CN111235691A - 一种纳滤抗菌材料、纳滤抗菌材料的制备方法及其用途 - Google Patents
一种纳滤抗菌材料、纳滤抗菌材料的制备方法及其用途 Download PDFInfo
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- CN111235691A CN111235691A CN202010078431.5A CN202010078431A CN111235691A CN 111235691 A CN111235691 A CN 111235691A CN 202010078431 A CN202010078431 A CN 202010078431A CN 111235691 A CN111235691 A CN 111235691A
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Classifications
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- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- A—HUMAN NECESSITIES
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- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
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- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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Abstract
本发明提供了一种纳滤抗菌材料、纳滤抗菌材料的制备方法及其用途，所述纳滤抗菌材料包含过氧化氢聚乙烯吡咯烷酮复合物和线性聚氨酯制成的壳核结构，其中，线性聚氨酯在壳层，过氧化氢和聚乙烯吡咯烷酮复合物在核层。本发明根据病毒表面蛋白结构的疏水和亲水基团的比例设计并制备了疏水和亲水壳核结构的纳米材料，研究了可以捕获并杀死病毒细菌的新材料，从而有效延长了口罩的佩戴时间，减少了浪费，真正起到了防疫防护的作用。
Description
技术领域
本发明属于生物材料技术领域，具体涉及一种具有壳核结构的具有湿度响应性智能杀菌纳米材料的制备方法及其在防护方面的应用。
背景技术
N95口罩中纳米纤维非织造布是一种有效的滤材，不仅对PM2.5等可吸入颗粒物截留率高。目前，聚合物纳米纤维主要由静电纺和离心纺制备。1967年，Chisholm等人发表了美国专利US3358323，据查这是将离心力用于聚合物加工的最早文献。这个专利设备可以提供造粒所需的挤出压力而不需要传统的挤出设备，并且该设备的结构比较简单。此后Chisholm等人对其进行了多方面研究与改进，并申请了美国专利，为离心纺丝技术的进一步研究奠定了基础。
1986年，欧洲专利EP0220727指出，离心纺丝时利用离心力代替压力泵，聚合物熔体经过挤压通过喷丝孔形成纤维。1999年，Jan和Aleksi利用旋转圆盘进行纺丝，研究了纺丝工艺参数以及溶液黏度等因素对所纺纤维直径的影响，2009年，Sarkar等人研究了一种新型离心纺丝方法，命名为Forcespinning，专利号为US20090280325A1，该方法通过多个微孔实现了纺丝的量化生产。同年，美国FibeRio科技股份有限公司成立。FibeRio公司在拉斯维加斯技术纺织品会议上，推出了基于Forcespinning技术的纳米纤维生产设备。这种离心纺丝设备的单孔产量可达 1g/min，纺制纤维的直径约300nm。
