CN116425946A - Polyurethane material based on curcumin and preparation method and application thereof - Google Patents
Polyurethane material based on curcumin and preparation method and application thereof Download PDFInfo
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- CN116425946A CN116425946A CN202310458595.4A CN202310458595A CN116425946A CN 116425946 A CN116425946 A CN 116425946A CN 202310458595 A CN202310458595 A CN 202310458595A CN 116425946 A CN116425946 A CN 116425946A
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- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 title claims abstract description 326
- 229940109262 curcumin Drugs 0.000 title claims abstract description 142
- 239000004148 curcumin Substances 0.000 title claims abstract description 141
- 235000012754 curcumin Nutrition 0.000 title claims abstract description 141
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000000463 material Substances 0.000 title claims abstract description 66
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- -1 amine modified curcumin Chemical class 0.000 claims abstract description 41
- 239000004970 Chain extender Substances 0.000 claims abstract description 39
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 16
- 230000003110 anti-inflammatory effect Effects 0.000 abstract description 10
- 150000002466 imines Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 92
- 239000000243 solution Substances 0.000 description 91
- 238000003756 stirring Methods 0.000 description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229920006264 polyurethane film Polymers 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- RMCLKZFGXBSDIO-UHFFFAOYSA-N 3,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC(O)O RMCLKZFGXBSDIO-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000941 anti-staphylcoccal effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- NVEPXBVOEVVLHX-UHFFFAOYSA-N pent-4-ene-2,3-diol Chemical compound CC(O)C(O)C=C NVEPXBVOEVVLHX-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 229940123208 Biguanide Drugs 0.000 description 1
- 206010019909 Hernia Diseases 0.000 description 1
- 208000037273 Pathologic Processes Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004283 biguanides Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 230000007123 defense Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009054 pathological process Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003222 pyridines Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6795—Unsaturated polyethers
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention belongs to the technical field of high polymer materials, and discloses a polyurethane material based on curcumin, and a preparation method and application thereof. The raw materials for preparing the curcumin-based polyurethane material comprise: curcumin chain extender and polyether amine modified curcumin. The curcumin chain extender and the polyether amine modified curcumin adopted by the invention both contain natural antibacterial and anti-inflammatory components curcumin, and the curcumin is taken as a main component synthesized by the polyurethane material, so that the content of the antibacterial and anti-inflammatory components in the polyurethane material can be obviously improved, the curcumin content in the polyurethane material can reach about 30 percent, and the transparency and mechanical property of the material are not affected; meanwhile, imine bonds in the polyether amine modified curcumin are reversible dynamic covalent bonds, and through permeation of water molecules, the imine dynamic bonds are slowly hydrolyzed, so that the curcumin can be effectively controlled to be slowly released.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyurethane material based on curcumin, and a preparation method and application thereof.
Background
Thermoplastic Polyurethane (TPU) is a polymeric material polymerized by the co-reaction of diisocyanate, a macromolecular polyol and a chain extender, which consists of soft segments and hard segments, which are connected by covalent bonds along a linear macromolecular backbone, and which can be made from different original molecular components. TPU has very good stability, chemical resistance, rebound resilience and mechanical properties, has smaller compression set and is widely used in the construction, automotive, aerospace, shoemaking industries, adhesives, coatings, synthetic leather and medical industries. In recent years, bio-based TPU made with renewable molecular building blocks have been used in the biomedical field due to their high tunability, mechanical properties of responsiveness, controlled biodegradation, and formation of low toxic residues. But has higher requirements on the biocompatibility and antibacterial property of materials in the medical field, especially in the aspect of in vivo tissue engineering scaffolds.
The polyurethane material with the antibacterial effect is mostly prepared by adding antibacterial agents into the polyurethane material for blending, wherein the added antibacterial agents are nano silver particles, nano zinc oxide, nano titanium oxide, quaternary ammonium salt, quaternary phosphonium salt, pyridine compounds, biguanides, alcohols, phenols, aldehydes, organic acids, halogen-containing compounds and the like. The antibacterial polyurethane material prepared by physically blending an antibacterial agent and polyurethane has the following disadvantages: the antibacterial agent has certain toxicity, and the physical blending mode loads the antibacterial agent, so that the loading capacity is low, the release of the antibacterial agent is difficult to control, and the aim of long-acting antibacterial is not achieved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the polyurethane material based on the curcumin contains high-content natural antibacterial and anti-inflammatory component curcumin, can effectively control the slow release of the curcumin, and has long-acting antibacterial and anti-inflammatory effects.
