CN116173313A - 一种具有自抑菌抗菌功能的医用手术膜材料制备方法 - Google Patents

一种具有自抑菌抗菌功能的医用手术膜材料制备方法 Download PDF

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Publication number
CN116173313A
CN116173313A CN202210825506.0A CN202210825506A CN116173313A CN 116173313 A CN116173313 A CN 116173313A CN 202210825506 A CN202210825506 A CN 202210825506A CN 116173313 A CN116173313 A CN 116173313A
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Prior art keywords
antibacterial
parts
fiber
alcohol
plant
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CN202210825506.0A
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Inventor
李维虎
闫成成
戴家兵
赵曦
朱宝凌
刘辉
郭文鹤
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Priority to CN202210825506.0A priority Critical patent/CN116173313A/zh
Publication of CN116173313A publication Critical patent/CN116173313A/zh
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Abstract

本发明公开了一种具有自抑菌抗菌功能的医用手术膜材料制备方法，涉及医用功能材料技术领域，本发明针对当前手术膜存在的问题，首先合成醇溶性阳离子聚氨酯，在合成过程中及成膜过程中引入有机及无机复合抗菌材料，并结合核‑壳静电纺丝技术及三维立体打印技术制备得到了具有物理曲孔结构的高透汽防水超细纤维医用手术膜；该手术膜材料不仅具有高效的水汽输运通道，同时通过钴60辐照灭菌后仍具有良好的柔韧性和优异的皮肤触感，与皮肤贴合性好，且力学性能强；此外，通过复合抗菌材料的引入赋予其自抑菌抗菌功能，对金黄色葡萄球菌及大肠杆菌具有优异的抗菌效果。

Description

一种具有自抑菌抗菌功能的医用手术膜材料制备方法
技术领域：
本发明涉及医用功能材料技术领域，具体涉及一种具有自抑菌抗菌功能的医用手术膜材料制备方法。
背景技术：
随着我国人口老龄化的不断加剧以及医护人员的严重短缺，我国医院对于一次性医用手术耗材的需求量急速上升。手术膜作为其中一种医疗耗材，因具有使用方便、可减少患者因手术操作或外部环境因素影响受感染的风险而得到广泛应用。但是，目前市场上的一次性使用医用手术膜主要由聚烯烃PE膜材料组成，普遍存在透气舒适性差的问题(这也是市场上PE手术膜经常有产品被召回的主要因素之一)，同时膜产品仅有物理屏障保护作用，不具有自抑菌抗菌的功能，导致医用手术膜在实际使用时，仍存在一定程度的感染风险。
