CN115636919B - 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 zwitterionic hydrophilic modification, prepolymer synthesis is performed, polyurethane synthesis is performed to obtain a high-performance polyurethane material which is not limited to be used for artificial menisci, and then products such as the artificial menisci are prepared through a 3D printing, mould pressing, dipping, spin coating or spraying method. In the invention, the high-performance polyurethane molecular chain contains a zwitterionic structure for improving the lubrication effect and a hydrophobic structure for maintaining the mechanical strength, so that 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, chain extender and the like, and the polyurethane can have excellent mechanical properties, wear resistance, aging resistance, corrosion resistance and the like by regulating and controlling the proportion between a hard segment and a soft segment in the synthesis process and selecting different chain extenders, so that the polyurethane material is widely applied to the fields of medical instruments, coatings, bearings, tires and the like. However, with the development of science and technology and the requirements of use environment, polyurethane materials are required to maintain excellent mechanical properties and have good lubricating properties under more and more conditions. For example, the mechanical strength and the friction coefficient are used for evaluating whether the polyurethane material for artificial meniscus can be used in human bodyCore criteria for long-term use. Commercially available BritishPolyurethane artificial meniscus and israelPolyurethane artificial meniscus has good biocompatibility and excellent mechanical properties, but has poor lubricating property due to material hydrophobicity, and is extremely easy to abrade joint cartilage to cause knee joint degenerative disease.
At present, the method for improving the lubricating property of polyurethane is to add inorganic/organic molecular fillers with water lubricating property into a polyurethane main body, but the binding force between the fillers and the polyurethane main body is poor, and an interface layer exists between the fillers, so that the fillers are easy to fall off from the main body and cannot be applied for a long time. Therefore, some attempts have been made to graft polyethylene glycol, epoxy resin, bioactive substances and the like onto the surface of polyurethane, so as to improve the water lubrication performance of polyurethane, for example, to graft epoxy resin (CN 109575233) onto the surface of polyurethane to improve the lubrication performance of the material, and polyurethane medical intervention catheters with excellent lubrication and wear resistance can be obtained, but the surface graft layer is easy to fall off, so that the polyurethane medical intervention catheters cannot be used for a long time.
In order to solve the above problems, one or more hydrophilic structures (CN 106967206a, CN111234170 a) such as chitosan, carboxymethyl chitosan and glycerophosphorylcholine are introduced into the polyurethane body, and it is proposed that the lubricating property of the modified material can be significantly improved. However, the hydrophilic group of the modified material can lead 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 that of natural menisci in a humoral environment for a long period of time, but have a tensile strength of only about 10MPa, which is insufficient to support in vivo application of artificial menisci. In order to improve the mechanical strength of hydrophilic polyurethane, the use of a cross-linking agent to improve the molecular structural stability of polyurethane (CN 111110927 a) is an effective method, but this can lead to materials that are difficult to process once formed, especially in favor of the production of artificial menisci.
Therefore, the polyurethane material has high mechanical strength and is convenient to operate and process, and the hydration layer can be formed on the surface of the polyurethane material by means of the hydrophilic structure in the structure in aqueous solution, so that the polyurethane can simultaneously meet the requirements of high mechanical strength and low friction coefficient, and the polyurethane material is a problem to be solved by the person skilled in the art.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method and application of high-performance polyurethane, and the high-performance polyurethane provided by the invention can be used for artificial meniscus to simultaneously meet the requirements of mechanical strength and friction coefficient of meniscus.
The invention provides a preparation method of high-performance polyurethane, which comprises the following steps:
carrying out polymerization reaction on diisocyanate, polyalcohol 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 structural compound shown in a formula I with a zwitterionic monomer to obtain a chain extender;
in the formula I, R 1 Selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 Selected from-H, C 1 ～C 20 Alkylene, C 1 ～C 20 Fluoroalkyl group, C 1 ～C 20 Containing silane groups, phenyl groups or benzyl groups;
R 3 and R is 5 Independently selected from C 2 ～C 6 An alkylene group;
R 4 and R is 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 agent to obtain high-performance polyurethane;
the preparation method of the end capping agent comprises the following steps:
reacting a structural compound of formula II with a zwitterionic monomer to obtain a blocking agent;
in formula II, R 1 And R is 1 ' independently selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 And R is 2 ' independently selected from-H, C 1 ～C 20 Alkylene, C 1 ～C 20 Fluoroalkyl group, C 1 ～C 20 Containing silane groups, phenyl groups or benzyl groups;
R 3 selected from C 2 ～C 6 An alkylene group;
R 4 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-chloro-2-oxo-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: (0-10);
the molar 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 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 according to the technical scheme.