The first aspect of the invention provides a polyurethane material based on curcumin, the raw materials for preparing the polyurethane material based on curcumin comprise: curcumin chain extender and polyether amine modified curcumin;
the curcumin chain extender has a structural general formula shown in the following formula (1):
a compound wherein R is a terminal or side chain containing one or more hydroxyl groups;
the structural general formula of the polyether amine modified curcumin is shown as the following formula (2):
wherein n is 1 Is an integer of 1 to 50, R 0 Is H or-CH 3 A group.
Preferably, the structural general formula of the curcumin-based polyurethane material is shown as the following formula (3):
wherein R is 1 Is diisocyanate, R 2 Is dihydric alcohol, m 2 Is an integer of 10 to 50, m 3 Is an integer of 10 to 50, m 4 E is a polyurethane repeating unit chain segment, and F is polyether amine modified curcumin.
Preferably, the curcumin chain extender is selected from one or more of the following compounds:
preferably, the polyetheramine modified curcumin is selected from one or more of the following compounds:
the second aspect of the invention provides a preparation method of the polyurethane material based on curcumin, which comprises the following steps: dissolving the curcumin chain extender in a polar solvent, mixing with dihydric alcohol, diisocyanate and HDI trimer, and reacting to obtain a curcumin polyurethane prepolymer;
and mixing the polyether amine modified curcumin and the curcumin polyurethane prepolymer, and reacting to obtain the curcumin-based polyurethane material.
Preferably, the preparation method of the curcumin-based polyurethane material comprises the following steps:
dissolving the curcumin chain extender in a polar solvent, adding dihydric alcohol and diisocyanate, stirring and reacting for 1-24 hours at 30-70 ℃, then adding HDI trimer, stirring and reacting for 3-24 hours at 40-60 ℃ to obtain a curcumin polyurethane prepolymer;
mixing the polyether amine modified curcumin and curcumin polyurethane prepolymer, and reacting to obtain the curcumin-based polyurethane material
Preferably, the mass ratio of the curcumin chain extender in the curcumin polyurethane prepolymer is 0.5-40%. More preferably, the curcumin chain extender accounts for 10-20% of the curcumin polyurethane prepolymer by mass.
Preferably, the preparation method of the curcumin chain extender comprises the following steps:
dissolving curcumin in a polar solvent, mixing with a compound with one or more hydroxyl groups at the tail end or side chains and an alkaline catalyst, and reacting to obtain the curcumin chain extender.
Preferably, the preparation method of the curcumin chain extender comprises the following steps:
dissolving curcumin in a polar solvent, adding a compound with one or more hydroxyl groups at the tail end or side chain and an alkaline catalyst, stirring for 8-60 hours at room temperature, pouring the mixed solution into water, washing the obtained precipitate with water, and drying to obtain the curcumin chain extender.
Preferably, the compound having one or more hydroxyl groups at the terminal or side chain comprises one or more of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, vinyl glycol ether, vinyl propylene glycol ether, and dihydroxypropyl methacrylate.
Preferably, the basic catalyst comprises potassium hydroxide and/or sodium hydroxide.
Preferably, the polar solvent comprises tetrahydrofuran and/or acetone.
Preferably, the glycol comprises polytetrahydrofuran glycol and/or polycaprolactone glycol.
Preferably, the diisocyanate comprises a mixture of one or more of diisocyanate comprising Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), hexamethylene Diisocyanate (HDI).
Preferably, the structural general formula of the curcumin polyurethane prepolymer is shown as the following formula (4):
wherein R is 1 Is one or more diisocyanates of TDI, HDI, MDI, IPDI, R 2 Is dihydric alcohol, m 2 Is an integer of 10 to 50, m 3 Is an integer of 10 to 50, m 4 And E is a polyurethane repeating unit chain segment, and is an integer of 1-50.
Preferably, the mass ratio of the curcumin polyurethane prepolymer to the polyether amine modified curcumin is 1-99.5. Further, the mass ratio of the curcumin polyurethane prepolymer to the polyether amine modified curcumin is 1-50. Further, the mass ratio of the curcumin polyurethane prepolymer to the polyether amine modified curcumin is 1-17.
