CN107724065A - 用于紫外防护的二氧化铈纳米颗粒改性棉纤维及制备方法 - Google Patents
用于紫外防护的二氧化铈纳米颗粒改性棉纤维及制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于紫外防护的二氧化铈纳米颗粒改性棉纤维,将二氧化铈纳米颗粒包覆在两层HBP‑NH2改性壳聚糖的中间,制备了HBP‑NH2改性壳聚糖/二氧化铈纳米颗粒/HBP‑NH2改性壳聚糖紫外防护涂层,其中HBP‑NH2改性壳聚糖和二氧化铈纳米颗粒发挥了协同作用,大大提高了二氧化铈纳米颗粒和棉纤维之间的结合牢度、紫外防护和耐洗性能。
Description
技术领域
本发明公开了一种用于紫外防护的二氧化铈纳米颗粒改性棉纤维及制备方法,属功能纳米材料和纺织材料领域。
背景技术
从20世纪90年开始,随着测量与表征技术的提高,纳米材料和纳米科技得到了飞速的发展。纳米材料是指尺寸处于1-100nm的材料,不同与块状材料,其拥有独特的光电磁特性,在电子、材料、医药、生物、机械、纺织、印染等各个领域得到广泛的研究和应用。就纺织领域而言,将纳米材料与纺织品相结合可有效改善纺织品的固有缺陷,扩大纺织品的适用范围,提高纺织品的附加值。大量的研究结果表明,使用二氧化钛、氧化锌、石墨烯、氧化石墨烯、碳纳米管、纳米银、纳米金等纳米材料整理纺织品,可赋予纺织品优异的抗菌、抗紫外、自清洁、抗黄变、导电、抗电磁辐射等性能。
以紫外防护功能为例,全球每天有约150万人因过量紫外线辐射而患皮肤黑色素瘤、鳞状细胞癌、基底细胞癌、慢性日光损伤、日光灼伤、皮质性白内障、角膜及结膜肿瘤等各种疾病,占全球患病总人数的0.1%。因此紫外线防护越来越受重视(于晓丽,曹鸿璋,张玉玺,刘铃声,弓永强. 二氧化铈抗紫外性能研究进展[J]. 稀土,2013,34(04):80-84)。普通纺织品经过过量紫外线照射也会导致织物变黄发脆,易褪色,强力大幅下降(闫鹏飞,朱艳.纳米材料在抗紫外线功能纺织品中的应用研究进展[J]. 山东化工,2016,45(11):37-38)。
二氧化铈具有独特的4F电子层结构,表现出较强的紫外屏蔽能力,并且由于其禁带宽度较大,对紫外线波段的屏蔽范围也较大。此外,二氧化铈无毒,较稳定,因此是紫外屏蔽剂的良好选择。浙江方圆检测集团股份有限公司楼陈钰以硝酸铈和柠檬酸为原料,通过溶胶-凝胶法制备纳米CeO2胶体,并经不同表面活性剂改性,通过轧烘焙工艺将其用于纯棉织物的抗紫外线整理。结果表明经CeO2溶胶整理的棉织物UPF值最高可达289(楼陈钰. 纳米CeO2溶胶的制备及其在棉织物抗紫外整理中的应用[J]. 上海纺织科技,2015,43(12):74-77)。江苏工业学院王辉使用简单的原位合成法在棉织物的表面生成CeO2纳米粒子,测试发现,这些CeO2纳米粒子明显提高了棉织物的抗紫外性能。
但是无机纳米材料改性纺织品主要通过物理吸附作用附着在纺织品的表面,这些无机纳米材料在纺织品表面的附着牢度差,洗涤后附着的无机纳米材料会不断脱落(王卓睿,邢建伟,徐成书. 纺织品无机纳米紫外线屏蔽剂研究进展[J]. 合成纤维,2015,44(08):27-31)。而使用化学交联剂增加固着牢度则会对人体产生潜在危害。此外,无机纳米颗粒具有巨大的比表面积和很高的表面能,因而容易发生团聚,如何提高无机纳米材料的分散均匀性也是一个需要解决的难点。
发明内容
本发明针对上述不足,提供一种用于紫外防护的二氧化铈纳米颗粒改性棉纤维及制备方法。
本发明通过下述技术方案予以实现:
(1)将棉纤维置于质量分数为10-18%的氢氧化钠溶液中,浴比1:50,70℃反应180min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性棉纤维;然后将上述氢氧化钠改性棉纤维分散于乙醇中,浴比1:50,80℃氮气保护条件下冷凝回流60min,加入醇醚磺基琥珀酸单酯二钠盐,匀速搅拌60min后,加入偶氮二异庚腈和过氧化二苯甲酰,继续搅拌反应1-12h,过滤后使用乙醇、去离子水反复清洗,真空烘干后得到阴离子化棉纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性棉纤维的质量比为1:1-1:3,所述偶氮二异庚腈的质量为氢氧化钠改性棉纤维的0.