CN115636919A - Preparation method and application of high-performance polyurethane - Google Patents
Preparation method and application of high-performance polyurethane Download PDFInfo
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Abstract
The invention provides a preparation method of high-performance polyurethane, and relates to the technical field of polyurethane. The high-performance polyurethane prepared by the invention has good lubricating property and excellent mechanical strength. The preparation method of the high-performance polyurethane provided by the invention comprises the following steps: the chain extender and the end capping agent are subjected to zwitterion hydrophilic modification, the prepolymer is synthesized, the polyurethane is synthesized to obtain a high-performance polyurethane material which is not limited to be used for the artificial meniscus, and then the artificial meniscus and other products are prepared by a method of 3D printing, mould pressing, dipping, spin coating or spraying. In the invention, because the molecular chain of the high-performance polyurethane contains a zwitterionic structure for improving the lubricating effect and a hydrophobic structure for maintaining the mechanical strength, the prepared high-performance polyurethane can simultaneously meet the requirements of low friction coefficient and high mechanical strength.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a preparation method and application of high-performance polyurethane, in particular to a preparation method of a high-performance polyurethane artificial meniscus.
Background
The polyurethane material is polymerized by isocyanate, polyol, a chain extender and the like, and the polyurethane can have excellent mechanical properties, wear resistance, aging resistance, corrosion resistance and the like by regulating the proportion between a hard section and a soft section in the synthesis process and selecting different chain extenders, so that the polyurethane material is widely applied to the fields of medical appliances, coatings, bearings, tires and the like. However, with the development of science and technology and the requirement of use environment, there is an increasing need for polyurethane materials that can maintain excellent mechanical properties and also have good lubricating properties. For example, mechanical strength and friction coefficient are the core criteria for evaluating whether polyurethane materials for artificial menisci can be used in humans for a long period of time. Commercial British
Polyurethane artificial meniscus and israel
Although the polyurethane artificial meniscus has good biocompatibility and excellent mechanical property, the lubricating property is poor due to the hydrophobicity of the material, and articular cartilage is easily abraded to cause degenerative change of knee joints.
At present, the method for improving the lubricating property of polyurethane generally comprises the step of adding inorganic/organic molecular fillers with water lubricating property into a polyurethane main body, but the bonding force between the fillers and the polyurethane main body is poor, and an interface layer exists between the fillers and the polyurethane main body, so that the fillers are easy to fall off from the main body, and the long-term application cannot be realized. Therefore, it has been tried to graft polyethylene glycol, epoxy resin, bioactive substances, etc. onto the surface of polyurethane to improve the water lubricity of polyurethane, for example, grafting epoxy resin (CN 109575233) onto the surface of polyurethane to improve the lubricity of the material, so as to obtain a polyurethane medical interventional catheter with excellent lubricity and wear resistance, but the grafted layer on the surface of the polyurethane would easily fall off, so that the polyurethane medical interventional catheter cannot be used for a long time.
In order to solve the problems, one or more hydrophilic structures (CN 106967206A, CN 111234170A) such as chitosan, carboxymethyl chitosan and glycerophosphorylcholine are introduced into the polyurethane body, so that the lubricating property of the modified material can be remarkably improved. However, the hydrophilic group of the modified material can cause water molecules to enter the polyurethane structure, so that the mechanical property of the material is greatly reduced, and the actual use requirement cannot be met. For example, glycerophosphorylcholine-modified polyurethanes can maintain a coefficient of friction similar to natural menisci for long periods of time in a body fluid environment, but have a tensile strength of only about 10MPa, which is insufficient to support in vivo applications of artificial menisci. In order to improve the mechanical strength of hydrophilic polyurethane, the method of improving the molecular structure stability of polyurethane (CN 111110927A) by using a cross-linking agent is an effective method, but this can cause that the material is difficult to process once being formed, and is especially not beneficial to the production of artificial menisci.
Therefore, it is an urgent need to solve the problem of the art to design a polyurethane material with high mechanical strength and easy operation and processing, and to reduce the friction coefficient of the polyurethane material by forming a hydrated layer on the surface of the hydrophilic structure in the structure in an aqueous solution, so that the polyurethane can satisfy the requirements of high mechanical strength and low friction coefficient.
Disclosure of Invention
In view of this, the present invention aims to provide a preparation method and an application of a high performance polyurethane, and the high performance polyurethane provided by the present invention can simultaneously satisfy requirements of mechanical strength and friction coefficient of a meniscus when being used for an artificial meniscus.
The invention provides a preparation method of high-performance polyurethane, which comprises the following steps:
carrying out polymerization reaction on diisocyanate, polyol and a catalyst to obtain a prepolymer;
carrying out chain extension reaction on the prepolymer and a chain extender to obtain high-performance polyurethane;
the preparation method of the chain extender comprises the following steps:
reacting a compound with a structure shown in a formula I with a zwitterion monomer to obtain a chain extender;
in the formula I, R 1 Is selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 Is selected from-H, C 1 ～C 20 Alkylene radical, C 1 ～C 20 Fluorine-containing alkyl group, C 1 ～C 20 Silane-containing groups, phenyl or benzyl;
R 3 and R 5 Independently selected from C 2 ～C 6 An alkylene group;
R 4 and R 6 Independently selected from-OH or-NH 2 。
Preferably, after the chain extension reaction is completed, the method further comprises:
carrying out end-capping reaction on the obtained reaction product and an end-capping reagent to obtain high-performance polyurethane;
the preparation method of the end-capping agent comprises the following steps:
reacting a compound with a structure shown in a formula II with a zwitterionic monomer to obtain an end-capping reagent;
in the formula II, R 1 And R 1 ' independently selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 And R 2 ' independently selected from-H, C 1 ～C 20 Alkylene radical, C 1 ～C 20 Fluorine-containing alkyl group, C 1 ～C 20 Silane-containing groups, phenyl or benzyl;
R 3 is selected from C 2 ～C 6 An alkylene group;
R 4 is selected from-OH or-NH 2 。
Preferably, the zwitterionic monomer is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone, acrylic acid, gamma-butyrolactone, delta-valerolactone or 2-chlorine-2-oxygen-1, 3, 2-dioxaphospholane.