过氧化氢俗称双氧水，一般用于物体表面消毒。医疗上常用3%的双氧水进行伤口或中耳炎消毒。当它与皮肤、口腔和黏膜的伤口、脓液或污物相遇时，立即分解生成氧。这种尚未结合成氧分子的氧原子，具有很强的氧化能力，与细菌接触时，能破坏细菌菌体，杀死细菌。
聚乙烯吡咯烷酮(polyvinyl pyrrolidone)简称PVP，是一种非离子型高分子化合物，具有水溶性高分子化合物的一般性质，胶体保护作用、成膜性、粘结性、吸湿性、增溶或凝聚作用，有优良的生理惰性，不参与人体新陈代谢，又具有优良的生物相容性，对皮肤、粘膜、眼等不形成任何刺激。从生物学的观点来看，PVP的分子结构特色类似于用简单的蛋白质模型的那种结构，甚至于它的水溶性对某些小分子的配合能力以及能够被某些蛋白质的沉淀剂硫酸铵、三氯乙酸、单宁酸和酚类所沉淀等特性也和蛋白质相溶，PVP被广泛地用作药物制剂的辅料。
聚氨酯作为常用的医用材料，根据其分子结构可分为线型和交联型两种，交联型结构中由于交联密度不同，可呈现硬质、软质或介乎两者之间的性能，具有高强度、高耐磨和耐溶剂等特点，可用于聚氨酯泡沫材料、聚氨酯弹性体、聚氨酯防水材料、聚氨酯涂料、聚氨酯胶黏剂以及生物医用材料等，但是不溶解在有机溶剂中，无法采用本发明采用的静电纺丝工艺进行加工制造；线性聚氨酯比如软质聚氨酯（PU）：主要是具有热塑性的线性结构，具有更好的回弹性和力学性能，具有更小的压缩变型性，比如以聚丙二醇（PPG）、PGA、PLA、PDO、PCL以及PEG中的一种或两种以上聚合而成的聚合物为软段，二异氰酸酯为硬段，比如以二苯甲烷二异氰酸酯（MDI）、甲苯二异氰酸酯（TDI）、1，6- 六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、赖氨酸二异氰酸酯、赖氨酸三异氰酸酯、顺式-环己烷二异氰酸酯、反式-环己烷二异氰酸酯、1，4-丁烷二异氰酸酯、丁烷二异氰酸酯、1，2-乙烷二异氰酸酯、1，3-丙烷二异氰酸酯、4，4’-亚甲基- 双( 环己基异氰酸酯)、异佛尔酮二异氰酸酯、2，4，4-三甲基1，6-己烷二异氰酸酯中的一种或两种，采用二醇、二胺或者含有相关基团的的壳聚糖作为扩链剂制备而成的聚氨酯，可用于制备防护用产品。
国内外多篇文献研究报道了聚氨酯材料具有良好的机械性能、生物相容性、血液相容性和易加工等特点，在药物缓释载体、医用外科用材料、组织工程支架等领域，是非常有前景的可降解医用材料，是一种优良的复合支架的成分。国内外很多文献都公开了制备可降聚氨酯的方案，比如以1,6-六亚甲基二异氰酸酯(HDI)为硬段、聚碳酸酯二元醇(PCDL)为软段、赖氨酸乙酯盐酸盐(Lys-OEt)作为扩链剂合成的聚氨酯；以L-赖氨酸为原料,将L-赖氨酸上羧基转化为酯基，在催化剂作用下合成L-赖氨酸二异氰酸酯(LDI)分别与不同分子量的聚乙二醇(PEG)或对羟乙基哌嗪(HEP)进行共聚得到的聚氨酯；将分子量为2000的聚(ε-己内酯)二元醇(PCL)与LDI反应生成预聚物，再与扩链剂1,4-丁二醇(BDO)反应合成聚氨酯(PU)等。
比较典型的专利文献如200580014001.0公开了一种用一步法来制备的可降解聚氨酯，主要用于生成低模量的聚氨酯弹性体，且反应产物很难控制，得到产物的分子量很宽；一般工业生产高性能聚氨酯多用二步法，先采用聚酯或者聚醚多元醇先和二异氰酸酯反应生成预聚体，再用二醇或者二胺扩链生成聚氨酯，得到的弹性体分子结构排列规整，力学性能更好，重复性好，产物性能很容易控制，为此，本发明为制备的具有抗菌性能的断裂伸长率可控的高性能的聚氨酯，采用了二步法来制备。