01%-0.5%,所述过氧化二苯甲酰的质量为氢氧化钠改性棉纤维的0.01%-0.5%;(2)将一定量的壳聚糖加入到0.5mol/L的乙酸溶液中搅拌至完全溶解,得到质量分数1-5%的壳聚糖溶液,然后加入氧化剂高碘酸钠,所述壳聚糖与高碘酸钠的质量比为5:1-1:1,在60℃下避光反应10-100min,用去离子水反复清洗,离心,真空干燥得到高碘酸钠改性壳聚糖;(3)使用TEMPO-NaOCl-NaBr体系继续氧化上述高碘酸钠改性壳聚糖,得到TEMPO-NaOCl-NaBr改性壳聚糖;(4)将上述TEMPO-NaOCl-NaBr改性壳聚糖加入到1-100g/L的端氨基超支化聚合物(HBP-NH2)水溶液中常温反应24h,抽滤、真空干燥得到HBP-NH2改性壳聚糖;(5)将上述阴离子化棉纤维浸渍在80℃质量分数1-5%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到壳聚糖改性棉纤维;(6)配制质量分数0.1-10%的六水合硝酸铈溶液,加入柠檬酸溶液,所述柠檬酸与六水合硝酸铈的质量比为5:1-1:1,90℃磁力搅拌30-300min,缓慢加入十二烷基硫酸钠(SDS),所述SDS与六水合硝酸铈的质量比为2-1-1:2,反应1h-3h,取出后用乙醇、去离子水反复清洗,离心,真空干燥得到二氧化铈纳米颗粒;(7)将上述壳聚糖改性棉纤维浸渍在70℃质量分数0.1-1%的二氧化铈纳米颗粒溶液中30-60min,得到二氧化铈改性棉纤维;(8)将上述二氧化铈改性棉纤维浸渍在80℃质量分数1-5%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到用于紫外防护的二氧化铈纳米颗粒改性棉纤维。
其中TEMPO-NaOCl-NaBr体系氧化壳聚糖的具体步骤可参考文献:王浩,凌志华,胡显荣,饶娟,赵敏. 选择性氧化壳聚糖对真丝织物姜黄染色性能的影响[J]. 印染助剂,2015,32(10):41-44。
与现有技术相比,本发明的优点在于:将二氧化铈纳米颗粒包覆在HBP-NH2改性壳聚糖中间,制备了类似三明治结构的HBP-NH2改性壳聚糖/二氧化铈纳米颗粒/HBP-NH2改性壳聚糖紫外防护涂层,大大提高了二氧化铈纳米颗粒的附着、抗紫外和耐洗性能。此外,由于HBP-NH2的络合作用,二氧化铈纳米颗粒均匀地分散在壳聚糖涂层中,有效地避免了二氧化铈纳米颗粒的团聚。
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)将棉纤维置于质量分数为10%的氢氧化钠溶液中,浴比1:50,70℃反应180min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性棉纤维;然后将上述氢氧化钠改性棉纤维分散于乙醇中,浴比1:50,80℃氮气保护条件下冷凝回流60min,加入醇醚磺基琥珀酸单酯二钠盐,匀速搅拌60min后,加入偶氮二异庚腈和过氧化二苯甲酰,继续搅拌反应1h,过滤后使用乙醇、去离子水反复清洗,真空烘干后得到阴离子化棉纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性棉纤维的质量比为1:1,所述偶氮二异庚腈的质量为氢氧化钠改性棉纤维的0.01%,所述过氧化二苯甲酰的质量为氢氧化钠改性棉纤维的0.01%;(2)将一定量的壳聚糖加入到0.5mol/L的乙酸溶液中搅拌至完全溶解,得到质量分数1%的壳聚糖溶液,然后加入氧化剂高碘酸钠,所述壳聚糖与高碘酸钠的质量比为5:1,在60℃下避光反应10min,用去离子水反复清洗,离心,真空干燥得到高碘酸钠改性壳聚糖;(3)使用TEMPO-NaOCl-NaBr体系继续氧化上述高碘酸钠改性壳聚糖,得到TEMPO-NaOCl-NaBr改性壳聚糖;(4)将上述TEMPO-NaOCl-NaBr改性壳聚糖加入到1g/L的端氨基超支化聚合物(HBP-NH2)水溶液中常温反应24h,抽滤、真空干燥得到HBP-NH2改性壳聚糖;(5)将上述阴离子化棉纤维浸渍在80℃质量分数1%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到壳聚糖改性棉纤维;(6)配制质量分数0.1%的六水合硝酸铈溶液,加入柠檬酸溶液,所述柠檬酸与六水合硝酸铈的质量比为5:1,90℃磁力搅拌30min,缓慢加入十二烷基硫酸钠(SDS),所述SDS与六水合硝酸铈的质量比为2:1,反应1h,取出后用乙醇、去离子水反复清洗,离心,真空干燥得到二氧化铈纳米颗粒;(7)将上述壳聚糖改性棉纤维浸渍在70℃质量分数0.1%的二氧化铈纳米颗粒溶液中30min,得到二氧化铈改性棉纤维;(8)将上述二氧化铈改性棉纤维浸渍在80℃质量分数1%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到用于紫外防护的二氧化铈纳米颗粒改性棉纤维。
