CN116370721A - 一种全可降解水凝胶涂层弹簧圈及其制备方法 - Google Patents
一种全可降解水凝胶涂层弹簧圈及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种全可降解水凝胶涂层弹簧圈及其制备方法,所述全可降解水凝胶涂层弹簧圈包括弹簧圈圈体,其中,所述弹簧圈圈体表面涂敷有水凝胶载药涂层,所述弹簧圈圈体内设置有抗解旋丝,所述弹簧圈圈体为可降解圈体,所述可降解圈体的材质为含有显影材料的可降解基材。本发明提供的全可降解水凝胶涂层弹簧圈及其制备方法,具备完全可降解性能,生物相容性好,具有致密填塞性、显影性能佳且安全可靠。
Description
技术领域
本发明涉及一种微创介入的医疗器械及其制备方法,尤其涉及一种全可降解水凝胶涂层弹簧圈及其制备方法。
背景技术
动脉瘤、消化道出血、肿瘤、富血肿瘤等是动脉常见的出血性疾病。以动脉瘤为例,若瘤体破裂,患者可能危及生命。对于该类疾病的治疗以前往往需要通过外科手术的方法,风险和创伤较大,尤其对于老年患者。随着医疗科技的进步和发展,血管内介入治疗已成为此类疾病的首选治疗方案。在众多方案中,弹簧圈栓塞治疗因其安全可靠、植入稳定、输送便捷等优势脱颖而出,受到医生和研发人员的青睐。
目前,弹簧圈栓塞器械根据材料和结构可分为裸金属弹簧圈和表面修饰类弹簧圈。裸金属弹簧圈是发展历史最久也是临床最常用的弹簧圈,其圈体材料为铂钨合金,自带金属显影功能,生物相容性较好,植入病灶后因血栓机制闭塞病变部位达到治疗效果。表面修饰类弹簧圈又分生物活性表面涂层弹簧圈、水凝胶弹簧圈和带纤维毛弹簧圈。生物活性表面涂层弹簧圈是指在裸金属弹簧圈的表面涂上具有促血栓作用的药物涂层,如凝血酶原复合物、维生素K、蛇毒血凝酶和硫酸鱼精蛋白等;水凝胶弹簧圈是指在弹簧圈内有水凝胶丝芯或圈体表层有水凝胶涂层,遇血液后膨胀,增加了器械的填塞性,同时水凝胶体积的额外膨胀增加了病灶的填充率,可减少弹簧圈的植入量,从而减轻患者经济负担及围术期时间;带纤维毛弹簧圈是指在弹簧圈体外嵌有高分子材质的纤毛,如尼龙、聚丙烯、聚四氟乙烯和聚乙交酯-丙交酯共聚物(PGLA)等。其通过微纤毛机械重叠,在病灶处搭建致密网络,改变血流动力学,达到快速稳定致栓的效果。目前临床使用的所有弹簧圈的圈体材质均为100%的铂钨合金,不具备可降解性能。在植入物到达病灶后,由于机械闭塞或血栓机制抑制血供,但植入物会永久留在体内。对于动脉瘤而言,金属弹簧圈的植入不能使瘤体缩小,因而会持续对瘤外的神经组织进行压迫,无法消除占位效应。金属材料的长期植入也可能会产生金属毒性,对人体造成一定的损害,其远期安全性仍有待考察。此外,金属的伪影也会影响术后随访期间的影像质量,给临床医生带来些许不便。
目前,有专利文献提及使用镁基合金制备可降解弹簧圈,但镁合金在体内的降解速度过快,病灶处还未达到栓塞治疗效果就可能已经降解完全;也有专利文献提及使用聚左旋乳酸(PLLA)缝合线绕制制备可降解弹簧圈,但此圈的物理强度有待考察且能否有良好的显影效果尚且未知。
