CN116041884A - 一种光固化3d打印水凝胶超材料的制备方法及应用 - Google Patents
一种光固化3d打印水凝胶超材料的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种光固化3D打印水凝胶超材料的制备方法及应用,该方法包括以下步骤:步骤1、将不饱和单体、水性光引发剂、交联剂和光吸收剂溶于溶剂中,制备光敏3D打印水凝胶墨水;步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,进行光固化3D打印,得到共价交联的水凝胶超材料结构;步骤3、将共价交联的水凝胶超材料置于金属盐溶液中浸泡交联;步骤4、将共价交联的双网络水凝胶超材料结构经过水透析平衡,制得光固化3D打印水凝胶超材料。本发明通过对光敏水凝胶墨水组分和金属离子配位浓度的调控,调节水凝胶超材料生物抗菌支架的力学性能,水凝胶超材料生物抗菌支架具有很好的支撑性和柔软性。
Description
技术领域
本发明属于光固化水凝胶材料和医用器械领域,具体涉及一种光固化3D打印水凝胶超材料的制备方法及应用。
背景技术
随着寿命的延长,人们患心血管疾病、食管癌、支气管肺癌的风险也急骤加大,已经成为威胁人生命健康的主要疾病。支架作为介入手术中常用的一种医疗器械,是目前治疗这些疾病最常见、有效的治疗措施。然而,目前临床使用的支架多为金属和高分子聚合物材质。金属支架在植入人体后会引起各种严重的并发症,例如引起皮内细胞结构和功能的受损、侵蚀气管黏膜血管引起的大出血、支架选择或置入不当引起的移位和变形等。此外,金属支架植入物无法依据食管、气管、血管的狭窄程度进行有差异化的支撑,会造成支撑力度不足或支撑力度过大的情况发生。近年来,随着3D打印技术的快速发展,研究者开始致力于研发具有复杂结构的个性化定制3D打印聚合物支架,而目前可用于3D打印聚合物支架的材料主要为ABS、PLA、PA等工程塑料和光敏树脂。然而,这些聚合物支架的力学性能和柔顺性较差,在弯曲程度较大、区域较长的管壁服役时容易造成管壁再狭窄、血栓形成、管壁损等问题,并且这类支架在扩张时会发生严重的轴向缩短现象,较难实现好的治疗效果。因此,从临床实用要求考虑,生物支架必须具有一定的柔韧性和支撑性、能同机体组织相缝合和贴合,能经受手术操作而不破碎、并不对机体组织造成机械损伤的力学性能。
在众多柔性聚合物材料中,水凝胶凭借其与生物组织相近的性质,引起了研究人员的关注。水凝胶作为一类具有三维交联网络结构的亲水性高分子材料,因其良好的生物相容性、物质交换能力、可调的力学性能、柔韧性和弹性,在组织工程领域、药物缓释领域、细胞培养支架领域得到广泛应用。然而,现有的水凝胶存在的主要问题是力学强度不够高、溶胀性较差、弹性和可加工性差、稳定性不能满足要求,进而制约了其在生物医用领域的应用。
近年来,光固化3D打印水凝胶因其更能精确的构建模拟人体软组织的高度复杂三维立体结构,因而在生物领域被广泛地用于支架的构建。但是对于体内生物支架而言,对材料性能和尺寸精度的要求比较高。然而现有的光固化3D打印水凝胶机械性能较差、打印分辨率低、易溶胀、功能性较差,不适于构建具有超高精度的复杂三维体内生物支架。在功能性方面,水凝胶在体内移植会面临被细菌感染病变的风险,因此需要设计具有抗菌功能的水凝胶支架材料。在机械性能方面,水凝胶生物支架的一个重要特点是必须富有弹性、柔软性以及良好的支撑性,因此需要通过从分子网络和几何结构设计来获得所需的材料特性。寻求和研制兼具生物相容性好、柔韧性和弹性好、机械强度较高、安全性的光固化3D打印高强度耐溶胀水凝胶体系是目前要解决的难题之一。
发明内容
本发明的目的是提供一种光固化3D打印水凝胶超材料的制备方法及应用,解决了现有的光固化3D打印水凝胶机械性能较差、打印分辨率低、易溶胀、功能性较差的问题。
为了达到上述目的,本发明采用以下技术方案:一种光固化3D打印水凝胶超材料的制备方法,包括以下步骤:
步骤1、将不饱和单体、水性光引发剂、交联剂和光吸收剂溶于溶剂中,制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将步骤1中光敏3D打印水凝胶墨水放入料槽中,进行光固化3D打印,得到共价交联的水凝胶超材料结构。