壳聚糖及其衍生物作为天然高分子絮凝剂，其杀菌作用已被认识和研究，特别是在医药领域中越来越受到广泛关注，壳聚糖及其衍生物的抑菌作用随着其自身和环境条件的改变而呈现出不同的结果，分析其原因，主要可能是壳聚糖的有效基因N可以与细菌细胞膜上的类脂、蛋。白质复合物反应，使蛋白质变性，改变细胞膜的通透性，或者与细菌细胞壁（尤其是革兰阳性菌细胞壁较厚，结构紧密，含有丰富的磷壁酸）形成一个负电荷环境，壳聚糖损坏细胞壁的完整性，或使细胞壁趋于溶解，直至细胞死亡。
研究结果表明相对分子量为1500的脱乙酰壳聚糖对细菌抑制力最强、壳聚糖六聚糖抗肿瘤活性最强，壳聚糖含有羟基和氨基能进行各种化学改性，比如季铵基团接枝、磺化、磷酸化、烷基化、羟乙基化、负载天然活性物质、负载金属或氧化物等从而改变壳聚糖的性质，如羧甲基壳聚糖的制备，提高了水溶性和抑菌性，具有良好的成膜性。
很多文献报道了在聚氨酯中引入壳聚糖抗菌剂的方法，比如物理改性、化学改性和复合改性等，TPU或PUP和壳聚糖共混得到的复合物，比如以甘油为增塑剂、聚氨酯预聚体为改性剂，在密炼机中改性水溶性壳聚糖，再比如有文献报道用表面光接枝改性壳聚糖，先合成叠氮对苯甲酸，在通过叠氮对苯甲酸向天然抗菌剂壳聚糖，亲水性改性剂聚乙二醇中引入叠氮基，合成了叠氮化壳聚糖和叠氮化聚乙二醇。然后将壳聚糖和聚乙二醇用光接枝的方法接枝到聚氨酯上，使聚氨酯表面具有抗菌特性和抗黏附性。
目前PM2.5防护口罩的标准为：PM2.5过滤效率≥95%，口罩吸气阻力≤230Pa，呼气阻力 ≤200Pa，但是没有杀菌能力，佩戴4小时后需要更换，造成了很大的浪费，尤其是在冬春流行病毒的高发期，口罩需要量大增。PM2.5口罩只能截留2.5um大小的颗粒物，无法截留100nm大小的病毒，在冠状病毒疫情的影响下，更是需要能截留颗粒大小为100nm的新基材口罩，为此，市场上急需要一种具有截留100nm左右病毒并且具有杀菌破坏病毒结构的功能性材料制成的N95防疫口罩。
本发明经过研究，设计了一款既能粘附捕捉又能杀死病毒的纳滤抗菌材料，该新材料可用于制备N99抗菌口罩，为医护人员提供了一种更安全的防护手段，有着非常重要的现实意义。
发明内容
本发明公开了一种纳滤抗菌材料、制备方法及其用途，本发明采用溶剂挥发法制备了直径在30-500nm的纳米纤维，根据病毒表面蛋白结构的疏水和亲水基团的比例设计了疏水和亲水壳核结构的材料，研究结果表明亲水材料PVP和疏水材料聚氨酯以1:2-6形成了多层纳米网状空穴结构，可以捕捉粘附大多数病毒细菌，从而有效的限制了病毒对机体的侵入，亲水材料PVP经过呼吸润湿后可以激发过氧化氢分解出活性氧，银离子也同时发挥了杀菌的协同效应，可以将捕获到的病毒细菌杀死在口罩表面，从而有效延长了口罩的佩戴时间，减少了浪费，真正起到了防疫防护的作用。亲水材料可以吸收呼吸的水分，过滤空气的同时保持适当的润适度，提高佩戴口罩的舒适性。
为解决上述技术问题，本发明的实施例提供一种纳滤抗菌材料，包含过氧化氢聚乙烯吡咯烷酮复合物和线性聚氨酯制成的壳核结构，其中，线性聚氨酯在壳层，过氧化氢和聚乙烯吡咯烷酮复合物在核层。
其中,所述过氧化氢聚乙烯吡咯烷酮复合物中进一步含有银离子。
其中，所述壳核结构的组成比例为：过氧化氢∶聚乙烯吡咯烷酮∶线性聚氨酯的重量百分比范围选择为1-10∶100-1000∶100-1000。
本发明中，所述的线性聚氨酯选自可溶解在有机溶剂中的聚氨酯，其中软段选自聚己内酯（PCL）、聚丙二醇（PPG）以及PEG中的一种或两种以上的聚合物，硬段选自二异氰酸酯，具体选自1，6-六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、二苯甲烷二异氰酸酯（MDI）、甲苯二异氰酸酯（TDI）中的一种或两种，扩链剂选自二醇、二胺或者拥有二醇或二胺的材料，比如低分子量的壳聚糖；其中聚乙烯吡咯烷酮选自PVPK10、20、30、40、50、60、70、80、90，优选 PVPk60、PVPk90中的一种或两种组合。
