CN108642858B - 一种可控降解医用缝合线的制备方法 - Google Patents
一种可控降解医用缝合线的制备方法 Download PDFInfo
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- CN108642858B CN108642858B CN201810385847.4A CN201810385847A CN108642858B CN 108642858 B CN108642858 B CN 108642858B CN 201810385847 A CN201810385847 A CN 201810385847A CN 108642858 B CN108642858 B CN 108642858B
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- A—HUMAN NECESSITIES
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- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
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- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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Abstract
本发明涉及一种可控降解医用缝合线的制备方法,先将壳聚糖纤维制成品在含有交联剂I的溶胀剂中浸泡后,轴向拉伸、清洗并干燥,获得增强的壳聚糖纤维;将增强的壳聚糖纤维浸入金属盐溶液获得可控降解壳聚糖纤维;然后,将羧甲基壳聚糖溶于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,再将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后烘干,再将上浆后的可控降解壳聚糖纤维浸入交联剂溶液II中交联,后烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维,最后对其着色消毒即得可控降解医用缝合线。本发明方法工艺简单、操作方便、成本低廉、能耗低,制得的医用缝合线的力学性能好且其降解周期一定,具有极好的推广价值。
Description
技术领域
本发明属于纤维增强领域,涉及一种可控降解医用缝合线的制备方法。
背景技术
壳聚糖纤维属于天然材料,具有无毒、止血、消炎等优点,与生物细胞有良好的相容性,免疫抗原性小,与体液和细胞不会产生排异反应;可生物可降解,在生物体内的降解产物为氨基葡萄糖;氨基葡萄糖对人体无害,在体内不会产生积聚,因而,壳聚糖在生物医药领域应用前景十分的广泛。壳聚糖及其衍生物作为组织支架、药物载体等具有促进伤口愈合、防止组织粘连、抗凝血、降脂、降胆固醇、抗溃疡、抗肿瘤等作用,常被用作医用缝合线,但受原材料影响,制约壳聚糖纤维发展的主要原因是壳聚糖纤维力学强度不高,常规纺丝得到的壳聚糖纤维的断裂强度仅为1.07cN/dtex,远远达不到实际应用的要求。因此,对壳聚糖纤维进行增强以提高其力学性能具有重要意义。常见增强壳聚糖纤维的方法有:交联增强、复合增强和纺丝成形过程中增强,壳聚糖纤维采用交联增强即采用双官能团物质对壳聚糖纤维交联,增加大分子链间的作用力,交联增强中交联反应一般仅发生在纤维表面,增强程度有限;复合增强即利用其它功能材料与壳聚糖进行混合使用,可综合利用各材料的优点,但随着其他物质的引入,会影响壳聚糖的生物相容性;纺丝成形中牵伸纤维主要采用热拉伸,升温会使分子间作用减弱,但热拉伸需要持续提供热量,能耗较大。
纤维应用前一般都需进行上浆处理,上浆的作用主要是对纤维/纱线进行表面浆料的涂覆和纱束间的填充,经纱表面浆料的厚度、均匀性,以及浆料的渗透性对经纱的性能有很大的影响。传统上浆方式主要是浸浆方式,近年来,主要进展的是在高压上浆、预湿上浆、冷上浆、拖浆式上浆和在线检测等方面。高压上浆可以紧密纱线结构,增加耐磨、降低毛羽,同时可以提高织机效率;预湿上浆可以改善吸浆条件,但它会使浆槽中浆液浓度出现较大波动;普通上浆中,浆料分子间主要通过分子间作用力连接,对纤维的力学性能增强有限。采用交联上浆剂上浆可明显增加纤维/纱线的力学性能。目前交联改性的交联过程都是在上浆之前,交联过程中浆料浓度增大,不利于后续的上浆,交联后上浆其交联剂、浆料与纤维的结合较差,得到产品的交联度及上浆率低,产品性能存在不足。
