Polymer composite material as well as preparation method and application thereof

Abstract

The invention discloses a polymer composite material as well as a preparation method and application thereof, and belongs to the field of biomedical materials. The polymer composite material comprises a degradable polymer matrix and a functionalized barium sulfate filler uniformly dispersed in the polymer matrix, and the functionalized barium sulfate is of a core-shell structure and is formed by wrapping a porous barium sulfate core with a polypyrrole shell layer. The polymer composite material prepared by the invention has good biocompatibility and a good X-ray developing function, and can respond to an external field to realize time-space controllable degradation; meanwhile, the degradation product can regulate the immune microenvironment and promote tissue repair, and can be applied to the development of various tissue engineering scaffolds, patches and biological nails in the biomedical field; moreover, the preparation method of the polymer composite material is simple in process, easy to implement and beneficial to popularization and application.

Description

Technical Field

[0001] This invention belongs to the field of biomedical materials, specifically relating to a tissue repair material, and particularly to a polymer composite material, its preparation method, and its application. Background Technology

[0002] Tissue engineering and regenerative repair strategies typically involve providing suitable implant materials to regenerate or replace damaged or injured tissue during the process of promoting intra-tissue healing. Ideally, during tissue growth, the implant material should maintain its mechanical properties and structural integrity for a sufficiently long time before rapidly degrading, leaving ample space for newly formed tissue. Currently, most surgical implants are made of non-degradable metals or polymers. Treatments such as metal grafts, which are most commonly used in clinical practice, often require a secondary repositioning surgery, causing considerable inconvenience for both doctors and patients. Therefore, designing and developing biodegradable tissue-engineered repair materials is gradually becoming a more efficient approach.

[0003] Biodegradable polymers, such as polylactic acid (PLA), polycaprolactone (PCL), and polyglycolic acid (PGA), possess excellent processability, superior mechanical properties, and bioactivity. They also exhibit harmless degradation and elimination characteristics (primarily described as the breakdown of large molecular chains into smaller fragments, ultimately decomposing into simple, stable products like water and carbon dioxide), making them promising scaffold materials for tissue engineering. However, when used as tissue engineering repair materials, their degradation rate can only be pre-set and adjusted by the molecular weight and crystallinity of the polymer matrix, the proportion of polymer components, and the use of composite organic or inorganic fillers. There is currently no effective method to adjust the degradation rate in real-time based on bone healing after implantation. Complex physiological environments (such as blood flow velocity, aerobic or anaerobic microorganisms, and enzymes) make the degradation behavior of scaffolds difficult to predict after implantation. If the degradation rate of the material does not match the rate of bone formation, it often leads to chronic inflammation and the formation of cavities at the implantation site, hindering bone healing speed and affecting bone healing quality. Therefore, there is an urgent need to develop a controllable degradation implant material. Meanwhile, tissue repair and regeneration is a complex process that requires the activation of the immune system and the proliferation and migration of effective cells. The unique surface properties and degradation products of implanted materials can lead to different functional transformations in surrounding adherent cells, further affecting treatment outcomes. Summary of the Invention

[0004] To address the aforementioned problems, the present invention aims to provide a polymer composite material, its preparation, and its application. The polymer composite material exhibits external field responsiveness, accelerating polymer degradation under external field response, achieving controllable degradation rates both in vivo and in vitro. Simultaneously, its degradation products can induce macrophages to polarize in an anti-inflammatory direction, regulating the abnormal immune microenvironment surrounding the implant, thus better promoting tissue repair and regeneration. It possesses excellent anti-inflammatory and repair-promoting properties, more quickly and efficiently meeting the requirements of tissue engineering, and can be applied to the preparation of tissue engineering materials in the biomedical field. The preparation method of the present invention is simple and easy to implement.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following specific technical solutions:

[0006] In a first aspect, the present invention provides a polymer composite material comprising: a biodegradable polymer matrix and a functionalized barium sulfate filler uniformly dispersed in the polymer matrix, wherein the functionalized barium sulfate has a core-shell structure and is formed by a porous barium sulfate core encapsulated by a polypyrrole shell.

[0007] In some specific examples of the present invention, the polymer is selected from at least one of polylactic acid, polyglycolic acid, polycaprolactone, polylactic acid-glycolic acid copolymer, poly(L-lactide-co-ε-caprolactone), polyhydroxy fatty acid ester, polytrimethylene carbonate, amino acid-based poly(ester urea), poly(ester amide), poly(ester urea) and poly(ester carbamate).

[0008] In some specific embodiments of the present invention, the porous barium sulfate has a particle size of 100 nm to 5 μm.

[0009] In some specific embodiments of the present invention, the thickness of the polypyrrole shell is 3 to 30 nm.

[0010] In some specific embodiments of the present invention, the polymer composite material is prepared by the following method:

[0011] Functionalized barium sulfate is added to a polymer solution and magnetically stirred at 20–80°C to form a polymer-functionalized barium sulfate mixed solution. The polymer-functionalized barium sulfate mixed solution is then uniformly coated onto a clean glass plate using a coating applicator and allowed to dry completely to obtain a polymer composite material.

[0012] In some specific embodiments of the present invention, the polymer solution is formed by dissolving a polymer in an organic solvent, wherein the polymer is selected from at least one of polylactic acid, polyglycolic acid, polycaprolactone, polylactic acid-glycolic acid copolymer, poly(L-lactide-co-ε-caprolactone), polyhydroxy fatty acid ester, polytrimethylene carbonate, amino acid-based poly(ester urea), poly(ester amide), poly(ester urea), and poly(ester urethane); and the solvent is selected from at least one of dioxane, N,N-dimethylformamide, hexafluoroisopropanol, dichloromethane, and acetone.

[0013] In some specific embodiments of the present invention, the concentration of the polymer solution is 30-50 mg / mL, preferably 40 mg / mL.

[0014] In some specific examples of the present invention, the mass ratio of the functionalized barium sulfate to the polymer is 1:9 to 1:1.

[0015] In some specific embodiments of the present invention, the magnetic stirring time is 1 to 32 hours during the formation of the polymer-functionalized barium sulfate mixed solution.

[0016] In some specific embodiments of the present invention, the drying temperature is 30–80°C and the drying time is 24–72 h.

[0017] In some specific embodiments of the present invention, the functionalized barium sulfate is prepared by the following method: porous barium sulfate is mixed with anhydrous ethanol and ultrasonically dispersed for 1 to 24 hours to form a homogeneous liquid; ferric chloride hexahydrate solution and pyrrole solution are added to it under stirring, followed by hydrochloric acid; the mixture is magnetically stirred at room temperature for 1 to 24 hours, and then centrifuged and washed to obtain the product.

