CN115558148B - 一种抗黏附医用聚氨酯膜及其制备方法和应用 - Google Patents
一种抗黏附医用聚氨酯膜及其制备方法和应用 Download PDFInfo
- Publication number
- CN115558148B CN115558148B CN202211190184.3A CN202211190184A CN115558148B CN 115558148 B CN115558148 B CN 115558148B CN 202211190184 A CN202211190184 A CN 202211190184A CN 115558148 B CN115558148 B CN 115558148B
- Authority
- CN
- China
- Prior art keywords
- polyurethane film
- epoxy
- adhesion
- zwitterionic
- medical polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
- C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Surgery (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明提供了一种抗黏附医用聚氨酯膜及其制备方法和应用,属于生物医用材料技术领域,该抗黏附医用聚氨酯膜的制备方法具体包括:(1)以环氧单体、两性离子单体和引发剂为原料发生聚合反应制备环氧‑两性离子共聚物;(2)通过环氧开环反应,将步骤(1)的环氧‑两性离子共聚物接枝到表面含有羟基基团的聚氨酯膜上,得到所述的抗黏附医用聚氨酯膜。本发明利用聚氨酯膜上的羟基与环氧‑两性离子共聚物发生环氧开环反应,从而在聚氨酯膜表面接枝两性离子聚合物,制备得到抗黏附医用聚氨酯膜;两性离子聚合物与聚氨酯膜通过共价键连接,结合力强,制得的抗黏附医用聚氨酯膜亲水性好,具有优异的抗蛋白与血小板黏附性能,血液相容性好。
Description
技术领域
本发明属于生物医用材料技术领域,具体涉及一种抗黏附医用聚氨酯膜及其制备方法和应用。
背景技术
生物医用高分子材料在植入式医疗材料中用途广泛,植入式生物医用高分子由于与血液直接接触,必须具有良好的血液相容性。血液相容性是指材料与血液接触时不引起血浆蛋白及血小板黏附,不发生血细胞破裂,不导致溶血、凝血以及血栓的形成。血液中含有大量的血浆蛋白和血小板,会与疏水的生物医用高分子材料表面发生疏水相互作用,导致血浆蛋白与血小板在材料表面的黏附,造成凝血或血栓。因此在实际应用中,必须提高植入式生物医用高分子材料的血液相容性,而表面抗血蛋白与血小板黏附改性是提高植入式生物医用高分子材料血液相容性的关键。
聚氨酯是一种常用的植入式生物医用高分子材料,由聚酯或聚醚等聚多元醇的柔性软段与二异氰酸酯和扩链剂等刚性硬段组成。聚氨酯材料具有微相分离结构,该结构与生物膜相似,因此聚氨酯膜被应用于人工心脏、人工瓣膜、人工血管、医用导管等植入式应用场景。作为一种直接接触血液的材料,聚氨酯膜的血液相容性具有较大的局限性。
为了解决聚氨酯膜应用中血浆蛋白与血小板的黏附问题,可以通过表面涂覆、化学接枝等手段在聚氨酯膜表面引入抗黏附物质,抑制血液与材料的相互作用,从而达到抗黏附的目的。
公开号为CN104262668A的中国专利文献公开了一种具有抗蛋白吸附和抗细胞黏附的聚氨酯材料及其制备方法:该方法对聚氨酯材料进行异氰酸酯化,并氨基化,固定溴引发剂后,引发乙烯基吡咯烷酮单体在材料表面接枝聚合。该方法制备的聚氨酯材料具有良好的亲水性,以及良好的抗牛血纤维蛋白原、牛血清白蛋白、溶菌酶吸附功能,同时具有抗小鼠成纤维细胞黏附的功能。但该方法过程较为繁琐,且在底膜材料上固定溴引发剂,需进一步考虑植入材料的安全性。
公开号为CN103772731A的中国专利文献公开了一种用两性离子聚合物表面修饰聚氨酯的方法,该方法首先由聚氨酯膜与二异氰酸酯反应,再与L-半胱氨酸或巯基脂肪醇反应;然后加入含磺基甜菜碱降冰片烯聚合物和光引发剂混合液,通过点击反应得到两性离子聚合物修饰的聚氨酯膜,提高了聚氨酯膜的亲水性与抗血小板黏附能力,具有良好的血液相容性,但两性离子聚合物的修饰过程较为复杂,改性聚氨酯膜的制备周期较长。
发明内容
本发明提供了一种抗黏附医用聚氨酯膜的制备方法,通过羟基-环氧反应在聚氨酯膜表面接枝两性离子亲水抗黏附层,结合力强、设备要求低、反应条件温和,制得的抗黏附医用聚氨酯膜亲水性好,具有优异的抗蛋白与血小板黏附性能,不引起溶血,血液相容性好。
具体采用的技术方案如下:
一种抗黏附医用聚氨酯膜的制备方法,包括以下步骤:
(1)以环氧单体、两性离子单体和引发剂为原料发生聚合反应制备环氧-两性离子共聚物;
(2)通过环氧开环反应,将步骤(1)的环氧-两性离子共聚物接枝到表面含有羟基基团的聚氨酯膜上,得到所述的抗黏附医用聚氨酯膜。
聚氨酯通常利用羟基封端聚合物和异氰酸酯以及扩链剂反应得到,由于异氰酸根反应活性大、毒性强、随时间变化明显,为了降低其残留,所以在反应过程中通常保持羟基基团过量,导致产品聚氨酯中一定会有残留的羟基。
本发明利用聚氨酯膜上的羟基与环氧-两性离子共聚物发生环氧开环反应,从而在聚氨酯膜表面接枝两性离子聚合物,制备得到抗黏附医用聚氨酯膜;两性离子聚合物与聚氨酯膜通过共价键连接,结合力强,且接枝的两性离子聚合物同时带有正电和负电基团,很容易形成水化层,具有较强的水合作用,从而具有抗血浆蛋白与血小板黏附的能力。本发明方法设备要求低,制备方法简单,便于在传统医用聚氨酯膜制备工艺基础上进行改进,实现放大生产,所得的抗黏附医用聚氨酯膜亲水性好,且具有优异的抗蛋白与血小板黏附性能。
