CN106634078A - 一种具有光催化特性的核壳结构杂化溶胶及其制备与应用 - Google Patents
一种具有光催化特性的核壳结构杂化溶胶及其制备与应用 Download PDFInfo
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- CN106634078A CN106634078A CN201611220615.0A CN201611220615A CN106634078A CN 106634078 A CN106634078 A CN 106634078A CN 201611220615 A CN201611220615 A CN 201611220615A CN 106634078 A CN106634078 A CN 106634078A
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Abstract
本发明公开了一种具有光催化特性的核壳结构杂化溶胶及其制备方法与应用,其是以光催化纳米微粒为核,采用原位聚合的方法,在纳米微粒表面聚合一层有机聚合物制备而成。该溶胶制备的涂膜液可在常温条件下直接涂覆于有机基材表面,形成一层透明薄膜,该薄膜与有机基材接触的一面可使光催化纳米微粒有效附着并产生自隔离效应,以有效避免纳米光催化剂在使用过程中对有机基材的破坏;而在一定的UV光或太阳光照射后,最外层的有机物可被纳米光催化剂分解、微粉化,从而使纳米光催化剂裸露出来,而使整个涂层具备良好的自洁、耐沾污的性能;此外,该薄膜还具有吸收隔离紫外线的功能,可对有机基材起到保色、耐老化等保护作用。
Description
技术领域
本发明属于涂层材料技术领域,具体涉及一种具有光催化特性的核壳结构杂化溶胶及其制备方法与应用。该溶胶添加少量助剂制成的涂膜液可在常温条件下直接涂覆在涂料、塑料板材等有机基材表面,产生自隔离效应,避免纳米二氧化钛光催化剂在使用过程中对有机基材的破坏,同时表现出具有光催化特征的亲水效应,从而使整个涂层具备良好的自洁、耐沾污性能,解决了纳米光催化剂溶胶在实际使用中的施工难题。
背景技术
对于外用装饰物(涂料、瓷砖、玻璃、铝板、塑料薄膜、帐篷以及水泥材料等)而言,装饰性是其基本功能。近年来,为了增强建筑外墙的装饰美观,所用外用装饰物的品种、规格、类别更具多样化,但其中很大一部分的表面存在微孔洞,防水、耐脏污性能较差。
众所周知,物体表面的赃污程度与其表面的亲水亲油性密切相关,如果物体表面是亲水的,则容易粘附沙尘等无机矿物质,反之,如果物体表面是亲油的,则容易粘附油烟等有机物。随着我国工业化、城市化进程加快,大气污染日益严重,空气中的有机污物急剧增加,外墙装饰物等暴露在空气中的物体表面很容易脏污,有机污垢较之无机物的粘附性更强,难以清除,而目前采用硅丙清漆或有机硅涂液罩面方法制得的涂层表面为疏水性,无法满足要求。因此,有必要研发亲水性的外用装饰物,以提高物体表面抗脏污能力。
结合光催化降解有机物、光催化抗菌杀菌和光诱导亲水性等多种功能的自洁净表面技术,早在20世纪90年代末在日本成功获得商业化应用,近年来发展更为迅速,是当代国际上制备自清洁涂层最成功有效的方法之一。为了在物体表面形成超亲水自洁净表面,需要解决纳米二氧化钛等光催化材料在各种基材表面的有效附着问题。现有常规工艺中已公开,对无机基材(瓷砖、玻璃、石材、亲水混凝土、金属板材等)采用高温处理,但其成本较高,能源浪费严重;对有机基材(涂料、PVC等)采用隔离层技术(如中国专利200710071104.1),即采用无机或有机材料对表层进行隔离预处理,再涂覆光催化剂涂层,以避免光催化剂对有机涂层的破坏,该法能较好保障涂料使用的耐久性问题,又能充分发挥光催化溶胶的抗污自洁性能,但该方法需进行二道施工,在实用性和经济上存在缺陷。
