阅读说明：本技术 自组装胶束、弥散增强耐磨耐疲劳仿生半月板及制备方法 (Self-assembled micelle, dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus and preparation method ) 是由 付晓阳 于 2021-09-18 设计创作，主要内容包括：本发明提供了一种自组装胶束、弥散增强耐磨耐疲劳仿生半月板及制备方法,所述自组装胶束的制备方法包括以下步骤：步骤1)：进行预聚反应,将大分子多元醇和增强酯类分子按照一定的比例加入反应器中,同时加入催化剂；步骤2)：预聚反应结束后加入扩链剂进行扩链；步骤3)：扩链结束后加入中和剂进行中和,获得合成的自组装胶束,本发明制备的弥散增强耐磨耐疲劳仿生半月板结构与天然半月板的结构更加相似,摩擦系数与天然半月板的摩擦系数更加相近,且具有良好的耐疲劳性能,将其应用于人工半月板领域,改善摩擦系数,植入人体后可有效保护软骨。(The invention provides a self-assembled micelle, a dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus and a preparation method thereof, wherein the preparation method of the self-assembled micelle comprises the following steps: step 1): performing prepolymerization reaction, adding the macromolecular polyol and the enhanced ester molecules into a reactor according to a certain proportion, and simultaneously adding a catalyst; step 2): adding a chain extender for chain extension after the prepolymerization reaction is finished; step 3): after chain extension is finished, a neutralizer is added for neutralization to obtain a synthetic self-assembled micelle, the structure of the dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus prepared by the method is more similar to that of a natural meniscus, the friction coefficient is more similar to that of the natural meniscus, and the bionic meniscus has good fatigue resistance, is applied to the field of artificial menisci, improves the friction coefficient, and can effectively protect cartilage after being implanted into a human body.)

1. A preparation method of self-assembled micelle is characterized by comprising the following steps:

step 1): performing prepolymerization reaction, adding the macromolecular polyol and the enhanced ester molecules into a reactor according to a certain proportion, and simultaneously adding a catalyst;

step 2): adding a chain extender for chain extension after the prepolymerization reaction is finished;

step 3): and adding a neutralizer for neutralization after the chain extension is finished to obtain the synthesized self-assembled micelle.

2. The method for preparing self-assembled micelles of claim 1, wherein the molar ratio of the macromolecular polyol to the reinforcing ester molecules to the chain extender is: 1: 1.5-4.5: 4 to 9.

3. The method for preparing self-assembled micelles of claim 1, wherein the macropolyol comprises one or more of polyester polyol comprising polyethylene adipate glycol, polybutylene adipate glycol and polyhexamethylene adipate glycol, and polyolefin polyol comprising polyethylene glycol, polypropylene glycol, polycaprolactone diol and polyglycerol.

4. The method for preparing self-assembled micelles of claim 1, wherein the reinforced ester molecules are one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone isocyanate.

5. The method for preparing self-assembled micelles of claim 1, wherein the catalyst is one or more of organotin, wherein organotin comprises dibutyltin dilaurate and stannous octoate.

6. The method for preparing self-assembled micelles of claim 5, wherein the chain extender is one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 4-butanediol, trimethylolpropane, ethylenediamine, propylenediamine and diethylenetriamine.

7. The method for preparing self-assembled micelles according to claim 1, wherein the neutralizing agent is one or more of dimethylethanolamine, triethylamine, dimethylisopropanolamine, sodium hydroxide, potassium hydroxide and ammonia water.

8. A self-assembled micelle prepared by the method for preparing a self-assembled micelle according to any one of claims 1 to 7, wherein the self-assembled micelle has a water content of 30 to 90%, a crystallinity of 20 to 80%, a porosity of 20 to 80%, a friction coefficient of less than 0.1, an elastic modulus of 0.35 to 6.5MPa, and a breaking strength of 2.0 to 25 MPa.