Preferably, the temperature of the polymerization reaction is 40-110 ℃, and the pressure is 0.05-2 MPa;
the temperature of the chain extension reaction is 40-110 ℃, and the pressure is 0.05-2 MPa;
the temperature of the end capping reaction is 40-110 ℃, and the pressure is 0.05-2 MPa.
Preferably, the molar ratio of isocyanate to polyol is 1: (0.1-0.9).
Preferably, the molar ratio of the chain extender to the end capping agent is 1: (0 to 10);
the mole number of NCO in the prepolymer and OH and NH in the chain extender and the end capping agent 2 The ratio of the total number of moles is 1: (0.8-1.2).
The invention provides a preparation method of an artificial meniscus, which comprises the following steps:
3D printing is carried out on the high-performance polyurethane to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method in the technical scheme.
Preferably, the 3D printing includes:
3D printing is carried out on the high-performance polyurethane and the high polymer material;
the high polymer material is selected from one or more of polyurethane, polylactic acid, polyether-ether-ketone, polycaprolactone, ABS resin or polyolefin.
The invention provides a preparation method of an artificial meniscus, which comprises the following steps:
adding the raw materials for preparing the high-performance polyurethane into an artificial meniscus mould for reaction and forming to obtain an artificial meniscus;
the raw materials for preparing the high-performance polyurethane are the prepolymer and the chain extender in the technical scheme;
or
Melting and molding the high-performance polyurethane in an artificial meniscus mold to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method in the technical scheme.
Preferably, after obtaining the artificial meniscus, the method further comprises:
modifying the artificial meniscus, the modifying agent comprising:
solutions of high performance polyurethanes;
the solvent in the solution of the high-performance polyurethane is one or more selected from ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide or hexafluoroisopropanol;
the modification method comprises the following steps:
dipping, spin coating or spraying a modifying agent onto the artificial meniscus;
the high-performance polyurethane is prepared by the method in the technical scheme.
The high-performance polyurethane prepared by the invention forms a short-range ordered hydration layer on the surface through the strong interaction between the anions and cations of the zwitter-ion group in the structure and water, thereby achieving the lubricating effect. In addition, in order to prevent water molecules from entering molecular chains and provide more physical crosslinking points, a hydrophobic group is introduced into the chemical structure of the material, so that the problem of great reduction of the mechanical property of the material caused by improvement of the lubricating property of polyurethane is solved. The preparation method of the high-performance polyurethane provided by the invention is simple and easy to implement, the material application range is wide, and the polyurethane artificial meniscus suitable for different disease requirements can be effectively prepared.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of high-performance polyurethane, which comprises the following steps:
carrying out polymerization reaction on diisocyanate, polyol and a catalyst to obtain a prepolymer;
carrying out chain extension reaction on the prepolymer and a chain extender to obtain high-performance polyurethane;
the preparation method of the chain extender comprises the following steps:
reacting a compound with a structure shown in a formula I with a zwitterion monomer to obtain a chain extender;
in the formula I, R 1 Is selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 Is selected from-H, C 1 ～C 20 Alkylene radical, C 1 ～C 20 Fluorine-containing alkyl group, C 1 ～C 20 Silane, phenyl or benzyl containing groups;
R 3 and R 5 Independently selected from C 2 ～C 6 An alkylene group;
R 4 and R 6 Independently selected from-OH or-NH 2 。
In the present invention, after the chain extension reaction is completed, the method preferably further comprises:
carrying out end-capping reaction on the obtained reaction product and an end-capping reagent to obtain high-performance polyurethane;
the preparation method of the end-capping agent comprises the following steps:
reacting a compound with a structure shown in a formula II with a zwitterionic monomer to obtain an end-capping reagent;
in the formula II, R 1 And R 1 ' independently selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 And R 2 ' independently selected from-H, C 1 ～C 20 Alkylene radical, C 1 ～C 20 Fluorine-containing alkyl group, C 1 ～C 20 Silane, phenyl or benzyl containing groups;
R 3 is selected from C 2 ～C 6 An alkylene group;
R 4 is selected from-OH or-NH 2 。
In the present invention, the preparation method of the high performance polyurethane preferably includes:
(1) And (3) performing zwitter-ion hydrophilic modification on the chain extender and the end capping reagent: n atoms in structures of the compound with the structure shown in the formula I and the compound with the structure shown in the formula II react with a zwitterion monomer in a reaction solvent to synthesize a chain extender and an end capping agent containing zwitterion groups.
(2) Prepolymer synthesis: diisocyanate, polyol and a catalyst are mixed and then subjected to polymerization reaction to prepare a prepolymer.
(3) And (3) polyurethane synthesis: and (3) carrying out chain extension reaction on the prepolymer and a chain extender, and if residual isocyanate functional groups still exist in the previous step of reaction, further carrying out reaction on the prepolymer and a blocking agent to prepare the high-performance polyurethane.
In the present invention, the isocyanate is preferably selected from any one or a combination of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, or lysine diisocyanate.
In the present invention, the polyol is preferably selected from any one or a combination of polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, castor oil polyol, soybean oil polyol or palm oil polyol.
In the present invention, the number average molecular weight of the polyol is preferably 500 to 4000, more preferably 1000 to 3500, more preferably 1500 to 3000, and most preferably 2000 to 2500.
In the present invention, the catalyst is preferably selected from any one or a combination of stannous octoate, dibutyltin oxide, dibutyltin dilaurate, monobutyltin oxide, tetraphenyltin, tri-N-butyltin acetate, tin acetate, triethylenediamine, cyclohexylmethyl tertiary amine, tetramethylalkylenediamine, N-dimethylbenzylamine or triethylamine.
