CN115252874B - 一种可生物降解医用绷带及其制备方法 - Google Patents
一种可生物降解医用绷带及其制备方法 Download PDFInfo
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- CN115252874B CN115252874B CN202210994664.9A CN202210994664A CN115252874B CN 115252874 B CN115252874 B CN 115252874B CN 202210994664 A CN202210994664 A CN 202210994664A CN 115252874 B CN115252874 B CN 115252874B
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- antibacterial
- stirring
- sodium alginate
- preparing
- medical bandage
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- D—TEXTILES; PAPER
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Toxicology (AREA)
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- Biochemistry (AREA)
- Microbiology (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明提供一种可生物降解医用绷带及其制备方法，单一的海藻酸盐敷料其力学性能和抗菌性能不足，在静电纺丝过程中引入聚乙烯醇、聚羟基丁酸酯共混提高力学性能与抗菌性能，使月桂基葡糖苷起到乳化作用，引入双金属基卟啉有机框架作为抗菌剂来大幅提高医用绷带的抗菌性及抗菌持久性；氧化获得醛基化的海藻酸钠，使其具有更高的化学反应活性，使抗菌浸渍液中壳聚糖和抗菌纤维中的氧化海藻酸钠混合后快速交联；以双金属卟啉有机框架纳米颗粒作为抗菌剂，采用共混纺丝提高抗菌剂的牢固性，从而实现对细菌的高效杀灭。
Description
技术领域
本发明涉及绷带领域，具体是一种可生物降解医用绷带及其制备方法。
背景技术
生物医学材料是具有诊断、治疗、修复或替换受损的组织、器官或改善生物体功能的一类材料，医用绷带是常见的生物医学材料。伴随着社会的高速发展和人们生活水平的提高，人们对生物组织有了进一步的认识，这对于生物医学材料的性能提出了更高的要求，比如医用绷带需具有维持创面湿润、抗菌等功能。
医用绷带为创口提供的湿润环境同样也适合病菌的生长和繁殖，现有市场通常让绷带包裹银粒子等抗菌离子用于杀菌，但是传统绷带的抗菌成分易脱落，会发生异物排斥反应，且敷料被浸透时易侵入病原体，换药过程易造成组织损伤等问题。且现有绷带大多为一次性用品，降解缓慢，大量堆积会增加环境污染。
发明内容
本发明的目的在于提供一种可生物降解医用绷带及其制备方法，以解决现有技术中的问题。
为了解决上述技术问题，本发明提供如下技术方案：
一种可生物降解医用绷带的制备方法，包括以下步骤：
S1：制备抗菌纤维：将氧化海藻酸钠、聚乙烯醇、去离子水超声搅拌，得到氧化海藻酸钠混合液，加入月桂基葡糖苷、三氯甲烷，超声均质，加入聚羟基丁酸酯、双金属基卟啉有机框架，连续振荡12h，再次超声均质，得到纺丝溶液，进行静电纺丝，得到抗菌纤维；
