CN104744716B - 一种壳聚糖与改性聚乙烯醇复合膜的制备方法 - Google Patents

一种壳聚糖与改性聚乙烯醇复合膜的制备方法 Download PDF

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CN104744716B
CN104744716B CN201510159071.0A CN201510159071A CN104744716B CN 104744716 B CN104744716 B CN 104744716B CN 201510159071 A CN201510159071 A CN 201510159071A CN 104744716 B CN104744716 B CN 104744716B
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modified polyvinylalcohol
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chitosan
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polyvinyl alcohol
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CN104744716A (zh
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倪才华
陶蕾
张丽萍
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Guangzhou Hong Wah minimally invasive Biological Technology Co., Ltd.
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Abstract

本发明公开了一种壳聚糖与改性聚乙烯醇复合膜的制备方法，该方法包括如下步骤：(1)将聚乙烯醇‑124与丁二酸酐反应得到改性聚乙烯醇；(2)将所述改性聚乙烯醇配成0.4wt％水溶液，然后逐滴加入到浓度为0.4wt％壳聚糖的醋酸溶液中得到混合溶液；(3)用0.01wt％的NaOH溶液调节所述混合溶液的pH值至5.5，静置1小时后去除表面气泡，得到铸膜液；(4)将所述铸膜液倒入培养皿中，将所述培养皿置于60℃烘箱中烘干至恒重，得到壳聚糖与改性聚乙烯醇复合膜。该方法所用的材料价格低廉，反应不复杂，因此产物成本不会太高，作为医用防粘连膜应用容易为多数普通患者接受。

Description

一种壳聚糖与改性聚乙烯醇复合膜的制备方法
技术领域
本发明涉及一种壳聚糖与改性聚乙烯醇复合膜的制备方法。
背景技术
外科手术中的组织粘连是常见的现象，也是在术后愈合过程中不可避免的病理生理过程。术后粘连和瘢痕组织的形成会引起腹膜粘连、肌腱粘连、眼眶损伤后软组织粘连、周围神经粘连等严重的并发症，常常阻碍人体的正常康复。在心胸外科、妇产科和骨科手术中，术后粘连是一种常见的现象。到目前为止预防粘连的方法主要有：药物治疗、生物疗法、改进外科手术和采用隔离物等。
壳聚糖是甲壳质脱乙酰基后的产物，是一种天然碱性多糖，具有生物相容性好、抑菌止血、促进组织再生、细胞粘附性强和可生物降解等优点，近年来关于壳聚糖的研究较多，壳聚糖薄膜或凝胶可以有效防止术后粘连的产生，减弱纤维性粘连程度。
近年来，聚电解质复合膜成为新型膜材料的重要组成部分，在相分离、纳滤、水果保鲜及生物医药等领域具有广泛应用。但纯壳聚糖膜性脆、在体液中降解和流失过快，应用受到一定限制。