In the present invention, the molar ratio of the isocyanate to the polyol is preferably 1: (0.1 to 0.9), more preferably 1: (0.2 to 0.5), most preferably 1: (0.3 to 0.4); the ratio of the mass of isocyanate to polyol and the mass of catalyst is preferably 1: (0.001 to 0.01), more preferably 1: (0.003-0.007), most preferably 1:0.005.
in the present invention, the polymerization reaction may be carried out under the action of a solvent; the ratio of the mass of the solvent to the total mass of diisocyanate, polyol and catalyst is preferably (0 to 20): 1, more preferably (0 to 10): 1, most preferably 5:1; the solvent is preferably selected from any one or combination of ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide or hexafluoroisopropanol.
In the present invention, the temperature of the polymerization reaction is preferably 40 to 110 ℃, more preferably 60 to 90 ℃, and most preferably 70 to 80 ℃; the time of the polymerization reaction is preferably 0.5 to 120 hours, more preferably 6 to 72 hours, more preferably 10 to 60 hours, more preferably 20 to 50 hours, and most preferably 30 to 40 hours; the pressure of the polymerization reaction is preferably 0.05 to 2MPa, more preferably 0.1 to 1MPa, more preferably 0.3 to 0.7MPa, and most preferably 0.5MPa.
In the present invention, in the formulae I and II, C 1 ～C 20 The alkylene group is independently preferably a saturated alkylene chain having a straight chain or a branched structure, more preferably C 1 ～C 12 Saturated with alkylene groups being straight-chainAnd an alkylene chain; c 1 ～C 20 The fluoroalkyl group is independently preferably a side chain in which H at a C atom in a straight or branched saturated alkylene chain in the structure is completely or partially substituted with F, more preferably C 3 ～C 12 A fluoroalkyl group, preferably a side chain in which H at a C atom in a straight-chain saturated alkylene chain in the structure is completely substituted with F; c 1 ～C 20 The silane group-containing side chain is preferably a side chain in which the chain end of a straight or branched saturated alkylene chain in the structure is substituted with trimethoxysilane or triethoxysilane, more preferably C 3 ～C 8 A side chain containing a silane group, preferably a structure in which the chain end of a straight-chain saturated alkylene chain is substituted with trimethoxysilane; c 2 ～C 6 The alkylene group is independently preferably a straight-chain or branched saturated alkylene chain, more preferably C 2 ～C 4 Alkylene groups, preferably straight saturated alkylene chains.
The source of the compound with the structure of formula I and the compound with the structure of formula II is not particularly limited, and the compound with the structure of formula I and the compound with the structure of formula II can be obtained by market purchase or preparation according to the conventional synthetic method in the field.
In the invention, the zwitterionic monomer is preferably selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone, acrylic acid, gamma-butyrolactone, delta-valerolactone or 2-chlorine-2-oxygen-1, 3, 2-dioxaphospholane, and is more preferably selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone or 2-chlorine-2-oxygen-1, 3, 2-dioxaphospholane; the molar ratio of the structural compound of the formula I to the monomer of the zwitterion is preferably (3-1): (1-3), more preferably (0.8-1): (1-1.2), most preferably 0.9:1.1; the reaction temperature is preferably 25-120 ℃, more preferably 40-60 ℃, and most preferably 50 ℃; the reaction time is preferably 0.5 to 120 hours, more preferably 12 to 72 hours, more preferably 20 to 60 hours, more preferably 30 to 50 hours, and most preferably 40 hours.
In the present invention, the chain extender preferably further includes: conventional chain extenders.
In the present invention, the conventional chain extender is preferably selected from any one or combination of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, cyclohexanediol, p-xylylene bis hydroxyethyl ether, toluenediamine, isophoronediamine, a compound of formula I or trimethylhexamethylenediamine.
In the invention, a product obtained by reacting a compound with a structure shown in formula I and a zwitterionic monomer is marked as a first chain extender, and a conventional chain extender is marked as a second chain extender; the molar ratio of the first chain extender to the second chain extender is preferably 1: (0 to 10), more preferably 1: (3-5), most preferably 1:4.
in the present invention, the chain extension reaction may be performed under the action of a solvent; the ratio of the mass of the solvent to the total mass of the prepolymer and the chain extender is preferably (0-20): 1, more preferably (0 to 10): 1, most preferably 5:1; the solvent is preferably selected from any one or a combination of ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethylsulfoxide or hexafluoroisopropanol.
In the invention, the temperature of the chain extension reaction is preferably 40-110 ℃, more preferably 60-90 ℃, and most preferably 70-80 ℃; the time of the chain extension reaction is preferably 0.5 to 120 hours, more preferably 6 to 72 hours, more preferably 10 to 60 hours, more preferably 20 to 50 hours, and most preferably 30 to 40 hours; the pressure of the chain extension reaction is preferably 0.05 to 2MPa, more preferably 0.1 to 1MPa, more preferably 0.3 to 0.7MPa, and most preferably 0.5MPa.
In the present invention, the molar ratio of the compound having the structure of formula II to the monomer of the zwitterion is preferably (3 to 1): (1 to 3), more preferably (0.8 to 1): (1-1.2), most preferably 0.9:1.1; the reaction temperature is preferably 25-120 ℃, more preferably 40-60 ℃, and most preferably 50 ℃; the reaction time is preferably 0.5 to 120 hours, more preferably 12 to 72 hours, more preferably 20 to 60 hours, more preferably 30 to 50 hours, and most preferably 40 hours.
In the present invention, the end-capping agent preferably further comprises: conventional blocking agents.
In the present invention, the conventional blocking agent is preferably selected from any one or a combination of methylethylketoxime, 3, 5-dimethylpyrazole, caprolactam, 3-isocyanatopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, anilinopropyltrimethoxysilane, anilinomethyltriethoxysilane, a compound of formula II or bis- [3- (trimethoxy silicon) -propyl ] -amine.
In the invention, a product obtained by reacting a compound with a structure shown in a formula II and a zwitterionic monomer is marked as a first end-capping reagent, and a conventional end-capping reagent is marked as a second end-capping reagent; the molar ratio of the first end-capping reagent to the second end-capping reagent is preferably 1: (0 to 10), more preferably 1: (3 to 5), most preferably 1:4.
in the present invention, the end-capping reaction may be performed under the action of a solvent; the ratio of the mass of the solvent to the total mass of the reaction product and the end-capping agent is preferably (0 to 20): 1, more preferably (0 to 10): 1, most preferably 5:1; the solvent is preferably selected from any one or combination of ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide or hexafluoroisopropanol.
