敏剂已经成为研究热点,其具有较低的气味、迁移性、毒性,同时还具有更好的耐黄变性;此外,与小分子光敏剂相比,它们的光引发效率得到提高,而且可以有效地减少氧抑制并改善UV固化材料的性能。
然而,与无机光敏剂相比,有机光敏剂在自由基聚合中存在的氧阻聚作用、挥发性光解碎片残留和膜迁移等缺点,在作为光敏剂添加到水性聚氨酯中时,仍然存在气味、毒性等缺点。
发明内容
本发明的目的之一是提供一种功能性纳米ZnO的制备方法,该方法制得的功能性纳米ZnO可以充当光敏剂和无机纳米填料的双重功能,从而与有机相紧密结合,以提高聚合物光固化涂层的综合性能,且环保无毒。
为实现上述目的,本发明采用了以下技术方案:一种功能性纳米ZnO的制备方法,包括如下步骤:
S1、室温下,在Zn(NO3)2水溶液中加入氢氧化钠水溶液和表面活性剂,搅拌均匀后转移至聚四氟乙烯反应釜中,在60-120℃下水热反应5-12h,自然冷却至室温后分离得到沉淀物,沉淀物用去离子水洗涤去除杂质,再用无水乙醇洗涤使沉淀分散更均匀,然后在40-100℃下干燥5-12h,制得纳米ZnO;
S2、在纳米ZnO中加入KH570硅烷偶联剂和无水乙醇,然后在N2气氛中于50-100℃温度下充分搅拌,反应2-8h后,分离得到沉淀物并去除上面吸附的过量硅烷,真空干燥后得到KH570硅烷偶联剂改性的功能性纳米ZnO。
作为功能性纳米ZnO的制备方法进一步的改进:
优选的,所述表面活性剂为十六烷基三甲基溴化铵即CTAB、十二烷基苯磺酸钠即SDBS、聚乙烯吡咯烷酮即PVP-K90中的一种。
优选的,所述表面活性剂为十六烷基三甲基溴化铵即SDBS。
优选的,步骤S1中所述Zn(NO3)2水溶液的浓度为0.1-2mol/L,氢氧化钠水溶液的浓度为0.5-4mol/L,Zn(NO3)2水溶液中所含Zn(NO3)2、氢氧化钠水溶液所含氢氧化钠和表面活性剂的质量比为7.4:8:1。
优选的,步骤S2中纳米ZnO与KH570硅烷偶联剂、无水乙醇的混合质量比为1:5:50。
本发明的目的之二是提供一种由上述制备方法制得的功能性纳米ZnO。
本发明的目的之三是提供一种上述功能性纳米ZnO在制备水性聚氨酯丙烯酸酯复合材料中的用途,包括如下步骤:
S21、将功能性纳米ZnO作为光敏剂添加到水性聚氨酯丙烯酸酯乳液即WPUA乳液中,添加量为0.5-3.0wt%,超声搅拌使功能性纳米ZnO均匀分散,得到WPUA复合乳液;
S22、得到通过成膜方式将WPUA复合乳液转移到聚四氟乙烯板上,在40-100℃下干燥0.5-4h,在功率为5-60W、波长为265-400nm的紫外光下照射固化,最后在50-100℃下干燥0.5-4h,即制得水性聚氨酯丙烯酸酯复合材料;
或者,将织物基基材在WPUA复合乳液中浸润后取出,在功率为5-60W、波长为265-400nm的紫外光下照射固化,再在50-100℃下干燥0.5-4h;重复织物基基材在WPUA复合乳液中浸润、干燥的步骤0次以上,即制得层数为1层以上的织物基水性聚氨酯丙烯酸酯复合材料。
作为功能性纳米ZnO在制备水性聚氨酯丙烯酸酯复合材料中的用途进一步的改进:
优选的,所述WPUA乳液的制备方法如下:
S11、在N2气氛中将聚丁二醇即PTMG-1000加入到四颈烧瓶中,然后缓慢滴加异佛尔酮二异氰酸酯即IPDI,所述PTMG-1000与IPDI的摩尔比为3.1:1,在50-100℃油浴下混合搅拌0.5-4h;
S12、在N2气氛中将异佛尔酮二异氰酸酯即IPDI加入到四颈烧瓶中,缓慢滴加2,2-二羟甲基丁酸即DMBA,所述IPDI与DMBA的摩尔比为1.2:1,在50-100℃油浴下反应0.5-4h;
S13、在N2气氛中将异佛尔酮二异氰酸酯即IPDI加入到四颈烧瓶中,缓慢滴加丙烯酸羟乙酯即HEA,所述IPDI与HEA的摩尔比为1:1,在50-100℃油浴下混合搅拌0.5-4h后,合成反应结束;