S2：用抗菌纤维制备绷带基料：抗菌纤维和天然纤维混合纺纱、混织，得到绷带基料；
S3：制备抗菌浸渍液：将壳聚糖、氢氧化钠溶液混合搅拌加入异丙醇、一氯乙酸，升温至60-65℃保温2-3h，将pH调节为7-7.2，用丙酮沉淀、过滤，洗涤、抽滤、真空干燥，得到O-羧甲基壳聚糖；将O-羧甲基壳聚糖、蒸馏水混合搅拌，超声分散20-30min，搅拌得到抗菌浸渍液；
S4：将绷带基料置于抗菌浸渍液中放置1-2h，取出后干燥，得到一种可生物降解医用绷带。
进一步的，天然纤维竹纤维、麻纤维、棉纤维中一种。
进一步的，在制备抗菌纤维中，氧化海藻酸钠、聚乙烯醇、聚羟基丁酸酯、双金属基卟啉有机框架的质量比为2：10：2：0.5。
进一步的，在制备抗菌浸渍液中，壳聚糖、一氯乙酸、异丙醇的质量体积比为15g：18g：150mL。
进一步的，静电纺丝的工作条件为：电压20kV，接收距离16cm，流速为1.6mL/h。
进一步的，超声均质的工作条件为：在超声波细胞粉碎机中以500W的功率均质8-10min。
进一步的，氧化海藻酸钠的制备包括以下步骤：
将海藻酸钠、蒸馏水混合搅拌，加入高碘酸钠，避光反应22-24h后加入乙二醇终止反应，加入氯化钠、乙醇，析出沉淀，抽滤，用乙醇析出，抽滤，在30-40℃下真空干燥22-24h得到氧化海藻酸钠。
进一步的，双金属基卟啉有机框架的制备包括以下步骤：
1)将对苯二甲酸、DMF混合搅拌，加入四氯化锆、DMF混合，搅拌条件下加入醋酸，超声分散，升温至110-120℃保温22-24h，离心、洗涤、干燥得到锆基有机框架；
2)将锆基有机框架、钛酸四丁酯、甲苯超声搅拌，在90-100℃保温22-24h，加入四(4-羧基苯基)卟啉、对苯二甲酸，超声搅拌30-60min，干燥，得到双金属基卟啉有机框架。
进一步的，在步骤1)中对苯二甲酸、四氯化锆的摩尔质量比为0.3mmol：70mg。
进一步的，在步骤2)中锆基有机框架、四(4-羧基苯基)卟啉、钛酸四丁酯的质量摩尔比为50mg：2.5mg：0.3mmol。
本发明的有益效果：
本发明提供一种可生物降解医用绷带及其制备方法，制备的医用绷带具有高效抗菌性、较好的力学性能、可生物降解性能以及生物相容性。
海藻酸钠是从天然藻类中提取出的多糖共聚物，是一种天然材料，与人体相容性较好；然而单一的海藻酸盐敷料其力学性能和抗菌性能不足，不能较好地支撑创面以及抑制创面感染菌滋生；因此，本发明在静电纺丝过程中引入聚乙烯醇、聚羟基丁酸酯共混提高力学性能与抗菌性能，抑制伤口的恶化，引入双金属基卟啉有机框架作为抗菌剂来大幅提高医用绷带的抗菌性及抗菌持久性；
但是聚羟基丁酸酯亲油性，海藻酸钠为亲水性，在常规情况下很难共溶解，为此，以月桂基葡糖苷、三氯甲烷为乳化剂，使月桂基葡糖苷起到乳化作用，降低共混溶液的表面张力，超声均质使其共混得到纺丝液，然后制备抗菌纤维；
本发明使用的是氧化海藻酸钠，氧化获得醛基化的海藻酸钠，使其具有更高的化学反应活性，因此将抗菌纤维制成的绷带基料在抗菌浸渍液中浸渍处理时，抗菌浸渍液中壳聚糖和抗菌纤维中的氧化海藻酸钠混合后快速交联，过程简单，时间可调，无须额外添加小分子交联剂，提高了生物安全性；
本发明以双金属卟啉有机框架纳米颗粒作为抗菌剂，采用共混纺丝提高抗菌剂的牢固性，从而实现对细菌的高效杀灭，制备的双金属卟啉有机框架纳米颗粒具有良好的1O2产生能力；本发明用处理后的壳聚糖作为抗菌浸渍液，使其通过形成氢键、金属-多酚配位、静电相互作用以及迈克尔加成/席夫碱反应等多种物理化学方式粘附在绷带基料上，通过其多酚介导方式将双金属卟啉有机框架纳米颗粒稳定牢固结合在绷带基料表面，从而提高其抗菌的持久性。
具体实施方式