In the present invention, the temperature of the end-capping reaction is preferably 40 to 110 ℃, more preferably 60 to 90 ℃, and most preferably 70 to 80 ℃; the end-capping reaction time is preferably 0.5 to 120 hours, more preferably 6 to 72 hours, more preferably 10 to 60 hours, more preferably 20 to 50 hours, and most preferably 30 to 40 hours; the pressure of the end-capping reaction is preferably 0.05 to 2MPa, more preferably 0.1 to 1MPa, more preferably 0.3 to 0.7MPa, and most preferably 0.5MPa.
In the present invention, the molar ratio of the chain extender to the end capping agent is preferably 1: (0 to 10), more preferably 1: (0 to 4), most preferably 1: (1-3).
In the invention, the mol number of NCO in the prepolymer and OH and NH in the chain extender and the end-capping reagent 2 The total molar ratio is preferably 1: (0.8 to 1.2), more preferably 1:1.
in the invention, when the chain extender contains the first chain extender, the end-capping reagent can adopt the first end-capping reagent and also can adopt the second end-capping reagent; when the end-capping reagent contains the first end-capping reagent, the chain extender may include a first chain extender and a second chain extender.
The invention provides a preparation method of an artificial meniscus, which comprises the following steps:
3D printing is carried out on the high-performance polyurethane to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method in the technical scheme.
In the present invention, the 3D printing preferably obtains a three-dimensional model of a natural meniscus in a human body by a correlation technique, and then performs a 3D printing process on the three-dimensional model.
In the preparation method of the high-performance polyurethane artificial meniscus, firstly, a three-dimensional model of a natural meniscus in a human body is obtained through a correlation technique, then, the three-dimensional model is subjected to 3D printing to obtain an artificial meniscus mold, and the artificial meniscus is obtained through further mold pressing or is directly subjected to 3D printing to obtain the artificial meniscus.
In the present invention, the 3D printing preferably includes:
and 3D printing is carried out on the high-performance polyurethane and the high polymer material.
In the present invention, the polymer material is preferably selected from one or more of polyurethane, polylactic acid, polyether ether ketone, polycaprolactone, ABS resin or polyolefin, and more preferably selected from polycaprolactone and/or polyolefin.
In the present invention, the mass ratio of the reaction product to the polymer material is preferably 1 (0.1 to 5), more preferably 1: (0.5 to 4), more preferably 1: (1 to 3), most preferably 1:2.
in the artificial meniscus material, the high-performance polyurethane is used as a main part, and one or more materials such as polyurethane, polylactic acid, polyether ether ketone, polycaprolactone, ABS resin or polyolefin can be added into the main part material to carry out common 3D printing treatment; preferably, the 3D printed artificial meniscus or the molded artificial meniscus is made of the high-performance polyurethane, the high-performance polyurethane and polycaprolactone, and the high-performance polyurethane and polyolefin.
The invention provides a preparation method of an artificial meniscus, which comprises the following steps:
melting and molding the high-performance polyurethane in an artificial meniscus mold to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method in the technical scheme.
The invention provides a preparation method of an artificial meniscus, which comprises the following steps:
reacting and molding the prepolymer and the chain extender (and the end capping agent) in an artificial meniscus mold to obtain an artificial meniscus;
the prepolymer, the chain extender and the end-capping reagent are the prepolymer, the chain extender and the end-capping reagent in the technical scheme.
In the invention, the material of the artificial meniscus mould can be stainless steel, aluminum, iron and other metal materials; or organic polymer materials such as polytetrafluoroethylene and ABS resin and composite materials thereof.
In the present invention, the melt forming and reaction forming conditions preferably independently include a heating temperature of 50 to 300 ℃, more preferably 70 to 180 ℃, more preferably 100 to 160 ℃, and most preferably 120 to 140 ℃; the heat preservation temperature is preferably 50-300 ℃, more preferably 80-130 ℃, and most preferably 100-120 ℃; the pressurizing pressure is preferably 0.5 to 50MPa, more preferably 5 to 10MPa, and most preferably 6 to 8MPa; the pressing time is preferably 20 to 180min, more preferably 30 to 60min, and most preferably 40 to 50min.
In the invention, the artificial meniscus material (high-performance polyurethane) can be directly melted and added into an artificial meniscus mould for remodeling and molding, or the required raw materials (prepolymer, chain extender and end-capping reagent) are added into the artificial meniscus mould for reaction and molding under certain conditions; and taking the molded artificial meniscus out of the mold to obtain the artificial meniscus.
In the present invention, after obtaining the artificial meniscus plate, it is preferable to further include:
modifying the artificial meniscus, the modifying agent comprising:
solutions of high performance polyurethanes;
the solvent in the solution of the high-performance polyurethane is selected from one or more of ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide or hexafluoroisopropanol, and more preferably selected from one or two of dimethylformamide and dimethyl sulfoxide;
the high-performance polyurethane is prepared by the method in the technical scheme.
In the present invention, the method of modification preferably comprises:
and (2) dipping the artificial meniscus in a solution of high-performance polyurethane, or carrying out spin coating or spray coating and drying on the artificial meniscus by adopting the solution of high-performance polyurethane to obtain the modified artificial meniscus.
In the present invention, it is preferable to modify a high-performance polyurethane artificial meniscus by dissolving the high-performance polyurethane in any one or a combination of ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or hexafluoroisopropanol to form a solution of a certain concentration; then dipping, spin coating or spray coating the artificial meniscus in the solution, and drying to obtain a modified artificial meniscus; preferably, the modified artificial meniscus is obtained by dissolving the high-performance polyurethane in a solution of dimethylformamide or dimethylsulfoxide and then immersing the solution.
The synthesis route of the modified chain extender and the modified end-capping reagent used in the invention is simple and quick, and the obtained modified single product has high yield and high purity; the high-performance polyurethane synthesized by the monomer has excellent performance; the mechanical strength and the friction coefficient of the artificial meniscus and the natural meniscus prepared by the high-performance polyurethane are matched.
The invention firstly functionalizes zwitterions of the chain extender and the end capping agent with hydrophobic chain segments, embeds the zwitterions into the main chain of the polyurethane, endows the polyurethane with the capability of hydration and lubrication, and solves the problem of how to balance high mechanical strength and low friction coefficient of the polyurethane. On one hand, the high-performance polyurethane material adsorbs a hydration layer on the surface of the polyurethane material through the anionic and cationic groups of zwitterions in the structure, and the hydration layers are difficult to overlap with each other due to the lower Gibbs free energy of water molecules in the hydration layer, so that the hydration layers can maintain good lubrication effect under large pressure; on the other hand, due to the fact that the hydrophobic structure is introduced into the polyurethane structure, when the polyurethane is subjected to hydration lubrication, hydrophobic association effect can be generated among hydrophobic chains in the structure, water molecules can be repelled from entering the interior of a molecular chain, and mechanical strength of the high-performance polyurethane is prevented from being greatly reduced.
The high-performance polyurethane material can be used for preparing artificial menisci in various ways, and materials with different mechanical strengths and good lubricating effect can be prepared by regulating and controlling the proportion of isocyanate, polyol, conventional chain extender, modified chain extender, conventional end capping agent and modified end capping agent in the synthesis process, and can also be applied to the fields of medical catheters, artificial corneas, ship coatings, water lubricated bearings and the like.
Example 1
A compound with a structure shown in formula I (wherein R is 1 is-CH 2 -，R 2 C being a straight chain 2 A saturated alkylene chain, R 3 Is C 2 Alkylene chain, R 4 is-OH, R 5 Is C 2 Alkylene chain, R 6 is-OH) and 1, 4-butyl sultone according to the molar ratio of 2.
Performing polymerization reaction on dicyclohexyl methane diisocyanate, polycarbonate polyol with the number average molecular weight of 1000 and stannous octoate to obtain a prepolymer; carrying out polyurethane synthesis reaction on the obtained prepolymer, 1, 4-butanediol and a modified chain extender; no end-capping agent; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 80 ℃, the total reaction time is 48h, the reaction pressure is 0.1MPa, dimethyl sulfoxide is used as a solvent in the reaction process, and the mass ratio of the reaction solvent to the raw materials is 6; in the synthesis process of the prepolymer, dicyclohexylmethane diisocyanate and polycarbonate polyol are reacted according to a molar ratio of 1; after the reaction is finished, carrying out polyurethane synthesis reaction, and reacting the NCO value of the synthesized prepolymer with the total OH value of 1, 4-butanediol and the modified chain extender according to the mole number of 1; adding 1, 4-butanediol and a modified chain extender at a molar ratio of 1; and after the reaction is finished, preparing the polyurethane material.
And (3) obtaining a three-dimensional model of the natural meniscus in the human body by a correlation technique, and directly 3D printing the prepared polyurethane material to obtain the artificial meniscus.
Example 2
A compound having the structure of formula I (wherein R 1 is-CH 2 NH-，R 2 Is a straight chain C 2 A saturated alkylene chain, R 3 Is C 4 Alkylene chain, R 4 is-OH, R 5 Is C 4 Alkylene chain, R 6 is-OH) and 1, 3-propane sultone according to the molar ratio of 1.5 at 37 ℃ for 12h to obtain the modified chain extender.
Carrying out polymerization reaction on 1, 4-cyclohexane diisocyanate, polyester polyol with the number average molecular weight of 2000 and dibutyltin dilaurate to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, cyclohexanediol, a modified chain extender and 3-mercaptopropyltrimethoxysilane; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 75 ℃, the total reaction time is 72h, the reaction pressure is 0.2MPa, and no solvent is added in the reaction process; in the synthesis process of the prepolymer, 1, 4-cyclohexane diisocyanate and polyester polyol react according to the molar ratio of 1; after the reaction is finished, carrying out polyurethane synthesis reaction, and reacting the NCO value of the prepolymer with the total OH value of the cyclohexanediol, the modified chain extender and the 3-mercaptopropyl trimethoxysilane according to a molar ratio of 1; during the synthesis of polyurethane, firstly adding cyclohexanediol and a modified chain extender; and 3-mercaptopropyl trimethoxy silane is added after the reaction is finished to prepare the polyurethane material.
Obtaining a three-dimensional model of a natural meniscus in a human body by a correlation technique, preparing an artificial meniscus mould by adopting an aluminum material, and then carrying out reaction forming on the prepared polyurethane material in the artificial meniscus mould under the conditions of reaction temperature of 100 ℃, holding temperature of 150 ℃, pressurizing pressure of 0.8MPa and pressurizing time of 180min to prepare the artificial meniscus.
Example 3
Reacting a compound having the structure of formula II (wherein R 1 is-CH 2 -，R 1 ' is-CH 2 -，R 2 Is a straight chain C 10 A saturated alkylene chain, R 2 ' is-H, R 3 Is C 2 Alkylene chain, R 4 is-OH) and acrylic acid according to the molar ratio of 1.
Carrying out polymerization reaction on hexamethylene diisocyanate, polycarbonate polyol with the number average molecular weight of 500 and stannous octoate to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, 1, 3-propylene glycol, a compound with a structure shown in formula II and a modified end-capping agent; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 60 ℃, the total reaction time is 120h, the reaction pressure is 0.15MPa, dimethyl sulfoxide is used as a solvent in the reaction process, and the mass ratio of the reaction solvent to the raw materials is 4; in the synthesis process of the prepolymer, hexamethylene diisocyanate and polycarbonate polyol are reacted according to the molar ratio of 1; after the reaction is finished, carrying out polyurethane synthesis reaction, and reacting the NCO value of the synthesis prepolymer with the total OH value of 1, 3-propylene glycol, the compound with the structure of formula II and the modified end-capping agent according to the mole number of 1.2, wherein the mole ratio of 1, 3-propylene glycol, the compound with the structure of formula II and the modified end-capping agent is 1.67; in the polyurethane synthesis, 1, 3-propylene glycol is added firstly, and after the reaction is finished, a compound with a structure shown in formula II and a modified end-capping agent are added to prepare the polyurethane material.