S14、将步骤S12的产物滴加到步骤S11中,50-100℃下搅拌0.5-4h;再向其中加入步骤S13的产物,50-100℃下搅拌0.5-4h,冷却至5-40℃后,加入三乙胺即TEA中和含有羧基的亲水扩链剂,添加量为TEA与DMBA的摩尔比1:1,反应0.5-4h后冷却至室温,加入H2O至反应体系的固含量为10-70wt%,搅拌乳化得到双键封端的聚氨酯乳液;
S15、取聚氨酯乳液与丙烯酸丁酯即BA、甲基丙烯酸甲酯即MMA混合置于四颈烧瓶中,所述聚氨酯乳液、BA、MMA的混合量摩尔比为3:3:2,在50-100℃下反应0.5-4h,然后滴加过硫酸铵即APS引发反应0.5-4h,最后反应再进行1-5h,制得水性聚氨酯丙烯酸酯乳液;
其中,步骤S11、S12、S13不分先后顺序。
优选的,步骤S3中所述织物基基材为棉、PET和PP中的一种。
本发明相比现有技术的有益效果在于:
1)本发明提供一种水性聚氨酯丙烯酸酯复合材料的制备方法,包括如下步骤:1.纳米ZnO的制备:氧化锌晶体的晶面生长速率决定了其生长形态,氧化锌每个晶面的生长速率为:通过调节晶体各晶面的生长速度可以制备出不同形貌的纳米ZnO。不同表面活性剂对氧化锌各晶面的表面能影响不同,从而改变其生长习性。因此,本发明使用不同的表面活性剂来得到不同形貌的纳米ZnO,其中选用十二烷基苯磺酸钠即SDBS作为表面活性剂制得的棒状纳米ZnO作为光敏剂对紫外光引发效果最好。
2.纳米ZnO的改性:纳米材料具有较高的比表面积和表面自由能,极易团聚,在有机基体中难以分散均匀,作为光敏剂时其光引发效率较低。因此,纳米材料的表面改性是改善其与基体之间分散性和相容性的关键工作。本发明通过KH570上的甲氧基与纳米ZnO表面的羟基进行水解缩合反应,引入反应基团对纳米ZnO进行改性,机制如下所示:
KH570改性后的纳米ZnO表面引入了硅氧烷和碳碳双键。在后期将纳米ZnO加入到WPUA乳液中进行紫外光固化时,引入的碳碳双键可以参与紫外光固化,进行自由基聚合,从而提高紫外光固化效率。在后期WPUA乳液固化成膜后,引入的硅氧烷倾向于向复合膜的表面迁移,从而提高其界面张力。
3.WPUA复合膜和织物基涂层的制备:光固化水性聚氨酯丙烯酸酯(WPUA)结合了光固化技术和水性涂料的优势,具有节约能源、生态环保绿色、经济、效率、多能等特点,属于绿色高效的环保型涂料。改性后的纳米ZnO在WPUA复合膜中充当了光敏剂和无机纳米填料的双重功能,增加纳米粒子与聚合物基体之间的相互作用,实现在高效紫外光引发的同时,也提高了WPUA复合膜的综合性能。此外,将WPUA复合乳液涂覆在不同织物基基材(棉、PET和PP)上,通过加入不同含量的纳米ZnO和增加浸涂层数来改变织物基涂层的界面张力,从而获得了亲水性和疏水性可调的织物基涂层。
2)光固化水性聚氨酯丙烯酸酯(WPUA)结合了光固化技术和水性涂料的优势,具有节约能源、生态环保绿色、经济、效率、多能等特点,属于绿色高效的环保型涂料。改性后的纳米ZnO在WPUA复合膜中充当了光敏剂和无机纳米填料的双重功能,增加纳米粒子与聚合物基体之间的相互作用,实现在高效紫外光引发的同时,也提高了WPUA复合膜的综合性能。此外,将WPUA复合乳液涂覆在不同织物基基材上,明显提高了织物基涂层对紫外光的吸收能力和机械性能。通过加入不同含量的纳米ZnO和增加浸涂层数来改变织物基涂层的界面张力,从而获得了亲水性和疏水性可调的织物基材料。
附图说明
图1中(a)-(c)是本发明实施例1采用不同表面活性剂制得的不同形貌的纳米ZnO;
图2是纯棉基、PP基、PET基和实施例6中不同光敏剂浓度的WPUA@ZnO NP的棉基、PP基和PET基复合材料的水接触角性能测试图;
