CN112127013B - 一种铜离子络合聚γ谷氨酸/壳聚糖/棉混纺抗菌针织物及其制备方法 - Google Patents
一种铜离子络合聚γ谷氨酸/壳聚糖/棉混纺抗菌针织物及其制备方法 Download PDFInfo
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Abstract
本发明属于功能纺织领域,具体涉及一种铜离子络合聚γ‑谷氨酸(γ‑PGA)/壳聚糖(CS)/棉混纺抗菌针织物及其制备方法。该针织物通过将壳聚糖与聚γ‑谷氨酸交联,然后加入铜氨络合离子溶液,制备成纺丝液,将纺丝液进行湿法纺丝,然后经拉伸、水洗、后整理、水洗、烘干,得到铜离子络合聚γ‑谷氨酸/壳聚糖复合纤维,利用棉纤维纱线与复合纤维制备混纺抗菌针织物。本发明中,γ‑PGA的羧基与CS的氨基具有很高的配位系数,结构稳定。聚‑γ谷氨酸可做保水剂,重金属离子吸附剂,可增加铜离子的负载率。本发明中壳聚糖与铜离子联合抗菌具有协同作用,最终制得的针织物具有更好的抗菌性能、防静电性和阻燃性,且抗菌耐久性强。
Description
技术领域
本发明涉及功能纺织领域,具体涉及一种铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)/棉混纺抗菌针织物及其制备方法。
背景技术
壳聚糖是一种天然的高分子化合物,是由几丁质经过脱乙酰作用得到的带正电荷的天然碱性多糖,在虾和蟹的壳中含量丰富。壳聚糖不仅具有良好的生物相容性,生物降解性和无毒性,而且还具有良好的抗菌性能,可抑制某些病原微生物(如大肠杆菌和金黄色葡萄球菌)的生长。壳聚糖的生物降解性也有助于防止其产品废弃后对环境的污染,并改善土壤的微生态性质。壳聚糖带有正电,利用此特点在液态介质中与带有负电荷的聚γ-谷氨酸交联。
聚γ-谷氨酸,简称γ-PGA,是一种由L-和D-谷氨酸单体通过γ-谷氨酰键在酶催化作用下,链接而成的一种非核糖体多肽,分子链上具有大量侧链羧基,可在分子内部或分子间形成氢键。具有生物可降解性、易于修饰性、保水性、增溶性、缓释性。
目前市场上壳聚糖纤维成本高,可纺性差,抗菌性干扰因素多如:PH、金属离子、脱乙酰度、分子量等等。此外,受细菌代谢产物复杂和生长环境变化多样的影响,壳聚糖纤维主要表现为抑菌性,不具有杀菌性。具有可纺性良好、优异服用性能的棉纤维,与壳聚糖纤维混和,提高棉网的强力,同时赋予混纺纱一定的抑菌性降低成本。但是原棉含有4%-12%的伴生物,而这些物质恰恰为细菌生长提供了碳源、氮源、无机盐以及某些生长因子,壳聚糖纤维束缚在纺织品中不易被溶解,这极大的促进了细菌的繁殖,降低了壳聚糖纤维的抑菌率,甚至过一段时间后完全的失去抑菌作用。中国专利CN101250759B公开了一种纺织加工领域中的医用壳聚糖纤维及其制备方法,该方法中以0.1%~1%的磷酸钠银对壳聚糖纤维进行活化处理,使生产的壳聚糖纤维含有银离子。银离子虽然可以杀灭或者抑制细菌,但银不属于人体必需的微量元素,且作为一种重金属元素,对人体还是具有潜在毒性的。此外,银离子化学性质较活泼,对光和热较敏感,特别是经紫外线长时间照射后会还原为黑色的单质银,不仅影响壳聚糖纤维及其制品的抗菌性,还影响白色或浅色制品的外观,极大地限制了其应用。
发明内容
本发明的目的是提供一种铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)/棉混纺抗菌针织物。
本发明还提供了一种铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)/棉混纺抗菌针织物的制备方法,该方法利用棉纤维纱线与复合纤维纱线制备混纺抗菌针织物提高壳聚糖的抗菌活性。
本发明为了实现上述目的采用的技术方案如下:
本发明一种铜离子络合聚γ-谷氨酸/壳聚糖/棉混纺抗菌针织物,该针织物通过将壳聚糖与聚γ-谷氨酸交联,然后加入铜氨络合离子溶液,制备成纺丝液,将纺丝液进行湿法纺丝,然后经拉伸、水洗、后整理、水洗、烘干,得到铜离子络合聚γ-谷氨酸/壳聚糖复合纤维,利用棉纤维纱线与复合纤维制备混纺抗菌针织物。
本发明还提供了一种铜离子络合聚γ-谷氨酸/壳聚糖/棉混纺抗菌针织物的制备方法,具体包括以下步骤:
(1)在铜盐溶液中滴加氨水,生成碱式硫酸铜沉淀,继续滴加氨水至沉淀完全溶解,得到铜氨络和离子溶液;
(2) 将20mg壳聚糖溶解于20ml乙酸溶液中,常温下搅拌均匀后用去离子水将其稀释制得壳聚糖溶液;将聚γ-谷氨酸溶液逐滴加到等体积的壳聚糖溶液中,磁力搅拌,充分混合,然后加入10mg二氧化钛、3mg抗老化剂、5mg硅烷偶联剂,磁力搅拌,加入铜氨络和离子溶液,离心,得到纺丝原液,纺丝原液在60℃下进行湿法纺丝,制得初生纤维;
(3) 将初生纤维进行拉伸、水洗、后整理、水洗、烘干工序,得到铜离子络合聚γ-谷氨酸/壳聚糖复合纤维,然后利用棉纤维纱线与复合纤维制备混纺抗菌针织物。
进一步的,步骤(1)中,所述的铜盐为硫酸铜、氯化铜、硝酸铜、醋酸铜中的一种;所述铜盐溶液的浓度为20mg/mL。
进一步的,步骤(2)中,所述乙酸溶液中乙酸的体积百分浓度为1%。
进一步的,步骤(2)中,所述聚γ-谷氨酸溶液的浓度为2mg/mL,溶剂为超纯水;所述稀释后的壳聚糖溶液浓度为2mg/mL;所述壳聚糖的脱乙酰度为80.0~95.0。
进一步的,步骤(2)中,所述抗老化剂为PP-g-AN(聚丙烯-丙烯腈接枝共聚物);所述PP-g-AN的接枝率为15%,分子量为40kDa。
进一步的,步骤(2)中,所述第一次磁力搅拌的时间为30min;第二次磁力搅拌的时间为2h;离心机离心的时间为40min。
进一步的,步骤(2)中,所述湿法纺丝参数为:在0.1-0.3MPa压力下将纺丝液经计量泵挤出纺丝,纺丝温度为60℃,喷丝板孔数50-200孔,孔径60-120μm,凝固浴牵伸比为0.75-1.05,水洗牵伸比为1.1-2.0。
本发明利用棉纤维纱线与复合纤维制备混纺抗菌针织物具体制备方法为:在软件中绘制织物编织图,运行无误后将编织图导入到针织电脑中;量取纯棉纤维纱线和复合纤维纱线数,然后将经纱放在整经板上整理好,在需要使用的纱嘴上更换成使用的纱线并设置度目数;然后通过穿综、穿筘整理后,把机头复位,开始打行定,行定打完后开始织物的正式编织,编织完成后再打一段行定,待完全离开卷布辊后剪下。
本发明所使用的聚γ-谷氨酸是由地衣芽孢杆菌(bacillus licheniformis)发酵提取得到的,其发酵提取方法包括以下步骤:
a称取基础培养基,溶解,得基础培养基溶液,然后称取优化培养基各成分加入至基础培养基溶液中,定容,固体NaOH调节pH至7.5;b将培养基分装至锥形瓶(50ml/瓶)中,经100-150℃灭菌,按2-10%的接种量将地衣芽孢杆菌接入培养基中,30-50℃摇床培养3-7天,得发酵液;
c将发酵液离心,取上层清液加入2-7倍体积的乙醇沉淀10-24h,离心,所得上清液重新用2-6倍体积的乙醇沉淀,离心,将沉淀烘干至恒重,得恒重样品;
d将恒重样品溶于蒸馏水中,透析纯化,得纯化样品;
e将纯化样品溶于蒸馏水中,喷雾干燥制得聚γ-谷氨酸粉末。
聚-γ谷氨酸制备过程中,步骤(a)中,所述优化培养基与基础培养基的体积比为1:4。
本发明所使用的基础培养基的原料组成为:胰蛋白胨 10g/L ,酵母提取物 5g/L,NaCl 10g/L;优化培养基原料组成为:NaCl 10-15g/L, α-酮戊二酸 1.0-2.5 g/L, Mn(Ⅱ)0.02-0.1 g/L, L-谷氨酰胺 0.2-1.0 g/L, 甘油5-15 g/L。
