CN112043873B - Organic polymer bridging-containing bio-inorganic composite structure material and preparation method and application thereof - Google Patents

Organic polymer bridging-containing bio-inorganic composite structure material and preparation method and application thereof Download PDF

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CN112043873B
CN112043873B CN202010973322.XA CN202010973322A CN112043873B CN 112043873 B CN112043873 B CN 112043873B CN 202010973322 A CN202010973322 A CN 202010973322A CN 112043873 B CN112043873 B CN 112043873B
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朱礼飞
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张腾飞
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Zhejiang Yongyu Biotechnology Co ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A61L27/105—Ceramics or glasses containing Al2O3
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/24—Collagen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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Abstract

The invention relates to an inorganic biological structure material containing organic polymer bridging, which structurally comprises a porous inorganic ceramic matrix, wherein the interior of the matrix contains inorganic oxide and built-in polymer crosslinked with the inorganic oxide, bridging polymer is filled between the inorganic ceramic matrixes, groups are distributed on the surface of the inorganic ceramic matrixes, and the bridging polymer is bonded through the groups; wherein the bridging polymer has an average molecular weight of 20-30% of the average molecular weight of the internal polymer. The inorganic biological structure material of the invention is widely applied to the fields of bone implantation and bone modification, and has the advantages of good biocompatibility, excellent strength and the like.

Description

Organic polymer bridging-containing bio-inorganic composite structure material and preparation method and application thereof
Technical Field
The invention relates to a polymer bridging-containing bio-inorganic composite structure material and a preparation method thereof, which are mainly applied to the fields of implanted medical machines and medical bionic materials, in particular to a material used for bone implantation and bone repair in vivo.
Background
The worldwide incidence and accidents of medical procedures, which is approaching 1000 thousands of times per year, have resulted in an increasing need for alternative materials for medical devices, particularly for man-made devices. Bone trauma is the most common creation in medical accidents. Most of the existing orthopedic surgeries require bone grafting, modification and filling. Among them, researches on bone filling and bone repair materials in human body cavities have also attracted attention of researchers. Such materials are generally composed of harmless components having the same or similar composition as human bone, do not produce a repulsive effect when implanted in the human body, are biocompatible, and maintain a certain strength for shape fixation after implantation.
US8147860B2 discloses a porous calcium phosphate implant composition of similar chemical composition to natural bone material, which composition contains, in addition to calcium phosphate, a foaming agent to promote the formation of interconnected pores and a cohesiveness agent to maintain the shape and hardness of the hardened composition. When added to the implant site, the calcium phosphate composition reconstitutes into bone. Methods of using the calcium phosphate compositions, for example, to repair or replace bone are also provided.
CN108273137A relates to a porous bionic skull repairing material which is a high polymer material, the structure of the material is consistent with that of a human skull, the surface layer is a compact layer, the inner layer is a loose layer, the compact layer is made of non-degradable or degradable high polymer material, and the compact layer on the surface layer is provided with blind holes with asymmetric structures; the loose layer has a three-dimensional porous structure, the surface of the porous structure is modified according to the needs, and a microenvironment and an antibacterial coating modified by bioactive substances can be attached to reduce infection.
The currently used bone implant materials include hydroxyapatite, calcium phosphate ceramics and other inorganic materials with good strength, but due to their strong compactness, the probability of the native tissues in the human body, such as blood, cells or drugs, penetrating through these bone regeneration materials is reduced, and the biocompatibility is reduced. In addition, the bone implant material matrix is composed of inorganic materials containing calcium, and the liquid generated in the human body can generate certain dissolving effect on the bone implant material, so that calcium ions can be precipitated. If too much calcium ions are extracted, the strength of the implanted bone material is affected. Therefore, there is a need for a bone regeneration material that is biocompatible and of suitable strength to address the deficiencies of the prior art. In addition to bio-inorganic ceramic materials, organic polymers are sometimes used as an additive component of bone defect repair materials, the main organic polymers of which include Polymethylmethacrylate (PMMA), polylactic acid (PLA) and polyglycolic acid PGA. Biocompatible bone implant materials are made by mixing PMMA and bioceramic particles, including polymethylmethacrylate, to make the PMMA-based composition partially absorbable, as described by Dalyn et al in U.S. patent No. 5800300B. However, the addition of organic polymers also has a problem of how to design the combination of organic materials and inorganic ceramic materials. The biocompatibility and the strength of the bond can also be adversely affected if significant interfacial effects are present.