Preferably, the preparation method of the polyetheramine modified curcumin comprises the following steps:
mixing curcumin and polyetheramine in a polar solvent, and reacting to obtain the polyetheramine modified curcumin.
Preferably, the preparation method of the polyetheramine modified curcumin comprises the following steps:
dissolving curcumin in a polar solvent to obtain a solution A;
dissolving polyetheramine in a polar solvent to obtain a solution B;
slowly dripping the solution A into the solution B, and stirring for 0.2-2 hours at room temperature to obtain the polyether amine modified curcumin.
Preferably, the molar ratio of polyetheramine to curcumin is 1.1-2. More preferably, the molar ratio of polyetheramine to curcumin is 1.5-2.
Preferably, the polyetheramine comprises one or more of polypropylene oxide ether amine (PPA-400), polypropylene oxide ether amine (PPA-1000), polypropylene oxide ether amine (PPA-2000), polyethylene oxide ether amine (PEA-400), polyethylene oxide ether amine (PEA-2000).
In a third aspect, the invention provides the use of the curcumin-based polyurethane material of the invention in medical devices or food packaging.
Specifically, the polyurethane material based on curcumin can be used for preparing antibacterial and anti-inflammatory functional implantable prostheses, such as hernia patches, surgical suture lines and the like; coating materials useful in medical devices, such as coating materials for implantable prosthetic stents, including bone repair stent materials, vascular stent materials; can be used as coating material for food package.
Based on the application, the invention also provides a prosthesis which comprises the curcumin-based polyurethane material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The curcumin chain extender and the polyether amine modified curcumin adopted by the invention both contain natural antibacterial and anti-inflammatory components curcumin, and the curcumin is taken as a main component synthesized by the polyurethane material, so that the content of the antibacterial and anti-inflammatory components in the polyurethane material can be obviously improved, the curcumin content in the polyurethane material can reach about 30 percent, and the transparency and mechanical property of the material are not affected; meanwhile, imine bonds in the polyether amine modified curcumin are reversible dynamic covalent bonds, and through permeation of water molecules, the imine dynamic bonds are slowly hydrolyzed, so that the curcumin can be effectively controlled to be slowly released, and the maximum drug effect of the curcumin can be ensured in a local microenvironment.
(2) The polyurethane material of the invention is loaded with high-content curcumin and can effectively control and release the curcumin, thereby having long-acting antibacterial and anti-inflammatory effects, and the curcumin in the polyurethane material of the invention can be slowly released for more than half a year in an ethanol/water acceleration simulation release system.
Drawings
The invention is further described below with reference to the drawings and examples.
FIG. 1 is an infrared spectrum of product 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the product 1 of the present invention;
FIG. 3 is an infrared spectrum of product 8 of the present invention;
FIG. 4 is an infrared spectrum of product 17 of the present invention;
FIG. 5 is an infrared spectrum of product 18 of the present invention;
FIG. 6 is a tensile stress pattern of the product 18 of the present invention;
FIG. 7 is a pictorial view of product 18 of the present invention;
FIG. 8 is a pictorial view of product 29 of the present invention;
FIG. 9 is a tensile stress pattern of product 29 of the present invention;
FIG. 10 is a graph showing the release of curcumin from product 29 of the present invention in a mixture of ethanol and PBS;
FIG. 11 is a graph showing the effect of the product 29 of the present invention on Staphylococcus aureus in the soak solutions obtained by soaking in PBS solution for different periods of time.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents, apparatus used in the examples below were obtained from conventional commercial sources, unless otherwise specified, or may be obtained by methods known in the art.
Some terms involved in the present invention are explained as follows:
room temperature: the temperature is 25+/-5 ℃.
Antibacterial: processes for killing bacteria or interfering with the growth and reproduction of bacteria and their activity are employed chemically or physically.
Anti-inflammatory: the tissue defends against the stimulation of various damaging factors, and the pathological process generated during the defense is inflammatory reaction, and the inflammation caused by the factors can be resisted by medicaments, so the process is called anti-inflammatory.
