CN111138582A - 一种含铜离子的阴离子聚合物水凝胶及制备方法与应用 - Google Patents
一种含铜离子的阴离子聚合物水凝胶及制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种含铜离子的阴离子聚合物水凝胶及制备方法与应用,所述制备方法为:(1)纯化烯烃单体:将含有单羧酸基烯烃单体、含有双羧酸基烯烃单体直接减压蒸馏;(2)制备纯化的烯烃单体的水溶液,添加铜离子水溶液、加入光引发剂和交联剂,在紫外光照下,聚合成水凝胶。本发明所述含铜离子的阴离子聚合物水凝胶制备的抗真菌涂层具有非常好的抗真菌性能,通过后整理方法在包括衣服,鞋底板,袜子,浴巾、毛毯等各种织物表面修饰一层所述涂层,其不仅能够有利于织物加快吸收汗液,而且抗真菌效率达到97%(织物经过洗涤30次后)。
Description
技术领域
本发明涉及生物医药或功能织物技术领域,特别是涉及一种含铜离子的阴离子聚合物水凝胶及制备方法与应用。
背景技术
浅部真菌病是当前最常见和高发的皮肤病,浅部真菌通常由红毛癣菌、须癣毛癣菌等组成,尤其在部队的发病率达10.50%。纺织品衣物时刻与皮肤密切接触,所致的机械磨损以及对局部皮肤温度、湿度、血流的作用,会对皮肤的屏障功能产生影响,浅部真菌病的发生在一定程度上也与之有关。另一方面,浅部真菌病具有一定传染性,通过鞋袜、浴巾、枕巾等衣物用具而致的间接传染是皮肤癣菌主要传播途径之一。近年来,随着生活水平的提高,人们的健康环保意识不断加强,在注重服装的美观、舒适性能的同时,对其卫生保健功能提出了更高的要求。生产具有抗菌功能的纺织品是使人们免受或少受致病微生物侵害的有效途径之一,因此具有抗菌功能的纺织品越来越受到人们的青睐。最近包括市场上开发出一系列抗菌织物,包括汉麻纤维坯布,含纳米银锦纶纤维坯布、无机银系抗菌剂整理后棉纤维坯布、载银纳米或者氧化锌锦纶纤维坯布等,以期对体癣、足癣等浅部真菌病的发病、传播起到一定的防治作用。
其中抗菌组分,如天然抗菌生物材料(如壳聚糖纤维),对霉菌、细菌都有很好的抗菌效果,由于其天然的特性,天然抗菌生物材料对人体的健康没有毒性作用,但是天然抗菌生物材料其加工条件很差,抗菌性能有限,且受到自然资源的限制;而对于大多数有机抗菌生物材料耐热性差、寿命较短、毒性大、易产生耐药性、难降解,使其在使用中存在严重的安全隐患,这些劣势限制了有机抗菌生物材料的进一步发展。无机抗菌生物材料却可以通过将无机生物材料固有的稳定性和抗菌成分的高效性、广谱性相结合。单独金属离子均具有良好的杀菌性能,但是银离子价格昂贵,且银离子的抗菌效果受光和热的影响,长期使用易被还原而降低抗菌效果。所以,研究一种新型金属离子的抗真菌涂层是非常有意义的,不仅能够降低成本,还能改善织物材料的高效抗真菌性能。
发明内容
本发明的目的是提供一种含铜离子的阴离子聚合物水凝胶及制备方法与应用,以解决上述现有技术存在的问题。
为实现上述目的,本发明提供了如下方案:
技术方案一:
本发明提供一种所述的含铜离子(或不含)的阴离子聚合物水凝胶的制备方法,将含有单羧酸基烯烃单体、含有双羧酸基烯烃单体和铜离子水溶液混合,加入光引发剂,然后在紫外光下聚合成水凝胶。
进一步的,所述的含铜离子的阴离子聚合物水凝胶的制备方法,包括以下步骤:
(1)纯化烯烃单体:将含有单羧酸基烯烃单体、含有双羧酸基烯烃单体直接减压蒸馏,控制好温度;
(2)添加铜离子水溶液,添加光引发剂和交联剂,在紫外光照下,聚合成水凝胶。
进一步的,所述光引发剂为2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(2959)。
进一步的,步骤(2)中所有烯烃单体质量之和与水的质量比为1:10~1:5000。
进一步的,光引发剂2959和烯烃单体之和的质量比为1:100~5:100。
进一步的,交联剂N,N'-亚甲基双丙烯酰胺和烯烃单体之和的质量比为0:1000~5:100。
进一步的,步骤(3)中聚合时间为5分钟~10分钟。
技术方案二:
本发明提供所述的制备抗真菌涂层的应用。优选将所述含铜离子的阴离子聚合物水凝胶制备的涂层构筑于各种布上,使得布具有抗真菌性能。
本发明公开了以下技术效果:
本发明所述含铜离子的阴离子聚合物水凝胶制备的抗真菌涂层具有非常好的抗真菌性能,市场上销售的抗菌袜子,未经过洗涤,如南极人袜子,其和红癣菌共培养4天后,抗真菌效率不到10%,而对于爱优恩袜子,虽然抗真菌比南极人稍微好些,不过抗菌效率不超过25%。本发明选用市场上无抗菌特性的包括衣服,鞋底板布,袜子,浴巾、毛巾等各种织物,通过后整理方法将其表面修饰一层含铜离子的阴离子聚合物水凝胶涂层,其不仅能够有利于织物加快吸收汗液,而且抗真菌效率达到97%(织物经过洗涤30次后)。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。
图1为阴离子聚合物水凝胶及织物表面涂层构筑示意图;
图2为各种水凝胶实物图及修饰好涂层的各种织物实物图;
图3为不同浓度的铜离子对真菌红癣菌的作用;
图4为含阴离子的聚合物水凝胶涂层对真菌作用;
图5为含铜离子的阴离子聚合物水凝胶涂层袜子和各种袜子织物对真菌作用。
具体实施方式
现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。
在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本申请说明书和实施例仅是示例性的。
实施例1
(1)含铜(不含)离子阴离子聚合物水凝胶制备
以单体丙烯酸(甲基丙烯酸/丁烯酸),衣康酸(顺丁烯二酸),两者之间的摩尔比10000:0~10000:1000,交联剂N,N'-亚甲基双丙烯酰胺,氯化铜(硫酸铜)和衣康酸(顺丁烯二酸)的物质的量之比为0:1~3:6。交联剂和单体之和的摩尔比1:1000~1:20,光引发剂2959和单体的质量比为1:100~5:100,单体之和与水质量比5:100~40:100。然后置于紫外线箱中,5分钟~10分钟光聚合,最后用酒精、水反复洗涤以除去其中的单体、交联剂以及光引发剂,(阴离子聚合物水凝胶及织物表面涂层构筑示意图见图1)所制备的水凝胶如图2a所示,所有的第一行从左到右边,依次为丙烯酸/衣康酸的摩尔比=10000/0,10000/10,10000/100,10000/1000,氯化铜和衣康酸的摩尔比为1:4,第二行从左到右边,依次为:丙烯酸/顺丁烯二酸的摩尔比=10000/0,10000/10,10000/100,10000/1000,氯化铜和顺丁烯二酸的摩尔比为1:4,第三行从左到右边,依次为甲基丙烯酸/衣康酸=10000/100,硫酸铜和衣康酸的摩尔比为1:4,丁烯酸/衣康酸=10000/100,硫酸铜和衣康酸的摩尔比为1:4,甲基丙烯酸/顺丁烯二酸的摩尔比=10000/100,硫酸铜和顺丁烯二酸的摩尔比为1:4,丁烯酸/顺丁烯二酸的摩尔比=10000/100,硫酸铜和顺丁烯二酸的摩尔比为1:4,选择一些上述制备的含铜离子的阴离子聚合物水凝胶,二元烯酸/单元烯酸的摩尔比=100/1,铜离子和衣康酸的摩尔比为1:4,交联剂N,N'-亚甲基双丙烯酰胺和烯烃单体之和的质量比为1:100,置于组织培养板上,每组三个平行实验。图2b所示为织物经过后整理后的图片,处理原液:衣康酸/丙烯酸摩尔比=10000/10,铜离子和衣康酸的摩尔比为1:4,交联剂N,N'-亚甲基双丙烯酰胺和烯烃单体之和的质量比为1:100,从第一行从左至右边依次是擦镜布,毛巾布,床单布,内库布,第二行从左至右边依次为耐克袜子布,李宁袜子布,AUN(爱优恩)抗菌袜子布(未修饰),南极人抗菌袜子布(未修饰),第三行从左至右边依次为全棉布,氨纶布,涤纶布,锦纶和棉复合布。选取一些经过后整理的织物与真菌红癣菌一起共培养研究。
真菌红癣菌和各种材料共培养
a.将保存的红色毛癣菌接种于马铃薯葡萄糖琼脂培养基(PDA)上30℃培养7-14天活化,此时细胞处于对数生长期。用接种钩勾刮取红色毛癣菌菌落,加入含有无菌0.85%吐温盐水1ml的(含有0.1%吐温80)无菌试管内,倒入研磨器研磨均匀至形成菌悬液。用血细胞计数板计数,调节菌液浓度为0.4×106~5×106cfu/ml备用。再将上述菌悬液用沙氏液体培养基1:50稀释至2倍终浓度((0.4-5)×104cfu/ml)。为保证实验的准确性再将部分菌悬液用生理盐水稀释10倍,取0.01ml(10μL)接种于沙氏琼脂平皿中,每天观察,计数菌落。