所述线性聚氨酯扩链剂优选壳聚糖及其衍生物，其中壳聚糖粘均分子量范围为：1000-5万，壳聚糖或其衍生物成分分子链片段在聚氨酯大分子中的含量为0.05-30%，壳聚糖或其衍生物中脱乙酰度大于50%，壳聚糖衍生物优选羧甲基壳聚糖或羟乙基壳聚糖中的一种。
本发明所述的有机溶剂，选自甲苯、对二甲苯、癸烷、乙酸异戊酯、己烷、苯、二氯甲烷、三氯甲烷、环己酮、甲酮、二甲基甲酰胺、庚烷、二甲氨基甲酰胺、四氢呋喃、石油醚、二甲亚砜、对苯二甲酸乙二醇酯中的一种或两种，优选四氢呋喃、癸烷、乙酸异戊酯、己烷、二氯甲烷、三氯甲烷、环己酮、二甲基甲酰胺以及庚烷中的一种或两种。
本发明还提供一种纳滤材料的制备方法，包括如下步骤：
a-1、将过氧化氢与聚乙烯基吡咯烷酮按重量百分比：1-10∶100-1000混合均匀制成复合溶液备用；
b-1、将线性聚氨酯溶解在有机溶剂中，配成5-15%溶液备用；
c-1、采用同轴喷头，核层为（A-1）溶液，壳层为（B-1）溶液，采用静电纺丝技术制成纳米纤维。
本发明还提供一种纳滤材料的制备方法，包括如下步骤：
a-2、将过氧化氢与聚乙烯基吡咯烷酮按重量百分比为1-10∶100-1000混合均匀制成复合溶液，按所需比例填加银离子，搅拌均匀备用；
b-2、将线性聚氨酯溶解在有机溶剂中，配成5-15%溶液备用；
c-2、采用同轴喷头，核层为（A-2）溶液，壳层为（B-2）溶液，采用静电纺丝设备制成纳米纤维具有杀菌功能的纳滤材料。
本发明还提供一种纳滤材料的用途，可用于制备防护用品，其中，所述防护口罩的制备方法如下：
a-3、含有熔喷材料的内层复合材料：将聚氨酯、聚丙烯、聚苯乙烯、聚硫醚或丙烯酸树脂聚合物材料中的一种，采用熔喷静电纺丝技术制备成多孔纳米微米纤维基材或者直接采购市售的熔喷静电纺丝材料与亲肤材料制成内层复合材料；
b-3、纳滤抗菌材料：将步骤（c-1）或（c-2）中制备的材料与（a-3）中熔喷材料复合成多层纤维，作为防护口罩的；也可将步骤（c-1）或（c-2）中：采用同轴喷头，将核层为（A-3）溶液，壳层为（B-3）溶液，通过静电纺丝技术直接喷涂在（A-3）中熔喷材料上作为防护口罩的中间抗菌层；
c-3、将与N95口罩类似的外层无纺布、纳滤抗菌材料和内层熔喷复合材料通过超声热压复合制成防护口罩的形状,装上呼吸阀即可。
其中，所述防护口罩为由外层无纺布、中间层纳滤抗菌材料和内层熔喷复合材料通过超声热压复合而成的三层结构，所述纳滤抗菌材料的厚度在50μm-1000μm之间、熔喷复合材料的厚度在0.5mm-1.5mm之间；所述纳滤抗菌材料由壳核结构的纳米纤维制成；所述纳米纤维直径为100-900nm，纳米纤维孔径为10-500nm，湿度响应性智能抑菌效率≥90％，过滤效率≥99%。
本发明的上述技术方案的有益效果如下：本发明研制的壳核结构的抗菌性材料，以期优异的透气性能、过滤效率和抑菌效果，有望为广大医护人员提供一款理想的防疫产品。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合具体实施例进行详细描述。
本发明的实施例提供一种纳滤抗菌材料，包含过氧化氢聚乙烯吡咯烷酮复合物和线性聚氨酯制成的壳核结构，其中，线性聚氨酯在壳层，过氧化氢和聚乙烯吡咯烷酮复合物在核层。
其中,所述过氧化氢聚乙烯吡咯烷酮复合物中进一步含有银离子。
其中，所述壳核结构的组成比例为：过氧化氢∶聚乙烯吡咯烷酮∶线性聚氨酯的重量百分比范围选择为1-10∶100-1000∶100-1000。
本发明中，所述的线性聚氨酯选自可溶解在有机溶剂中的聚氨酯，其中软段选自聚己内酯（PCL）、聚丙二醇（PPG）以及PEG中的一种或两种以上的聚合物，硬段选自二异氰酸酯，具体选自1，6-六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、二苯甲烷二异氰酸酯（MDI）、甲苯二异氰酸酯（TDI）中的一种或两种，扩链剂选自二醇、二胺或者拥有二醇或二胺的材料，比如低分子量的壳聚糖；其中聚乙烯吡咯烷酮选自PVPK10、20、30、40、50、60、70、80、90，优选 PVPk60、PVPk90中的一种或两种组合。