发明内容：
针对目前医用手术膜在实际医疗应用过程中存在的问题，本发明提出在合成高分子量的醇溶性阳离子聚氨酯的基础上，引入有机及无机抗菌成分并结合核-壳静电纺丝技术和3D打印技术，制备一种具有高透汽舒适度、贴肤性好且具有自抑菌抗菌功能的医用手术膜；该手术膜材料中的纤维直径及抗菌成分的分散比例可通过工艺参数来进行调控，使其透汽的同时仍具有防水、自抑菌抗菌功能。本发明制备的医用手术膜材料有望在医用手术包、儿童留置针、创可贴、婴儿肚脐贴、导管固定及多种医用手术粘贴等领域得到应用。
本发明所要解决的技术问题在于提供一种具有自抑菌抗菌功能的医用手术膜材料制备方法，包括以下步骤：
(1)醇溶性阳离子聚氨酯的合成；
(2)植物抗菌提取液的制备及添加无机纳米抗菌剂制备复合抗菌剂；
(3)以醇溶性阳离子聚氨酯乳液作为壳层，复合抗菌剂溶液作为核层，利用核-壳静电纺丝技术和3D立体打印技术制备手术膜材料；
(4)烘干成膜，真空包装，灭菌。
步骤(1)中所述醇溶性阳离子聚氨酯采用以下重量份的原料合成得到：
聚醚多元醇30～80份，有机硅聚醚多元醇10～50份，多异氰酸酯30～100份，有机硅小分子单体1～15份，小分子扩链剂5～30份，阳离子亲水扩链剂5～25份、三丹油抗菌剂0.5～15份，交联剂0.1～10份，催化剂0.1～10份，乳化剂0.1～8份，消泡剂1～10份，中和剂5～30份，乙醇5～50份，去离子水100～500份。本发明采用环保型的醇溶性方法合成醇溶性阳离子聚氨酯，主要考虑乙醇为环保型溶剂且挥发速度快，不易残留在材料中，对人体无任何危害。同时合成的聚氨酯分子量较高。
优选地，所述醇溶性阳离子聚氨酯采用以下重量份的原料合成得到：
聚醚多元醇40～80份，有机硅聚醚多元醇20～50份，多异氰酸酯40～100份，有机硅小分子单体3～12份，小分子扩链剂5～25份，阳离子亲水扩链剂5～20份、三丹油抗菌剂1.5～10份，交联剂0.5～8份，催化剂0.5～8份，乳化剂0.5～8份，消泡剂1～8份，中和剂5～20份，乙醇5～50份，去离子水150-500份。
优选地，所述聚醚多元醇选自聚氧化乙烯二醇、聚四氢呋喃二醇、聚醚三醇、聚醚四醇、四氢呋喃-氧化乙烯共聚二醇、Mannich聚醚二醇中的一种或多种。
优选地，所述有机硅聚醚多元醇为我司自制的含有硅氧键或有机硅改性的聚醚多元醇，分子量为1000-5000，具体选自型号SC-101、SC-103、SC-105中的一种或多种。主要作用是提高手术膜材料的亲肤感、耐水性及柔韧性。
优选地，所述多异氰酸酯选自四甲基苯二甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、1,6-己二异氰酸酯、4,4'-二异氰酸酯二环己基甲烷、甲基环己基二异氰酸酯和降冰片烷二异氰酸酯中的一种或多种。
优选地，所述有机硅小分子单体为端羟基或端氨基的有机硅氧烷扩链剂，具体选自KH550、KH560、KH570、KH602、KH610、端羟基聚二甲基硅氧烷(PDMS-OH)中的一种或多种。
优选地，所述小分子扩链剂选自1,4丁二醇、乙二醇、一缩二乙二醇和新戊二醇、1,4-环己烷二甲醇(CHDM)中的一种或多种。
优选地，所述阳离子亲水扩链剂旨在所合成聚氨酯链段上引入叔胺化基团，具体选自二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺、叔丁基二乙醇胺、二甲基乙醇胺、双(2-羟丙基)苯胺中的一种或多种。
