Artificial meniscus and preparation method thereof

Abstract

The invention belongs to the field of medical composite materials. The invention relates to an artificial meniscus and a preparation method thereof. The method comprises the following steps: preparing a mold for manufacturing a disc-shaped artificial meniscus; a functional fiber fabric is arranged on the inner side of the mold; adding a modified polyurethane-based material solution into the mold, defoaming, and standing to obtain a molded substance I; placing the molded substance I in a glutaraldehyde solution for 5-10 hours to obtain a molded substance II; and putting the molded substance II into a calcium bromide solution for 2-5 hours to obtain a target product. The artificial meniscus effectively solves the problems of poor mechanical property, cartilage contusion and the like of the existing artificial meniscus.

Description

Technical Field

[0001] The invention relates to an artificial meniscus and a preparation method thereof, and belongs to the field of biocomposite materials. Background Art

[0002] Meniscus is a crescent-shaped fibrocartilage tissue composed of water, extracellular matrix and meniscus cells. Meniscus exists in the joints of the knee, wrist and jaw. The knee meniscus is located between the femur and the tibial plateau and plays an important role. It is subjected to various loads in daily life and sports activities, such as compression, rotation, stretching, shearing, etc. The functions of the meniscus mainly include: bearing weight, improving the adaptability of the tibiofemoral joint, maintaining the stability of the knee joint, buffering stress and shock, lubricating the joint, and increasing the contact area of ​​the joint. When the meniscus is bruised, the normal function of the knee joint will be greatly attenuated, the knee joint will be seriously burdened, especially during intense sports activities, and the meniscus cannot be regenerated. Therefore, it is urgent to develop an artificial meniscus substitute to provide the corresponding functions of the removed natural meniscus, thereby slowing down or even avoiding the wear of the articular cartilage.

[0003] The ideal meniscus substitute should have similar geometric features to the natural meniscus, anisotropic mechanical properties, excellent biocompatibility and long-term stability in vivo. To this end, researchers have developed various types of meniscus substitutes, including polytetrafluoroethylene, polyester, porous polyurethane, polyvinyl alcohol hydrogel, polycarbonate polyurethane, etc. However, the above meniscus substitutes all have some shortcomings, such as: polytetrafluoroethylene materials have low strength and poor wear resistance, and are prone to deformation and wear after implantation, resulting in the deposition of fragments in the joint cavity and the formation of synovitis, damaging the articular cartilage; polyester also has synovitis and articular cartilage wear; porous polyurethane also has the problem of damaging the articular cartilage; polyvinyl alcohol hydrogel has poor mechanical properties; polycarbonate polyurethane has a large friction coefficient and damages the cartilage tissue, etc.

[0004] Therefore, considering the above scientific research status and the urgent need for artificial meniscus, it is of great significance to develop an artificial meniscus material with high mechanical properties, low wear and high biocompatibility. Summary of the invention

[0005] The purpose of the present invention is to provide an artificial meniscus and a preparation method thereof in view of the problems of poor mechanical properties and cartilage contusion in the artificial meniscus in the prior art. The present invention prepares the artificial meniscus material by molecular design and prepares it by structural optimization design. The technical solution adopted by the present invention to solve the technical problem is: The present invention provides a method for preparing a modified polyurethane-based material, comprising the following steps: S11, subjecting hydroxymethyldioxolane and dimethyl carbonate to transesterification reaction to obtain an intermediate product 1I; S12, subjecting the intermediate product 1I to a ring-opening reaction with a diamine to obtain an intermediate product 1II; S13, blending the intermediate product 1II with the amino-containing biomacromolecule to obtain the target product, i.e., a modified polyurethane-based material.

[0006] Furthermore, the molar ratio of the hydroxymethyldioxolane to dimethyl carbonate is 2:1.

[0007] Further, the molar ratio of the intermediate product II to the diamine is 1:1; and The diamine is a macromolecular diamine and a small molecular diamine added in a molar ratio of 2.0-3.0:7.0-8.0.

[0008] Further, the macromolecular diamine is polyethylene glycol diamine and / or polyether diamine; and The small molecule diamine is a mixture of aliphatic diamine and aromatic diamine.

[0009] Further, the ratio of the intermediate product III to the amino-containing biomacromolecule is 7.5-9.5 g: 0.5-2.5 g; and The amino-containing biomacromolecules include gelatin and chitosan.

[0010] The present invention also provides a modified polyurethane-based material, which is prepared by the above-mentioned preparation method.

[0011] Another object of the present invention is to provide a method for preparing a functional fiber fabric, comprising the following steps: S21, condensing the dibasic acid and the polyamine A to obtain an intermediate product 2I; S22, subjecting the intermediate product 1I to a ring-opening reaction with a polyamine B to obtain an intermediate product 2II; S23, subjecting the intermediate product 2I and the intermediate product 2II to a polycondensation reaction to obtain an intermediate product 2III; S24, free radical polymerization of acrylamide and zwitterion to obtain intermediate product 2IV; S25, blending the intermediate product 2III and the intermediate product 2IV, spinning and combing to obtain a functional fiber fabric.

[0012] Furthermore, the molar ratio of the dibasic acid to the polyamine A is 0.5-2.0:1.0; and The dibasic acid includes terephthalic acid; The polyamine A is added by molar ratio of diamine to triamine of 0.8-1.0:0-0.2; The diamine is a water-soluble diamine; including polyether diamine; The triamine includes melamine.

[0013] Furthermore, the molar ratio of the intermediate product 1I to the polyamine B is 0.5-2.0:1.0; and The polyamine A is added by molar ratio of diamine to triamine of 0.8-1.0:0-0.2; The diamine is a water-soluble diamine; including polyether diamine; The triamine includes melamine.

[0014] Furthermore, the intermediate product 2I and the intermediate product 2II are added in a molar ratio of 1.0:1.0.

[0015] Further, the molar ratio of acrylamide to zwitterion is 0.7-0.9:0.1-0.3; and, The zwitterion is phosphorylcholine or betaine.

[0016] Furthermore, the usage ratio of the intermediate product 2III and the intermediate product 2 IV is 7.0-9.0g:1.0-3.0g.

[0017] The present invention also provides a functional fiber fabric prepared by the above-mentioned preparation method.

[0018] Another object of the present invention is to provide a method for preparing an artificial meniscus, comprising: S31, preparing a mold for making a disc-shaped artificial meniscus; S32, arranging a functional fiber fabric inside the mold; S33, adding a modified polyurethane-based material solution into the mold, removing bubbles, and allowing to stand to obtain a molded object I; Wherein, the outer end of the artificial meniscus is connected to the functional fiber fabric; S34, placing the formed object I in a glutaraldehyde solution for 5-10 hours to obtain a formed object II; S35, placing the formed product II in a calcium bromide solution for 2-5 hours to obtain the target product, namely, an artificial meniscus.

[0019] Furthermore, the preparation method of the glutaraldehyde solution is as follows: Add the glutaraldehyde aqueous solution to acetonitrile, add a solid moisture desiccant, seal and dry for 0.5 h, and filter to obtain a glutaraldehyde acetonitrile solution; The usage ratio of the glutaraldehyde aqueous solution, acetonitrile and solid moisture desiccant is 10-20 mL: 480-490 mL: 100 g; The concentration (w / v) of the glutaraldehyde aqueous solution is 50%.

[0020] Furthermore, the concentration of calcium bromide is 0.01-0.1 g / mL.

[0021] The present invention also provides an artificial meniscus, which is prepared by the above-mentioned preparation method.