为了改善壳聚糖膜的性能，本发明提供了一种制备壳聚糖与改性聚乙烯醇复合膜的方法，用此方法合成得到的复合膜可有效改善纯壳聚糖膜力学性能、延长降解时间的方法。聚乙烯醇(PVA)具有良好的生物相容性和亲水性，是最常见的生物医用材料，可应用于伤口敷料、药物输送]等方面。另外，PVA成膜性好，与CS有良好的相容性，最为突出的优点在于PVA膜具有优异的力学性能。目前PVA与CS复合有两种常见的方法：共混和化学交联。PVA与壳聚糖物理共混后，主要依靠分子间氢键作用形成均相体系，成膜后，在体液中易溶胀溶解，导致膜快速流失，难以起到防粘连的作用。化学交联法制备的PVA与CS复合物，虽能得到性能优良的医用材料，但化学交联剂多为戊二醛等有毒物质，或对人体健康有一定的负面影响。
发明内容
本发明目的是：提供一种壳聚糖与改性聚乙烯醇复合膜的制备方法，克服纯壳聚糖膜的缺陷，改进其性能以满足用作医用防粘连。
本发明的技术方案是：
一种壳聚糖与改性聚乙烯醇复合膜的制备方法，该方法包括如下步骤：
(1)将聚乙烯醇-124与丁二酸酐反应得到改性聚乙烯醇；
(2)将所述改性聚乙烯醇配成0.4wt％水溶液，然后逐滴加入到浓度为0.4wt％壳聚糖的醋酸溶液中得到混合溶液；
(3)用0.01wt％的NaOH溶液调节所述混合溶液的pH值至5.5，静置1小时后去除表面气泡，得到铸膜液；和
(4)将所述铸膜液倒入培养皿中，将所述培养皿置于60℃烘箱中烘干至恒重，得到壳聚糖与改性聚乙烯醇复合膜。
进一步的，步骤(1)中将聚乙烯醇-124与丁二酸酐反应得到改性聚乙烯醇包括：将聚乙烯醇-124溶解在二甲亚砜溶剂中形成20wt％的聚乙烯醇-124溶液，再将丁二酸酐溶解在二甲亚砜溶剂中形成20wt％的丁二酸酐溶液，按照所述丁二酸酐与所述聚乙烯醇-124中-OH的摩尔比分别为1:10、1.25:10、1.6:10、2.0:10、2.5:10计算，将所述丁二酸酐溶液滴加至聚乙烯醇-124溶液内，在75℃的温度下，在800r/min的条件下机械搅拌5小时后停止加热，冷却至室温后，缓慢滴加到过量的含5～10wt％NaOH的乙醇溶液中，产物析出后用乙醇反复洗涤浸泡，50℃真空干燥至恒重后，得到纯净的改性聚乙烯醇并保存，得到5种改性聚乙烯醇，分别命名为SP1、SP2、SP3、SP4、SP5。
进一步的，步骤(2)中所述改性聚乙烯醇分别用SP1、SP2、SP3、SP4、SP5，将其分别配成0.4wt％的水溶液，然后分别滴加到等质量的0.4wt％壳聚糖的醋酸溶液混合制成混合液。
进一步的，步骤(2)中将所述改性聚乙烯醇配成0.4wt％水溶液，然后逐滴加入到浓度为0.4wt％壳聚糖的醋酸溶液中得到混合溶液包括：将所述改性聚乙烯醇溶于去离子水，配制0.4wt％的水溶液，将1wt％醋酸水溶液为溶剂，配制0.4wt％壳聚糖溶液，并用直径为0.45μm的针头式滤器过滤除去微量不溶杂质，然后将所述水溶液液逐滴加入到过滤后的所述壳聚糖溶液，按速度为1000r/min搅拌混合溶液至均匀。
本发明的优点是：
1.对PVA进行羧基化改性，改性产物与壳聚糖分子间不仅有氢键作用，还有更强的离子键作用，提高了复合膜在模拟体液中的稳定性和力学性能，提供其足够的应用强度，从而达到防粘连的目的。
2.纯粹壳聚糖膜降解太快，容易从伤口部位流失，影响防粘连效果，本发明的壳聚糖与改性聚乙烯醇复合膜中，由于聚乙烯醇参与薄膜的形成，使壳聚糖降解变缓，延长了阻隔时间，增强了应用效果。
3.本发明所选用的材料PVA和壳聚糖已经被证明生物相容性好，小分子的丁二酸酐与PVA反应、并经过去除未反应的小分子后，所得产物无毒无害，生物相容性好，无细胞毒性，可以满足人体内植入材料的安全性要求。
4.本发明所选用的材料价格低廉，反应不复杂，因此产物成本不会太高，容易为多数普通患者接受。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述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它的附图。其中，
图1为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的改性聚乙烯醇的红外光谱图；
图2为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的改性聚乙烯醇的核磁共振谱图；