步骤3、将步骤2中共价交联的水凝胶超材料置于金属盐溶液中浸泡,进行溶剂置换和金属配位交联。
步骤4、将步骤3中的共价交联和金属配位交联的双网络水凝胶超材料结构经过水透析平衡,制得高强韧的光固化3D打印水凝胶超材料。
进一步地,步骤1中不饱和单体为丙烯酰胺、羟乙基丙烯酰胺、二甲基丙烯酰胺、N-异丙基丙烯酰胺、丙烯酰吗啉、丙烯酸、乙烯基咪唑、N-乙烯吡咯烷酮中的一种或两种;不饱和单体在光敏3D打印水凝胶墨水中的质量百分比为30~60%。
进一步地,步骤1中水性光引发剂为苯基2,4,6-三甲基苯甲酰基磷酸锂盐、偶氮二异丁脒盐酸盐、苯基双2,4,6-三甲基苯甲酰基磷酸钠盐、苯基双2,4,6-三甲基苯甲酰基磷酸锂盐、聚乙二醇/苯基双2,4,6-三甲基苯甲酰基氧化膦中的一种;光引发剂试剂与不饱和单体质量的质量百分比为0.1~1%。
进一步地,步骤1中交联剂为N,N'-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、丙烯酸酸锌、甲基丙烯酸锌、含双键的脲基交联剂中的一种;交联剂与不饱和单体质量百分比为0.2~2%。
进一步地,步骤1中光吸收剂为柠檬黄、核黄素、2,2'-二羟基-4,4'-二甲氧基二苯甲酮-5,5'-二磺酸钠中的一种;光吸收剂与光敏3D打印水凝胶墨水的质量百分比为2~6‰。
进一步地,步骤1中溶剂为水和二甲基亚砜的混合溶剂;水和二甲基亚砜的质量比为(7~3):(3~7)。
进一步地,步骤2中光固化3D打印的光源波长为385~405nm;光源强度为300~800mW;单层曝光时间为5~60s;单层切片厚度为0.05~0.2mm。
进一步地,步骤3中金属盐溶液为硝酸锌、错酸锌、氯化锌中的一种;金属盐溶液的浓度为0.1~1.0mol/L;水凝胶超材料结构在金属盐溶液中的浸泡时间为3~14天;水凝胶超材料结构经水透析平衡所需的时间为3~14天。
本发明采用的另一技术方案如下:一种制备方法获得的光固化3D打印水凝胶超材料。
本发明采用的另一技术方案如下:光固化3D打印水凝胶超材料在制作生物抗菌支架方面的应用,生物抗菌支架为心脏支架、血管支架、气管支架、食管支架中的任意一种或两种以上。
本发明的有益效果:
1、本发明制备得到的光固化3D打印水凝胶超材料具有可调控的力学性能和可调的力学超材料结构;
2、本发明提供的方法能够制备机械强度较高、生物相容性好、柔韧性和弹性好、结构可设计的水凝胶超材料结构。
3、通过金属有机配位结构形成的双网络结构水凝胶不仅改善了水凝胶的力学性能,而且还赋予了水凝胶优异的抗菌性能。水凝胶超材料具有打印分辨率高、不宜溶胀等优点,适于构建具有超高精度的复杂三维体内生物支架;
4、利用光固化3D打印的优势,可实现水凝胶超材料生物抗菌支架的个性化快速制造。
5、与传统的金属支架和聚合支架相比,利用本发明方法制备得到的水凝胶超材料制备得到的生物抗菌支架具有优异的力学性能和柔顺性,在弯曲程度较大、区域较长的管壁服役时不会造成管壁再狭窄、血栓形成、管壁损等问题,并且这类支架在扩张时不会发生严重的轴向缩短现象,具有非常好的应用前景。
附图说明
图1为本发明光固化3D打印水凝胶超材料制备的流程示意图;
图2为实施例1中光固化3D打印水凝胶超材料的结构图;
图3为实施例2中光固化3D打印水凝胶超材料的结构图;
图4为实施例3中光固化3D打印水凝胶超材料的结构图;
图5为实施例4中光固化3D打印水凝胶超材料的结构图;
图6为实施例5中光固化3D打印水凝胶超材料的结构图;
图7为实施例6中光固化3D打印水凝胶超材料的结构图;
图8为实施例7中光固化3D打印水凝胶超材料的结构图;
图9为实施例8中光固化3D打印水凝胶超材料的结构图;
图10为实施例9中水凝胶超材料生物抗菌支架的结构图;
图11(a)为实施例9中水凝胶超材料生物抗菌支架抗菌测试前的抗菌性能图;
图11(b)为实施例9中水凝胶超材料生物抗菌支架抗菌测试后的抗菌性能图;
图12为对比例1中光固化3D打印水凝胶超材料的结构图;
图13为实施例1~实施例4中光固化3D打印水凝胶超材料的机械性能测试曲线图;
图14为实施例5~实施例8中光固化3D打印水凝胶超材料的机械性能测试曲线图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,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。