本发明制备聚-γ谷氨酸过程中,喷雾干燥的工作参数为:最大水分蒸发量50kg/h,入口温度200℃,出口温度85℃,离心喷雾头机械转动,转速18000r/min。
与现有技术相比,本发明的有益效果为:
(1)本发明使用的聚-γ谷氨酸和壳聚糖为无色无毒无味且易降解的微生物发酵提取物,γ-PGA 的羧基与CS的氨基具有很高的配位系数,结构稳定。聚-γ谷氨酸具有粘性,可做保水剂,重金属离子吸附剂,可增加铜离子的负载率。
(2)本发明中壳聚糖与铜离子联合抗菌具有协同作用,最终制得的针织物具有更好的抗菌性能,且抗菌耐久性强。
(3)本发明制备的针织物通过交联和络合,克服了无机铜引发的环境及毒性问题,制得的混纺针织物由于本身具有高效抗菌功能,其制品无需进行抗菌后整理,降低了生产成本,且可生物降解,对环境无污染。
(4)本发明制备的抗菌针织物较在织物中添加抗菌剂而言具有持久抗菌效果,能保证织物自然风格,舒适性良好,省略后整理工序,操作简单,使用方便。
附图说明
图1为本发明制得的复合纤维抗菌能力测试图。
具体实施方式
通过下面实例说明本发明的具体实施方式,但本发明的保护内容,不仅局限于此。
实施例1
(1)在10mg/mL硫酸铜溶液中滴加氨水,则有浅蓝色的碱式硫酸铜沉淀生成,继续滴加氨水至沉淀完全溶解,得到铜氨络和离子溶液;
(2)将壳聚糖溶解于体积浓度为1%的乙酸溶液中,常温下搅拌均匀后用去离子水将其稀释制得浓度为2mg/mL壳聚糖溶液(脱乙酰度为85.0);制备聚γ-谷氨酸溶液,将聚γ-谷氨酸溶液逐滴加到等体积的壳聚糖溶液中,磁力搅拌30min,充分混合,然后加入10mg二氧化钛、3mg抗老化剂、5mg硅烷偶联剂,磁力搅拌2h,加入铜氨络和离子溶液,离心40min,除上清液,用20ml 1%乙酸溶液溶解沉淀,得到纺丝原液,纺丝液进行湿法纺丝,具体工作参数为:在0.3MPa压力下将纺丝液经计量泵挤出纺丝,纺丝温度为25℃,喷丝板孔数200孔,孔径120μm,凝固浴牵伸比为1.05,水洗牵伸比为2.0;
(3)将制得的初生纤维进行拉伸、水洗、后整理、水洗、烘干工序,得到铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)复合纤维;
(4)在软件中绘制织物编织图,运行无误后将编织图导入到针织电脑中;量取纯棉纤维纱线和复合纤维纱线数,然后将经纱放在整经板上整理好,在需要使用的纱嘴上更换成使用的纱线并设置度目数;然后通过穿综、穿筘整理后,把机头复位,开始打行定,行定打完后开始织物的正式编织,编织完成后再打一段行定,待完全离开卷布辊后剪下。
实施例2
(1)在10mg/mL氯化铜溶液中滴加氨水,则有浅蓝色的碱式硫酸铜沉淀生成,继续滴加氨水至沉淀完全溶解,得到铜氨络和离子溶液;
(2)将壳聚糖溶解于体积浓度为1%的乙酸溶液中,常温下搅拌均匀后用去离子水将其稀释制得浓度为2mg/mL壳聚糖溶液(脱乙酰度为95.0);制备聚γ-谷氨酸溶液,将聚γ-谷氨酸溶液逐滴加到等体积的壳聚糖溶液中,磁力搅拌30min,充分混合,然后加入10mg二氧化钛、3mg抗老化剂、5mg硅烷偶联剂,磁力搅拌2h,加入铜氨络和离子溶液,离心40min,除上清液,用20ml 1%乙酸溶液溶解沉淀,得到纺丝原液,纺丝液在30℃下进行湿法纺丝,具体工作参数为:在0.2MPa压力下将纺丝液经计量泵挤出纺丝,纺丝温度为25℃,喷丝板孔数100孔,孔径100μm,凝固浴牵伸比为1.0,水洗牵伸比为1.5;
(3)将制得的初生纤维进行拉伸、水洗、后整理、水洗、烘干工序,得到铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)复合纤维;