因此,为解决上述问题,开发一款具备可降解性能的,生物相容性好,具有致密填塞性、显影性能佳且安全可靠的医用弹簧圈具有重大意义。
发明内容
本发明所要解决的技术问题是提供一种全可降解水凝胶涂层弹簧圈及其制备方法,具备可降解性能,生物相容性好,具有致密填塞性、显影性能佳且安全可靠。
本发明为解决上述技术问题而采用的技术方案是提供一种全可降解水凝胶涂层弹簧圈,包括弹簧圈圈体,其中,所述弹簧圈圈体表面涂敷有水凝胶载药涂层,所述弹簧圈圈体内设置有抗解旋丝,所述弹簧圈圈体为可降解圈体,所述可降解圈体的材质为含有显影材料的可降解基材。
进一步地,所述可降解基材为聚乳酸、聚左旋乳酸、聚羟基乙酸、聚乙交酯-丙交酯共聚物、聚乙二醇、聚对二氧环己酮、聚己内酯中的任意一种或多种的组合。
进一步地,所述显影材料为硫酸钡、钨粉、钽粉、磷酸铋、羟基磷灰石、三碘苯酚或其他含碘物质中的任意一种或多种的组合。
进一步地,所述可降解圈体的丝径范围在0.02-0.2mm之间,一级线圈的直径在0.05-1mm之间,二级螺旋线圈的直径在0.2-5mm之间,分子量的大小为1万-6.6万。
进一步地,所述可降解基材为聚乙交酯-丙交酯共聚物,K值范围介于0.12-0.18之间。
进一步地,所述抗解旋丝的材质为聚丙烯、聚乙烯、聚异戊二烯、镍钛合金、镁合金、聚对二氧环己酮中的任意一种;所述水凝胶载药涂层的厚度为0.01-1mm;所述水凝胶载药涂层是聚丙烯酸类凝胶涂层、聚丙烯酰胺类凝胶涂层、聚碳酸脂类凝胶涂层、聚氨酯类凝胶涂层、两亲性嵌段共聚物类凝胶涂层、透明酯酸类凝胶涂层、壳聚糖类凝胶涂层、海藻酸盐类凝胶涂层、聚乙二醇类凝胶涂层、聚乙烯醇类凝胶涂层、卡拉胶类凝胶涂层中的任意一种。
本发明为解决上述技术问题还提供一种上所述的全可降解水凝胶涂层弹簧圈的制备方法,其中,包括如下步骤:步骤S1:将可降解基材与显影材料直接共混、接枝或沉积后,通过静电纺丝技术制成细丝,再将细丝经芯棒模具绕制缠结,最后将芯棒和细丝整体放入可精密温控的热定型烘箱进行定型;在室温下退火,制备得到具有显影性能的可降解弹簧圈;步骤S2:将抗解旋丝的头尾两端置入可降解弹簧圈内,并与弹簧圈的头尾两端通过焊接工艺或胶粘方式连接形成一体;步骤S3:制备水凝胶载药溶液,将水凝胶载药溶液涂覆于弹簧圈圈体表面,干燥成膜,在弹簧圈圈体表面形成水凝胶载药涂层。
进一步地,所述步骤S1中芯棒是直径为0.1-0.5mm之间的不锈钢棒材;细丝在绕制时,线圈之间的间隙宽度为0.0008英寸-0.008英寸,绕制角度为65°-80°;热定型温度的范围为120℃-250℃,热定型的时间为5-45分钟。
进一步地,所述步骤S2采用的胶粘剂为聚酯类、聚氨酯类、聚酰胺类、α-氰基丙烯酸酯类等胶粘剂中的任意一种或多种。
进一步地,所述步骤S3包括:将一定质量的海藻酸钠溶于生理盐水中,制得溶液A;将一定质量的丙烯酰胺类物质溶于去离子水中,再依次加入一定质量的碳酸钙和促血栓药物进行均匀混合,制得溶液B;将溶液A和溶液B混合,进行均匀搅拌和加热,再加入引发剂进行聚合反应,制得溶液C;将溶液C自然冷却后可得水凝胶溶液。
