Polymeric materials, methods of making and using the same

Abstract

This application provides a polymeric material, its preparation method, and its applications. The raw materials for preparing the polymeric material include diols or diamines containing disulfide bonds, polylactic acid diols, isocyanate polymers, and catalysts. The polymeric material includes a cross-linked network containing disulfide bonds and a cross-linked network containing urethane groups. This polymeric material possesses repairable, remodelable, reusable, and recyclable properties, and also exhibits excellent degradability, biocompatibility, and shape memory properties.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to polymer materials, their preparation methods and applications. Background Technology

[0002] Clinically, external fixation is commonly used after fractures or orthopedic surgeries to prevent secondary injury and promote healing. However, plaster casts suffer from drawbacks such as high density, poor breathability, long curing time, inability to be reshaped, and poor X-ray permeability, hindering timely monitoring of postoperative recovery. Therefore, plaster casts are increasingly being replaced by medical thermoplastic sheets, which possess shape memory properties, X-ray permeability, excellent plasticity, good breathability, and convenient adjustability. Medical thermoplastic sheets soften at specific temperatures (e.g., 60-80℃), allowing for precise shaping to perfectly conform to the body part. Upon cooling, they retain their shape, providing stable support and protection. They are widely used for fracture and joint dislocation fixation, conservative treatment of bone tumors, post-burn and plastic surgery fixation, and radiotherapy positioning.

[0003] Currently, most medical thermoplastic sheets in related technologies are prepared through chemical crosslinking, peroxidation crosslinking, and ultraviolet light crosslinking, which cannot achieve repair, remodeling, reuse, and recycling, thus limiting their application value and economic efficiency throughout their entire life cycle. Summary of the Invention

[0004] Based on this, this application provides a polymer material with repairable, remodelable, reusable, and recyclable properties, as well as its preparation method and application.

[0005] The first aspect of this application provides a polymer material, the raw materials for preparing the polymer material including a diol or diamine containing disulfide bonds, polylactic acid diol, isocyanate polymer and catalyst; the polymer material includes a crosslinked network containing disulfide bonds and a crosslinked network containing urethane groups.

[0006] In some embodiments, the glass transition temperature of the polymer material is 40°C-90°C.

[0007] In some embodiments, the relative molecular weight of the polylactic acid segments in the polymer material is 500-2000.

[0008] In some embodiments, the relative molecular weight of the diol or diamine containing disulfide bonds is ≤500.

[0009] In some embodiments, the polylactic acid diol has a relative molecular weight of 500-2000.

[0010] In some embodiments, the molar ratio of the diol or diamine containing disulfide bonds to the polylactic acid diol is (0.5-2):1.

[0011] In some embodiments, the ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and the polylactic acid diol is (1-1.2):1.

[0012] In some embodiments, the mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, the polylactic acid diol, and the isocyanate polymer is 0.5wt%-6wt%.

[0013] In some embodiments, the diol or diamine containing a disulfide bond includes one or more of 2,2'-diaminodiphenyl disulfide, bis(2-hydroxyethyl) disulfide, 4,4′-dihydroxydiphenyl disulfide, 3,3′-dithiodiphenylphenol, cystamine, 4,4′-diaminodiphenyl disulfide, and 3,3′-dithiodiphenylamine.

[0014] In some embodiments, the isocyanate polymer includes one or more of polyhexamethylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate trimer, L-lysine triisocyanate, and triphenyl isocyanate thiophosphate.

[0015] In some embodiments, the catalyst includes one or more of organotin catalysts, tin salt catalysts, organozinc catalysts, and zinc salt catalysts.

[0016] In some embodiments, the catalyst comprises one or more of dibutyltin dilaurate, zinc acetate, stannous octoate, stannous isooctanoate, and zinc acetylacetonate.

[0017] A second aspect of this application provides a method for preparing a polymer material, comprising the following steps:

[0018] The polymer material is prepared by curing a mixture comprising a diol or diamine containing disulfide bonds, polylactic acid diol, isocyanate polymer, and a catalyst.

[0019] In some embodiments, the polylactic acid diol has a relative molecular weight of 500-2000.

[0020] In some embodiments, the relative molecular weight of the diol or diamine containing disulfide bonds is ≤500.

[0021] In some embodiments, the molar ratio of the diol or diamine containing disulfide bonds to the polylactic acid diol is (0.5-2):1.

[0022] In some embodiments, the ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and the polylactic acid diol is (1-1.2):1.

[0023] In some embodiments, the mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, the polylactic acid diol, and the isocyanate polymer is 0.5wt%-6wt%.