9. A method for preparing a dispersion-strengthened wear-resistant fatigue-resistant biomimetic meniscus based on the self-assembled micelle of claim 8, wherein the method for preparing the artificial meniscus comprises the following steps:

s1: emulsifying the self-assembled micelle at a certain speed, and uniformly dispersing the synthesized self-assembled micelle into an aqueous solution to obtain a water-soluble high polymer material;

s2: adding a water-soluble high polymer material into a hydrogel solution, uniformly mixing the water-soluble high polymer material at high temperature and high pressure, and combining molecular chains of micelles and molecular chains of a matrix material together through a hydrogen bond effect, wherein the molecular chains of the micelles are inserted into the molecular chains of the matrix material, and the molecular chains of the micelles form micelles at high temperature and high pressure to have a reinforcing effect on the matrix, so that the double-network composite hydrogel material containing the hydrogen bond is prepared;

s3: quantitatively pushing the double-network composite hydrogel material into a mold cavity through a screw at a certain speed, and preparing a molded artificial meniscus with accurate size and similar shape to a natural meniscus through injection molding;

s4: and performing repeated cyclic low-temperature crosslinking on the molded artificial meniscus to prepare the dispersion-strengthened wear-resistant fatigue-resistant bionic meniscus.

10. A dispersion-strengthened wear-resistant fatigue-resistant biomimetic meniscus prepared by the preparation method of the dispersion-strengthened wear-resistant fatigue-resistant biomimetic meniscus according to claim 9, wherein the dispersion-strengthened wear-resistant fatigue-resistant biomimetic meniscus can reduce wear on cartilage and protect knee joints during use.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of biomedical materials, in particular to a self-assembled micelle, dispersion-enhanced wear-resistant and fatigue-resistant bionic meniscus and a preparation method thereof.

[ background of the invention ]

The meniscus is the cartilage between the tibial plateau and the femoral condyle, is one of the important components of the knee joint, and has the functions of buffering joint pressure and stabilizing the joint. However, meniscus damage can be caused by factors such as incorrect motion, violent impacts, and chronic injury, and to some extent, partial or total removal of the meniscus is required. If meniscus reconstruction is not performed after the meniscectomy, cartilage of femoral condyles is finally worn, so that arthritis is caused, and a patient with severe arthritis needs knee joint replacement, so that reconstruction after the meniscectomy is necessary. Meniscal reconstruction has primarily involved allograft and replacement of menisci (or artificial menisci). Allografts have a limited number of donors and require waiting for an appropriate donor; the artificial meniscus has low price, rich source and good biocompatibility, so the artificial meniscus becomes the current research hotspot. The current meniscal substitute is a collagen meniscus graftPolyurethane implant (a)And). The use of all three products requires the retention of the full meniscal edges and front and rear corners,andsuccessful use of meniscal tissue is dependent on the red zone portion of the meniscal tissue and is subject to degradation in vivo. Has been proved by researchAndhas higher friction coefficient in the using process, and the cartilage can be damaged by long-time friction after the cartilage repair implant is implanted into a human body.

The polyhydroxylated alcohol hydrogel has higher crystallinity, is a hydrogel elastomer, is very similar to human articular cartilage, has good lubricating property and very low friction coefficient, and the porous structure of the hydrogel has sufficient shock absorption capacity and good biocompatibility. The polyester material has excellent wear resistance, water is used as a dispersion medium, the micelle can be automatically assembled in a solution, the compounding operation with the polyhydroxy alcohol compound is simple, the addition of the polyester does not influence the porous structure of the polyhydroxy alcohol hydrogel, the toughness can be improved, the joint synovial fluid can be fully diffused into the polyhydroxy alcohol hydrogel, the friction coefficient of the artificial meniscus material is fully reduced by combining the polyester and the polyhydroxy alcohol hydrogel, the surface lubricity of the artificial meniscus material is improved, the wear to the cartilage can be avoided in the using process, and the effect of protecting the cartilage is achieved.

Accordingly, there is a need to develop a self-assembled micelle, dispersion-enhanced wear-resistant fatigue-resistant biomimetic meniscus and a method of preparation that address the deficiencies of the prior art to address or mitigate one or more of the problems set forth above.