核壳型乳液是在80年代Okubo提出“粒子设计”的概念之后,采用种子乳液聚合法制备具有异相(核/壳)结构乳胶粒子的新型聚合物乳液。由于核/壳结构乳胶粒的核、壳层之间可能存在接技、互穿或离子键合,使它不同于一般的共混物。核-壳结构的纳米复合材料中,复合颗粒由中心粒子(核)和包覆层物质(壳)组成,按包覆层的形态不同可分为均匀涂层包覆和粒子包覆两种。在无机粒子外包覆聚合物这类杂化纳米粒子,一般是以无机粒子作为模板,主要是通过乳液聚合方法,利用胶体化学的原理,控制聚合反应在无机粒子表面的发生而形成包覆。
发明内容
本发明的目的在于提供一种具有光催化特性的核壳结构杂化溶胶及其制备方法与应用。该溶胶制备的涂膜液能够直接涂敷在有机基底表面,其施工简便,且其形成的涂层具有良好自洁、耐沾污、防水、保色、耐老化等性能,能满足对外用装饰材料的多方面需求。
为实现上述目的,本发明采用如下技术方案:
一种具有光催化特性的核壳结构杂化溶胶,其是以光催化纳米微粒为核,采用原位聚合的方法,在光催化纳米微粒表面聚合一层有机聚合物而制备得到(其结构示意图如图1);
其中,所述光催化纳米微粒的粒径为5~20nm;
所述有机聚合物包括有机硅树脂、丙烯酸树脂、聚氨酯树脂中的一种或几种。
所述光催化纳米微粒为纳米TiO2微粒,或在纳米TiO2中掺杂金属或金属氧化物而制得的混合微粒;
所述金属包括铁、铂、镍、铑、银、金中的一种或几种,所述金属氧化物包括SiO2、ZnO、WO3、SrTiO3中的一种或几种。
所述纳米TiO2来源于钛酸酯、钛酸盐或其混合物。
所述核壳结构杂化溶胶可采用四种方法进行制备:
第一种是采用溶胶凝胶法合成水性过氧化钛前驱体,然后将其加入到含硅酸乙酯的酸性甲醇溶液中,400~1000W超声分散5~30min后,在超声条件下于50~80℃加水反应2~6h,再加入硅烷偶联剂继续反应1~2h,在硅酸乙酯、硅烷偶联剂水解的同时,使水性过氧化钛前驱体脱水形成纳米二氧化钛微粒,从而直接合成所述核壳结构杂化溶胶;
所述含硅酸乙酯的酸性甲醇溶液中,甲醇与硅酸乙酯的摩尔比为10~20:1,溶液pH=1;
所用硅烷偶联剂的浓度为0.1~1.0vol%。
第二种是采用溶胶凝胶法合成表面含有钛羟基(Ti-O-H)而带负电荷的纳米二氧化钛溶胶,然后在其中加入表面带正电荷的水性有机聚合物,并加入无机纳米微粒分散稳定剂,400~1000W超声分散5~30min,利用静电吸附使水性有机聚合物吸附在纳米二氧化钛微粒表面,再在超声条件下升温至60~80℃,保温1~2h进行脱水缩合反应,制得所述核壳结构杂化溶胶;
所述水性有机聚合物包括丙烯酸树脂、有机硅树脂、聚氨酯树脂或其混合物;
所述无机纳米微粒分散稳定剂包括硅酸镁铝、硅溶胶。
第三种是采用溶胶凝胶法合成表面含有钛羟基(Ti-O-H)而带负电荷的纳米二氧化钛溶胶,400~1000W超声分散5~30min后,加入含丙烯酸类单体的纳米微乳,采用半连续乳液聚合法,在超声条件下升温至70~90℃,恒温反应1~2h,制得所述杂化溶胶。
所述丙烯酸类单体为甲基丙烯酸甲酯、甲基丙烯酸叔丁酯、丙烯酰胺、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸羟乙酯、甲基丙烯酸和丙烯酸中的一种或几种。