专利CN201510182592.8公开了一种中温纺织上浆方法,其主要技术方案是包括以下步骤,上浆剂的制备、上浆,将所需清水加入到调浆桶中,开动搅拌,将得到的上浆剂干品加入到调浆桶中,将普通未变性的淀粉加入到调浆桶中,搅拌,再次加入骤一得到的上浆剂干品,继续搅拌,然后开始通蒸汽加温,升温后,停止通蒸汽,保温搅拌30分钟,用泵输送到浆槽中,开动浆纱机,开始浆纱。此种方法中在浆料中加入了交联剂,但交联反应发生在上浆之前,浆料粘度增大,不利于上浆。
此外,采用可降解的手术缝合线可避免伤口痊愈后后期拆线,所以近年来手术缝合线的可降解化是一个趋势,以壳聚糖、聚乳酸、胶原蛋白等为化学组成的医用手术缝合线逐渐发展起来。虽然壳聚糖纤维是一种生物可降解的材料,但其降解周期固定,往往难以满足实际应用的需求。不同手术下伤口的愈合时间不同,因此对于缝合线的降解周期也有一定的要求。目前市场上可降解的手术缝合线的降解周期普遍较短。本发明成功地控制了壳聚糖手术缝合线的降解周期,扩大了壳聚糖手术缝合线的应用范围。
因此,研究一种操作简单、生产成本低、能耗低、降解周期可控且上浆剂的交联反应发生在上浆后的使壳聚糖纤维力学性能强度显著提高的可控降解医用缝合线的制备方法,成为目前亟待解决的技术问题。
发明内容
本发明的目的是针对现有技术中壳聚糖纤维生产成本高、力学性能差、降解周期固定以及交联反应发生在上浆前导致浆料粘度增大等缺点,提供一种操作简单、生产成本低、能耗低、降解周期可控且上浆剂的交联反应发生在上浆后的使壳聚糖纤维力学性能强度显著提高的可控降解医用缝合线的制备方法。
为了达到上述目的,本发明采用的技术方案是:
一种可控降解医用缝合线的制备方法,首先,将壳聚糖纤维制成品在含有交联剂I的溶胀剂中浸泡后,轴向拉伸、清洗并干燥,获得增强的壳聚糖纤维;其次,将增强的壳聚糖纤维浸入金属盐溶液获得可控降解壳聚糖纤维;然后,将羧甲基壳聚糖溶于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,再将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后烘干,再将上浆后的可控降解壳聚糖纤维浸入交联剂溶液II中交联,后烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维,最后对羧甲基壳聚糖上浆可控降解壳聚糖纤维着色消毒即得可控降解医用缝合线;
所述壳聚糖纤维制成品为经湿法纺丝成形的壳聚糖纤维;
所述可控降解医用缝合线的降解周期为28~90天,普通壳聚糖纤维在人体3周后其质量损失率即达到40%以上,本发明通过壳聚糖的交联和金属离子络合成功延长了壳聚糖的降解周期。其与壳聚糖纤维制成品相比,其断裂强度提高25~35%,取向度提高35~42%,结晶度提高13~20%,打结强度提高10~15%。本发明的壳聚糖纤维是复丝纤维,但本发明的保护范围并不仅限于复丝纤维,单丝纤维也可适用于本发明。
作为优选的技术方案:
如上所述的一种可控降解医用缝合线的制备方法,所述含交联剂I的溶胀剂的pH为6.0~6.5,溶胀剂pH过高则不能达到溶胀的目的,pH过低,壳聚糖会溶解;所述浸泡是指将壳聚糖纤维制成品在含交联剂I的溶胀剂中进行超声处理,处理时间为10~20min,采用超声处理能使已成型的壳聚糖纤维分子链与小分子间充分接触,以提高交联效果,时间过短达不到交联效果,时间过长对溶胀作用不利。
如上所述的一种可控降解医用缝合线的制备方法,所述溶胀剂为稀醋酸、稀盐酸、草酸或柠檬酸;所述交联剂I为醛、京尼平、醚或离子液体;所述醛在含交联剂I的溶胀剂中的含量为2~4wt%,浸泡温度为30~40℃;所述京尼平在含交联剂I的溶胀剂中的含量为0.2~0.5wt%,浸泡温度为20~30℃;所述醚在含交联剂I的溶胀剂中的含量为0.1~0.3wt%,浸泡温度为20~30℃;所述离子液体在含交联剂I的溶胀剂中的含量为10~15wt%,浸泡温度为40~60℃。上述各种交联剂的含量设置与浸泡处理时间都在特定的范围内,若所采取的含量过低或者过高,浸泡的时间过长或过短会导致交联影响到壳聚糖的降解周期,交联剂的含量越高,在同样的人体液的酶降解环境和酶降解时间下,其质量的损失率就越小,降解周期越长。