[ summary of the invention ]

In view of the above, the invention provides a self-assembled micelle, dispersion-enhanced wear-resistant and fatigue-resistant bionic meniscus and a preparation method thereof, wherein soluble polyester and a polyhydroxy alcohol material are compounded to prepare a hydrogen bond composite hydrogel material, the structure of the hydrogen bond composite hydrogel material is more similar to that of a natural meniscus, the friction coefficient of the hydrogen bond composite hydrogel material is more similar to that of the natural meniscus, and the hydrogen bond composite hydrogel material has good fatigue resistance.

In one aspect, the present invention provides a method for preparing a self-assembled micelle, the method comprising the steps of:

step 1): performing prepolymerization reaction, adding the macromolecular polyol and the enhanced ester molecules into a reactor according to a certain proportion, and simultaneously adding a catalyst;

step 2): adding a chain extender for chain extension after the prepolymerization reaction is finished;

step 3): and adding a neutralizer for neutralization after the chain extension is finished to obtain the synthesized self-assembled micelle.

The above aspect and any possible implementation manner further provide an implementation manner, where the molar ratio of the macromolecular polyol, the reinforcing ester molecules and the chain extender is: 1: 1.5-4.5: 4 to 9.

The above aspects and any possible implementations further provide an implementation in which the macro-polyol comprises one or more of a polyester polyol and a polyolefin polyol, wherein the polyester polyol comprises polyethylene adipate glycol, polybutylene adipate glycol, and polyhexamethylene adipate glycol, and the polyolefin polyol comprises polyethylene glycol, polypropylene glycol, polycaprolactone diol, and polyglycerol.

There is further provided in accordance with any of the above aspects and possible implementations, an implementation in which the reinforcing ester molecules include one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone isocyanate.

The above aspects and any possible implementations further provide an implementation in which the catalyst is one or more of organotin, wherein organotin includes dibutyltin dilaurate and stannous octoate.

The above aspects and any possible implementations further provide an implementation in which the chain extender includes one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 4-butanediol, trimethylolpropane, ethylenediamine, propylenediamine, and diethylenetriamine.

The above aspects and any possible implementations further provide an implementation where the neutralizing agent includes one or more of dimethylethanolamine, triethylamine, dimethylisopropanolamine, sodium hydroxide, potassium hydroxide, and ammonia.

The above aspects and any possible implementation manner further provide a self-assembled micelle, which is prepared by the preparation method of the self-assembled micelle, wherein the water content of the self-assembled micelle is 30-90%, the crystallinity is 20-80%, the porosity is 20-80%, the friction coefficient is less than 0.1, the elastic modulus is 0.35-6.5 MPa, and the breaking strength is 2.0-25 MPa.

The above aspects and any possible implementation manners further provide a preparation method of a dispersion-strengthened wear-resistant fatigue-resistant biomimetic meniscus, based on the self-assembled micelle, the preparation method of the artificial meniscus comprises the following steps:

s1: emulsifying the self-assembled micelle at a certain speed, and uniformly dispersing the synthesized self-assembled micelle into an aqueous solution to obtain a water-soluble high polymer material;

s2: adding a water-soluble high polymer material into a hydrogel solution, uniformly mixing the water-soluble high polymer material at high temperature and high pressure, and combining molecular chains of micelles and molecular chains of a matrix material together through a hydrogen bond effect, wherein the molecular chains of the micelles are inserted into the molecular chains of the matrix material, and the molecular chains of the micelles form micelles at high temperature and high pressure to have a reinforcing effect on the matrix, so that the double-network composite hydrogel material containing the hydrogen bond is prepared;

s3: quantitatively pushing the double-network composite hydrogel material into a mold cavity through a screw at a certain speed, and preparing a molded artificial meniscus with accurate size and similar shape to a natural meniscus through injection molding;

s4: and performing repeated cyclic low-temperature crosslinking on the molded artificial meniscus to prepare the dispersion-strengthened wear-resistant fatigue-resistant bionic meniscus.

The aspect and any possible implementation manner described above further provide a dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus, and by the preparation method of the dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus, the dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus can reduce wear on cartilage and protect knee joints in the use process.