进一步地,在混合后的溶液C中,所述海藻酸钠的质量浓度为0.1-3%;所述丙烯酰胺类物质的质量浓度为5-40%;所述碳酸钙的质量浓度为2-6%;所述促血栓药物的质量浓度为0.1-1.5%;所述引发剂的质量浓度为2-8%;所述丙烯酰胺类物质是N-异丙基丙烯酰胺、2-丙烯酰氨基-2-甲基丙磺酸中的任意一种;所述促血栓药物是维生素K、氨甲苯酸、蛇毒血凝酶、凝血酶原复合物、氨基己酸、凝血酶和冻干人纤维蛋白原、安络血、酚磺乙胺、班尼芬、阿尔法9SD凝结因素中的任意一种或多种;所述引发剂是过硫酸铵、过氧化氢、过硫酸钾、过氧化苯甲酰、过氧化甲乙酮、过氧化苯甲酰叔丁酯中的任意一种;加热反应的温度范围为30-80℃,聚合反应时间为1-5h。
进一步地,所述步骤S3中涂覆方式为喷涂、刷涂、静电涂敷、浸涂、旋涂或延流;涂覆完成后干燥温度范围为20-230℃,压力范围为0.001-3bar,干燥时间为2-256h。
本发明对比现有技术有如下的有益效果:本发明提供的全可降解水凝胶涂层弹簧圈,栓塞致密性高、生物相容性好、显影性能优异且具备完全可降解性能,从而解决目前弹簧圈栓塞填充率低、金属植入物无法降解而产生占位效应等问题,同时又满足弹簧圈在推送过程中的显影功能。具体优点如下:
1、本发明的弹簧圈在人体内最终会完全降解。对于动脉瘤而言,可完全消除不可降解材料带来的占位效应,减轻患者痛苦;
2、本发明的弹簧圈由一种或多种可降解材料混合制成,通过调整原材料的组分可调节弹簧圈的物理强度、降解时间等性能。
3、本发明的弹簧圈中的硫酸钡或碘等非金属显影物质在患者体内不会产生金属伪影,便于医生术中或术后的观察。
4、本发明的弹簧圈表面的水凝胶载药涂层遇水或血液可快速膨胀,最终的体积可达膨胀前的3-5倍,大幅增加栓塞密度,减少线圈的植入数量,从而减轻患者经济负担及医生围术期时间。
5、本发明的弹簧圈表面的水凝胶载药涂层内含有促血栓药物,在植入至病灶区域后可与血液反应,快速致栓,增加栓塞密度及闭塞成功率。
6、本发明的含水凝胶载药涂层的弹簧圈相较于含凝胶内芯的弹簧圈,在膨胀时不会被限制在圈体内,因而具有更大的膨胀体积,涂层内的促血栓药物也能更快速地响应。
附图说明
图1为本发明实施例的弹簧圈结构示意图;
图2为图1的剖面结构示意图;
图3为本发明弹簧圈治疗动脉瘤示意图;
图4为本发明弹簧圈横截面结构示意图。
具体实施方式
下面结合附图和实施例对本发明作进一步的描述。
图1为本发明实施例的弹簧圈结构示意图;图2为图1的剖面结构示意图;图4为本发明弹簧圈横截面结构示意图。
请参见图1、图2和图4,本发明提供的全可降解水凝胶涂层弹簧圈,其主要由弹簧圈圈体10、水凝载药涂层55和抗解旋丝20,其中弹簧圈圈体10为完全可降解弹簧圈圈体,并具有可显影微粒30。
