CN106012495B - 一种具有防护功能的麻织物及其制备方法 - Google Patents
一种具有防护功能的麻织物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有防护功能的麻织物及其制备方法,包括了麻织物的预处理、氧化处理、壳聚糖乙酸溶液的配制、壳聚糖改性氧化麻织物的制备和茶多酚对壳聚糖改性麻织物的复合整理等制备步骤,本发明首先采用高碘酸或高碘酸盐对麻织物进行选择性氧化,产生活性基团醛基‑CHO可与含‑NH2的壳聚糖发生亚胺化反应,在不使用任何交联剂或其它化学添加剂的条件下,两者产生了化学键合,增强了后序整理过程中织物对茶多酚的吸附能力,促进茶多酚与麻织物的结合,避免茶多酚功能整理过程使用其它试剂,本发明的产品具有良好的抗菌、抗皱和抗紫外线等多功能性;该产品的制备工艺简单,操作方便,制备过程中也实现了清洁化生产,符合生态纺织品的要求。
Description
技术领域
本发明涉及一种麻织物的改性方法,尤其涉及一种具有抗菌、抗皱、抗紫外线等多功能性的麻织物的处理方法。
背景技术
麻纤维是天然纤维素纤维,具有可再生性、生物可降解性以及无毒无污染的特点。麻纤维以其优雅的光泽、良好的吸湿放湿性和天然抗菌性而广泛应用于服装、家用和产业用等纺织品领域。但麻纤维存在易起皱、尺寸不稳定等缺点;而且在夏季穿着时,麻织物的防紫外线性能也需进一步提高。随着新品种、高性能和多功能的纺织纤维材料不断出现,在客观上对麻纤维及其制品的要求也越来越高。开发麻纤维及其制品的多功能化改性以及提高其附加值和性能已成为人们研究的一大方向。
由于目前研制的功能整理剂大多依靠物理吸附附着在麻纤维及其制品表面,但是两者结合不牢固。因此麻纤维传统改性中,需要采用化学交联剂(树脂、乙二醛、有机硅和多元羧酸等)或偶联剂的“桥联”作用将其功能整理剂接枝到麻纤维上,从而达到改善麻纤维性能和赋予其功能耐久性的目的。然而,麻纤维制品传统改性存在一定弊端,如树脂或乙二醛整理后会使麻织物上残留和释放出甲醛,对人体产生较大危害;而交联剂或偶联剂接枝改性的麻纤维表面不可避免地交联了一层化学物质,影响了天然麻纤维的优良特性,并对人体健康产生负面影响。因此,传统的改性技术在赋予麻纤维素纤维制品功能的同时,对生态环境和人体健康危害严重,难以满足生态性、多功能性和持久性的多重要求。
茶叶是我国丰富的天然植物资源,茶多酚又是从茶叶中分离提取出的三十多种酚类化合物的复合体,主要为黄烷醇(儿茶素)类,其占总量的60~80%。茶多酚由于其特殊的成分和结构具有许多独特的生理活性,如优良的抗氧化能力、抗辐射、消炎杀菌、抗紫外线等功能,目前已被广泛应用于医药保健、食品加工、日用化工、精细化工等领域。近年来国内外研究人员将茶多酚作为天然染料用于纺织品染色和功能性整理进行了一定的研究,茶多酚的改性处理不仅可以使织物具有独特的色泽,还可以赋予织物很多天然的保健功能。但在茶多酚染整过程中常常需要使用化学交联剂或媒染剂增强茶多酚与纤维的结合牢度,会对环境或人体健康产生负面影响,因而限制了茶多酚在纺织品上的应用。