优选地，所述三丹油抗菌剂为具有广谱抗菌作用、高效低毒的三嗪类抗菌剂，其分子结构上的羟基可以和NCO基团反应，将抗菌剂引入到聚氨酯分子链上，进而实现抗菌剂在膜上的均匀分布。
优选地，所述交联剂选自三羟甲基丙烷、1,2,6-己三醇、甲基葡萄糖苷和蔗糖中的一种或多种。
优选地，所述催化剂选自二月桂酸二丁基锡、羧酸锌、羧酸铋和钛酸四丁酯中的一种或多种。
优选地，所述乳化剂选自OP-10、十二烷基苯磺酸钠中的一种或多种。
优选地，所述消泡剂为聚硅氧烷共聚物类消泡剂。
优选地，所述中和剂选自冰醋酸、乙醇酸、乙酸酐、柠檬酸中的一种或多种。
优选地，所述乙醇为工业级浓度≥95％的乙醇溶液。
本发明在聚氨酯中引入三丹油抗菌剂的基础上，通过额外引入天然植物提取液及无机抗菌纳米颗粒来进一步提高膜材料的自抑菌抗菌效果。
步骤(2)中所述植物抗菌提取液的制备步骤为：将植物纤维经晾晒、烘干得到干燥的植物纤维；对干燥的植物纤维进行粉碎，将所得植物纤维粗料粉体与纤维活化溶剂体系混合处理得到活化后的纤维素；将活化后的纤维素过滤后烘干得到活化纤维素粉；将活化纤维素粉加入纤维溶解溶剂体系进行热溶解，过滤，得到植物抗菌提取液。
优选地，所述植物纤维为具有天然抗菌抑菌作用的植物纤维，包括竹、苎麻、蒲葵等棕榈类天然抗菌植物。
优选地，所述植物纤维粗料粉体按照固液比(0.5～2):(5～35)与纤维活化溶剂体系混合。
优选地，所述纤维活化溶剂体系选自氮甲基氧化吗啉、N,N-二甲基乙酰胺、高锰酸钾、氯化锂/氯化锌、乙二胺、多聚甲醛、二甲基亚砜、氢氧化钠、尿素、离子液体中的至少两种，且采用常温或者加热的方式对纤维粉体进行活化处理。进一步优选地，所述离子液体为咪唑类离子液体、吡啶类离子液体、季铵盐类离子液体、季铵盐类离子液体的一种或多种组合。
优选地，所述纤维溶解溶剂体系选自乙酸酐/浓硫酸体系、顺丁烯二酐/浓硫酸体系、乙酸酐/对甲苯磺酸体系、邻苯二甲酸酐/磷酸体系中的一种或多种。该纤维溶解溶剂体系是在酸催化的条件下采用乙酰化试剂对纤维素进行改性，对纤维素进行酯化反应以提高其反应活性并进一步降低其在水体系混合溶剂中的溶解难度。
优选地，所述活化纤维素粉按照固液比(1-10):(10-100)加入纤维溶解溶剂体系。
步骤(2)中所述复合抗菌剂是由前述制备的植物抗菌提取液添加0.3-1.5wt％的无机纳米抗菌剂和0.1-1wt％的悬浮剂制成。
本发明在得到的植物抗菌提取液的基础上加入无机纳米抗菌剂，并添加适量悬浮剂以增大纳米颗粒的阻尼系数，防止无机纳米颗粒发生沉降及团聚，使其进一步与植物抗菌液混合均匀。
优选地，所述无机纳米抗菌剂为具有抗菌抗病毒作用的无机颗粒且粒径在5-50nm范围内，具体选自纳米氧化亚铜、纳米氧化锌，纳米二氧化铈、纳米二氧化钛中的一种或多种。
优选地，所述悬浮剂具体选自羧甲基纤维素钠、聚丙烯酰胺(分子量在10万-100万)、非离子型聚氧乙烯脂肪胺(醇)、聚氧乙烯脂肪醇硫酸盐、聚乙烯醇1788、明胶、蛋清液中的一种或多种。
步骤(3)是将上述制备的高分子量醇溶性阳离子聚氨酯乳液作为壳层3D纺丝原液固定到3D打印纺丝机上，将上述制备的复合抗菌剂作为核层3D纺丝原液同样固定到3D打印纺丝机上。壳层3D纺丝原液的浓度为15～35％，核层3D纺丝原液的浓度为10～35％。然后采用电压范围在5～20KV的直流电压进行3D垂直向下纺丝，打印机上下、左右、前后移动距离均为10±0.5cm，且移动过程中为平行移动，注射速度控制在0.5-5mL/h，针头内径为0.01～0.05mm，外径为0.05～0.1mm，接受距离控制在8～20cm，三层铺展的纤维层单层厚度控制在0.02～0.03mm，层间厚度为50-100μm。且基材采用PTFE、离型纸或者芳纶基布，基板采用矿氧紫铜材质并接地。纺丝完成后将纤维层和基材从基板上揭下。