图3是纯棉基、PP基、PET基和实施例6中不同光敏剂浓度的WPUA@ZnO NP的棉基、PP基和PET基复合材料的吸水率性能测试。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明,基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
本实施例提供一种纳米ZnO的制备方法,具体包括如下步骤:
采用水热合成法,室温下,在烧杯中加入0.25mol/L的Zn(NO3)2水溶液20mL、2mol/L的氢氧化钠水溶液20mL和0.2g表面活性剂(CTAB或SDBS或PVP-K90)。然后,将上述混合溶液搅拌均匀,转移至聚四氟乙烯反应釜中,放入鼓风干燥箱中120℃水热反应12h。反应结束后,自然冷却至室温。将混合物转移至试管中,8000r/min离心5min。沉淀用去离子水洗涤两次,以除去沉淀中的可溶性杂质,再用无水乙醇洗涤两次,以减少沉淀中颗粒的团聚,使沉淀分散更均匀。最后,在60℃下干燥12h得到三种不同形貌的纳米ZnO产物,缩写为ZnO NPs。
添加三种不同表面活性剂(CTAB、SDBS、PVP-K90)制备的纳米ZnO的SEM图像分别如图1(a)-(c)所示。由图1可知,添加阳离子表面活性剂CTAB时,制备的产物纳米ZnO为圆针状结构,面积大小不等;制备过程中添加阴离子表面活性剂SDBS时,制备的产物纳米ZnO为多边形的棒状结构,棒的直径与长度不是十分均匀;制备过程中添加非离子表面活性剂PVP-K90时,制备得到的纳米ZnO为花状结构,呈现无序堆积的状态,并且末端为锥形。在制备过程中使用不同表面活性剂可以得到不同形貌的纳米ZnO,这是因为纳米微晶的生长是以表面能降低为驱动力,各个晶面竞争生长的过程。不同表面活性剂对纳米ZnO各晶面的表面能影响不同,从而改变其生长习性。
实施例2
本实施例提供一种改性的纳米ZnO制备方法,具体包括如下步骤:
取实施例1中以SDBS为表面活性剂制得的纳米ZnO,在四颈烧瓶中加入3.0g的纳米ZnO、15g的KH570、150ml的无水乙醇,然后在N2气氛下于70℃搅拌反应5h。反应后,将其转移到试管中以5000r/min离心15min。通过索氏提取法用乙醇洗涤沉淀物12h以去除吸附在纳米ZnO上的过量硅烷。最后,将沉淀物在60℃下真空干燥12h,得到KH570改性的纳米ZnO。
实施例3
本实施例提供一种WPUA乳液的制备方法,具体包括如下步骤:
合成反应在N2气氛中,油浴进行。反应一:先将50g的PTMG-1000加入到四颈烧瓶中,然后缓慢滴加3.5994g的IPDI,在80℃下混合搅拌2h。反应二:以同样的反应条件将6.1405g的IPDI加入到四颈烧瓶中,缓慢滴加3.4106g的DMBA,反应1.5h。反应三:将12.9879g的IPDI加入到四颈烧瓶中,缓慢滴加6.7837g的HEA,在70℃下混合搅拌2h后结束反应。将反应二的产物滴加到反应一中,80℃下搅拌2h;再向其中加入反应三的产物,70℃下搅拌2h合成反应结束。
合成反应结束后冷却至30℃后,加入2.3294g的TEA(TEA:DMBA=1:1)中和亲水扩链剂中的羧基,反应0.5h后冷却至室温,加入固含量为30%的H2O,搅拌乳化得到双键封端的聚氨酯乳液。取40g聚氨酯乳液,与2.1994g的BA、1.1454g的MMA混合置于四颈烧瓶中,在80℃下反应0.5h,然后滴加0.0334g的APS(BA和MMA总质量的1%)引发1.5h左右,最后反应再进行3h,制得水性聚氨酯丙烯酸酯乳液即WPUA乳液。
实施例4
本实施例提供一种水性聚氨酯丙烯酸酯复合材料的制备方法,该复合材料为复合膜,具体包括如下步骤:
S1、取实施例2制得的KH570改性的纳米ZnO,将KH570改性的纳米ZnO加入到实施例3制备的WPUA乳液中,添加浓度分别为0.5wt%、1.0wt%、1.5wt%,超声搅拌5min,使光敏剂均匀分散在乳液中,得到WPUA@ZnO NP复合乳液1-3。