下面将结合本发明的实施例，对本发明中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明，若本发明实施例中有涉及方向性指示诸如上、下、左、右、前、后……，则该方向性指示仅用于解释在某一特定姿态如各部件之间的相对位置关系、运动情况等，如果该特定姿态发生改变时，则该方向性指示也相应地随之改变。另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现时应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。
以下结合具体实施例对本发明的技术方案做进一步详细说明，应当理解，以下实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1
一种可生物降解医用绷带的制备方法，包括以下步骤：
S1：制备抗菌纤维：将2g氧化海藻酸钠、10g聚乙烯醇、188g去离子水超声搅拌，得到氧化海藻酸钠混合液，加入10mL月桂基葡糖苷、10mL三氯甲烷，超声均质，加入2g聚羟基丁酸酯、0.5g双金属基卟啉有机框架，连续振荡12h，再次超声均质，得到纺丝溶液，进行静电纺丝，得到抗菌纤维；
静电纺丝的工作条件为：电压20kV，接收距离16cm，流速为1.6mL/h；
超声均质的工作条件为：在超声波细胞粉碎机中以500W的功率均质8min；
氧化海藻酸钠的制备包括以下步骤：
将1g海藻酸钠、50mL蒸馏水混合搅拌，加入10.7g高碘酸钠，避光反应22h后加入乙二醇终止反应，加入1.5g氯化钠、100mL乙醇，析出沉淀，抽滤，用乙醇析出，抽滤，在30℃下真空干燥24h得到氧化海藻酸钠；
双金属基卟啉有机框架的制备包括以下步骤：
1)将0.3mmol对苯二甲酸、13mLDMF混合搅拌，加入70mg四氯化锆、13mLDMF混合，搅拌条件下加入0.51mL醋酸，超声分散，升温至110℃保温24h，离心、洗涤、干燥得到锆基有机框架；
2)将50mg锆基有机框架、0.3mmol钛酸四丁酯、20mL甲苯超声搅拌，在90℃保温24h，加入2.5mg四(4-羧基苯基)卟啉、10mg对苯二甲酸、90mLDMF，超声搅拌30min，干燥，得到双金属基卟啉有机框架；
S2：用抗菌纤维制备绷带基料：抗菌纤维和竹纤维混合纺纱、混织，得到绷带基料；
S3：制备抗菌浸渍液：将15g壳聚糖、63mL氢氧化钠溶液混合搅拌加入150mL异丙醇、18g一氯乙酸，升温至60℃保温3h，将pH调节为7，用丙酮沉淀、过滤，洗涤、抽滤、真空干燥，得到O-羧甲基壳聚糖；将10gO-羧甲基壳聚糖、90g蒸馏水混合搅拌，超声分散20min，搅拌得到抗菌浸渍液；
S4：将绷带基料置于抗菌浸渍液中放置1h，取出后干燥，得到一种可生物降解医用绷带。
实施例2
一种可生物降解医用绷带的制备方法，包括以下步骤：
S1：制备抗菌纤维：将1g氧化海藻酸钠、5g聚乙烯醇、99g去离子水超声搅拌，得到氧化海藻酸钠混合液，加入5mL月桂基葡糖苷、5mL三氯甲烷，超声均质，加入1g聚羟基丁酸酯、0.25g双金属基卟啉有机框架，连续振荡12h，再次超声均质，得到纺丝溶液，进行静电纺丝，得到抗菌纤维；
静电纺丝的工作条件为：电压20kV，接收距离16cm，流速为1.6mL/h；
超声均质的工作条件为：在超声波细胞粉碎机中以500W的功率均质9min；
氧化海藻酸钠的制备包括以下步骤：
将1g海藻酸钠、50mL蒸馏水混合搅拌，加入10.7g高碘酸钠，避光反应23h后加入乙二醇终止反应，加入1.5g氯化钠、100mL乙醇，析出沉淀，抽滤，用乙醇析出，抽滤，在35℃下真空干燥23h得到氧化海藻酸钠；
双金属基卟啉有机框架的制备包括以下步骤：
