CN116375963A - 一种水性聚氨酯防黏附涂层的制备方法和应用 - Google Patents
一种水性聚氨酯防黏附涂层的制备方法和应用 Download PDFInfo
- Publication number
- CN116375963A CN116375963A CN202310250585.1A CN202310250585A CN116375963A CN 116375963 A CN116375963 A CN 116375963A CN 202310250585 A CN202310250585 A CN 202310250585A CN 116375963 A CN116375963 A CN 116375963A
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- fluorinated
- acrylic
- polyurethane emulsion
- reacting
- 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.)
- Pending
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 97
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 95
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 15
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Chemical group 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 12
- 150000002009 diols Chemical group 0.000 claims abstract description 12
- 239000004417 polycarbonate Substances 0.000 claims abstract description 12
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Chemical group 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 125000003827 glycol group Chemical group 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical group 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000001723 curing Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000007774 longterm Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 229920006264 polyurethane film Polymers 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 208000007536 Thrombosis Diseases 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 238000012258 culturing Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 108010087230 Sincalide Proteins 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000010609 cell counting kit-8 assay Methods 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 208000015181 infectious disease Diseases 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 tetramethylene, hexamethylene Chemical group 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 102000004506 Blood Proteins Human genes 0.000 description 1
- 108010017384 Blood Proteins Proteins 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 206010062546 Thrombosis in device Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000006143 cell culture medium Substances 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- VUUAEBBAUMJPRE-UHFFFAOYSA-N ethyl n-fluorocarbamate Chemical compound CCOC(=O)NF VUUAEBBAUMJPRE-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 230000000004 hemodynamic effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000000642 iatrogenic effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000036407 pain Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 210000000626 ureter Anatomy 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
-
- 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
- A61L29/085—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
- 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
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
本发明属于医疗器械的表面涂层材料合成及应用技术领域,本发明提供了一种水性聚氨酯防黏附涂层的制备方法和应用等,新的氟化水性聚氨酯乳液由含丙烯基多氟化物与水性聚氨酯分散液反应得到;所述含丙烯基多氟化物中氟原子个数为10~14;所述水性聚氨酯分散液的聚氨酯分子链中,以脂肪族聚碳酸酯二醇和聚乙二醇结构为软段,4,4'‑二环己基甲烷二异氰酸酯结构为硬段,2,2‑二羟甲基丙酸结构为内乳化剂部分,并且含有双硫键结构。本发明提供的氟化水性聚氨酯材料及其涂层具有优异的生物相容性和防黏附性,可应用于长期置留介入类医疗器械。
Description
技术领域
本发明属于医疗器械的表面涂层材料合成及应用技术领域,具体为一种氟化水性聚氨酯乳液、防黏附涂层及制备方法和应用,包括一种水性聚氨酯防黏附涂层的制备方法等。
背景技术
医疗器械包括介入类,例如,输尿管支架用于人体输尿管的支撑和引流,人体内留置时间为30天到1年不等。血管内导管包括中心静脉导管、外周静脉导管、动脉导管、球囊扩张导管、漂浮导管等,是血流动力学监测、安全输液、静脉营养支持及血液透析等治疗手段的主要依赖途径,已成为临床医疗实践中不可或缺的重要医疗器械。目前,长期介入类医疗器械存在结垢(如输尿管支架在留置过程中,其表面有尿液中的沉积物附着或嵌入形成坚硬外壳的现象)、引发感染、血栓阻塞等问题,给患者造成多重痛苦并增加医疗费用。因此,长期留置医疗器械领域,开发有效防止沉积物附着、细菌粘黏、血浆蛋白和血小板黏附的防黏附涂层具有重要意义。
具有低表面能的氟原子在热力学驱动力下倾向于迁移到聚合物-空气表界面形成防黏附层。聚氨酯因其与众多聚合物之间具有良好的相容性,而被广泛用于医疗行业。因此,氟功能化的水性聚氨酯可被用于医疗器械的防黏附涂层材料。