Compared with the prior art, the invention can obtain the following technical effects:

(1) the waterborne polyurethane prepared by the invention has uniform particle size distribution and moderate viscosity, can be self-assembled into micelles under high temperature and high pressure, and has good biocompatibility;

(2) according to the invention, the water-based polyurethane is added into the artificial meniscus material, the water content of the artificial meniscus material is similar to that of a natural meniscus material, so that the toughness of the artificial meniscus material can be improved, the friction resistance of the artificial meniscus material can be improved, and the bionic performance is better;

(3) the artificial meniscus prepared by the method has better adaptability with the femoral condyle.

Of course, it is not necessary for any one product in which the invention is practiced to achieve all of the above-described technical effects simultaneously.

[ description of the drawings ]

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a graph of the change in strain with fatigue number in an artificial meniscus fatigue test prepared according to the present invention;

FIG. 2 is a graph comparing stress-strain curves before and after fatigue for an artificial meniscus prepared according to the present invention;

FIG. 3 is a graph of the friction coefficient of an artificial meniscus prepared in example 3 of the present invention;

wherein, the Number of cycles, Strain, and Stress are shown in the figure.

[ detailed description ] embodiments

For better understanding of the technical solutions of the present invention, the following detailed descriptions of the embodiments of the present invention are provided with reference to the accompanying drawings.

It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The invention provides a self-assembled micelle, a dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus and a preparation method thereof, wherein the preparation method of the self-assembled micelle comprises the following steps:

step 1): performing prepolymerization reaction, adding the macromolecular polyol and the enhanced ester molecules into a reactor according to a certain proportion, and simultaneously adding a catalyst;

step 2): adding a chain extender for chain extension after the prepolymerization reaction is finished;

step 3): and adding a neutralizer for neutralization after the chain extension is finished to obtain the synthesized self-assembled micelle.

The molar ratio of the macromolecular polyol to the reinforced ester molecules to the chain extender is as follows: 1: 1.5-4.5: 4-9; the neutralization dose is as follows: 0.01moL to 0.03moL, and the catalyst is excessive. The macromolecular polyol comprises one or more of polyester polyol and polyolefin polyol, wherein the polyester polyol comprises polyethylene adipate glycol, polybutylene adipate glycol and polyhexamethylene adipate glycol, and the polyolefin polyol comprises polyethylene glycol, polypropylene glycol, polycaprolactone diol and polyglycerol. The reinforced ester molecules comprise one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone isocyanate. The catalyst is one or more of organic tin, wherein the organic tin comprises dibutyltin dilaurate and stannous octoate. The chain extender is a macromolecule containing hydroxyl, and comprises one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 4-butanediol, trimethylolpropane, ethylenediamine, propylenediamine and diethylenetriamine. The neutralizing agent comprises one or more of dimethylethanolamine, triethylamine, dimethylisopropanolamine, sodium hydroxide, potassium hydroxide and ammonia water.

The invention also provides a self-assembled micelle prepared by the preparation method of the self-assembled micelle, wherein the water content of the self-assembled micelle is 30-90%, the crystallinity is 20-80%, the porosity is 20-80%, the friction coefficient is less than 0.1, the elastic modulus is 0.35-6.5 MPa, and the breaking strength is 2.0-25 MPa.

The invention also provides a preparation method of the dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus, which is based on the self-assembled micelle and comprises the following steps:

s1: emulsifying the self-assembled micelle at a certain speed, and uniformly dispersing the synthesized self-assembled micelle into an aqueous solution to obtain a water-soluble high polymer material;

s2: adding a water-soluble high polymer material into a hydrogel solution, uniformly mixing the water-soluble high polymer material at high temperature and high pressure, and combining molecular chains of micelles and molecular chains of a matrix material together through a hydrogen bond effect, wherein the molecular chains of the micelles are inserted into the molecular chains of the matrix material, and the molecular chains of the micelles form micelles at high temperature and high pressure to have a reinforcing effect on the matrix, so that the double-network composite hydrogel material containing the hydrogen bond is prepared;

s3: quantitatively pushing the double-network composite hydrogel material into a mold cavity through a screw at a certain speed, and preparing a molded artificial meniscus with accurate size and similar shape to a natural meniscus through injection molding;

s4: and performing repeated cyclic low-temperature crosslinking on the molded artificial meniscus to prepare the dispersion-strengthened wear-resistant fatigue-resistant bionic meniscus.

The invention also provides a dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus which can be used as an articular cartilage, an artificial ligament, an artificial tendon, an artificial blood vessel or an intervertebral disc implant and can be realized by adjusting the proportion of the water-soluble high polymer material to the hydrogel solution through the preparation method of the dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus.

The self-assembled micelle is micron-sized, and the self-assembled micelle is dispersed and distributed in the hydrogel solution to obtain the porous material with high toughness and high wear resistance. The principle is as follows: dispersing a polymer chain into a hydrogel solution, forming micelles in the solution by linear or branched polymers containing chemical groups capable of generating hydrogen bonds under high temperature and high pressure, dispersing and distributing, and obtaining the crystallized hydrogel with the double-network structure through multiple low-temperature crosslinking, wherein the hydrogel has the properties of high toughness and high wear resistance.

Wherein the polymer chain is emulsion polymer, and the molecular weight and water solubility are controlled by changing the synthesis ratio and synthesis conditions. The polymer can be automatically assembled into micelles in a hydrogel solution, the self-assembled micelles have good biocompatibility, are dispersed in a hydrogel material, can improve the toughness and the wear resistance, obtain a high-strength wear-resistant fatigue-resistant meniscus implant, reduce the wear to cartilage in the use process and protect knee joints. The composite hydrogel can be used for preparing meniscus implants, and can also be applied to self-assembly micelle dispersion reinforced high-toughness and high-wear-resistance materials in medical fields such as other articular cartilages, artificial ligaments, artificial tendons, artificial blood vessels, intervertebral disc implants and the like by adjusting the proportion of hydrogel solution to micelles.

When the self-assembly micelle dispersion reinforced high-toughness and high-wear-resistance material is prepared, firstly, a high-molecular composite hydrogel material needs to be prepared, a synthesized high-molecular chain is an emulsion polymer and can be automatically assembled into micelles at high temperature and high pressure, a large number of hydrogen bonds are formed between the micelle and matrix hydrogel to obtain a double-network structure, then, a dispersed and distributed crystallization area is obtained through multiple low-temperature crosslinking, the micelle is added to regulate and control the microstructure of the hydrogel material, the porosity of the hydrogel material is improved, the mechanical property of the hydrogel material is synergistically improved, the high porosity can promote pressure release and free access of joint synovial fluid, the toughness and wear resistance of the hydrogel material can be enhanced, the performance of the prepared artificial meniscus is similar to that of an autologous meniscus, the wear to cartilage can be reduced in use, and the material can be used for preparing the artificial meniscus and also can be applied to other articular cartilage, artificial ligament, artificial tendon, artificial blood vessel, intervertebral disc implant and other medical fields.

The macromolecular composite hydrogel has high porosity and self-repairing capability, the microstructure of the macromolecular composite hydrogel is a mutually communicated pore structure, the microporous structures can transmit load in the stress process, joint synovial fluid in the macromolecular composite hydrogel can be discharged in time in the stress process to generate larger deformation, and the pore structures can absorb the liquid in the non-stress state and return to the original shape;

the water content of the polymer composite hydrogel is 30-90%, the crystallinity is 20-80%, the porosity is 20-80%, the friction coefficient is less than 0.1, the elastic modulus is 0.35-6.5 MPa, and the breaking strength is 2.0-25 MPa; the self-assembled micelle component is an aqueous polymer material, including water-soluble or water-emulsion-forming polymers, including polyethylene glycol, polyacrylic acid, polymaleic anhydride, polyethylene oxide, polyurethane, polyester, cellulose, derivatives, and the like, but not limited to the above-mentioned polymer materials;

the water-soluble polymer is a soluble polyester polymer obtained by carrying out catalytic reaction on an alcoholic hydroxyl compound, an ester polymer, a chain extender and a neutralizer through a catalyst and then emulsifying; the matrix material has good biocompatibility and mechanical property, and comprises polyethylene glycol, polyvinyl alcohol, polycaprolactone, polylactic acid, a silica gel material, gelatin, collagen, polypeptide, cellulose, polysaccharide and the like; the alcoholic hydroxyl compound is one or more of polyester polyol and polyolefin polyol, wherein the polyester polyol comprises polyethylene glycol adipate glycol, polybutylene glycol adipate glycol and polyhexamethylene glycol adipate glycol, the polyolefin polyol comprises polyethylene glycol, polypropylene glycol, polycaprolactone diol and polyglycerol, and the polyethylene glycol adipate glycol and the polyethylene glycol are preferred;

the ester polymer is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI) and isophorone isocyanate (IPDI), and hexamethylene diisocyanate is preferred; the catalyst is one or more of organic tin, wherein dibutyltin dilaurate and stannous octoate are contained, and stannous octoate is preferred; the chain extender is a macromolecule containing hydroxyl, wherein the macromolecule contains one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 4-butanediol, trimethylolpropane, ethylenediamine, propylenediamine and diethylenetriamine, and dimethylolbutyric acid is preferred. The neutralizer is one or more of dimethylethanolamine, triethylamine, dimethylisopropanolamine, sodium hydroxide, potassium hydroxide and ammonia water, and preferably the ammonia water.

The preparation method of the reinforced meniscus mainly comprises the following steps:

the method comprises the following steps: preparation of self-assembled micelles

The preparation of self-assembled micelles is prepared by stepwise polymerization. Firstly, performing prepolymerization reaction, adding macromolecular polyol and enhanced ester molecules into a reactor according to a certain proportion, and simultaneously adding a catalyst, wherein the polyol is used for enhancing the water solubility of the micelle and the flexibility of a molecular chain, and the ester molecules are used for enhancing the physical strength of the material; adding a chain extender for chain extension after the prepolymerization reaction is finished so as to improve the molecular weight of the micelle; after the chain extension is finished, adding a neutralizer for neutralization, wherein the neutralizer has the function of increasing the water solubility of the micelle; and finally, emulsifying at a certain speed to uniformly disperse the synthesized self-assembled micelle into the aqueous solution to obtain the water-soluble high polymer material.

Step two: preparation of composite hydrogel material

Adding the self-assembled micelle prepared in the step one into a hydrogel solution, uniformly mixing the self-assembled micelle with the hydrogel solution at high temperature and high pressure, and combining a molecular chain of the micelle with a molecular chain of a matrix material through a hydrogen bond effect, wherein the molecular chain of the micelle is inserted into the molecular chain of the matrix material, and the molecular chain of the micelle forms micelle at high temperature and high pressure to enhance the matrix, so that the double-network composite hydrogel material containing the hydrogen bond is prepared;

step three: shaping of artificial menisci

The hydrogel material mixed at high temperature and high pressure in the step two has good fluidity, the hydrogel material is quantitatively pushed into the die cavity at a certain speed through the screw, and the artificial meniscus which is accurate in size and similar to the natural meniscus in shape can be prepared through injection molding, and the artificial meniscus has high production efficiency and stable quality.

Step four: augmentation of artificial menisci

And (4) performing low-temperature crosslinking for multiple cycles on the artificial meniscus formed by injection molding in the step three. A large number of hydrogen bonds exist between the self-assembled micelle and the matrix material, and the hydrogen bonds have directionality, are favorable for oriented arrangement between molecules and are easy to crystallize. With the increase of the times of low-temperature crosslinking, the molecular chains of the uncrystallized part can be rearranged to generate more hydrogen bonds, so that the number of crystallization regions can be increased, the number of connecting action points between the two molecular chains can be increased, the crystallization regions are distributed in a dispersed manner, and the mechanical property of the material can be integrally improved.