图3为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的聚乙烯醇改性前后的热失重曲线，其中，a为PVA、b为SP1、c为SP2、d为SP3、e为SP4、f为SP5；
图4为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的0.4wt％的壳聚糖醋酸水溶液与0.4wt％的不同比例改性聚乙烯醇水溶液的等质量混合后所得壳聚糖与改性聚乙烯醇复合膜的红外图谱；
图5为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的壳聚糖与改性聚乙烯醇复合膜的热失重曲线，其中，a为CS/SP1、b为CS/SP2、c为CS/SP3、d为CS/SP4、e为CS/SP5；
图6为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的壳聚糖与改性聚乙烯醇复合膜的接触角；
图7为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的壳聚糖与改性聚乙烯醇复合膜在生理盐水中的平衡溶胀度；和，
图8为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的壳聚糖与改性聚乙烯醇复合膜的体外细胞毒性评价3T3细胞显微照片，其中，A为阳性对照组(含0.64％苯酚的RPMI-1640培养基)、B为阴性对照组(RPMI-1640完全培养基)、C和D为实验组(壳聚糖与改性聚乙烯醇复合膜CS/SP1和CS/SP5浸提液的RPMI-1640培养基)。
具体实施方式
本发明提供一种壳聚糖与改性聚乙烯醇复合膜的制备方法，包括以下步骤：
(1)将聚乙烯醇-124与丁二酸酐反应得到改性聚乙烯醇；
(2)将所述改性聚乙烯醇配成0.4wt％水溶液，然后逐滴加入到浓度为0.4wt％壳聚糖的醋酸溶液中得到混合溶液；
(3)用0.01wt％的NaOH溶液调节所述混合溶液的pH值至5.5，静置1小时后去除表面气泡，得到铸膜液；和
(4)将所述铸膜液倒入培养皿中，将所述培养皿置于60℃烘箱中烘干至恒重，得到壳聚糖与改性聚乙烯醇复合膜。
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施方式对本发明作进一步详细的说明。
一种壳聚糖与改性聚乙烯醇复合膜的制备方法，包括：
步骤一：将聚乙烯醇-124与丁二酸酐反应得到改性聚乙烯醇；
在一个实施例中，该步骤可以具体如下执行：将聚乙烯醇-124溶解在二甲亚砜溶剂中形成20wt％的聚乙烯醇-124溶液，再将丁二酸酐溶解在二甲亚砜溶剂中形成20wt％的丁二酸酐溶液，按照所述丁二酸酐与所述聚乙烯醇-124中-OH的摩尔比分别为1:10、1.25:10、1.6:10、2.0:10、2.5:10计算，将所述丁二酸酐溶液滴加至聚乙烯醇-124溶液内，在75℃的温度下，在800r/min的条件下机械搅拌5小时后停止加热，冷却至室温后，缓慢滴加到过量的含5～10wt％NaOH的乙醇溶液中，产物析出后用乙醇反复洗涤浸泡，50℃真空干燥至恒重后，得到纯净的改性聚乙烯醇并保存，得到5种改性聚乙烯醇，分别命名为SP1、SP2、SP3、SP4、SP5。
步骤二：将所述改性聚乙烯醇配成0.4wt％水溶液，然后逐滴加入到浓度为0.4wt％壳聚糖的醋酸溶液中得到混合溶液；
在一个实施例中，该步骤可以具体如下执行：将所述改性聚乙烯醇溶于去离子水，配制0.4wt％的水溶液，将1wt％醋酸水溶液为溶剂，配制0.4wt％壳聚糖溶液，并用直径为0.45μm的针头式滤器过滤除去微量不溶杂质，然后将所述水溶液液逐滴加入到过滤后的所述壳聚糖溶液，按速度为1000r/min搅拌混合溶液至均匀，其中所述改性聚乙烯醇分别用SP1、SP2、SP3、SP4、SP5，将其分别配成0.4wt％的水溶液，然后分别滴加到等质量的0.4w％壳聚糖的醋酸溶液混合制成混合液。
步骤三：用0.01wt％的NaOH溶液调节所述混合溶液的pH值至5.5，静置1小时后去除表面气泡，得到铸膜液；和