现阶段,用于制备氟功能化水性聚氨酯的方法主要有:1.通过聚氨酯化学,将羟基功能化的氟化物引入到聚氨酯分子链上;2.通过过硫酸盐催化的烯烃click化学,将含双键的氟化物引入到聚氨酯分子链上。就第一种方法而言,当氟含量过高时,聚氨酯分子链的高疏水性会导致制备的水性聚氨酯分散液不稳定,甚至使聚氨酯分子链不能在水中分散。而通过烯烃click化学引入氟化物的方法中,双键封端的聚氨酯预聚物与双键功能化氟化物乳液聚合需要添加大量的过硫酸盐催化剂。
发明内容
针对上述问题,本发明提供一种新的氟化水性聚氨酯乳液制备方法和应用。本发明提供的氟化水性聚氨酯材料及其涂层具有优异的生物相容性和防黏附性,可应用于长期置留介入类医疗器械。
本发明提供一种氟化水性聚氨酯乳液,其由含丙烯基多氟化物与水性聚氨酯分散液反应得到;
所述含丙烯基多氟化物中氟原子个数为10~14;所述水性聚氨酯分散液的聚氨酯分子链中,以脂肪族聚碳酸酯二醇和聚乙二醇结构为软段,4,4'-二环己基甲烷二异氰酸酯结构为硬段,2,2-二羟甲基丙酸结构为内乳化剂部分,并且含有双硫键结构。
优选地,所述含丙烯基多氟化物为甲基丙烯酸十二氟庚酯。
本发明提供如前文所述的氟化水性聚氨酯乳液的制备方法,包括以下步骤:
S1、将异氰酸酯基封端的聚氨酯预聚物与2,2-二羟甲基丙酸在溶剂中反应,得到聚氨酯溶液;所述聚氨酯预聚物由脂肪族聚碳酸酯二醇、聚乙二醇和4,4'-二环己基甲烷二异氰酸酯聚合形成;
S2、将所述聚氨酯溶液与胺基功能化的双硫化物进行反应,并在水中分散,去除所述溶剂,得到水性聚氨酯分散液;
S3、将所述水性聚氨酯分散液与含丙烯基多氟化物进行反应,得到氟化水性聚氨酯乳液。
优选地,步骤S1中,所述反应的温度为70-90℃,时间为1-3h;所述溶剂为丙酮。
优选地,步骤S2中,所述反应的温度为70-90℃,时间为1-3h。
优选地,步骤S2中,所述反应之后还进行中和,通过机械搅拌在水中分散至少20分钟,去除所述溶剂得到水性聚氨酯分散液。
优选地,步骤S3具体包括:将含丙烯基多氟化物加入所述水性聚氨酯分散液中,搅拌分散后升温至70-85℃,在不使用催化剂条件下反应1-3h,得到氟化水性聚氨酯乳液。
优选地,所述胺基功能化的双硫化物为4,4-二氨基二苯二硫。
本发明提供一种氟化水性聚氨酯的制备方法,由前文所述的双硫键-烯加成反应制得。
本发明提供一种防黏附涂层,由前文所述的氟化水性聚氨酯乳液经涂覆、干燥固化形成。
本发明还提供如前文所述的防黏附涂层在介入类医疗器械中的应用。
与现有技术相比,本发明实施例将双硫键引入到水性聚氨酯分子链中,其与丙烯基多氟化物通过双硫键-烯的加成反应,在无需使用过硫酸盐催化剂的条件下制得氟化水性聚氨酯乳液。本发明避免了过硫酸盐催化剂的使用,使氟化水性聚氨酯乳液中无过硫酸盐残留,所得防黏附涂层具有优异的生物相容性。并且,所述氟化水性聚氨酯材料具有低表面能,可用于长期置留介入类医疗器械表面防黏附涂层。
附图说明
图1为本发明实施例中双硫键-烯加成反应制备氟化水性聚氨酯材料的流程示意图;
图2为实施例1中氟化水性聚氨酯膜FTIR谱图;
图3为实施例1中氟化水性聚氨酯膜拉曼谱图;
图4为实施例2中的铺板实验测定氟化水性聚氨酯和无氟聚氨酯膜的细菌数。
具体实施方式
下面对本申请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申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,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,都属于本申请保护的范围。
本发明提供了一种氟化水性聚氨酯乳液,其由含丙烯基多氟化物与水性聚氨酯分散液反应得到;
所述含丙烯基多氟化物中氟原子个数为10~14;所述水性聚氨酯分散液的聚氨酯分子链中,以脂肪族聚碳酸酯二醇和聚乙二醇结构为软段,4,4'-二环己基甲烷二异氰酸酯结构为硬段,2,2-二羟甲基丙酸结构为内乳化剂部分,并且含有双硫键结构。
本发明实施例提供了如前文所述的氟化水性聚氨酯乳液的制备方法,包括以下步骤:
S1、将异氰酸酯基封端的聚氨酯预聚物与2,2-二羟甲基丙酸反应,并加入适量丙酮,调节体系粘度,得到聚氨酯溶液;所述聚氨酯预聚物由脂肪族聚碳酸酯二醇、聚乙二醇和4,4'-二环己基甲烷二异氰酸酯聚合形成;
S2、将所述聚氨酯溶液与4,4-二氨基二苯二硫等胺基功能化的双硫化物进行反应,并在水中分散,去除所述溶剂,得到水性聚氨酯分散液;
S3、将所述水性聚氨酯分散液与含丙烯基多氟化物进行反应,得到氟化水性聚氨酯乳液。
本发明实施例提供了一种新的氟化水性聚氨酯材料及其防黏附涂层的制备方法,可在不加入催化剂情况下,通过双硫键-烯的加成反应制备氟功能化的水性聚氨酯乳液。在本发明实施例中,首先,种子乳液聚合不会影响聚氨酯分子链在水中分散性。其次,由于芳香族双硫化物的高动态性,在温和的条件下即可断裂生成硫自由基,进而与含双键的氟化物反应,此过程避免了催化剂的使用。
参见图1,图1为本发明实施例中双硫键-烯加成反应制备氟化水性聚氨酯材料的流程示意图。
本发明实施例首先制备获得聚氨酯预聚物,可将脂肪族聚碳酸酯二醇(PCD)、聚乙二醇(PEG)和4,4'-二环己基甲烷二异氰酸酯(HMDI)混合,加入催化剂二月桂酸二丁基锡(DBTDL),在80℃反应2h,聚合形成所述聚氨酯预聚物。反应式如下所示:
其中,所述脂肪族聚碳酸酯二醇的脂肪碳链可以为四亚甲基、六亚甲基等;脂肪族聚碳酸酯二醇分子量300-2000。并且,所述聚乙二醇分子量600-2000。所述的催化剂也可以采用其他有机锡类、钛类等,优选的催化剂为有机锡类,用量0.1wt%-0.5wt%。作为优选,所述的二元醇与二异氰酸酯原料摩尔比1:2;反应温度优选为70-90℃,进一步优选为80℃,反应时间可为1-3h。
所述的聚氨酯预聚物结构简要表示如下,其也可以采用市售;
本发明实施例将得到的聚氨酯预聚物与2,2-二羟甲基丙酸进行扩链反应,2,2-二羟甲基丙酸(DMPA)也作为内乳化剂,并加入适量的丙酮等溶剂调节体系粘度,反应后得聚氨酯溶液。二羟甲基丙酸(分子式是C5H10O4)在水性聚氨酯制造中既是扩链剂,又能使聚氨酯获得自乳化性能,可制成稳定性优良的自乳化性水性聚氨酯。
在本发明实施例上述的步骤中,对所述2,2-二羟甲基丙酸的用量没有特殊限定,只需能使聚氨酯分子链在水中分散即可;所述反应的温度可为70-90℃,优选为80℃,所述反应的时间可为1-3h,优选为1.5-2h。所得的聚氨酯溶液中,水性聚氨酯结构简要表示如下:
本发明实施例将所述的聚氨酯溶液与芳香族双硫化物,如4,4-二氨基二苯二硫进行反应,所述的胺基功能化的双硫化物优选为4,4-二氨基二苯二硫。反应结束后,可用三乙胺进行中和,通过机械搅拌在水中分散至少20分钟,旋蒸除去上述的溶剂丙酮,得到水性聚氨酯分散液。
在本发明中,所采用的4,4-二氨基二苯二硫是含有双硫键(-S-S-)的芳香族二胺,结构式如下。本发明将双硫键引入到水性聚氨酯分子结构中,以便后续制备氟化水性聚氨酯材料(Fluorinated waterborne polyurethane)。所述反应的温度优选为70-90℃,更优选为80℃;时间可为1-3h。然后,本发明实施例用与DMPA等摩尔量的三乙胺中和(Neutralizationg),可在5000-6000rpm转速下,水中乳化分散(Emulsification),时间优选30分钟,得到二硫键功能化的水性聚氨酯。
去除丙酮后,本发明实施例将含丙烯基多氟化物加入上述水性聚氨酯分散液中,优选搅拌分散30分钟,然后温度升温至70-85℃,在不使用催化剂条件下可反应1-3h,得到氟化水性聚氨酯乳液。
其中,所述含丙烯基多氟化物中氟(F)原子个数为10~14,优选为11~12;所述含丙烯基多氟化物进一步优选为甲基丙烯酸十二氟庚酯,结构如下所示。所述含丙烯基多氟化物的用量可为5.3wt%-17.5wt%;进行氟化反应的温度优选为80℃,且无需使用催化剂。
本发明实施例首先通过种子乳液聚合得到水性聚氨酯分散液,不会影响聚氨酯分子链在水中分散性;所述水性聚氨酯分散液的聚氨酯分子链中,以脂肪族聚碳酸酯二醇和聚乙二醇结构为软段,4,4'-二环己基甲烷二异氰酸酯结构为硬段,2,2-二羟甲基丙酸结构为扩链部分,并且含有双硫键结构。再次,由于本发明所用的芳香族双硫化物的高动态性,在不使用催化剂的温和条件下即可断裂生成硫自由基,进而与含双键的氟化物反应,使得到的氟化水性聚氨酯材料的生物相容性较好,利于应用。在本发明的实施例中,所述氟化水性聚氨酯乳液无催化剂残留,粒径:180nm-290nm;含氟量:3wt%-7wt%;固含量:2wt%-40wt%。
本发明提供了一种防黏附涂层,由前文所述的氟化水性聚氨酯乳液经涂覆、干燥固化形成。具体地,将医用器械浸渍到氟化水性聚氨酯中,或将氟化水性聚氨酯喷涂到医用器械上,80-110℃干燥5-30分钟。重复涂敷,干燥过程直至涂层厚度在0.1-240μm的范围内、优选在0.5-120μm的范围内、更优选在1-25μm的范围内。所述的医疗器械材质例如:聚氨酯、尼龙及尼龙弹性体、聚砜、聚乙烯、聚氯乙烯、硅胶等。