1)将0.3mmol对苯二甲酸、13mLDMF混合搅拌，加入70mg四氯化锆、13mLDMF混合，搅拌条件下加入0.51mL醋酸，超声分散，升温至115℃保温23h，离心、洗涤、干燥得到锆基有机框架；
2)将50mg锆基有机框架、0.3mmol钛酸四丁酯、20mL甲苯超声搅拌，在95℃保温23h，加入2.5mg四(4-羧基苯基)卟啉、10mg对苯二甲酸、90mLDMF，超声搅拌30-60min，干燥，得到双金属基卟啉有机框架；
S2：用抗菌纤维制备绷带基料：抗菌纤维和竹纤维混合纺纱、混织，得到绷带基料；
S3：制备抗菌浸渍液：将15g壳聚糖、63mL氢氧化钠溶液混合搅拌加入150mL异丙醇、18g一氯乙酸，升温至65℃保温2.5h，将pH调节为7.1，用丙酮沉淀、过滤，洗涤、抽滤、真空干燥，得到O-羧甲基壳聚糖；将15gO-羧甲基壳聚糖、85g蒸馏水混合搅拌，超声分散25min，搅拌得到抗菌浸渍液；
S4：将绷带基料置于抗菌浸渍液中放置1.5h，取出后干燥，得到一种可生物降解医用绷带。
实施例3
一种可生物降解医用绷带的制备方法，包括以下步骤：
S1：制备抗菌纤维：将4g氧化海藻酸钠、20g聚乙烯醇、376g去离子水超声搅拌，得到氧化海藻酸钠混合液，加入20mL月桂基葡糖苷、20mL三氯甲烷，超声均质，加入4g聚羟基丁酸酯、1g双金属基卟啉有机框架，连续振荡12h，再次超声均质，得到纺丝溶液，进行静电纺丝，得到抗菌纤维；
静电纺丝的工作条件为：电压20kV，接收距离16cm，流速为1.6mL/h；
超声均质的工作条件为：在超声波细胞粉碎机中以500W的功率均质10min；
氧化海藻酸钠的制备包括以下步骤：
将1g海藻酸钠、50mL蒸馏水混合搅拌，加入10.7g高碘酸钠，避光反应24h后加入乙二醇终止反应，加入1.5g氯化钠、100mL乙醇，析出沉淀，抽滤，用乙醇析出，抽滤，在40℃下真空干燥22h得到氧化海藻酸钠；
双金属基卟啉有机框架的制备包括以下步骤：
1)将0.3mmol对苯二甲酸、13mLDMF混合搅拌，加入70mg四氯化锆、13mLDMF混合，搅拌条件下加入0.51mL醋酸，超声分散，升温至120℃保温22h，离心、洗涤、干燥得到锆基有机框架；
2)将50mg锆基有机框架、0.3mmol钛酸四丁酯、20mL甲苯超声搅拌，在100℃保温22h，加入2.5mg四(4-羧基苯基)卟啉、10mg对苯二甲酸、90mLDMF，超声搅拌30min，干燥，得到双金属基卟啉有机框架；
S2：用抗菌纤维制备绷带基料：抗菌纤维和竹纤维混合纺纱、混织，得到绷带基料；
S3：制备抗菌浸渍液：将15g壳聚糖、63mL氢氧化钠溶液混合搅拌加入150mL异丙醇、18g一氯乙酸，升温至65℃保温2h，将pH调节为7.2，用丙酮沉淀、过滤，洗涤、抽滤、真空干燥，得到O-羧甲基壳聚糖；将10gO-羧甲基壳聚糖、40g蒸馏水混合搅拌，超声分散20-30min，搅拌得到抗菌浸渍液；
S4：将绷带基料置于抗菌浸渍液中放置2h，取出后干燥，得到一种可生物降解医用绷带。
对比例1
以实施例3为对照组，用海藻酸钠替换氧化海藻酸钠，其他工序正常。
对比例2
以实施例3为对照组，没有添加聚乙烯醇，其他工序正常。
对比例3
以实施例3为对照组，没有添加聚羟基丁酸酯，其他工序正常。
对比例4
以实施例3为对照组，没有添加月桂基葡糖苷，其他工序正常。
对比例5
以实施例3为对照组，没有添加双金属基卟啉有机框架，其他工序正常。
对比例6
以实施例3为对照组，没有制备锆基有机框架，其他工序正常。
对比例7
以实施例3为对照组，没有添加四(4-羧基苯基)卟啉，其他工序正常。
对比例8
以实施例3为对照组，没有添加钛酸四丁酯，其他工序正常。
对比例9