第四种是将硅酸乙酯、结构式为R1 pSiXq(OR2)t的可水解硅化合物与钛酸酯或钛酸盐共同溶于溶剂中,然后加入乙酰丙酮及浓盐酸,超声分散5~30min,再加入无水乙醇与5wt%盐酸按体积比1:1的混合溶液,在50~80℃条件下恒温水解反应2~4h,制得所述核壳结构杂化溶胶;
其中,所述硅酸乙酯、可水解硅化合物、钛酸酯或钛酸盐与溶剂的摩尔用量比为1:0.1~0.5:1:10~20;
所用溶剂为甲醇、乙醇、异丙醇或丙酮中的一种或几种;
与常规制备方法相比,本发明中四种制备方法的反应过程均可在常压、低温(60~100℃)条件下进行,反应条件简单,且所制备的杂化溶胶中的纳米TiO2粒子为锐钛矿型,结晶度高,光催化性能优,纳米粒径小(5~20 nm)。
在本发明核壳结构杂化溶胶中加入助剂及溶剂制成涂膜液(涂膜液中杂化溶胶的有效固含量为1~10wt%,助剂的含量为0.1~5wt%),所得涂膜液可在常温条件下直接涂覆在涂料、油漆、瓷砖、塑料板材、保温隔热墙体、有机玻璃、交通路网声屏障等有机基材表面,形成一层透明薄膜。
如图2所示,以本发明核壳结构杂化溶胶制备的涂膜液在成膜过程中由于“同性相吸、异性相拆”的原理,会产生自分层,而在微观上表现为三层结构,其中,有机聚合物在有机基材表面聚集,干燥成膜后在有机基材表面形成一层自隔离透明层,而使纳米光催化剂能有效附着在有机基材表面,并可有效避免纳米光催化剂在使用过程中对有机基材的破坏,省去了常规工艺中需涂覆无机隔离层的麻烦;而纳米光催化剂由于粒径小、比表面积大、表面能大,在成膜过程中除部分与有机聚合物形成钛氧硅碳(Ti-O-Si-C)或钛氧碳(Ti-O-C)键外,其余部分容易富集于靠近空气的中间层;而涂膜液中的有机聚合物除大部分富集于基材表面形成隔离薄膜外,小部分在靠近空气的最外层形成一层很薄的有机层,该有机层在UV光或太阳光照射一定时间(正常情况下7~15天)后,可被纳米光催化剂分解、微粉化,从而使纳米光催化剂微粒裸露出来,使其表现出具有光催化特征的亲水效应,从而使整个涂层具备良好的自洁、耐沾污性能;同时,由于所形成的涂层具有吸收、隔离紫外线的功能,可对有机基材起到保色、耐老化等保护作用,并具有一定防水性能。
附图说明
图1为本发明所制备核壳结构杂化溶胶的结构示意图,其中,1为光催化纳米微粒,2为包覆的有机聚合物。
图2为本发明核壳结构杂化溶胶经涂覆后的使用原理示意图。
图3为实施例1所制备核壳结构杂化溶胶的TEM图(A)及XRD图(B)。
图4为实施例5所制备掺金纳米二氧化钛溶胶的TEM图。
图5为用实施例1制备的涂膜液与某品牌硅树脂罩光清漆处理的物件,经户外暴晒后表面自清洁对比情况图。
图6为紫外光照射前后,实施例5制备的含掺金核壳结构杂化溶胶的涂膜液与市场上常用的保色罩面剂及空白样品涂覆于普通涂料涂层表面后的效果对比图,其中,A为照射前,B为照射后。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1:
1、水性过氧化钛前驱体(PTC)的制备:
1)在冰水浴条件下将40g的TiCl4以1滴/s的速度滴入强烈搅拌的1000mL纯水中,制得0.2mol/L的TiCl4溶液;
2)用质量分数为2%的氨水调节溶液的pH值至8,得到正钛酸沉淀,用去离子水洗涤沉淀10遍;
3)将沉淀分散于200mL质量浓度为10%的过氧化氢溶液中,制备得到水性过氧化钛前驱体(PTC)。
2、有机硅粘接剂前驱体的制备:将25mL硅酸乙酯及1.5mL硝酸到加入250mL甲醇溶液中,600W超声分散30min,得到pH=1的含硅酸乙酯的甲醇溶液,即为有机硅粘接剂前驱体。