In one embodiment, it is preferable that the water-based polymer material is a soluble polyester material;

in one embodiment, it is preferable that the base material is a polyol polymer material;

in one embodiment, it is preferable that the molar ratio of the alcoholic hydroxyl compound, the ester polymer and the chain extender is: 1: 1.5-4.5: 4-9;

in one embodiment, it is preferable that the alcohol compound is one or more of polyester polyol and polyolefin polyol, wherein the polyester polyol is polyethylene glycol adipate glycol, polybutylene adipate glycol, and polyhexamethylene glycol adipate glycol, and the polyolefin polyol is polyethylene glycol, polypropylene glycol, polycaprolactone diol, and polyglycerol, preferably polyethylene glycol adipate glycol and polyethylene glycol.

In one embodiment, the ester polymer is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), isophorone isocyanate (IPDI), preferably hexamethylene diisocyanate;

in one embodiment, it is preferred that the catalyst is one or more of organotin, among which dibutyltin dilaurate, stannous octoate, preferably stannous octoate;

in one embodiment, the chain extender is preferably a hydroxyl-containing polymer, wherein the hydroxyl-containing polymer is one or more of dimethylolpropionic acid, dimethylolbutyric acid, 1, 4-butanediol, trimethylolpropane, ethylenediamine, propylenediamine and diethylenetriamine, and dimethylolbutyric acid is preferred;

in one embodiment, the neutralizing agent is one or more of dimethylethanolamine, triethylamine, dimethylisopropanolamine, sodium hydroxide, potassium hydroxide and ammonia water, preferably ammonia water;

the preparation method comprises the following steps:

the method comprises the following steps: preparation of self-assembled micelles

Adding two alcoholic hydroxyl compounds (polyethylene glycol adipate, glycol and polyethylene glycol) into a reaction container according to a certain proportion, stirring and mixing for 30-60 min, then adding 10-12 g of hexamethylene diisocyanate to react for 30-60 min, and simultaneously adding 4-8 drops of catalyst; after the reaction is finished, adding 3-5 g of dimethylolbutyric acid for chain extension, and stirring for reaction for 2-3 h; adding 3-5 ml of ammonia water for neutralization after chain expansion, and stirring for reaction for 2-3 h; and finally, adding deionized water at a certain speed (5-30 rpm) for stirring and emulsifying. The reaction temperature for synthesizing the polyester is 75 ℃, a proper amount of acetone is required to be added during chain extension, neutralization and emulsification so as to reduce the viscosity, and the acetone in the emulsion is removed through reduced pressure distillation after the emulsification is finished.

Step two: preparation of composite hydrogel material

Adding the micelle into a polyhydroxy alcohol compound, wherein the content of the micelle is 5% -40%, and uniformly mixing at the temperature of 100-120 ℃ and under the pressure of 0.1-0.2 MPa.

Step three: shaping of artificial menisci

And (3) adding the composite hydrogel material prepared in the step two into automatic injection molding equipment, aligning a mold of the artificial meniscus with an injection port, wherein the injection pressure of the equipment is 30-50 MPa, the injection temperature is 70-100 ℃, and the single injection amount is 10-20 g.

Step four: augmentation of artificial menisci

And (3) placing the injection-molded artificial meniscus at the temperature of-20 to-30 ℃ for low-temperature crosslinking for 3-10 times.

The graph of the change of strain with the fatigue times in the fatigue test of the prepared artificial meniscus is shown in fig. 1, and the comparison graph of the stress-strain curves before and after the fatigue of the prepared artificial meniscus is shown in fig. 2.

Example 1:

the method comprises the following steps: preparation of self-assembled micelles

Adding polyethylene glycol adipate glycol and polyethylene glycol into a reaction container according to a certain ratio (3:1), stirring and mixing for 30min, then adding 10g hexamethylene diisocyanate to react for 3h, and simultaneously adding 4 drops of catalyst; after the reaction is finished, 2.97g of dimethylolbutyric acid is added for chain extension, and the mixture is stirred for reaction for 3 hours; adding 3ml of ammonia water for neutralization after the chain expansion, and stirring for reaction for 3 hours; finally, deionized water is added at the speed of 5rpm for stirring and emulsification, and the stirring speed is 1200 rpm. During chain extension, neutralization and emulsification, a proper amount of acetone is required to be added to reduce viscosity, and after emulsification is finished, the acetone in the emulsion is removed through reduced pressure distillation.