可降解弹簧圈圈体材料为全可降解的医用高分子材料,可以是聚乳酸(PLA)、聚左旋乳酸(PLLA)、聚羟基乙酸(PGA)、聚乙交酯-丙交酯共聚物(PGLA)、聚乙二醇(PEG)、聚对二氧环己酮(PDO)、聚己内酯(PCL)等中的任意一种或多种的混合。在可降解材料中直接共混或接枝或沉积显影材料后,可使弹簧圈在X射线下具备显影功能。显影材料可以是硫酸钡(BaSO4)、钨粉(W)、钽粉(Ta)、磷酸铋(BiPO4)、羟基磷灰石(HAP)、三碘苯酚或其他含碘物质等中的任意一种或多种,优选含碘的物质,如碘海醇、碘化油等。将复合材料经静电纺丝技术制成细丝,再将细丝经芯棒模具绕制缠结,最后将芯棒和细丝整体放入可精密温控的热定型烘箱进行定型。芯棒可以是直径为0.05-1mm之间的不锈钢棒材,直径范围优选0.1-0.5mm;细丝在绕制时,线圈之间的间隙宽度可以是0.0005英寸-0.01英寸,绕制角度可以是60°-90°,优选间隙宽度范围为0.0008英寸-0.008英寸,优选绕制角度范围为65°-80°;热定型温度的范围可以是60℃-800℃,优选温度范围为120℃-250℃;热定型的时间范围可以是3-60分钟,优选时间范围为5-45分钟。完毕后取出器材并在室温下退火,便可制备具有显影性能的可降解弹簧圈。弹簧圈丝径的范围在0.02-0.2mm之间,一级线圈的直径在0.05-1mm之间,二级螺旋圈的直径在0.2-5mm之间。通过调整可降解材料的分子量或组分,可以调节弹簧圈的硬度、物理性能、降解周期等性能。
弹簧圈的柔软度或柔顺性是由弹簧的K因子决定的,K因子又与弹簧初级丝的厚度及缠绕的紧密度成比例。K值越小,弹簧圈柔顺性越好。通过调整可降解聚合物材料的配方或比例可以纺丝出不同丝径和物理强度的细丝,从而可制备出不同柔顺性的弹簧圈。一般的,弹簧圈的K值范围介于0.1-0.35之间。一般的,弹簧圈的K值不会超过0.5,若超过0.5,则其柔顺性可能会变差,可能不适于动脉瘤等疾病的治疗,易造成病灶处破裂。一般的,弹簧圈的K值不会低于0.1,若低于0.1,则其会因过于柔软而导致物理强度可能不够,无法达到治疗的效果。此方案中,例如使用一定量的PLA和PGA共聚可得K值约为0.12-0.18的PGLA共聚物,其柔顺性较好,再通过调整分子量的大小改变其降解性能和力学性能。
抗解旋丝的材质可以是聚丙烯(PP)、聚乙烯(PE)、聚异戊二烯(PI)、镍钛合金、镁合金等中的任意一种。抗解旋丝优选聚对二氧环己酮(PDO)材质。PDO材料中的醚键赋予了其良好的柔韧性和抗拉强度,且抗弯曲疲劳性好,在常温下可弯折多次而不变形损坏。选用高分子量的PDO作为抗解旋丝,其所承受的拉力可大于1N,在术中更不容易解旋。PDO材料又具备良好的生物相容性和生物可降解性,可在体内自然降解,且PDO材质稳定,不会与弹簧圈其他组分材料发生不兼容性的反应。抗解旋丝的整体长度不超过弹簧圈长度,直径在0.01-0.3mm之间。抗解旋丝的头尾两端以焊接形式或使用胶粘剂与弹簧圈头尾两端连接形成一体。胶粘剂可以是聚酯类、聚氨酯类、聚酰胺类、α-氰基丙烯酸酯类等胶粘剂中的任意一种或多种。