Disclosure of Invention
The present invention includes an inorganic biostructural material comprising an organic polymeric bridge. The structure comprises a porous inorganic ceramic matrix and a built-in polymer which is crosslinked with inorganic oxide in the matrix, wherein bridging polymers are filled between the inorganic ceramic matrixes, groups are distributed on the surface of the inorganic ceramic matrix, and the bridging polymers are bonded through the groups; wherein the bridging polymer has an average molecular weight of at least 20-30% of the average molecular weight of the internal polymer.
The inorganic bioceramic matrix comprises inorganic salts such as calcium-containing phosphate and silicate.
The polymer includes a synthetic polymer or a natural polymer, such as collagen. A patient who has been introduced with a bone implant material can substantially or completely absorb some or all of the structures of the present invention through biochemical, biological and metabolic processes of the human body. In general, the structure of the porous material is interconnected, for example, to form an open-cell structure.
The pores may be macroporous or microporous, with diameters in the range of about 1-1000 microns.
In the porous inorganic ceramic matrix, the void volume is uniformly distributed in the volume of the inorganic ceramic matrix, accounting for 20 to 60%, preferably 30 to 50%, of the volume.
The composite material of the present invention can be applied to bone implantation or bone repair.
When the composite structure material is prepared, a porous inorganic ceramic matrix can be formed in advance, and then a bridging polymer is filled in the porous structure.
Preferably, the preparation method of the porous inorganic ceramic matrix comprises the steps of mixing inorganic oxide, a cross-linked polymer, a proper amount of pore-forming agent and ethanol to form a composite precursor, placing the mixture into a mold, placing the mold in a closed environment, heating to a sintering temperature to perform anaerobic sintering and sintering for a certain time, discharging gas at a constant temperature, and cooling to form the porous inorganic ceramic matrix containing the cross-linked built-in polymerized polymer.
After the porous ceramic matrix is prepared, the bridging polymer is filled into the porous ceramic matrix to form the biological inorganic composite structural material.
The specific filling method comprises the steps of firstly pressing the porous ceramic matrix into the porous inorganic ceramic matrix under the heating condition, and forming the inorganic composite structural material required by the invention through in-situ polymerization in a mold under a specific pressure and a specific temperature. Since the bioceramic matrix has sufficient strength and elasticity, it is desirable to use a compression molding process. Meanwhile, the biological composite material manufactured by the method has high toughness while ensuring the strength; and also has excellent biocompatibility.
The raw materials used in the preparation of the inorganic ceramic matrix comprise the following components in percentage by mass based on the total mass of the raw materials:
inorganic oxide(s): 10-58% SiO2、3-15％Na2O、15-29％CaO、1-8.5％P2O5、1-15％K2O、1-6％MgO2The balance being Al2O3。
The polymer which generates crosslinking with inorganic oxide in the porous ceramic matrix is at least more than one of 0.1-5% of polyglutamic acid, 0.1-2% of collagen, 0.1-5% of modified polylactic acid, 0.1-1% of inositol hexaphosphate and 0.1-10% of inositol phosphate based on the total mass of the raw materials.
The bridging polymer is 0.1-20% of carboxymethyl chitosan based on the total mass of the raw materials.
Specifically, the technical scheme provided by the invention comprises the following steps:
a bio-inorganic composite structural material containing organic polymer bridges structurally comprises a porous inorganic ceramic matrix, wherein an inorganic oxide and a built-in polymer crosslinked with the inorganic oxide are contained in the matrix, meanwhile, bridging polymers are filled between the inorganic ceramic matrix, groups are distributed on the surface of the inorganic ceramic matrix, and the bridging polymers are bonded through the groups; wherein the bridging polymer has an average molecular weight of 20-30% of the average molecular weight of the internal polymer.
Preferably, the inorganic bioceramic matrix comprises an inorganic salt such as a calcium-containing oxide or phosphate or silicate.
Preferably, the built-in polymer comprises a synthetic polymer or a natural polymer; preferably, one or more of polyglutamic acid, collagen, modified polylactic acid, inositol hexaphosphate, and inositol phosphate are included.
Preferably, the structures of the porous material are interconnected, e.g. may form an open cell structure.
Preferably, the pores may be macroporous or microporous, with diameters in the range of about 1-1000 microns.
Preferably, the porous inorganic ceramic matrix has a void volume uniformly distributed in the basic volume of the bioceramic, which is between 20 and 60%, preferably between 30 and 50%, of the volume.
The invention also includes a method for preparing the inorganic biological composite structure material containing the organic polymer bridging, which can form a porous inorganic ceramic matrix in advance and then fill bridging polymer in the pores of the inorganic ceramic matrix,
the preparation method of the porous inorganic ceramic matrix comprises the following steps: mixing inorganic oxide with a cross-linked polymer, a proper amount of pore-forming agent and alcohol to form an inorganic ceramic precursor, pouring the ceramic precursor into a mold, placing the mold in a closed environment, heating to a sintering temperature, carrying out oxygen-free sintering for a certain time, carrying out constant-temperature air release, and cooling to form a porous inorganic ceramic matrix containing the cross-linked built-in polymer;
after the porous inorganic ceramic matrix is prepared, the bridging polymer is filled into the porous inorganic ceramic matrix, and the filling method specifically comprises the following steps:
the bridging polymer is pressed into the porous inorganic ceramic matrix under the heating condition, and the final inorganic composite structure material is formed by in-situ polymerization in a mold under the specific pressure and the specific temperature.
Preferably, the raw materials used in the preparation of the porous inorganic ceramic matrix comprise, by mass fraction based on the total amount of the raw materials:
inorganic oxide(s): 10-58% SiO2、3-15％Na2O、15-29％CaO、1-8.5％P2O5、1-15％K2O、1-6％MgO2。
The built-in polymer which generates crosslinking with inorganic oxide in the porous ceramic matrix is one or more of 0.1-5% of polyglutamic acid, 0.1-2% of collagen, 0.1-5% of modified polylactic acid, 0.1-1% of inositol hexaphosphate and 0.1-10% of inositol phosphate based on the total mass of raw materials;
preferably, the bridging polymer is 0.1-20% of carboxymethyl chitosan by mass fraction.
The invention also comprises the application of the biological inorganic composite structure material containing the organic polymer bridging, and the composite material can be applied to the field of bone implantation or bone repair.
Preferably, the pore-forming agent is ammonia water or starch.
Preferably, the sintering temperature in the step 1) is 450-700 ℃, and the sintering time is 30-200 min.
Preferably, the specific pressure in the step 2) is 15-30MPa, and the specific temperature is 300-400 ℃.
The invention provides a porous inorganic composite structure material filled by bridging polymers, aiming at the problem of taking account of the strength and the biocompatibility of a bone implant material in the prior art.
Bridging polymers are filled in the substrate pore cavities of the inorganic ceramics, and the substrate which is originally cut and separated by the holes is connected, so that inorganic salts or inorganic oxides distributed in the substrate form a connected network framework through the bridging polymers, and the strength of the holes is reduced. Meanwhile, the bridging polymer is uniformly filled into the holes by in-situ polymerization under the pressing condition, even a primary and uniform protective film can be formed on the surface of the inorganic matrix, and the dissolution loss of inorganic salts or inorganic oxide substances, particularly calcium ions, in the composite material can be effectively prevented.
On the other hand, when the porous ceramic matrix is prepared, a crosslinked built-in polymer is introduced into an inorganic salt or an inorganic oxide to obtain groups containing the built-in polymer on the surface of the porous ceramic matrix, and in the subsequent process of filling the bridging polymer, the bridging polymer is bonded with the inorganic ceramic matrix through the groups.
Detailed Description
In the embodiment, the invention will more clearly explain the implementation manner of the technical scheme.
Particular embodiments include the preparation of a bio-inorganic composite structure material comprising organic polymer bridges.