(4)在软件中绘制织物编织图,运行无误后将编织图导入到针织电脑中;量取纯棉纤维纱线和复合纤维纱线数,然后将经纱放在整经板上整理好,在需要使用的纱嘴上更换成使用的纱线并设置度目数;然后通过穿综、穿筘整理后,把机头复位,开始打行定,行定打完后开始织物的正式编织,编织完成后再打一段行定,待完全离开卷布辊后剪下。
实施例3
(1)在10mg/mL硝酸铜溶液中滴加氨水,则有浅蓝色的碱式硫酸铜沉淀生成,继续滴加氨水至沉淀完全溶解,得到铜氨络和离子溶液;
(2)将壳聚糖溶解于体积浓度为1%的乙酸溶液中,常温下搅拌均匀后用去离子水将其稀释制得浓度为2mg/mL壳聚糖溶液(脱乙酰度为80.0);制备聚γ-谷氨酸溶液,将聚γ-谷氨酸溶液逐滴加到等体积的壳聚糖溶液中,磁力搅拌30min,充分混合,然后加入10mg二氧化钛、3mg抗老化剂、5mg硅烷偶联剂,磁力搅拌2h,加入铜氨络和离子溶液,离心40min,得到除上清液,用20ml 1%乙酸溶液溶解沉淀,纺丝原液,纺丝液在30℃下进行湿法纺丝,具体工作参数为:在0.1MPa压力下将纺丝液经计量泵挤出纺丝,纺丝温度为25℃,喷丝板孔数50孔,孔径60μm,凝固浴牵伸比为0.75,水洗牵伸比为1.1;
(3)将制得的初生纤维进行拉伸、水洗、后整理、水洗、烘干工序,得到铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)复合纤维;
(4)在软件中绘制织物编织图,运行无误后将编织图导入到针织电脑中;量取纯棉纤维纱线和复合纤维纱线数,然后将经纱放在整经板上整理好,在需要使用的纱嘴上更换成使用的纱线并设置度目数;然后通过穿综、穿筘整理后,把机头复位,开始打行定,行定打完后开始织物的正式编织,编织完成后再打一段行定,待完全离开卷布辊后剪下。
性能测试:
(1)以金黄色葡萄球菌、大肠杆菌为试验菌株,培养取对数生长期的菌液,将铜离子络合聚γ-谷氨酸、聚γ-谷氨酸/壳聚糖、铜离子络合聚γ-谷氨酸/壳聚糖分别溶解到一定的浓度,采用二倍稀释法进行最小抑菌浓度(MIC) 的测定。结果显示铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)对金黄色葡萄球菌、链球菌、大肠杆菌的抑菌活性优于铜离子络合聚γ-谷氨酸、聚γ-谷氨酸/壳聚糖。
表1抑菌活性
(2)采用大肠杆菌和金黄色葡萄球菌为试验菌种,按照ISO 22196-2007和QB/T 2591-2003标准进行抗菌能力测试,拟用牛津杯法对本发明制得铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)的纺丝纤维进行检测,检测试验纤维的24h抑菌圈大小,参照GB 4789.2-2010标准进行试验前后的菌落总数测定,菌落培养条件为37±1℃、相对湿度大于90%,所得试验数据使用SPSS13.0软件进行统计处理,P<0.05表示有显著性差异,得到24h抑菌圈大小,从图1中可以看出铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)的抑菌效果优于铜离子络合聚γ-谷氨酸(γ-PGA)和聚γ-谷氨酸(γ-PGA)/壳聚糖(CS),铜离子络合聚γ-谷氨酸(γ-PGA)对大肠杆菌的抑菌效果较聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)有微弱优势,聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)对金黄色葡萄球菌的抑菌效果较铜离子络合聚γ-谷氨酸(γ-PGA)有微弱优势。
(3) 将铜离子络合聚γ谷氨酸/壳聚糖/棉混纺抗菌针织物剪碎,用液氮研磨,获得悬浮溶液。采用大肠杆菌和金黄色葡萄球菌为试验菌种,检测本发明制得混纺抗菌针织物的抗菌能力,设置对照组,对照组1为利用铜离子络合聚γ-谷氨酸(γ-PGA)制备的针织物,制备方法基本同实施例1;如表2,结果显示针织物具有良好的抑菌效果。