水凝胶载药涂层的材料可以是聚丙烯酸类凝胶涂层、聚丙烯酰胺类凝胶涂层、聚碳酸脂类凝胶涂层、聚氨酯类凝胶涂层、两亲性嵌段共聚物类凝胶涂层、透明酯酸类凝胶涂层、壳聚糖类凝胶涂层、海藻酸盐类凝胶涂层、聚乙二醇类凝胶涂层、聚乙烯醇类凝胶涂层、卡拉胶类凝胶涂层等中的任意一种。任意能使得水凝胶具备遇水膨胀及载药性能的原材料都可适用于此。水凝胶涂层的原材料优选使用丙烯酰胺类原料,因其结构单元中含酰胺基团,容易形成氢键,从而具有更优的水溶性和化学活性。将一定质量的海藻酸钠溶于生理盐水中,制得溶液A;将一定质量的丙烯酰胺类物质溶于去离子水中,再依次加入一定质量的碳酸钙和促血栓药物进行均匀混合,制得溶液B。将溶液A和溶液B混合,进行均匀搅拌和加热,再加入引发剂进行聚合反应,制得溶液C。将溶液C自然冷却后可得水凝胶溶液。在混合后整体溶液中,海藻酸钠的质量浓度为0.1-3%,优选0.1-1.5%;丙烯酰胺类物质的质量浓度为5-40%,优选10-30%;碳酸钙的质量浓度为2-6%,优选3.5-5%;促血栓药物的质量浓度为0.1-1.5%,优选0.5-1%;引发剂的质量浓度为2-8%,优选3-5%。丙烯酰胺类物质可以是N-异丙基丙烯酰胺、2-丙烯酰氨基-2-甲基丙磺酸中的任意一种。促血栓药物可以是维生素K、氨甲苯酸、蛇毒血凝酶、凝血酶原复合物、氨基己酸、凝血酶和冻干人纤维蛋白原、安络血、酚磺乙胺、班尼芬、阿尔法9SD凝结因素等中的任意一种或多种。引发剂可以是过硫酸铵、过氧化氢、过硫酸钾、过氧化苯甲酰、过氧化甲乙酮、过氧化苯甲酰叔丁酯等中的任意一种。加热反应的温度范围为30-80℃,优选40-55℃;聚合反应时间为1-5h,优选1.5-3h。
将抗解旋丝的头尾两端置入弹簧圈圈体内,并与弹簧圈的头尾两端通过焊接工艺或胶粘技术进行连接形成一体。特殊地,抗解旋丝在弹簧圈的中心位置,从而使得其在输送阶段受力更均匀。接着,将水凝胶载药溶液涂覆于弹簧圈圈体表面。涂覆方式可以是喷涂、刷涂、静电涂敷、浸涂、旋涂或延流等,优选喷涂的方式,因此方法涂覆更均匀且厚度可控。涂层的厚度范围在0.01-1mm之间,优选0.01-0.5mm,更优选0.01-0.1mm。涂覆完成后将涂层进行干燥成膜,温度范围为20-230℃,优选30-120℃;压力范围为0.001-3bar,优选0.002-1bar;干燥时间2-256h,优选6-96h。成膜完成后自然冷却,得到最终的弹簧圈产品。如图3所示,15为动脉瘤瘤体、25为弹簧圈、35为血管,膨胀后的弹簧圈25几乎填满动脉瘤瘤体15;图4中45为弹簧圈圈体,55为水凝胶载药涂层。
实施例1
本实施例的全可降解水凝胶涂层弹簧圈原材料为分子量高的聚对二氧环己酮(PDO)。PDO在医疗领域常用作医用缝合线,其生物相容性好,在体内可完全降解,且高分子量的PDO的降解周期约6-12个月,避免了器械还未达到栓塞治疗效果就提前降解的风险。将PDO与硫酸钡(BaSO4)、磷酸铋(BiPO4)或含碘物质的非金属显影材料反应混合后,可具备在X射线下的显影性,且不会产生金属伪影。材料经纺丝、绕制、热定型等精密工艺制成弹簧圈。将抗解旋丝置入弹簧圈圈体中,并将其头尾两端以焊接或粘胶的形式与弹簧圈头尾两端连接,最后将水凝胶载药溶液涂覆于弹簧圈圈体表面。抗解旋丝的材料为分子量更高的PDO。水凝胶载药涂层是基于丙烯酰胺为原料的材料。