实施例2:
(1)将棉纤维置于质量分数为15%的氢氧化钠溶液中,浴比1:50,70℃反应180min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性棉纤维;然后将上述氢氧化钠改性棉纤维分散于乙醇中,浴比1:50,80℃氮气保护条件下冷凝回流60min,加入醇醚磺基琥珀酸单酯二钠盐,匀速搅拌60min后,加入偶氮二异庚腈和过氧化二苯甲酰,继续搅拌反应2h,过滤后使用乙醇、去离子水反复清洗,真空烘干后得到阴离子化棉纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性棉纤维的质量比为1:2,所述偶氮二异庚腈的质量为氢氧化钠改性棉纤维的0.2%,所述过氧化二苯甲酰的质量为氢氧化钠改性棉纤维的0.3%;(2)将一定量的壳聚糖加入到0.5mol/L的乙酸溶液中搅拌至完全溶解,得到质量分数3%的壳聚糖溶液,然后加入氧化剂高碘酸钠,所述壳聚糖与高碘酸钠的质量比为3:1,在60℃下避光反应30min,用去离子水反复清洗,离心,真空干燥得到高碘酸钠改性壳聚糖;(3)使用TEMPO-NaOCl-NaBr体系继续氧化上述高碘酸钠改性壳聚糖,得到TEMPO-NaOCl-NaBr改性壳聚糖;(4)将上述TEMPO-NaOCl-NaBr改性壳聚糖加入到10g/L的端氨基超支化聚合物(HBP-NH2)水溶液中常温反应24h,抽滤、真空干燥得到HBP-NH2改性壳聚糖;(5)将上述阴离子化棉纤维浸渍在80℃质量分数2%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到壳聚糖改性棉纤维;(6)配制质量分数3%的六水合硝酸铈溶液,加入柠檬酸溶液,所述柠檬酸与六水合硝酸铈的质量比为3:1,90℃磁力搅拌90min,缓慢加入十二烷基硫酸钠(SDS),所述SDS与六水合硝酸铈的质量比为1:1,反应2h,取出后用乙醇、去离子水反复清洗,离心,真空干燥得到二氧化铈纳米颗粒;(7)将上述壳聚糖改性棉纤维浸渍在70℃质量分数0.5%的二氧化铈纳米颗粒溶液中45min,得到二氧化铈改性棉纤维;(8)将上述二氧化铈改性棉纤维浸渍在80℃质量分数2%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到用于紫外防护的二氧化铈纳米颗粒改性棉纤维。
实施例3:
(1)将棉纤维置于质量分数为18%的氢氧化钠溶液中,浴比1:50,70℃反应180min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性棉纤维;然后将上述氢氧化钠改性棉纤维分散于乙醇中,浴比1:50,80℃氮气保护条件下冷凝回流60min,加入醇醚磺基琥珀酸单酯二钠盐,匀速搅拌60min后,加入偶氮二异庚腈和过氧化二苯甲酰,继续搅拌反应8h,过滤后使用乙醇、去离子水反复清洗,真空烘干后得到阴离子化棉纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性棉纤维的质量比为1:3,所述偶氮二异庚腈的质量为氢氧化钠改性棉纤维的0.5%,所述过氧化二苯甲酰的质量为氢氧化钠改性棉纤维的0.4%;(2)将一定量的壳聚糖加入到0.5mol/L的乙酸溶液中搅拌至完全溶解,得到质量分数5%的壳聚糖溶液,然后加入氧化剂高碘酸钠,所述壳聚糖与高碘酸钠的质量比为1:1,在60℃下避光反应100min,用去离子水反复清洗,离心,真空干燥得到高碘酸钠改性壳聚糖;(3)使用TEMPO-NaOCl-NaBr体系继续氧化上述高碘酸钠改性壳聚糖,得到TEMPO-NaOCl-NaBr改性壳聚