Preferably, the 3D printing includes:
3D printing is carried out on the high-performance polyurethane and the high-molecular material;
the polymer material is one or more selected from 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 raw materials for preparing high-performance polyurethane into an artificial meniscus mould for reaction molding 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 (b)
Melting and molding high-performance polyurethane in an artificial meniscus mold to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method according to the technical scheme.
Preferably, the artificial meniscus obtaining further comprises:
modifying the artificial meniscus, the modifying agent comprising:
a solution of high performance polyurethane;
the solvent in the high-performance polyurethane solution 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 spray coating the modified reagent on the artificial meniscus;
the high-performance polyurethane is prepared by the method according to the technical scheme.
The high-performance polyurethane prepared by the invention forms a short-range ordered hydration layer on the surface of the polyurethane through the strong interaction between anions and cations of the zwitterionic groups in the structure and water, thereby achieving the lubricating effect. In addition, in order to prevent water molecules from entering the molecular chain and provide more physical crosslinking points, hydrophobic groups are introduced into the chemical structure of the material, so that the problem that the mechanical property of the material is greatly reduced due to the improvement of the lubricating property of polyurethane is solved. The preparation method of the high-performance polyurethane is simple and easy to implement, has wide material application range, and can effectively prepare the polyurethane artificial meniscus suitable for different disease conditions.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of high-performance polyurethane, which comprises the following steps:
carrying out polymerization reaction on diisocyanate, polyalcohol 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 structural compound shown in a formula I with a zwitterionic monomer to obtain a chain extender;
in the formula I, R 1 Selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 Selected from-H, C 1 ～C 20 Alkylene, C 1 ～C 20 Fluoroalkyl group, C 1 ～C 20 Containing silane groups, phenyl groups or benzyl groups;
R 3 and R is 5 Independently selected from C 2 ～C 6 An alkylene group;
R 4 and R is 6 Independently selected from-OH or-NH 2 。
In the present invention, the chain extension reaction preferably further comprises:
carrying out end capping reaction on the obtained reaction product and an end capping agent to obtain high-performance polyurethane;
the preparation method of the end capping agent comprises the following steps:
reacting a structural compound of formula II with a zwitterionic monomer to obtain a blocking agent;
in formula II, R 1 And R is 1 ' independently selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 And R is 2 ' independently selected from-H, C 1 ～C 20 Alkylene, C 1 ～C 20 Fluoroalkyl group, C 1 ～C 20 Containing silane groups, phenyl groups or benzyl groups;
R 3 selected from C 2 ～C 6 An alkylene group;
R 4 selected from-OH or-NH 2 。
In the present invention, the preparation method of the high-performance polyurethane preferably comprises:
(1) Zwitterionic hydrophilic modification of chain extenders and endcapping agents: based on the N atom in the structures of the compound with the structure I and the compound with the structure II and the zwitterionic monomer, the chain extender and the end capping agent containing the zwitterionic group are synthesized.
(2) Prepolymer synthesis: the prepolymer is prepared by mixing diisocyanate, polyol and catalyst and then carrying out polymerization reaction.
(3) Polyurethane synthesis: and (3) carrying out chain extension reaction on the prepolymer and a chain extender, and if the residual isocyanate functional groups remain in the previous 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, cyclohexane dimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl m-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyl diphenylmethane diisocyanate or lysine diisocyanate.
In the present invention, the polyol is preferably 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, tetramethylalkylene diamine, N-dimethylbenzylamine, or triethylamine.
In the present invention, the molar ratio of isocyanate to 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 to 0.007), most preferably 1:0.005.
in the present invention, the polymerization reaction may be performed 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, a step of; the solvent is preferably any one or a 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 polymerization 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 polymerization reaction is preferably 0.05 to 2MPa, more preferably 0.1 to 1MPa, still more preferably 0.3 to 0.7MPa, and most preferably 0.5MPa.
In the present invention, in the formula I and the formula II, C 1 ～C 20 The alkylene groups are independently preferably saturated alkylene chains having a linear or branched structure, more preferably C 1 ～C 12 Alkylene is a straight saturated alkylene chain; c (C) 1 ～C 20 The fluoroalkyl group is independently preferably a side chain in which H on the C atom in the saturated alkylene chain, which is straight or branched in structure, is completely or partially substituted with F, more preferably C 3 ～C 12 A fluoroalkyl group, preferably a side chain in which H on the C atom in the straight saturated alkylene chain in the structure is completely substituted with F; c (C) 1 ～C 20 The silane-group-containing independent side chain having a saturated alkylene chain which is preferably straight or branched in structure and whose chain end is substituted by trimethoxysilane or triethoxysilane, more preferably C 3 ～C 8 A side chain containing a silane group, preferably a chain end of a straight saturated alkylene chain in the structure substituted with trimethoxysilane; c (C) 2 ～C 6 The alkylene groups are independently preferably saturated alkylene chains having a linear or branched structure, more preferably C 2 ～C 4 Alkylene groups, preferably straight saturated alkylene chains.
