CN106377801A - 超滑血管内导管涂层及其制备方法 - Google Patents
超滑血管内导管涂层及其制备方法 Download PDFInfo
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- CN106377801A CN106377801A CN201611013478.3A CN201611013478A CN106377801A CN 106377801 A CN106377801 A CN 106377801A CN 201611013478 A CN201611013478 A CN 201611013478A CN 106377801 A CN106377801 A CN 106377801A
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- 238000000034 method Methods 0.000 claims abstract description 32
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
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- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
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- 210000004204 blood vessel Anatomy 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 2
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- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
- A61L29/16—Biologically active materials, e.g. therapeutic substances
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Biomedical Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明提供一种超滑血管内导管涂层,利用由催化剂或引发剂、溶剂、硅烷或硅酮单体组成的涂层液,在水分子参与下,采用室温固化或紫外接枝法制备得到。本发明提供的导管涂层具有较小的接触角滞后,赋予导管超滑性能,在不添加抗菌剂和抗凝剂时具有优异的抗细菌粘附和抗全血粘附性能,可以有效预防由导管引发的感染和凝血等并发症的出现。本发明提供的制备方法仅需将导管浸入涂层液中极短时间,然后在室温下固化或紫外照射较短时间,即可得到超滑抗菌抗凝血涂层,该方法操作简单,易于规模化生产,在导管领域具有广阔的应用前景。
Description
技术领域
本发明涉及血管内导管领域,具体涉及一种超滑血管内导管涂层及其制备方法。
背景技术
人口老龄化、生态环境持续恶化等因素导致各类疾病的发病率急速升高,进而促进了我国医疗市场需求的迅速增长,使医疗器械行业得到了快速发展。医用导管作为医疗器械的重要组成部分被称为危重病患者的“生命线”。其中,血管内导管是一类可全部或部分进入心血管系统,用于诊断和治疗目的的多腔或单腔管状医疗器械。血管内导管是静脉营养、血流监测、安全输液及血液透析等治疗手段的主要途径。血管内导管包括经外周穿刺的中心静脉导管、经外周穿刺的静脉导管、中心静脉导管、静脉内导管、头皮静脉导管和脐静脉导管等。
然而,由于导管材料的疏水特性,当导管接触血液后,血浆中的蛋白质在疏水表面大量吸附,并发生构象变化,继而引发血小板的粘附与激活,同时释放大量的凝血因子,在纤维蛋白原、凝血因子和激活血小板的共同作用下形成血栓。同时,材料表面吸附的蛋白质可以促进细菌的粘附和生物膜的形成。生物膜的存在可进一步引发凝血的发生,形成恶性循环。上述过程不仅加重了医疗负担,影响病患健康,严重时甚至会导致死亡。目前,虽然各类新型血管内导管不断面世,但其面临的两个主要问题-细菌感染和凝血问题仍未能有效解决。