[0018] In some specific embodiments of the present invention, the concentration of the homogenizing solution is 10 to 100 mg / mL, preferably 20 mg / mL.

[0019] In some specific embodiments of the present invention, the ferric chloride hexahydrate solution is composed of ferric chloride hexahydrate and deionized water, with a concentration of 10-120 mg / mL; the pyrrole solution is composed of pyrrole monomer and deionized water, with a concentration of 1-30 mg / mL.

[0020] In some specific embodiments of the present invention, the molar ratio of the porous barium sulfate, ferric chloride hexahydrate, pyrrole monomer, and hydrochloric acid is 1:(2-6):(1-3):(0.1-1).

[0021] In some specific embodiments of the present invention, the hydrochloric acid is concentrated hydrochloric acid, for example, hydrochloric acid with a mass fraction of 37%.

[0022] In some specific embodiments of the present invention, the porous barium sulfate has a particle size of 100 nm to 5 μm.

[0023] In some specific embodiments of the present invention, the porous barium sulfate is prepared by the following method: barium chloride-aqueous dispersion is mixed with polyvinyl alcohol and then slowly added to an ammonium sulfate aqueous solution under magnetic stirring. After stirring evenly, the mixture is allowed to stand, centrifuged, and washed to obtain barium sulfate precipitate; then dried and sintered to obtain porous barium sulfate.

[0024] The barium chloride-aqueous dispersion was prepared by mixing deionized water and barium chloride evenly.

[0025] Preferably, the mass of the polyvinyl alcohol is 1wt%-10wt% of barium chloride, and the molar ratio of barium chloride to ammonium sulfate is 1:(1-2).

[0026] Preferably, in the preparation of the porous barium sulfate, the magnetic stirring time is 1-12 hours and the standing time is 1-48 hours.

[0027] Preferably, in the preparation of the porous barium sulfate, the drying temperature is 30-80°C and the drying time is 1-72 h.

[0028] Preferably, in the preparation of the porous barium sulfate, the sintering temperature is 500-800℃ and the sintering time is 1-24h.

[0029] In this invention, the room temperature is 15–30°C.

[0030] Testing revealed that the polymer composite material exhibits excellent mechanical, photothermal, X-ray imaging, and degradation properties. In particular, its in vitro degradation rate can be nearly 100 times faster than the bulk polymer degradation rate. Furthermore, by adjusting external field parameters, altering the characteristics of the functionalized barium sulfate filler, and controlling the ratio of functionalized barium sulfate to the polymer matrix, the in vitro and in vivo degradation rate of the composite material can be controlled. This allows for the matching of polymer composite materials with a balanced strength and degradation rate according to actual needs. Simultaneously, the degradation products of the polymer composite material can induce macrophages to polarize towards the M2 anti-inflammatory direction. Therefore, as degradation occurs, the released degradation products, upon contact with surrounding cells, especially macrophages, can intervene and regulate the macrophage polarization phenotype transformation, inducing the production of more anti-inflammatory factors, creating an immune microenvironment conducive to tissue regeneration and healing, and promoting the secretion of anti-inflammatory and repair factors. It possesses good biocompatibility and tissue repair-promoting properties. When implanted as an implant material, the polymer composite material can simultaneously achieve controlled degradation and immune microenvironment regulation, enabling highly efficient tissue engineering treatment and significantly improving patient recovery and quality of life.

[0031] Compared with the prior art, the present invention has at least the following beneficial technical effects:

[0032] (1) The polymer composite material of the present invention possesses excellent mechanical properties, photothermal properties, X-ray imaging properties, and good biocompatibility. It also exhibits controllable in vitro and in vivo degradation, and the degradation products demonstrate macrophage polarization responsiveness and promote macrophage participation in immune microenvironment regulation, exhibiting good anti-inflammatory and repair-promoting properties, thus enhancing tissue remodeling, integration, and regeneration. Unlike existing technologies where the degradation rate after material implantation cannot be adjusted according to actual physiological conditions, the polymer composite material of the present invention, through external field-controlled degradation, has the advantage of spatiotemporal dynamic regulation, enabling "on / off" degradation that can be adjusted to match the degradation rate with tissue regeneration. This is extremely important for tissue defect repair. Moreover, the external field, especially the near-infrared light field, is not limited by application scenarios, has strong penetration depth, and few side effects, providing precise treatment for tissue repair. X-ray visualization and controllable degradation rate also allow for personalized treatment plans.

[0033] (2) The preparation method of the present invention is simple and easy to implement. Using the method of the present invention, polymer composite materials with controllable degradation rate and anti-inflammatory and repair-promoting properties can be obtained. While ensuring that the degradation rate matches the tissue regeneration, the immune microenvironment is regulated to enhance the active remodeling, integration and regeneration of tissues. It can be used to construct excellent tissue engineering implant materials. Attached Figure Description

[0034] Figure 1 The X-ray diffraction patterns are those of the product PBA obtained in Comparative Example 1, the product PLA obtained in Comparative Example 2, the product PBP3 obtained in Example 1, the product PBP1 obtained in Example 2, and the product PBP2 obtained in Example 3.

[0035] Figure 2 The graphs are obtained by FTIR analysis of the product BA from step ① in Example 1, the product Bpy-4 from step ② in Example 1, the product Bpy-1 from step ② in Example 2, and the product Bpy-8 from step ② in Example 3.

[0036] Figure 3A and Figure 3B The image shows the results of scanning electron microscopy and transmission electron microscopy analysis of the product BA obtained in step ① of Example 1.

[0037] Figure 4 This is a transmission electron microscopy (TEM) analysis result of the product Bpy-4 obtained in step ② of Example 1.

[0038] Figure 5A This is a scanning electron microscope image of PBP3, the product obtained in Example 1.

[0039] Figure 5B This is a scanning electron microscope image of PBP1, the product obtained in Example 2.

[0040] Figure 5C This is a scanning electron microscope image of PBP2, the product obtained in Example 3.

[0041] Figure 6 This is a comparison chart of the mechanical property test results of PBP3 obtained in Example 1, PBA obtained in Comparative Example 1, and pure PLA obtained in Comparative Example 2.

[0042] Figure 7 The graphs show the real-time infrared heating curves of the polymer composite materials prepared in Examples 1-3, the product PBA obtained in Comparative Example 1, and the pure PLA product in Comparative Example 2 under infrared laser irradiation.