The sources of the compounds of the formula I and the formula II are not particularly limited, and the compounds can be obtained by market purchase or can be prepared according to a conventional synthesis method in the field.
In the present invention, the zwitterionic monomer is preferably one or more selected from 1, 3-propane sultone, 1, 4-butane sultone, acrylic acid, gamma-butyrolactone, delta-valerolactone or 2-chloro-2-oxo-1, 3, 2-dioxaphospholane, more preferably one or more selected from 1, 3-propane sultone, 1, 4-butane sultone or 2-chloro-2-oxo-1, 3, 2-dioxaphospholane; the molar ratio of the structural compound of formula I to the zwitterionic monomer is preferably (3-1): (1 to 3), more preferably (0.8 to 1): (1 to 1.2), most preferably 0.9:1.1; the temperature of the reaction is preferably 25 to 120 ℃, more preferably 40 to 60 ℃, 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 comprises: conventional chain extenders.
In the present invention, the conventional chain extender is preferably selected from any one or a combination of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, cyclohexanediol, terephthalene glycol bishydroxyethyl ether, toluenediamine, isophoronediamine, a compound of formula I, or trimethylhexamethylenediamine.
In the invention, a product obtained by reacting a structural compound shown in the formula I with a zwitterionic monomer is named as a first chain extender, and a conventional chain extender is named 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 to 20): 1, more preferably (0 to 10): 1, most preferably 5:1, a step of; the solvent is preferably any one or a 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 chain extension reaction is preferably 40 to 110 ℃, more preferably 60 to 90 ℃, and most preferably 70 to 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, still more preferably 0.3 to 0.7MPa, and most preferably 0.5MPa.
In the present invention, the molar ratio of the structural compound of formula II to the zwitterionic monomer is preferably (3 to 1): (1 to 3), more preferably (0.8 to 1): (1 to 1.2), most preferably 0.9:1.1; the temperature of the reaction is preferably 25 to 120 ℃, more preferably 40 to 60 ℃, 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 blocking agent preferably further comprises: conventional capping agents.
In the present invention, the conventional blocking agent is preferably selected from any one or combination of ethyl ketoxime, 3, 5-dimethylpyrazole, caprolactam, 3-isocyanatopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, phenylpropyl trimethoxysilane, phenylmethyl triethoxysilane, a compound of formula II or bis- [3- (trimethoxy silicon) -propyl ] -amine.
In the invention, the product obtained by reacting the structural compound of the formula II with the zwitterionic monomer is marked as a first end-capping agent, and the conventional end-capping agent is marked as a second end-capping agent; the molar ratio of the first end-capping agent to the second end-capping agent is preferably 1: (0 to 10), more preferably 1: (3-5), most preferably 1:4.
In the present invention, the 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 capping agent is preferably (0 to 20): 1, more preferably (0 to 10): 1, most preferably 5:1, a step of; the solvent is preferably any one or a 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 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 capping reaction is preferably 0.05 to 2MPa, more preferably 0.1 to 1MPa, still 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 present invention, the number of moles of NCO in the prepolymer and OH and NH in the chain extender and the capping agent 2 The total molar ratio is preferably 1: (0.8 to 1.2), more preferably 1:1.
In the present invention, when the chain extender contains the first chain extender, the blocking agent may be either the first blocking agent or the second blocking agent; when the blocking agent contains the first blocking agent, the first chain extender and the second chain extender may be used in the 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 according to 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 related technique, and then performs a 3D printing process on the three-dimensional model.
According to the preparation method of the high-performance polyurethane artificial meniscus, a three-dimensional model of a natural meniscus in a human body is obtained through a related technology, then 3D printing treatment is carried out on the three-dimensional model to obtain an artificial meniscus mould, and the artificial meniscus is obtained through further mould pressing or direct 3D printing.
In the present invention, the 3D printing preferably includes:
and 3D printing is carried out on the high-performance polyurethane and the high-molecular 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, 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: (1-3), most preferably 1:2.
in the invention, the material of the artificial meniscus takes the high-performance polyurethane as a main part, and one or more materials such as polyurethane, polylactic acid, polyether ether ketone, polycaprolactone, ABS resin or polyolefin and the like can be added into the main part material for common 3D printing treatment; preferred materials for 3D printing or molding the artificial meniscus are the high performance polyurethanes, high performance polyurethanes and polycaprolactone, high performance polyurethanes and polyolefin described above.
The invention provides a preparation method of an artificial meniscus, which comprises the following steps:
melting and molding high-performance polyurethane in an artificial meniscus mold to obtain an artificial meniscus;
the high-performance polyurethane is prepared by the method according to the technical scheme.
