CN107815866A - 一种具有三明治结构的纳米银抗菌纤维素纤维 - Google Patents
一种具有三明治结构的纳米银抗菌纤维素纤维 Download PDFInfo
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Abstract
本发明公开了一种具有三明治结构的纳米银抗菌纤维素纤维,所述纤维素纤维复合材料包括纤维素纤维和外层的纳米银抗菌涂层;所述纳米银抗菌涂层具有三明治结构,其中上下两层为牛血清白蛋白(BSA)层,中间层为纳米银颗粒;所述纳米银颗粒均匀分散在BSA层中。本发明将纳米银颗粒包覆在BSA中间,制备了三明治结构的BSA/纳米银/BSA抗菌涂层,大大提高了纳米银颗粒的附着、抗菌和耐洗性能。
Description
技术领域
本发明涉及一种具有三明治结构的纳米银抗菌纤维素纤维,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。
以抗菌性能为例,纺织品容易滋生微生物。自然界中的微生物群落广泛地存在于周围的环境中,一旦遇到适宜的湿度、养分和温度能够迅速滋生。滋生在纺织品上的微生物不仅影响到纺织品的服用性能,而且损害使用者的身体健康。因此如何抑制或杀灭附着于纺织品的微生物是纺织行业迫切需要解决的问题。抗菌纺织品可以提高纺织品的附加值,满足人们对健康、环保的需求,因此越来越受到重视,市场潜力巨大。在众多的纺织品抗菌剂中,银系抗菌剂占据着重要的位置。银系抗菌剂具有很高的抗菌活性和安全性;同时银系抗菌剂还不易产生抗药性,具有良好的耐久性。银系抗菌剂的抗菌效率和其表面积的关系极大,银颗粒的尺寸越小,抗菌性能越高,因此在银系抗菌剂中,1-100纳米的纳米银颗粒尤其受到关注(张峰. 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)。
目前纳米银颗粒改性纺织品的方法主要是后整理法。该方法虽然赋予了纺织品一定的抗菌性能(周婷婷,林红,陈宇岳. 纳米银的制备及其对涤纶织物抗菌整理[J]. 纺织学报,2011,32(12):98-102;张德锁,廖艳芬,林红,陈宇岳. 纳米银的制备及对真丝织物的抗菌整理[J]. 丝绸,2013,50(07):5-11;缪宏超,林红,陈宇岳. 仙人掌纳米银的制备及其对桑蚕丝织物的抗菌整理[J]. 纺织学报,2010,31(03):88-91.),但是纳米银颗粒附着在纺织品的表面,会对纺织品固有的手感、透气、透湿、光泽等性能产生不利的影响。更为关键的是,这些纳米银颗粒在纺织品表面的附着牢度差,洗涤后附着的纳米银颗粒会不断脱落(石雪. 纳米银在织物表面的原位还原及其抗菌效果的研究[D].东华大学,2011;郭荣辉,彭灵慧,王翔. 纳米银涂覆织物研究进展[J]. 成都纺织高等专科学校学报,2015,32(04):5-11;梁雪,付元俞,王淑瑶,胡可,刘啸天,刘耀文. 纳米银抗菌性能的研究现状[J]. 化工新型材料,2016,44(02):240-243),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。
发明内容
本发明针对上述不足,提供一种具有三明治结构的纳米银抗菌纤维素纤维,所述纤维素纤维复合材料包括位于内层的纤维素纤维和位于外层的纳米银抗菌涂层;所述纳米银抗菌涂层具有三明治结构,其中上下两层为牛血清白蛋白(BSA)层,中间层为纳米银颗粒;所述纳米银颗粒均匀分散在BSA层中。