[0043] Figure 8 These are comparative images of in vitro CT imaging analysis of the polymer composite materials prepared in Examples 1, 4, and 5, and pure PLA.

[0044] Figure 9 These are in vitro photocontrolled degradation results of the polymer composite materials prepared in Examples 1, 4 and 5, as well as the product PBA obtained in Comparative Example 1 and the product pure PLA obtained in Comparative Example 2.

[0045] Figure 10 The cell viability results were obtained by CCK-8 assay in the presence of the degradation product Bpy-4.

[0046] Figure 11A A comparative figure showing the results of in vitro immunofluorescence staining of bone marrow-derived macrophages (BMDM) co-cultured with different degradation products.

[0047] Figure 11B Is it using ImageJ? Figure 11A A comparison of the results of quantitative analysis of the mean fluorescence intensity of bone marrow-derived macrophages (BMDM).

[0048] Figure 12 These are H&E staining images of various organs and tissues of mice 2 weeks after the polymer composite material prepared in Example 1 of this invention was implanted subcutaneously. Detailed Implementation

[0049] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and do not represent or limit the scope of protection of the present invention; the scope of protection of the present invention is defined by the claims.

[0050] Unless otherwise specified, all reagents or instruments used in the following examples and comparative examples are commercially available products.

[0051] I. Preparation Method

[0052] Example 1

[0053] ① Prepare a barium chloride-water dispersion by stirring 50 mL of deionized water and 5.2 g of barium chloride evenly. Add 0.156 g of polyvinyl alcohol (type 1788, molecular weight 130.14200) to the dispersion and slowly add it to 25 mL of aqueous solution containing 3.3 g of ammonium sulfate under magnetic stirring. Stir evenly for 4 h and let stand for 24 h. Centrifuge at 11000 r / min for 15 min. Wash the separated solid phase with deionized water and centrifuge. Repeat several times. Dry at 60℃ for 48 h and sinter at 600℃ for 4 h to obtain product BA for later use.

[0054] ② Mix 0.6g of the product BA obtained in step ① with 30mL of anhydrous ethanol and sonicate for 8h to form a homogeneous solution with a concentration of 20mg / mL. Under continuous stirring, add 60mL of ferric chloride hexahydrate solution (containing 2.88g of ferric chloride hexahydrate and 60mL of deionized water) and 60mL of pyrrole solution (containing 336μL of pyrrole monomer and 60mL of deionized water). Use 50μL of concentrated hydrochloric acid (mass fraction of 37%) as an oxidation accelerator. After reacting for 4h under full magnetic stirring at room temperature (26℃), centrifuge at 11000r / min for 15min and wash the obtained solid phase with deionized water to obtain product Bpy-4 for later use.

[0055] ③ Mix 0.057g of the product Bpy-4 obtained in step ② into a polylactic acid-dioxane solution with a concentration of 40mg / mL (composed of 0.4g polylactic acid and 10mL dioxane solution), and stir magnetically at 40℃ for 24h to form a polymer-functionalized barium sulfate mixed solution; use a coating applicator (height set to 0.05mm) to evenly coat the polymer-functionalized barium sulfate mixed solution onto a clean glass plate, and dry it thoroughly in an oven at 37℃ for 48h to evaporate the solvent, to obtain the target product PBP3.

[0056] Example 2

[0057] ① Prepare a barium chloride-water dispersion by stirring 50 mL of deionized water and 5.2 g of barium chloride evenly. Add 0.156 g of polyvinyl alcohol (type 1788, molecular weight 130.14200) to the dispersion and slowly add it to 25 mL of aqueous solution containing 3.3 g of ammonium sulfate under magnetic stirring. Stir evenly for 4 h and let stand for 24 h. Centrifuge at 11000 r / min for 15 min. Wash the separated solid phase with deionized water and centrifuge. Repeat several times. Dry at 60℃ for 48 h and sinter at 600℃ for 4 h to obtain product BA for later use.

[0058] ② Mix 0.6g of the product BA obtained in step ① with 30mL of anhydrous ethanol and sonicate for 8h to form a homogeneous solution with a concentration of 20mg / mL. Under continuous stirring, add 60mL of ferric chloride hexahydrate solution (containing 2.88g of ferric chloride hexahydrate and 60mL of deionized water) and 60mL of pyrrole solution (containing 336μL of pyrrole monomer and 60mL of deionized water). Use 50μL of concentrated hydrochloric acid (mass fraction of 37%) as an oxidation accelerator. After reacting for 1h under full magnetic stirring at room temperature (26℃), centrifuge at 11000r / min for 15min and wash the obtained solid phase with deionized water to obtain product Bpy-1 for later use.

[0059] ③ Mix 0.057g of the product Bpy-1 obtained in step ② into a polylactic acid-dioxane solution with a concentration of 40mg / mL (composed of 0.4g polylactic acid and 10mL dioxane solution), and stir magnetically at 40℃ for 24h to form a polymer-functionalized barium sulfate mixed solution; use a coating applicator (height set to 0.05mm) to evenly coat the polymer-functionalized barium sulfate mixed solution onto a clean glass plate, and dry it thoroughly in an oven at 37℃ for 48h to evaporate the solvent, to obtain the target product PBP1.

[0060] Example 3

[0061] ① Prepare a barium chloride-water dispersion by stirring 50 mL of deionized water and 5.2 g of barium chloride evenly. Add 0.156 g of polyvinyl alcohol (type 1788, molecular weight 130.14200) to the dispersion and slowly add it to 25 mL of aqueous solution containing 3.3 g of ammonium sulfate under magnetic stirring. Stir evenly for 4 h and let stand for 24 h. Centrifuge at 11000 r / min for 15 min. Wash the separated solid phase with deionized water and centrifuge. Repeat several times. Dry at 60℃ for 48 h and sinter at 600℃ for 8 h to obtain product BA for later use.

[0062] ② Mix 0.6g of the product BA obtained in step ① with 30mL of anhydrous ethanol and sonicate for 8h to form a homogeneous solution with a concentration of 20mg / mL. Under continuous stirring, add 60mL of ferric chloride hexahydrate solution (containing 2.88g of ferric chloride hexahydrate and 60mL of deionized water) and 60mL of pyrrole solution (containing 336μL of pyrrole monomer and 60mL of deionized water). Use 50μL of concentrated hydrochloric acid (mass fraction of 37%) as an oxidation accelerator. After reacting for 8h under full magnetic stirring at room temperature (26℃), centrifuge at 11000r / min for 15min and wash the obtained solid phase with deionized water to obtain product Bpy-8 for later use.