Obtaining a three-dimensional model of a natural meniscus in a human body by a related technology, preparing an artificial meniscus mould by adopting a stainless steel material, and then directly melting, remolding and molding the prepared polyurethane material in the artificial meniscus mould under the conditions of heating temperature of 180 ℃, keeping temperature of 180 ℃, pressurizing pressure of 10MPa and pressurizing time of 120min to prepare the artificial meniscus.
Example 4
A compound of the structure I (wherein R) 1 is-CH 2 -，R 2 Is a straight chain C 11 A saturated alkylene chain, R 3 Is C 2 Alkylene chain, R 4 is-OH, R 5 Is C 2 Alkylene chain, R 6 is-OH) and 1, 4-butyl sultone according to the molar ratio of 1.
Reacting a compound having the structure of formula II (wherein R 1 is-CH 2 NH-，R 1 ' is-CH 2 CH 2 -，R 2 Is a straight chain C 10 Side chains of saturated alkylene chains in which H on the C atom is completely substituted by F, R 2 ' is-H, R 3 Is C 2 Alkylene chain, R 4 is-NH 2 ) And reacting the modified end-capping reagent with 1, 4-butanesultone at a molar ratio of 2.
Carrying out polymer reaction on toluene diisocyanate, polyether polyol with the number average molecular weight of 1000 and dibutyltin dilaurate to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, the modified chain extender and the modified end-capping reagent; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 75 ℃, the total reaction time is 72h, the reaction pressure is 0.1MPa, dimethylformamide is used as a solvent in the reaction process, and the mass ratio of the reaction solvent to the raw materials is 5; in the synthesis process of the prepolymer, toluene diisocyanate and polyether polyol are reacted according to the molar ratio of 1; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the synthesized prepolymer and OH + NH of the modified chain extender and the modified end-capping reagent 2 The total value is reacted according to the mole number of 1; in the polyurethane synthesis, firstly adding a modified chain extender; and adding a modified end-capping agent after the reaction is finished to prepare the polyurethane material.
Obtaining a three-dimensional model of a natural meniscus in a human body by a related technology, preparing an artificial meniscus mould by adopting a polytetrafluoroethylene material, and then mixing the prepared polyurethane material and ABS resin according to a mass ratio of 2.
Example 5
A compound with a structure shown in formula I (wherein R is 1 is-CH 2 NH-，R 2 Is a straight chain C 10 Side chain of saturated alkylene chain substituted at chain end by trimethoxy silane, R 3 Is C 4 Alkylene chain, R 4 is-NH 2 ，R 5 Is C 4 Alkylene chain, R 6 is-NH 2 ) And reacting the modified chain extender with 1, 4-butanesultone according to a molar ratio of 1.
Reacting a compound having the structure of formula II (wherein R 1 is-CH 2 -，R 1 ' is-CH 2 -，R 2 Is a straight chain C 8 Side chains of saturated alkylene chains in which H on the C atom is completely substituted by F, R 2 ' is a straight chain C 8 Side chains of saturated alkylene chains in which H on the C atom is completely substituted by F, R 3 Is C 4 Alkylene chain, R 4 is-OH) and delta-valerolactone according to the molar ratio of 1.
Performing polymerization reaction on trimethyl-1, 6-hexamethylene diisocyanate, polyether polyol with the number average molecular weight of 2000 and dibutyltin dilaurate to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, 1, 4-butanediol, a modified chain extender, aniline propyl trimethoxy silane and a modified end capping agent; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 85 ℃, the total reaction time is 96h, the reaction pressure is 1.0MPa, dimethyl sulfoxide is used as a solvent in the reaction process, and the mass ratio of the reaction solvent to the raw materials is 8; in the synthesis process of the prepolymer, trimethyl-1, 6-hexamethylene diisocyanate and polyether polyol are reacted according to the molar ratio of 1; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the synthesized prepolymer and OH + NH of 1, 4-butanediol, modified chain extender, aniline propyl trimethoxy silane and modified end capping agent 2 The total is reacted according to a mole ratio of 1, 4-butanediol, modified chain extender, anilinopropyltrimethoxysilane to modified end-capping agent of 0.75; in the polyurethane synthesis, 1, 4-butanediol and a modified chain extender are firstly added; adding aniline propyl trimethoxy silane and modified end capping agent after the reaction is finished to prepareAnd preparing the polyurethane material.
Obtaining a three-dimensional model of a natural meniscus in a human body by a correlation technique, and mixing the prepared polyurethane material and polycaprolactone according to a mass ratio of 1.
Example 6
A compound with a structure shown in formula I (wherein R is 1 is-CH 2 CH 2 -，R 2 C being a straight chain 10 Side chains of saturated alkylene chains in which H on the C atom is completely substituted by F, R 3 Is C 2 Alkylene chain, R 4 is-NH 2 ，R 5 Is C 2 Alkylene chain, R 6 is-OH) and 2-chloro-2-oxo-1, 3, 2-dioxaphospholane according to the molar ratio of 3 to react for 24 hours at 100 ℃ to obtain the modified chain extender.
Reacting a compound of formula II (wherein R 1 is-CH 2 -，R 1 ' is-CH 2 -，R 2 Is a straight chain C 2 A saturated alkylene chain, R 2 ' straight chain C 2 A saturated alkylene chain, R 3 Is C 2 Alkylene chain, R 4 is-OH) and 2-chloro-2-oxo-1, 3, 2-dioxaphospholane react for 24 hours at the temperature of 100 ℃ according to the molar ratio of 3.