步骤四：将所述铸膜液倒入培养皿中，将所述培养皿置于60℃烘箱中烘干至恒重，得到壳聚糖与改性聚乙烯醇复合膜。
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和实施例进一步说明本发明的技术方案。但是本发明不限于所列出的实施例，还应包括在本发明所要求的权利范围内其他任何公知的改变。
首先，此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例，也不是单独的或选择性的与其他实施例互相排斥的实施例。
其次，本发明利用结构示意图等进行详细描述，在详述本发明实施例时，为便于说明，示意图会不依一般比例作局部放大，而且所述示意图只是实例，其在此不应限制本发明保护的范围。此外，在实际制作中应包含长度、宽度及深度的三维空间。
另外，本发明中所讲的字母简称，均为本领域固定简称，其中部分字母文解释如下：PVA：聚乙烯醇-124；CS：壳聚糖。
实施例一
改性聚乙烯醇的合成
将聚乙烯醇-124配制成20wt％的二甲亚砜溶液，再将丁二酸酐配制成25wt％的二甲亚砜溶液，按照丁二酸酐与聚乙烯醇中-OH的摩尔比分别为1:10、1.25:10、1.6:10、2.0:10、2.5:10计算，将丁二酸酐溶液滴加至聚乙烯醇溶液内，在75℃的温度下，机械搅拌(800r/min)5小时后停止加热，冷却至室温后，缓慢滴加到过量的含5～10wt％NaOH的乙醇溶液中，产物析出后用乙醇反复洗涤浸泡，50℃真空干燥至恒重后，得到纯净的改性聚乙烯醇并保存。
表1改性聚乙烯醇的合成及分析结果
实施例二
改性聚乙烯醇的红外光谱分析
按表1所示配方合成得到改性聚乙烯醇后，采用傅立叶红外光谱仪对其进行红外表征，扫描范围在4000～500cm-1的波数范围内，分辨率为4cm-1，结果请参阅图1。图1为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的改性聚乙烯醇的红外光谱图，如图1所示，PVA链段中-OH的吸收峰出现在3200～3600cm-1波段，2930cm-1处的特征峰是-CH2的非对称伸缩振动吸收峰，而-CH2的对称弯曲振动吸收峰出现在1450cm-1处。聚乙烯醇经丁二酸酐改性后，在1750cm-1处出现酯键中C＝O的对称伸缩振动峰，在1580cm-1和1408cm-1处出现羧酸盐的特征吸收峰，这表明丁二酸酐已成功修饰PVA。另外，随着丁二酸酐投料量的增加，-OH的吸收峰峰形变宽，强度变强，且向高波数移动，这表明随着丁二酸酐投料的增加，聚乙烯醇羧基化程度增加。
实施例三
改性聚乙烯醇的核磁共振(1H-NMR)分析：
以四甲基硅烷为内标物，氘代DMSO为溶剂，样品浓度约为10mg/ml，使用1H-NMR测试改性聚乙烯醇的结构，请参阅图2，图2为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的改性聚乙烯醇的核磁共振谱图，如图2所示，δ2.50为溶剂DMSO峰，δ3.50为水峰，δ0为TMS峰。从图中可以看到PVA中各质子峰分别为：δ1.10～δ1.70为CH2的质子峰，δ3.70～δ3.97为CH的质子峰，δ4.15～δ4.70为OH的质子峰。PVA经丁二酸酐修饰后，CH的质子峰出现在δ4.80～δ5.20处，δ2.24～δ2.49为丁二酸酐上CH2和CH2质子峰叠加后形成的多重峰，这些峰的出现说明丁二酸酐修饰反应可顺利进行。
实施例四
改性聚乙烯醇的热重分析
请参阅图3，图3为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的聚乙烯醇改性前后的热失重曲线，如图3所示，其给出了聚乙烯醇及改性聚乙烯醇的热重分析表征结果，曲线a、b、c、d、e、f分别是PVA，SP1，SP2，SP3,SP4，SP5的热失重曲线。PVA的失重分为三个阶段：第一阶段是PVA主链的热分解，主要集中在250～400℃之间；第二阶段是PVA主链降解后残留的端炔基化合物继续降解为碳和烃类，热分解温度始于400℃。与纯PVA的热分解行为相比，丁二酸酐修饰后PVA主链热分解开始的温度下降，第二阶段分解质量增加，且热分解残留质量增加。随着PVA羧基化程度的增加，丁二酸酯基团含量增加，热分解后生成更多的丁二酸和水，使PVA-124主链上的-OH以更不稳定的-OH2+结构存在，促进主链的热降解。