将一定量的海藻酸钠溶于生理盐水中,制得溶液A;将一定量的丙烯酰胺类物质溶于去离子水中,再依次加入一定量的碳酸钙和促血栓药物进行均匀混合,制得溶液B。将溶液A和溶液B混合,进行均匀搅拌和加热,再加入引发剂进行聚合反应,制得溶液C。将溶液C自然冷却后可得水凝胶溶液。在混合后整体溶液中,海藻酸钠的质量浓度为0.5%;丙烯酰胺类物质的质量浓度为20%;碳酸钙的质量浓度为4%;促血栓药物的质量浓度为0.5%;引发剂的质量浓度为4%。丙烯酰胺类物质可以是N-异丙基丙烯酰胺、2-丙烯酰氨基-2-甲基丙磺酸中的任意一种。促血栓药物可以是维生素K、氨甲苯酸、蛇毒血凝酶、凝血酶原复合物、氨基己酸、凝血酶和冻干人纤维蛋白原、安络血、酚磺乙胺、班尼芬、阿尔法9SD凝结因素等中的任意一种或多种。引发剂可以是过硫酸铵、过氧化氢、过硫酸钾、过氧化苯甲酰、过氧化甲乙酮、过氧化苯甲酰叔丁酯等中的任意一种。加热反应的温度范围为50℃;聚合反应时间为2h。水凝胶溶液制备后采用喷涂方式涂覆于弹簧圈圈体表面,厚度为0.05mm,干燥温度70℃,压力0.5bar,干燥时间24h。
实施例2
该实施例的整体实施过程与实施例一大体一致,与实施例一的区别在于弹簧圈原材料的组分不同。该弹簧圈的原料为聚己内酯(PCL)和聚乳酸(PLA)的共聚物。PCL和PLA都具备一定的形状记忆功能,可制备形圈能力较优的弹簧圈;PCL的降解周期较久,PLA的降解周期较短,其共聚物综合了它们的降解时间。
虽然本发明已以较佳实施例揭示如上,然其并非用以限定本发明,任何本领域技术人员,在不脱离本发明的精神和范围内,当可作些许的修改和完善,因此本发明的保护范围当以权利要求书所界定的为准。
Claims (13)
1.一种全可降解水凝胶涂层弹簧圈,包括弹簧圈圈体,其特征在于,所述弹簧圈圈体表面涂敷有水凝胶载药涂层,所述弹簧圈圈体内设置有抗解旋丝,所述弹簧圈圈体为可降解圈体,所述可降解圈体的材质为含有显影材料的可降解基材。
2.如权利要求1所述的全可降解水凝胶涂层弹簧圈,其特征在于,所述可降解基材为聚乳酸、聚左旋乳酸、聚羟基乙酸、聚乙交酯-丙交酯共聚物、聚乙二醇、聚对二氧环己酮、聚己内酯中的任意一种或多种的组合。
3.如权利要求1所述的全可降解水凝胶涂层弹簧圈,其特征在于,所述显影材料为硫酸钡、钨粉、钽粉、磷酸铋、羟基磷灰石、三碘苯酚或其他含碘物质中的任意一种或多种的组合。
4.如权利要求1所述的全可降解水凝胶涂层弹簧圈,其特征在于,所述可降解圈体的丝径范围在0.02-0.2mm之间,一级线圈的直径在0.05-1mm之间,二级螺旋线圈的直径在0.2-5mm之间,分子量的大小为1万-6.6万。
5.如权利要求1所述的全可降解水凝胶涂层弹簧圈,其特征在于,所述可降解基材为聚乙交酯-丙交酯共聚物,K值范围介于0.12-0.18之间。
6.如权利要求1所述的全可降解水凝胶涂层弹簧圈,其特征在于,所述抗解旋丝的材质为聚丙烯、聚乙烯、聚异戊二烯、镍钛合金、镁合金、聚对二氧环己酮中的任意一种。