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纤维素;然后将上述氢氧化钠改性纤维素分散于乙醇中,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纤维素纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性纤维素的质量比为1:1-1:3,所述偶氮二异庚腈的质量为氢氧化钠改性纤维素的0.01%-0.5%,所述过氧化二苯甲酰的质量为氢氧化钠改性纤维素的0.01%-0.5%。(2)将上述阴离子纤维素纤维浸渍在60℃的质量分数0.1-1%的牛血清白蛋白(BSA)溶液中60min,得到BSA改性纤维素纤维。(3)配制1-100g/L的硝酸银水溶液,缓慢加入甘氨酸和十二烷基硫酸钠,所述甘氨酸与硝酸银的质量比为5:1-1:1,所述十二烷基硫酸钠与硝酸银的质量比为1:5-1:10,超声均匀后,常温下磁力搅拌30-300min,用乙醇和去离子水反复清洗、离心、干燥处理后得到纳米银颗粒。(4)将上述纳米银颗粒重新分散于去离子水中,得到质量分数0.1-1%的纳米银溶液,然后将上述BSA改性纤维素纤维浸渍在纳米银溶液中10-100min,得到纳米银改性纤维素纤维。(5)将上述纳米银改性纤维素纤维浸渍在60℃的质量分数0.1-1%的BSA溶液中60min,用去离子水反复清洗、干燥处理。
与现有技术相比,本发明的优点在于:将纳米银颗粒包覆在BSA中间,制备了三明治结构的BSA/纳米银/BSA抗菌涂层,大大提高了纳米银颗粒的附着、抗菌和耐洗性能。
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;然后将上述氢氧化钠改性棉分散于乙醇中,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的0.01%,所述过氧化二苯甲酰的质量为氢氧化钠改性棉的0.01%。(2)将上述阴离子棉纤维浸渍在60℃的质量分数0.1%的牛血清白蛋白(BSA)溶液中60min,得到BSA改性棉。(3)配制1g/L的硝酸银水溶液,缓慢加入甘氨酸和十二烷基硫酸钠,所述甘氨酸与硝酸银的质量比为5:1,所述十二烷基硫酸钠与硝酸银的质量比为1:5,超声均匀后,常温下磁力搅拌30min,用乙醇和去离子水反复清洗、离心、干燥处理后得到纳米银颗粒。(4)将上述纳米银颗粒重新分散于去离子水中,得到质量分数0.1%的纳米银溶液,然后将上述BSA改性棉浸渍在纳米银溶液中10min,得到纳米银改性棉。(5)将上述纳米银改性棉浸渍在60℃的质量分数0.1%的BSA溶液中60min,用去离子水反复清洗、干燥处理。
实施例2:
(1)将亚麻纤维置于质量分数为11%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亚麻;然后将上述氢氧化钠改性亚麻分散于乙醇中,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3h,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亚麻纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性亚麻的质量比为1:2,所述偶氮二异庚腈的质量为氢氧化钠改性亚麻的0.1%,所述过氧化二苯甲酰的质量为氢氧化钠改性亚麻的0.1%。(2)将上述阴离子亚麻浸渍在60℃的质量分数0.5%的牛血清白蛋白(BSA)溶液中60min,得到BSA改性亚麻。(3)配制10g/L的硝酸银水溶液,缓慢加入甘氨酸和十二烷基硫酸钠,所述甘氨酸与硝酸银的质量比为2:1,所述十二烷基硫酸钠与硝酸银的质量比为1:8,超声均匀后,常温下磁力搅拌100min,用乙醇和去离子水反复清洗、离心、干燥处理后得到纳米银颗粒。(4)将上述纳米银颗粒重新分散于去离子水中,得到质量分数0.5%的纳米银溶液,然后将上述BSA改性亚麻浸渍在纳米银溶液中50min,得到纳米银改性亚麻。(5)将上述纳米银改性亚麻浸渍在60℃的质量分数0.5%的BSA溶液中60min,用去离子水反复清洗、干燥处理。
实施例3:
(1)将竹原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竹原纤维;然后将上述氢氧化钠改性竹原纤维分散于乙醇中,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9h,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竹原纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性竹原纤维的质量比为1:3,所述偶氮二异庚腈的质量为氢氧化钠改性竹原纤维的0.5%,所述过氧化二苯甲酰的质量为氢氧化钠改性竹原纤维的0.5%。(2)将上述阴离子竹原纤维浸渍在60℃的质量分数1%的牛血清白蛋白(BSA)溶液中60min,得到BSA改性竹原纤维。(3)配制50g/L的硝酸银水溶液,缓慢加入甘氨酸和十二烷基硫酸钠,所述甘氨酸与硝酸银的质量比为1:1,所述十二烷基硫酸钠与硝酸银的质量比为1:10,超声均匀后,常温下磁力搅拌300min,用乙醇和去离子水反复清洗、离心、干燥处理后得到纳米银颗粒。(4)将上述纳米银颗粒重新分散于去离子水中,得到质量分数1%的纳米银溶液,然后将上述BSA改性竹原纤维浸渍在纳米银溶液中100min,得到纳米银改性竹原纤维。(5)将上述纳米银改性竹原纤维浸渍在60℃的质量分数1%的BSA溶液中60min,用去离子水反复清洗、干燥处理。
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 (6)
1.一种具有三明治结构的纳米银抗菌纤维素纤维,其特征在于:所述纤维素纤维复合材料包括位于内层的纤维素纤维和位于外层的纳米银抗菌涂层;所述纳米银抗菌涂层具有三明治结构,其中上下两层为牛血清白蛋白(BSA)层,中间层为纳米银颗粒;所述纳米银颗粒均匀分散在BSA层中。
2.根据权利要求1所述的一种具有三明治结构的纳米银抗菌纤维素纤维及其制备方法,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所述的一种具有三明治结构的纳米银抗菌纤维素纤维及其制备方法,其特征在于,所述内层纤维素纤维和外层纳米银抗菌涂层通过静电引力、氢键和范德华力结合。
4.根据权利要求1所述的一种具有三明治结构的纳米银抗菌纤维素纤维及其制备方法,其特征在于,所述三明治结构的纳米银抗菌涂层上下两层BSA层和中间层纳米银颗粒层通过静电引力、氢键和范德华力结合。
5.根据权利要求1所述的一种具有三明治结构的纳米银抗菌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纤维素;然后将上述氢氧化钠改性纤维素分散于乙醇中,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纤维素纤维;所述醇醚磺基琥珀酸单酯二钠盐与氢氧化钠改性纤维素的质量比为1:1-1:3,所述偶氮二异庚腈的质量为氢氧化钠改性纤维素的0.01%-0.5%,所述过氧化二苯甲酰的质量为氢氧化钠改性纤维素的0.01%-0.5%;
步骤二:将上述阴离子纤维素纤维浸渍在60℃的质量分数0.1-1%的牛血清白蛋白(BSA)溶液中60min,得到BSA改性纤维素纤维;
步骤三:配制1-100g/L的硝酸银水溶液,缓慢加入甘氨酸和十二烷基硫酸钠,所述甘氨酸与硝酸银的质量比为5:1-1:1,所述十二烷基硫酸钠与硝酸银的质量比为1:5-1:10,超声均匀后,常温下磁力搅拌30-300min,用乙醇和去离子水反复清洗、离心、干燥处理后得到纳米银颗粒;
步骤四:将上述纳米银颗粒重新分散于去离子水中,得到质量分数0.1-1%的纳米银溶液,然后将上述BSA改性纤维素纤维浸渍在纳米银溶液中10-100min,得到纳米银改性纤维素纤维;
步骤五:将上述纳米银改性纤维素纤维浸渍在60℃的质量分数0.1-1%的BSA溶液中60min,用去离子水反复清洗、干燥处理。
6.按权利要求5制备方法得到的一种具有三明治结构的纳米银抗菌纤维素纤维。
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