环氧-两性离子共聚物的合成是构建亲水抗黏附层的关键,优选的,步骤(1)中,环氧单体为甲基丙烯酸缩水甘油酯、4-羟基丁基丙烯酸酯缩水甘油醚或烯丙醇缩水甘油醚,两性离子单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵、3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯和2-甲基丙烯酰氧基乙基磷酰胆碱中的至少一种。
引发剂选自偶氮二异丁腈、过氧化二酰、偶氮二异戊腈或偶氮二异庚腈。
优选的,聚合反应体系中,环氧单体与两性离子单体的摩尔比为1:9-9:1,引发剂用量为环氧单体与两性离子单体总量的1-8mol%。
优选的,所述的聚合反应时间为3-10h,温度为50-90℃。
具体的,步骤(1)中,将环氧单体、两性离子单体和引发剂混合,在50-90℃加热搅拌的条件下反应3-10h,得到粗产物溶液,将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到所述的环氧-两性离子共聚物。
所述的环氧-两性离子共聚物的结构式表示为:
其中,R1为所述的两性离子单体残基,R2为所述的环氧单体残基,m和n均为1-100的正整数。
优选的,所述的环氧-两性离子共聚物的数均分子量为20000-30000。
优选的,步骤(2)中,环氧开环反应的具体步骤为:将表面含有羟基基团的聚氨酯膜置于环氧-两性离子共聚物溶液中进行接枝反应,接枝反应温度为50-90℃,接枝反应时间为6-24h。
进一步优选的,环氧-两性离子共聚物溶液浓度为5-30mg/mL,在上述优选的范围内制得的产品膜的亲水性较好,原料利用率高。
步骤(2)中,环氧开环反应的催化剂为三乙胺溶液、十二烷基三甲基氯化铵、十二烷基二甲基苄基氯化铵、十二烷基二甲基苄基溴化铵、吡啶、氢氧化钾或氢氧化钠。
步骤(2)中,所述的表面含有羟基基团的聚氨酯膜可以由医用聚氨酯溶液通过溶剂蒸发得到。
优选的,考虑到聚氨酯膜的强度和表面羟基含量,所述的医用聚氨酯溶液由硬度划分为55D、80D或90A的医用级聚氨酯颗粒溶于有机溶剂制得,所述的医用聚氨酯溶液的质量浓度为5-20wt%;溶剂蒸发方式为自然干燥或加热真空干燥。在上述参数下制得的聚氨酯膜具有良好的拉伸强度,植入体内后耐血液冲击性能好。
进一步优选的,所述的有机溶剂包括丙酮、N,N-二甲基甲酰胺、四氢呋喃、N,N-二甲基乙酰胺和N-甲基吡咯烷酮中的至少一种。
本发明还提供了所述的抗黏附医用聚氨酯膜的制备方法制得的抗黏附医用聚氨酯膜,所述的抗黏附医用聚氨酯膜包括聚氨酯层和两性离子亲水抗黏附层。
本发明还提供了所述的抗黏附医用聚氨酯膜在植入式医用材料领域中的应用。
与现有技术相比,本发明的有益效果在于:
(1)本发明在引发剂的作用下,将环氧单体与两性离子单体自由基聚合,合成环氧-两性离子共聚物,再通过羟基-环氧反应在聚氨酯膜表面锚定两性离子,两性离子聚合物与聚氨酯膜通过共价键连接,结合力强,构建的两性离子亲水抗黏附层比表面涂覆、表面沉积等改性方法制得的修饰层更加稳定,避免在受到血液冲刷后脱落的风险。
(2)本发明在聚氨酯膜上接枝环氧-两性离子共聚物,制备两性离子亲水抗黏附层,制备得到了具有良好的抗蛋白与血小板黏附性能的、亲水性优异的抗黏附医用聚氨酯膜,水接触角最低达到44°,较未改性的聚氨酯膜水接触角降低了50°左右。
(3)本发明通过优化聚氨酯溶液浓度、溶剂组成和溶剂蒸发方式调控聚氨酯膜的结构和性质,使得聚氨酯薄膜具有良好的拉伸强度,植入体内后耐血液冲击性能得到大幅度的提高,避免在使用过程中出现破损从而导致医疗事故,延长了该聚氨酯膜的使用寿命。
(4)本发明提供的抗黏附医用聚氨酯膜的制备方法简单、容易储存且使用寿命长、制备成本低、无有毒有害物质残留、便于实现放大制备生产,在在植入式医用材料领域有着广泛的应用前景和参考价值。
附图说明
图1为实施例3中环氧-两性离子共聚物合成路线图。
图2为实施例3中环氧-两性离子修饰聚氨酯膜表面的示意图。
图3为实施例3中的抗黏附医用聚氨酯膜与对比例1中的聚氨酯膜的XPS分析结果图。
图4为实施例3中的抗黏附医用聚氨酯膜与对比例1中的聚氨酯膜的水接触角对比图。
图5为实施例3中的抗黏附医用聚氨酯膜与对比例1中的聚氨酯膜的蛋白质黏附对比图,其中,A为对比例1的聚氨酯膜,B为实施例3的抗黏附医用聚氨酯膜,C为膜上黏附的荧光蛋白的荧光强度对比图。
图6为实施例3中的抗黏附医用聚氨酯膜与对比例1中的聚氨酯膜的血小板黏附对比图,其中,A为对比例1的聚氨酯膜,B为实施例3的抗黏附医用聚氨酯膜。
具体实施方式
下面结合附图与实施例,进一步阐明本发明。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。
本实施例中,医用级聚氨酯颗粒采购于路博润公司,两性离子单体3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯(CAS号:24249-95-4)、2-甲基丙烯酰氧基乙基磷酰胆碱(CAS:67881-98-5)、[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵(CAS:3637-26-1)均采购于上海源叶生物科技有限公司。
实施例1