如上所述的一种可控降解医用缝合线的制备方法,所述醛为2,5-呋喃二甲醛、戊二醛或乙二醛;所述醚为乙二醇二缩水甘油醚;所述离子液体为含羟基的离子液体、含羧基的离子液体、含磺酸基的离子液体或含氨基酸类的离子液体。
如上所述的一种可控降解医用缝合线的制备方法,所述含羟基的离子液体为氯化1-羟乙基-3-甲基咪唑、1-羟乙基-3-甲基咪唑四氟硼酸盐或1-羟基-N,N,N,三甲基乙胺六氟磷酸盐;所述含羧基的离子液体为氯化1-羧甲基-3-甲基咪唑、溴化1-羧甲基-3-甲基咪唑、1-羧甲基-3-甲基咪唑六氟磷酸盐或N-羧甲基吡啶六氟磷酸盐;所述含磺酸基的离子液体为N-磺酸丁基-3-甲基咪唑硫酸氢盐、N-磺酸丁基-3-甲基咪唑对甲苯磺酸盐或N-磺酸丁基吡啶硫酸氢盐;所述含氨基酸类的离子液体为丙氨酸1-丁基-3-甲基咪唑盐、谷氨酸1-乙基-3-甲基咪唑盐或天冬氨酸1-丁基-3-乙基咪唑盐。
如上所述的一种可控降解医用缝合线的制备方法,所述轴向拉伸是在壳聚糖纤维制成品完全浸没于含交联剂的溶胀剂后进行的,壳聚糖纤维制成品部分浸没于含交联剂的溶胀剂即进行轴向拉伸也可实现对壳聚糖纤维的增强,但增强效果略差;所述轴向拉伸的张力为80~350cN,拉伸温度为25~40℃,拉伸倍数为1.1~1.9倍,拉伸时间为1~3h,张力过小,分子链不能在张力的作用的移动,张力过大,纤维会被拉断;壳聚糖的溶胀的过程需要一定的时间,时间短,达不到溶胀的目的;所述清洗为将拉伸后的纤维放入去离子水中浸泡,清洗时间为0.5~1h,清洗的目的是为了去除多余的氢离子,时间过短,氢离子不能够被完全去除,浸泡时间过长影响市场效率。
根据权利要求1所述的一种可控降解医用缝合线的制备方法,其特征在于,所述金属盐溶液为Cu(OAc2)·H2O、LaC13·nH2O、FeSO4·7H2O、Zn(OAc)2·4H2O或FeC13·6H2O的醋酸溶液;金属盐溶液中金属盐的摩尔量为壳聚糖摩尔量的1~3.5倍,金属盐的含量过高,将会导致壳聚糖分子链上与金属形成配位键的配位节点变弱;所述增强的壳聚糖纤维在金属盐溶液的浸泡时间为0.8~1.5h,浸泡温度为25~40℃。
如上所述的一种可控降解医用缝合线的制备方法,所述干燥采用烘干方式,烘干温度为60~80℃,时间为3~4h;所述壳聚糖纤维制成品预先烘干处理,温度为60~80℃,时间为1~3h。
如上所述的一种可控降解医用缝合线的制备方法,所述羧甲基壳聚糖与水的质量比为2~7:100~150,上述比例过小,浆料粘度低,上浆率低;比例过大,浆料粘度高,浆料的渗透性差,不利用上浆;所述羧甲基壳聚糖溶于水是在200~250rpm的速度下搅拌溶解的,搅拌速率小,溶解时间长;搅拌速率过大,可能会切断壳聚糖大分子链,造成分子量降低;所述烘干的温度为45~60℃,烘干温度过高会导致壳聚糖纤维分解;所述交联剂溶液II为Ca2+的水溶液,其浓度为3~9wt%,浓度低,交联程度不够,而浓度达到9wt%,交联度达到饱和,同时,Ca2+的水溶液不仅可为氯化钙水溶液、磷酸二氢钙水溶液、硝酸钙水溶液、碳酸氢钙水溶液、硫酸氢钙水溶液、亚硫酸氢钙水溶液、次氯酸钙水溶液、溴化钙水溶液、碘化钙水溶液、氯酸钙水溶液、高氯酸钙水溶液、高锰酸钙水溶液,其他含有Ca2+的水溶液也可适用于本发明;所述交联剂溶液II中交联的时间为5~10min,温度为15~40℃,交联时间短,交联不完全;交联10min,交联度达到饱和,交联度不再随交联时间的增加而增加。
如上所述的一种可控降解医用缝合线的制备方法,所述着色消毒是指将羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精30~60min,最终真空干燥包装即得可控降解医用缝合线。
发明机理:
本发明的可控降解医用缝合线的制备方法,先将壳聚糖纤维制成品在pH为6.0~6.5的含交联剂Ⅰ的溶胀剂中浸泡后,壳聚糖中的氨基一部分与溶胀剂中的酸中电离的氢离子结合,另一部分可与交联剂小分子的功能基团反应,在拉伸增强和化学交联增强的协同作用下,可提高纤维产品的性能,具体如下:
一方面,壳聚糖纤维分子链上含有大量的氨基,与酸中电离的氢离子相结合,形成NH3 +,使壳聚糖转变为阳离子聚合物电解质,破坏了氢键结构,使其分子链发生一定程度的解缠,形成一种溶胀体。当溶液中的阳离子聚合物电解质达到一定数量后,壳聚糖大分子溶胀程度增大,直至完全溶解。醋酸作为壳聚糖的良溶剂,其作为溶胀剂时需采用较低浓度才能只溶胀不溶解。溶胀状态下的壳聚糖纤维分子间作用力弱,此时由于张力的存在,使纤维处于拉伸状态,使分子链取向度、结晶度随着外加张力的增大而增大,结晶趋于完整,提高了纤维强度与模量。