[0063] ③ Mix 0.057g of the product Bpy-8 obtained in step ② into a polylactic acid-dioxane solution with a concentration of 40mg / mL (composed of 0.4g polylactic acid and 10mL dioxane solution), and stir magnetically at 40℃ for 24h to form a polymer-functionalized barium sulfate mixed solution; use a coating applicator (height set to 0.05mm) to evenly coat the polymer-functionalized barium sulfate mixed solution onto a clean glass plate, and dry it thoroughly in an oven at 37℃ for 48h to evaporate the solvent, to obtain the target product PBP2.

[0064] Example 4

[0065] ① Prepare a barium chloride-water dispersion by stirring 50 mL of deionized water and 5.2 g of barium chloride evenly. Add 0.156 g of polyvinyl alcohol (type 1788, molecular weight 130.14200) to the dispersion and slowly add it to 25 mL of aqueous solution containing 3.3 g of ammonium sulfate under magnetic stirring. Stir evenly for 4 h and let stand for 24 h. Centrifuge at 11000 r / min for 15 min. Wash the separated solid phase with deionized water and centrifuge. Repeat several times. Dry at 60℃ for 48 h and sinter at 600℃ for 4 h to obtain product BA for later use.

[0066] ② Mix 0.6g of the product BA obtained in step ① with 30mL of anhydrous ethanol and sonicate for 8h to form a homogeneous solution with a concentration of 20mg / mL. Under continuous stirring, add 60mL of ferric chloride hexahydrate solution (containing 2.88g of ferric chloride hexahydrate and 60mL of deionized water) and 60mL of pyrrole solution (containing 336μL of pyrrole monomer and 60mL of deionized water). Use 50μL of concentrated hydrochloric acid (mass fraction of 37%) as an oxidation accelerator. After reacting for 4h under full magnetic stirring at room temperature (26℃), centrifuge at 11000r / min for 15min and wash the obtained solid phase with deionized water to obtain product Bpy-4 for later use.

[0067] ③ Mix 0.133g of the product Bpy-4 obtained in step ② into a polylactic acid-dioxane solution with a concentration of 40mg / mL (composed of 0.4g polylactic acid and 10mL dioxane solution), and stir magnetically at 40℃ for 24h to form a polymer-functionalized barium sulfate mixed solution; use a coating applicator (height set to 0.05mm) to evenly coat the polymer-functionalized barium sulfate mixed solution onto a clean glass plate, and dry it thoroughly in an oven at 37℃ for 48h to evaporate the solvent, to obtain the target product polymer composite material PBPy25.

[0068] Example 5

[0069] ① Prepare a barium chloride-water dispersion by stirring 50 mL of deionized water and 5.2 g of barium chloride evenly. Add 0.156 g of polyvinyl alcohol (type 1788, molecular weight 130.14200) to the dispersion and slowly add it to 25 mL of aqueous solution containing 3.3 g of ammonium sulfate under magnetic stirring. Stir evenly for 4 h and let stand for 24 h. Centrifuge at 11000 r / min for 15 min. Wash the separated solid phase with deionized water and centrifuge. Repeat several times. Dry at 60℃ for 48 h and sinter at 600℃ for 8 h to obtain product BA for later use.

[0070] ② 0.6 g of the product BA obtained in step ① was mixed with 30 mL of anhydrous ethanol and sonicated for 8 h to form a homogeneous solution with a concentration of 20 mg / mL. Under continuous stirring, 60 mL of ferric chloride hexahydrate solution (containing 2.88 g of ferric chloride hexahydrate and 60 mL of deionized water) and 60 mL of pyrrole solution (containing 336 μL of pyrrole monomer and 60 mL of deionized water) were added. 50 μL of concentrated hydrochloric acid (mass fraction of 37%) was used as an oxidation accelerator. After reacting for 4 h under full magnetic stirring at room temperature (26 °C), the mixture was centrifuged at 11000 r / min for 15 min and the resulting solid phase was washed with deionized water to obtain product Bpy-4 for later use.

[0071] ③ Mix 0.4g of the product Bpy-4 obtained in step ② into a polylactic acid-dioxane solution with a concentration of 40mg / mL (composed of 0.4g polylactic acid and 10mL dioxane solution), and stir magnetically at 40℃ for 24h to form a polymer-functionalized barium sulfate mixed solution; use a coating applicator (height set to 0.05mm) to evenly coat the polymer-functionalized barium sulfate mixed solution onto a clean glass plate, and dry it thoroughly in an oven at 37℃ for 48h to evaporate the solvent, to obtain the target product polymer composite material PBPy50.

[0072] Preparation of PBA in Comparative Example 1

[0073] ① Prepare a barium chloride-water dispersion by stirring 50 mL of deionized water and 5.2 g of barium chloride evenly. Add 0.156 g of polyvinyl alcohol (type 1788, molecular weight 130.14200) to the dispersion and slowly add it to 25 mL of aqueous solution containing 3.3 g of ammonium sulfate under magnetic stirring. Stir evenly for 4 h and let stand for 24 h. Centrifuge at 11000 r / min for 15 min. Wash the separated solid phase with deionized water and centrifuge. Repeat several times. Dry at 60℃ for 48 h and sinter at 600℃ for 4 h to obtain product BA for later use.

[0074] ② Mix 0.4g of the product BA obtained in step ① into a polylactic acid-dioxane solution with a concentration of 40mg / mL (composed of 0.4g of polylactic acid and 10mL of dioxane solution), and stir magnetically at 40℃ for 24h to form a polymer-porous barium sulfate mixed solution; use a coating applicator (height set to 0.05mm) to evenly coat the polymer-porous barium sulfate mixed solution onto a clean glass plate, and dry it thoroughly in an oven at 37℃ for 48h to evaporate the solvent, thereby obtaining the composite material PBA of the product polymer and porous barium sulfate.

[0075] Preparation of Comparative Example 2 PLA

[0076] A 40 mg / mL polylactic acid-dioxane solution (composed of 0.4 g polylactic acid and 10 mL dioxane solution) was magnetically stirred at 40 °C for 24 h. Then, the polylactic acid-dioxane solution was evenly coated onto a clean glass plate using a coating applicator (height set to 0.05 mm). The plate was then thoroughly dried in a 37 °C oven for 48 h to evaporate the solvent, yielding the product, pure PLA.