(1)将硬度为55D的医用级聚氨酯颗粒加热干燥,随后溶解于四氢呋喃中室温机械搅拌6h,配制质量浓度为5wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在自然干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制4-羟基丁基丙烯酸酯缩水甘油醚与[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵的混合溶液(4-羟基丁基丙烯酸酯缩水甘油醚含量为10mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量1mol%的偶氮二异丁腈,然后将反应体系置于三口烧瓶中,在50℃条件下反应10h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物白色固体粉末,该环氧-两性离子共聚物为聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-4-羟基丁基丙烯酸酯缩水甘油醚);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于5mg/mL聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-4-羟基丁基丙烯酸酯缩水甘油醚)溶液中,随后按照每毫升聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-4-羟基丁基丙烯酸酯缩水甘油醚)溶液加入100μL吡啶溶液作为催化剂,在50℃条件下反应24h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
实施例2
(1)将硬度为80D的医用级聚氨酯颗粒加热干燥,随后溶解于N,N-二甲基甲酰胺中室温机械搅拌6h,配制质量浓度为8wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在60℃下真空干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制甲基丙烯酸缩水甘油酯与3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯的混合溶液(甲基丙烯酸缩水甘油酯含量为10mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量3mol%的偶氮二异丁腈,然后将反应体系置于三口烧瓶中,在70℃条件下反应4h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物白色固体粉末,该环氧-两性离子共聚物为聚(3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯-co-甲基丙烯酸缩水甘油酯);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于7mg/mL聚(3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯-co-甲基丙烯酸缩水甘油酯)溶液中,随后按照每毫升聚(3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯-co-甲基丙烯酸缩水甘油酯)溶液加入100μL十二烷基三甲基氯化铵溶液作为催化剂,在50℃条件下反应6h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
实施例3
(1)将硬度为90A的医用级聚氨酯颗粒加热干燥,随后溶解于N,N-二甲基甲酰胺中室温机械搅拌6h,配制质量浓度为10wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在60℃下真空干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制甲基丙烯酸缩水甘油酯与[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵的混合溶液(甲基丙烯酸缩水甘油酯含量为20mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量1mol%的偶氮二异丁腈,然后将反应体系置于三口烧瓶中,在70℃条件下反应6h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物白色固体粉末,该环氧-两性离子共聚物为聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于7mg/mL聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯)溶液中,随后按照每毫升聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯)溶液加入100μL三乙胺溶液作为催化剂,在60℃条件下反应12h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
实施例4