步骤(4)中所述烘干是在真空条件下进行梯度加热。烘干的目的是去除残余溶剂，获得核-壳纤维曲孔结构手术膜。在45-90℃的温度范围内进行梯度加热，升温速率为1-3℃/min，使得纤维层间受热均匀，不易产生空气层等问题，且快速烘干，形成水汽输运通道，达到较好的防水透湿透气效果。
步骤(4)中所述灭菌为钴60辐照灭菌，采用10-15GKy剂量的钴60辐照3-5h。测试发现，本发明制备的手术膜辐照后没有发生结构或性能上的变化，避免了传统环氧乙烷灭菌导致手术膜残留环氧乙烷的问题，且同时避免的聚烯烃材料辐照后发脆的问题，提高了灭菌生产效率。
本发明的有益效果是：针对当前手术膜存在的问题，本发明以市场应用为导向，首先合成醇溶性阳离子聚氨酯，在合成过程中及成膜过程中引入有机及无机复合抗菌材料，并结合核-壳静电纺丝技术及三维立体打印技术制备得到了具有物理曲孔结构的高透汽防水超细纤维医用手术膜；该手术膜材料不仅具有高效的水汽输运通道，经测试透湿量高达6000～10000g/m2·24h，同时通过钴60辐照灭菌后仍具有良好的柔韧性和优异的皮肤触感，与皮肤贴合性好，且拉伸强度为15～25MPa，永久变形≤1.5％，伸长率300～600％；此外，通过复合抗菌材料的引入赋予其自抑菌抗菌功能，对金黄色葡萄球菌及大肠杆菌具有优异的抗菌效果，其潜在的广谱抗菌抗病毒效果也具有巨大的应用价值及市场前景。
具体实施方式：
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
实施例1
(1)高分子量醇溶性阳离子水性聚氨酯的合成：将Mannich聚醚二醇、有机硅聚醚多元醇真空脱水后备用；称取Mannich聚醚二醇50g、有机硅聚醚多元醇SC-105 35g以及异佛尔酮二异氰酸酯45g在90℃下充分反应2.5h，然后测量NCO基团达到理论剩余值后，采用冷媒快速降温至50℃，加入端羟基PDMS3g，小分子扩链剂乙二醇6g，阳离子亲水扩链剂二乙醇胺5g，三丹油3g，1,2,6-己三醇0.5g，羧酸铋催化剂0.5g，并通入氮气保护，保温反应3h，测试剩余NCO值不在变化后，采用循环水缓慢降温至30℃，加入中和剂冰醋酸5.2g及稀释封端乙醇30g，去离子水350g，然后加入OP-10 0.2g在高速剪切作用下乳化，乳化期间加入聚硅氧烷共聚物类消泡剂1g，搅拌10min完成乳化，最后将合成的醇溶性聚氨酯在55℃下熟化14h，即可获得分子量在12000-15000的醇溶性阳离子聚氨酯乳液。
(2)植物抗菌提取液的制备及与无机抗菌材料的混合：将蒲葵纤维在25～35℃外界环境温度下晾晒2周，将其水分含量降低至≤30％，然后将其置于高温烘箱中100℃烘干15h，控制其含水率在<5％，得到干燥的蒲葵纤维；采用转速为18000r/min的四刀头高速粉碎机对干燥的植物纤维进行粉碎细化，并用100目的滤网过滤后得到粗料粉体，然后将植物纤维粗料粉体按照固液比0.5:15与纤维活化溶剂体系(氮甲基氧化吗啉：四乙基氯化铵离子液体＝2:1)混合，然后将混合液在95℃热处理5h，降至室温并经超声处理1h，制得活化后的纤维素；将活化后的纤维素用100目滤网过滤，然后在135℃烘箱中烘干去除溶剂，得到活化纤维素粉；将活化纤维素粉按照固液比5:100加入纤维素溶解体系溶剂(邻苯二甲酸酐/磷酸＝3:1)，在85℃下热溶解5h，在经过超声处理2h得到纤维素抗菌溶液，经滤网过滤后得到浓度25％的植物抗菌提取液。