[0022] Beneficial effects of the present invention: (1) The present invention provides an artificial meniscus, which is composed of an internal matrix material and an external functional fiber fabric. The internal matrix material is a modified polyurethane-based material mainly composed of a non-isocyanate polyurethane structure and is blended with amino-containing biomacromolecules. First, non-isocyanate polyurethane avoids the use of toxic isocyanate structures, and the molecules are more designable; at the same time, there are a large number of hydroxyl groups in the macromolecular chain, which can form intramolecular hydrogen bond rings or intermolecular hydrogen bonds, effectively improving the mechanical properties; second, hydroxyl groups that are not involved in intramolecular or intermolecular hydrogen bond pairing can form hydrogen bonds with biomacromolecules to improve compatibility; third, non-isocyanate polyurethane can be designed with molecular functionalization on the amine source, and the use of large molecular water-soluble diamines and small molecular diamines can effectively improve the hydrophilicity and mechanical properties of the matrix; fourth, amino-containing biomacromolecules provide excellent biocompatibility, which is beneficial to cell proliferation and differentiation, and can also participate in chemical reactions with external functional fiber fabrics.

[0023] (2) The present invention provides an artificial meniscus, which is composed of an internal matrix material and an external functional fiber fabric. The external functional fiber fabric is mainly composed of a non-isocyanate polyurethane structure and a polyamide structure block copolymer, and is mixed with a polyamide / zwitterionic copolymer and spun. First, polyamide fiber has excellent mechanical properties and chemical corrosion resistance, which can effectively ensure the dimensional retention of the material in a complex environment; second, the non-isocyanate polyurethane structure in the functional fiber fabric has excellent compatibility with the internal matrix material, and can form hydrogen bonds to reduce relative slip during stress deformation; third, the polyamide / zwitterionic copolymer component provides hydrophilicity for the functional fiber fabric, effectively improving the lubrication performance between the artificial meniscus and the cartilage tissue, reducing wear and less contusion; fourth, the ammonium salt, phosphate or sulfonate in the zwitterionic structure is similar to the cell composition structure, which can promote joint lubrication, reduce inflammation, and protect cartilage.

[0024] (3) The present invention provides a method for preparing an artificial meniscus, wherein the internal matrix material and the external functional fiber fabric are placed in a mold and cross-linked with glutaraldehyde and calcium bromide. First, glutaraldehyde can react with the amino groups remaining in the matrix material and the functional fiber fabric to undergo an aldehyde-amine condensation cross-linking reaction, thereby improving the mechanical properties of the matrix and effectively reducing the relative slip between the matrix material and the functional fiber fabric, thereby further improving the mechanical properties; second, the calcium ions in the calcium bromide coordinate with amino groups, carbonyl groups, phosphate groups (or sulfonic acid groups), etc., thereby improving the mechanical properties; third, the bromide ions in the calcium bromide have the function of inducing chondrocyte regeneration and differentiation, and can effectively promote cartilage repair; and the bromide ions form an ammonium salt structure with the ammonium group, which has a sustained release and long-lasting effect. DETAILED DESCRIPTION

[0025] The present invention is described in detail below with reference to the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present invention, and are not intended to limit the scope of the present invention.

[0026] The purpose of the present invention is to develop an artificial meniscus to solve the problems of poor mechanical properties and cartilage contusion in the existing artificial meniscus.

[0027] The idea is to achieve this by taking the main physical properties of the natural meniscus (tensile strength 13.25MPa, friction coefficient 0.14, relative cell survival rate 100%) as the target, using polyurethane as the main material, and improving the mechanical properties of the material and the problem of cartilage contusion through chemical modification and physical structure design. First, the overall structure is designed, with modified polyurethane as the matrix material; and a "mesh cover" is designed for this matrix material, and then the matrix material and the "mesh cover" are formed into a whole to solve the problem of insufficient mechanical properties; at the same time, the matrix material and the "mesh cover" are chemically modified to solve the problems of poor mechanical properties and cartilage contusion; in addition, for cartilage contusion, on the one hand, the friction coefficient is reduced; on the other hand, it is solved by promoting cartilage proliferation compensation.

[0028] For chemical modification, the matrix is ​​specifically: polycarbonate polyurethane is used as the main matrix, and the preparation method of non-isocyanate polyurethane is adopted to avoid the use of toxic isocyanate monomers. At the same time, the polyurethane structure prepared by this method has better mechanical properties; it is blended with amino-containing biomacromolecules to improve its hydrophilicity, which is beneficial to biocompatibility; the external "mesh cover" is specifically: prepared by copolymerization of polyamide and polyurethane, which not only improves the compatibility with the matrix but also provides the mechanical strength of the fiber structure; and is blended with polyamide / zwitterionic copolymer to enhance water solubility; in addition, the structure of zwitterionic can re-form new ions with calcium bromide ions, which has the effect of promoting cartilage proliferation. The two materials are "integrated" according to the structural design, placed in aldehyde solution for cross-linking to form a whole, and placed in calcium bromide solution to form new functions.

[0029] The theoretical basis for the realization is: to modify the polyurethane material, firstly, carry out an ester exchange reaction between hydroxymethyldioxolane and dimethyl carbonate, then carry out ring opening with polyamine to prepare non-isocyanate polyurethane material, and then blend it with amino-containing biomacromolecules. Functional fiber fabric ("mesh"), prepare polyamide and polyurethane prepolymer separately, then carry out condensation reaction preparation, then prepare polyamide / zwitterionic copolymer by free radical polymerization, and finally blend them. "Integration", place the two materials in an aldehyde solution according to the structural design to carry out an aldehyde-amine condensation reaction; take them out, place them in a calcium bromide solution for ion exchange, and obtain the target product, artificial meniscus. The embodiments of the present invention are as follows: The embodiment of the present invention provides a method for preparing a modified polyurethane-based material, comprising the following steps: S11, N2 protection, hydroxymethyldioxolane and dimethyl carbonate were mixed, the catalyst was added, stirred, the temperature was raised to 160-180°C, the reaction was carried out for 1-3h, and the intermediate product 1I was obtained by distillation under reduced pressure.

[0030] The molar ratio of the hydroxymethyldioxolane to dimethyl carbonate is 2:1.

[0031] The amount of the catalyst used is 0.1-0.2wt% of the total mass of the reactants; The catalyst may be titanium glycolate, tetrabutyl titanate or tetraisopropyl titanate, etc., and tetrabutyl titanate is preferred.

[0032] S12, N2 protection, add the intermediate product 1I and diamine to N,N-dimethylformamide A, stir, heat to 80-100°C and react for 6-8h, continue to heat to 100-120°C and react for 1-2h; after the reaction, distill under reduced pressure to obtain the intermediate product 1II.

[0033] The usage ratio of the intermediate product 1I, diamine, and N,N-dimethylformamide A is 1 mol: 1 mol: 400 mL; The diamine is a macromolecular diamine and a small molecular diamine added in a molar ratio of 2.0-3.0:7.0-8.0.

[0034] The macromolecular diamine is polyethylene glycol diamine and / or polyether diamine; The molecular weight of the polyethylene glycol diamine is 300-1000, specifically 300, 400, 600, 1000, etc., or can be customized as required.

[0035] The molecular weight of the polyether diamine is 300-1000, specifically 300, 500, 600, 1000, etc., or can be customized as required.

[0036] The small molecule diamine is a mixture of aliphatic diamine and aromatic diamine in a molar ratio of 0.5-0.7:0.3-0.5; The aliphatic diamine may be isophoronediamine, triethylenetetramine, tetraethylenepentamine, cyclohexanediamine, ethylenediamine, propylenediamine, tetramethylenediamine, pentanediamine, hexanediamine, 1,12-diaminododecane, etc., and triethylenetetramine is preferred.

[0037] The aromatic diamine may be p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, etc., and p-phenylenediamine is preferred.