Specifically, during preparation, a porous inorganic ceramic matrix may be formed in advance, and then the pores of the inorganic ceramic matrix may be filled with a bridging polymer. Comprises the following steps
1. Based on the total mass of the raw materials, selecting inorganic oxide comprising 10-58% of SiO2、3-15％Na2O、15-29％CaO、1-8.5％P2O5、1-15％K2O、1-6％MgO2The balance being Al2O3(ii) a Selecting built-in polymer which is one or more of 0.1-5% of polyglutamic acid, 0.1-2% of collagen, 0.1-5% of modified polylactic acid, 0.1-1% of inositol hexaphosphate and 0.1-10% of inositol phosphate based on the total mass fraction of raw materials; selecting ammonia water or starch as pore-forming agent; selecting the bridging polymer as 0.1-20% carboxymethyl chitosan based on the raw material weight;
2. stirring inorganic oxide, cross-linked polymer, a proper amount of pore-forming agent and alcohol by strong magnetic force to form an inorganic ceramic precursor, pouring the ceramic precursor into a mold with a certain shape, placing the mold in a closed environment, heating to the sintering temperature of 450 DEG and 700 ℃, carrying out anaerobic sintering and sintering for 30-200min, keeping the temperature for 5min for deflation, then cooling at the speed of 5 ℃/min to form a porous inorganic ceramic matrix containing the cross-linked built-in polymer, washing the porous inorganic ceramic matrix in absolute ethyl alcohol, and drying;
3. after the porous ceramic matrix is prepared, the bridging polymer is filled into the porous ceramic matrix, and the specific filling method comprises the following steps:
firstly, 0.1-20% of carboxymethyl chitosan based on the total mass fraction of raw materials is taken as a bridging polymer, the bridging polymer is pressed into a porous inorganic ceramic matrix under the heating condition, the temperature and the pressure are kept for 1-3h in a mold under the pressure of 15-30MPa and the temperature of 300-400 ℃, and the final inorganic composite structural material is formed through in-situ polymerization.
Wherein different embodiments select different component mass fractions. The following table
Components SiO2 Na2O CaO P2O5 K2O MgO2 Al2O3
Example 1 30.5 7.4 23.6 4.2 6.9 5.0 22.4
Example 2 21.4 5.2 16.5 2.9 4.8 3.5 45.7
Example 3 39.7 10.4 28.4 5.9 9.7 3.7 2.3
Example 4 38.7 9.4 16.7 5.3 8.8 3.8 17.3
Example 5 34.8 8.4 26.9 4.8 7.9 5.7 11.5
Example 6 36.3 8.8 28.1 5.0 8.2 6.0 7.7
Example 7 39.7 9.6 24.7 5.5 9.0 4.9 6.7
Furthermore, the invention designs a cross experiment by taking the types of built-in polymers, the types of pore-forming agents, the sintering temperature, the content of bridging polymers, the polymerization pressure and the polymerization temperature as variables, and partial embodiments adopting different process parameters are designed as follows.
Figure BDA0002684885620000051
In which mechanical properties with respect to strength were tested on the inorganic composite materials of selected examples.
Figure BDA0002684885620000052
Figure BDA0002684885620000061
Meanwhile, the present invention conducted biocompatibility test experiments on selected examples. Evaluation of the potential cytotoxicity in biomaterials and medical devices or leachable components using in vitro cytotoxicity assays is a common biocompatibility test method. Generally in vitro cell culture methods.
The specific test method comprises the following steps: the mouse osteoblast line MC3T3-E1 was sequentially inoculated onto a 24-well cell culture plate, the number of cells inoculated per well was 5X 100, the cells were cultured for 1, 3, and 5 days together with the bio-inorganic composite structural material prepared in examples 6 and 7, and a standard negative reference group and a bio-inorganic composite structural material experimental group were set, each group having 3 more wells at each time point. 1. The culture solution was collected 3 and 5 days later, and the supernatant was centrifuged and the cytotoxicity of the LDH activity evaluation material was measured according to the instructions of the Lactate Dehydrogenase (LDH) cytotoxicity assay kit.
And (3) test results: the results of measuring LDH activity of the cells incubated for 1, 3 and 5 days with the example groups are shown in the following table.
LDH Activity Culturing for 1 day Culturing for 3 days Culturing for 5 days
Negative reference group 193 310 415
Example 6 191 263 353
Example 7 194 269 361
LDH is a protein which is stably existed in cytoplasm under the normal condition, when the cell membrane is damaged, LDH in cytoplasm is released to the outside of cells, so that LDH activity in the culture medium is in direct proportion to the death number of the cells, and the OD value read by an enzyme-labeling instrument of the detection kit is in positive linear correlation with the LDH activity, namely the smaller the value is, the lower the toxicity of the sample is. The data in the table show that the activity of the example group is close to that of the negative reference group after 1 day of incubation, and no significant difference exists. The LDH activity of the co-cultured groups of the bio-inorganic composite structural material of the example group after 3 days and 5 days was significantly lower than that of the negative reference group. The test result shows that the biological inorganic composite structure material has no cytotoxicity, can improve the cell activity and reduce the release of LDH. Therefore, the product of the invention has better biocompatibility.