(1)将硬度为90A的医用级聚氨酯颗粒加热干燥,随后溶解于四氢呋喃中室温机械搅拌6h,配制质量浓度为12wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在60℃下真空干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制烯丙醇缩水甘油醚与3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯的混合溶液(烯丙醇缩水甘油醚含量为30mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量3mol%的过氧化二酰,然后将反应体系置于三口烧瓶中,在80℃反应条件下反应6h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物白色固体粉末,该环氧-两性离子共聚物为聚(3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯-co-烯丙醇缩水甘油醚);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于13mg/mL聚(3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯-co-烯丙醇缩水甘油醚)溶液中,随后按照每毫升聚(3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯-co-烯丙醇缩水甘油醚)溶液加入100μL十二烷基二甲基苄基氯化铵溶液作为催化剂,在60℃条件下反应10h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
实施例5
(1)将硬度为90A的医用级聚氨酯颗粒加热干燥,随后溶解于N-甲基吡咯烷酮中室温机械搅拌6h,配制质量浓度为15wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在60℃下真空干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制甲基丙烯酸缩水甘油酯与[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵的混合溶液(甲基丙烯酸缩水甘油酯含量为40mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量3mol%的偶氮二异戊腈,然后将反应体系置于三口烧瓶中,在90℃反应条件下反应6h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物白色固体粉末,该环氧-两性离子共聚物为聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于15mg/mL聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯)溶液中,随后按照每毫升聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯)溶液加入100μL十二烷基二甲基苄基溴化铵溶液作为催化剂,在60℃条件下反应12h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
实施例6
(1)将硬度为50D的医用级聚氨酯颗粒加热干燥,随后溶解于四氢呋喃中室温机械搅拌6h,配制质量浓度为16wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在60℃下真空干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制烯丙醇缩水甘油醚与[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵的混合溶液(烯丙醇缩水甘油醚含量为60mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量8mol%的偶氮二异庚腈,然后将反应体系置于三口烧瓶中,在80℃反应条件下反应6h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物白色固体粉末,该环氧-两性离子共聚物为聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-烯丙醇缩水甘油醚);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于15mg/mL聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯)溶液中,随后按照每毫升聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-烯丙醇缩水甘油醚)溶液加入100μL氢氧化钾溶液作为催化剂,在60℃条件下反应16h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
实施例7