并且,本发明还提供了如前文所述的防黏附涂层在介入类医疗器械中的应用。具体地,将所述的氟化水性聚氨酯乳液涂覆到医疗器械表面,干燥固化,得到防黏附的氟化水性聚氨酯涂层。在本发明实施例中,所述的介入类医疗器械包括但不限于:输尿管支架、血管内导管。
血栓是指导管相关性血栓,引起导管相关性血栓发生的原因较多,主要分药物因素、患者因素、导管因素以及医源性因素四类。其中,导管因素是根据临床研究发现,置入患者血管内的导管材质,也会影响导管相关性血栓的发生率。若患者血管内导管是由聚乙烯、聚氯乙烯材质制成的,则对血管造成损伤并激发感染的可能性较高,从而导致患者出现导管相关性血栓。本发明优选聚氨酯、硅橡胶等材质的血管内导管,进行表面涂层。
本发明实施例通过双硫键-烯的加成反应制得氟化水性聚氨酯材料,避免了过硫酸盐催化剂的使用,使所得防黏附涂层具有优异的生物相容性,可用于长期置留介入类医疗器械。本发明所述的氟化水性聚氨酯乳液在基材表面形成涂层,不仅生物相容性优异,而且赋予医疗器械优异的防黏附性能,进而有效防止输尿管支架结垢、引发感染,防止血管内导管血栓形成,使医疗器械可长期留置体内。
为了更好理解本发明技术内容,下面提供具体实施例,对本发明做进一步的说明。
实施例1
将脂肪族聚碳酸酯二醇(Mn=2000g/mol)16g、聚乙二醇(Mn=2000g/mol)4g和4,4'-二环己基甲烷二异氰酸酯5.25g混合,加入催化剂DBTDL,在80℃反应2h,聚合形成聚氨酯预聚物;然后加入2,2-二羟甲基丙酸1.07g,并加入适量的丙酮调节体系粘度,在80℃反应2h。将得到的聚氨酯溶液与4,4-二氨基二苯二硫0.5g,在80℃进行反应,2h后,用与DMPA等摩尔量的三乙胺中和,在6000rpm转速下,水中分散30分钟。旋蒸除去丙酮后,将甲基丙烯酸十二氟庚酯2.68g加入得到的水性聚氨酯分散液中,搅拌分散30分钟,然后温度升至80℃,反应2小时得氟功能化水性聚氨酯乳液。
产物结构表征参见图2和图3。如图2所示,FTIR谱图中没有探测到2270cm-1处异氰酸酯基(-NCO)峰,说明异氰酸酯基完全反应生成氨酯基和脲基。归属于氨酯基和脲基的C=O伸缩振动峰出现在1704.9cm-1处。而谱图中出现的C-F(1220.8cm-1)及甲基丙烯酸十二氟庚酯的C-H(972.1cm-1)峰,说明甲基丙烯酸十二氟庚酯通过双硫键-烯加成反应引入到聚氨酯分子链中。图3为氟化水性聚氨酯膜拉曼谱图,图中亦出现双硫键的特征峰,说明4,4-二氨基二苯二硫成功引入到聚氨酯分子链中。综上,通过FTIR及拉曼测试,证明本申请通过双硫键-烯加成反应成功合成了氟化水性聚氨酯。
实施例2
将实施例1得到的氟化水性聚氨酯乳液涂覆到医疗器械表面,100-110℃干燥15-20分钟。重复涂敷,干燥过程直至涂层厚度在5-20μm的范围内。所述的医疗器械材质:常规医用聚氨酯。
防粘附性能测试
通过采用菌落计数法来评价涂层的抗细菌粘附性能。将分装好的金黄色葡萄球菌菌种放在-80℃的冰箱中。取100μL上述菌种与10mL LB液体培养基到摇菌管中,放在细菌摇床上,在37℃,120r/min条件下,振荡24h。取8mL上述菌液到离心管中,在3000r/min的条件下,离心10min,保留下层的细菌沉淀,用PBS溶液分散至细菌浓度为108CFU/mL(酶标仪测定,OD值为0.1)。将1cm×1cm的氟功能化聚氨酯膜(Fluorinated PU)和无氟聚氨酯膜(Fluorine-free PU)分别置于24孔板中,取10μL的108CFU/mL菌液,滴加到硅片表面,盖上PE膜(0.7cm×0.7cm),在37℃的生物培养箱中培养4h,随后用1mL的PBS溶液冲洗聚氨酯膜3次。把聚氨酯膜放入离心管中,加入2mL PBS,超声2分钟,取200μL离心管中液体到装有LB固体培养基的培养皿上,用10个无菌珠在LB固体培养基表面摇匀,在37℃的生物培养箱中培养24h,取出培养皿,根据铺板实验照片,统计细菌数(BacterialCount)。
如图4所示,经铺板实验检测,氟化水性聚氨酯膜表面检测到2.0×102CFU/cm2活细菌,无氟聚氨酯膜表面检测到6.1×106CFU/cm2活细菌,说明本方案制备的氟化水性聚氨酯膜具有优异的防粘附性能。
生物相容性测试(细胞毒性)