作为对比,取184作为光敏剂,加入到实施例3制备的WPUA乳液中,添加浓度分别为0.5wt%、1.0wt%、1.5wt%,超声搅拌5min,使光敏剂均匀分散在乳液中,得到WPUA@184复合乳液4-6。
S2、将WPUA复合乳液1-6分别通过制膜方式转移到聚四氟乙烯板上,在60℃烘箱中干燥2h,在365nm紫外灯(6w)下照射固化,最后在80℃烘箱中干燥0.5h。固化后,将复合膜剥离并放入干燥器中备用,分别命名为WPUA@ZnO NP复合膜和WPUA@184复合膜。
用UV-Vis-NIR分光光度计测试了不同含量的184和纳米ZnO光引发制备的WPUA复合膜的吸光度,如下表1所示。在相同的光敏剂含量下,WPUA@ZnO NP复合膜的吸光度均比WPUA@184复合膜的吸光度高。结果表明,WPUA@ZnO NP复合膜具有更强的紫外光吸收能力,通过将纳米ZnO掺入WPUA基体中,可以有效吸收约400nm以下的紫外光。因此,纳米ZnO与WPUA的复合结构可以潜在地应用于紫外线屏蔽材料和光学材料,如涂料、化妆品和塑料。
表1不同光敏剂和光敏剂含量的复合膜的吸光度
实施例5
本实施例提供一种水性聚氨酯丙烯酸酯复合材料的制备方法,该复合材料为PP基复合涂层,具体包括如下步骤:
S1、取实施例2制得的KH570改性的纳米ZnO作为光敏剂,加入到实施例3制备的WPUA乳液中,添加浓度为0.5wt%,超声搅拌5min,使光敏剂均匀分散在乳液中,得到WPUA@ZnO NP复合乳液。
取184作为光敏剂加入到实施例3制备的WPUA乳液中,添加浓度为0.5wt%,超声搅拌5min,使光敏剂均匀分散在乳液中,得到WPUA@184复合乳液。
S2、将PP基基材浸入WPUA@ZnO NP复合乳液中10min后取出,然后在365nm紫外光下取出并固化,最后在80℃下干燥0.5h,得到PP-WPUA@ZnO NP涂层,重复PP基基材在WPUA复合乳液中浸润、干燥的步骤分别为0、1、2、3次,制得浸涂层数分别为1、2、3、4的PP-WPUA@ZnONP复合涂层。
将PP基基材浸入WPUA@184复合乳液中10min后取出,然后在365nm紫外光下取出并固化,最后在80℃下干燥0.5h,得到PP-WPUA@184涂层,重复PP基基材在WPUA复合乳液中浸润、干燥的步骤分别为0、1、2、3次,制得浸涂层数分别为1、2、3、4的PP-WPUA@184复合涂层。
以未经处理的PP基基材作为对照,对浸涂层数分别为1、2、3、4的PP-WPUA@ZnO NP复合涂层和浸涂层数分别为1、2、3、4的PP-WPUA@184复合涂层进行测试,应力-应变数据如下表2所示。由下表2可知,随着浸涂层数的增加,PP-WPUA@184涂层的断裂伸长率呈现出降低的趋势,其抗拉强度均比纯PP低,而PP-WPUA@ZnO NP涂层的抗拉强度和断裂伸长率均比纯PP高。将PP-WPUA@ZnO NP涂层与PP-WPUA@184涂层相比,其抗拉强度提高了41.10%,断裂伸长率提高了34.75%。结果表明,以纳米ZnO作为光敏剂制备的WPUA复合乳液的力学性能优于184,说明纳米ZnO不仅作为光敏剂具有高效的紫外光引发性能,还能够复合改性WPUA复合膜的力学性能。
表2PP基基材和不同浸涂层数复合涂层的应力-应变测试
实施例6
本实施例提供一种水性聚氨酯丙烯酸酯复合材料的制备方法,该复合材料分别为棉基、PP基和PET基的复合涂层,具体包括如下步骤:
S1、取实施例2制得的KH570改性的纳米ZnO作为光敏剂,加入到实施例3制备的WPUA乳液中,添加浓度分别为0.5wt%、1.0wt%、1.5wt%、2.0wt%、2.5wt%、3.0wt%,超声搅拌5min,使光敏剂均匀分散在乳液中,分别得到不同光敏剂浓度的WPUA@ZnO NP复合乳液。