所述线性聚氨酯扩链剂优选壳聚糖及其衍生物，其中壳聚糖粘均分子量范围为：1000-5万，壳聚糖或其衍生物成分分子链片段在聚氨酯大分子中的含量为0.05-30%，壳聚糖或其衍生物中脱乙酰度大于50%，壳聚糖衍生物优选羧甲基壳聚糖或羟乙基壳聚糖中的一种。
本发明所述的有机溶剂，选自甲苯、对二甲苯、癸烷、乙酸异戊酯、己烷、苯、二氯甲烷、三氯甲烷、环己酮、甲酮、二甲基甲酰胺、庚烷、二甲氨基甲酰胺、四氢呋喃、石油醚、二甲亚砜、对苯二甲酸乙二醇酯中的一种或两种，优选四氢呋喃、癸烷、乙酸异戊酯、己烷、二氯甲烷、三氯甲烷、环己酮、二甲基甲酰胺以及庚烷中的一种或两种。
本发明还提供一种纳滤材料的制备方法，包括如下步骤：
a-1、将过氧化氢与聚乙烯基吡咯烷酮按重量百分比：1-10∶100-1000混合均匀制成复合溶液备用；
b-1、将线性聚氨酯溶解在有机溶剂中，配成5-15%溶液备用；
c-1、采用同轴喷头，核层为（A-1）溶液，壳层为（B-1）溶液，采用静电纺丝技术制成纳米纤维。
本发明还提供一种纳滤材料的制备方法，包括如下步骤：
a-2、将过氧化氢与聚乙烯基吡咯烷酮按重量百分比为1-10∶100-1000混合均匀制成复合溶液，按所需比例填加银离子，搅拌均匀备用；
b-2、将线性聚氨酯溶解在有机溶剂中，配成5-15%溶液备用；
c-2、采用同轴喷头，核层为（A-2）溶液，壳层为（B-2）溶液，采用静电纺丝设备制成纳米纤维具有杀菌功能的纳滤材料。
本发明还提供一种纳滤材料的用途，可用于制备防护用品，其中，所述防护口罩的制备方法如下：
a-3、含有熔喷材料的内层复合材料：将聚氨酯、聚丙烯、聚苯乙烯、聚硫醚或丙烯酸树脂聚合物材料中的一种，采用熔喷静电纺丝技术制备成多孔纳米微米纤维基材或者直接采购市售的熔喷静电纺丝材料与亲肤材料制成内层复合材料；
b-3、纳滤抗菌材料：将步骤（c-1）或（c-2）中制备的材料与（a-3）中熔喷材料复合成多层纤维，作为防护口罩的；也可将步骤（c-1）或（c-2）中：采用同轴喷头，将核层为（A-3）溶液，壳层为（B-3）溶液，通过静电纺丝技术直接喷涂在（A-3）中熔喷材料上作为防护口罩的中间抗菌层；
c-3、将与N95口罩类似的外层无纺布、纳滤抗菌材料和内层熔喷复合材料通过超声热压复合制成防护口罩的形状,装上呼吸阀即可。
其中，所述防护口罩为由外层无纺布、中间层纳滤抗菌材料和内层熔喷复合材料通过超声热压复合而成的三层结构，所述纳滤抗菌材料的厚度在50μm-1000μm之间、熔喷复合材料的厚度在0.5mm-1.5mm之间；所述纳滤抗菌材料由壳核结构的纳米纤维制成；所述纳米纤维直径为100-900nm，纳米纤维孔径为10-500nm，湿度响应性智能抑菌效率≥90％，过滤效率≥99%。
下面结合具体实施例进一步阐述本发明的技术方案。
实施例一：制备本发明具有壳核结构的多孔纳米纤维
原料1：将PVPK90配置成2.5%溶液备用；
原料2：取5%浓度的H2O2备用；
原料3：线性聚氨酯（软缎为PCL，硬段为IPDI，扩链剂为1、4丁二醇，重均分子量范围为15-25万）用三氯甲烷溶解，配制成5%溶液备用；
原料4：Ag离子，浓度为3000ppm；
制备方法：
按配方比例，将原料1、2和4混合，25度搅拌4h以上备用，用常规静电纺丝设备，采用同轴喷头，其中内芯接1、2或4混合溶液，外层接3号原料，在电压20-30kv，纺丝距离在30cm，纺丝的流速为0.1ml/分钟，温度在25℃，接收器为滚筒，纺丝一段时间既得。
实施例二、调整聚氨酯和PVP比例制备具有壳核结构的多孔纳米纤维
制备方法：