Naphthalene diisocyanate, polyester polyol with the number average molecular weight of 3000, 1, 6-hexanediol and triethylene diamine are subjected to polymerization reaction to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, a modified chain extender, 3-mercaptopropyl trimethoxy silane and a modified end-capping agent; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 90 ℃, the total reaction time is 120h, the reaction pressure is 0.1MPa, and no solvent is added in the reaction process; in the synthesis process of the prepolymer, naphthalene diisocyanate and polyester polyol are reacted according to the molar ratio of 1; after the reaction is finished, carrying out polyurethane synthesis reaction, and reacting the NCO value of the synthesis prepolymer with OH + NH of 1, 6-hexanediol, a modified chain extender, 3-mercaptopropyl trimethoxy silane and a modified end-capping reagent 2 The total is reacted according to the mole number of 1The ratio is 1.67; in the polyurethane synthesis, 1, 6-hexanediol and a modified chain extender are added firstly; and 3-mercaptopropyl trimethoxy silane and a modified end-capping agent are added after the reaction is finished to prepare the polyurethane material.
Obtaining a three-dimensional model of natural meniscus in a human body by a correlation technique, preparing an artificial meniscus mould by adopting an iron material, and then carrying out reaction forming on the prepared polyurethane material in the artificial meniscus mould under the conditions of reaction temperature of 100 ℃, holding temperature of 150 ℃, pressurizing pressure of 0.8MPa and pressurizing time of 180min to prepare the artificial meniscus; and repeatedly soaking the artificial meniscus in a toluene solution containing the polyurethane material, and drying to prepare the modified artificial meniscus.
Example 7
A compound of the structure I (wherein R) 1 is-CH 2 -，R 2 Is a straight chain C 11 A saturated alkylene chain, R 3 Is C 4 Alkylene chain, R 4 is-OH, R 5 Is C 4 Alkylene chain, R 6 is-OH) and 1, 3-propane sultone according to the molar ratio of 1.
Reacting a compound of formula II (wherein R 1 is-CH 2 NH-，R 1 ' is-CH 2 NH-，R 2 Is a straight chain C 10 Side chains of saturated alkylene chains having the chain ends substituted by triethoxysilane, R 2 ' straight chain C 10 Side chains of saturated alkylene chains in which H on the C atom is completely substituted by F, R 3 Is C 6 Alkylene chain, R 4 is-NH 2 ) And reacting the modified end-capping reagent with 1, 4-butanesultone according to a molar ratio of 1.
Performing polymerization reaction on norbornane diisocyanate, 1, 4-cyclohexane diisocyanate, castor oil polyol with the number average molecular weight of 4000 and triethylene diamine to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, toluenediamine, a modified chain extender, 3-aminopropyltrimethoxysilane and a modified end-capping agent; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 75 ℃, and the total reaction is carried outThe reaction time is 96 hours, the reaction pressure is 0.8MPa, hexafluoroisopropanol is used as a solvent in the reaction process, and the mass ratio of the reaction solvent to the raw materials is 5; in the synthesis process of the prepolymer, the total molar value of norbornane diisocyanate and 1, 4-cyclohexane diisocyanate and the molar value of castor oil polyol are reacted according to a molar ratio of 1; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the synthesized prepolymer and OH + NH of toluenediamine, modified chain extender, 3-aminopropyl trimethoxy silane and modified end-capping reagent 2 The total is reacted according to a mole number of 1; in the polyurethane synthesis, firstly, adding toluenediamine and a modified chain extender; and (3) adding 3-aminopropyl trimethoxy silane and a modified end-capping agent after the reaction is finished to prepare the polyurethane material.
Obtaining a three-dimensional model of a natural meniscus in a human body by a correlation technique, wherein the prepared polyurethane material, polylactic acid and polyolefin are mixed according to the ratio of 3:1, mixing the components in a mass ratio, and directly performing 3D printing to obtain an artificial meniscus; and coating the dimethyl formamide solution containing the polyurethane on the artificial meniscus in a spinning way, and drying to prepare the modified artificial meniscus.
Example 8
A compound with a structure shown in formula I (wherein R is 1 is-CH 2 CH 2 -，R 2 C being a straight chain 10 Side chain of saturated alkylene chain substituted at chain end by trimethoxy silane, R 3 Is C 2 Alkylene chain, R 4 is-OH, R 5 Is C 2 Alkylene chain, R 6 is-OH) and 1, 4-butyl sultone according to the molar ratio of 2 to react for 36h at 60 ℃ to obtain the modified chain extender 1.
A compound with a structure shown in formula I (wherein R is 1 is-CH 2 NH-，R 2 C being a straight chain 10 Side chains of saturated alkylene chains in which H on the C atom is completely substituted by F, R 3 Is C 2 Alkylene chain, R 4 is-NH 2 ，R 5 Is C 2 Alkylene chain, R 6 is-NH 2 ) Reacting the modified chain extender with 1, 4-butanesultone according to a molar ratio of 2.
Carrying out polymerization reaction on toluene diisocyanate, polycarbonate polyol with the number average molecular weight of 2000 and tetraphenyltin to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, 1, 3-propylene glycol, a modified chain extender 1 and a modified chain extender 2; no end-capping agent; wherein the temperature of prepolymer synthesis and polyurethane synthesis is 90 ℃, the total reaction time is 64h, the reaction pressure is 0.1MPa, dimethylacetamide is used as a solvent in the reaction process, and the mass ratio of the reaction solvent to the raw materials is 10; in the synthesis process of the prepolymer, toluene diisocyanate and polycarbonate polyol are reacted according to the molar ratio of 1; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the synthesized prepolymer and OH + NH of 1, 3-propylene glycol, modified chain extender 1 and modified chain extender 2 2 The total is reacted according to the molar number of 1; in the polyurethane synthesis, 1, 3-propylene glycol and a molar ratio of the modified chain extender 1 to the modified chain extender 2 is 1.
Obtaining a three-dimensional model of a natural meniscus in a human body by a related technology, preparing an artificial meniscus mould by adopting a stainless steel material, and then mixing the prepared polyurethane material and polyether-ether-ketone according to a mass ratio of 1; and spraying butyl acetate containing the polyurethane on the artificial meniscus, and drying to prepare the modified artificial meniscus.