(1)将硬度为90A的医用级聚氨酯颗粒加热干燥,随后溶解于四氢呋喃中室温机械搅拌6h,配制质量浓度为18wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在自然干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制甲基丙烯酸缩水甘油酯与2-甲基丙烯酰氧基乙基磷酰胆碱的混合溶液(甲基丙烯酸缩水甘油酯含量为70mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量7mol%的偶氮二异戊腈,然后将反应体系置于三口烧瓶中,在90℃反应条件下反应10h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物固体粉末,该环氧-两性离子共聚物为聚(2-甲基丙烯酰氧基乙基磷酰胆碱-co-甲基丙烯酸缩水甘油酯);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于20mg/mL聚(2-甲基丙烯酰氧基乙基磷酰胆碱-co-甲基丙烯酸缩水甘油酯)溶液中,随后按照每毫升聚(2-甲基丙烯酰氧基乙基磷酰胆碱-co-甲基丙烯酸缩水甘油酯)溶液加入100μL氢氧化钠溶液作为催化剂,在90℃条件下反应6h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
实施例8
(1)将硬度为90A的医用级聚氨酯颗粒加热干燥,随后溶解于四氢呋喃中室温机械搅拌6h,配制质量浓度为20wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在60℃下真空干燥条件下制备得到聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干;
(2)配制4-羟基丁基丙烯酸酯缩水甘油醚与2-甲基丙烯酰氧基乙基磷酰胆碱的混合溶液(4-羟基丁基丙烯酸酯缩水甘油醚含量为90mol%),搅拌均匀后氮气吹扫,随后加入环氧单体与两性离子单体总量5mol%的过氧化二酰,然后将反应体系置于三口烧瓶中,在90℃反应条件下反应3h,反应结束后将粗产物溶液滴入无水乙醇中得到沉淀,沉淀溶于水中并经冷冻干燥得到环氧-两性离子共聚物白色固体粉末,该环氧-两性离子共聚物为聚(2-甲基丙烯酰氧基乙基磷酰胆碱-co-4-羟基丁基丙烯酸酯缩水甘油醚);
(3)将步骤(1)得到的表面含有羟基基团的医用聚氨酯膜片置于30mg/mL聚(2-甲基丙烯酰氧基乙基磷酰胆碱-co-4-羟基丁基丙烯酸酯缩水甘油醚)溶液中,随后按照每毫升聚(2-甲基丙烯酰氧基乙基磷酰胆碱-co-4-羟基丁基丙烯酸酯缩水甘油醚)溶液加入100μL氢氧化钠溶液作为催化剂,在60℃条件下反应24h,反应结束后取出膜片,去离子水冲洗三次,自然晾干后得到所述的抗黏附医用聚氨酯膜。
对比例1
将硬度为90A的医用级聚氨酯颗粒加热干燥,随后溶解于N,N-二甲基甲酰胺中室温机械搅拌6h,配制质量浓度为10wt%的聚氨酯溶液,随后将聚氨酯溶液倒入玻璃模具中,在60℃下真空干燥条件下制备得到初态聚氨酯膜,将该聚氨酯膜置于无水乙醇和超纯水中交替清洗去除杂质,自然晾干。
样品分析
(1)形貌及元素分析
实施例3中环氧-两性离子共聚物的合成路线图如图1所示,环氧-两性离子修饰聚氨酯膜表面的示意图如图2所示,其中,x和y均为1-100的正整数;制备得到的产品抗黏附医用聚氨酯膜的XPS结果如图3所示,通过在聚氨酯膜表面接枝聚([2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵-co-甲基丙烯酸缩水甘油酯),使得聚氨酯膜表面被检测到特征硫元素,证明了两性离子亲水抗黏附层的成功构建,而对比例1中的聚氨酯膜没有硫元素的出现。
(2)抗黏附医用聚氨酯膜的亲水性能
分别裁取一定面积的实施例3中的产品抗黏附医用聚氨酯膜与对比例1中的聚氨酯膜,将其置于静态水接触角仪上,测量水接触角大小,结果如图4所示,实施例3的产品抗黏附医用聚氨酯膜相比对比例1的聚氨酯膜水接触角大幅度下降,水接触角为44°,具有良好的亲水性能。
(3)抗黏附医用聚氨酯膜的抗蛋白黏附性能
分别裁取一定面积的实施例3中的产品抗黏附医用聚氨酯膜与对比例1中的聚氨酯膜置于12孔板中,向其中加入1mg/mL荧光素标记的牛血清白蛋白(BSA-FITC)溶液,随后放入恒温振荡培养箱中在37℃下孵育一定时间,孵育结束后取出膜片并用PBS缓冲液清洗三次,随后拍摄膜片表面的荧光图像并统计荧光强度,结果如图5所示,其中,A为对比例1的聚氨酯膜,B为实施例3的抗黏附医用聚氨酯膜;C为膜上黏附的荧光蛋白的荧光强度对比图;对比例1的聚氨酯膜表面黏附大量的牛血清白蛋白,而实施例3中的产品抗黏附医用聚氨酯膜表面几乎无牛血清白蛋白黏附,证明本发明中的抗黏附医用聚氨酯膜具有良好的抗蛋白黏附能力。
(4)抗黏附医用聚氨酯膜的抗血小板黏附性能
分别裁取一定面积的实施例3中的产品抗黏附医用聚氨酯膜与对比例1中的聚氨酯膜置于12孔板中,加入富血小板血浆。随后放入恒温振荡培养箱中在37℃下孵育一定时间,孵育结束后取出膜片并用PBS缓冲液清洗三次,随后将膜片置于戊二醛溶液中固定过夜,取出膜片后经过清洗、系列浓度梯度乙醇脱水、充分干燥后拍摄膜片表面SEM图像,结果如图6所示,其中,A为对比例1的聚氨酯膜,B为实施例3的抗黏附医用聚氨酯膜;对比例1的聚氨酯膜表面黏附大量的血小板,而实施例3中的产品抗黏附医用聚氨酯膜表面几乎无血小板黏附,证明本发明中的抗黏附医用聚氨酯膜具有良好的抗血小板黏附能力。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上所述的仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种抗黏附医用聚氨酯膜的制备方法,其特征在于,包括以下步骤:
(1)以环氧单体、两性离子单体和引发剂为原料发生聚合反应制备环氧-两性离子共聚物;
(2)通过环氧开环反应,将步骤(1)的环氧-两性离子共聚物接枝到表面含有羟基基团的聚氨酯膜上,得到所述的抗黏附医用聚氨酯膜;