糖;(4)将上述TEMPO-NaOCl-NaBr改性壳聚糖加入到50g/L的端氨基超支化聚合物(HBP-NH2)水溶液中常温反应24h,抽滤、真空干燥得到HBP-NH2改性壳聚糖;(5)将上述阴离子化棉纤维浸渍在80℃质量分数5%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到壳聚糖改性棉纤维;(6)配制质量分数10%的六水合硝酸铈溶液,加入柠檬酸溶液,所述柠檬酸与六水合硝酸铈的质量比为1:1,90℃磁力搅拌300min,缓慢加入十二烷基硫酸钠(SDS),所述SDS与六水合硝酸铈的质量比为1:2,反应3h,取出后用乙醇、去离子水反复清洗,离心,真空干燥得到二氧化铈纳米颗粒;(7)将上述壳聚糖改性棉纤维浸渍在70℃质量分数1%的二氧化铈纳米颗粒溶液中60min,得到二氧化铈改性棉纤维;(8)将上述二氧化铈改性棉纤维浸渍在80℃质量分数5%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到用于紫外防护的二氧化铈纳米颗粒改性棉纤维。
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 (2)
1.用于紫外防护的二氧化铈纳米颗粒改性棉纤维及其制备方法,其特征在于,包括以下步骤:
(1)将棉纤维置于质量分数为10-18%的氢氧化钠溶液中,浴比1:50,70℃反应180min,用去离子水反复洗至中性,烘干后得到氢氧化钠改性棉纤维;然后将上述氢氧化钠改性棉纤维分散于乙醇中,浴比1:50,80℃氮气保护条件下冷凝回流60min,加入醇醚磺基琥珀酸单酯二钠盐,匀速搅拌60min后,加入偶氮二异庚腈和过氧化二苯甲酰,继续搅拌反应1-12h,过滤后使用乙醇、去离子水反复清洗,真空烘干后得到阴离子化棉纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性棉纤维的质量比为1:1-1:3,所述偶氮二异庚腈的质量为氢氧化钠改性棉纤维的0.01%-0.5%,所述过氧化二苯甲酰的质量为氢氧化钠改性棉纤维的0.01%-0.5%;(2)将一定量的壳聚糖加入到0.5mol/L的乙酸溶液中搅拌至完全溶解,得到质量分数1-5%的壳聚糖溶液,然后加入氧化剂高碘酸钠,所述壳聚糖与高碘酸钠的质量比为5:1-1:1,在60℃下避光反应10-100min,用去离子水反复清洗,离心,真空干燥得到高碘酸钠改性壳聚糖;(3)使用TEMPO-NaOCl-NaBr体系继续氧化上述高碘酸钠改性壳聚糖,得到TEMPO-NaOCl-NaBr改性壳聚糖;(4)将上述TEMPO-NaOCl-NaBr改性壳聚糖加入到1-100g/L的端氨基超支化聚合物(HBP-NH2)水溶液中常温反应24h,抽滤、真空干燥得到HBP-NH2改性壳聚糖;(5)将上述阴离子化棉纤维浸渍在80℃质量分数1-5%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到壳聚糖改性棉纤维;(6)配制质量分数0.1-10%的六水合硝酸铈溶液,加入柠檬酸溶液,所述柠檬酸与六水合硝酸铈的质量比为5:1-1:1,90℃磁力搅拌30-300min,缓慢加入十二烷基硫酸钠(SDS),所述SDS与六水合硝酸铈的质量比为2-1-1:2,反应1h-3h,取出后用乙醇、去离子水反复清洗,离心,真空干燥得到二氧化铈纳米颗粒;(7)将上述壳聚糖改性棉纤维浸渍在70℃质量分数0.1-1%的二氧化铈纳米颗粒溶液中30-60min,得到二氧化铈改性棉纤维;(8)将上述二氧化铈改性棉纤维浸渍在80℃质量分数1-5%的HBP-NH2改性壳聚糖溶液中60min,用去离子水反复清洗、干燥处理得到用于紫外防护的二氧化铈纳米颗粒改性棉纤维。
2.按权利要求1制备方法得到的用于紫外防护的二氧化铈纳米颗粒改性棉纤维。
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CN117468163B (zh) * | 2023-12-25 | 2024-03-26 | 江苏青昀新材料有限公司 | 一种自清洁闪蒸片材及其轧制工艺 |
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