细胞毒性实验采用CCK-8法测试。将氟功能化聚氨酯膜和无氟聚氨酯膜用0.9%的生理盐水在37℃浸泡24h,体外培养L929细胞,并制备细胞悬液,将1×104个细胞/100μL接种至96孔板中,每组3个重复,在37℃培养箱中孵育24h。将浸提液加入到贴壁生长的L929小鼠纤维细胞表面,培养24h后取出细胞培养液,再将10μL的CCK-8溶液和90μL的培养基加入细胞,在生物培养箱培养2h后测450nm处的OD值。空白组具有培养基和CCK-8溶液而没有细胞,阳性对照组不加样品只加细胞培养液,使用如下公式计算细胞活性。
经测试,氟化水性聚氨酯膜的细胞存活率为91.2%,膜在体外细胞毒性反应级别为一级。
由以上实施例可知,本发明实施例将双硫键引入到水性聚氨酯分子链中,其与丙烯基多氟化物通过双硫键-烯的加成反应,在无需使用过硫酸盐催化剂的条件下制得氟化水性聚氨酯乳液。本发明避免了过硫酸盐催化剂的使用,使氟化水性聚氨酯乳液中无过硫酸盐残留,所得防黏附涂层具有优异的生物相容性。并且,所述氟化水性聚氨酯材料具有低表面能,可用于长期置留介入类医疗器械表面防黏附涂层。
本文中应用了具体个例对本发明的原理及实施方式进行了阐述,以上实例的说明只是用于帮助理解本发明的方法及其核心思想。以上所述仅是本发明的优选实施方式,应当指出,由于文字表达的有限性,而客观上存在无限的具体结构,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进、润饰或变化,也可以将上述技术特征以适当的方式进行组合;这些改进润饰、变化或组合,或未经改进将发明的构思和技术方案直接应用于其它场合的,均应视为本发明的保护范围。
Claims (10)
1.一种氟化水性聚氨酯乳液,其特征在于,由含丙烯基多氟化物与水性聚氨酯分散液反应得到;
所述含丙烯基多氟化物中氟原子个数为10~14;所述水性聚氨酯分散液的聚氨酯分子链中,以脂肪族聚碳酸酯二醇和聚乙二醇结构为软段,4,4'-二环己基甲烷二异氰酸酯结构为硬段,2,2-二羟甲基丙酸结构为内乳化剂部分,并且含有双硫键结构。
2.根据权利要求1所述的氟化水性聚氨酯乳液,其特征在于,所述含丙烯基多氟化物为甲基丙烯酸十二氟庚酯。
3.如权利要求1或2所述的氟化水性聚氨酯乳液的制备方法,包括以下步骤:
S1、将异氰酸酯基封端的聚氨酯预聚物与2,2-二羟甲基丙酸在溶剂中反应,得到聚氨酯溶液;所述聚氨酯预聚物由脂肪族聚碳酸酯二醇、聚乙二醇和4,4'-二环己基甲烷二异氰酸酯聚合形成;
S2、将所述聚氨酯溶液与胺基功能化的双硫化物进行反应,并在水中分散,去除所述溶剂,得到水性聚氨酯分散液;
S3、将所述水性聚氨酯分散液与含丙烯基多氟化物进行反应,得到氟化水性聚氨酯乳液。
4.根据权利要求3所述的氟化水性聚氨酯乳液的制备方法,其特征在于,步骤S1中,所述反应的温度为70-90℃,时间为1-3h;所述溶剂为丙酮。
5.根据权利要求3所述的氟化水性聚氨酯乳液的制备方法,其特征在于,步骤S2中,所述反应的温度为70-90℃,时间为1-3h。
6.根据权利要求5所述的氟化水性聚氨酯乳液的制备方法,其特征在于,步骤S2中,所述反应之后还进行中和,通过机械搅拌在水中分散至少20分钟,去除所述溶剂得到水性聚氨酯分散液。
7.根据权利要求3-6任一项所述的氟化水性聚氨酯乳液的制备方法,其特征在于,步骤S3具体包括:将含丙烯基多氟化物加入所述水性聚氨酯分散液中,搅拌分散后升温至70-85℃,在不使用催化剂条件下反应1-3h,得到氟化水性聚氨酯乳液。
8.根据权利要求7所述的氟化水性聚氨酯乳液的制备方法,其特征在于,所述胺基功能化的双硫化物为4,4-二氨基二苯二硫。
9.一种防黏附涂层,由权利要求1或2所述的氟化水性聚氨酯乳液经涂覆、干燥固化形成。
10.如权利要求9所述的防黏附涂层在介入类医疗器械中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310250585.1A CN116375963A (zh) | 2023-03-13 | 2023-03-13 | 一种水性聚氨酯防黏附涂层的制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310250585.1A CN116375963A (zh) | 2023-03-13 | 2023-03-13 | 一种水性聚氨酯防黏附涂层的制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116375963A true CN116375963A (zh) | 2023-07-04 |