[0038] S13, adding the intermediate product 1II and the amino-containing biomacromolecule to hot N,N-dimethylformamide B, stirring continuously for 3-5 hours at 40-60° C., and distilling under reduced pressure to obtain the target product, i.e., the modified polyurethane-based material.

[0039] The usage ratio of the intermediate product 1II to the amino-containing biomacromolecule and N,N-dimethylformamide B is 7.5-9.5 g: 0.5-2.5 g: 100 mL.

[0040] The amino-containing biomacromolecules include gelatin and chitosan; The gelatin is commercially available animal-derived gelatin; The deacetylation degree of the chitosan is ≥95%.

[0041] The preparation method of the modified polyurethane-based material described in the present invention adopts a non-isocyanate polyurethane synthesis method. The hydroxyl groups generated by its ring-opening polymerization can form intramolecular or intermolecular hydrogen bonds, and the mechanical properties are better. After blending it with gelatin or chitosan, the hydrophilicity and biocompatibility can be improved, and it can undergo a cross-linking reaction with glutaraldehyde, so that it has the ability to resist complex forces as a whole.

[0042] The present invention also provides a method for preparing a functional fiber fabric, comprising the following steps: S21, add dibasic acid, polyamine A and deionized water A into a reactor, protect with N2, heat to 240-260°C, 1.5-1.7MPa, react for 2-4h; reduce to normal pressure, continue to react for 2-3h; after the reaction is completed, evacuate for 1h to obtain the intermediate product 2I.

[0043] The usage ratio of the dibasic acid, polyamine A, and deionized water A is 0.5-2.0 mol: 1.0 mol: 300 mL; The dibasic acid includes terephthalic acid; it can also be glutaric acid, adipic acid, etc.

[0044] The polyamine A is added by molar ratio of diamine to triamine of 0.8-1.0:0-0.2; The diamine is a water-soluble diamine; including polyether diamine; The triamine includes melamine; it can be a mixture of melamine and 1,2,3-propylenetriamine in a molar ratio of 2.0-4.0:1.0 or melamine and 1,3,5-triphenylamine in a molar ratio of 1.0-2.0:1.0.

[0045] S22, N2 protection, add the intermediate product 1I and polyamine B to N,N-dimethylformamide C, stir, heat to 80-100°C and react for 6-8h, continue to heat to 100-120°C and react for 1-2h; after the reaction, distill under reduced pressure to obtain the intermediate product 2II.

[0046] The usage ratio of the intermediate product 1I, polyamine B, and N,N-dimethylformamide C is 0.5-2.0 mol: 1.0 mol: 500 mL; The polyamine B is added by a molar ratio of diamine to triamine of 0.8-1.0:0-0.2; The diamine is a water-soluble diamine; including polyether diamine; The triamine includes melamine; it can be a mixture of melamine and 1,2,3-propylenetriamine in a molar ratio of 2.0-4.0:1.0 or melamine and 1,3,5-triphenylamine in a molar ratio of 1.0-2.0:1.0.

[0047] S23, subjecting the intermediate product 2I and the intermediate product 2II to a condensation polymerization reaction to obtain an intermediate product 2III.

[0048] The intermediate product 2I and the intermediate product 2II are added in a molar ratio of 1.0:1.0.

[0049] The reaction process adopted for the S23 polycondensation reaction depends on the end-capping groups in S21 and S22: if S21 is a carboxyl end-capping structure and S22 is an amino end-capping structure, the polycondensation reaction of S23 is the same as S21, which is a polyamide synthesis process step; conversely, if S21 is an amino end-capping structure and S22 is an intermediate product 1I end-capping structure; then the polycondensation reaction of S23 is the same as S22, which is a polyurethane synthesis process step.

[0050] S24, add acrylamide, zwitterion and photoinitiator to N,N-dimethylformamide D, place under UV lamp for irradiation for 10-50 minutes, remove the UV lamp, distill under reduced pressure, add methanol to the concentrate to produce a precipitate, filter, take the precipitate, and vacuum dry at 60°C for 8 hours to obtain the intermediate product 2IV.

[0051] The usage ratio of acrylamide, zwitterion and N,N-dimethylformamide D is 0.7-0.9 mol: 0.1-0.3 mol: 500 mL; The zwitterion is phosphorylcholine or betaine; The phosphorylcholine may be 2-methacryloyloxyethyl phosphorylcholine or the like; The betaine may be methacryloylethyl sulfobetaine, acryloylethyl sulfobetaine or 4-[[2-(methacryloyloxy)ethyl]dimethylamino]butane-1-sulfonate, etc.

[0052] The amount of the photoinitiator is 1-5wt% of the total mass of the reactants; The photoinitiator is a commonly used photoinitiator, which may be photoinitiator 1173, photoinitiator 184, photoinitiator 2959, photoinitiator 369 or photoinitiator TPO, etc.; and the photoinitiator described in the following embodiments of the present invention is photoinitiator 1173.

[0053] The UV light intensity is 200-600 mW / cm 2 ; Specifically, it can be 200mW / cm 2 , 300 mW / cm 2 , 400 mW / cm 2 , 500 mW / cm 2 , 600 mW / cm 2 ; and, the UV light intensity described in the following embodiments of the present invention is 400 mW / cm 2 .

[0054] S25, dissolving the intermediate product 2III and the intermediate product 2IV in deionized water B, stirring for 2-3 hours, degassing, passing through a spinning device under stirring conditions, combing with a carding machine, preparing by a needle punching method, and cutting, inspecting, and sterilizing to obtain a functional fiber fabric.

[0055] The usage ratio of the intermediate product 2III, the intermediate product 2 IV and the deionized water B is 7.0-9.0 g: 1.0-3.0 g: 1000 mL.

[0056] The functional fiber fabric of the present invention has a suspended amino structure, so at least one of the polyamine A and the polyamine B has a triamine structure.

[0057] The functional fiber fabric described in the present invention is mainly composed of a polyamide / polyurethane block structure and a polyamide / zwitterionic copolymer as a supplementary blend. First, the polyamide in the polyamide / polyurethane structure has excellent mechanical strength, and the polyurethane has excellent compatibility with the matrix; at the same time, the dimensional stability of the polyamide is combined with the flexibility of the polyurethane, and the advantages are complementary, so that the mechanical strength of the polyamide, the dimensional stability and the flexibility of the polyurethane can be combined; on the other hand, the polyamide / zwitterionic copolymer has excellent water solubility, and can adsorb calcium ions through coordination and electrostatic effects, and can adsorb bromide ions through electrostatic effects, giving the functionality of promoting cartilage proliferation. The functional fiber fabric has the functions of reducing the relative slip between the fiber and the matrix, strong fiber dimensional stability, excellent corrosion resistance, and adsorbing bromide ions at the same time. In addition, the hanging amino groups in the functional fiber fabric can be used as a reaction structure anchor to further provide mechanical properties; at the same time, as a "protective mesh" of the matrix material, it can effectively protect the dimensional stability of the product.

[0058] The embodiment of the present invention also provides a method for preparing an artificial meniscus, comprising: S31, preparing a mold for making a disc-shaped artificial meniscus.

[0059] S32, disposing a functional fiber fabric inside the mold.

[0060] S33, adding the modified polyurethane-based material solution into the mold, removing bubbles, and letting it stand to obtain a molded object I.

[0061] Wherein, the outer end of the artificial meniscus is connected to the functional fiber fabric; The modified polyurethane-based material solution described in the following examples of the present invention is prepared by mixing the modified polyurethane-based material with N,N-dimethylformamide E in a dosage ratio of 10 g:100 mL.