3、核壳结构杂化溶胶的制备:取制得的有机硅粘接剂前驱体100mL,在600W超声条件下于50℃恒温水浴锅中滴加水性过氧化钛前驱体50mL,滴加过程采用质量分数为5%的硝酸控制溶液pH值在3.0~4.0,滴加完后继续搅拌2h,并滴加去离子水50mL,然后水解反应3h,再加入1 mL的KH560(γ-缩水甘油醚氧丙基三甲氧基硅烷)进行改性反应1h,于室温下陈化24h,制得所述杂化溶胶。
4、涂膜液的制备:取所制备杂化溶胶200mL,在搅拌条件下加入2g分散剂SN-5040、10g成膜助剂丙二醇丙醚,再加质量分数为2%的氨水调节pH值至7.0,加水调节产品的固含量为5.0%,充分搅拌均匀作为涂膜液。
图3为本实施例所制备核壳结构杂化溶胶的TEM图(A)及经50℃烘干后的XRD图(B)。检测结果表明,纳米TiO2的晶型为锐钛矿型,结晶度高,粒径约为10.2nm。
实施例2:
1、纳米TiO2溶胶的制备:
1)在冰水浴条件下将0.1mol的TiOSO4以1滴/s的速度滴入强烈搅拌的1000mL纯水中,制得0.1mol/L的TiOSO4溶液;
2)用氨水调节溶液的pH值至8,得到正钛酸沉淀,用去离子水洗涤沉淀10遍;
3)将沉淀分散于400mL质量浓度为30%的过氧化氢溶液中,制备得到水性过氧化钛(PTC)溶液;
4)将上述所制备的PTC溶液加水稀释至1000mL,升温至80℃并保温回流3h,制得纳米TiO2溶胶,所得溶胶含有大量未完全反应的钛羟基(Ti-O-H)而使溶胶带负电荷。
2、核壳结构杂化溶胶的制备:取上述制备的纳米TiO2溶胶200mL,加入5mL固含量为20%的无机纳米SiO2溶胶、40 mL固含量为30%的丙烯酸树脂乳液(“汉高”公司生产的商品名为KD6),并加纯水至400 mL,600W下超声分散20min,然后升温至80℃,保温反应1h进行脱水缩合反应,制得杂化溶胶。
涂膜液的制备同实施例1。
实施例3:
1、纳米TiO2溶胶的制备同实施例2。
2、纳米有机微乳液中间体的制备:
1)将反应单体甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)、乳化剂OP-10与纯水按质量比3:2:1.5:0.2:10配成预乳化混合物600mL;
2)在装有搅拌器、回流冷凝管、温度计的四口瓶中先加入200mL上述预乳化混合物,再加入pH调节缓冲剂(质量分数为5%的碳酸氢钠)调节pH至6,机械搅拌分散1h,然后升温至75℃,再加入引化剂(质量分数为5%的过硫酸钾水溶液)20 mL,反应维持半小时形成种子,再升温至80℃,然后连续滴加剩余的预乳化混合物,并再同步滴加40mL引发剂,用1-1.5h滴加完毕后,继续恒温反应1h,冷却降温至40℃以下,得到稳定的纳米有机微乳液中间体。
3、核壳结构杂化溶胶的制备:取制得的纳米TiO2溶胶100mL,加入1.5g表面活性剂DC01,置于50℃恒温水浴锅中600W超声分散20min,然后加入制得的纳米有机微乳液中间体200mL,并加蒸馏水至400mL,在600W超声条件下升温至80℃,恒温反应1h,制得所述杂化溶胶。
涂膜液的制备同实施例1。
实施例4:
将0.2mol的硅酸乙酯、0.05mol的KH560(γ-缩水甘油醚氧丙基三甲氧基硅烷)及0.2mol的正钛酸丁酯加入到100mL无水乙醇中,然后加入0.01mol的乙酰丙酮及0.5mL的浓盐酸,600W超声分散30min,再在所得溶液中滴加无水乙醇与质量分数为5%的盐酸按体积比1:1配制的混合溶液,在60℃、pH 2~5条件下超声水解反应4h,制得所述杂化溶胶。