涂层技术是提高血管内导管抗菌和抗凝血性能的有效途径。目前,常采用亲水性材料或同时使用亲水性材料和杀菌物质对导管进行改性,也可同时采用润滑剂和杀菌物质进行改性。然而,亲水性涂层无法完全避免血液组分的粘附、激活及细菌的粘附。杀菌物质血液相容性差,且部分杀菌物质可诱发细菌产生耐药性。润滑剂易流失进入血液,可能诱发血液疾病。具有自清洁性能的“憎一切”表面需有较低的接触角滞后,此类表面的超滑性能使其在面对复杂生物流体时仍具有十分优异的抗粘附效果。理想状态的自清洁表面需具有极小的接触角滞后,此时液体在固体表面易滚动。接触角滞后(即前进角大于后退角)的程度代表液体从固体表面脱离的难易程度。前进角和后退角差值越大,液体越难从固体表面脱离,差值越小则易脱离。因此,构建一类具有较小的接触角滞后的超滑导管涂层可有效抑制导管表面的细菌粘附和凝血的发生。
发明内容
本发明的目的在于克服传统导管涂层在抗菌和抗凝血方面的缺陷,采用不同方法催化或引发硅烷或硅酮的接枝聚合,提供一-种简单制备超滑导管涂层的方法。
本发明提供的制备超滑导管涂层的方法是一种利用碱催化剂、酸催化剂催化或采用紫外光引发剂引发硅烷或硅酮在导管表面接枝聚合的方法,包括如下步骤:
将硅烷或硅酮10-20重量份、碱催化剂、酸催化剂或引发剂1-3重量份及溶剂100重量份以上述比例在反应瓶中搅拌混合均匀得到导管涂层液,所述搅拌混合操作是在20-40℃,搅拌速度1000-2000rpm,混合时间5-10min条件下进行。将导管采用等离子体法或限制光催化氧化法处理,然后浸入上述导管涂层液中固定时间,并在相对湿度为50%-80%条件下催化(针对碱催化剂和酸催化剂体系)或紫外照射条件下(针对引发剂体系)引发接枝聚合反应。待反应完成后,采用去离子水和溶剂反复清洗,即得具有超滑性能的导管涂层。
上述方法中,所述硅烷或硅酮是指二甲基二甲氧基硅烷、三甲基甲氧基硅烷、六甲基二硅氧烷、氯二甲基辛硅烷、苯基氯硅烷、甲基三氯硅烷、三甲氧基丙基硅烷、八甲基环四硅氧烷、乙烯基三甲基硅烷等中的一种或多种。
上述方法中,所述酸催化剂是指布朗斯台德酸或路易斯酸,如硫酸、磷酸、硝酸、硼酸、磺酸、卤代磺酸、三氟化硼、三氯化铁、三氯化铝等中的一种。
上述方法中,所述碱催化剂是指氢氧化铯、氢氧化钾、氢氧化钠、氢氧化锂、季铵碱、季磷碱、磷腈碱等中的一种。
上述方法中,引发剂是指二苯甲酮、过氧化苯甲酰、过氧化二异丙苯、过氧化二叔丁基和过氧化苯甲酸叔丁基酯等中的一种。
上述方法中,等离子体法是指利用电离的气体对材料表面进行处理以产生活性基团。电离的导电气体由电子、正负离子、激发态的原子或分子或光子等粒子组成。适用于等离子体的气体包括:氧气、氩气、氮气、氨气、氢气及二氧化碳气体等。
上述方法中,光催化氧化法是指利用过硫酸盐和紫外光辐照使材料表面产生羟基。过硫酸盐包括:过硫酸钾、过硫酸钠和过硫酸铵。
上述方法中,所述溶剂是指硅烷或硅酮的良溶剂。具体的良溶剂是本领域技术人员所已知的。具体可为异丙醇、乙醇、丁醇、二甲醚、四氯化碳等中的一种。
根据本发明的涂层基本可以适用于任意类型的基材,尤其可用于基材为聚合物的导管改性,这些聚合物包括聚氯乙烯、聚苯乙烯、聚砜、聚乙烯、超高分子量聚乙烯、聚对苯二甲酸乙二醇酯、有机硅橡胶、聚丙烯、聚酰亚胺、聚全氟乙丙烯、聚四氟乙烯、膨体聚四氟乙烯、全氟烷氧基树脂等。
与现有技术相比,本发明的有益效果是:
1.本发明采用简单工艺即可获得基于有机硅材料的具有超滑性能的导管涂层,该涂层具有优异的透明性。
2.本发明中制备的超滑涂层无需抗菌剂和抗凝剂添加,即具有优异的抗菌和抗凝血性能。
3.采用接枝聚合法制备基于有机硅材料的“憎一切”超滑导管涂层,与现有导管涂层相比不会引起由抗菌剂引发的细菌耐药性问题和有抗凝剂引发的自发性出血等问题。
附图说明
为更清晰地描述本发明实施例或技术方案,下面将对附图做简要介绍,以下图示仅为本发明实施例的部分图,本领域技术人员可根据提供附图获得其他附图。
图1为本发明实施例1中聚苯乙烯表面金黄色葡萄球菌细菌密度。
图2为本发明实施例1中八甲基环四硅氧烷开环接枝改性后样品表面金黄色葡萄球菌细菌密度。
图3为本发明实施例1中聚苯乙烯表面全血粘附。
图4为本发明实施例1中八甲基环四硅氧烷开环接枝改性后样品表面全血粘附。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明,但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
实施例1
碱催化硅烷开环接枝聚合的方法:
1)将乙醇100重量份,八甲基环四硅氧烷10重量份,氢氧化钾1重量份在1000rpm转速下混合均匀,并在室温下静止30min,制得导管涂层液;
2)将不同材质导管(聚氯乙烯、聚苯乙烯、聚砜、聚乙烯、超高分子量聚乙烯、聚对苯二甲酸乙二醇酯、有机硅橡胶、聚丙烯、聚酰亚胺、聚全氟乙丙烯、聚四氟乙烯、膨体聚四氟乙烯、全氟烷氧基树脂等)采用光催化氧化法进行处理使导管表面产生大量羟基;