[0077] II. Identification and Characterization

[0078] 2.1 Composition Identification

[0079] X-ray diffraction analysis was performed on the products PBA obtained in Comparative Example 1, PLA obtained in Comparative Example 2, PBP3 obtained in Example 1, PBP1 obtained in Example 2, and PBP2 obtained in Example 3, respectively. The results are as follows: Figure 1 As shown.

[0080] Figure 1 In the XRD patterns of PBA obtained in Comparative Example 1, PBP3 obtained in Example 1, PBP1 obtained in Example 2, and PBP3 obtained in Example 3, characteristic diffraction peaks of PLA and barium sulfate were observed simultaneously. The two main diffraction peaks at approximately 16.8° and 19.2° were attributed to PLA. Furthermore, comparing the XRD patterns of PBP3, PBP1, and PBP2 obtained by adding functionalized barium sulfate in each example with the XRD pattern of PBA obtained by adding pure barium sulfate in Comparative Example 1, it was found that the relative intensity of the characteristic diffraction peak of PLA in the XRD patterns of the products obtained in each example was higher and narrower, indicating that the crystallinity of polylactic acid in the products obtained in each example was improved.

[0081] Infrared spectroscopy characterization was performed on product BA from step ① of Comparative Example 1, product Bpy-4 from step ② of Example 1, product Bpy-1 from step ② of Example 2, and product Bpy-8 from step ② of Example 3. The results are as follows: Figure 2 As shown.

[0082] Figure 2In the IR spectrum of product BA from step ① of Comparative Example 1, typical infrared characteristic spectra of barium sulfate were observed. In the IR spectra of product Bpy-4 from step ② of Example 1, product Bpy-1 from step ② of Example 2, and product Bpy-8 from step ② of Example 3, in addition to the infrared characteristic peaks of barium sulfate, a peak located at 910 cm⁻¹ was also observed. -1 1339cm -1 1566cm -1 Infrared characteristic peaks belonging to polypyrrole=CN, CN and C=C.

[0083] Combination Figure 1 and Figure 2 It can be seen that the product obtained in step ① is barium sulfate, the product obtained in step ② is polypyrrole-modified barium sulfate, and the product PBP3 obtained in Example 1, the product PBP1 obtained in Example 2, and the product PBP2 obtained in Example 3 are composite materials of barium sulfate modified with polypyrrole to different degrees and polylactic acid.

[0084] 2.2 Morphological Analysis

[0085] The product BA obtained in step ① of Example 1 was analyzed by scanning electron microscopy and transmission electron microscopy, and the results are as follows: Figure 3A and Figure 3B As shown. Figure 3A Scanning electron microscope images and Figure 3B The transmission electron microscopy images all show that the barium sulfate surface obtained in step ① has a clear porous structure. Figure 3A The scanning electron microscope (SEM) images also show that the barium sulfate obtained in step ① has a particle size of 100 nm to 5 μm. Therefore, it can be determined that the product BA obtained in step ① is porous barium sulfate.

[0086] Transmission electron microscopy analysis was performed on the product Bpy-4 obtained in step ② of Example 1, and the results are as follows: Figure 4 As shown. Figure 4 The transmission electron microscope image shows that the product Bpy-4 obtained in step ② of Example 1 has a significant core-shell structure. The shell has polymer lattice fringes, and the core structure also has obvious lattice fringes. This means that the barium sulfate in Bpy-4 is completely and uniformly wrapped by the polypyrrole shell, and the thickness of the polypyrrole shell is 9.2 to 25.4 nm.

[0087] Similarly, transmission electron microscopy (TEM) analysis was performed on product Bpy-1 obtained in step ② of Example 2 and product Bpy-8 obtained in step ② of Example 3. Likewise, these products all exhibit a significant core-shell structure, with polymer lattice fringes in the shell and distinct lattice fringes in the core structure. Barium sulfate is completely and uniformly encapsulated by the polypyrrole shell. The thicknesses of the polypyrrole shell are 3.4–10.6 nm and 3.2–3.8 nm, respectively.

[0088] The product PBP3 obtained in Example 1 was analyzed by scanning electron microscopy, and the results are as follows: Figure 5A As shown. Figure 5A SEM images show that in the product PBP3 obtained in Example 1, functionalized barium sulfate (circled in yellow in the reference image) is tightly embedded in the polylactic acid matrix, uniformly dispersed, and exhibits good dispersibility. The composite material as a whole has a significant polylactic acid dendritic crystalline morphology. Simultaneously, the products PBP1 obtained in Example 2 and PBP2 obtained in Example 3 were also analyzed by scanning electron microscopy, as shown... Figure 5B and Figure 5C As shown, it can also be seen that the functionalized barium sulfate in the product (the position circled in yellow in the figure) is tightly embedded in the polylactic acid matrix, uniformly dispersed, and has good dispersibility. The composite material as a whole has a significant polylactic acid dendritic crystal morphology.

[0089] The surface micromorphology of PBP3 obtained in Example 1, PBP1 obtained in Example 2, and PBP2 obtained in Example 3 were analyzed by AFM. The results showed that the products obtained in each example had rough surfaces with a surface roughness range of 100 to 800 nm, and the surface roughness of PBP3 was greater than that of PBP1 and PBP2.

[0090] 2.3 Mechanical property testing

[0091] Mechanical properties were tested on the product PBP3 obtained in Example 1, the product PBA obtained in Comparative Example 1, and the product PLA obtained in Comparative Example 2. In short, tensile tests were performed on each product using an electronic universal testing machine at a test speed of 5 mm / min. A 20 mm × 10 mm specimen was held in a pneumatic clamp with an effective loading length ≥ 10 mm. The electronic universal testing machine was started, the tensile test was conducted, and the data were recorded. The mechanical property test results are compared to... Figure 6 As shown, compared to the tensile strength of 9.6 MPa for PBA obtained in Comparative Example 1 and the tensile strength of 16.1 MPa for pure PLA in Comparative Example 2, the tensile strength of PBP3 obtained in Example 1 is significantly enhanced (26.0 MPa), indicating that it has significantly enhanced mechanical properties. There were no significant differences in the test results between samples tested repeatedly under the same experimental conditions.

[0092] 2.4 Photothermal performance test

[0093] The photothermal effects of products Bpy-4 obtained in step ② of Example 1, Bpy-1 obtained in step ② of Example 2, and Bpy-8 obtained in step ② of Example 3 were analyzed. In short, each product was irradiated with a 1W 808nm near-infrared laser, using water as a dispersant at a concentration of 200μg / mL. Pure water was used as a control, and the temperature was measured. The results showed that after irradiation with an 808nm near-infrared laser for 20 minutes, the products obtained in step ② of each example showed a significant temperature rise, which was 10–30°C higher than that of pure water. This indicates that the products obtained in step ② of each example possess excellent photothermal properties and are functionalized barium sulfate.