实施例五
壳聚糖与改性聚乙烯醇复合膜的制备
称取2克壳聚糖(CS，脱乙酰度96.4％)，将其溶解在498毫升1.0wt％的醋酸水溶液中，搅拌均匀，用直径为0.45μm的针头式滤器过滤除去微量不溶杂质；另外将改性聚乙烯醇SP1溶于去离子水，配制0.4wt％的SP1水溶液500毫升；将50克0.4wt％SP1溶液逐滴加入到过滤后的50克0.4wt％壳聚糖溶液中，混合搅拌均匀，然后用0.01wt％的NaOH溶液调节共混溶液的pH至5.5，静置去除表面气泡后，得到铸膜液，将铸膜液倒入12cm×12cm的培养皿中，于60℃烘箱中烘干至恒重，得到复合膜CS/SP1。
分别用SP2、SP3、SP4、SP5代替SP1，其他操作同上，制备其余四种壳聚糖与改性聚乙烯醇复合膜，命名为：CS/SP2、CS/SP3、CS/SP4、CS/SP5。
实施例六
壳聚糖与改性聚乙烯醇复合膜的力学性能测试
按照GBT 1040.3-2006标准将复合膜制成2型样条，用电子拉力机对样条进行力学性能测试，测试条件：25℃，RH(空气湿度)50％，拉伸速度5mm/min。
表2壳聚糖与改性聚乙烯醇复合膜的力学性能
实施例七
壳聚糖与改性聚乙烯醇复合膜的红外光谱测试
取实施例五所得到的壳聚糖与改性聚乙烯醇复合膜样品CS/SP1、CS/SP2、CS/SP3、CS/SP4、CS/SP5，采用傅立叶红外光谱仪对其进行红外表征，扫描范围在4000～500cm-1的波数范围内，分辨率为4cm-1。请参阅图4，图4为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的0.4wt％的壳聚糖醋酸水溶液与0.4wt％的不同比例改性聚乙烯醇水溶液的等质量混合后所得壳聚糖与改性聚乙烯醇复合膜的红外图谱，如图4所示，CS与改性PVA复合后，CS的O-H、N-H与酰胺基中C＝O的特征峰及SP的C-O特征峰发生偏移，这与CS与SP分子间存在氢键有关；CS中N-H弯曲振动峰向高波数偏移，与羧酸盐中的C＝O峰重合，说明-NH2以-NH3+形式存在；因此，CS与改性PVA分子中可能存在离子键作用。
实施例八
壳聚糖与改性聚乙烯醇复合膜的热失重曲线
请参阅图5，图5为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的壳聚糖与改性聚乙烯醇复合膜的热失重曲线，如图5所示，其给出了CS与SP1、SP3、SP5以1：0.3的质量比混合后，复合膜的热失重曲线。从图中可以看出复合膜的热降解分为两个阶段，在100-195℃温度范围内的热降解是聚电解质离子间脱水引起的；第二阶段是主链降解。各膜的热分解与两组分单独的热分解趋势不一致，说明样品膜形成均匀结构，可以看出随着复合膜中PVA羧基化程度的增加，膜热降解最大速度时的温度由260℃降低至236℃，在550℃时膜热分解残留质量由30.67％增至41.65％，复合膜的热降解速率较为缓和，复合膜仍具有一定的热稳定结构。
实施例九
壳聚糖与改性聚乙烯醇复合膜的接触角测试
请参阅图6，图6为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的壳聚糖与改性聚乙烯醇复合膜的接触角，如图6所示，随着壳聚糖与改性聚乙烯醇复合膜中改性聚乙烯醇含量的增加，水接触角增大，这些现象与聚电解质复合物的生成量增加、亲水基团-NH3+、-COO-、-OH减少有关。因此，可以通过改变复合体系中壳聚糖与改性聚乙烯醇质量比，调控所制复合膜的亲疏水性，从而设计不同亲疏水性能的复合膜，满足对生物膜材料的不同要求。
实施例十
壳聚糖与改性聚乙烯醇复合膜在生理盐水中的平衡溶胀度测试