Performance detection
The menisci prepared in the examples 1 to 8, natural pig menisci and polyurethane materials sold in the market are tested for mechanical property and friction property; the mechanical property test refers to the determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber of GBT 528-2009 in national standard; the friction performance test adopts a friction coefficient test machine UMT to test the friction coefficient, and the test conditions are as follows: the friction pair is an articular cartilage-high-performance polyurethane system, the friction form is reciprocating circular friction, the friction solution is 3mg/mL HA water solution, the friction pressure is 0.8MPa, the friction rate is 10mm/s, the friction frequency is 1Hz, the friction time is 10min, and the friction temperature is 33 ℃. The detection results are as follows:
the polyurethane artificial meniscus prepared by the invention can form a short-range ordered hydration layer on the surface through the strong interaction between the anions and cations of the zwitterion group in the structure and water, thereby achieving the lubricating effect. Meanwhile, the hydrophobic groups in the polyurethane artificial meniscus structure solve the problem of mechanical property reduction caused by the improvement of lubricating property because of preventing water molecules from entering molecular chains and providing more physical crosslinking points. The high-performance polyurethane material provided by the invention is simple and feasible in preparation method and wide in material application range, and the prepared artificial meniscus can be customized individually and can be effectively suitable for meniscus injury patients with different disease requirements.
While the invention has been described and illustrated with reference to specific embodiments thereof, these descriptions and illustrations do not limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (10)
1. A method for preparing high-performance polyurethane comprises the following steps:
carrying out polymerization reaction on diisocyanate, polyol and a catalyst to obtain a prepolymer;
carrying out chain extension reaction on the prepolymer and a chain extender to obtain high-performance polyurethane;
the preparation method of the chain extender comprises the following steps:
reacting a compound with a structure shown in a formula I with a zwitterion monomer to obtain a chain extender;
in the formula I, R 1 Is selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 Is selected from-H, C 1 ～C 20 Alkylene radical, C 1 ～C 20 Fluorine-containing alkyl group, C 1 ～C 20 Silane, phenyl or benzyl containing groups;
R 3 and R 5 Independently selected from C 2 ～C 6 An alkylene group;
R 4 and R 6 Independently selected from-OH or-NH 2 。
2. The method of claim 1, wherein after the chain extension reaction is completed, further comprising:
carrying out end-capping reaction on the obtained reaction product and an end-capping reagent to obtain high-performance polyurethane;
the preparation method of the end-capping agent comprises the following steps:
reacting a compound with a structure shown in a formula II with a zwitterionic monomer to obtain an end-capping reagent;
in the formula II, R 1 And R 1 ' independently selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 And R 2 ' independently selected from-H, C 1 ～C 20 Alkylene radical, C 1 ～C 20 Fluorine-containing alkyl group, C 1 ～C 20 Silane-containing groups, phenyl or benzyl;
R 3 is selected from C 2 ～C 6 An alkylene group;
R 4 is selected from-OH or-NH 2 。
3. The method according to claim 1 or 2, wherein the zwitterionic monomer is selected from one or more of 1, 3-propane sultone, 1, 4-butane sultone, acrylic acid, gamma-butyrolactone, delta-valerolactone or 2-chloro-2-oxo-1, 3, 2-dioxaphospholane.
4. The process according to claim 2, wherein the polymerization reaction is carried out at a temperature of 40 to 110 ℃ and a pressure of 0.05 to 2MPa;
the temperature of the chain extension reaction is 40-110 ℃, and the pressure is 0.05-2 MPa;
the temperature of the end capping reaction is 40-110 ℃, and the pressure is 0.05-2 MPa.
5. The process according to claim 1, wherein the molar ratio of isocyanate to polyol is 1: (0.1-0.9).
6. The method of claim 2, wherein the molar ratio of the chain extender to the end-capping agent is 1: (0-10);
the mole number of NCO in the prepolymer and OH and NH in the chain extender and the end capping reagent 2 The ratio of the total number of moles is 1: (0.8-1.2).
7. A method of preparing an artificial meniscus comprising:
3D printing is carried out on the high-performance polyurethane to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method of claim 1.
8. The method of claim 7, wherein the 3D printing comprises:
3D printing is carried out on the high-performance polyurethane and the high polymer material;
the high polymer material is selected from one or more of polyurethane, polylactic acid, polyether-ether-ketone, polycaprolactone, ABS resin or polyolefin.
9. A method of preparing an artificial meniscus comprising:
reacting and molding the prepolymer and the chain extender in an artificial meniscus mold to obtain an artificial meniscus;
the prepolymer and the chain extender are the prepolymer and the chain extender in claim 1;
or
Melting and molding the high-performance polyurethane in an artificial meniscus mold to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method of claim 1.
10. The method of any of claims 7 to 9, wherein said obtaining an artificial meniscus further comprises:
modifying the artificial meniscus, the modifying agent comprising:
solutions of high performance polyurethanes;
the solvent in the solution of the high-performance polyurethane is selected from one or more of ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide or hexafluoroisopropanol;
the high-performance polyurethane is prepared by the method of claim 1.
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| WO2019209348A1 (en) * | 2018-04-28 | 2019-10-31 | Liang Wang | Polyurethane elastomer with high ultimate elongation |
| CN111234170A (en) * | 2020-01-15 | 2020-06-05 | 中国科学院长春应用化学研究所 | Polyurethane material, preparation method thereof and application of polyurethane material in artificial meniscus material |
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| US20190112411A1 (en) * | 2017-03-02 | 2019-04-18 | Chinese Academy Of Sciences, Ningbo Institute Of Material Technology & Engineering | Elastomer, method for preparation thereof, and use thereof |
| WO2019209348A1 (en) * | 2018-04-28 | 2019-10-31 | Liang Wang | Polyurethane elastomer with high ultimate elongation |
| CN110181806A (en) * | 2019-06-03 | 2019-08-30 | 北京科技大学 | The low temperature 3D printing method of degradable aqueous polyurethane with biocompatible |
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