涂膜液的制备同实施例1。
实施例5:
1、低温制备掺金纳米二氧化钛溶胶:
1)在冰水浴条件下制备0.2mol/L的TiOSO4溶液1000mL,用氨水调节溶液的pH值至8,得到正钛酸沉淀,用去离子水洗涤沉淀10遍;然后将沉淀分散于200mL质量浓度为20%的过氧化氢溶液中,制备得到水性过氧化钛前驱体;
2)将质量浓度为20%的柠檬酸溶液100 mL加热到100℃,然后加入质量浓度为1%的氯金酸溶液10g,回流30min,然后将其加入水性过氧化钛前驱体中,升温至100℃继续回流4h,制得掺金纳米二氧化钛溶胶。
2、掺金核壳结构杂化溶胶的制备:取上述制备的掺金纳米二氧化钛溶胶200mL,加入5mL固含量为20%的无机纳米SiO2溶胶、40 mL固含量为30%的丙烯酸树脂乳液,并加纯水至400 mL,600W下超声分散20min,然后升温至80℃,保温反应1h进行脱水缩合反应,制得杂化溶胶。
涂膜液的制备同实施例1。
图4为本实施例所制备掺金纳米二氧化钛溶胶的TEM图。从图中可以看出,Au粒子成功掺杂在二氧化钛溶胶中。
实际应用效果:
1、成膜性能检测:
将实施例1-5制备的涂膜液3g分别倒入60mm表面皿中,于常温下干燥,干燥后可形成一层完整、均匀、透明的膜,用手指擦没有划痕,说明所得涂层的附着力良好。
2、光催化自清洁性能检测:
取实施例1-5制备的涂膜液少量,于常温下涂覆(可采用提拉、喷涂或滚涂)于玻璃上,常温下干燥形成透明的涂层,按照GB/T 23764-2009方法检测其光催化自清洁性能,结果见表1。
表1 自洁性能检测结果
结果表明,初始时涂层表面体现为疏水性,接触角在50°以上,随着光照时间的延长,接触角降至15°以下,说明涂层表面有机层被分解、氧化,因而表现出具有光催化特征的亲水效应。
3、耐沾污性能检测:
选用某知名品牌的真石漆,按JG/T 24-2000“合成树脂乳液砂壁状建筑涂料”中规定进行制样,对实施例1-5制备的涂膜液和某品牌硅树脂罩光清漆分别进行耐沾污性比较,结果见表2。
表2 耐沾污性能比较
图5为经实施例1制备的涂膜液与某品牌硅树脂罩光清漆处理后的物件户外暴晒后的自清洁效果图。由图中也可以看出,经本发明涂膜液处理后的表面较罩光清漆处理后的表面更加洁净。
4、耐老化性能检测:
在石棉水泥板上,按照GB/T9755-2001《合成树脂乳液外墙涂料》要求刷涂二道外墙涂料,干燥7d后,再将实施例1-5制备的杂化溶胶的涂膜液分别涂覆在其一半表面上,干燥2d后,参照GB/T9755-2001标准进行耐人工气侯老化性能对比检测,检测结果如表3。
表3 耐人工气侯老化性能试验结果
检测结果表明,涂覆涂膜液后的涂料板经400h耐人工气候老化性照射后,变色性能均有所改善(由1级提升为0级)。
5、保色性能检测
将实施例1-5制备的涂膜液与市场上常用的保色罩面剂及空白样品同时涂覆于普通涂料涂层表面,干燥成膜后,放在紫外光(波长365nm,光强13mw/cm2)下照射50h,然后与未照射前的效果进行对比,结果显示,与市场上常用的保色罩面剂及空白样品相比,经本发明涂膜液涂覆后具有较好保色效果。
图6为紫外光照射前后,实施例5制备的含掺金核壳结构杂化溶胶的涂膜液与常用的保色罩面剂及空白样品涂覆于普通涂料涂层表面后的效果对比图。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (8)