[0094] The photothermal effect of product PBP3 obtained in Example 1, product PBP1 obtained in Example 2, and product PBP2 obtained in Example 3 was analyzed. In short, each product was irradiated with a 1W 808nm infrared laser while wetted in water. The real-time infrared temperature rise curves under infrared laser irradiation are shown below. Figure 7 As shown, after irradiation with an 808nm near-infrared laser for 5 minutes, compared to the similar temperature rise of 3.7℃ for product PBA obtained in Comparative Example 1 and product PLA obtained in Comparative Example 2, product PBP3 obtained in Example 1 achieved a temperature rise of 31.5℃, product PBP1 obtained in Example 2 achieved a temperature rise of 20.1℃, and product PBP2 obtained in Example 3 achieved a temperature rise of 25.5℃. This indicates that products PBP3 obtained in Example 1, PBP1 obtained in Example 2, and PBP2 obtained in Example 3 possess excellent photothermal properties.

[0095] 2.5 Development Performance Test

[0096] The products PBP3 obtained in Example 1, PBPy25 obtained in Example 4, and PBPy50 obtained in Example 5 were subjected to in vitro CT imaging analysis, with PLA obtained in Comparative Example 2 used as a control. In short, each product was cut into a pentagram shape and placed in a 1.5 mL EP tube, then scanned using a high-resolution micro-CT scanner. The CT scan results are as follows: Figure 8 As shown. It can be seen that under X-ray irradiation, PLA appears transparent with almost no visible edge shape; while the pentagram shape of PBP3, PBPy25, and PBPy50 is clearly visible with obvious grayscale and has developing effect, especially PBPy50, which has the best developing effect.

[0097] 2.6 In vitro photocontrolled degradation test

[0098] The products PBP3 (also known as PBPy12.5) obtained in Example 1, PBPy25 obtained in Example 4, and PBPy50 obtained in Example 5 were subjected to in vitro photocontrolled degradation analysis. Meanwhile, the products PBA obtained in Comparative Example 1 and PLA obtained in Comparative Example 2 were used as controls. In short, the target analytes were completely immersed in glass petri dishes containing 30 mL of Na₂CO₃ solution at pH 8.5. The dishes were then irradiated with a 1 W 808 nm infrared laser at 37°C for 7 days. The appearance and mass changes of each product before and after irradiation were photographed and recorded. The degradation results are as follows: Figure 9 As shown, under the same conditions, pure PLA and PBA showed no obvious damage to their appearance. In contrast, PBPy12.5, PBPy25, and PBPy50 exhibited visible degradation damage. Specifically, pure PLA and PBA had degradation losses of 0.24% and 5.96%, respectively. In comparison, PBPy12.5 experienced a degradation loss of 16.16% after near-infrared light irradiation, with the degradation rate accelerating to 67 times that of PLA and 5 times that of PBA. PBPy25 experienced a degradation loss of 23.25% after near-infrared light irradiation, with the degradation rate accelerating to 97 times that of PLA and 4 times that of PBA. PBPy50 experienced a degradation loss of 20.69% after near-infrared light irradiation, with the degradation rate accelerating to 86 times that of PLA and 3.5 times that of PBA. Therefore, the degradation of the polymer composite materials prepared by this invention exhibits light field response characteristics. Furthermore, by adjusting the preparation parameters of the method of this invention, polymer composite materials with different in vitro degradation rates can be obtained.

[0099] The degradation product of Comparative Example 1 was BA, and the degradation products of each example were functionalized barium sulfate (the degradation product of Example 1 was BPy-4, the degradation product of Example 2 was BPy-1, the degradation product of Example 3 was BPy-8, the degradation product of Example 4 was BPy-4, and the degradation product of Example 5 was BPy-4).

[0100] 2.7 In vitro biocompatibility test

[0101] The biocompatibility of the degradation product BPy-4 from Example 1 was tested, as follows:

[0102] Macrophage BMDM was prepared at a rate of 2×10 5Cells were seeded at a density of 10 cells / well in 24-well plates, with 1 mL of α-medium added to each well. After culturing at 37°C and 5% CO2 for 24 hours, macrophages (BMDM) were co-cultured with 1 mL of α-medium containing 30 μg / mL BPy-4 and normal α-medium, respectively, designated as the BPy-4 and Blank control groups. At 24 h, 48 h, and 72 h, the medium was removed, and 50 μL of CCK-8 solution (Dojindo) and 500 μL of α-medium (Gibco) were added to each well. After culturing in the dark at 37°C for 2 hours, 120 μL of the solution from each well was transferred to another 96-well plate, and the absorbance at 450 nm was measured using a microplate reader (Multiskanmk 3, Thermo Fisher Scientific). The OD value was used to assess cell viability. Results are as follows: Figure 10 As shown, the degradation product BPy-4 from Example 1, at a high concentration of 30 μg / mL, showed a significant increase in OD value at 24 h compared to the blank control group (Blank), no significant difference at 48 h, and a significant increase again at 72 h. This indicates that macrophages exhibited good adhesion and proliferation properties in the BPy-4 co-culture environment, demonstrating that functionalized barium sulfate BPy-4 has good biocompatibility.

[0103] 2.8 In vitro anti-inflammatory analysis

[0104] The degradation products of each example and Comparative Example 1 were analyzed for their in vitro anti-inflammatory effects using in vitro immunofluorescence staining. Specifically, the degradation products were sterilized by soaking in 75% alcohol for 24 hours. A 1×1 cm... 2 Quartz slides were placed at the bottom of a 24-well plate and sterilized with ample ultraviolet light in preparation for cell seeding. Bone marrow-derived macrophages (BMDM) were then seeded at 1 × 10⁻⁶ cells / well. 5Cells / well were seeded onto quartz plates, and 1 mL of α-medium containing different degradation products at a concentration of 3 mg / mL was added. The plates were co-cultured at 37°C in a 5% CO2 atmosphere. After 3 days, the quartz plates were transferred to new 24-well plates and then immersed in 4% paraformaldehyde for fixation at room temperature for 15 minutes. The samples were washed with PBS and infiltrated with 0.4% Triton solution for 15 minutes, followed by blocking with PBS containing 2% fetal bovine serum (Cellmax) and 2% bovine serum albumin (Sigma) for 1 hour. Then, the plates were incubated with the first antibody iNOS, CD206 (Abcam, 1:500 rabbit anti-mouse iNOS, 1:800 mouse anti-mouse CD206, PBS containing 2% bovine serum albumin) and the second antibody (Abcam, 1:250 donkey anti-rabbit Alexa Fluor-555, 1:500 goat anti-mouse Alexa Fluor-488, PBS containing 2% bovine serum albumin) in the dark at room temperature with shaking for 1 hour. Subsequently, the samples were stained with DAPI (Sigma) in the dark for 15 minutes, rinsed with PBS solution, and sealed with anti-fading culture medium. Images of all groups were acquired using a laser confocal fluorescence microscope with the same exposure time. The staining results are as follows: Figure 11A As shown. ImageJ was used to quantitatively analyze the mean fluorescence intensity of BMDM cells. The analysis results are as follows. Figure 11B As shown.