另一方面,在溶胀的同时,引入化学改性的交联步骤,壳聚糖分子链上的羟基和氨基都可以与醛类、醚类、离子液体以及京尼平上的活性官能基团发生化学反应,从而形成单分子或者多分子形式进行交联,因此,可减缓纤维在人体的溶菌酶等降解酶下的质量损失速率,延长手术缝合线的降解周期。。
然后将纤维浸入金属盐溶液中,让过渡金属或稀土金属离子在极稀的溶液中与壳聚糖分子上的—NH2、—OH配位,形成壳聚糖金属配合物;配位键的形成可能会使配位结点附近的某些键能变弱,形成有利于壳聚糖分子链断裂的弱势结构,控制金属盐滴加速度使这些配位结点和弱势结构在壳聚糖分子链上分布均匀;人体内的溶菌酶可使壳聚糖在配位结点或临近的弱势结构处断链。通过控制金属盐的加入量及其它反应条件来控制壳聚糖降解程度。通过交联和金属离子配位的协同作用,实现了对纤维的可控降解处理,实现对纤维降解周期的延长。
最后对溶胀拉伸后的壳聚糖纤维进行上浆交联,对上浆剂进行交联可明显增加浆料与纤维/纱线的结合的强度,目前现有技术中交联反应一般需要在液态环境下才能发生,即上浆前交联剂与浆料发生交联反应,但交联后的浆料浓度增大,不利于后续的上浆。
本发明采用壳聚糖纤维上浆从未使用过的原位交联技术,先对增强壳聚糖纤维进行上浆烘干,再将上浆后的增强壳聚糖纤维浸入交联剂中交联,保证了交联反应在上浆后发生,避免了浆料粘度增加的问题。上浆后交联的处理技术与现有的交联后上浆方式相比,一方面避免了浆料粘度增加的问题,另一方面,上浆后交联其交联剂、浆料与纤维的结合更加紧密,得到产品的交联度及上浆率更佳,产品性能更好,由于交联和溶胀拉伸都在纤维成型后的后处理工艺中,所以每种工艺都不能使所有的分子链间的氢键破坏或者在其间形成化学键,在两者的协同作用下,对于纤维的增强效果无疑是更好的。
有益效果:
(1)本发明的一种可控降解医用缝合线的制备方法,通过将先纤维在交联剂下分子链间交联,再浸入金属盐溶液中,通过交联和金属离子的协同作用,实现手术缝合线的可控降解;
(2)本发明的一种可控降解医用缝合线的制备方法,在上浆后交联,避免了交联浆料浓度增大,不利于上浆的问题,且工艺简单,操作方便,成本低廉,能耗低,极具应用前景;
(3)本发明的一种可控降解医用缝合线的制备方法,先对壳聚糖纤维进行上浆,然后将烘干后的上浆壳聚糖纤维束浸入交联剂溶液中,发生交联反应,在纤维表面形成一层致密的交联网络结构,极大地提升了壳聚糖纤维以及最终制得的医用缝合线的力学强度;
(4)本发明的一种可控降解医用缝合线的制备方法,使用含有交联剂的溶胀剂对壳聚糖纤维进行处理,一方面,利用稀酸对壳聚糖纤维的溶胀作用,以及拉伸状态中张力的作用,使纤维分子链取向度和结晶度增大,晶粒亦变大,结晶趋于完整,有利于纤维强度与模量的提高,另一方面,壳聚糖分子链上的羟基和氨基与醛类、醚类、离子液体以及京尼平上的活性官能基团发生化学反应,从而形成单分子或者多分子形式进行交联,有效提高了纤维以及最终制得的医用缝合线的力学性能。
具体实施方式
下面结合具体实施方式,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在60℃进行预先烘干处理3h,然后完全浸没于pH为6.3的戊二醛-稀醋酸的混合溶液后在35℃的温度下超声处理15min,其中,戊二醛的含量为混合溶液的3wt%,接着在张力为80cN,拉伸温度为35℃,拉伸倍数为1.1的条件下轴向拉伸2h,最后将拉伸后的纤维放入去离子水中浸泡0.5h后在65℃烘干干燥3.5h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入25℃的Cu(OAc2)·H2O的醋酸溶液0.8h,获得可控降解壳聚糖纤维,其中Cu(OAc2)·H2O的醋酸溶液中Cu(OAc2)·H2O的摩尔量为壳聚糖摩尔量的1倍;
(3)将羧甲基壳聚糖在200rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为3:120,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在55℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为15℃、浓度为3wt%的氯化钙水溶液中交联8min,在55℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精30min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为35天,其与壳聚糖纤维制成品相比,其断裂强度提高30%,取向度提高37%,结晶度提高16%,打结强度提高13%。