The invention provides a preparation method of an artificial meniscus, which comprises the following steps:
reacting and forming the prepolymer and a chain extender (and a blocking agent) in an artificial meniscus mould to obtain an artificial meniscus;
the prepolymer, the chain extender and the end capping agent are the prepolymer, the chain extender and the end capping agent according to the technical scheme.
In the invention, the artificial meniscus mould can be made of metal materials such as stainless steel, aluminum, iron and the like; or organic polymer materials such as polytetrafluoroethylene and ABS resin, and composite materials thereof.
In the present invention, the melt molding and reaction molding conditions preferably independently include a heating temperature of 50 to 300 ℃, more preferably 70 to 180 ℃, still more preferably 100 to 160 ℃, and most preferably 120 to 140 ℃; the temperature of the heat preservation 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 180 minutes, more preferably 30 to 60 minutes, and most preferably 40 to 50 minutes.
In the invention, the artificial meniscus material (high-performance polyurethane) can be directly melted and added into an artificial meniscus mould for reshaping and shaping, or the needed raw materials (prepolymer, chain extender and end capping agent) are added into the artificial meniscus mould for reaction and shaping under certain conditions; and taking the molded artificial meniscus out of the mold to obtain the artificial meniscus.
In the present invention, the obtaining of the artificial meniscus preferably further comprises:
modifying the artificial meniscus, the modifying agent comprising:
a solution of high performance polyurethane;
the solvent in the high-performance polyurethane solution is one or more selected from ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, toluene, dimethylformamide, dimethylacetamide, dimethyl sulfoxide or hexafluoroisopropanol, and more preferably one or two selected from dimethylformamide and dimethyl sulfoxide;
the high-performance polyurethane is prepared by the method according to the technical scheme.
In the present invention, the method of modification preferably comprises:
immersing the artificial meniscus in a high-performance polyurethane solution, or spin-coating or spray-coating the artificial meniscus by adopting the high-performance polyurethane solution, and drying to obtain the modified artificial meniscus.
In the present invention, it is preferable to modify the 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, and hexafluoroisopropanol to form a solution having a certain concentration; then immersing, spin-coating or spraying the artificial meniscus in the solution, and drying to obtain a modified artificial meniscus; preferably, the high-performance polyurethane is dissolved in dimethylformamide and dimethyl sulfoxide solution, and then immersed to obtain the modified artificial meniscus.
The synthesis route of the modified chain extender and the modified end capping agent 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 friction coefficient of the artificial meniscus and the natural meniscus prepared by the high-performance polyurethane are matched.
The invention firstly functionalizes the chain extender and the end capping agent with hydrophobic chain segments in a zwitterionic way, embeds the chain extender and the end capping agent into the main chain of polyurethane, endows the polyurethane with the capability of hydration lubrication, and solves the problem of how to balance high mechanical strength and low friction coefficient of the polyurethane. According to the high-performance polyurethane material, on one hand, a hydration layer is adsorbed on the surface of the polyurethane material through anionic and cationic groups of amphoteric ions in the structure, and the hydration layer is difficult to overlap with each other because the Gibbs free energy of water molecules in the hydration layer is low, so that the hydration layer can maintain good lubrication effect under high pressure; on the other hand, as the hydrophobic structure is introduced into the polyurethane structure, hydrophobic association is generated between hydrophobic chains in the structure when the polyurethane is hydrated and lubricated, so that water molecules can be repelled from entering the inside of the molecular chains, and the mechanical strength of the high-performance polyurethane is prevented from being greatly reduced.
The high-performance polyurethane material can be used for preparing artificial meniscus in various modes, and can be used for preparing materials with different mechanical strengths and good lubricating effect 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 cornea, ship coatings, water-lubricated bearings and the like.
Example 1
Compounds of the structure of formula I (wherein R 1 is-CH 2 -，R 2 C is straight chain 2 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 react for 18 hours at 40 ℃ according to the mol ratio of 2:1, and the modified chain extender is obtained.
Polymerizing dicyclohexylmethane 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 and 1, 4-butanediol and modified chain extender; no end-capping agent; wherein the temperature of the prepolymer synthesis and the polyurethane synthesis is 80 ℃, the total reaction time is 48 hours, the reaction pressure is 0.1MPa, the reaction process uses dimethyl sulfoxide as a solvent, and the mass ratio of the reaction solvent to the raw materials is 6:1; in the prepolymer synthesis process, dicyclohexylmethane diisocyanate and polycarbonate polyol are reacted according to the molar ratio of 1:0.5; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the synthesized prepolymer and the total OH value of the 1, 4-butanediol and the modified chain extender are reacted according to the mole number of 1:1; adding 1, 4-butanediol and a modified chain extender in a molar ratio of 1:1; after the reaction is finished, the polyurethane material is prepared.
Through the related technology, a three-dimensional model of the natural meniscus in the human body is obtained, and the prepared polyurethane material is directly 3D printed to obtain the artificial meniscus.