The following specific examples were made for the preparation of curcumin chain extender:
example 1
The preparation method of the curcumin chain extender comprises the following steps:
5g of curcumin is dissolved in 30g of tetrahydrofuran solution, then 1.8g of 2-hydroxyethyl methacrylate is added, 10mg of potassium hydroxide is added, stirring is carried out for 40 hours at room temperature, then the mixture is poured into 500g of water for sinking, the precipitate is centrifuged, the water is used for washing for 5 times, and the product 1 is obtained after vacuum drying. The structural formula of the product is as follows:
the infrared spectrum of the product 1 is shown in FIG. 1, HEMA-Cur in FIG. 1 is shown as a curcumin chain extender modified by 2-hydroxyethyl methacrylate, and Wavenumber is shown as absorption wavelength. Wherein 3400-3600cm- 1 The absorption peak at the position is the absorption peak of hydroxyl in curcumin phenolic hydroxyl and 2-hydroxyethyl methacrylate (HEMA); the absorbance peak at 1710 is that of the ester linkage in HEMA.
The nuclear magnetic pattern of the product 1 is shown in figure 2; the peak at 9.5-9.7ppm is curcumin phenolic hydroxyl absorption peak; the peak at 4.4-4.5ppm is the hydroxyl absorption peak on HEMA. The disappearance of the characteristic peak on the HEMA double bond of about 5.5 to 5.8 proves that the synthesis reaction is successful.
Example 2
The preparation method of the curcumin chain extender comprises the following steps:
5g of curcumin is dissolved in 30g of tetrahydrofuran solution, then 1.7g of hydroxyethyl acrylate is added, 10mg of potassium hydroxide is added, stirring is carried out for 40 hours at room temperature, then the mixture is poured into 500g of water for sinking, the precipitate is centrifuged, the water is used for cleaning for 5 times, and the product 2 is obtained after vacuum drying. The structural formula of the product is as follows:
example 3
The preparation method of the curcumin chain extender comprises the following steps:
5g of curcumin is dissolved in 30g of tetrahydrofuran solution, then 2g of hydroxypropyl acrylate is added, 10mg of potassium hydroxide is added, stirring is carried out for 40 hours at room temperature, then the mixture is poured into 500g of water for sinking, the precipitate is centrifuged, the water is used for cleaning for 5 times, and the product 3 is obtained after vacuum drying. The structural formula of the product is as follows:
example 4
The preparation method of the curcumin chain extender comprises the following steps:
5g of curcumin is dissolved in 30g of tetrahydrofuran solution, then 2.3g of hydroxypropyl methacrylate is added, then 10mg of potassium hydroxide is added, stirring is carried out for 40 hours at room temperature, then the mixture is poured into 500g of water for sinking, the precipitate is centrifuged, the water is used for washing for 5 times, and the product 4 is obtained after vacuum drying. The structural formula of the product is as follows:
example 5
The preparation method of the curcumin chain extender comprises the following steps:
5g of curcumin is dissolved in 30g of tetrahydrofuran solution, then 2g of vinyl propylene glycol ether is added, 10mg of potassium hydroxide is added, stirring is carried out for 40 hours at room temperature, then the mixture is poured into 500g of water for sinking, the precipitate is centrifuged, the precipitate is washed with water for 5 times, and the product 5 is obtained after vacuum drying. The structural formula of the product is as follows:
example 6
The preparation method of the curcumin chain extender comprises the following steps:
5g of curcumin is dissolved in 30g of tetrahydrofuran solution, then 2g of vinyl glycol ether is added, 10mg of potassium hydroxide is added, stirring is carried out for 40 hours at room temperature, then the mixture is poured into 500g of water for sinking, the precipitate is centrifuged, the precipitate is washed with water for 5 times, and the product 6 is obtained after vacuum drying. The structural formula of the product is as follows:
example 7
The preparation method of the curcumin chain extender comprises the following steps:
5g of curcumin is dissolved in 30g of tetrahydrofuran solution, then 2g of dihydroxypropyl methacrylate is added, then 10mg of potassium hydroxide is added, stirring is carried out for 40 hours at room temperature, then the mixture is poured into 500g of water for sinking, the precipitate is centrifuged, the water is used for washing for 5 times, and the product 7 is obtained after vacuum drying. The structural formula of the product is as follows:
the following specific examples were made for the preparation of polyetheramine modified curcumin:
example 8
The preparation method of the polyether amine modified curcumin comprises the following steps:
0.5g of curcumin is dissolved in 20g of tetrahydrofuran solution to prepare solution A, 0.6g of polypropylene oxide ether amine PPA-400 is added into 20g of tetrahydrofuran solution to prepare solution B, the solution A is slowly dripped into the solution B, and the solution A is stirred at room temperature for 30 minutes to obtain a product 8 solution, wherein the solid content is 2.676wt%. The structural formula of the product is as follows:
the infrared spectrum of product 8 is shown in figure 3. 3400-3500cm -1 Amino absorption peaks on polyetheramines; 3500-3600cm -1 The broad absorption peak is the absorption peak of phenolic hydroxyl group on curcumin; 1420-1470cm -1 The absorption peak at this point is a characteristic absorption peak of the generated imine bond.