[0024] In some embodiments, the diol or diamine containing a disulfide bond includes one or more of 2,2'-diaminodiphenyl disulfide, bis(2-hydroxyethyl) disulfide, 4,4′-dihydroxydiphenyl disulfide, 3,3′-dithiodiphenylphenol, cystamine, 4,4′-diaminodiphenyl disulfide, and 3,3′-dithiodiphenylamine.

[0025] In some embodiments, the isocyanate polymer includes one or more of polyhexamethylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate trimer, L-lysine triisocyanate, and triphenyl isocyanate thiophosphate.

[0026] In some embodiments, the catalyst includes one or more of organotin catalysts, tin salt catalysts, organozinc catalysts, and zinc salt catalysts.

[0027] In some embodiments, the catalyst comprises one or more of dibutyltin dilaurate, zinc acetate, stannous octoate, stannous isooctanoate, and zinc acetylacetonate.

[0028] In some embodiments, the curing temperature is 40℃-140℃ and the time is 1h-12h.

[0029] The third aspect of this application provides the application of a polymer material prepared by the preparation method of the polymer material of the first aspect of this application or the polymer material of the second aspect of this application in the preparation of medical surgical fixation materials.

[0030] The aforementioned polymer material is prepared from raw materials including diols or diamines containing disulfide bonds, polylactic acid diols, isocyanate polymers, and catalysts. The polymer material obtained from these raw materials simultaneously comprises a cross-linking network containing disulfide bonds and a cross-linking network containing urethane groups, i.e., it contains a dual dynamic cross-linking network. The cross-linking network containing disulfide bonds can undergo a dynamic exchange reaction at 50℃-80℃, endowing the polymer material with excellent reprocessability; the cross-linking network containing urethane groups can undergo a dynamic exchange reaction at 120℃-160℃, endowing the polymer material with excellent creep resistance. Therefore, the presence of these two cross-linking networks gives the polymer material reprocessable and recyclable characteristics, as well as good creep resistance, enabling repair, remodeling, reuse, and recycling. Simultaneously, this material exhibits excellent degradability, biocompatibility, and shape memory properties. When used as a medical surgical fixation material, it can solve the problem that current medical shell fixation materials prepared using chemical cross-linking methods cannot be recycled and processed into new materials, achieving recycling and reuse. Attached Figure Description

[0031] To better describe and illustrate the embodiments or examples provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments or examples, or the best mode of conduct of these applications as currently understood. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings:

[0032] Figure 1 This is a schematic diagram of a dual dynamic exchange network in a polymer material.

[0033] Figure 2 The stress-strain curves are for Examples 1-12.

[0034] Figure 3 The energy storage modulus-temperature curves are for Examples 1-12.

[0035] Figure 4 The loss factor-temperature curves for Examples 1-12 are shown.

[0036] Figure 5 The shape memory cycle curves are from Examples 1 to 6.

[0037] Figure 6 The shape memory cycle curves are from Examples 7 to 12.

[0038] Figure 7 The stress relaxation curves for Examples 1-12 at different temperatures are shown.

[0039] Figure 8The stress relaxation curves for Comparative Example 1 at different temperatures are shown.

[0040] Figure 9 The stress relaxation curves for Comparative Example 2 are shown at different temperatures.

[0041] Figure 10 The calculation of the activation energy of network topology rearrangement in Examples 1-12.

[0042] Figure 11 Images of the samples prepared in Examples 1-4 and the reprocessing process.

[0043] Figure 12 Images of the samples prepared in Examples 5-8 and the reprocessing process.

[0044] Figure 13 Images of the samples prepared in Examples 9-12 and the reprocessing process.

[0045] Figure 14 The stress-strain curves are those of the materials prepared in Examples 1-12 after reprocessing.

[0046] Figure 15 Cell color photographs of the materials prepared in Examples 1-12 for cytotoxicity testing.

[0047] Figure 16 This is a design drawing of the material prepared in Example 3 used as a medical surgical fixation brace.

[0048] Figure 17 The material prepared in Example 3 is used as a medical surgical fixation brace in surgical fixation.

[0049] Figure 18 The material prepared in Example 3 was used for digital X-ray examination of a human body after wearing a medical surgical fixation brace. Detailed Implementation

[0050] To facilitate understanding of the present invention, a more complete description of this application will be provided below with reference to relevant embodiments. Preferred embodiments of the present application are given below. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that a thorough and complete understanding of the disclosure of this application will be achieved.