In conclusion, the inorganic composite material prepared by the embodiments of this section has excellent biocompatibility and ensures the strength required for implanting the material into the body.

Claims (13)

1. A method for preparing a bio-inorganic composite structural material comprising an organic polymer bridge, comprising the steps of:
during the preparation, a porous inorganic ceramic matrix is formed in advance, and then bridging polymers are filled in the holes of the inorganic ceramic matrix,
1) the preparation method of the porous inorganic ceramic matrix comprises the following steps: mixing and stirring inorganic oxide, a cross-linked polymer, a proper amount of pore-forming agent and alcohol to form an inorganic ceramic precursor, pouring the ceramic precursor into a mold, placing the mold in a closed environment, heating to a sintering temperature for oxygen-free sintering, sintering for a certain time, discharging gas at a constant temperature, and cooling to form a porous inorganic ceramic matrix containing the cross-linked built-in polymer;
2) after the porous inorganic ceramic matrix is prepared, the bridging polymer is filled into the porous inorganic ceramic matrix, and the filling method specifically comprises the following steps:
firstly, pressing bridging polymer into a porous inorganic ceramic matrix under the condition of heating, and forming a final inorganic composite structure material through in-situ polymerization in a mold under a specific pressure and a specific temperature;
the inorganic composite structure material structurally comprises a porous inorganic ceramic matrix, wherein the interior of the matrix contains inorganic oxide and a built-in polymer crosslinked with the inorganic oxide, a bridging polymer is filled between the inorganic ceramic matrixes, groups are distributed on the surface of the inorganic ceramic matrix, and the bridging polymer is bonded through the groups;
wherein the bridging polymer has an average molecular weight of 20-30% of the average molecular weight of the internal polymer.
2. A method of making a bio-inorganic composite structure comprising organic polymer bridges according to claim 1, said inorganic bio-ceramic matrix comprising calcium oxide or phosphate, silicate.
3. The method of claim 1, wherein the internal polymer comprises a synthetic polymer or a natural polymer.
4. The method for preparing a bio-inorganic composite structural material comprising organic polymer bridges according to claim 3, wherein the built-in polymer is one or more of polyglutamic acid, collagen and modified polylactic acid.
5. The method for preparing a composite structural material comprising an organic polymer bridge according to claim 1, wherein the porous inorganic ceramic matrix comprises the following raw materials in percentage by mass based on the total amount of the raw materials:
inorganic oxide(s): 10-58% SiO2、3-15％Na2O、15-29％CaO、1-8.5％P2O5、1-15％K2O、1-6％MgO2The balance being Al2O3。
6. The method for preparing a composite bio-inorganic structure material comprising an organic polymer bridge according to claim 1, wherein the built-in polymer is one or more of 0.1-5% of polyglutamic acid, 0.1-2% of collagen, and 0.1-5% of modified polylactic acid by mass based on the total amount of raw materials.
7. The method according to claim 1, wherein the porous inorganic ceramic matrix is interconnected in structure.
8. The method of claim 1, wherein the pores are macro-or micro-porous and have a diameter in the range of 1-1000 μm.
9. The method according to claim 1, wherein the porous inorganic ceramic matrix has a void volume uniformly distributed in the volume of the inorganic ceramic matrix, which is 20-60% of the volume.
10. The method for preparing a bio-inorganic composite structural material comprising an organic polymer bridge according to claim 1, wherein the bridging polymer is carboxymethyl chitosan in an amount of 0.1 to 20% by mass based on the total amount of the raw materials.
11. The method of claim 1, wherein the pore-forming agent is ammonia or starch.
12. The method as claimed in claim 1, wherein the sintering temperature in step 1) is 450-700 ℃.
13. The method for preparing the bio-inorganic composite structural material comprising organic polymer bridge as claimed in claim 1, wherein the specific pressure in step 2) is 15-30MPa, and the specific temperature is 300-400 ℃.
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