[0105] Depend on Figure 11A and Figure 11B It is evident that, compared to the degradation product BA in Comparative Example 1, BPy-4 under the same culture conditions can induce more macrophages to polarize towards the anti-inflammatory M2 phenotype, indicating that BPy-4, as a degradation product, has an anti-inflammatory induction effect; compared to the degradation product B in Comparative Example 1, BPy-1 under the same culture conditions can induce more macrophages to polarize towards the anti-inflammatory M2 phenotype, indicating that BPy-1, as a degradation product, has an anti-inflammatory induction effect; compared to the degradation product B in Comparative Example 1, BPy-8 under the same culture conditions can induce more macrophages to polarize towards the anti-inflammatory M2 phenotype, indicating that BPy-8, as a degradation product, has an anti-inflammatory induction effect.

[0106] 2.9 In vivo experiments

[0107] 2.9.1 In vivo subcutaneous biocompatibility analysis:

[0108] Four 7-week-old C57BL mice (from the Sir Run Run Shaw Medical College, Zhejiang University) were randomly selected. After dehairing and anesthetizing with isoflurane, a 6 mm diameter polymer composite material PBP3 was implanted subcutaneously in the back. The wound was then sutured with 4-0 monofilament absorbable sutures. The surgical wounds of the mice were monitored daily. All mice were euthanized 2 weeks postoperatively. Tissues from the heart, liver, spleen, lungs, and kidneys of each mouse were extracted, rinsed with saline, and then fixed in neutral buffered formalin for 3 days. After fixation, the tissues were dehydrated under tap water with continuously increasing ethanol concentration. With the aid of a tissue processor, the dehydrated tissues were infiltrated and embedded in paraffin. The resulting tissue blocks were stored for sectioning. The tissue sections were stained with hematoxylin and eosin, and all histological images were taken under a microscope.

[0109] The results are as follows Figure 12 As shown, HE staining results revealed that the structures and morphologies of each organ were normal, with no abnormal pathological changes such as degeneration, necrosis, or inflammation, indicating that the polymer composite material PBP3 has good biocompatibility.

[0110] 2.9.2 In vivo subcutaneous biodegradation experiment:

[0111] Sixteen 7-week-old SD rats (from the Sir Run Run Shaw Medical College, Zhejiang University) were randomly selected. After removing the hair from their backs and anesthetizing them with isoflurane, a 6 mm diameter test material was implanted subcutaneously in their backs. The wound was then sutured with 4-0 monofilament absorbable sutures. Phototherapy of the implanted material began on the third postoperative day, with 1W 808nm laser illumination every two days for 20 minutes each time. Four rats were euthanized at 1, 2, 3, and 4 weeks post-surgery. The material was removed, washed, dried, and the mass changes before and after degradation were recorded. The polymer composite material PBP3 obtained in Example 1 and the product PLA of Comparative Example 2 were used as test materials, and the results of the two were compared. The results after 4 weeks showed that both the implanted material pure PLA and PBP3 showed degradation loss, indicating that the degradation of the implanted material can be regulated by the external light field. Moreover, the degradation loss of the implanted material pure PLA was less than 20%, while the degradation loss of the implanted material PBP3 was more than twice that of pure PLA. It can be seen that the degradation of the implanted material PBP3 was significantly accelerated under the action of the external light field, and the external light field has a better control and acceleration effect on its degradation rate in vivo.

[0112] In summary, the polymer composite materials obtained in the above embodiments possess excellent mechanical properties, photothermal properties, X-ray imaging properties, and degradation properties. In particular, their degradation rate can be accelerated to nearly 100 times the degradation rate of the polymer matrix. By adjusting external field parameters, selecting functionalized barium sulfate fillers with different properties, and changing the ratio of functionalized barium sulfate to the polymer matrix, the in vivo and in vitro degradation rate of the composite material can be adjusted. This allows for the matching of polymer composite materials with a balance between strength and degradation rate according to actual needs, thus achieving spatiotemporal controllable degradation characteristics. Simultaneously, the degradation products of the polymer composite material can induce macrophages to polarize towards the M2 anti-inflammatory direction. Therefore, as degradation occurs, the released degradation products, upon contact with surrounding cells, especially macrophages, can intervene and regulate the macrophage polarization phenotype transformation, inducing the production of more anti-inflammatory related factors, creating an immune microenvironment conducive to tissue regeneration and healing, and promoting the secretion of anti-inflammatory and repair factors. This demonstrates good biocompatibility and tissue repair-promoting properties. When implanted as an implant material, the polymer composite material can simultaneously achieve controllable degradation and immune microenvironment regulation, enabling highly efficient tissue engineering treatment and significantly improving patient recovery and quality of life. Therefore, polymer composite materials can be applied to various biomedical fields, including the development of various tissue engineering scaffolds, patches, and bio-nails.

[0113] In particular, in the performance comparison of the products obtained in each embodiment with those in Comparative Examples 1 and 2, it can be found that:

[0114] (1) Compared to the tensile strength of 16.1 MPa of pure PLA in Comparative Example 2, the tensile strength of PBA, the product with porous barium sulfate added in Comparative Example 1, was significantly reduced to only 9.6 MPa. This means that the addition of porous barium sulfate filler reduced the mechanical properties of the polymer matrix. In contrast, the tensile strength of each product with functionalized barium sulfate added in the embodiments of the present invention was enhanced. For example, the product PBP3 obtained in Example 1 had a significantly enhanced tensile strength (26.0 MPa). This indicates that in the polymer composite material of the present invention, functionalized barium sulfate, as a filler, is filled and uniformly dispersed in the biodegradable polymer matrix, which can maintain or even increase the good mechanical properties of the original polymer itself, providing good mechanical support for tissue engineering.