步骤(1)中,环氧单体为甲基丙烯酸缩水甘油酯、4-羟基丁基丙烯酸酯缩水甘油醚或烯丙醇缩水甘油醚,两性离子单体为[2-(甲基丙烯酰基氧基)乙基]二甲基-(3-磺酸丙基)氢氧化铵、3-[[2-(甲基丙烯酰氧)乙基]二甲基铵]丙酸酯和2-甲基丙烯酰氧基乙基磷酰胆碱中的至少一种;
所述的表面含有羟基基团的聚氨酯膜由医用聚氨酯溶液通过溶剂蒸发得到,所述的医用聚氨酯溶液由硬度划分为55D、80D或90A的医用级聚氨酯颗粒溶于有机溶剂制得。
2.根据权利要求1所述的抗黏附医用聚氨酯膜的制备方法,其特征在于,步骤(1)中,环氧单体与两性离子单体的摩尔比为1:9-9:1,引发剂用量为环氧单体与两性离子单体总量的1-8mol%。
3.根据权利要求1所述的抗黏附医用聚氨酯膜的制备方法,其特征在于,所述的聚合反应时间为3-10h,温度为50-90℃。
4.根据权利要求1所述的抗黏附医用聚氨酯膜的制备方法,其特征在于,步骤(2)中,环氧开环反应的具体步骤为:将表面含有羟基基团的聚氨酯膜置于环氧-两性离子共聚物溶液中进行接枝反应,接枝反应温度为50-90℃,接枝反应时间为6-24h。
5.根据权利要求4所述的抗黏附医用聚氨酯膜的制备方法,其特征在于,环氧-两性离子共聚物溶液浓度为5-30mg/mL。
6.根据权利要求1所述的抗黏附医用聚氨酯膜的制备方法,其特征在于,所述的医用聚氨酯溶液的质量浓度为5-20wt%;溶剂蒸发方式为自然干燥或加热真空干燥。
7.根据权利要求1-6任一所述的抗黏附医用聚氨酯膜的制备方法制得的抗黏附医用聚氨酯膜,其特征在于,所述的抗黏附医用聚氨酯膜包括聚氨酯层和两性离子亲水抗黏附层。
8.根据权利要求7所述的抗黏附医用聚氨酯膜在植入式医用材料领域中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211190184.3A CN115558148B (zh) | 2022-09-28 | 2022-09-28 | 一种抗黏附医用聚氨酯膜及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211190184.3A CN115558148B (zh) | 2022-09-28 | 2022-09-28 | 一种抗黏附医用聚氨酯膜及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115558148A CN115558148A (zh) | 2023-01-03 |
CN115558148B true CN115558148B (zh) | 2023-05-23 |
Family
ID=84743297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211190184.3A Active CN115558148B (zh) | 2022-09-28 | 2022-09-28 | 一种抗黏附医用聚氨酯膜及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115558148B (zh) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107236143A (zh) * | 2017-07-21 | 2017-10-10 | 天津大学 | 阳离子‑两性离子共聚物涂层及其制备方法和应用 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130171026A1 (en) * | 2011-12-29 | 2013-07-04 | General Electric Company | Porous membranes having a polymeric coating and methods for their preparation and use |
CN106421906B (zh) * | 2016-07-12 | 2019-06-21 | 天津大学 | 带有环氧官能团的两性离子无规共聚物表面修饰涂层及制备方法和应用 |
CN106750450B (zh) * | 2016-11-07 | 2020-10-27 | 西安科技大学 | 含有环氧磷酰胆碱聚合物与多巴胺交联粘附仿生涂层的制备方法 |
CN113877006A (zh) * | 2021-09-24 | 2022-01-04 | 宁波健世科技股份有限公司 | 一种改性高分子膜材料及其制备方法 |
-
2022
- 2022-09-28 CN CN202211190184.3A patent/CN115558148B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107236143A (zh) * | 2017-07-21 | 2017-10-10 | 天津大学 | 阳离子‑两性离子共聚物涂层及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN115558148A (zh) | 2023-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ishihara et al. | Synthesis of phospholipid polymers having a urethane bond in the side chain as coating material on segmented polyurethane and their platelet adhesion-resistant properties | |