[0062] S34, placing the formed product I in a glutaraldehyde solution for 5-10 hours to obtain a formed product II.

[0063] The preparation method of the glutaraldehyde solution is as follows: The glutaraldehyde aqueous solution was added to acetonitrile, and a solid moisture desiccant was added. After sealing and drying for 0.5 h, the mixture was filtered to obtain a glutaraldehyde acetonitrile solution.

[0064] The usage ratio of the glutaraldehyde aqueous solution, acetonitrile and solid moisture desiccant is 10-20 mL: 480-490 mL: 100 g; The concentration (w / v) of the glutaraldehyde aqueous solution is 50%.

[0065] S35, placing the formed product II in a calcium bromide solution for 2-5 hours, placing the product in a dialysis bag, and dialyzing it with deionized water for 3 days, replacing the dialysate once a day, and freeze-drying to obtain the target product, i.e., the artificial meniscus.

[0066] The calcium bromide concentration is 0.01-0.1 g / mL.

[0067] The solutions described in the following examples of the present invention, unless otherwise specified, are all made of water.

[0068] The artificial meniscus of the present invention uses a self-made modified polyurethane material as a matrix material and a functional fiber fabric as an external "binding" material. After being impregnated with glutaraldehyde, the amino-containing biomacromolecules in the matrix material and the hanging amino groups of the external "binding" material can undergo an aldehyde-amine condensation reaction, so that the external "binding" material firmly wraps the matrix material to form an integrated material; at the same time, after being impregnated with a calcium bromide solution, bromide ions, calcium ions and ammonium ions and phosphate ions in zwitterions act due to electrostatic force and ring tension, and the ion radius of bromide ions and calcium ions is smaller than that of atomic clusters such as ammonium ions and phosphate ions. Finally, bromide ions are more likely to combine with positive and negative ions of ammonium ions, and calcium ions are combined with phosphate ions, thereby improving the sustained release effect of bromide ions, promoting the proliferation and differentiation of chondrocytes, compensating for worn cartilage, and improving the service life.

[0069] In order to further understand the present invention, an artificial meniscus provided by the present invention is described in detail below in conjunction with specific embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0070] A method for preparing a modified polyurethane-based material comprises the following steps: S11, N2 protection, hydroxymethyldioxolane and dimethyl carbonate were mixed, tetrabutyl titanate was added, stirred, heated to 170°C, reacted for 1.5h, and distilled under reduced pressure to obtain intermediate product 1I.

[0071] The molar ratio of the hydroxymethyldioxolane to dimethyl carbonate is 2:1.

[0072] The amount of tetrabutyl titanate used is 0.15wt% of the total mass of the reactants.

[0073] Its infrared data are as follows: 3414 cm -1 :-OH does not exist; 1801 cm -1 :Cyclic ester -C=O exists; 1732cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0074] S12, N2 protection, add the intermediate product 1I and diamine to N,N-dimethylformamide A, stir, heat to 90°C and react for 6.5h, continue to heat to 110°C and react for 1.5h; after the reaction, distill under reduced pressure to obtain the intermediate product 1II.

[0075] The usage ratio of the intermediate product 1I, diamine, and N,N-dimethylformamide A is 1 mol: 1 mol: 400 mL; The diamines are macromolecular diamine and small molecular diamine, which are added in a molar ratio of 2.5:7.5.

[0076] The macromolecular diamine is polyethylene glycol diamine, and the molecular weight is 400.

[0077] The small molecule diamine is a mixture of triethylenetetramine and p-phenylenediamine in a molar ratio of 0.6:0.4.

[0078] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3317 cm -1 : -NH- exists (single peak); 1801 cm -1 :Cyclic ester -C=O does not exist; 1725-1735cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0079] S13, adding the intermediate product 1II and gelatin to hot N,N-dimethylformamide B, stirring continuously at 50° C. for 4 h, and distilling under reduced pressure to obtain the target product, i.e., the modified polyurethane-based material.

[0080] The usage ratio of the intermediate product 1II to gelatin and N,N-dimethylformamide B is 8.5 g:1.5 g:100 mL.

[0081] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists and is enhanced; 1725-1735cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0082] A method for preparing a functional fiber fabric comprises the following steps: S21, add phthalic acid, polyamine A and deionized water A into a reactor, protect with N2, heat to 250°C, 1.6MPa, and react for 3h; reduce to normal pressure and continue to react for 2.5h; after the reaction is completed, evacuate for 1h to obtain the intermediate product 2I.

[0083] The usage ratio of the phthalic acid, the polyamine A and the deionized water A is 2.0 mol: 1.0 mol: 300 mL.

[0084] The polyamine A is a diamine and a triamine added in a molar ratio of 0.9:0.1; The diamine is polyether diamine with a molecular weight of 500; The triamine is a mixture of melamine and 1,2,3-propylenetriamine in a molar ratio of 3.0:1.0.

[0085] Its infrared data are as follows: 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1664cm -1 :Amide-C=O exists; 3402cm -1 :-OH exists and weakens; 1764cm -1 : Carboxylic acid -C=O exists and weakens.

[0086] S22, N2 protection, add the intermediate product 1I and polyamine B to N,N-dimethylformamide C, stir, heat to 90°C and react for 6.5h, continue to heat to 110°C and react for 1.5h; after the reaction, distill under reduced pressure to obtain the intermediate product 2II.

[0087] The usage ratio of the intermediate product 1I, polyamine B, and N,N-dimethylformamide C is 0.5 mol: 1.0 mol: 500 mL; The polyamine B is a diamine and a triamine added in a molar ratio of 0.9:0.1; The diamine is polyether diamine with a molecular weight of 500; The triamine is a mixture of melamine and 1,2,3-propylenetriamine in a molar ratio of 3.0:1.0.

[0088] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3318 cm -1 :-NH- exists; 1801 cm -1 :Ring-C=O does not exist; 1725-1735cm -1 :-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0089] S23, add intermediate product 2I, intermediate product 2II and deionized water into the reactor, protect with N2, heat to 255°C, 1.6MPa, react for 3h; reduce to normal pressure, continue to react for 2.5h; after the reaction is completed, evacuate for 1h to obtain intermediate product 2III.

[0090] The intermediate product 2I, intermediate product 2II and deionized water are added in a ratio of 1.0 mol:1.0 mol:300 mL.

[0091] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1764cm -1 :Carboxylic acid-C=O does not exist; 1725-1735cm -1 : Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0092] S24, acrylamide, 2-methacryloyloxyethyl phosphorylcholine, and photoinitiator 1173 were added to N,N-dimethylformamide D, and irradiated under UV lamp for 30 min, then the UV lamp was removed, and vacuum distillation was performed. Methanol was added to the concentrate to produce a precipitate, which was filtered and the precipitate was vacuum dried at 60°C for 8 h to obtain the intermediate product 2IV ( ).

[0093] The usage ratio of acrylamide, 2-methacryloyloxyethyl phosphorylcholine, and N,N-dimethylformamide D is 0.8 mol: 0.2 mol: 500 mL; The amount of the photoinitiator 1173 used is 3 wt % of the total mass of the reactants.

[0094] Its infrared data are as follows: 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1187cm -1 :-P=O exists; 1606cm -1 、811cm -1 :-C=C- does not exist.

[0095] S25, dissolving the intermediate product 2III and the intermediate product 2IV in deionized water B, stirring for 2.5 hours, degassing, passing through a spinning device under stirring conditions, combing with a carding machine, preparing by a needle punching method, and cutting, inspecting, and sterilizing to obtain a functional fiber fabric.

[0096] The usage ratio of the intermediate product 2III, the intermediate product 2 IV, and the deionized water B is 8.0 g: 2.0 g: 1000 mL.