以实施例3为对照组，没有制备抗菌浸渍液，其他工序正常。
所用原料来源：
竹纤维的处理：将竹材切割为2m长的竹段后，放入竹材剖片机剖为6片，在高压渗透罐中进行软化处理，氢氧化钠溶液浓度为6％，处理时间36h，压力为1.5MPa，将软化后的竹片放入开纤机进行碾压，开纤后经梳理得到竹纤维。
聚乙烯醇P816862、异丙醇I811925、一氯乙酸C922218、乙二醇E808735、海藻酸钠S817372、高碘酸钠S817518、对苯二甲酸P816020、四氯化锆Z888687、壳聚糖C804730、聚羟基丁酸酯P909977、钛酸四丁酯T818869、DMF：N,N-二甲基甲酰胺N807505：上海麦克林生化科技有限公司；醋酸、丙酮、甲苯、NaOH、硝酸、乙醇、氯化钠，分析纯：国药化学试剂有限公司；三氯甲烷(分析纯)：西陇化工股份有限公司；月桂基葡糖苷(APG)：山东优索化工科技有限公司；竹纤维(长度10cm，细度300μm)：广东广宁县青皮竹；四(4-羧基苯基)卟啉(＞97.0％)：梯希爱(上海)化成工业发展有限公司。
性能测试：对实施例1-3、对比例1-9所制得的医用绷带进行性能测试；
测试绷带的拉伸强度：在20℃、相对湿度65％的条件下，样品尺寸长100mm、宽20mm、厚4mm，使用电子万能材料试验机测试样品拉伸性能，夹持距离为5mm，拉伸速度为50mm/min；每个样品测5次，取平均值；
抗菌性测试：参考《纺织品材料上耐细菌整理：评定》中改良实验方法来检测；
选用革兰氏阴性大肠杆菌作为测试菌种，空白对照为纯聚乙烯纺丝膜进行抗菌测试；试样尺寸2.5cm×2.5cm；在试样中心滴加25μL菌液，另一片试样覆盖后加上无菌砝码，接触时间10min，37℃培养24h后，记录细菌菌落数；抑菌率计算方法如下：R＝(B－A)/B×100％式中：R为抑菌率，％；A为实验组菌落数量，B为对照组菌落数量，CFU；
抗菌持久性测试：经过1000次标准洗涤，观察样品抗菌性；
体外细胞毒性测试：参考ISO10993-5《医疗器械生物学评价第5部分：体外细胞毒性试验》实验方法进行测试：将L-929(ATCCCL-1)小鼠成纤维细胞传代培养5次，接种于96孔板，添加杜氏改良Eagle培养基，转移至5％二氧化碳细胞培养箱，在37℃保温24h，孵育8h后添加50μL吩嗪硫酸甲酯溶液，37℃避光4h，用酶标仪测定490nm下的光密度来评价细胞增殖情况，当细胞存活率≥70％时可判定样品安全无毒；具体数据如表1；
表1
本发明提供一种可生物降解医用绷带及其制备方法，制备的医用绷带具有高效抗菌性、较好的力学性能、可降解性能以及生物相容性。
将实施例3与对比例1进行对比可知，本发明使用的是氧化海藻酸钠，氧化获得醛基化的海藻酸钠，使其具有更高的化学反应活性，因此将抗菌纤维制成的绷带基料在抗菌浸渍液中浸渍处理时，抗菌浸渍液中壳聚糖和抗菌纤维中的氧化海藻酸钠混合后快速交联，过程简单，时间可调，无须额外添加小分子交联剂，提高了生物安全性；
将实施例3与对比例2、对比例3进行对比可知，本发明在静电纺丝过程中引入聚乙烯醇、聚羟基丁酸酯共混提高力学性能与抗菌性能，抑制伤口的恶化；
将实施例3与对比例4进行对比可知，但是聚羟基丁酸酯亲油性，海藻酸钠为亲水性，在常规情况下很难共溶解，为此，以月桂基葡糖苷、三氯甲烷为乳化剂，使月桂基葡糖苷起到乳化作用，降低共混溶液的表面张力，超声均质使其共混得到纺丝液，然后制备抗菌纤维；
将实施例3与对比例5进行对比可知，本发明以双金属卟啉有机框架纳米颗粒作为抗菌剂，采用共混纺丝提高抗菌剂的牢固性，从而实现对细菌的高效杀灭，制备的双金属卟啉有机框架纳米颗粒具有良好的1O2产生能力；