Example 2
Compounds of formula I (wherein R 1 is-CH 2 NH-，R 2 C is straight chain 2 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 react for 12 hours at 37 ℃ according to the mol ratio of 1:1.5, and the modified chain extender is obtained.
Polymerizing 1, 4-cyclohexane diisocyanate, polyester polyol with the number average molecular weight of 2000 and dibutyl tin dilaurate to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, cyclohexanediol, a modified chain extender and 3-mercaptopropyl trimethoxy silane; wherein the temperature of the prepolymer synthesis and the polyurethane synthesis is 75 ℃, the total reaction time is 72 hours, the reaction pressure is 0.2MPa, and no solvent is added in the reaction process; in the prepolymer synthesis process, 1, 4-cyclohexane diisocyanate and polyester polyol react according to a molar ratio of 1:0.3; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the prepolymer and the total OH value of cyclohexanediol, the modified chain extender and 3-mercaptopropyl trimethoxy silane are reacted according to the mole number of 1:0.8, wherein the mole ratio of cyclohexanediol, the modified chain extender and 3-mercaptopropyl trimethoxy silane is 0.33:0.67:0.5; in polyurethane synthesis, firstly adding cyclohexanediol and a modified chain extender; after the reaction is finished, adding 3-mercaptopropyl trimethoxy silane to prepare the polyurethane material.
A three-dimensional model of a natural meniscus in a human body is obtained through a related technology, an artificial meniscus mould is prepared by adopting an aluminum material, and then the prepared polyurethane material is subjected to reaction molding in the artificial meniscus mould under the conditions of a reaction temperature of 100 ℃, a holding temperature of 150 ℃, a pressurizing pressure of 0.8MPa and a pressurizing time of 180min, so that the artificial meniscus is prepared.
Example 3
Compounds of the structure of formula II (wherein R 1 is-CH 2 -，R 1 ' is-CH 2 -，R 2 C is straight chain 10 Saturated alkylene chain, R 2 ' is-H, R 3 Is C 2 Alkylene chain, R 4 And (3) reacting the modified end capping agent with acrylic acid for 96 hours at 60 ℃ according to a molar ratio of 1:2.
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 structural compound of a formula II and a modified end capping agent; wherein the temperature of the prepolymer synthesis and the polyurethane synthesis is 60 ℃, the total reaction time is 120 hours, the reaction pressure is 0.15MPa, the reaction process uses dimethyl sulfoxide as a solvent, and the mass ratio of the reaction solvent to the raw materials is 4:1; in the prepolymer synthesis process, hexamethylene diisocyanate and polycarbonate polyol are reacted according to a molar ratio of 1:0.6; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the synthetic prepolymer, 1, 3-propanediol, the structural compound of the formula II and the total OH value of the modified end capping agent are reacted according to the mole number of 1:1.2, wherein the mole ratio of the 1, 3-propanediol, the structural compound of the formula II and the modified end capping agent is 1:0.67:1.33; in the polyurethane synthesis, firstly, 1, 3-propylene glycol is added, and after the reaction is finished, the structural compound of the formula II and a modified end capping agent are added to prepare the polyurethane material.
A three-dimensional model of a natural meniscus in a human body is obtained through a related technology, an artificial meniscus mould is prepared by adopting a stainless steel material, and then the prepared polyurethane material is directly melted and remolded in the artificial meniscus mould for forming under the conditions of heating temperature of 180 ℃, holding temperature of 180 ℃, pressurizing pressure of 10MPa and pressurizing time of 120min, so that the artificial meniscus is prepared.
Example 4
Compounds of the structure of formula I (wherein R 1 is-CH 2 -，R 2 C is straight chain 11 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 react for 24 hours at 40 ℃ according to the mol ratio of 1:1, thus obtaining the modified chain extender.
Compounds of the structure of formula II (wherein R 1 is-CH 2 NH-，R 1 ' is-CH 2 CH 2 -，R 2 C is straight chain 10 Side chain in which H on C atom in saturated alkylene chain is completely substituted by F, R 2 ' is-H, R 3 Is C 2 Alkylene chain, R 4 is-NH 2 ) Reacting with 1, 4-butyl sultone for 24 hours at 38 ℃ according to a molar ratio of 2:1 to obtain the modified end capping agent.
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 agent; wherein the temperature of the prepolymer synthesis and the polyurethane synthesis is 75 ℃, the total reaction time is 72h, the reaction pressure is 0.1MPa, and the reaction is carried out In the reaction process, dimethylformamide is used as a solvent, and the mass ratio of the reaction solvent to the raw materials is 5:1; in the prepolymer synthesis process, toluene diisocyanate and polyether polyol are reacted according to a molar ratio of 1:0.5; after the reaction is finished, polyurethane synthesis reaction is carried out, and the NCO value of the synthesized prepolymer, the modified chain extender and OH+NH of the modified end capping agent are mixed 2 The total value is reacted according to the mole number of 1:1, wherein the modified chain extender and the modified end capping agent are fed according to the mole ratio of 2:1; in polyurethane synthesis, a modified chain extender is firstly added; and adding a modified end capping agent after the reaction is finished to prepare the polyurethane material.