[0097] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1725-1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists; 1187cm -1 :-P=O exists.

[0098] A method for preparing an artificial meniscus, comprising: S31, preparing a mold for making a disc-shaped artificial meniscus.

[0099] S32, disposing a functional fiber fabric inside the mold.

[0100] S33, adding the modified polyurethane-based material solution into the mold, removing bubbles, and letting it stand to obtain a molded object I.

[0101] Wherein, the outer end of the artificial meniscus is connected to the functional fiber fabric.

[0102] S34, placing the formed product I in a glutaraldehyde solution for 10 hours to obtain a formed product II.

[0103] The preparation method of the glutaraldehyde solution is as follows: The glutaraldehyde aqueous solution was added to acetonitrile, and a solid moisture desiccant was added. After sealing and drying for 0.5 h, the mixture was filtered to obtain a glutaraldehyde acetonitrile solution.

[0104] The usage ratio of the glutaraldehyde aqueous solution, acetonitrile and solid moisture desiccant is 10 mL:490 mL:100 g; The concentration (w / v) of the glutaraldehyde aqueous solution is 50%.

[0105] S35, placing the formed product II in a calcium bromide solution for 4 hours, placing the product in a dialysis bag, and dialyzing it with deionized water for 3 days, replacing the dialysate once a day, and freeze-drying to obtain the target product, i.e., the artificial meniscus.

[0106] The calcium bromide concentration is 0.04 g / mL.

[0107] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material comprises the following steps: S11, N2 protection, hydroxymethyldioxolane and dimethyl carbonate were mixed, tetrabutyl titanate was added, stirred, heated to 160°C, reacted for 3h, and distilled under reduced pressure to obtain intermediate product 1I.

[0108] The molar ratio of the hydroxymethyldioxolane to dimethyl carbonate is 2:1.

[0109] The amount of tetrabutyl titanate used is 0.2 wt % of the total mass of the reactants.

[0110] Its infrared data are as follows: 3414 cm -1 :-OH does not exist; 1801 cm -1 :Cyclic ester -C=O exists; 1732cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0111] S12, N2 protection, add the intermediate product 1I and diamine to N,N-dimethylformamide A, stir, heat to 80°C and react for 8h, continue to heat to 100°C and react for 2h; after the reaction, distill under reduced pressure to obtain the intermediate product 1II.

[0112] The usage ratio of the intermediate product 1I, diamine, and N,N-dimethylformamide A is 1 mol: 1 mol: 400 mL; The diamines are macromolecular diamine and micromolecular diamine, which are added in a molar ratio of 3.0:7.0.

[0113] The macromolecular diamine is polyethylene glycol diamine, and the molecular weight is 400.

[0114] The small molecule diamine is a mixture of triethylenetetramine and p-phenylenediamine in a molar ratio of 0.6:0.4.

[0115] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3317 cm -1 : -NH- exists (single peak); 1801 cm -1:Cyclic ester -C=O does not exist; 1725-1735cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0116] S13, adding the intermediate product 1II and gelatin to hot N,N-dimethylformamide B, stirring continuously at 40° C. for 5 h, and distilling under reduced pressure to obtain the target product, i.e., the modified polyurethane-based material.

[0117] The usage ratio of the intermediate product 1II to gelatin and N,N-dimethylformamide B is 8.5 g:1.5 g:100 mL.

[0118] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists and is enhanced; 1725-1735cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0119] A method for preparing a functional fiber fabric comprises the following steps: S21, add phthalic acid, polyamine A and deionized water A into a reactor, protect with N2, heat to 240°C, 1.7MPa, and react for 4h; reduce to normal pressure and continue to react for 2h; after the reaction is completed, evacuate for 1h to obtain the intermediate product 2I.

[0120] The usage ratio of the phthalic acid, the polyamine A and the deionized water A is 2.0 mol: 1.0 mol: 300 mL.

[0121] The polyamine A is a diamine and a triamine added in a molar ratio of 1.0:0; that is, no triamine is added.

[0122] The diamine is polyether diamine with a molecular weight of 500.

[0123] Its infrared data are as follows: 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1664cm -1 :Amide-C=O exists; 3402cm -1 :-OH exists and weakens; 1764cm -1 : Carboxylic acid -C=O exists and weakens.

[0124] S22, N2 protection, add the intermediate product 1I and polyamine B to N,N-dimethylformamide C, stir, heat to 100°C and react for 6 hours, continue to heat to 120°C and react for 1 hour; after the reaction is completed, distill under reduced pressure to obtain the intermediate product 2II.

[0125] The usage ratio of the intermediate product 1I, polyamine B, and N,N-dimethylformamide C is 0.5 mol: 1.0 mol: 500 mL; The polyamine B is a diamine and a triamine added in a molar ratio of 0.8:0.2; The diamine is polyether diamine with a molecular weight of 500; The triamine is a mixture of melamine and 1,2,3-propylenetriamine in a molar ratio of 2.0:1.0.

[0126] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3318 cm -1 :-NH- exists; 1801 cm -1 :Ring-C=O does not exist; 1725-1735cm -1 :-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0127] S23, add intermediate product 2I, intermediate product 2II and deionized water into the reactor, protect with N2, heat to 255°C, 1.6MPa, react for 3h; reduce to normal pressure, continue to react for 2.5h; after the reaction is completed, evacuate for 1h to obtain intermediate product 2III.

[0128] The intermediate product 2I, intermediate product 2II and deionized water are added in a ratio of 1.0 mol:1.0 mol:300 mL.

[0129] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1764cm -1 :Carboxylic acid-C=O does not exist; 1725-1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0130] S24, acrylamide, 2-methacryloyloxyethyl phosphorylcholine, and photoinitiator 1173 were added to N,N-dimethylformamide D, and irradiated under UV lamp for 10 min, then the UV lamp was removed, and vacuum distillation was performed. Methanol was added to the concentrate to produce a precipitate, which was filtered and the precipitate was taken and vacuum dried at 60°C for 8 h to obtain the intermediate product 2IV ( ).

[0131] The usage ratio of acrylamide, 2-methacryloyloxyethyl phosphorylcholine, and N,N-dimethylformamide D is 0.7 mol: 0.3 mol: 500 mL; The amount of the photoinitiator 1173 used is 5 wt % of the total mass of the reactants.

[0132] Its infrared data are as follows: 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1187cm -1 :-P=O exists; 1606cm -1 、811cm -1 :-C=C- does not exist.

[0133] S25, dissolving the intermediate product 2III and the intermediate product 2IV in deionized water B, stirring for 2 hours, degassing, passing through a spinning device under stirring conditions, combing with a carding machine, preparing by a needle punching method, and cutting, inspecting, and sterilizing to obtain a functional fiber fabric.

[0134] The usage ratio of the intermediate product 2III, the intermediate product 2 IV, and deionized water B is 9.0 g: 1.0 g: 1000 mL.

[0135] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1725-1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists; 1187cm -1 :-P=O exists.

[0136] A method for preparing an artificial meniscus, comprising: S31, preparing a mold for making a disc-shaped artificial meniscus.

[0137] S32, disposing a functional fiber fabric inside the mold.

[0138] S33, adding the modified polyurethane-based material solution into the mold, removing bubbles, and letting it stand to obtain a molded object I.

[0139] Wherein, the outer end of the artificial meniscus is connected to the functional fiber fabric.

[0140] S34, placing the formed product I in a glutaraldehyde solution for 5 hours to obtain a formed product II.

[0141] The preparation method of the glutaraldehyde solution is as follows: The glutaraldehyde aqueous solution was added to acetonitrile, and a solid moisture desiccant was added. After sealing and drying for 0.5 h, the mixture was filtered to obtain a glutaraldehyde acetonitrile solution.