(3)在上述植物抗菌提取液的基础上，加入0.05％的氧化亚铜纳米抗菌颗粒(粒径50±5nm)，并添加3g分子量在～50W的50％阳离子聚丙烯酰胺水溶液以增大纳米颗粒的阻尼系数，通过AK高速剪切分散20min后得到浓度15％的复合抗菌剂溶液。
(4)将上述醇溶性阳离子聚氨酯乳液和复合抗菌剂溶液作为3D纺丝原液分别灌注到2个50mL注射容器中，并将其固定到3D打印纺丝装置上，接收基板首先采用矿氧紫铜板作为底部基材并接地，然后在基板上固定一层离型纸，电压选择10KV，接受距离12cm，注射速度0.3ml/h，通过调节纺丝时间及移动距离控制微纳米纤维层的堆积厚度为0.015mm，喷三层后结束。
(5)3D打印完成后将纤维层连同基材同时从基板揭下进行真空干燥，并从室温25℃升温至90℃，采用梯度加热的方式进行热处理3.5h，第一阶段升温速率控制在1℃/min，升温时间为35min，第二阶段升温时间为10min，升温速率控制在2℃/min，升至温度后在90℃下保温热处理2.5h。该步骤可实现在去除残余溶剂的同时，促进纤维间的黏连、增强，进而构造形成曲孔结构及水汽输运通道，达到较好的透气防水效果。
(6)将符合纤维层裁剪成直径＞80mm的圆形，通过采用静水压测量仪及织物透湿透气测量仪测试获得，制备的手术膜耐水压高达150kPa，、透湿量为10000g·m-2·d-1，且采用拉力机测试去除基布后的手术膜的拉伸强度为20MPa，伸长率为350％。最后将制备得到的自抑菌手术膜真空包装后采用10GKy剂量的钴60辐照5h，即获得灭菌后的手术膜产品。
实施例2
(1)高分子量醇溶性阳离子水性聚氨酯的合成：将聚四氢呋喃二醇、有机硅聚醚多元醇真空脱水后备用；称取聚四氢呋喃二醇80g、有机硅聚醚多元醇SC-103 50g以及异佛尔酮二异氰酸酯50g、降冰片烷二异氰酸酯50g在90℃下充分反应2.5h，然后测量NCO基团达到理论剩余值后，采用冷媒快速降温至50℃，加入端羟基PDMS 12g，小分子扩链剂乙二醇20g，阳离子亲水扩链剂二乙醇胺10g，三丹油8g，1,2,6-己三醇2g，羧酸铋催化剂1g，并通入氮气保护，保温反应3h，测试剩余NCO值不在变化后，采用循环水缓慢降温至30℃，加入中和剂柠檬酸10g及稀释封端乙醇50g，去离子水500g，然后加入OP-10 1g在高速剪切作用下乳化，乳化期间加入聚硅氧烷共聚物类消泡剂2g，搅拌10min完成乳化，最后将合成的醇溶性聚氨酯在55℃下熟化24h，即可获得分子量在18000-20000的醇溶性阳离子聚氨酯乳液。
(2)植物抗菌提取液的制备及与无机抗菌材料的混合：将蒲葵纤维在25～35℃外界环境温度下晾晒2周，将其水分含量降低至≤30％，然后将其置于高温烘箱中110℃烘干15h，控制其含水率在<5％，得到干燥的蒲葵纤维；采用转速为18000r/min的四刀头高速粉碎机对干燥的植物纤维进行粉碎细化，并用100目的滤网过滤后得到粗料粉体，然后将植物纤维粗料粉体按照固液比0.5:15与纤维活化溶剂体系(氮甲基氧化吗啉：四乙基氯化铵离子液体＝2:1)混合，将混合液在95℃热处理5h，然后降至室温并经超声处理1h，制得活化后的纤维素；将活化后的纤维素用100目滤网过滤，然后在135℃烘箱中烘干去除溶剂，得到活化纤维素粉；将活化纤维素粉按照固液比5:100加入纤维素溶解体系溶剂(邻苯二甲酸酐/磷酸＝3:1)，在85℃下热溶解5h，在经过超声处理2h得到纤维素抗菌溶液，经滤网过滤后得到浓度25％的植物抗菌提取液。