Family
ID=86972233
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310250585.1A Pending CN116375963A (zh) | 2023-03-13 | 2023-03-13 | 一种水性聚氨酯防黏附涂层的制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116375963A (zh) |
-
2023
- 2023-03-13 CN CN202310250585.1A patent/CN116375963A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3368582B1 (en) | Polyurethane/urea materials | |
US6177523B1 (en) | Functionalized polyurethanes | |
EP0396431B1 (en) | Elastomeric segmented hydrophilic polyetherurethane based lubricious coatings | |
DE69818063T2 (de) | Silizium enthaltender kettenverlängerer | |
AU2007233559C1 (en) | Biostable polyurethanes | |
US20210268543A1 (en) | Surfaces resistant to bacterial adhesion | |
CA2039393C (en) | Melt processable polyurethaneurea copolymers and method for their preparation | |
JPS62500726A (ja) | 生物適合性表面に関する改良 | |
JPH05507953A (ja) | ポリウレタンまたはポリウレタン尿素エラストマー組成物 | |
JPH04226119A (ja) | 生体内で安定なポリウレタンおよびその製造方法 | |
JPH0410892B2 (zh) | ||
US7538163B2 (en) | Modification of thermoplastic polymers | |
US8647718B2 (en) | Wet lubricant surface coating having excellent durability, method for surface coating, and a medical device having the surface coating | |
CN114456346B (zh) | 具有生物稳定性和力学稳定性的聚氨酯及制备方法与应用 | |
CN112831013B (zh) | 一种功能化聚氨酯及其制备方法和应用 | |
CN116375963A (zh) | 一种水性聚氨酯防黏附涂层的制备方法和应用 | |
CN114015015B (zh) | 一种聚氨酯、其制备方法及应用 | |
CN110885422B (zh) | 一种含二碲的可降解聚碳酸酯聚氨酯及其制备方法 | |
Nor et al. | Palm kernel oil-based polyurethane film: Biocompatibility and antibacterial activity studies | |
CN116376087B (zh) | 一种聚氨酯材料表面的亲水抗菌抗污改性方法 | |
EP4316541A1 (en) | Composition for medical use and application of same | |
CN115490827A (zh) | 聚碳酸酯聚二甲基硅氧烷型聚氨酯脲及制备方法 | |
WO2023100827A1 (ja) | 医療機器 | |
BRPI1106992A2 (pt) | Uso de membranas biopoliméricas em próteses cardiovasculares | |
CN117843909A (zh) | 一种聚氨酯或聚氨酯脲材料及其制备方法和应用 |
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 |