将膜剪成大小为3cm×3cm的正方形膜，然后将膜分别浸入到0.9wt％NaCl溶液中，并置于37℃恒温震荡水浴锅中，6h后用滤纸拭去表面水分，称质量，当质量基本不变时溶胀度达到平衡，记平衡溶胀度为S0。平行测定3次，取平均值。平衡溶胀度的计算公式如下：
m0和mb分别为溶胀前后复合膜的质量(g)
请参阅图7，图7为本发明的一种壳聚糖与改性聚乙烯醇复合膜的制备方法中的壳聚糖与改性聚乙烯醇复合膜在生理盐水中的平衡溶胀度。如图7所示，改性聚乙烯醇含量较少时，复合膜溶胀度较大，此时壳聚糖分子链上分布大量带正电荷的-NH3+，分子链间相互排斥，易于伸展，复合膜具有较高的溶胀比；随着复合膜中SP含量的增加，复合膜的溶胀度降低，这可能是因为随着复合膜中改性聚乙烯醇含量的增加，聚电解质复合物生成量增加，复合膜中游离的亲水性基团-NH3+、-COO-减少，从而引起复合膜吸水量下降。当复合膜中CS与改性聚乙烯醇的质量比一定时，随着PVA羧基化程度的增加，复合膜的吸水量减少，这与聚电解质复合物的大量生成有关。
实施例十一
壳聚糖与改性聚乙烯醇复合膜的体外细胞毒性评价
用MTT法评估复合膜的体外细胞毒性。取对数生长期的3T3细胞，按照每孔2.4×104Cell接种于96孔培养板中，置于37℃、5％CO2培养箱中用含有10％胎牛血清的RPMI-1640培养基(RPMI-1640完全培养基)培养24h后弃去培养基。将6cm2不同的复合膜样品(CS/SP1；CS/SP5)经过高温灭菌后分别置于1ml生理盐水中(37℃)浸提6h、12h、24h、48h，浸提液经RPMI-1640完全培养基稀释至0.1μL/μL，稀释后的浸提液作为样品组。每孔加入100μLRPMI-1640完全培养基、含0.64％苯酚的RPMI-1640培养基、含复合膜浸提液的RPMI-1640完全培养基依次作为阴性对照组、阳性对照组和实验组，每组均设6个复孔，置于37℃、5％CO2培养箱中培养48h后，每孔加入20μLMTT并培养4h。结晶全部溶解后，采用酶联免疫检测仪于570nm测定其吸光度,并计算细胞存活率。
图8是3T3细胞经过各种条件培养处理后的显微照片：A:阳性对照组(含0.64％苯酚的RPMI-1640培养基)；B:阴性对照组(RPMI-1640完全培养基)；C，D:实验组(壳聚糖与改性聚乙烯醇复合膜CS/SP1和CS/SP5浸提液的RPMI-1640培养基)。
可以看出阳性对照组的细胞几乎完全圆缩死亡，阴性对照组的细胞生长状态良好，细胞核饱满，立体感强，细胞贴壁生长良好，形态正常，这说明复合膜对细胞生长无影响，计算得到的细胞存活率均大于80％，满足体内安全性要求。
综上所述，本发明公开了一种壳聚糖与改性聚乙烯醇复合膜的制备方法，本方法首先以聚乙烯醇(PVA)为原料，用丁二酸酐与之反应，使聚乙烯醇主链的羟基部分转化成羧基，制备羧基化程度不同的改性聚乙烯醇(SP)；然后以壳聚糖(CS)为基体，将改性聚乙烯醇与壳聚糖通过聚电解质的相互作用复合，采用溶液浇铸法制备了CS与SP壳聚糖与改性聚乙烯醇复合膜。复合膜性能测试结果表明：与纯壳聚糖膜相比较，壳聚糖与改性聚乙烯醇复合膜的力学强度提高，断裂伸长率增加，亲水性增强，细胞毒性小于1级，作为医用防粘剂具有潜在的应用前景。
应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。

Claims (4)

1.一种壳聚糖与改性聚乙烯醇复合膜的制备方法，其特征在于，该方法包括如下步骤：
(1)将聚乙烯醇-124与丁二酸酐反应得到改性聚乙烯醇,按照所述丁二酸酐与所述聚乙烯醇-124中-OH的摩尔比分别为1:10、1.25:10、1.6:10、2.0:10、2.5:10计算；
(2)将所述改性聚乙烯醇配成0.4wt％水溶液，然后逐滴加入到浓度为0.4wt％壳聚糖的醋酸溶液中得到混合溶液；
(3)用0.01wt％的NaOH溶液调节所述混合溶液的pH值至5.5，静置1小时后去除表面气泡，得到铸膜液；和
(4)将所述铸膜液倒入培养皿中，将所述培养皿置于60℃烘箱中烘干至恒重，得到壳聚糖与改性聚乙烯醇复合膜。
2.根据权利要求1所述的壳聚糖与改性聚乙烯醇复合膜的制备方法，其特征在于：步骤(1)中将聚乙烯醇-124与丁二酸酐反应得到改性聚乙烯醇包括：将聚乙烯醇-124溶解在二甲亚砜溶剂中形成20wt％的聚乙烯醇-124溶液，再将丁二酸酐溶解在二甲亚砜溶剂中形成20wt％的丁二酸酐溶液，按照所述丁二酸酐与所述聚乙烯醇-124中-OH的摩尔比分别为1:10、1.25:10、1.6:10、2.0:10、2.5:10计算，将所述丁二酸酐溶液滴加至聚乙烯醇-124溶液内，在75℃的温度下，在800r/min的条件下机械搅拌5小时后停止加热，冷却至室温后，缓慢滴加到过量的含5～10wt％NaOH的乙醇溶液中，产物析出后用乙醇反复洗涤浸泡，50℃真空干燥至恒重后，得到纯净的改性聚乙烯醇并保存，得到5种改性聚乙烯醇，分别命名为SP1、SP2、SP3、SP4、SP5。
3.根据权利要求2所述的壳聚糖与改性聚乙烯醇复合膜的制备方法，其特征在于：所述改性聚乙烯醇分别用SP1、SP2、SP3、SP4、SP5，将其分别配成0.4wt％的水溶液，然后分别滴加到等质量的0.4wt％壳聚糖的醋酸溶液混合制成混合液。
4.根据权利要求1所述的壳聚糖与改性聚乙烯醇复合膜的制备方法，其特征在于，步骤(2)中将所述改性聚乙烯醇配成0.4wt％水溶液，然后逐滴加入到浓度为0.4wt％壳聚糖的醋酸溶液中得到混合溶液包括：将所述改性聚乙烯醇溶于去离子水，配制0.4wt％的水溶液，将1wt％醋酸水溶液为溶剂，配制0.4wt％壳聚糖溶液，并用直径为0.45μm的针头式滤器过滤除去微量不溶杂质，然后将所述水溶液液逐滴加入到过滤后的所述壳聚糖溶液，按速度为1000r/min搅拌混合溶液至均匀。
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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107619486A (zh) * 2017-09-12 2018-01-23 南京中医药大学 一种控制壳聚糖‑过渡金属盐体系热降解的方法
CN108342040B (zh) * 2018-01-11 2020-12-25 青岛海尔股份有限公司 一种冰箱用保鲜膜、其制备方法和保鲜盒
CN108867164A (zh) * 2018-06-20 2018-11-23 广州市宝绅纸塑有限公司 一种改良高分子涂布液及其制备方法与应用
CN109867823A (zh) * 2019-01-10 2019-06-11 安徽工程大学 一种壳聚糖-聚乙烯醇复合膜及其制备方法与应用
CN111269515B (zh) * 2020-04-04 2022-04-29 北京农学院 一种具有抑菌功能的可降解薄膜及其制备方法
CN112029158B (zh) * 2020-07-31 2021-06-08 华南理工大学 一种具有二氧化碳响应行为的壳聚糖基复合响应膜及其制备方法与应用
CN113121854A (zh) * 2021-04-22 2021-07-16 黄丹耒 一种使用生物基材料制备的抗菌除味片及其应用
CN114409936B (zh) * 2021-12-29 2023-07-21 太原理工大学 添加精氨酸化壳聚糖与氧化锌纳米粒子的复合薄膜的制备方法
CN114805872B (zh) * 2022-05-07 2023-11-10 辽宁大学 一种葡萄糖糖基化米糠蛋白-壳聚糖功能性复合膜及其制备方法
CN115537030A (zh) * 2022-09-27 2022-12-30 张大庆 一种亲水性壳聚糖复合物溶液的制备及在液态地膜中的应用

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5241797B2 (zh) * 1974-04-05 1977-10-20
DE3871962T2 (de) 1987-01-16 1993-02-04 Kuraray Co Aufzeichnungsmittel fuer tinte.
US5646206A (en) * 1993-04-23 1997-07-08 The United States Of America As Represented By The Secretary Of Agriculture Films fabricated from mixtures of pectin and poly(vinyl alchohol)
EP0712635B1 (en) * 1994-05-13 2003-05-02 Kuraray Co., Ltd. Medical polymer gel
DE19604706A1 (de) * 1996-02-09 1997-08-14 Merck Patent Gmbh Vernetzungsprodukte von Aminogruppen-haltigen Biopolymeren
US5980883A (en) * 1996-10-02 1999-11-09 Kuraray Co., Ltd. Polymer gel for medical use
JP4056859B2 (ja) * 2002-11-11 2008-03-05 日本合成化学工業株式会社 水溶性フィルム
CN100493688C (zh) 2006-01-26 2009-06-03 中国科学院大连化学物理研究所 一种聚乙烯醇/壳聚糖共混膜的制备方法
WO2008063468A2 (en) * 2006-11-13 2008-05-29 The Procter & Gamble Company Water-soluble detergent pouch
US20080110370A1 (en) * 2006-11-13 2008-05-15 Verrall Andrew P Water-soluble film
US20080176985A1 (en) * 2006-11-13 2008-07-24 Verrall Andrew P Water-soluble film
CN101440136B (zh) * 2008-12-12 2011-07-06 中国海洋大学 胺糖化几丁聚糖复合物的制备方法
CN101798393B (zh) 2009-02-10 2012-06-06 同济大学 一种季铵化壳聚糖/聚乙烯醇膜的制备方法
JP5663174B2 (ja) 2010-02-15 2015-02-04 日本パーカライジング株式会社 表面処理皮膜を有するアルミニウム又はアルミニウム合金材料及びその表面処理方法
CN101792540B (zh) * 2010-02-23 2012-01-11 厦门大学 一种碳纳米管壳聚糖复合膜及其制备方法
EP2739977A1 (en) * 2011-08-01 2014-06-11 Massachusetts Institute of Technology Photoluminescent nanostructure-based sensors
CN102671555B (zh) 2012-05-18 2014-07-23 江南大学 一种壳聚糖/聚乙烯醇混合膜的制备方法和应用
US20160128947A1 (en) * 2012-10-22 2016-05-12 Stc. Unm Bioadhesive films for local and/or systemic delivery
LT2740685T (lt) * 2012-12-06 2017-04-10 Mayr-Melnhof Karton Ag Dengtos pakavimo medžiagos gamybos būdas ir hidrofobinių mišinių pakavimo medžiaga su bent vienu apsauginiu sluoksniu
SG11201602292SA (en) * 2013-09-25 2016-04-28 Engene Inc Dually derivatized chitosan nanoparticles and methods of making and using the same for gene transfer in vivo
US9956181B2 (en) * 2015-09-11 2018-05-01 Shaker A. Mousa Composition of nanoformulated lycopene and method of using the composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"壳聚糖-聚乙烯醇复合膜的成膜特性研究";王易等;《安徽农业科学》;20141231;第42卷(第8期);第2223-2224页 *
"羧丁酰壳聚糖水凝胶的制备与性能研究";文凤;《羧丁酰壳聚糖水凝胶的制备与性能研究》;20131128;第16页2.2.3部分 *

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