(3)在上述植物抗菌提取液的基础上，加入0.05％的氧化亚铜纳米抗菌颗粒(粒径50±5nm)，并添加8g分子量在～50W的50％阳离子聚丙烯酰胺水溶液、3g蛋清液以增大纳米颗粒的阻尼系数，通过AK高速剪切分散20min后得到浓度20％的复合抗菌剂溶液。
(4)将上述醇溶性阳离子聚氨酯乳液和复合抗菌剂溶液作为3D纺丝原液分别灌注到2个50mL注射容器中，并将其固定到3D打印纺丝装置上，接收基板首先采用矿氧紫铜板作为底部基材并接地，然后在基板上固定一层离型纸，电压选择20KV，接受距离15cm，注射速度0.5ml/h，通过调节纺丝时间及移动距离控制微纳米纤维层的堆积厚度为0.015mm，喷三层后结束。
(5)3D打印完成后将纤维层连同基材同时从基板揭下进行真空干燥，并从室温25℃升温至90℃，采用梯度加热的方式进行热处理3.5h，第一阶段升温速率控制在1℃/min，升温时间为35min，第二阶段升温时间为10min，升温速率控制在2℃/min，升至温度后在90℃下保温热处理2.5h。该步骤可实现在去除残余溶剂的同时，促进纤维间的黏连、增强，进而构造形成曲孔结构及水汽输运通道，达到较好的透气防水效果。
(6)将符合纤维层裁剪成直径＞80mm的圆形，通过采用静水压测量仪及织物透湿透气测量仪测试获得，制备的手术膜耐水压高达180kPa，、透湿量为8500g·m-2·d-1，且采用拉力机测试去除基布后的手术膜的拉伸强度为25MPa，伸长率为600％。最后将制备得到的自抑菌手术膜真空包装后采用15GKy剂量的钴60辐照3h，即获得灭菌后的手术膜产品。
实施例3
(1)高分子量醇溶性阳离子水性聚氨酯的合成：将Mannich聚醚二醇、四氢呋喃-氧化乙烯共聚二醇、有机硅聚醚多元醇真空脱水后备用；称取Mannich聚醚二醇50g、四氢呋喃-氧化乙烯共聚二醇25g、有机硅聚醚多元醇SC-10135g以及异佛尔酮二异氰酸酯75g在90℃下充分反应2.5h，然后测量NCO基团达到理论剩余值后，采用冷媒快速降温至65℃，加入端氨基KH602偶联剂8g，小分子扩链剂乙二醇6g，阳离子亲水扩链剂N-甲基二乙醇胺8g，三丹油8g，1,2,6-己三醇1.5g，羧酸铋催化剂1.5g，并通入氮气保护，然后保温反应3h，测试剩余NCO值不在变化后，采用循环水缓慢降温至30℃，加入中和剂冰醋酸8g及稀释封端乙醇45g，去离子水480g，然后加入OP-10 0.8g在高速剪切作用下乳化，乳化期间加入聚硅氧烷共聚物类消泡剂1g，搅拌10min完成乳化，最后将合成的醇溶性聚氨酯在55℃下熟化24h，即可获得分子量在20000-21000的醇溶性阳离子聚氨酯乳液。
(2)植物抗菌提取液的制备及与无机抗菌材料的混合：将竹纤维在25～35℃外界环境温度下晾晒2周，将其水分含量降低至≤30％，然后将其置于高温烘箱中100℃烘干18h，控制其含水率在<5％，得到干燥的蒲葵纤维，采用转速为18000r/min的四刀头高速粉碎机对干燥的植物纤维进行粉碎细化，并用100目的滤网过滤后得到粗料粉体，然后将植物纤维粗料粉体按照固液比1.5:15与纤维活化溶剂体系(氮甲基氧化吗啉：四乙基氯化铵离子液体＝2:1)混合，然后将混合液在95℃热处理5h，然后降至室温并经超声处理1h，制得活化后的纤维素；将活化后的纤维素用100目滤网过滤，然后在135℃烘箱中烘干去除溶剂，得到活化纤维素粉；将活化纤维素粉按照固液比5:100加入纤维素溶解体系溶剂(邻苯二甲酸酐/磷酸＝3:1)，在85℃下热溶解5h，在经过超声处理2h得到纤维素抗菌溶液，经滤网过滤后得到浓度30％的植物抗菌提取液。