S2、将棉基、PP基和PET基基材分别浸入不同光敏剂浓度的WPUA@ZnO NP复合乳液中10min后取出,然后在365nm紫外光下取出并固化,最后在80℃下干燥0.5h,分别得到不同光敏剂浓度的WPUA@ZnO NP的棉基、PP基和PET基复合涂层。
1)、对实施例6中不同光敏剂浓度的WPUA@ZnO NP的棉基、PP基和PET基复合涂层进行水接触角性能测试,结果如图2的柱状图所示。
当改性后的纳米ZnO在WPUA乳液中的添加量由0增加至含量为1.5wt%时,水接触角随着纳米ZnO含量的增加而增大,当纳米ZnO含量为1.5wt%以后,水接触角随着纳米ZnO含量的增加而减小,棉涂层从亲水变为疏水再变为亲水。这是因为改性后的纳米ZnO上接有Si,纳米ZnO的含量增加,Si的含量也增加。Si倾向于迁移到复合材料的表面,从而增加棉涂层的界面张力。随着纳米ZnO含量的增加,硅氧烷接枝物上不饱和双键的自聚合可能导致棉涂层的界面张力降低,从而降低其水接触角。
纯PET浸涂WPUA@ZnO NP复合乳液后,水接触角均大于90°,PET涂层由亲水变为疏水。这是因为复合乳液中的硅氧烷迁移到涂层表面。此外,纯PET材料的表面粗糙度较低。当复合乳液浸入PET材料中时,涂层的表面粗糙度增加,从而增加了PET涂层的界面张力。
当纳米ZnO在WPUA乳液中的添加量由1.5wt%增加至含量为3wt%范围内,PP涂层的水接触角随着改性后的纳米ZnO含量的增加逐渐减小,PP涂层由疏水变为亲水。这是因为复合乳液中含有亲水基团COO-,纯PP材料浸涂在复合乳液中会降低涂层的疏水性。另外,纯PP材料的表面粗糙度高,复合乳液会填满复合乳液中的孔隙,使得PP涂层表面的粗糙度降低,从而降低了PP涂层的界面张力。因此,获得了一种可调节亲水性和疏水性的织物基涂层。
2)、将棉基、PP基和PET基基材,以及实施例6中不同光敏剂浓度的WPUA@ZnO NP的棉基、PP基和PET基复合涂层进行吸水率性能测试,吸水率曲线如图3所示。
由图3可知,纯棉和纯PET的吸水率比较大,因为纯棉和纯PET都是亲水材料。当纯棉和纯PET浸涂WPUA复合乳液作为织物基涂层时,它们的吸水率分别降低了约71.65%和68.10%。这是因为硅氧烷附着在改性的纳米ZnO上,硅氧烷倾向于迁移到复合材料的表面,从而增加了棉涂层和PET涂层之间的界面张力,提高了耐水性。纯PP的吸水率为0%,因为纯PP材料是疏水材料。当纯PP浸涂WPUA复合乳液作为织物基涂层时,其吸水率显著增加。这是因为复合乳液中含有亲水基团COO-,纯PP材料浸涂在复合乳液中会降低涂层的界面张力。结果表明,WPUA@ZnO NP复合乳液可以明显提高棉和PET涂层的耐水性。
本领域的技术人员应理解,以上所述仅为本发明的若干个具体实施方式,而不是全部实施例。应当指出,对于本领域的普通技术人员来说,还可以做出许多变形和改进,所有未超出权利要求所述的变形或改进均应视为本发明的保护范围。
Claims (9)
1.一种功能性纳米ZnO的制备方法,其特征在于,包括如下步骤:
S1、室温下,在Zn(NO3)2水溶液中加入氢氧化钠水溶液和表面活性剂,搅拌均匀后转移至聚四氟乙烯反应釜中,在60-120℃下水热反应5-12h,自然冷却至室温后分离得到沉淀物,沉淀物用去离子水洗涤去除杂质,再用无水乙醇洗涤使沉淀分散更均匀,然后在40-100℃下干燥5-12h,制得纳米ZnO;
S2、在纳米ZnO中加入KH570硅烷偶联剂和无水乙醇,然后在N2气氛中于50-100℃温度下充分搅拌,反应2-8h后,分离得到沉淀物并去除上面吸附的过量硅烷,真空干燥后得到KH570硅烷偶联剂改性的功能性纳米ZnO。