Example 9
The preparation method of the polyether amine modified curcumin comprises the following steps:
0.5g of curcumin is dissolved in 20g of tetrahydrofuran solution to prepare solution A, 3g of polypropylene oxide ether amine PPA-2000 is added into 20g of tetrahydrofuran solution to prepare solution B, the solution A is slowly dripped into the solution B, and the solution A is stirred at room temperature for 30 minutes to obtain a product 9 solution, wherein the solid content is 8.046wt%. The structural formula of the product is as follows:
example 10
The preparation method of the polyether amine modified curcumin comprises the following steps:
0.5g of curcumin is dissolved in 20g of tetrahydrofuran solution to prepare solution A, 3g of polypropylene oxide ether amine PPA-1000 is added into 20g of tetrahydrofuran solution to prepare solution B, the solution A is slowly dripped into the solution B, and the solution A is stirred at room temperature for 30 minutes to obtain a product 10 solution, wherein the solid content is 8.046wt%. The structural formula of the product is as follows:
example 11
The preparation method of the polyether amine modified curcumin comprises the following steps:
dissolving 0.5g of curcumin in 20g of tetrahydrofuran solution to prepare solution A, adding 0.6g of polyethylene oxide ether amine PEA-400 into 20g of tetrahydrofuran solution to prepare solution B, slowly dripping the solution A into the solution B, and stirring at room temperature for 30 minutes to obtain a product 11 solution, wherein the solid content is 2.676wt%, and the structural formula of the product is as follows:
example 12
The preparation method of the polyether amine modified curcumin comprises the following steps:
dissolving 0.5g of curcumin in 20g of tetrahydrofuran solution to prepare solution A, adding 20g of tetrahydrofuran solution into 3g of polyethylene glycol ether amine PEA-2000 to prepare solution B, slowly dripping the solution A into the solution B, and stirring at room temperature for 30 minutes to obtain a product 12 solution, wherein the solid content is 8.046wt%, and the structural formula of the product is as follows:
the solid content in examples 8-12 above refers to polyetheramine modified curcumin.
The following specific examples are made for the preparation of curcumin polyurethane prepolymer:
example 13
The preparation method of the curcumin polyurethane prepolymer comprises the following steps:
firstly, adding 0.5g of curcumin chain extender into 20mL of tetrahydrofuran solution, stirring to dissolve, adding 5g of polytetrahydrofuran glycol (Mn=1000), then adding 0.6g of IPDI, stirring at 60 ℃ to react for 6 hours, then adding 1.2g of HDI trimer, stirring at 50 ℃ to react for 12 hours, and obtaining curcumin polyurethane prepolymer solution, wherein the solid content is 26.74wt%, and the curcumin chain extender is 6.85wt% in the polymer according to the feeding ratio.
Example 14
The preparation method of the curcumin polyurethane prepolymer comprises the following steps:
firstly, adding 1g of curcumin chain extender into 20mL of acetone solution, stirring to dissolve, adding 5g of polytetrahydrofuran glycol (Mn=1000), then adding 0.6g of IPDI, stirring at 60 ℃ to react for 6 hours, then adding 1.2g of HDI trimer, stirring at 50 ℃ to react for 12 hours, and obtaining curcumin polyurethane prepolymer solution, wherein the solid content of the product 14 is 26.74wt%, and the polymer contains 12.82wt% of curcumin chain extender according to the feeding ratio.
Example 15
The preparation method of the curcumin polyurethane prepolymer comprises the following steps:
firstly, adding 2g of curcumin chain extender into 40mL of tetrahydrofuran solvent, stirring to dissolve, adding 5g of polytetrahydrofuran glycol (Mn=1000), then adding 1g of IPDI, stirring at 60 ℃ to react for 6 hours, then adding 1.5g of HDI trimer, stirring at 50 ℃ to react for 12 hours, thus obtaining curcumin polyurethane prepolymer solution, wherein the solid content of the product 15 is 19.19wt%, and the polymer contains 21.wt1% of curcumin chain extender according to the feeding ratio.