按配方比例，将原料1、2和4混合，25度搅拌4h以上备用，用常规静电纺丝设备，采用同轴喷头，其中内芯接1、2或4混合溶液，外层接3号原料，在电压20-30kv，纺丝距离在30cm，纺丝的流速为0.2ml/分钟，温度在25℃，接收器为滚筒，纺丝时间为60分钟得到一张膜。
实施例三：采用扩链剂为壳聚糖的抗菌聚氨酯材料制备具有壳核结构的多孔纳米纤维
原料1：将PVPK90配置成2.5%溶液备用；
原料2：取5%浓度的H2O2备用；
原料3：线性聚氨酯（软缎为PCL，硬段为IPDI，扩链剂为羧甲基壳聚糖，重均分子量范围为15-25万）用三氯甲烷溶解，配制成5%溶液备用；
原料4：Ag离子，浓度为3000ppm；
实施例四：实施例一至三的配方制备的纳米纤维抑菌试验研究
1、试验方法：将纺丝所得材料剪成直径5mm的样品备用，用无菌绵蘸取浓度为5×105CFU/ml-5×106CFU/ml大肠杆菌试验用菌悬液，在琼脂培养基平板表面均匀涂抹3次，每个平皿中放置一片样片，贴服完整，放置于37℃恒温培养箱中培养18h，计数菌落数，同时用游标卡尺测量从样片边缘到有细菌密集生长边缘的距离，用mm表示抑菌环直径。
2、结果如下：
备注：抑菌环直径大于7mm，可认为有抑菌效果。
结论：
1、各配方制备的材料均表现出了一定的抑菌效果，其中配方二、四和六均表现出了优良的抑菌效果，随着聚氨酯比例的增加，双氧水和银离子溶出量减少，抑菌效果下降。
2、银离子浓度的填加，明显提高了材料的抑菌效果，显示了与双氧水的协同抑菌效应。
3、实施例三中，采用抗菌聚氨酯制备的壳核结构的纳米纤维复合材料，6组实验均无菌落生长，显示了非常显著的抑菌效果。
根据病毒疏水蛋白和亲水蛋白的比例，为使材料具有更广谱的抑菌效果，本发明过氧化氢∶聚乙烯吡咯烷酮∶线性聚氨酯的重量百分比范围选择为1-10∶100-1000∶100-1000。
实施例五、制备三层防护口罩
选用市售无纺布、本发明纳滤抗菌材料和熔喷复合材料（市售内层熔喷材料和亲肤内层无纺布材料复合而成），通过超声热压（温度为140-150度）复合成三层结构，其中所述纳滤抗菌材料的纳米纤维直径为100-900nm，纳米纤维孔径为10-150nm，由多层多空纳米纤维制成，厚度在50μm-80μm之间、熔喷复合材料的厚度在1.3mm左右。
采用实施例一和三中的材料制备一批口罩，采用滤料测试机测定过滤效率和吸气阻力，结果如下：
实施例一的材料制备的口罩：
实施例三的材料制备的口罩：
以上结果显示，随着聚氨酯在体系中比例的增加，呼吸阻力呈现规律性的降低，过滤效率均高于N95口罩的标准要求。
综上，本发明研制的壳核结构的抗菌性材料，以期优异的透气性能、过滤效率和抑菌效果，有望为广大医护人员提供一款理想的防疫产品。
Claims (9)
1.一种纳滤抗菌材料，其特征在于,包含过氧化氢聚乙烯吡咯烷酮复合物和线性聚氨酯制成的壳核结构，其中，线性聚氨酯在壳层，过氧化氢和聚乙烯吡咯烷酮复合物在核层。
2.根据权利要求1所述的纳滤抗菌材料，其特征在于,所述过氧化氢聚乙烯吡咯烷酮复合物中进一步含有银离子。
3.根据权利要求1所述的纳滤材料，其特征在于，所述壳核结构的组成比例为：过氧化氢∶聚乙烯吡咯烷酮∶线性聚氨酯的重量百分比范围选择为1-10∶100-1000∶100-1000。
4.根据权利要求1-3中任一项所述的纳滤抗菌材料，其特征在于，所述线性聚氨酯选自可溶解在有机溶剂中的聚氨酯，其中软段选自聚己内酯PCL、聚丙二醇PPG以及PEG中的一种或两种以上的聚合物，硬段选自二异氰酸酯，具体选自1，6-六亚甲基二异氰酸酯HDI、异氟尔酮二异氰酸酯IPDI、二苯甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI中的一种或两种；其中聚乙烯吡咯烷酮选自PVPK10、20、30、40、50、60、70、80、90，优选 PVPk60、PVPk90中的一种或两种组合。