壳聚糖是甲壳素的脱乙酰化产物,是自然界中唯一的碱性多糖。壳聚糖具有无毒、无味及良好的生物降解性、可再生性、抗菌防腐性、成膜性等优良性能。为了实现壳聚糖和茶多酚两种天然高分子材料在麻纤维多功能化改性中的应用,本发明采用麻织物经高碘酸或高碘酸盐选择性氧化后,再经壳聚糖和茶多酚生态复合整理技术,使其产品具有良好的抗菌、防皱、防紫外线等多功能性,且具有良好的功能耐久性。该功能整理过程不使用任何交联剂或金属媒染剂,且采用的整理剂无毒环保,实现了清洁化生产,符合生态纺织品的要求。本发明利用壳聚糖改性氧化麻织物后吸附茶多酚共同制备功能麻织物的方法尚未见任何报道。本发明的目的在于提供一种具有持久抗菌、防皱和防紫外线等多功能性麻织物,其中包括苎麻、亚麻、黄麻等麻纤维织物。与一般麻织物的功能改性相比,采用壳聚糖改性氧化麻织物后吸附茶多酚的方法对麻织物进行的功能改性,满足了生态性、多功能性和持久性的多重要求,且方法简单、安全。
发明内容
本发明的目的在于克服现有技术的不足,提供了提供一种具有持久抗菌、防皱以及防紫外线等多功能性麻织物,以解决现有技术中的麻织物功能单一,功能改性产品危害性较大的技术问题。
本发明是通过以下技术方案实现的:本发明公开了一种具有防护功能麻织物的制备方法,包括以下制备步骤:
1)麻织物的预处理:将麻织物加入到碱性溶液中,室温下搅拌后,水洗,再将麻织物放入酸性溶液中浸泡,再水洗,晾干后即得到碱化麻织物;
2)麻织物的氧化处理:将配制好的高碘酸与步骤1)中得到的碱化麻织物按浴比50:1进行混合,40~60℃水浴条件下进行避光反应,反应结束后,将麻织物取出并水洗,先将水洗后的麻织物置于丙三醇溶液中浸泡,然后再将其放入去离子水中浸泡,洗涤晾干后即得氧化麻织物,备用;
3)壳聚糖乙酸溶液的配制:将壳聚糖加入到乙酸溶液中进行溶解,配制壳聚糖乙酸溶液,其中所述壳聚糖乙酸溶液中壳聚糖的质量浓度为0.5~4%;
4)壳聚糖改性氧化麻织物的制备:将步骤3)中配制的壳聚糖乙酸溶液与步骤2)中得到的氧化麻织物按浴比50:1进行混合,浸润后,水浴条件下持续搅拌1~2h,然后将麻织物水洗后置于烘箱中进行烘干,最后将其洗涤晾干后即得壳聚糖改性氧化麻织物,备用;
5)茶多酚对壳聚糖改性麻织物的复合整理:将步骤4)中制备的壳聚糖改性氧化麻织物按浴比1:50投入到茶多酚溶液中,加热下持续搅拌1~1.5h,然后将麻织物水洗后置于烘箱中进行烘干,最后将麻织物洗涤晾干后即得复合整理的麻织物。
进一步的,由于麻纤维具有较高的结晶度,在进行氧化反应前进行碱预活化反应,有利于后序氧化反应效率的提高,所以步骤1)中碱性溶液为15~25wt%的氢氧化钠溶液,酸性溶液为质量浓度为5~10%的乙酸溶液,室温下搅拌的时间为20~60min。
进一步的,本发明采用高碘酸对麻织物进行选择性氧化,产生新的活性基团醛基-CHO,使纤维素可与含-NH2的壳聚糖发生亚胺化反应。步骤2)中所述高碘酸的浓度为2~10g/L,避光反应的时间0.5~3h,也可以采用浓度为2~10g/L高碘酸盐进行选择性氧化;步骤2)中也可先将水洗后的麻织物置于丙酮溶液中浸泡,然后再将其放入去离子水中浸泡。
进一步的,为了能够将壳聚糖进行溶解完全,步骤3)中所述乙酸溶液为体积浓度为1~4%的乙酸溶液。
进一步的,为了不破坏麻织物的表面结构以及更好的改性,步骤4)中水浴的温度为40~60℃,将水洗后的麻织物置于烘箱中先在80℃条件下预烘5~10min,然后在140~160℃焙烘3min,然后再将麻织物洗涤晾干。
进一步的,为了更好的对改性麻织物进行复合整理,步骤5)中茶多酚溶液的浓度为6~20g/L,加热的温度为60~90℃,将水洗后的麻织物置于烘箱中先在80℃条件下预烘5~10min,然后在140~160℃焙烘3min,最后将麻织物洗涤晾干后即得复合整理的麻织物。
进一步的,为了适用于更多的麻织物,麻织物的种类可以是苎麻、亚麻或黄麻中的任一种。
进一步的,由于本发明先采用高碘酸或高碘酸盐对麻织物进行选择性氧化,产生新的活性基团醛基-CHO,使纤维素可与含-NH2的壳聚糖发生亚胺化反应,在不使用任何交联剂或其它化学添加剂的条件下,两者之间产生了化学键合,使壳聚糖牢固地固着在麻织物表面。而壳聚糖分子中含有的羟基和游离的氨基有利于增强后序整理过程中织物对茶多酚的吸附能力,促进茶多酚与麻织物的结合牢度,从而避免茶多酚染色或功能整理过程使用任何交联剂或金属媒染剂,为了能够更好的进行复合整理,所述壳聚糖的脱乙酰度为80~95%。
本发明采用资源丰富的壳聚糖和天然植物提取物茶多酚作为整理剂,运用生态整理技术提高麻产品的多功能性,增加了其附加值。本发明首先采用高碘酸或高碘酸盐对麻织物进行选择性氧化,产生新的活性基团醛基-CHO,使纤维素可与含-NH2的壳聚糖发生亚胺化反应,在不使用任何交联剂或其它化学添加剂的条件下,两者之间产生了化学键合,使壳聚糖牢固地固着在麻织物表面。而壳聚糖分子中含有的羟基和游离的氨基有利于增强后序整理过程中织物对茶多酚的吸附能力,促进茶多酚与麻织物的结合牢度,从而避免茶多酚染色或功能整理过程使用任何交联剂或金属媒染剂。本发明具有持久抗菌、防皱和防紫外线等多重功能,其中包括苎麻、亚麻、黄麻等麻纤维织物。与一般麻织物的功能改性相比,采用壳聚糖改性氧化麻织物后吸附茶多酚的方法对麻织物进行的功能改性,满足了生态性、多功能性和持久性的多重要求,且方法简单、安全。
附图说明
图1为苎麻织物处理前后的红外光谱分析图谱。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
将苎麻织物加入到15wt%的氢氧化钠溶液中,在室温下搅拌20min,水洗3次,再在质量浓度为5%的冰乙酸中浸泡30min,最后水洗晾干后得到碱化苎麻织物;
配制浓度为2g/L的高碘酸钠溶液置于棕色锥形瓶中,按50:1的浴比加入上述制得的碱化苎麻织物,在40℃水浴避光反应0.5h,得到氧化苎麻织物;将氧化苎麻织物取出冲洗后置于丙三醇溶液中浸泡2h,再放入去离子水中浸泡24h。最后洗涤晾干后得到氧化苎麻织物;
将称取的脱乙酰度为80%的壳聚糖加入到体积浓度为1%的稀乙酸溶液中,使壳聚糖完全溶解于乙酸溶液,其中壳聚糖乙酸溶液中壳聚糖的质量浓度为4%;
将配置的质量浓度为4%的壳聚糖整理液按浴比50:1加入氧化苎麻织物,浸润后在40℃下持续搅拌1h,得到改性苎麻织物;将其水洗后置于烘箱80℃预烘5min,140℃焙烘3min,最后洗涤晾干后得到壳聚糖改性氧化苎麻织物;
按浴比1:50将壳聚糖改性氧化苎麻织物投入到浓度为6g/L的茶多酚溶液中,在60℃下持续搅拌1h,得到处理后的苎麻织物;将其水洗后置于烘箱80℃预烘5min,140℃焙烘3min,最后洗涤晾干后得到复合整理的苎麻织物。
采用GB/T 18830-2002《纺织品防紫外线性能的评定》进行检测,测得织物的紫外线防护指数(UPF值)为42.4;采用的是GB/T 3819-1997《纺织品织物折痕回复性的测定》进行检测,测得织物的折皱角回复角(经向+纬向)达到168°;通过振荡烧瓶法定量实验测得织物对大肠杆菌的抗菌率达到96.5%,金黄色葡萄球菌的抗菌率达到98.6%。
实施例2:
将亚麻织物加入到25wt%的氢氧化钠溶液中,在室温下搅拌60min,水洗5次,再在质量浓度为5%的冰乙酸中浸泡30min,最后水洗晾干后得到碱化亚麻织物;
配制浓度为10g/L的高碘酸溶液置于棕色锥形瓶中,按50:1的浴比加入上述制得的碱化亚麻织物,在60℃水浴避光反应3h,得到氧化亚麻织物;将氧化亚麻织物取出冲洗后置于丙酮溶液中浸泡2h,再放入去离子水中浸泡24h。最后洗涤晾干后得到氧化亚麻织物;
将称取的脱乙酰度为95%壳聚糖加入到体积浓度为4%的稀乙酸溶液中,使壳聚糖完全溶解于乙酸溶液,其中壳聚糖乙酸溶液中壳聚糖的质量浓度为0.5%;
将配置的质量浓度为0.5%的壳聚糖整理液按浴比50:1加入氧化亚麻织物,浸润后在60℃下持续搅拌2h,得到改性亚麻织物;将其水洗后置于烘箱80℃预烘10min,150℃焙烘3min,最后洗涤晾干后得到壳聚糖改性氧化亚麻织物;
按浴比1:50将壳聚糖改性氧化亚麻织物投入到浓度为20g/L的茶多酚溶液中,在90℃下持续搅拌1.5h,得到处理后的亚麻织物;将其水洗后置于烘箱80℃预烘5min,150℃焙烘3min,最后洗涤晾干后得到复合整理的亚麻织物。
采用GB/T 18830-2002《纺织品防紫外线性能的评定》进行检测,测得织物的紫外线防护指数(UPF值)为45.6;采用的是GB/T 3819-1997《纺织品织物折痕回复性的测定》进行检测,测得织物的折皱角回复角(经向+纬向)达到186.5°;通过振荡烧瓶法定量实验测得织物对大肠杆菌的抗菌率达到97.9%,金黄色葡萄球菌的抗菌率达到99.5%。
实施例3:
将黄麻织物加入到20wt%的氢氧化钠溶液中,在室温下搅拌40min,水洗3次,再在质量浓度为5%的冰乙酸中浸泡30min,最后水洗晾干后得到碱化黄麻织物;
配制浓度为8g/L的高碘酸钠溶液置于棕色锥形瓶中,按50:1的浴比加入上述制得的碱化黄麻织物,在50℃水浴避光反应2h,得到氧化黄麻织物;将氧化黄麻织物取出冲洗后置于丙酮溶液中浸泡2h,再放入去离子水中浸泡24h。最后洗涤晾干后得到氧化黄麻织物;
将称取的脱乙酰度为85%壳聚糖加入到体积浓度为1%的稀乙酸溶液中,使壳聚糖完全溶解于乙酸溶液,其中壳聚糖乙酸溶液中壳聚糖的质量浓度为4%;
将配置的质量浓度为4%壳聚糖整理液按浴比50:1加入氧化黄麻织物,浸润后在60℃下持续搅拌1h,得到改性黄麻织物;将其水洗后置于烘箱80℃预烘10min,160℃焙烘3min,最后洗涤晾干后得到壳聚糖改性氧化黄麻织物;
按浴比1:50将壳聚糖改性氧化黄麻织物投入到浓度为15g/L的茶多酚溶液中,在70℃下持续搅拌1h,得到处理后的黄麻织物;将其水洗后置于烘箱80℃预烘5min,150℃焙烘3min,最后洗涤晾干后得到复合整理的黄麻织物。
采用GB/T 18830-2002《纺织品防紫外线性能的评定》进行检测,测得织物的紫外线防护指数(UPF值)为50.4;采用的是GB/T 3819-1997《纺织品织物折痕回复性的测定》进行检测,测得织物的折皱角回复角(经向+纬向)达到177.5°;通过振荡烧瓶法定量实验测得织物对大肠杆菌的抗菌率达到98.5%,金黄色葡萄球菌的抗菌率达到99.4%。
实施例4
如图1所示,图中a为苎麻织物的红外光谱;b为经过高碘酸钠溶液氧化后的苎麻织物的红外光谱;c为壳聚糖改性氧化苎麻的红外光谱曲线;对比曲线a和b可以看出,经氧化后的苎麻织物在1730cm-1附近出现了醛基中C=O的特征吸收峰。而经壳聚糖整理液处理后,曲线c中醛基中C=O伸缩振动峰强都有所减弱,且在1660cm-1及1545cm-1附近分别出现了C=N和C-N吸收峰。这现象说明苎麻纤维经过选择性氧化后生成的活性醛基,能够与壳聚糖分子链上的氨基结合,形成亚胺结构。由此可见,壳聚糖与氧化苎麻织物发生了化学交联反应,两者之间形成了牢固的化学键结合。
Claims (4)
1.一种具有防护功能麻织物的制备方法,其特征在于,包括以下制备步骤:
1)麻织物的预处理:将麻织物加入到碱性溶液中,室温下搅拌后,水洗,再将麻织物放入酸性溶液中浸泡,再水洗,晾干后即得到碱化麻织物;
2)麻织物的氧化处理:将配制好的高碘酸与步骤1)中得到的碱化麻织物按浴比50:1进行混合,40~60℃水浴条件下进行避光反应,反应结束后,将麻织物取出并水洗,先将水洗后的麻织物置于丙三醇溶液中浸泡,然后再将其放入去离子水中浸泡,洗涤晾干后即得氧化麻织物,备用;
3)壳聚糖乙酸溶液的配制:将壳聚糖加入到乙酸溶液中进行溶解,配制壳聚糖乙酸溶液,其中所述壳聚糖乙酸溶液中壳聚糖的质量浓度为0.5~4%;
4)壳聚糖改性氧化麻织物的制备:将步骤3)中配制的壳聚糖乙酸溶液与步骤2)中得到的氧化麻织物按浴比50:1进行混合,浸润后,水浴条件下持续搅拌1~2h,然后将麻织物水洗后置于烘箱中进行烘干,最后将其洗涤晾干后即得壳聚糖改性氧化麻织物,备用;
5)茶多酚对壳聚糖改性麻织物的复合整理:将步骤4)中制备的壳聚糖改性氧化麻织物按浴比1:50投入到茶多酚溶液中,加热下持续搅拌1~1.5h,然后将麻织物水洗后置于烘箱中进行烘干,最后将麻织物洗涤晾干后即得复合整理的麻织物;其中:
步骤1)中所述碱性溶液为15~25wt%的氢氧化钠溶液,所述酸性溶液为质量浓度为5~10%的乙酸溶液,室温下搅拌的时间为20~60min;
步骤2)中所述高碘酸的浓度为2~10g/L,所述避光反应的时间0.5~3h;步骤3)中所述乙酸溶液为体积浓度为1~4%的乙酸溶液;
步骤4)中水浴的温度为40~60℃,将水洗后的麻织物置于烘箱中先在80℃条件下预烘5~10min,然后在140~160℃焙烘3 min,然后再将麻织物洗涤晾干;
步骤5)中所述茶多酚溶液的浓度为6~20g/L,所述加热的温度为60~90℃,将水洗后的麻织物置于烘箱中先在80℃条件下预烘5~10min,然后在140~160℃焙烘3 min,最后将麻织物洗涤晾干后即得复合整理的麻织物。
2.如权利要求1所述的一种具有防护功能麻织物的制备方法,其特征在于,所述麻织物为苎麻、亚麻或黄麻中的任一种。
3.如权利要求1所述的一种具有防护功能麻织物的制备方法,其特征在于,所述壳聚糖的脱乙酰度为80~95%。
4.一种具有防护功能麻织物,其特征在于,所述具有防护功能麻织物是通过权利要求1~3所述的一种具有防护功能麻织物的制备方法中任一方法制备的。
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