(3)在上述植物抗菌提取液的基础上，加入0.05％的氧化亚铜纳米抗菌颗粒(粒径50±5nm)，并添加3g分子量在～50W的50％阳离子聚丙烯酰胺水溶液以增大纳米颗粒的阻尼系数，通过AK高速剪切分散20min后得到浓度25％的复合抗菌剂溶液。
(4)将上述醇溶性阳离子聚氨酯乳液和复合抗菌剂溶液作为3D纺丝原液分别灌注到2个50mL注射容器中，并将其固定到3D打印纺丝装置上，接收基板首先采用矿氧紫铜板作为底部基材并接地，然后在基板上固定一层离型纸，电压选择25KV，接受距离18cm，注射速度0.5ml/h，通过调节纺丝时间及移动距离控制微纳米纤维层的堆积厚度为0.015mm，喷三层后结束。
(5)3D打印完成后将纤维层连同基材同时从基板揭下进行真空干燥，并从室温25℃升温至90℃，采用梯度加热的方式进行热处理3.5h，第一阶段升温速率控制在1℃/min，升温时间为35min，第二阶段升温时间为10min，升温速率控制在2℃/min，升至温度后在90℃下保温热处理2.5h。该步骤可实现在去除残余溶剂的同时，促进纤维间的黏连、增强，进而构造形成曲孔结构及水汽输运通道，达到较好的透气防水效果。
(6)将符合纤维层裁剪成直径＞80mm的圆形，通过采用静水压测量仪及织物透湿透气测量仪测试获得，制备的手术膜耐水压高达200kPa，、透湿量为9000g·m-2·d-1，且采用拉力机测试去除基布后的手术膜的拉伸强度为23MPa，伸长率为550％。最后将制备得到的自抑菌手术膜真空包装后采用15GKy剂量的钴60辐照5h，即获得灭菌后的手术膜产品。
表1抗菌测试结果
Figure BDA0003746353690000101
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (10)

1.一种具有自抑菌抗菌功能的医用手术膜材料制备方法，其特征在于，包括以下步骤：
(1)醇溶性阳离子聚氨酯的合成；
(2)植物抗菌提取液的制备及添加无机纳米抗菌剂制备复合抗菌剂；
(3)以醇溶性阳离子聚氨酯乳液作为壳层，复合抗菌剂溶液作为核层，利用核-壳静电纺丝技术和3D立体打印技术制备手术膜材料；
(4)烘干成膜，真空包装，灭菌。
2.根据权利要求1所述的制备方法，其特征在于：步骤(1)中所述醇溶性阳离子聚氨酯采用以下重量份的原料合成得到：
聚醚多元醇30～80份，有机硅聚醚多元醇10～50份，多异氰酸酯30～100份，有机硅小分子单体1～15份，小分子扩链剂5～30份，阳离子亲水扩链剂5～25份、三丹油抗菌剂0.5～15份，交联剂0.1～10份，催化剂0.1～10份，乳化剂0.1～8份，消泡剂1～10份，中和剂5～30份，乙醇5～50份，去离子水100～500份。
3.根据权利要求2所述的制备方法，其特征在于：所述聚醚多元醇选自聚氧化乙烯二醇、聚四氢呋喃二醇、聚醚三醇、聚醚四醇、四氢呋喃-氧化乙烯共聚二醇、Mannich聚醚二醇中的一种或多种；
所述有机硅聚醚多元醇为我司自制的含有硅氧键或有机硅改性的聚醚多元醇，分子量为1000-5000，选自型号SC-101、SC-103、SC-105中的一种或多种；
所述多异氰酸酯选自四甲基苯二甲基二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、1,6-己二异氰酸酯、4,4'-二异氰酸酯二环己基甲烷、甲基环己基二异氰酸酯和降冰片烷二异氰酸酯中的一种或多种；