Step two: preparation of composite hydrogel material

Adding a soluble polyester material into a polyethylene glycol solution, wherein the content of the soluble polyester is 10%, and uniformly mixing at the temperature of 110 ℃ and the pressure of 0.15 MPa;

step three: artificial meniscus formation

Injecting the composite hydrogel material prepared in the step two into a meniscus shape, wherein the injection pressure is 35MPa, and the injection rate is 10 ml/s;

step four: artificial meniscus strengthening

And (3) placing the artificial meniscus plate in the step three at the temperature of-25 ℃, taking out the artificial meniscus plate after low-temperature crosslinking for 5 hours, and repeatedly operating for 4 times.

Example 2:

the method comprises the following steps: preparation of self-assembled micelles

Adding polyethylene glycol adipate glycol and polyethylene glycol into a reaction container according to a certain ratio (3:1), stirring and mixing for 30min, then adding 10g hexamethylene diisocyanate to react for 3h, and simultaneously adding 4 drops of catalyst; after the reaction is finished, 2.97g of dimethylolbutyric acid is added for chain extension, and the mixture is stirred for reaction for 3 hours; adding 3ml of ammonia water for neutralization after the chain expansion, and stirring for reaction for 3 hours; finally, deionized water is added at the speed of 5rpm for stirring and emulsification, and the stirring speed is 1200 rpm. During chain extension, neutralization and emulsification, a proper amount of acetone is required to be added to reduce viscosity, and after emulsification is finished, the acetone in the emulsion is removed through reduced pressure distillation.

Step two: preparation of composite hydrogel material

Adding a soluble polyester material into a polyethylene glycol solution, wherein the content of the soluble polyester is 15%, and uniformly mixing at the temperature of 110 ℃ and the pressure of 0.15 MPa;

step three: artificial meniscus formation

Injecting the composite hydrogel material prepared in the step two into a meniscus shape, wherein the injection pressure is 35MPa, and the injection rate is 10 ml/s;

step four: artificial meniscus strengthening

And (3) placing the artificial meniscus plate in the step three at-30 ℃, crosslinking for 4 hours at low temperature, taking out, and repeatedly operating for 6 times.

Example 3:

the method comprises the following steps: preparation of self-assembled micelles

Adding polyethylene glycol adipate glycol and polyethylene glycol into a reaction container according to a certain ratio (3:1), stirring and mixing for 30min, then adding 10g hexamethylene diisocyanate to react for 3h, and simultaneously adding 4 drops of catalyst; after the reaction is finished, 2.97g of dimethylolbutyric acid is added for chain extension, and the mixture is stirred for reaction for 3 hours; adding 3ml of ammonia water for neutralization after the chain expansion, and stirring for reaction for 3 hours; finally, deionized water is added at the speed of 5rpm for stirring and emulsification, and the stirring speed is 1200 rpm. During chain extension, neutralization and emulsification, a proper amount of acetone is required to be added to reduce viscosity, and after emulsification is finished, the acetone in the emulsion is removed through reduced pressure distillation.

Step two: preparation of composite hydrogel material

Adding soluble polyester material into polyethylene glycol solution, wherein the content of soluble polyester is 20%, mixing uniformly at 110 deg.C and 0.15MPa,

step three: artificial meniscus formation

Injecting the composite hydrogel material prepared in the step two into a meniscus shape, wherein the injection pressure is 35MPa, and the injection rate is 10 ml/s;

step four: artificial meniscus strengthening

Placing the artificial meniscus plate in the third step at-25 ℃, cross-linking at low temperature for 5h, taking out, and repeatedly operating for 8 times;

the friction coefficient of the prepared artificial meniscus was plotted as shown in fig. 3.

The self-assembled micelle, dispersion-enhanced wear-resistant fatigue-resistant bionic meniscus and the preparation method provided by the embodiment of the application are described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.

It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a commodity or system that includes the element.

It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.

The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.