本发明一种光固化3D打印水凝胶超材料的制备方法最关键的步骤是利用混合溶剂来调控水凝胶的打印性能,而利用金属离子配位和水平衡后处理也是是增强机械特性最关键的步骤,并且利用金属离子配位的组分赋予其优异的抗菌性能。
以下通过实施例1-9以及对比例对本发明提供的一种光固化3D打印水凝胶超材料的制备方法进行详细的阐述。
实施例1
如图1所示,本发明一种光固化3D打印水凝胶超材料的制备方法,包括以下步骤:
步骤1、将35.54g丙烯酰胺、9.41g乙烯基咪唑、0.22g水溶性光引发剂LAP、0.34g脲基交联剂和0.06g柠檬黄溶解在100mL水和二甲亚砜(质量比7:3)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间10s;单层切片厚度优选为0.1mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应7天;
步骤4、将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡7天得到光固化3D打印双网络水凝胶超材料。
实施例2
步骤1、将34.12g丙烯酰胺、11.29g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.34g脲基交联剂,0.006g柠檬黄溶解在100mL水和二甲亚砜(质量比7:3)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度500mW;单层曝光时间20s;单层切片厚度优选为0.15mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应10天。
步骤4、将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡10天得到光固化3D打印双网络水凝胶超材料。
实施例3
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.34g脲基交联剂,0.006g柠檬黄溶解在100mL水和二甲亚砜(质量比7:3)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度600mW;单层曝光时间30s;单层切片厚度优选为0.05mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应5天。
步骤4、最后将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡5天得到光固化3D打印双网络水凝胶超材料。
实施例4
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.34gN,N-亚甲基双丙烯酰胺,0.006g柠檬黄溶解在100mL水和二甲亚砜(质量比6:4)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间20s;单层切片厚度优选为0.1mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应5天。
步骤4、最后将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡5天得到光固化3D打印双网络水凝胶超材料。
实施例5
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.34gN,N-亚甲基双丙烯酰胺,0.006g柠檬黄溶解在100mL水和二甲亚砜(质量比5:5)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间20s;单层切片厚度优选为0.1mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应10天。
步骤4、最后将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡10天得到光固化3D打印双网络水凝胶超材料。
实施例6