[0142] The usage ratio of the glutaraldehyde aqueous solution, acetonitrile and solid moisture desiccant is 20 mL:480 mL:100 g; The concentration (w / v) of the glutaraldehyde aqueous solution is 50%.

[0143] S35, placing the formed product II in a calcium bromide solution for 5 hours, placing the product in a dialysis bag, and dialyzing it with deionized water for 3 days, replacing the dialysate once a day, and freeze-drying to obtain the target product, i.e., the artificial meniscus.

[0144] The calcium bromide concentration is 0.01 g / mL.

[0145] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material comprises the following steps: S11, N2 protection, hydroxymethyldioxolane and dimethyl carbonate were mixed, tetrabutyl titanate was added, stirred, heated to 180°C, reacted for 1h, and distilled under reduced pressure to obtain intermediate product 1I.

[0146] The molar ratio of the hydroxymethyldioxolane to dimethyl carbonate is 2:1.

[0147] The amount of tetrabutyl titanate used is 0.1wt% of the total mass of the reactants.

[0148] Its infrared data are as follows: 3414 cm -1 :-OH does not exist; 1801 cm -1 :Cyclic ester -C=O exists; 1732cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1:-COC- exists.

[0149] S12, N2 protection, add the intermediate product 1I and diamine to N,N-dimethylformamide A, stir, heat to 100°C and react for 6 hours, continue to heat to 120°C and react for 1 hour; after the reaction is completed, distill under reduced pressure to obtain the intermediate product 1II.

[0150] The usage ratio of the intermediate product 1I, diamine, and N,N-dimethylformamide A is 1 mol: 1 mol: 400 mL; The diamines are macromolecular diamine and micromolecular diamine, which are added in a molar ratio of 2.0:8.0.

[0151] The macromolecular diamine is polyethylene glycol diamine, and the molecular weight is 400.

[0152] The small molecule diamine is a mixture of triethylenetetramine and p-phenylenediamine in a molar ratio of 0.6:0.4.

[0153] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3317 cm -1 : -NH- exists (single peak); 1801 cm -1 :Cyclic ester -C=O does not exist; 1725-1735cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0154] S13, adding the intermediate product 1II and gelatin into hot N,N-dimethylformamide B, stirring continuously at 60° C. for 3 h, and distilling under reduced pressure to obtain the target product, i.e., the modified polyurethane-based material.

[0155] The usage ratio of the intermediate product 1II to gelatin and N,N-dimethylformamide B is 8.5 g:1.5 g:100 mL.

[0156] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists and is enhanced; 1725-1735cm -1 :Ester-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0157] A method for preparing a functional fiber fabric comprises the following steps: S21, add phthalic acid, polyamine A and deionized water A into a reactor, protect with N2, heat to 260°C, 1.5MPa, react for 2h; reduce to normal pressure, continue to react for 3h; after the reaction is completed, evacuate for 1h to obtain the intermediate product 2I.

[0158] The usage ratio of the phthalic acid, the polyamine A and the deionized water A is 2.0 mol: 1.0 mol: 300 mL.

[0159] The polyamine A is a diamine and a triamine added in a molar ratio of 0.8:0.2; The diamine is polyether diamine with a molecular weight of 500; The triamine is a mixture of melamine and 1,2,3-propylenetriamine in a molar ratio of 4.0:1.0.

[0160] Its infrared data are as follows: 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1664cm -1 :Amide-C=O exists; 3402cm -1 :-OH exists and weakens; 1764cm -1 : Carboxylic acid -C=O exists and weakens.

[0161] S22, N2 protection, add the intermediate product 1I and polyamine B to N,N-dimethylformamide C, stir, heat to 80°C and react for 8 hours, continue to heat to 100°C and react for 2 hours; after the reaction is completed, distill under reduced pressure to obtain the intermediate product 2II.

[0162] The usage ratio of the intermediate product 1I, polyamine B, and N,N-dimethylformamide C is 0.5 mol: 1.0 mol: 500 mL; The polyamine B is a diamine and a triamine added in a molar ratio of 1.0:0; that is, no triamine is added.

[0163] The diamine is polyether diamine with a molecular weight of 500.

[0164] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3318 cm -1 :-NH- exists; 1801 cm -1 :Ring-C=O does not exist; 1725-1735cm -1 :-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0165] S23, add intermediate product 2I, intermediate product 2II and deionized water into the reactor, protect with N2, heat to 255°C, 1.6MPa, react for 3h; reduce to normal pressure, continue to react for 2.5h; after the reaction is completed, evacuate for 1h to obtain intermediate product 2III.

[0166] The intermediate product 2I, intermediate product 2II and deionized water are added in a ratio of 1.0 mol:1.0 mol:300 mL.

[0167] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1764cm -1 :Carboxylic acid-C=O does not exist; 1725-1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists.

[0168] S24, acrylamide, 2-methacryloyloxyethyl phosphorylcholine, and photoinitiator 1173 were added to N,N-dimethylformamide D, and irradiated under UV lamp for 50 min, then the UV lamp was removed, and vacuum distillation was performed. Methanol was added to the concentrate to produce a precipitate, which was filtered and the precipitate was taken and vacuum dried at 60°C for 8 h to obtain the intermediate product 2IV ( ).

[0169] The usage ratio of acrylamide, 2-methacryloyloxyethyl phosphorylcholine, and N,N-dimethylformamide D is 0.9 mol: 0.1 mol: 500 mL; The amount of the photoinitiator 1173 used is 1 wt % of the total mass of the reactants.

[0170] Its infrared data are as follows: 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1187cm -1 :-P=O exists; 1606cm -1 、811cm -1 :-C=C- does not exist.

[0171] S25, dissolving the intermediate product 2III and the intermediate product 2IV in deionized water B, stirring for 3 hours, degassing, passing through a spinning device under stirring conditions, combing with a carding machine, preparing by a needle punching method, and cutting, inspecting, and sterilizing to obtain a functional fiber fabric.

[0172] The usage ratio of the intermediate product 2III, the intermediate product 2 IV and the deionized water B is 7.0 g:3.0 g:1000 mL.

[0173] Its infrared data are as follows: 3407 cm -1 :-OH exists; 3322 cm -1 :-NH- exists; 3017 cm -1 :-CH benzene ring exists; 1725-1735cm -1 :Ester-C=O exists; 1664cm -1 :Amide-C=O exists; 1255 cm -1 、1110cm -1 :-COC- exists; 1187cm -1 :-P=O exists.

[0174] A method for preparing an artificial meniscus, comprising: S31, preparing a mold for making a disc-shaped artificial meniscus.

[0175] S32, disposing a functional fiber fabric inside the mold.

[0176] S33, adding the modified polyurethane-based material solution into the mold, removing bubbles, and letting it stand to obtain a molded object I.

[0177] Wherein, the outer end of the artificial meniscus is connected to the functional fiber fabric.

[0178] S34, placing the formed product I in a glutaraldehyde solution for 10 hours to obtain a formed product II.

[0179] The preparation method of the glutaraldehyde solution is as follows: The glutaraldehyde aqueous solution was added to acetonitrile, and a solid moisture desiccant was added. After sealing and drying for 0.5 h, the mixture was filtered to obtain a glutaraldehyde acetonitrile solution.

[0180] The usage ratio of the glutaraldehyde aqueous solution, acetonitrile and solid moisture desiccant is 10 mL:490 mL:100 g; The concentration (w / v) of the glutaraldehyde aqueous solution is 50%.

[0181] S35, placing the formed product II in a calcium bromide solution for 2 hours, placing the product in a dialysis bag, and dialyzing it with deionized water for 3 days, replacing the dialysate once a day, and freeze-drying to obtain the target product, i.e., an artificial meniscus.