实施例2
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在60℃进行预先烘干处理3h,然后完全浸没于pH为6.3的戊二醛-稀醋酸的混合溶液后在35℃的温度下超声处理15min,其中,戊二醛的含量为混合溶液的3wt%,接着在张力为80cN,拉伸温度为35℃,拉伸倍数为1.1的条件下进行轴向拉伸2h,最后将拉伸后的纤维放入去离子水中浸泡0.5h后在65℃烘干干燥4h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入40℃的LaC13·nH2O的醋酸溶液1.5h,获得可控降解壳聚糖纤维,其中LaC13·nH2O的醋酸溶液中LaC13·nH2O的摩尔量为壳聚糖摩尔量的3.5倍;
(3)将羧甲基壳聚糖在220rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为5:100,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在45℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为40℃、浓度为9wt%的磷酸二氢钙水溶液中交联6min,在40℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精40min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为28天,其与壳聚糖纤维制成品相比,其断裂强度提高35%,取向度提高42%,结晶度提高20%,打结强度提高12%。
实施例3
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在65℃进行预先烘干处理2h,然后完全浸没于pH为6.1的乙二醛-稀醋酸的混合溶液后在40℃的温度下超声处理20min,其中,乙二醛的含量为混合溶液的4wt%,接着在张力为300cN,拉伸温度为25℃,拉伸倍数为1.8的条件下进行轴向拉伸1.5h,最后将拉伸后的纤维放入去离子水中浸泡0.6h后在60℃烘干干燥3h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入30℃的FeSO4·7H2O的醋酸溶液1h,获得可控降解壳聚糖纤维,其中FeSO4·7H2O的醋酸溶液中FeSO4·7H2O的摩尔量为壳聚糖摩尔量的2倍;
(3)将羧甲基壳聚糖在250rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为4:130,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在50℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为20℃、浓度为6wt%的硝酸钙水溶液中交联7min,在50℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精50min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为50天,其与壳聚糖纤维制成品相比,其断裂强度提高32%,取向度提高38%,结晶度提高18%,打结强度提高14%。
实施例4
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在75℃进行预先烘干处理1h,然后完全浸没于pH为6.5的乙二醇二缩水甘油醚-稀盐酸的混合溶液后在20℃的温度下超声处理15min,乙二醇二缩水甘油醚的含量为混合溶液的0.1wt%,接着在张力为180cN,拉伸温度为30℃,拉伸倍数为1.4的条件下进行轴向拉伸3h,最后将拉伸后的纤维放入去离子水中浸泡1h后在75℃烘干干燥3.5h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入30℃的Zn(OAc)2·4H2O的醋酸溶液0.9h,获得可控降解壳聚糖纤维,其中Zn(OAc)2·4H2O的醋酸溶液中Zn(OAc)2·4H2O的摩尔量为壳聚糖摩尔量的2.5倍;