According to the method, a three-dimensional model of a natural meniscus in a human body is obtained through a related technology, a polytetrafluoroethylene material is adopted to prepare an artificial meniscus mould, then the polyurethane material and the ABS resin which are prepared are mixed according to a mass ratio of 2:1, the heating temperature is 230 ℃, the holding temperature is 230 ℃, the pressurizing pressure is 20MPa, and under the condition that the pressurizing time is 60min, the artificial meniscus is prepared by directly melting, remolding and forming in the artificial meniscus mould.
Example 5
Compounds of the structure of formula I (wherein R 1 is-CH 2 NH-，R 2 C is straight chain 10 Side chain of saturated alkylene chain with trimethoxysilane substituted at chain end, R 3 Is C 4 Alkylene chain, R 4 is-NH 2 ，R 5 Is C 4 Alkylene chain, R 6 is-NH 2 ) Reacting with 1, 4-butyl sultone for 48h at 75 ℃ according to a molar ratio of 1:2 to obtain the modified chain extender.
Compounds of the structure of formula II (wherein R 1 is-CH 2 -，R 1 ' is-CH 2 -，R 2 C is straight chain 8 Side chain in which H on C atom in saturated alkylene chain is completely substituted by F, R 2 ' C being straight chain 8 Side chain in which H on C atom in saturated alkylene chain is completely substituted by F, R 3 Is C 4 Alkylene chain, R 4 is-OH) and delta-valerolactone are reacted for 48 hours at 75 ℃ according to the mol ratio of 1:2, thus obtaining the modified end capping agent.
By trimethyl-1, 6-Performing polymerization reaction on hexamethylene diisocyanate, polyether polyol with 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 the prepolymer synthesis and the polyurethane synthesis is 85 ℃, the total reaction time is 96 hours, the reaction pressure is 1.0MPa, the reaction process uses dimethyl sulfoxide as a solvent, and the mass ratio of the reaction solvent to the raw materials is 8:1; in the prepolymer synthesis process, trimethyl-1, 6-hexamethylene diisocyanate and polyether polyol are reacted according to a molar ratio of 1:0.2; 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 are mixed 2 The total value is reacted according to the mole number of 1:1.2, wherein the mole ratio of the 1, 4-butanediol, the modified chain extender, the aniline propyl trimethoxy silane and the modified end capping agent is 0.75:2.25:0.25:0.75; in polyurethane synthesis, 1, 4-butanediol and a modified chain extender are firstly added; after the reaction is finished, adding the aniline propyl trimethoxy silane and the modified end capping agent to prepare the polyurethane material.
Through a related technology, a three-dimensional model of a natural meniscus in a human body is obtained, and the prepared polyurethane material and polycaprolactone are mixed according to a mass ratio of 1:1 and are directly subjected to 3D printing to obtain the artificial meniscus.
Example 6
Compounds of the structure of formula I (wherein R 1 is-CH 2 CH 2 -，R 2 C is straight chain 10 Side chain in which H on C atom in saturated alkylene chain 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 a molar ratio of 3:1 at 100 ℃ for 24 hours to obtain the modified chain extender.
Compounds of the structure of formula II (wherein R 1 is-CH 2 -，R 1 ' is-CH 2 -，R 2 C is straight chain 2 Saturated alkylene chain, R 2 ' C being straight chain 2 Saturated alkylene chain, R 3 Is C 2 Alkylene chain, R 4 is-OH) and 2-chloro-2-oxo-1, 3, 2-dioxaphospholane according to a molar ratio of 3:1 at 100 ℃ for 24 hours to obtain the modified end capping agent.
Polymerizing naphthalene diisocyanate, polyester polyol with a number average molecular weight of 3000, 1, 6-hexanediol and triethylenediamine to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, the modified chain extender, the 3-mercaptopropyl trimethoxy silane and the modified end capping agent; wherein the temperature of the prepolymer synthesis and the 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 process of prepolymer synthesis, naphthalene diisocyanate and polyester polyol are reacted according to a molar ratio of 1:0.1; after the reaction is finished, polyurethane synthesis reaction is carried out, and NCO value of the synthesized prepolymer and OH+NH of 1, 6-hexanediol, modified chain extender, 3-mercaptopropyl trimethoxy silane and modified end capping agent are mixed 2 The total value is reacted according to the mole number of 1:0.8, wherein the mole ratio of 1, 6-hexanediol, modified chain extender, 3-mercaptopropyl trimethoxy silane and modified end capping agent is 1.67:0.33:0.17:0.83; in polyurethane synthesis, firstly adding 1, 6-hexanediol and a modified chain extender; after the reaction is finished, adding 3-mercaptopropyl trimethoxy silane and a modified end capping agent to prepare the polyurethane material.