1.一种具有光催化特性的核壳结构杂化溶胶,其特征在于,所述杂化溶胶是以光催化纳米微粒为核,采用原位聚合的方法,在光催化纳米微粒表面聚合一层有机聚合物而制备得到;
其中,所述光催化纳米微粒的粒径为5~20nm;
所述有机聚合物包括有机硅树脂、丙烯酸树脂、聚氨酯树脂中的一种或几种。
2.根据权利要求1所述具有光催化特性的核壳结构杂化溶胶,其特征在于,所述光催化纳米微粒为纳米TiO2微粒,或在纳米TiO2中掺杂金属或金属氧化物而制得的混合微粒;
所述金属包括铁、铂、镍、铑、银、金中的一种或几种,所述金属氧化物包括SiO2、ZnO、WO3、SrTiO3中的一种或几种。
3.根据权利要求2所述具有光催化特性的核壳结构杂化溶胶,其特征在于,所述纳米TiO2来源于钛酸酯、钛酸盐或其混合物。
4.一种制备如权利要求1所述核壳结构杂化溶胶的方法,其特征在于,其步骤包括:采用溶胶凝胶法合成水性过氧化钛前驱体,然后将其加入到含硅酸乙酯的酸性甲醇溶液中,400~1000W超声分散5~30min后,在超声条件下于50~80℃加水反应2~6h,再加入硅烷偶联剂继续反应1~2h,在硅酸乙酯、硅烷偶联剂水解的同时,使水性过氧化钛前驱体脱水形成纳米二氧化钛微粒,从而直接合成所述核壳结构杂化溶胶;
所述含硅酸乙酯的酸性甲醇溶液中,甲醇与硅酸乙酯的摩尔比为10~20:1,溶液pH=1。
5.一种制备如权利要求1所述核壳结构杂化溶胶的方法,其特征在于,其步骤包括:采用溶胶凝胶法合成纳米二氧化钛溶胶,然后在其中加入水性有机聚合物,并加入无机纳米微粒分散稳定剂,400~1000W超声分散5~30min,再在超声条件下升温至60~80℃,保温1~2h进行脱水缩合反应,制得所述核壳结构杂化溶胶;
所述水性有机聚合物包括丙烯酸树脂、有机硅树脂、聚氨酯树脂或其混合物;
所述无机纳米微粒分散稳定剂包括硅酸镁铝、硅溶胶。
6.一种制备如权利要求1所述核壳结构杂化溶胶的方法,其特征在于,其步骤包括:采用溶胶凝胶法合成纳米二氧化钛溶胶,400~1000W超声分散5~30min后,加入含丙烯酸类单体的纳米微乳,采用半连续乳液聚合法,在超声条件下升温至70~90℃,恒温反应1~2h,制得所述杂化溶胶。
所述丙烯酸类单体为甲基丙烯酸甲酯、甲基丙烯酸叔丁酯、丙烯酰胺、丙烯酸丁酯、丙烯酸-2-乙基己酯、丙烯酸羟乙酯、甲基丙烯酸和丙烯酸中的一种或几种。
7.一种制备如权利要求1所述核壳结构杂化溶胶的方法,其特征在于,其步骤包括:将硅酸乙酯、结构式为R1 pSiXq(OR2)t的可水解硅化合物与钛酸酯或钛酸盐共同溶于溶剂中,然后加入乙酰丙酮及浓盐酸,超声分散5~30min,再加入无水乙醇与5wt%盐酸按体积比1:1的混合溶液,在50~80℃条件下恒温反应2~4h制得所述核壳结构杂化溶胶;
其中,硅酸乙酯、可水解硅化合物、钛酸酯或钛酸盐与溶剂的摩尔用量比为1:0.1~0.5:1:10~20;
所用溶剂为甲醇、乙醇、异丙醇或丙酮中的一种或几种。
8.一种如权利要求1所述核壳结构杂化溶胶的应用,其特征在于,将所述核壳结构杂化溶胶与助剂、溶剂混合制成涂膜液,在常温条件下直接涂敷在有机基材表面;
所述涂膜液中核壳结构杂化溶胶的有效固含量为1~10wt%,助剂的含量为0.1~5wt%,余量为溶剂;其中,所述助剂包括分散剂、成膜助剂;所述溶剂包括水、甲醇、乙醇、异丙醇或丙酮中的任意一种或几种;
所述有机基材包括涂料、油漆、塑料板材、保温隔热墙体、有机玻璃、交通路网声屏障。
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