Park et al. | PDMS-based polyurethanes with MPEG grafts: synthesis, characterization and platelet adhesion study | |
JP3836444B2 (ja) | ハイドロキシアパタイト複合体およびその製造方法、ならびに、それを用いた医療用材料 | |
Ishihara et al. | Improved blood compatibility of segmented polyurethanes by polymeric additives having phospholipid polar groups. I. Molecular design of polymeric additives and their functions | |
AU711425B2 (en) | Fluoroligomer surface modifiers for polymers and articles made therefrom | |
Park et al. | Polysulfone-graft-poly (ethylene glycol) graft copolymers for surface modification of polysulfone membranes | |
US8142717B2 (en) | Oxygenator of a hollow fiber membrane type | |
Wang et al. | A facile way to prepare anti-fouling and blood-compatible polyethersulfone membrane via blending with heparin-mimicking polyurethanes | |
Ishihara et al. | Improvement of blood compatibility on cellulose hemodialysis membrane: IV. Phospholipid polymer bonded to the membrane surface | |
CN115558148B (zh) | 一种抗黏附医用聚氨酯膜及其制备方法和应用 | |
EP2100627B1 (en) | (meth)acrylate copolymer, process for producing the same and medical device | |
EP0921139A1 (en) | Modified polymers containing poly(2-hydroxyethyl (meth)acrylate) segment in the molecule | |
Yang et al. | Preparation of poly (acrylic acid) modified polyurethane membrane for biomaterial by UV radiation without degassing | |
CN1673271A (zh) | 以聚偏氟乙烯/聚氨酯共混膜为基膜的pH敏感膜及其制备工艺 | |
Moriwaki et al. | Phospholipid polymer hydrogels with rapid dissociation for reversible cell immobilization | |
Li et al. | AB crosslinked polymer latexes via concentrated emulsion polymerization | |
US20040127986A1 (en) | Ionic electroactive graft copolymer with a fluorine-containing backbone and a carbazole-containing side chain, blend thereof and actuator | |
Aguilar et al. | Polymeric active coatings with functionality in vascular applications | |
Park et al. | Sulfonated poly (ethylene glycol) containing methacrylate copolymer surfaces; preparation, characterization and in vitro biocompatibility | |
US7368505B2 (en) | Graft copolymers | |
JP4097762B2 (ja) | 抗血栓性医用材料 | |
CN109646716B (zh) | 人工角膜光学中心部及其制备方法和人工角膜 | |
JP4604177B2 (ja) | 抗血栓性高分子組成物 | |
JPS60119955A (ja) | 生体材料用の合成高分子体 | |
Jain et al. | Investigation of Water Sorption and Blood Compatible Behaviors of Polyethylene Glycol (PEG)—Plasticized Membranes of Poly (Vinyl Alcohol-g-Acrylonitrile) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |