CN107460724A - 基于纳米氧化锌的多功能纤维素纤维 - Google Patents
基于纳米氧化锌的多功能纤维素纤维 Download PDFInfo
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Abstract
本发明公开了一种基于纳米氧化锌的多功能纤维素纤维及其制备方法,将阳离子化纤维素纤维依次浸渍在阴离子型氧化锌溶液体系和阳离子型氧化锌溶液体系中进行自组装,最终得到基于纳米氧化锌的多功能纤维素纤维。纳米氧化锌通过静电引力层层自组装牢固结合,赋予了纤维素纤维优异的抗菌、抗紫外、抗皱、抗黄变和耐洗等性能。本发明将静电层层自组装技术和纳米氧化锌应用于纺织领域,有助于克服纺织产业品种单一、技术含量低、产品附加值不高的现状,对于实现纺织产业的转型升级和可持续发展有重要意义。
Description
技术领域
本发明涉及一种基于纳米氧化锌的多功能纤维素纤维,属纺织领域。
背景技术
长期以来,纤维素一直是纺织、造纸的主要工业原料,以其可再生性、生物可降解性及成本优势日益受到人们的重视,在药物控制、释放技术、固定化技术、生物传感器、膜材料、功能化学品及添加剂等方面显示出良好的发展前景。由于耕地的减少和石油、天然气等化石资源的日益枯竭,合成纤维的产量将会受到越来越多的制约。而纤维素作为一种绿色、环保、可再生的资源,获得了一个空前的发展机遇(超支化聚合物的制备及对棉纤维的功能化改性[D].苏州大学,2009)。
无机纳米材料是指尺寸处于1-100nm的材料,相对于其它纳米材料,无机纳米材料具有制备简单,成本低廉、粒径均一等优势,在光催化、太阳能电池、生物、医药、纺织、印染、可穿戴电子设备等领域有着广泛的研究和应用。在众多类型的无机纳米材料中,氧化锌占据着重要的位置。纳米氧化锌是一种重要的光电半导体材料,在室温下具有较宽的禁带宽度(3.37eV)和较大的激子束缚能。其具有许多优良的物理和化学性能,如较高的化学稳定性,无毒和非迁移性,低介电常数,光催化性能,荧光性,压电性,吸收和散射紫外线的能力等,因此纳米氧化锌在许多领域都具有重要的研究意义,并表现出诱人的应用前景。近年来纳米氧化锌已作为催化剂,气体传感器,半导体器件,压敏电阻,压电器件,场致发射显示器和紫外遮光材料等而被广泛应用。
在纺织领域,纳米氧化锌可用于抑菌和除臭材料、紫外线屏蔽材料,荧光和催化材料等。将氧化锌与纤维素纤维相结合可有效改善纤维素纤维固有缺陷,扩大纤维素纤维适用范围,提高纤维素纤维的附加值。以最常用的纤维素纤维——棉纤维为例,使用纳米氧化锌改性可赋予棉纤维优异的抗菌、抗紫外、抗皱、抗黄变等性能(胡香玉. 基于纳米氧化锌的超疏水抗紫外棉织物整理[D].东华大学,2013;张瑞萍,杨静新,尤克非. 纳米氧化锌在棉织物功能整理中的应用[J]. 上海纺织科技,2005,(12):14-16;王浩,黄晨,林红,陈宇岳. 棉织物的纳米氧化锌抗紫外整理[J]. 印染,2006,(06):1-3)。
但是目前纳米氧化锌对纤维素纤维的改性主要是通过后整理法来实现。后整理法主要采用浸渍、浸轧、涂层或喷涂等方法将纳米材料整理到纤维上,并使之固着在纺织材料上的一种方法。后整理法具有工艺简单、可操作性强等优势。但加工过程中存在纳米材料易团聚,纳米材料在纤维和织物表面分布不均匀,纳米材料与纤维结合牢度低的问题(超支化聚合物纳米材料的制备及对纺织品的改性研究[D].苏州大学,2013)。
发明内容
本发明针对上述不足,提供基于纳米氧化锌的多功能纤维素纤维及其制备方法。
本发明通过下述技术方案予以实现:
(1)将纤维素纤维置于质量分数为20%的氢氧化钠溶液中,浴比1:50,90℃反应120min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性纤维素纤维;然后将氢氧化钠改性纤维素纤维重新分散于去离子水中,浴比1:50,加入三甲基烯丙基氯化铵,其中三甲基烯丙基氯化铵和氢氧化钠改性纤维素纤维的质量比为1:5-1:10,60-80℃反应1-24h,用去离子水反复清洗,烘干后得到三甲基烯丙基氯化铵改性纤维素纤维;将三甲基烯丙基氯化铵改性纤维素纤维重新分散于去离子水中,浴比1:50,缓慢加入1-100g/L的聚酰胺-胺PAMAM水溶液,所述PAMAM水溶液与三甲基烯丙基氯化铵改性纤维素纤维水溶液的体积比为1:5-1:10,75-95℃反应60-120min,取出后清洗烘干得到阳离子化纤维素纤维。(2)配制1mol/L的氯化锌溶液,然后逐滴加入1mol/L的氢氧化钠水溶液,所述氢氧化钠溶液和氯化锌溶液的体积比为1:2-2:1,超声混合均匀后,缓慢加入十二烷基硫酸钠,所述十二烷基硫酸钠和氯化锌的质量比为1:1-3:1,超声2h,移至反应釜中160℃反应6-12h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(3)将PAMAM和六水合硝酸锌分别配制成1-100g/L和1mol/L的水溶液,所述PAMAM和六水合硝酸锌水溶液的体积比为1:1-5:1,混合搅拌均匀后,移至反应釜中200℃反应5h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(4)将步骤二中的氧化锌纳米颗粒配制成质量分数0.1-5%的水溶液,然后将步骤一中的阳离子化纤维素纤维浸渍在纳米氧化锌水溶液中30-60min,浴比1:10,取出后用去离子水反复冲洗,烘干;然后将步骤三中的氧化锌纳米颗粒配制成质量分数0.1-5%的水溶液,将上述纤维素纤维浸渍在纳米氧化锌水溶液中30-60min,浴比1:10,取出后用去离子水反复冲洗,烘干,至此已将一层纳米氧化锌整理到纤维素纤维的表面,随后重复上述操作,根据需要决定纤维素纤维表面纳米氧化锌整理的层数。
与现有技术相比,本发明的优点在于:纳米氧化锌通过静电引力层层自组装牢固结合,赋予了纤维素纤维优异的抗菌、抗紫外、抗黄变和耐洗等性能,有助于克服纺织产业品种单一、技术含量低、产品附加值不高的现状,对于实现纺织产业的转型升级和可持续发展有重要意义。
具体实施方式
下面结合具体实施方式,进一步阐述本发明。
实施例1:
(1)将棉布置于质量分数为20%的氢氧化钠溶液中,浴比1:50,90℃反应120min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性棉布;然后将氢氧化钠改性棉布重新分散于去离子水中,浴比1:50,加入三甲基烯丙基氯化铵,其中三甲基烯丙基氯化铵和氢氧化钠改性棉布的质量比为1:5,60℃反应1h,用去离子水反复清洗,烘干后得到三甲基烯丙基氯化铵改性棉布;将三甲基烯丙基氯化铵改性棉布重新分散于去离子水中,浴比1:50,缓慢加入1g/L的聚酰胺-胺PAMAM水溶液,所述PAMAM水溶液与三甲基烯丙基氯化铵改性棉布水溶液的体积比为1:5,75℃反应60min,取出后清洗烘干得到阳离子化棉布。(2)配制1mol/L的氯化锌溶液,然后逐滴加入1mol/L的氢氧化钠水溶液,所述氢氧化钠溶液和氯化锌溶液的体积比为1:1,超声混合均匀后,缓慢加入十二烷基硫酸钠,所述十二烷基硫酸钠和氯化锌的质量比为1:1,超声2h,移至反应釜中160℃反应6h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(3)将PAMAM和六水合硝酸锌分别配制成1g/L和1mol/L的水溶液,所述PAMAM和六水合硝酸锌水溶液的体积比为1:1,混合搅拌均匀后,移至反应釜中200℃反应5h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(4)将步骤二中的氧化锌纳米颗粒配制成质量分数1%的水溶液,然后将步骤一中的阳离子化棉布浸渍在纳米氧化锌水溶液中30min,浴比1:10,取出后用去离子水反复冲洗,烘干;然后将步骤三中的氧化锌纳米颗粒配制成质量分数1%的水溶液,将上述棉布浸渍在纳米氧化锌水溶液中30min,浴比1:10,取出后用去离子水反复冲洗,烘干,得到基于纳米氧化锌的多功能棉布。