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.34g聚乙二醇二甲基丙烯酸酯,0.006g柠檬黄溶解在100mL水和二甲亚砜(质量比4:6)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间20s;单层切片厚度优选为0.1mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应12天。
步骤4、最后将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡12天得到光固化3D打印双网络水凝胶超材料。
实施例7
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.34g脲基交联剂,0.006g柠檬黄溶解在100mL水和二甲亚砜(质量比3:7)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间20s;单层切片厚度优选为0.1mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应7天。
步骤4、最后将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡7天得到光固化3D打印双网络水凝胶超材料。
实施例8
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.34g脲基交联剂,0.006g核黄素溶解在100mL水和二甲亚砜(质量比7:3)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间20s;单层切片厚度优选为0.05mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应7天。
步骤4、最后将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡7天得到光固化3D打印双网络水凝胶超材料。
实施例9
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.57g脲基交联剂,0.006g 2,2'-二羟基-4,4'-二甲氧基二苯甲酮-5,5'-二磺酸钠溶解在100mL水和二甲亚砜(质量比7:3)的混合溶剂中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间10s;单层切片厚度优选为0.1mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
步骤3、将共价交联的水凝胶超材料浸泡在0.1mol/L的硝酸锌溶液中进行溶剂置换和金属配位反应7天。
步骤4、将溶剂置换和金属配位后的水凝胶超材料结构经过缓慢的水透析平衡7天得到光固化3D打印双网络水凝胶超材料。
对比例1
步骤1、将32.69g丙烯酰胺、13.18g乙烯基咪唑、0.23g水溶性光引发剂LAP,0.57g脲基交联剂,0.006g柠檬黄溶解在100mL水中制备光敏3D打印水凝胶墨水。
步骤2、利用软件建立三维超材料结构模型,将光敏3D打印水凝胶墨水放入料槽中,在3D打印的参数为:光源波长405nm;光源强度800mW;单层曝光时间10s;单层切片厚度优选为0.1mm的条件下进行光固化3D打印来得到共价交联的水凝胶超材料结构。
实验结果:
图2~图9为实施例1~实施例8的光固化3D打印双网络水凝胶超材料结构图,由图2~图9可以看出,水凝胶超材料结构具有很好的形状保真度。
图12为对比例1的光固化3D打印双网络水凝胶超材料结构图,由图12可以看出,水凝胶超材料结构有明显的粘连和发胀。
图10为实施例9的光固化3D打印水凝胶超材料生物抗菌支架,由图10可以看出,水凝胶超材料生物抗菌支架具有很好的形状保真度。
图11(a)与图11(b)为实施例9的光固化3D打印水凝胶超材料生物抗菌支架对金黄色葡萄球菌(S.aureus)的抗菌性能,将水凝胶浸入培养基中后,在共培养24小时后,金黄色葡萄球菌菌株的生长受到抑制,且从培养前后的琼脂平板数的数量上讲,水凝胶超材料生物抗菌支架对金黄色葡萄球菌具有很好的抗菌性能。