将实施例3与对比例6、对比例7、对比例8、对比例9进行对比可知，本发明用处理后的壳聚糖作为抗菌浸渍液，使其通过形成氢键、金属-多酚配位、静电相互作用以及迈克尔加成/席夫碱反应等多种物理化学方式粘附在绷带基料上，通过其多酚介导方式将双金属卟啉有机框架纳米颗粒稳定牢固结合在绷带基料表面，从而提高其抗菌的持久性。
以上所述仅为本发明的为实施例，并非因此限制本发明的专利范围，凡是在本发明的发明构思下，利用本发明说明书所作的等效结构变换，或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。
Claims (9)
1.一种可生物降解医用绷带的制备方法，其特征在于，包括以下步骤：
S1：制备抗菌纤维：将氧化海藻酸钠、聚乙烯醇、去离子水超声搅拌，得到氧化海藻酸钠混合液，加入月桂基葡糖苷、三氯甲烷，超声均质，加入聚羟基丁酸酯、双金属基卟啉有机框架，连续振荡12h，再次超声均质，得到纺丝溶液，进行静电纺丝，得到抗菌纤维；
双金属基卟啉有机框架的制备包括以下步骤：
1)将对苯二甲酸、DMF混合搅拌，加入四氯化锆、DMF混合，搅拌条件下加入醋酸，超声分散，升温至110-120℃保温22-24h，离心、洗涤、干燥得到锆基有机框架；
2)将锆基有机框架、钛酸四丁酯、甲苯超声搅拌，在90-100℃保温22-24h，加入四(4-羧基苯基)卟啉、对苯二甲酸、DMF，超声搅拌30-60min，干燥，得到双金属基卟啉有机框架；
S2：用抗菌纤维制备绷带基料：抗菌纤维和天然纤维混合纺纱、混织，得到绷带基料；
S3：制备抗菌浸渍液：将壳聚糖、氢氧化钠溶液混合搅拌加入异丙醇、一氯乙酸，升温至60-65℃保温2-3h，将pH调节为7-7.2，用丙酮沉淀、过滤，洗涤、抽滤、真空干燥，得到O-羧甲基壳聚糖；将O-羧甲基壳聚糖、蒸馏水混合搅拌，超声分散20-30min，搅拌得到抗菌浸渍液；
S4：将绷带基料置于抗菌浸渍液中放置1-2h，取出后干燥，得到一种可生物降解医用绷带。
2.根据权利要求1所述的一种可生物降解医用绷带的制备方法，其特征在于，在制备抗菌纤维中，氧化海藻酸钠、聚乙烯醇、聚羟基丁酸酯、双金属基卟啉有机框架的质量比为2：10：2：0.5。
3.根据权利要求1所述的一种可生物降解医用绷带的制备方法，其特征在于，在制备抗菌浸渍液中，壳聚糖、一氯乙酸、异丙醇的质量体积比为15g：18g：150mL。
4.根据权利要求1所述的一种可生物降解医用绷带的制备方法，其特征在于，静电纺丝的工作条件为：电压20kV，接收距离16cm，流速为1.6mL/h。
5.根据权利要求1所述的一种可生物降解医用绷带的制备方法，其特征在于，超声均质的工作条件为：在超声波细胞粉碎机中以500W的功率均质8-10min。
6.根据权利要求1所述的一种可生物降解医用绷带的制备方法，其特征在于，氧化海藻酸钠的制备包括以下步骤：
将海藻酸钠、蒸馏水混合搅拌，加入高碘酸钠，避光反应22-24h后加入乙二醇终止反应，加入氯化钠、乙醇，析出沉淀，抽滤，用乙醇析出，抽滤，在30-40℃下真空干燥22-24h得到氧化海藻酸钠。
7.根据权利要求1所述的一种可生物降解医用绷带的制备方法，其特征在于，在步骤1)中对苯二甲酸、四氯化锆的摩尔质量比为0.3mmol：70mg。
8.根据权利要求1所述的一种可生物降解医用绷带的制备方法，其特征在于，在步骤2)中锆基有机框架、四(4-羧基苯基)卟啉、钛酸四丁酯的质量摩尔比为50mg：2.5mg：0.3mmol。
9.一种可生物降解医用绷带，其特征在于，由权利要求1-8中任一项所述制备方法制备得到。
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