[0115] (2) All functionalized barium sulfate and polymer composite materials in the embodiments of the present invention have excellent photothermal properties.

[0116] (3) The polymer composite materials of each embodiment of the present invention are clearly visible under X-ray irradiation, with obvious grayscale, and have the effect of developing.

[0117] (4) In vitro degradation experiments showed that after 7 days of near-infrared light irradiation, pure PLA and PBA showed no obvious damage, with degradation losses of 0.24% and 5.96%, respectively. The polymer composite materials (PBPy12.5, PBPy25, and PBPy50) of the various embodiments of the present invention showed visible degradation damage, with degradation losses of 16.16%, 23.25%, and 20.69%, respectively. In vivo subcutaneous biodegradation experiments showed that after implantation and 4 weeks of in vivo light irradiation, both pure PLA and PBP3 showed degradation losses: the degradation loss of the implanted material pure PLA was less than 20%, while the degradation loss of the implanted material PBP3 was more than twice that of pure PLA. It can be seen that the polymer composite material of the present invention has a significant accelerated degradation in vivo and in vitro compared to the polymer bulk, and "on / off" degradation can be achieved by controlling the external light field.

[0118] (5) In vitro biocompatibility experiments showed that fibroblasts had good cell activity in the presence of degradation products of the polymer composite material of the present invention, indicating that it has good biocompatibility; in vivo subcutaneous biocompatibility experiments showed that no abnormalities were observed in various tissues and organs after implantation of the polymer composite material of the present invention, indicating that it has good biocompatibility.

[0119] (6) In vitro immunofluorescence staining experiments showed that compared with pure barium sulfate, photothermal barium titanate, as a degradation product, can induce more macrophages to polarize to the anti-inflammatory M2 phenotype and promote macrophages to participate in the regulation of the immune microenvironment, thus having anti-inflammatory induction and repair-promoting effects.

[0120] Furthermore, by adjusting the preparation parameters of this invention, the thickness, dispersion, and embedding degree of the outer polypyrrole shell in functionalized barium sulfate, as well as the content and type of functionalized barium sulfate, can be adjusted, thereby obtaining polymer composite materials with different morphologies, mechanical properties, photothermal properties, and degradation rates. Simultaneously, by controlling different light field parameters, the polymer composite materials can exhibit different degrees of photothermal response and possess different degradation rates. Utilizing the light field response, the polymer composite materials possess spatiotemporally tunable on / off degradation, which can better match the tissue repair rate. In addition, functionalized barium sulfate, as the main degradation product, will adjust the macrophage polarization phenotype in the immune microenvironment, timely adjust the secretion of signaling factors in the immune microenvironment, fully mobilize related cell functions, and create an immune microenvironment conducive to tissue regeneration and healing. Therefore, using the method of this invention, polymer composite materials with controllable degradation rates and anti-inflammatory and repair-promoting properties can be obtained, ensuring a degradation rate matching tissue regeneration while regulating the immune microenvironment to enhance active tissue remodeling, integration, and regeneration, which can be used to construct excellent tissue-engineered implant materials.

[0121] Therefore, it is evident that the objective of this invention has been fully and effectively achieved. The function and structural principles of this invention have been demonstrated and explained in the embodiments. Any modifications can be made to the implementation methods without departing from these principles. Therefore, this invention includes all modified embodiments based on the spirit and scope of the claims.

Claims

1. A polymer composite material, characterized in that, include: A biodegradable polymer matrix and a functionalized barium sulfate filler uniformly dispersed in the polymer matrix, wherein the functionalized barium sulfate has a core-shell structure, consisting of a porous barium sulfate core encapsulated by a polypyrrole shell.

2. The polymer composite material according to claim 1, characterized in that, The polymer is selected from at least one of polylactic acid, polyglycolic acid, polycaprolactone, polylactic acid-glycolic acid copolymer, poly(L-lactide-co-ε-caprolactone), polyhydroxy fatty acid ester, polytrimethylene carbonate, amino acid-based poly(ester urea), poly(ester amide), poly(ester urea) and poly(ester carbamate).

3. The polymer composite material according to claim 1, characterized in that, The porous barium sulfate has a particle size of 100 nm to 5 μm, and the polypyrrole shell has a thickness of 3 to 30 nm.

4. The polymer composite material according to any one of claims 1 to 3, prepared by the following method: Functionalized barium sulfate is added to a polymer solution and magnetically stirred at 20–80°C to form a polymer-functionalized barium sulfate mixed solution. The polymer-functionalized barium sulfate mixed solution is then uniformly coated onto a clean glass plate using a coating applicator and allowed to dry completely to obtain a polymer composite material.

5. The polymer composite material according to claim 4, characterized in that, The polymer solution is formed by dissolving a polymer in an organic solvent, wherein the polymer is selected from at least one of polylactic acid, polyglycolic acid, polycaprolactone, polylactic acid-glycolic acid copolymer, poly(L-lactide-co-ε-caprolactone), polyhydroxy fatty acid ester, polytrimethylene carbonate, amino acid-based poly(ester urea), poly(ester amide), poly(ester urea), and poly(ester urethane); and the solvent is selected from at least one of dioxane, N,N-dimethylformamide, hexafluoroisopropanol, dichloromethane, and acetone.

6. The polymer composite material according to claim 4, characterized in that, The concentration of the polymer solution is 30–50 mg / mL.

7. The polymer composite material according to claim 5, characterized in that, The mass ratio of the functionalized barium sulfate to the polymer is 1:9 to 1:

1.

8. The polymer composite material according to claim 4, characterized in that, The functionalized barium sulfate is prepared by the following method: porous barium sulfate is mixed with anhydrous ethanol and ultrasonically dispersed for 1-24 hours to form a homogeneous liquid; ferric chloride hexahydrate solution and pyrrole solution are added to it under stirring, followed by hydrochloric acid; the mixture is magnetically stirred at room temperature for 1-24 hours, and then centrifuged and washed to obtain the product.

9. The polymer composite material according to claim 8, characterized in that, The porous barium sulfate is prepared by the following method: barium chloride-aqueous dispersion is mixed with polyvinyl alcohol and then slowly added to ammonium sulfate aqueous solution under magnetic stirring. After stirring evenly, it is allowed to stand, centrifuged, and washed to obtain barium sulfate precipitate; then dried and sintered to obtain porous barium sulfate.

10. The use of the polymer composite material as described in any one of claims 1 to 9.

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