5.根据权利要求1-3中任一项所述的纳滤抗菌材料，其特征在于，所述线性聚氨酯优选具有抗菌活性的聚氨酯材料，其中软段选自聚己内酯PCL、聚丙二醇PPG以及PEG中的一种或两种以上的聚合物，硬段选自二异氰酸酯，具体选自1，6-六亚甲基二异氰酸酯HDI、异氟尔酮二异氰酸酯IPDI、二苯甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI中的一种或两种，扩链剂选自壳聚糖及其衍生物，其中壳聚糖粘均分子量范围为：1000-5万，壳聚糖或其衍生物成分分子链片段在聚氨酯大分子中的含量为0.05-30%，壳聚糖或其衍生物中脱乙酰度大于50%。
6.一种权利要求1-5中任一项所述的纳滤材料的制备方法，其特征在于，包括如下步骤：
a-1、将过氧化氢与聚乙烯基吡咯烷酮按重量百分比：1-10∶100-1000混合均匀制成复合溶液备用；
b-1、将线性聚氨酯溶解在有机溶剂中，配成5-15%溶液备用；
c-1、采用同轴喷头，核层为（A-1）溶液，壳层为（B-1）溶液，采用静电纺丝技术制成纳米纤维。
7.一种权利要求1-5中任一项所述的纳滤材料的制备方法，其特征在于，包括如下步骤：
a-2、将过氧化氢与聚乙烯基吡咯烷酮按重量百分比为1-10∶100-1000混合均匀制成复合溶液，按所需比例填加银离子，搅拌均匀备用；
b-2、将线性聚氨酯溶解在有机溶剂中，配成5-15%溶液备用；
c-2、采用同轴喷头，核层为（A-2）溶液，壳层为（B-2）溶液，采用静电纺丝设备制成纳米纤维具有杀菌功能的纳滤材料。
8.一种权利要求1-5中任一项所述的纳滤材料及按照权利要求6或7所述的制备方法制备的纳滤材料的用途，其特征在于，可用于制备防护用品，其中，所述防护口罩的制备方法如下：
a-3、含有熔喷材料的内层复合材料：将聚氨酯、聚丙烯、聚苯乙烯、聚硫醚或丙烯酸树脂聚合物材料中的一种，采用熔喷静电纺丝技术制备成多孔纳米微米纤维基材或者直接采购市售的熔喷静电纺丝材料与亲肤材料制成内层复合材料；
b-3、纳滤抗菌材料：将步骤（c-1）或（c-2）中制备的材料与（a-3）中熔喷材料复合成多层纤维，作为防护口罩的；也可将步骤（c-1）或（c-2）中：采用同轴喷头，将核层为（A-3）溶液，壳层为（B-3）溶液，通过静电纺丝技术直接喷涂在（A-3）中熔喷材料上作为防护口罩的中间抗菌层；
c-3、将与N95口罩类似的外层无纺布、纳滤抗菌材料和内层熔喷复合材料通过超声热压复合制成防护口罩的形状,装上呼吸阀即可。
9.根据权利要求8所述的纳滤材料的用途，其特征在于，所述防护口罩为由外层无纺布、中间层纳滤抗菌材料和内层熔喷复合材料通过超声热压复合而成的三层结构，所述纳滤抗菌材料的厚度在50μm-1000μm之间、熔喷复合材料的厚度在0.5mm-1.5mm之间；所述纳滤抗菌材料由壳核结构的纳米纤维制成；所述纳米纤维直径为100-900nm，纳米纤维孔径为10-500nm，湿度响应性智能抑菌效率≥90％，过滤效率≥99%。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625341A (zh) * | 2020-12-07 | 2021-04-09 | 上海大学 | 一种可降解回收的熔喷料及其制备方法 |
| CN115961383A (zh) * | 2022-12-16 | 2023-04-14 | 烟台泰和新材料股份有限公司 | 一种抗菌聚氨酯纤维材料及其制备方法 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991007184A1 (en) * | 1989-11-08 | 1991-05-30 | Gaf Chemicals Corporation | SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP and H2O¿2? |
| CN103074734A (zh) * | 2013-01-31 | 2013-05-01 | 东华大学 | 静电纺丝法制备抗菌性纳米银复合纳米纤维毡的制备方法 |
| CN104083946A (zh) * | 2014-06-27 | 2014-10-08 | 上海洁晟环保科技有限公司 | 抗菌口罩滤片及其制备方法和抗菌口罩 |
| CN104872865A (zh) * | 2015-06-04 | 2015-09-02 | 盐城工业职业技术学院 | 一种可生物降解环保防尘口罩纳米滤芯的生产方法 |
| WO2018090925A1 (zh) * | 2016-11-16 | 2018-05-24 | 华南理工大学 | 一种皮肤烧伤修复材料及其制备方法 |
| CN108993167A (zh) * | 2018-08-13 | 2018-12-14 | 北京化工大学常州先进材料研究院 | 一种抗菌的静电纺丝纳米纤维空气过滤材料的制备及应用 |
| CN109503797A (zh) * | 2018-10-28 | 2019-03-22 | 凯斯蒂南京医疗器械有限公司 | 一种具有抗菌活性的医用可降解聚氨酯及其用途 |
-
2020
- 2020-02-03 CN CN202010078431.5A patent/CN111235691A/zh not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991007184A1 (en) * | 1989-11-08 | 1991-05-30 | Gaf Chemicals Corporation | SUBSTANTIALLY ANHYDROUS COMPLEXES OF PVP and H2O¿2? |
| CN103074734A (zh) * | 2013-01-31 | 2013-05-01 | 东华大学 | 静电纺丝法制备抗菌性纳米银复合纳米纤维毡的制备方法 |
| CN104083946A (zh) * | 2014-06-27 | 2014-10-08 | 上海洁晟环保科技有限公司 | 抗菌口罩滤片及其制备方法和抗菌口罩 |
| CN104872865A (zh) * | 2015-06-04 | 2015-09-02 | 盐城工业职业技术学院 | 一种可生物降解环保防尘口罩纳米滤芯的生产方法 |
| WO2018090925A1 (zh) * | 2016-11-16 | 2018-05-24 | 华南理工大学 | 一种皮肤烧伤修复材料及其制备方法 |
| CN108993167A (zh) * | 2018-08-13 | 2018-12-14 | 北京化工大学常州先进材料研究院 | 一种抗菌的静电纺丝纳米纤维空气过滤材料的制备及应用 |
| CN109503797A (zh) * | 2018-10-28 | 2019-03-22 | 凯斯蒂南京医疗器械有限公司 | 一种具有抗菌活性的医用可降解聚氨酯及其用途 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625341A (zh) * | 2020-12-07 | 2021-04-09 | 上海大学 | 一种可降解回收的熔喷料及其制备方法 |
| CN115961383A (zh) * | 2022-12-16 | 2023-04-14 | 烟台泰和新材料股份有限公司 | 一种抗菌聚氨酯纤维材料及其制备方法 |
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