(3)将羧甲基壳聚糖在210rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为2:150,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在45℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为30℃、浓度为7wt%的碳酸氢钙水溶液中交联10min,在45℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精45min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为90天,其与壳聚糖纤维制成品相比,其断裂强度提高25%,取向度提高35%,结晶度提高13%,打结强度提高10%。
实施例5
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在70℃进行预先烘干处理2.5h,然后完全浸没于pH为6.2的京尼平-稀盐酸的混合溶液后在25℃的温度下超声处理15min,其中,京尼平的含量为混合溶液的0.4wt%,接着在张力为350cN,拉伸温度为40℃,拉伸倍数为1.9的条件下进行轴向拉伸2.5h,最后将拉伸后的纤维放入去离子水中浸泡0.5h后在80℃烘干干燥4h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入28℃的FeC13·6H2O的醋酸溶液1.2h,获得可控降解壳聚糖纤维,其中FeC13·6H2O的醋酸溶液中FeC13·6H2O的摩尔量为壳聚糖摩尔量的3倍;
(3)首先将羧甲基壳聚糖在200rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为7:100,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在60℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为25℃、浓度为5wt%的硫酸氢钙水溶液中交联9min,在60℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精60min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为28天,其与壳聚糖纤维制成品相比,其断裂强度提高35%,取向度提高42%,结晶度提高20%,打结强度提高15%。
实施例6
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在80℃进行预先烘干处理3h,然后完全浸没于pH为6.0的氯化1-羟乙基-3-甲基咪唑-稀盐酸的混合溶液后在40℃的温度下超声处理10min,其中,氯化1-羟乙基-3-甲基咪唑的含量为混合溶液的10wt%,接着在张力为120cN,拉伸温度为25℃,拉伸倍数为1.2的条件下进行轴向拉伸2h,最后将拉伸后的纤维放入去离子水中浸泡0.9h后在60℃烘干干燥3.5h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入25℃的Cu(OAc2)·H2O的醋酸溶液1h,获得可控降解壳聚糖纤维,其中Cu(OAc2)·H2O的醋酸溶液中Cu(OAc2)·H2O的摩尔量为壳聚糖摩尔量的2.25倍;
(3)将羧甲基壳聚糖在240rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为3:140,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在55℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为33℃、浓度为9wt%的氯酸钙水溶液中交联5min,在55℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精50min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为80天,其与壳聚糖纤维制成品相比,其断裂强度提高28%,取向度提高36%,结晶度提高15%,打结强度提高15%。
实施例7