2.根据权利要求1所述的功能性纳米ZnO的制备方法,其特征在于,所述表面活性剂为十六烷基三甲基溴化铵即CTAB、十二烷基苯磺酸钠即SDBS、聚乙烯吡咯烷酮即PVP-K90中的一种。
3.根据权利要求2所述的功能性纳米ZnO的制备方法,其特征在于,所述表面活性剂为十六烷基三甲基溴化铵即SDBS。
4.根据权利要求1所述的功能性纳米ZnO的制备方法,其特征在于,步骤S1中所述Zn(NO3)2水溶液的浓度为0.1-2mol/L,氢氧化钠水溶液的浓度为0.5-4mol/L,Zn(NO3)2水溶液中所含Zn(NO3)2、氢氧化钠水溶液所含氢氧化钠和表面活性剂的质量比为7.4:8:1。
5.根据权利要求1所述的功能性纳米ZnO的制备方法,其特征在于,步骤S2中纳米ZnO与KH570硅烷偶联剂、无水乙醇的混合质量比为1:5:50。
6.一种权利要求1-5任意一项的制备方法制得的功能性纳米ZnO。
7.一种由权利要求6所述的功能性纳米ZnO在制备水性聚氨酯丙烯酸酯复合材料中的用途,其特征在于,包括如下步骤:
S21、将功能性纳米ZnO作为光敏剂添加到水性聚氨酯丙烯酸酯乳液即WPUA乳液中,添加量为0.5-3.0wt%,超声搅拌使功能性纳米ZnO均匀分散,得到WPUA复合乳液;
S22、得到通过成膜方式将WPUA复合乳液转移到聚四氟乙烯板上,在40-100℃下干燥0.5-4h,在功率为5-60W、波长为265-400nm的紫外光下照射固化,最后在50-100℃下干燥0.5-4h,即制得水性聚氨酯丙烯酸酯复合材料;
或者,将织物基基材在WPUA复合乳液中浸润后取出,在功率为5-60W、波长为265-400nm的紫外光下照射固化,再在50-100℃下干燥0.5-4h,重复织物基基材在WPUA复合乳液中浸润、干燥的步骤0次以上,即制得层数为1层以上的织物基的水性聚氨酯丙烯酸酯复合材料。
8.根据权利要求7所述功能性纳米ZnO在制备水性聚氨酯丙烯酸酯复合材料中的用途,其特征在于,所述WPUA乳液的制备方法如下:
S11、在N2气氛中将聚丁二醇即PTMG-1000加入到四颈烧瓶中,然后缓慢滴加异佛尔酮二异氰酸酯即IPDI,所述PTMG-1000与IPDI的摩尔比为3.1:1,在50-100℃油浴下混合搅拌0.5-4h;
S12、在N2气氛中将异佛尔酮二异氰酸酯即IPDI加入到四颈烧瓶中,缓慢滴加2,2-二羟甲基丁酸即DMBA,所述IPDI与DMBA的摩尔比为1.2:1,在50-100℃油浴下反应0.5-4h;
S13、在N2气氛中将异佛尔酮二异氰酸酯即IPDI加入到四颈烧瓶中,缓慢滴加丙烯酸羟乙酯即HEA,所述IPDI与HEA的摩尔比为1:1,在50-100℃油浴下混合搅拌0.5-4h后,合成反应结束;
S14、将步骤S12的产物滴加到步骤S11中,50-100℃下搅拌0.5-4h;再向其中加入步骤S13的产物,50-100℃下搅拌0.5-4h,冷却至5-40℃后,加入三乙胺即TEA中和含有羧基的亲水扩链剂,添加量为TEA与DMBA的摩尔比1:1,反应0.5-4h后冷却至室温,加入H2O至反应体系的固含量为10-70wt%,搅拌乳化得到双键封端的聚氨酯乳液;
S15、取聚氨酯乳液与丙烯酸丁酯即BA、甲基丙烯酸甲酯即MMA混合置于四颈烧瓶中,所述聚氨酯乳液、BA、MMA的混合量摩尔比为3:3:2,在50-100℃下反应0.5-4h,然后滴加过硫酸铵即APS引发反应0.5-4h,最后反应再进行1-5h,制得水性聚氨酯丙烯酸酯乳液;
其中,步骤S11、S12、S13不分先后顺序。
9.根据权利要求7所述功能性纳米ZnO在制备水性聚氨酯丙烯酸酯复合材料中的用途,其特征在于,步骤S3中所述织物基基材为棉、PET和PP中的一种。
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