Obtaining a three-dimensional model of a natural meniscus in a human body through a related technology, preparing an artificial meniscus mould by adopting an iron material, and then performing reaction forming in the artificial meniscus mould under the conditions that the reaction temperature is 100 ℃, the holding temperature is 150 ℃, the pressurizing pressure is 0.8MPa and the pressurizing time is 180min to prepare the artificial meniscus; repeatedly dipping the artificial meniscus in toluene solution containing the polyurethane material, and drying to prepare the modified artificial meniscus.
Example 7
Compounds of the structure of formula I (wherein R 1 is-CH 2 -，R 2 C is straight chain 11 Saturated alkylene chain, R 3 Is C 4 An alkylene group is used as a chain,R 4 is-OH, R 5 Is C 4 Alkylene chain, R 6 is-OH) and 1, 3-propane sultone react for 12 hours at 45 ℃ according to the mol ratio of 1:1, thus obtaining the modified chain extender.
Compounds of the structure of formula II (wherein R 1 is-CH 2 NH-，R 1 ' is-CH 2 NH-，R 2 C is straight chain 10 Side chain of saturated alkylene chain with triethoxysilane substituted at chain end, R 2 ' C being straight chain 10 Side chain in which H on C atom in saturated alkylene chain is completely substituted by F, R 3 Is C 6 Alkylene chain, R 4 is-NH 2 ) And reacting with 1, 4-butanesulfonic acid lactone for 24 hours at 60 ℃ according to a molar ratio of 1:1 to obtain the modified end capping agent.
Polymerizing norbornane diisocyanate, 1, 4-cyclohexane diisocyanate, castor oil polyol with a number average molecular weight of 4000 and triethylenediamine to obtain a prepolymer; carrying out polyurethane synthesis reaction on the prepolymer, toluenediamine, a modified chain extender, 3-aminopropyl trimethoxy silane and a modified end capping agent; wherein the temperature of the prepolymer synthesis and the polyurethane synthesis is 75 ℃, the total 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 5:1; in the prepolymer synthesis process, the total mole value of the norbornane diisocyanate and the 1, 4-cyclohexane diisocyanate and the mole value of the castor oil polyol react according to the mole ratio of 1:0.4, and the mole ratio of the norbornane diisocyanate to the 1, 4-cyclohexane diisocyanate is 1:1; after the reaction is finished, polyurethane synthesis reaction is carried out, and NCO value of the synthesized prepolymer and OH+NH of toluenediamine, modified chain extender, 3-aminopropyl trimethoxy silane and modified end capping agent are carried out 2 The total value is reacted according to the mole number of 1:0.95, wherein the mole ratio of toluene diamine, modified chain extender, 3-aminopropyl trimethoxy silane and modified end capping agent is 0.5:0.5:1:3; in polyurethane synthesis, toluene diamine and a modified chain extender are firstly added; after the reaction is finished, adding 3-aminopropyl trimethoxy silane and a modified end capping agent to prepare the polyurethane material.
The three-dimensional model of the natural meniscus in the human body is obtained by the related technology, and the prepared polyurethane material, polylactic acid and polyolefin are adopted according to the ratio of 3:1: mixing the materials according to the mass ratio of 1, and directly performing 3D printing to obtain an artificial meniscus; and spin-coating the dimethylformamide solution containing the polyurethane on the artificial meniscus, and drying to prepare the modified artificial meniscus.
Example 8
Compounds of the structure of formula I (wherein R 1 is-CH 2 CH 2 -，R 2 C is straight chain 10 Side chain of saturated alkylene chain with trimethoxysilane substituted at chain end, 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 react for 36 hours at 60 ℃ according to the mol ratio of 2:1, thus obtaining the modified chain extender 1.
Compounds of the structure of formula I (wherein R 1 is-CH 2 NH-，R 2 C is straight chain 10 Side chain in which H on C atom in saturated alkylene chain 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 ) And reacting with 1, 4-butanesulfonic acid lactone for 36 hours at 60 ℃ according to a molar ratio of 2:1 to obtain the modified chain extender 2.