Example 16
The preparation method of the curcumin polyurethane prepolymer comprises the following steps:
firstly, adding 1g of curcumin chain extender into 20mL of tetrahydrofuran solvent, stirring to dissolve, adding 5g of polycaprolactone diol (Mn=1000), then adding 0.6g of IPDI, stirring at 60 ℃ to react for 6 hours, then adding 1.2g of HDI trimer, stirring at 50 ℃ to react for 12 hours, and obtaining curcumin polyurethane prepolymer solution, wherein the solid content of the product 16 is 28.06wt%, and the polymer contains 12.82wt% of curcumin chain extender according to the feeding ratio.
The solid content in examples 13 to 16 above refers to curcumin polyurethane prepolymer.
The curcumin polyurethane prepolymer is prepared into a film, and the following specific examples are made:
example 17
The curcumin polyurethane prepolymer solution obtained in example 13 is coated into a film, and then baked for 24 hours at 80 ℃ to obtain a curcumin-based polyurethane film, and a product 17.
The infrared spectrum of product 17 is shown in figure 4. 1735cm -1 The absorption peak at the position is carbonyl absorption peak on polyurethane; 1540cm -1 The polyurethane N-H absorption peak is shown.
Example 18
The curcumin-based polyurethane film obtained in example 14 was obtained by coating the curcumin polyurethane prepolymer solution into a film and then baking at 80 ℃ for 24 hours.
The infrared spectrum of product 18 is shown in figure 5. 1420-1470cm -1 The absorption peak at the position is the characteristic absorption peak of the generated imine bond; 1730cm -1 The absorption peak at the position is carbonyl absorption peak on polyurethane; 1540cm -1 The polyurethane N-H absorption peak is positioned; 1080cm -1 The peak at the peak is polyether absorption peak.
The tensile Stress spectrum of the product 18 is shown in FIG. 6, in which the ordinate "Stress" represents tensile Stress and the abscissa "Stress" represents tensile deformation. The elongation at break of the curcumin-based polyurethane film is 245%, and the breaking strength is 23MPa.
A physical diagram of product 18 is shown in FIG. 7. The curcumin chain extender content in the product 18 was 12.82%, and its transparency was still very high.
Example 19
The curcumin-based polyurethane film obtained in example 15 was coated with the curcumin polyurethane prepolymer solution to form a film, and then baked at 80 ℃ for 24 hours to obtain a product 19.
Example 20
The curcumin-based polyurethane film obtained in example 16 was coated into a film, and then baked at 80 ℃ for 24 hours, thus obtaining a product 20.
The following specific examples were made for the preparation of curcumin based polyurethane materials:
example 21
The preparation method of the polyurethane material based on curcumin comprises the following steps:
firstly, 10g of the curcumin polyurethane prepolymer solution prepared in the example 14 is added into a stirring tank, stirring is started, then 6g of the polyether amine modified curcumin solution prepared in the example 8 is slowly dripped into the stirring tank, after dripping is finished, stirring is carried out for 30 minutes at room temperature, and then the curcumin-based polyurethane material solution is obtained, and a product 21 is obtained. According to the feeding ratio, the total mass of the curcumin accounting for 14.6 percent of the total mass of the polymer can be calculated.
Example 22
The preparation method of the polyurethane material based on curcumin comprises the following steps:
firstly, 10g of the curcumin polyurethane prepolymer solution prepared in the example 14 is added into a stirring tank, stirring is started, then 20g of the polyether amine modified curcumin solution prepared in the example 8 is slowly dripped into the stirring tank, after dripping is finished, stirring is carried out for 30 minutes at room temperature, and then the curcumin-based polyurethane material solution is obtained, and a product 22. According to the feeding ratio, the total mass of the curcumin accounting for 18 percent of the total mass of the polymer can be calculated.