[0182] The calcium bromide concentration is 0.1 g / mL.

[0183] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S12, The small molecule diamine is a mixture of triethylenetetramine and p-phenylenediamine in a molar ratio of 0.5:0.5.

[0184] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S12, The small molecule diamine is a mixture of triethylenetetramine and p-phenylenediamine in a molar ratio of 0.7:0.3.

[0185] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S13, The usage ratio of the intermediate product 1II to gelatin and N,N-dimethylformamide B is 7.5 g:2.5 g:100 mL.

[0186] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S13, The usage ratio of the intermediate product 1II to gelatin and N,N-dimethylformamide B is 9.5 g:0.5 g:100 mL.

[0187] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S12, The macromolecular diamine is a mixture of polyethylene glycol diamine and polyether diamine in a mass ratio of 3:1; The molecular weight of the polyethylene glycol diamine is 400; The molecular weight of the polyether diamine is 500.

[0188] The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S13, The amino-containing biomacromolecule is chitosan.

[0189] The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S21 and S22, The teramine is a mixture of melamine and 1,3,5-triphenylamine in a molar ratio of 1.0:1.0.

[0190] The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S21 and S22, The teramine is a mixture of melamine and 1,3,5-triphenylamine in a molar ratio of 2.0:1.0.

[0191] The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric. In S21, the triamine is melamine and 1,2,3-propylenetriamine in a molar ratio of 2.0:1.0; and In S22, the triamine is melamine and 1,2,3-propylenetriamine in a molar ratio of 4.0:1.0.

[0192] The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S21, The usage ratio of terephthalic acid, polyamine A and deionized water A is 1.8 mol: 1.0 mol: 300 mL.

[0193] The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S22, The usage ratio of the intermediate product 1I, polyamine B, and N,N-dimethylformamide C is 0.7 mol: 1.0 mol: 500 mL.

[0194] The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric. In S21, the usage ratio of terephthalic acid, polyamine A, and deionized water A is 0.5 mol: 1.0 mol: 300 mL; and In S22, the usage ratio of the intermediate product 1I, the polyamine B, and the N,N-dimethylformamide C is 2.0 mol: 1.0 mol: 500 mL; and S23, N2 protection, add intermediate product 2I and intermediate product 2II to N,N-dimethylformamide, stir, heat to 100°C and react for 6h, continue to heat to 120°C and react for 1h; after the reaction, distill under reduced pressure to obtain intermediate product 2III.

[0195] The usage ratio of the intermediate product 2I, the intermediate product 2II and N,N-dimethylformamide is 1 mol: 1 mol: 400 mL.

[0196] The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S24, The zwitterion is methacryloylethyl sulfobetaine.

[0197] An artificial meniscus in the following comparative examples is compared with Example 1: Comparative Example 1 The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S12, The diamine is a macromolecular diamine and a small molecular diamine added in a molar ratio of 0:10, that is, no macromolecular diamine is added.

[0198] Comparative Example 2 The rest is the same as in Example 1, except that: A method for preparing a modified polyurethane-based material, wherein in S13, The usage ratio of the intermediate product 1II to gelatin and N,N-dimethylformamide B is 10 g:0 g:100 mL; that is, no gelatin is added.

[0199] Comparative Example 3 The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric. In S21, the dosage ratio of phthalic acid, polyamine A, and deionized water A is 1.0 mol: 1.0 mol: 300 mL; and In S25, the intermediate 2III is replaced with 2I.

[0200] Comparative Example 4 The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric comprises the following steps: In S22, the usage ratio of the intermediate product 1I, the polyamine B, and the N,N-dimethylformamide C is 1.0 mol: 1.0 mol: 500 mL; and In S25, the intermediate 2III is replaced with 2I.

[0201] Comparative Example 5 The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S21 and S22, The polyamines are all diamines.

[0202] Comparative Example 6 The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S21 and S22, The polyether diamine is replaced by triethylenetetramine.

[0203] Comparative Example 7 The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S25, The usage ratio of the intermediate product 2III, the intermediate product 2 IV, and the deionized water B is 10.0 g: 0 g: 1000 mL, that is, the intermediate product 2IV is not added.

[0204] Comparative Example 8 The rest is the same as in Example 1, except that: A method for preparing a functional fiber fabric, wherein in S24, The usage ratio of acrylamide, 2-methacryloyloxyethyl phosphorylcholine, and N,N-dimethylformamide D is 1.0 mol: 0 mol: 500 mL, that is, 2-methacryloyloxyethyl phosphorylcholine is not added.

[0205] Comparative Example 9 The rest is the same as in Example 1, except that: In a method for preparing an artificial meniscus, no immersion operation of glutaraldehyde-acetonitrile solution is performed.

[0206] Comparative Example 10 The rest is the same as in Example 1, except that: The invention discloses a method for preparing an artificial meniscus, which does not involve the impregnation operation of a calcium bromide solution.

[0207] Comparative Example 11 The rest is the same as in Example 1, except that: A method for preparing an artificial meniscus, wherein S35, The calcium bromide was replaced with calcium chloride.

[0208] The physical properties of the artificial menisci prepared in Examples 1-16 of the present invention and Comparative Examples 1-11 were measured respectively, and the results are shown in Table 1.

[0209] Firstly, it can be concluded from Examples 1-16 in Table 1 that the artificial meniscus of the present invention has excellent mechanical properties, low friction properties, biocompatibility, and the ability to promote chondrocyte proliferation and differentiation.

[0210] Second, it can be observed from Example 1 and Comparative Examples 1-2 that the artificial meniscus in the present invention uses a homemade modified polyurethane material as the internal matrix material, which can effectively improve the mechanical properties after modification with a macromolecular water-soluble diamine; and can improve the biocompatibility and the proliferation and differentiation ability of chondrocytes after modification with gelatin.

[0211] Third, it can be observed from Example 1 and Comparative Examples 3-8 that the artificial meniscus in the present invention uses a homemade functional fiber fabric as an external material, which has the characteristics of improving mechanical properties, low friction properties and promoting bone tissue generation; among them, it can be observed from Comparative Examples 3-4 that the structure with polyamide and polyurethane blocks has excellent mechanical properties (polyamide has excellent mechanical strength, polyurethane provides compatibility with polyester, and synergistically improves mechanical properties); and Comparative Example 5 can be observed that a small amount of unreacted amino groups in the triamine are cross-linked with glutaraldehyde as hanging chains, which improves the overall mechanical properties. mechanical properties; compared with the implementation of comparative examples 6-7, it can be observed that the water-soluble diamine can provide toughness and improve the mechanical properties on the one hand; on the other hand, it provides hydrophilicity, and cooperates with the polyamide copolymer to provide hydrophilicity, thereby improving the lubrication performance between the artificial meniscus and the cartilage tissue and reducing the friction coefficient; compared with the implementation of comparative examples 7-8, it can be observed that the polyamide / zwitterion copolymer effectively improves the lubrication performance between the artificial meniscus and the cartilage tissue, reduces wear and less contusion; and, the ammonium salt, phosphate or sulfonate in the zwitterion structure is similar to the cell composition structure, which can promote joint lubrication, reduce inflammation and protect cartilage.

[0212] Fourth, it can be observed from Example 1 and comparative examples 9-11 that the artificial meniscus in the present invention has excellent mechanical properties and the function of promoting cartilage tissue proliferation; among them, it can be observed from comparative example 9 that glutaraldehyde can be used as a cross-linking agent to improve the mechanical properties; it can be observed from comparative examples 10-11 that calcium ions have an auxiliary effect on improving the mechanical properties; bromide ions have the function of inducing chondrocyte regeneration and differentiation, and can effectively promote cartilage repair; they can compensate for the wear of cartilage tissue and effectively extend the service life of the material.