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在65℃进行预先烘干处理1.5h,然后完全浸没于pH为6.5的1-羟乙基-3-甲基咪唑四氟硼酸盐-草酸的混合溶液后在50℃的温度下超声处理14min,其中,1-羟乙基-3-甲基咪唑四氟硼酸盐的含量为混合溶液的13wt%,接着在张力为300cN,拉伸温度为25℃,拉伸倍数为1.8的条件下进行轴向拉伸2h,最后将拉伸后的纤维放入去离子水中浸泡0.6h后在80℃烘干干燥4h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入35℃的LaC13·nH2O的醋酸溶液1h,获得可控降解壳聚糖纤维,其中LaC13·nH2O的醋酸溶液中LaC13·nH2O的摩尔量为壳聚糖摩尔量的2倍;
(3)将羧甲基壳聚糖在250rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为5:130,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在45℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为20℃、浓度为4wt%的溴化钙水溶液中交联6min,在50℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精40min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为45天,其与壳聚糖纤维制成品相比,其断裂强度提高30%,取向度提高40%,结晶度提高20%,打结强度提高13%。
实施例8
一种可控降解医用缝合线的制备方法,步骤如下:
(1)首先将壳聚糖纤维制成品(经湿法纺丝成形的壳聚糖纤维)在70℃进行预先烘干处理3h,然后完全浸没于pH为6.4的1-羟基-N,N,N,三甲基乙胺六氟磷酸盐-柠檬酸的混合溶液后在60℃的温度下超声处理16min,其中,1-羟基-N,N,N,三甲基乙胺六氟磷酸盐的含量为混合溶液的14wt%,接着在张力为290cN,拉伸温度为40℃,拉伸倍数为1.7的条件下进行轴向拉伸3h,最后将拉伸后的纤维放入去离子水中浸泡0.5h后在60℃烘干干燥3h,即获得增强的壳聚糖纤维;
(2)将增强的壳聚糖纤维浸入40℃的FeC13·6H2O的醋酸溶液1.5h,获得可控降解壳聚糖纤维,其中FeC13·6H2O的醋酸溶液中FeC13·6H2O的摩尔量为壳聚糖摩尔量的2倍;
(3)将羧甲基壳聚糖在230rpm的速度下搅拌溶解于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,其中羧甲基壳聚糖和水的质量比为6:100,然后将可控降解壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后在50℃的温度下烘干,最后将上浆后的可控降解壳聚糖纤维浸入温度为38℃、浓度为3wt%的高锰酸钙水溶液中交联8min,在45℃的温度下烘干制得羧甲基壳聚糖上浆可控降解壳聚糖纤维;
(4)对羧甲基壳聚糖上浆可控降解壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精30min,最终真空干燥包装即得可控降解医用缝合线。
最终制得的可控降解医用缝合线的降解周期为82天,其与壳聚糖纤维制成品相比,其断裂强度提高32%,取向度提高40%,结晶度提高15%,打结强度提高14%。
实施例9~10
一种可控降解医用缝合线的制备方法,其制备步骤与实施例4基本相同,不同之处在于,乙二醇二缩水甘油醚占混合溶液的含量以及超声处理过程中的浸泡温度不同,最终制得可控降解医用缝合线的性能参数也不同,具体如下:(表中A、B、C及D分别为可控降解医用缝合线与壳聚糖纤维制成品相比,断裂强度、取向度、结晶度及打结强度的提高率,E为可控降解医用缝合线的降解周期)
实施例10~11
一种可控降解医用缝合线的制备方法,其制备步骤与实施例5基本相同,不同之处在于,京尼平占混合溶液的含量以及超声处理过程中的浸泡温度不同,最终制得可控降解医用缝合线的性能参数也不同,具体如下:(表中A、B、C及D分别为可控降解医用缝合线与壳聚糖纤维制成品相比,断裂强度、取向度、结晶度及打结强度的提高率,E为可控降解医用缝合线的降解周期)
京尼平的含量 | 浸泡温度 | A | B | C | D | E(d) | |