Example 23
The preparation method of the polyurethane material based on curcumin comprises the following steps:
firstly, 10g of the curcumin polyurethane prepolymer solution prepared in the example 14 is added into a stirring tank, stirring is started, then 30g of the polyether amine modified curcumin solution prepared in the example 8 is slowly dripped into the stirring tank, after dripping is finished, stirring is carried out for 30 minutes at room temperature, and then the curcumin-based polyurethane material solution is obtained, and a product 23. According to the feeding ratio, the total mass of the curcumin accounting for 21.83 percent of the total mass of the polymer can be calculated.
Example 24
The preparation method of the polyurethane material based on curcumin comprises the following steps:
firstly, 10g of curcumin polyurethane prepolymer solution prepared in example 14 is added into a stirring tank, stirring is started, then 50g of polyether amine modified curcumin solution prepared in example 8 is slowly dripped into the stirring tank, after dripping is finished, stirring is carried out for 30 minutes at room temperature, and then curcumin-based polyurethane material solution is obtained, and a product 24 is obtained. According to the feeding ratio, the total mass of the curcumin accounting for 23.3 percent of the total mass of the polymer can be calculated.
Example 25
The preparation method of the polyurethane material based on curcumin comprises the following steps:
firstly, 10g of the curcumin polyurethane prepolymer solution prepared in the example 15 is added into a stirring tank, stirring is started, then 60g of the polyether amine modified curcumin solution prepared in the example 8 is slowly dripped into the stirring tank, after dripping is finished, stirring is carried out for 30 minutes at room temperature, and then the curcumin-based polyurethane material solution is obtained, and a product 25. According to the feeding ratio, the total mass of the curcumin accounting for 30.4 percent of the total mass of the polymer can be calculated.
Example 26
The preparation method of the polyurethane material based on curcumin comprises the following steps:
firstly, 10g of the curcumin polyurethane prepolymer solution prepared in the example 14 is added into a stirring tank, stirring is started, then 30g of the polyether amine modified curcumin solution prepared in the example 11 is slowly dripped into the stirring tank, after dripping is finished, stirring is carried out for 30 minutes at room temperature, and then the curcumin-based polyurethane material solution is obtained, and a product 26. According to the feeding ratio, the total mass of the curcumin accounting for 21.83 percent of the total mass of the polymer can be calculated.
The following specific examples were made with curcumin based polyurethane materials prepared as films:
example 27
The curcumin-based polyurethane material solution obtained in example 21 was coated into a film and then baked at 80 ℃ for 24 hours to obtain a curcumin-based polyurethane film, product 27.
Example 28
The curcumin-based polyurethane material solution obtained in example 22 was coated into a film, and then baked at 80 ℃ for 24 hours, thus obtaining a curcumin-based polyurethane film, and a product 28.
Example 29
The curcumin-based polyurethane material solution obtained in example 23 was coated into a film, and then baked at 80 ℃ for 24 hours, thus obtaining a curcumin-based polyurethane film, product 29.
A physical diagram of product 29 is shown in FIG. 8. The curcumin content of the product 29 was about 21.8% and its transparency was still very high.
The tensile stress pattern of product 29 is shown in figure 9. The elongation at break of the curcumin-based polyurethane film was 1450% and the breaking strength was 34MPa.
The release profile of product 29 in a mixture of ethanol and PBS (mass ratio=1/3) is shown in fig. 10. As can be seen from the figure, curcumin was released for 6 months in ethanol/PBS mixed solution, with a release of about 62%.
The effect of the product 29 on the anti-Staphylococcus aureus of the soak solution obtained by soaking in PBS solution for different times is shown in FIG. 11. As can be seen from the figure, the solution after soaking in the product 29 for 6 hours has a remarkable antibacterial effect, and the antibacterial effect of the film soaking solution is more remarkable with the prolonged soaking time.
Example 30
The curcumin-based polyurethane material solution obtained in example 24 was coated into a film, and then baked at 80 ℃ for 24 hours, thus obtaining a curcumin-based polyurethane film, and a product 30.
Example 31
The curcumin-based polyurethane material solution obtained in example 25 was coated into a film, and then baked at 80 ℃ for 24 hours, thus obtaining a curcumin-based polyurethane film, product 31.
Example 32
The curcumin-based polyurethane material solution obtained in example 26 was coated into a film, and then baked at 80 ℃ for 24 hours, thus obtaining a curcumin-based polyurethane film, and a product 32.
The ratios of curcumin in the above products 17-20 and 27-32 are shown in Table 1 below.