Polymerizing 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 the prepolymer synthesis and the polyurethane synthesis is 90 ℃, the total reaction time is 64h, the reaction pressure is 0.1MPa, the reaction process uses dimethylacetamide as a solvent, and the mass ratio of the reaction solvent to the raw materials is 10:1; in the prepolymer synthesis process, toluene diisocyanate and polycarbonate polyol are reacted according to a molar ratio of 1:0.3; after the reaction is finished, polyurethane synthesis reaction is carried out, and NCO value of the synthesized prepolymer and OH+NH of 1, 3-propanediol, modified chain extender 1 and modified chain extender 2 are mixed 2 The total value reacts according to the mole number of 1:1; in the course of the synthesis of the polyurethane,adding 1, 3-propylene glycol, and preparing polyurethane material after the reaction, wherein the mole ratio of the modified chain extender 1 to the modified chain extender 2 is 1:2:1.
Obtaining a three-dimensional model of a natural meniscus in a human body through a related technology, preparing an artificial meniscus mould by adopting a stainless steel material, mixing the polyurethane material and the polyether-ether-ketone which are prepared according to a mass ratio of 1:2 at a heating temperature of 150 ℃, a holding temperature of 150 ℃, a pressurizing pressure of 30MPa and a pressurizing time of 90min, and directly melting, remolding and forming in the artificial meniscus mould to prepare the artificial meniscus; and spraying butyl acetate containing the polyurethane on the artificial meniscus, and drying to prepare the modified artificial meniscus.
Performance detection
The mechanical properties and the friction properties of the menisci prepared in examples 1 to 8 and natural porcine menisci and the commercially available polyurethane materials were tested; the mechanical property test refers to national standard GBT 528-2009 determination of tensile stress strain properties of vulcanized rubber or thermoplastic rubber; 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 mode is reciprocating circulation friction, the friction solution is 3mg/mL HA aqueous 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 application can form a hydration layer with short-range order on the surface of the polyurethane artificial meniscus through the strong interaction between anions and cations of zwitterionic groups in the structure and water, thereby achieving the lubricating effect. Meanwhile, hydrophobic groups in the polyurethane artificial meniscus structure solve the problem of mechanical property reduction caused by the improvement of lubricating property by preventing water molecules from entering a molecular chain and providing more physical crosslinking points. The preparation method of the high-performance polyurethane material provided by the application is simple and easy to implement, the application range of the material is wide, the prepared artificial meniscus can be customized individually, and the high-performance polyurethane material can be effectively applied to meniscus injury patients with different illness requirements.
While the application has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the application. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the application as defined by the following claims, so as to adapt the objective, spirit and scope of the application. All such modifications are intended to be within the scope of this appended claims. 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 an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (9)
1. A method for preparing high performance polyurethane, comprising:
carrying out polymerization reaction on diisocyanate, polyalcohol 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 structural compound shown in a formula I with a zwitterionic monomer to obtain a chain extender;
in the formula I, R 1 Selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 Selected from-H, C 1 ～C 20 Alkylene, C 1 ～C 20 Fluoroalkyl group, C 1 ～C 20 Containing silane groups, phenyl groups or benzyl groups;
R 3 and R is 5 Independently selected from C 2 ～C 6 An alkylene group;
R 4 and R is 6 Independently selected from-OH or-NH 2 ；
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.
2. The method of claim 1, wherein the chain extension reaction further comprises, after completion:
carrying out end capping reaction on the obtained reaction product and an end capping agent to obtain high-performance polyurethane;
the preparation method of the end capping agent comprises the following steps:
reacting a structural compound of formula II with a zwitterionic monomer to obtain a blocking agent;
in formula II, R 1 And R is 1 ' independently selected from-CH 2 -，-CH 2 CH 2 -or-CH 2 NH-；
R 2 And R is 2 ' independently selected from-H, C 1 ～C 20 Alkylene, C 1 ～C 20 Fluoroalkyl group, C 1 ～C 20 Containing silane groups, phenyl groups or benzyl groups;
R 3 selected from C 2 ～C 6 An alkylene group;
R 4 selected from-OH or-NH 2 。
3. The method 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.
4. The method of claim 1, wherein the molar ratio of isocyanate to polyol is 1: (0.1-0.9).
5. The method of claim 2, wherein the chain extender and endcapping agent are present in a molar ratio of 1: (0-10);
the molar 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 moles is 1: (0.8-1.2).
6. 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.
7. The method of claim 6, wherein the 3D printing comprises:
3D printing is carried out on the high-performance polyurethane and the high-molecular material;
the polymer material is one or more selected from polyurethane, polylactic acid, polyether ether ketone, polycaprolactone, ABS resin or polyolefin.
8. A method of preparing an artificial meniscus comprising:
reacting and forming the prepolymer and a chain extender in an artificial meniscus mould to obtain an artificial meniscus;
the prepolymer and chain extender are the prepolymer and chain extender of claim 1;
or (b)
Melting and molding 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.
9. The method according to any one of claims 6 to 8, wherein the obtaining of the artificial meniscus further comprises:
modifying the artificial meniscus, the modifying agent comprising:
a solution of high performance polyurethane;
the solvent in the high-performance polyurethane solution is one or more selected from 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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