所述有机硅小分子单体为端羟基或端氨基的有机硅氧烷扩链剂，具体选自KH550、KH560、KH570、KH602、KH610、端羟基聚二甲基硅氧烷中的一种或多种；
所述小分子扩链剂选自1,4丁二醇、乙二醇、一缩二乙二醇和新戊二醇、1,4-环己烷二甲醇中的一种或多种；
所述阳离子亲水扩链剂选自二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺、叔丁基二乙醇胺、二甲基乙醇胺、双(2-羟丙基)苯胺中的一种或多种；
所述交联剂选自三羟甲基丙烷、1,2,6-己三醇、甲基葡萄糖苷和蔗糖中的一种或多种；
所述催化剂选自二月桂酸二丁基锡、羧酸锌、羧酸铋和钛酸四丁酯中的一种或多种；
所述乳化剂选自OP-10、十二烷基苯磺酸钠中的一种或多种；
所述消泡剂为聚硅氧烷共聚物类消泡剂；
所述中和剂选自冰醋酸、乙醇酸、乙酸酐、柠檬酸中的一种或多种；
所述乙醇为工业级浓度≥95％的乙醇溶液。
4.根据权利要求1所述的制备方法，其特征在于：步骤(2)中所述植物抗菌提取液的制备步骤为：将植物纤维经晾晒、烘干得到干燥的植物纤维；对干燥的植物纤维进行粉碎，将所得植物纤维粗料粉体与纤维活化溶剂体系混合处理得到活化后的纤维素；将活化后的纤维素过滤后烘干得到活化纤维素粉；将活化纤维素粉加入纤维溶解溶剂体系进行热溶解，过滤，得到植物抗菌提取液。
5.根据权利要求4所述的制备方法，其特征在于：所述植物纤维为具有天然抗菌抑菌作用的植物纤维；所述植物纤维粗料粉体按照固液比(0.5～2):(5～35)与纤维活化溶剂体系混合；所述纤维活化溶剂体系选自氮甲基氧化吗啉、N,N-二甲基乙酰胺、高锰酸钾、氯化锂/氯化锌、乙二胺、多聚甲醛、二甲基亚砜、氢氧化钠、尿素、离子液体中的至少两种，且采用常温或者加热的方式对纤维粉体进行活化处理；所述离子液体为咪唑类离子液体、吡啶类离子液体、季铵盐类离子液体、季铵盐类离子液体的一种或多种组合。
6.根据权利要求4所述的制备方法，其特征在于：所述活化纤维素粉按照固液比(1-10):(10-100)加入纤维溶解溶剂体系；所述纤维溶解溶剂体系选自乙酸酐/浓硫酸体系、顺丁烯二酐/浓硫酸体系、乙酸酐/对甲苯磺酸体系、邻苯二甲酸酐/磷酸体系中的一种或多种。
7.根据权利要求1所述的制备方法，其特征在于：步骤(2)中所述复合抗菌剂是由所述植物抗菌提取液添加0.3-1.5wt％的无机纳米抗菌剂和0.1-1wt％的悬浮剂制成。
8.根据权利要求7所述的制备方法，其特征在于：所述无机纳米抗菌剂为具有抗菌抗病毒作用的无机颗粒且粒径在5-50nm范围内，具体选自纳米氧化亚铜、纳米氧化锌，纳米二氧化铈、纳米二氧化钛中的一种或多种；所述悬浮剂选自羧甲基纤维素钠、聚丙烯酰胺、非离子型聚氧乙烯脂肪胺(醇)、聚氧乙烯脂肪醇硫酸盐、聚乙烯醇1788、明胶、蛋清液中的一种或多种。
9.根据权利要求1所述的制备方法，其特征在于：步骤(3)是将所述高分子量醇溶性阳离子聚氨酯乳液作为壳层3D纺丝原液固定到3D打印纺丝机上，将所述复合抗菌剂作为核层3D纺丝原液同样固定到3D打印纺丝机上。
10.根据权利要求1所述的制备方法，其特征在于：步骤(4)中所述烘干是在真空条件下进行梯度加热；所述灭菌为钴60辐照灭菌，采用10-15GKy剂量的钴60辐照3-5h。
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