Table 1 ratio of curcumin in the product
| Compounds of formula (I) | Curcumin accounts for the total mass (%) |
| Product 17 | 6.85 |
| Product 18 | 12.82 |
| Product 19 | 21.1 |
| |
12.82 |
| Product 27 | 14.6 |
| Product 28 | 18 |
| Product 29 | 21.83 |
| |
23.3 |
| Product 31 | 30.4 |
| Product 32 | 21.83 |
The test results of the above products 1-12 and curcumin against Staphylococcus aureus are shown in Table 2.
Table 2 results of product anti-staphylococcus aureus test
The test results of the above-described product 18 and product 29 infusions against Staphylococcus aureus are shown in Table 3.
TABLE 3 test results of the product soaking solutions against Staphylococcus aureus
| Soaking liquid | Film quality | PBS solution | Soaking time | Antibacterial effect (%) |
| Product 18 | 0.1g | 5mL | For 6 |
60 |
| Product 18 | 0.1g | 5mL | For 1 |
70 |
| Product 18 | 0.1g | 5mL | For 7 |
80 |
| Product 18 | 0.1g | 5mL | For 60 days | 86 |
| Product 29 | 0.1g | 5mL | For 6 |
80 |
| Product 29 | 0.1g | 5mL | For 1 |
90 |
| Product 29 | 0.1g | 5mL | For 7 days | 92 |
| Product 29 | 0.1g | 5mL | For 60 days | 97 |
While the preferred embodiments of the present invention have been illustrated and described, the present invention is not limited to the embodiments, and various equivalent modifications and substitutions can be made by one skilled in the art without departing from the spirit of the present invention, and these are intended to be included in the scope of the present invention as defined in the appended claims.
Claims (10)
1. A curcumin-based polyurethane material, characterized in that raw materials for preparing the curcumin-based polyurethane material include: curcumin chain extender and polyether amine modified curcumin;
the curcumin chain extender has a structural general formula shown in the following formula (1):
a compound wherein R is a terminal or side chain containing one or more hydroxyl groups;
the structural general formula of the polyether amine modified curcumin is shown as the following formula (2):
wherein n is 1 Is an integer of 1 to 50, R 0 Is H or-CH 3 A group.
2. The curcumin-based polyurethane material according to claim 1, wherein the structural general formula of the curcumin-based polyurethane material is represented by the following formula (3):
wherein R is 1 Is diisocyanate, R 2 Is dihydric alcohol, m 2 Is an integer of 10 to 50, m 3 Is an integer of 10 to 50, m 4 E is a polyurethane repeating unit chain segment, and F is polyether amine modified curcumin.
3. The curcumin-based polyurethane material according to claim 1, wherein the curcumin chain extender is selected from one or more of the following compounds:
4. the curcumin-based polyurethane material according to claim 1, wherein the polyetheramine-modified curcumin is selected from one or more of the following compounds:
5. a process for the preparation of a curcumin based polyurethane material as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
dissolving the curcumin chain extender in a polar solvent, mixing with dihydric alcohol, diisocyanate and HDI trimer, and reacting to obtain a curcumin polyurethane prepolymer;
and mixing the polyether amine modified curcumin and the curcumin polyurethane prepolymer, and reacting to obtain the curcumin-based polyurethane material.
6. The preparation method of the curcumin chain extender according to claim 5, comprising the following steps:
dissolving curcumin in a polar solvent, mixing with a compound with one or more hydroxyl groups at the tail end or side chains and an alkaline catalyst, and reacting to obtain the curcumin chain extender.
7. The preparation method according to claim 5, wherein the curcumin polyurethane prepolymer has a structural general formula shown in the following formula (4):
wherein R is 1 Is one or more diisocyanates of TDI, HDI, MDI, IPDI, R 2 Is dihydric alcohol, m 2 Is an integer of 10 to 50, m 3 Is an integer of 10 to 50, m 4 And E is a polyurethane repeating unit chain segment, and is an integer of 1-50.
8. The preparation method of the polyether amine modified curcumin according to claim 5, comprising the following steps:
mixing curcumin and polyetheramine in a polar solvent, and reacting to obtain the polyetheramine modified curcumin.
9. Use of the curcumin-based polyurethane material as defined in any one of claims 1 to 4 in medical devices or food packaging.
10. A prosthesis comprising the curcumin-based polyurethane material as claimed in any one of claims 1 to 4.
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