表2 针织物抑菌效果
从上述实施例可以得出,本发明制备的铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)/棉混纺抗菌针织物抑菌效果明显,且本发明制备方法简单,原料成本较低。本发明制备的铜离子络合聚γ-谷氨酸(γ-PGA)/壳聚糖(CS)/棉混纺抗菌针织物可应用于多个领域,应用范围广泛。
Claims (8)
1.一种铜离子络合聚γ-谷氨酸/壳聚糖/棉混纺抗菌针织物的制备方法,其特征在于,该针织物通过将壳聚糖与聚γ-谷氨酸交联,然后加入铜氨络合离子溶液,制备成纺丝液,将纺丝液进行湿法纺丝,然后经拉伸、水洗、后整理、水洗、烘干,得到铜离子络合聚γ-谷氨酸/壳聚糖复合纤维,利用棉纤维纱线与复合纤维制备混纺抗菌针织物;
具体包括以下步骤:
(1)在铜盐溶液中滴加氨水,生成碱式硫酸铜沉淀,继续滴加氨水至沉淀完全溶解,得到铜氨络和离子溶液;
(2) 将20mg壳聚糖溶解于20ml乙酸溶液中,常温下搅拌均匀后用去离子水将其稀释制得壳聚糖溶液;将聚γ-谷氨酸溶液逐滴加到等体积的壳聚糖溶液中,磁力搅拌,充分混合,然后加入10mg二氧化钛、3mg抗老化剂、5mg硅烷偶联剂,磁力搅拌,加入铜氨络和离子溶液,离心,得到纺丝原液,纺丝原液在60℃下进行湿法纺丝,制得初生纤维;
(3) 将初生纤维进行拉伸、水洗、后整理、水洗、烘干工序,得到铜离子络合聚γ-谷氨酸/壳聚糖复合纤维,然后利用棉纤维纱线与复合纤维制备混纺抗菌针织物。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述的铜盐为硫酸铜、氯化铜、硝酸铜、醋酸铜中的一种;所述铜盐溶液的浓度为20mg/mL。
3.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述乙酸溶液中乙酸的体积百分浓度为1%。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述聚γ-谷氨酸溶液的浓度为2mg/mL;所述稀释后的壳聚糖溶液浓度为2mg/mL;所述壳聚糖的脱乙酰度为80.0~95.0。
5.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述抗老化剂为PP-g-AN聚丙烯-丙烯腈接枝共聚物;所述PP-g-AN的接枝率为15%,分子量为40kDa。
6.根据权利要求1所述的复合纤维的制备方法,其特征在于,步骤(2)中,所述第一次磁力搅拌的时间为30min;第二次磁力搅拌的时间为2h;离心机离心的时间为40min。
7.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,所述湿法纺丝参数为:在0.1-0.3MPa压力下将纺丝液经计量泵挤出纺丝,纺丝温度为60℃,喷丝板孔数50-200孔,孔径60-120μm,凝固浴牵伸比为0.75-1.05,水洗牵伸比为1.1-2.0。
8.根据权利要求1-7任一项所述的制备方法,其特征在于:所述利用棉纤维纱线与复合纤维制备混纺抗菌针织物具体制备方法为:在软件中绘制织物编织图,运行无误后将编织图导入到针织电脑中;量取纯棉纤维纱线和复合纤维纱线数,然后将经纱放在整经板上整理好,在需要使用的纱嘴上更换成使用的纱线并设置度目数;然后通过穿综、穿筘整理后,把机头复位,开始打行定,行定打完后开始织物的正式编织,编织完成后再打一段行定,待完全离开卷布辊后剪下。
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