b.将100μL系列铜离子或者涂层含铜离子以及各种布(如全棉布,氨纶布,涤纶布,锦纶等或其混合物)(10mm×10mm)分别加入96孔细胞培养板中的各孔,将100μL不含涂层的沙氏液体培养基加入第9列作为生长对照(阳性对照),取200μL沙氏液体培养基加入作为阴性对照。同时设3行复孔。加入已制备的真菌悬液100μL于各孔中,阴性对照孔不加,最终菌接种液浓度为(0.4-5)×104cfu/ml,28℃温箱内孵育96h。于孵育结束前3~4h,每孔加入MTT液20μL,继续培养3~4h后,吸出上清液(细菌培养液)100μL,加入二甲基亚砜(DMSO)100μL使蓝紫色结晶甲臜充分溶解(线粒体中的琥珀酸脱氢酶能使外源性MTT还原为水不溶性的蓝紫色结晶甲臜),震荡5min后,用酶标仪测吸光度OD值(测量波长530nm)。抑制率=(1-测定孔OD值/阳性对照孔OD值)×100%。或者共培养四天后,取0.01ml(10μL)接种于沙氏琼脂平皿中,每天观察拍照。
不同的浓度铜离子对抗真菌活性评价
MTT测试结果表明,铜离子在100μM以下,抗真菌性能不到30%,当铜离子在1000μM以下,抗真菌性能达到80%(图3)。
不同的阴离子水凝胶对抗真菌活性评价
MTT测试结果表明,各种含铜阴离子聚合物水凝胶,抗真菌效率都达到90%(图4)。
不同的含铜离子的阴离子水凝胶涂层修饰的织物和各种市场袜子织物对抗真菌活性评价
涂板实验表明(图5),市场上抗菌袜子南极人和爱优恩,织物里含有银颗粒对真菌的杀菌性能比较差,耐克运动袜,几乎没有抗真菌性能,而经过后整理涂层处理后,抗真菌性能非常好,水凝胶制备的涂层能应用于各种织物中。
由上述结果表明本发明所述含铜离子的阴离子聚合物水凝胶制备的抗真菌涂层具有非常好的抗真菌性能,市场上销售的抗菌袜子,未经过洗涤,如南极人袜子,其和红癣菌共培养4天后,抗真菌效率不到10%,而对于爱优恩袜子,虽然抗真菌比南极人稍微好些。本发明选用市场上无抗菌特性的包括衣服,鞋底板布,袜子,浴巾等各种织物,通过后整理方法将其表面修饰一层含铜离子的阴离子聚合物水凝胶涂层,其不仅能够有利于织物加快吸收汗液,而且抗真菌效率达到97%(织物经过洗涤30次后)。
以上所述的实施例仅是对本发明的优选方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种变形和改进,均应落入本发明权利要求书确定的保护范围内。
Claims (10)
1.一种含铜离子的阴离子聚合物水凝胶,其特征在于,含有以下原料:含有单羧酸基的烯烃单体、含有双羧酸基的烯烃单体、交联剂、光引发剂和铜离子水溶液。
2.根据权利要求1所述的一种含铜离子的阴离子聚合物水凝胶,其特征在于,所有烯烃单体之和与铜离子的摩尔比为1:1~10:1。
3.根据权利要求1所述的一种含铜离子的阴离子聚合物水凝胶,其特征在于,所述含有单羧酸基的烯烃单体为丙烯酸、甲基丙烯酸或丁烯酸中的一种或多种。
4.根据权利要求1所述的一种含铜离子的阴离子聚合物水凝胶,其特征在于,所述含有双羧酸基的烯烃单体为衣康酸、丙二酸或丁二酸中的一种或多种。
5.根据权利要求1所述的一种含铜离子的阴离子聚合物水凝胶,其特征在于,所述铜离子的水溶液为氯化铜溶液或者硫酸铜溶液。
6.一种权利要求1所述的含铜离子的阴离子聚合物水凝胶的制备方法,其特征在于,将含有单羧酸基烯烃单体、含有双羧酸基烯烃单体和铜离子水溶液混合,加入光引发剂,然后在紫外光下聚合成水凝胶。
7.根据权利要求6所述的含铜离子的阴离子聚合物水凝胶的制备方法,其特征在于,包括以下步骤:
(1)纯化烯烃单体:将单羧酸基烯烃单体、双羧酸基烯烃单体直接减压蒸馏,控制好温度;
(2)添加铜离子水溶液,添加光引发剂和交联剂,在紫外光照下,聚合成水凝胶。
8.根据权利要求7所述的含铜离子的阴离子聚合物水凝胶的制备方法,其特征在于,所述光引发剂为2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮。
9.根据权利要求7所述的含铜离子的阴离子聚合物水凝胶的制备方法,其特征在于,步骤(2)中所有烯烃单体质量之和与水的质量比为1:10~1:50。
10.权利要求1~5任一项所述的含铜离子的阴离子聚合物水凝胶在制备抗真菌涂层中的应用。
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