7.如权利要求1所述的全可降解水凝胶涂层弹簧圈,其特征在于,所述水凝胶载药涂层的厚度为0.01-1mm;所述水凝胶载药涂层是聚丙烯酸类凝胶涂层、聚丙烯酰胺类凝胶涂层、聚碳酸脂类凝胶涂层、聚氨酯类凝胶涂层、两亲性嵌段共聚物类凝胶涂层、透明酯酸类凝胶涂层、壳聚糖类凝胶涂层、海藻酸盐类凝胶涂层、聚乙二醇类凝胶涂层、聚乙烯醇类凝胶涂层、卡拉胶类凝胶涂层中的任意一种。
8.一种如权利要求1-7任一项所述的全可降解水凝胶涂层弹簧圈的制备方法,其特征在于,包括如下步骤:
步骤S1:将可降解基材与显影材料直接共混、接枝或沉积后,通过静电纺丝技术制成细丝,再将细丝经芯棒模具绕制缠结,最后将芯棒和细丝整体放入可精密温控的热定型烘箱进行定型;在室温下退火,制备得到具有显影性能的可降解弹簧圈;
步骤S2:将抗解旋丝的头尾两端置入可降解弹簧圈内,并与弹簧圈的头尾两端通过焊接工艺或胶粘方式连接形成一体;
步骤S3:制备水凝胶载药溶液,将水凝胶载药溶液涂覆于弹簧圈圈体表面,干燥成膜,在弹簧圈圈体表面形成水凝胶载药涂层。
9.如权利要求8所述的全可降解水凝胶涂层弹簧圈的制备方法,其特征在于,所述步骤S1中芯棒是直径为0.1-0.5mm之间的不锈钢棒材;细丝在绕制时,线圈之间的间隙宽度为0.0008英寸-0.008英寸,绕制角度为65°-80°;热定型温度的范围为120℃-250℃,热定型的时间为5-45分钟。
10.如权利要求8所述的全可降解水凝胶涂层弹簧圈的制备方法,其特征在于,所述步骤S2采用的胶粘剂为聚酯类、聚氨酯类、聚酰胺类、α-氰基丙烯酸酯类胶粘剂中的任意一种或多种。
11.如权利要求8所述的全可降解水凝胶涂层弹簧圈的制备方法,其特征在于,所述步骤S3包括:
将一定质量的海藻酸钠溶于生理盐水中,制得溶液A;
将一定质量的丙烯酰胺类物质溶于去离子水中,再依次加入一定质量的碳酸钙和促血栓药物进行均匀混合,制得溶液B;
将溶液A和溶液B混合,进行均匀搅拌和加热,再加入引发剂进行聚合反应,制得溶液C;
将溶液C自然冷却后可得水凝胶溶液。
12.如权利要求11所述的全可降解水凝胶涂层弹簧圈的制备方法,其特征在于,在混合后的溶液C中,所述海藻酸钠的质量浓度为0.1-3%;所述丙烯酰胺类物质的质量浓度为5-40%;所述碳酸钙的质量浓度为2-6%;所述促血栓药物的质量浓度为0.1-1.5%;所述引发剂的质量浓度为2-8%;所述丙烯酰胺类物质是N-异丙基丙烯酰胺、2-丙烯酰氨基-2-甲基丙磺酸中的任意一种;所述促血栓药物是维生素K、氨甲苯酸、蛇毒血凝酶、凝血酶原复合物、氨基己酸、凝血酶和冻干人纤维蛋白原、安络血、酚磺乙胺、班尼芬、阿尔法9SD凝结因素中的任意一种或多种;所述引发剂是过硫酸铵、过氧化氢、过硫酸钾、过氧化苯甲酰、过氧化甲乙酮、过氧化苯甲酰叔丁酯中的任意一种;加热反应的温度范围为30-80℃,聚合反应时间为1-5h。
13.如权利要求8所述的全可降解水凝胶涂层弹簧圈的制备方法,其特征在于,所述步骤S3中涂覆方式为喷涂、刷涂、静电涂敷、浸涂、旋涂或延流;涂覆完成后干燥温度范围为20-230℃,压力范围为0.001-3bar,干燥时间为2-256h。
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