3)将步骤2)中处理后的导管浸入步骤1)混合均匀的导管涂层液中1-3min,然后缓慢取出并将导管在室温、相对湿度为50%-80%条件下固化3-5min。待固化完毕后,采用超声清洗3-5次,后用用去离子水和乙醇反复清洗,得到具有超滑性能涂层的导管。
实施例2
酸催化硅烷接枝聚合的方法:
1)将异丙醇100重量份,二甲基二甲氧基硅烷10重量份,硫酸(2.0wt%)1重量份在1000rpm转速下混合均匀,并在室温下静止30min,制得导管涂层液;
2)将不同材质导管(聚氯乙烯、聚苯乙烯、聚砜、聚乙烯、超高分子量聚乙烯、聚对苯二甲酸乙二醇酯、有机硅橡胶、聚丙烯、聚酰亚胺、聚全氟乙丙烯、聚四氟乙烯、膨体聚四氟乙烯、全氟烷氧基树脂等)采用光催化氧化法进行处理,赋予导管表面大量羟基;
3)将步骤2)中处理后的导管浸入步骤1)混合均匀的导管涂层液中5-20sec,然后缓慢取出并将导管在室温、相对湿度为50%-80%条件下固化3-5min。待固化完毕后,采用超声清洗3-5次,后用去离子水和异丙醇反复清洗,得到具有超滑性能涂层的导管。
实施例3
紫外引发接枝聚合的方法:
1)将乙醇100重量份,乙烯基三甲基硅烷10重量份,二苯甲酮1重量份在1000rpm转速下混合均匀,并在室温下避光静止30min,制得导管涂层液;
2)将不同材质导管(聚氯乙烯、聚苯乙烯、聚砜、聚乙烯、超高分子量聚乙烯、聚对苯二甲酸乙二醇酯、有机硅橡胶、聚丙烯、聚酰亚胺、聚全氟乙丙烯、聚四氟乙烯、膨体聚四氟乙烯、全氟烷氧基树脂等)采用等离子体法处理;
3)将步骤2)中处理后的导管浸入步骤1)混合均匀的导管涂层液中5min,然后缓慢取出导管,待溶剂挥发后,利用紫外光引发接枝聚合,紫外灯波段范围350-400nm,峰值波长为365nm,紫外照射时间2-5min。待反应完毕后,采用去离子水和乙醇反复清洗,得到具有超滑性能涂层的导管。
Claims (10)
1.一种超滑血管内导管涂层液,所述导管涂层液包括以下组分:
溶剂 100重量份,
硅烷或硅酮单体 10-20重量份,
催化剂或引发剂 1-3重量份,
所述溶剂为硅烷或硅酮单体及催化剂或引发剂的良溶液;
所述硅烷或硅酮选自二甲基二甲氧基硅烷、三甲基甲氧基硅烷、六甲基二硅氧烷、氯二甲基辛硅烷、苯基氯硅烷、甲基三氯硅烷、三甲氧基丙基硅烷、八甲基环四硅氧烷、乙烯基三甲基硅烷中的一种或多种;
所述催化剂为碱。
2.根据权利要求1所述的导管涂层液,其特征在于,所述溶剂为异丙醇、乙醇、丁醇、二甲醚、四氯化碳中的一种。
3.根据权利要求1所述的导管涂层液,其特征在于,所述催化剂为布朗斯台德酸或路易斯酸催化剂。
4.根据权利要求3所述的导管涂层液,其特征在于,所述催化剂为硫酸、磷酸、硝酸、硼酸、磺酸、卤代磺酸、三氟化硼、三氯化铁、三氯化铝中的一种。
5.根据权利要求1所述的导管涂层液,其特征在于,所述催化剂为氢氧化铯、氢氧化钾、氢氧化钠、氢氧化锂、季铵碱、季磷碱、磷腈碱中的一种。
6.根据权利要求1所述的导管涂层液,其特征在于,所述引发剂为二苯甲酮、过氧化苯甲酰、过氧化二异丙苯、过氧化二叔丁基和过氧化苯甲酸叔丁基酯中的一种。
7.一种超滑血管内导管涂层的制备方法,包括以下步骤:
A)制备如权利要求1所述的导管涂层液:将硅烷或硅酮、催化剂或引发剂及溶剂以不同比例在反应瓶中搅拌混合均匀,所述搅拌混合操作是在20-40℃,搅拌速度1000-2000rpm,混合时间5-10min条件下进行;
B)将导管采用限制光催化氧化法或等离子体法处理;
C)将所述步骤B)中得到的导管浸入步骤A)中的导管涂层液中固定时间,针对含碱催化剂涂层液,将其在相对湿度为50%-80%条件下,催化单体接枝聚合;针对含酸催化剂涂层液,将其在相对湿度为50%-80%条件下,催化接枝聚合;针对含引发剂涂层液,将其在紫外照射条件(紫外灯功率为400瓦)下进行接枝聚合反应;待反应完成后,采用去离子水和溶剂反复清洗,即得具有超滑性能的导管涂层。
8.根据权利要求7所述的超滑血管内导管涂层制备方法,其特征在于,当其用于紫外引发接枝聚合时,所述导管涂层液包含乙烯基单体,步骤A)在避光条件下进行。
9.根据权利要求7或8所述的超滑血管内导管涂层制备方法,其特征在于,所述步骤B)中采用等离子体法处理导管时,所用气体为氧气、氩气、氮气、氨气、氢气及二氧化碳气体中的一种。
10.根据权利要求7或8所述的超滑血管内导管涂层制备方法,其特征在于,所述步骤B)中采用限制光催化氧化法处理导管时,所用过硫酸盐为过硫酸钾、过硫酸钠和过硫酸铵中的一种。
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