实施例10 | 0.2wt% | 30℃ | 25% | 36% | 16% | 15% | 88 |
实施例11 | 0.5wt% | 30℃ | 26% | 40% | 20% | 12% | 60 |
实施例12~21
一种可控降解医用缝合线的制备方法,其制备步骤与实施例7基本相同,不同之处在于,离子液体的种类以及其占混合溶液的含量不同,最终制得可控降解医用缝合线的性能参数也不同,具体如下:(表中A、B、C及D分别为可控降解医用缝合线与壳聚糖纤维制成品相比,断裂强度、取向度、结晶度及打结强度的提高率,E为可控降解医用缝合线的降解周期)
Claims (9)
1.一种高强医用缝合线的制备方法,其特征是:首先,将壳聚糖纤维制成品在含交联剂I的溶胀剂中浸泡后,轴向拉伸、清洗后干燥,获得增强的壳聚糖纤维;然后,将羧甲基壳聚糖溶于水后,经真空脱泡处理制得交联羧甲基壳聚糖上浆剂,再将增强的壳聚糖纤维浸入交联羧甲基壳聚糖上浆剂中均匀上浆后烘干,再将上浆后的增强的壳聚糖纤维浸入交联剂溶液II中交联,后烘干制得羧甲基壳聚糖上浆壳聚糖纤维,最后对羧甲基壳聚糖上浆壳聚糖纤维着色消毒即得高强医用缝合线;
所述壳聚糖纤维制成品为经湿法纺丝成形的壳聚糖纤维;
所述溶胀剂为稀醋酸、稀盐酸、草酸或柠檬酸;所述交联剂I为醛、京尼平、醚或离子液体;所述醛为2,5-呋喃二甲醛、戊二醛或乙二醛;所述醚为乙二醇二缩水甘油醚;所述离子液体为含羟基的离子液体、含羧基的离子液体、含磺酸基的离子液体或含氨基酸类的离子液体;所述含交联剂I的溶胀剂的pH为6.0~6.5;
所述交联剂溶液II为Ca2+的水溶液,其浓度为3~9wt%;
所述高强医用缝合线与壳聚糖纤维成品相比,其断裂强度提高38~48%,取向度提高39~45%,结晶度提高18~25%,打结强度提高10~15%,针线的连接强度提高15~20%。
2.根据权利要求1所述的一种高强医用缝合线的制备方法,其特征在于,所述在溶胀剂中轴向拉伸是指壳聚糖纤维制成品完全浸没于含交联剂I的溶胀剂中;所述干燥采用烘干方式,烘干温度为60~80℃,时间为3~4h;所述壳聚糖纤维制成品预先烘干处理,温度为60~80℃,时间为1~3h;所述浸泡是指将壳聚糖纤维制成品在含交联剂I的溶胀剂中进行超声处理,处理时间为10~20min。
3.根据权利要求2所述的一种高强医用缝合线的制备方法,其特征在于,所述醛在含交联剂I的溶胀剂中的含量为2~4wt%,浸泡温度为30~40℃;所述京尼平在含交联剂I的溶胀剂中的含量为0.2~0.5wt%,浸泡温度为20~30℃;所述醚在含交联剂I的溶胀剂中的含量为0.1~0.3wt%,浸泡温度为20~30℃;所述离子液体在含交联剂I的溶胀剂中的含量为10~15wt%,浸泡温度为40~60℃。
4.根据权利要求1所述的方法,其特征在于,所述含羟基的离子液体为氯化1-羟乙基-3-甲基咪唑、1-羟乙基-3-甲基咪唑四氟硼酸盐或1-羟基-N,N,N,三甲基乙胺六氟磷酸盐;所述含羧基的离子液体为氯化1-羧甲基-3-甲基咪唑、溴化1-羧甲基-3-甲基咪唑、1-羧甲基-3-甲基咪唑六氟磷酸盐或N-羧甲基吡啶六氟磷酸盐;所述含磺酸基的离子液体为N-磺酸丁基-3-甲基咪唑硫酸氢盐、N-磺酸丁基-3-甲基咪唑对甲苯磺酸盐或N-磺酸丁基吡啶硫酸氢盐;所述含氨基酸类的离子液体为丙氨酸1-丁基-3-甲基咪唑盐、谷氨酸1-乙基-3-甲基咪唑盐或天冬氨酸1-丁基-3-乙基咪唑盐。
5.根据权利要求1所述的一种高强医用缝合线的制备方法,其特征在于,所述轴向拉伸的张力为80~350cN,拉伸温度为25~40℃,拉伸倍数为1.1~1.9倍,拉伸时间为1~3h;所述清洗为将拉伸后的纤维放入去离子水中浸泡,浸泡时间为0.5~1h。
6.根据权利要求1所述的一种高强医用缝合线的制备方法,其特征在于,所述羧甲基壳聚糖与水的质量比为2~7:100~150。
7.根据权利要求1所述的一种高强医用缝合线的制备方法,其特征在于,所述羧甲基壳聚糖溶于水是在200~250rpm的速度下搅拌溶解的;所述烘干的温度为45~60℃。
8.根据权利要求1所述的一种高强医用缝合线的制备方法,其特征在于,所述交联剂溶液II中交联的时间为5~10min,温度为15~40℃。
9.根据权利要求1所述的一种高强医用缝合线的制备方法,其特征在于,所述着色消毒是指将羧甲基壳聚糖上浆壳聚糖纤维淋涂着色剂后烘干,再浸入医用酒精30~60min,最终真空干燥包装即得高强医用缝合线。
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