实施例2:
(1)将亚麻布置于质量分数为20%的氢氧化钠溶液中,浴比1:50,90℃反应120min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性亚麻布;然后将氢氧化钠改性亚麻布重新分散于去离子水中,浴比1:50,加入三甲基烯丙基氯化铵,其中三甲基烯丙基氯化铵和氢氧化钠改性亚麻布的质量比为1:6,70℃反应12h,用去离子水反复清洗,烘干后得到三甲基烯丙基氯化铵改性亚麻布;将三甲基烯丙基氯化铵改性亚麻布重新分散于去离子水中,浴比1:50,缓慢加入10g/L的聚酰胺-胺PAMAM水溶液,所述PAMAM水溶液与三甲基烯丙基氯化铵改性亚麻布水溶液的体积比为1:6,85℃反应90min,取出后清洗烘干得到阳离子化亚麻布。(2)配制1mol/L的氯化锌溶液,然后逐滴加入1mol/L的氢氧化钠水溶液,所述氢氧化钠溶液和氯化锌溶液的体积比为1:2,超声混合均匀后,缓慢加入十二烷基硫酸钠,所述十二烷基硫酸钠和氯化锌的质量比为2:1,超声2h,移至反应釜中160℃反应9h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(3)将PAMAM和六水合硝酸锌分别配制成10g/L和1mol/L的水溶液,所述PAMAM和六水合硝酸锌水溶液的体积比为2:1,混合搅拌均匀后,移至反应釜中200℃反应5h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(4)将步骤二中的氧化锌纳米颗粒配制成质量分数2%的水溶液,然后将步骤一中的阳离子化亚麻布浸渍在纳米氧化锌水溶液中60min,浴比1:10,取出后用去离子水反复冲洗,烘干;然后将步骤三中的氧化锌纳米颗粒配制成质量分数2%的水溶液,将上述亚麻布浸渍在纳米氧化锌水溶液中60min,浴比1:10,取出后用去离子水反复冲洗,烘干,至此已将一层纳米氧化锌整理到亚麻布的表面,随后重复两次上述操作,得到基于纳米氧化锌的多功能亚麻布。
实施例3:
(1)将粘胶织物置于质量分数为20%的氢氧化钠溶液中,浴比1:50,90℃反应120min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性粘胶织物;然后将氢氧化钠改性粘胶织物重新分散于去离子水中,浴比1:50,加入三甲基烯丙基氯化铵,其中三甲基烯丙基氯化铵和氢氧化钠改性粘胶织物的质量比为1:10,80℃反应24h,用去离子水反复清洗,烘干后得到三甲基烯丙基氯化铵改性粘胶织物;将三甲基烯丙基氯化铵改性粘胶织物重新分散于去离子水中,浴比1:50,缓慢加入100g/L的聚酰胺-胺PAMAM水溶液,所述PAMAM水溶液与三甲基烯丙基氯化铵改性粘胶织物水溶液的体积比为1:5-1:10,95℃反应120min,取出后清洗烘干得到阳离子化粘胶织物。(2)配制1mol/L的氯化锌溶液,然后逐滴加入1mol/L的氢氧化钠水溶液,所述氢氧化钠溶液和氯化锌溶液的体积比为2:1,超声混合均匀后,缓慢加入十二烷基硫酸钠,所述十二烷基硫酸钠和氯化锌的质量比为3:1,超声2h,移至反应釜中160℃反应12h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(3)将PAMAM和六水合硝酸锌分别配制成20g/L和1mol/L的水溶液,所述PAMAM和六水合硝酸锌水溶液的体积比为5:1,混合搅拌均匀后,移至反应釜中200℃反应5h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒。(4)将步骤二中的氧化锌纳米颗粒配制成质量分数5%的水溶液,然后将步骤一中的阳离子化粘胶织物浸渍在纳米氧化锌水溶液中60min,浴比1:10,取出后用去离子水反复冲洗,烘干;然后将步骤三中的氧化锌纳米颗粒配制成质量分数5%的水溶液,将上述粘胶织物浸渍在纳米氧化锌水溶液中60min,浴比1:10,取出后用去离子水反复冲洗,烘干,至此已将一层纳米氧化锌整理到粘胶织物的表面,随后重复三次上述操作,得到基于纳米氧化锌的多功能粘胶织物。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (7)
1.基于纳米氧化锌的多功能纤维素纤维的制备方法,其特征在于:
步骤一:将纤维素纤维置于质量分数为20%的氢氧化钠溶液中,浴比1:50,90℃反应120min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性纤维素纤维;然后将氢氧化钠改性纤维素纤维重新分散于去离子水中,浴比1:50,加入三甲基烯丙基氯化铵,其中三甲基烯丙基氯化铵和氢氧化钠改性纤维素纤维的质量比为1:5-1:10,60-80℃反应1-24h,用去离子水反复清洗,烘干后得到三甲基烯丙基氯化铵改性纤维素纤维;将三甲基烯丙基氯化铵改性纤维素纤维重新分散于去离子水中,浴比1:50,缓慢加入1-100g/L的聚酰胺-胺PAMAM水溶液,75-95℃反应60-120min,取出后清洗烘干得到阳离子化纤维素纤维;
步骤二:配制1mol/L的氯化锌溶液,然后逐滴加入1mol/L的氢氧化钠水溶液,超声混合均匀后,缓慢加入十二烷基硫酸钠,超声2h,移至反应釜中160℃反应6-12h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒;
步骤三:将PAMAM和六水合硝酸锌分别配制成1-100g/L和1mol/L的水溶液,混合搅拌均匀后,移至反应釜中200℃反应5h,用乙醇和去离子水反复清洗、离心、干燥处理后得到氧化锌纳米颗粒;
步骤四:将步骤二中的氧化锌纳米颗粒配制成质量分数0.1-5%的水溶液,然后将步骤一中的阳离子化纤维素纤维浸渍在纳米氧化锌水溶液中30-60min,浴比1:10,取出后用去离子水反复冲洗,烘干;然后将步骤三中的氧化锌纳米颗粒配制成质量分数0.1-5%的水溶液,将上述纤维素纤维浸渍在纳米氧化锌水溶液中30-60min,浴比1:10,取出后用去离子水反复冲洗,烘干,至此已将一层纳米氧化锌整理到纤维素纤维的表面,随后重复上述操作,根据需要决定纤维素纤维表面纳米氧化锌整理的层数。
2.根据权利要求1所述的基于纳米氧化锌的多功能纤维素纤维的制备方法,其特征在于,所述纤维素纤维包括天然纤维素纤维和再生纤维素纤维。
3.根据权利要求1所述的基于纳米氧化锌的多功能纤维素纤维的制备方法,其特征在于,所述PAMAM水溶液与三甲基烯丙基氯化铵改性纤维素纤维水溶液的体积比为1:5-1:10。
4.根据权利要求1所述的基于纳米氧化锌的多功能纤维素纤维的制备方法,其特征在于,所述氢氧化钠溶液和氯化锌溶液的体积比为1:2-2:1。
5.根据权利要求1所述的基于纳米氧化锌的多功能纤维素纤维的制备方法,其特征在于,所述十二烷基硫酸钠和氯化锌的质量比为1:1-3:1。
6.根据权利要求1所述的基于纳米氧化锌的多功能纤维素纤维的制备方法,其特征在于,所述PAMAM和六水合硝酸锌水溶液的体积比为1:1-5:1。
7.按权利要求1制备方法得到的一种基于纳米氧化锌的多功能纤维素纤维。
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