[0213] In summary, the artificial meniscus of the present invention uses a homemade modified polyurethane material as the internal matrix material and a homemade functional fiber fabric as the external restraint material, and is prepared by cross-linking and calcification, and has obvious advantages in mechanical properties, low wear, and promoting chondrocyte proliferation.

[0214] The test method is as follows: (1) Tensile strength and elongation at break: Tested in accordance with the method described in GB / T 1040.3-2006. The sample to be tested was immersed in sterile phosphate buffer at 37°C for 0, 48, and 96 days, then taken out and stabilized to room temperature for testing.

[0215] (2) Friction coefficient: The friction tester (BRUKER UMT) was used for testing. The test conditions were reciprocating motion, 1 Hz frequency, 0.4 N load, simulated joint fluid lubrication, porcine femoral condylar cartilage as the friction pair, and room temperature. The test was terminated when the friction coefficient was constant. The samples were immersed in sterile phosphate buffer at 37°C for 0, 48, and 96 days, and then taken out and stabilized to room temperature for testing.

[0216] (3) Cytotoxicity: Referring to the standard GB / T 16886.5-2003, the material was immersed in the culture medium for 7 and 14 days, and the extract was used to culture NIH3T3 cells, and then the cytotoxicity was evaluated (relative cell survival rate>80%, which means good biocompatibility).

[0217] (4) Cell differentiation test: On the 14th day of ATDC5 cell culture, the content of glycosaminoglycan (GAG) secreted by the cultured ATDC5 cells differentiated into chondrocytes was quantitatively detected, and the dsDNA (double-stranded DNA) content was measured. The content of dsDNA per microgram was calculated, and then the data was normalized.

[0218] Preparation of papain lysis buffer: Dissolve the following ingredients in PBS: 50 mM Na3PO4, 20 mM Nacetyl cysteine, 28 μL / mL papain, filter through 0.22 μm filter membrane, and store at 4°C.

[0219] Lysis of cells: Transfer the cultured monolayer cells or cultured cell clusters to the well plate, wash twice with PBS, add 300 μL papain lysis solution to the well plate, seal the well plate with sealing film and keep it in a 60℃ water bath for 16 hours. After completion, centrifuge the well plate and mix the lysis solution by blowing with a 200μL pipette tip. Transfer the lysis solution to a 1.5mL EP tube, centrifuge and take the supernatant for immediate determination or store at 80℃ for later use. This sample is used for the determination of double-stranded DNA (ds DNA) and GAG content.

[0220] Determination of ds DNA content: The lysate samples obtained by cell lysis were taken and the concentration of dsDNA was tested by Nanodrop instrument.

[0221] GAG content determination: The lysate sample obtained by cell lysis was reacted with DMMB staining solution at a volume ratio of 1:6. After completion, the absorbance at 525 nm was detected on an ELISA reader and standardized with the ds DNA content to calculate the relative content of GAG per microgram of ds DNA.

[0222] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A method for preparing a modified polyurethane-based material, characterized in that: The following steps are involved: S11, subjecting hydroxymethyldioxolane and dimethyl carbonate to transesterification reaction to obtain an intermediate product 1I; S12, subjecting the intermediate product 1I to a ring-opening reaction with a diamine to obtain an intermediate product 1II; S13, blending the intermediate product 1II with the amino-containing biomacromolecule to obtain the target product, i.e., a modified polyurethane-based material.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the hydroxymethyldioxolane to dimethyl carbonate is 2:

1.

3. The preparation method according to claim 1, characterized in that: The molar ratio of the intermediate product II to the diamine is 1:1; and The diamine is a macromolecular diamine and a small molecular diamine added in a molar ratio of 2.0-3.0:7.0-8.

0.

4. The preparation method according to claim 3, characterized in that: The macromolecular diamine is polyethylene glycol diamine and / or polyether diamine; and The small molecule diamine is a mixture of aliphatic diamine and aromatic diamine.

5. The preparation method according to claim 1, characterized in that: The ratio of the intermediate product III to the amino-containing biomacromolecule is 7.5-9.5 g: 0.5-2.5 g; and The amino-containing biomacromolecules include gelatin and chitosan.

6. A modified polyurethane-based material, characterized in that: Prepared by the preparation method according to any one of claims 1 to 5.

7. A method for preparing a functional fiber fabric, characterized in that: The following steps are involved: S21, condensing the dibasic acid and the polyamine A to obtain an intermediate product 2I; S22, subjecting the intermediate product 1I to a ring-opening reaction with a polyamine B to obtain an intermediate product 2II; S23, subjecting the intermediate product 2I and the intermediate product 2II to a polycondensation reaction to obtain an intermediate product 2III; S24, free radical polymerization of acrylamide and zwitterion to obtain intermediate product 2IV; S25, blending the intermediate product 2III and the intermediate product 2IV, spinning and combing to obtain a functional fiber fabric.

8. The preparation method according to claim 7, characterized in that: The molar ratio of the dibasic acid to the polyamine A is 0.5-2.0:1.0; and The dibasic acid includes terephthalic acid; The polyamine A is added by molar ratio of diamine to triamine of 0.8-1.0:0-0.2; The diamine is a water-soluble diamine; including polyether diamines; The triamine includes melamine.

9. The preparation method according to claim 7, characterized in that: The molar ratio of the intermediate product 1I to the polyamine B is 0.5-2.0:1.0; and The polyamine A is added by molar ratio of diamine to triamine of 0.8-1.0:0-0.2; The diamine is a water-soluble diamine; including polyether diamine; The triamine includes melamine.

10. The preparation method according to claim 7, characterized in that: The intermediate product 2I and the intermediate product 2II are added in a molar ratio of 1.0:1.

0.

11. The preparation method according to claim 7, characterized in that: The molar ratio of acrylamide to zwitterion is 0.7-0.9:0.1-0.3; and The zwitterion is phosphorylcholine or betaine.

12. The preparation method according to claim 7, characterized in that: The usage ratio of the intermediate product 2III and the intermediate product 2 IV is 7.0-9.0 g:1.0-3.0 g.

13. A functional fiber fabric, characterized in that: Prepared by the preparation method according to any one of claims 7 to 12.

14. A method for preparing an artificial meniscus, characterized in that: include: S31, preparing a mold for making a disc-shaped artificial meniscus; S32, arranging a functional fiber fabric inside the mold; S33, adding a modified polyurethane-based material solution into the mold, removing bubbles, and standing to obtain a molded object I; Wherein, the outer end of the artificial meniscus is connected to the functional fiber fabric; S34, placing the formed object I in a glutaraldehyde solution for 5-10 hours to obtain a formed object II; S35, placing the formed product II in a calcium bromide solution for 2-5 hours to obtain the target product, namely, an artificial meniscus.

15. The preparation method according to claim 14, characterized in that: The preparation method of the glutaraldehyde solution is as follows: Add the glutaraldehyde aqueous solution to acetonitrile, add a solid moisture desiccant, seal and dry for 0.5 h, and filter to obtain a glutaraldehyde acetonitrile solution; The usage ratio of the glutaraldehyde aqueous solution, acetonitrile and solid moisture desiccant is 10-20 mL: 480-490 mL: 100 g; The concentration (w / v) of the glutaraldehyde aqueous solution is 50%.

16. The preparation method according to claim 14, characterized in that: The calcium bromide concentration is 0.01-0.1 g / mL.

17. An artificial meniscus, characterized in that: Prepared by the preparation method according to any one of claims 14 to 16.

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