图13为实施例1~实施例4的光固化3D打印双网络水凝胶超材料的机械性能测试,力学性能测试结果显示,本发明光固化3D打印双网络水凝胶超材料在应变为863±14%时,拉伸强度达到5.19±0.72MPa,弹性模量为2.11±0.01MPa,韧性为22.72±1.75MJ/m3。
图14为实施例5~实施例8的光固化3D打印双网络水凝胶超材料的机械性能测试,力学性能测试结果显示,本发明光固化3D打印双网络水凝胶超材料在应变为552±24%时,拉伸强度达到1.85±0.23MPa,弹性模量为0.41±0.01MPa,韧性为3.63±0.41MJ/m3。
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但应当认识到上述的描述不应被认为是对本发明的限制。在本领域技术人员阅读了上述内容后,对于本发明的多种修改和替代都将是显而易见的。因此,本发明的保护范围应由所附的权利要求来限定。
Claims (10)
1.一种光固化3D打印水凝胶超材料的制备方法,其特征在于,包括以下步骤:
步骤1、将不饱和单体、水性光引发剂、交联剂和光吸收剂溶于溶剂中,制备光敏3D打印水凝胶墨水;
步骤2、利用软件建立三维超材料结构模型,将所述步骤1中光敏3D打印水凝胶墨水放入料槽中,进行光固化3D打印,得到共价交联的水凝胶超材料结构;
步骤3、将所述步骤2中共价交联的水凝胶超材料置于金属盐溶液中浸泡,进行溶剂置换和金属配位交联;
步骤4、将所述步骤3中的共价交联和金属配位交联的双网络水凝胶超材料结构经过水透析平衡,制得高强韧的光固化3D打印水凝胶超材料。
2.如权利要求1所述的光固化3D打印水凝胶超材料的制备方法,其特征在于,步骤1中所述不饱和单体为丙烯酰胺、羟乙基丙烯酰胺、二甲基丙烯酰胺、N-异丙基丙烯酰胺、丙烯酰吗啉、丙烯酸、乙烯基咪唑、N-乙烯吡咯烷酮中的一种或两种;所述光敏3D打印水凝胶墨水中不饱和单体的质量占比为30~60%。
3.如权利要求1所述的光固化3D打印水凝胶超材料的制备方法,其特征在于,步骤1中所述水性光引发剂为苯基2,4,6-三甲基苯甲酰基磷酸锂盐、偶氮二异丁脒盐酸盐、苯基双2,4,6-三甲基苯甲酰基磷酸钠盐、苯基双2,4,6-三甲基苯甲酰基磷酸锂盐、聚乙二醇/苯基双2,4,6-三甲基苯甲酰基氧化膦中的一种;所述光引发剂试剂在不饱和单体中质量占比为0.1~1%。
4.如权利要求1所述的光固化3D打印水凝胶超材料的制备方法,其特征在于,步骤1中所述交联剂为N,N'-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、丙烯酸酸锌、甲基丙烯酸锌、含双键的脲基交联剂中的一种;所述交联剂在不饱和单体中质量占比为0.2~2%。
5.如权利要求1所述的光固化3D打印水凝胶超材料的制备方法,其特征在于,步骤1中所述光吸收剂为柠檬黄、核黄素、2,2'-二羟基-4,4'-二甲氧基二苯甲酮-5,5'-二磺酸钠中的一种;所述光吸收剂在光敏3D打印水凝胶墨水中的质量占比为2~6‰。
6.如权利要求1所述的光固化3D打印水凝胶超材料的制备方法,其特征在于,步骤1中所述溶剂为水和二甲基亚砜的混合溶剂;所述水和二甲基亚砜的质量比为(7~3):(3~7)。
7.如权利要求1所述的光固化3D打印水凝胶超材料的制备方法,其特征在于,步骤2中所述光固化3D打印的光源波长为385~405nm;光源强度为300~800mW;单层曝光时间为5~60s;单层切片厚度为0.05~0.2mm。
8.如权利要求1所述的光固化3D打印水凝胶超材料的制备方法,其特征在于,步骤3中所述金属盐溶液为硝酸锌、错酸锌、氯化锌中的一种;所述金属盐溶液的浓度为0.1~1.0mol/L;所述水凝胶超材料结构在金属盐溶液中的浸泡时间为3~14天;所述水凝胶超材料结构经水透析平衡所需的时间为3~14天。
9.一种如权利要求1-8中任意一种制备方法获得的光固化3D打印水凝胶超材料。
10.如权利要求9所述光固化3D打印水凝胶超材料在制作生物抗菌支架方面的应用,所述生物抗菌支架为心脏支架、血管支架、气管支架、食管支架中的任意一种或两种以上。
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