[0051] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0052] As used herein, the terms "and / or," "or / and," and "and / or" encompass any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that, in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR."

[0053] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0054] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0055] This document only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0056] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows temperature fluctuations within the precision range controlled by the instrument, such as ±5°C, ±4°C, ±3°C, ±2°C, or ±1°C.

[0057] In this document, the term "suitable" as used in phrases such as "suitable combination," "suitable method," and "any suitable method" refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0058] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0059] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0060] In the description of the application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0061] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions. Unless otherwise specified, all technical features and optional technical features of this application can be combined to form new technical solutions.

[0062] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, but sequentially is preferred.

[0063] Currently, medical thermoplastic sheets are mainly thermosetting polymer materials with melt transition temperatures of around 60℃-80℃, prepared by chemical crosslinking of polycaprolactone and polyester. However, most medical thermoplastic sheets in related technologies are prepared through chemical crosslinking, peroxidation crosslinking, and ultraviolet light crosslinking, which cannot achieve repair, remodeling, reuse, or recycling. In other words, existing fixation materials are mostly "disposable" products, lacking the ability to be repaired, remodeled, and recycled at the product level, thus limiting their application value and economic viability throughout their entire life cycle.

[0064] To address the aforementioned issues, this application utilizes diamines or diols containing disulfide bonds, polylactic acid diols, polyisocyanates, and catalysts to prepare polymeric materials. These materials simultaneously comprise cross-linked networks containing disulfide bonds and cross-linked networks containing urethane groups, exhibiting reprocessability, recyclability, and good creep resistance, enabling repair, remodeling, reuse, and recycling. When using these polymeric materials to prepare medical surgical fixation materials, they can be laser-cut according to the required geometry and dimensions of the fixation area. Heating the material to near its glass transition temperature allows it to deform and wrap around the fixation area, while cooling solidifies it for fixation. Compared to currently used medical splints, the medical surgical fixation materials prepared using this polymeric material are biodegradable, possess excellent cell compatibility, are recyclable, and reprocessable. Furthermore, the material exhibits high strength, shape retention rate, and recovery rate, along with better X-ray permeability and fixation effect. Used medical surgical fixation materials can be recycled and reprocessed using the dynamic properties of a dual-dynamic structure to obtain new splint materials, demonstrating sustainability and environmental friendliness.

[0065] The first aspect of this application provides a polymer material, the raw materials for preparing the polymer material including a diol or diamine containing disulfide bonds, polylactic acid diol, isocyanate polymer and catalyst; the polymer material includes a crosslinked network containing disulfide bonds and a crosslinked network containing urethane groups.

[0066] It should be noted that the polymer material prepared from diols or diamines containing disulfide bonds, polylactic acid diols, isocyanate polymers and catalysts is polylactic acid-based polyurethane.

[0067] Understandably, the polymer material of this application is prepared from raw materials including diols or diamines containing disulfide bonds, polylactic acid diols, isocyanate polymers, and catalysts. The polymer material prepared from these raw materials simultaneously comprises a cross-linking network containing disulfide bonds and a cross-linking network containing urethane groups, i.e., it contains a dual dynamic cross-linking network. The cross-linking network containing disulfide bonds can undergo a dynamic exchange reaction at 50℃-80℃, endowing the polymer material with excellent reprocessability; the cross-linking network containing urethane groups can undergo a dynamic exchange reaction at 120℃-160℃, endowing the polymer material with excellent creep resistance. Therefore, the presence of these two cross-linking networks gives the polymer material reprocessable and recyclable characteristics, as well as good creep resistance, enabling repair, remodeling, reuse, and recycling. Simultaneously, this material possesses excellent mechanical strength, X-ray penetration, degradability, biocompatibility, and shape memory properties. When used as a medical surgical fixation material, it can solve the problem that current medical shell fixation materials prepared using chemical cross-linking methods cannot be recycled and processed into new materials, achieving recycling and reuse.

[0068] A schematic diagram of the dual dynamic exchange network of the polymer material is shown below. Figure 1 As shown.

[0069] In some embodiments, the glass transition temperature of the polymer material is 40°C-90°C; for example, it can be, but is not limited to, 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, 52°C, 54°C, 56°C, 58°C, 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, or any range between two of the above temperatures. This facilitates the use of polymer materials for medical external fixation.

[0070] As one possible implementation, the relative molecular weight of the polylactic acid segments in the polymer material is 500-2000; for example, it can be, but is not limited to, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, or any two of the above values. This facilitates the control of the glass transition temperature of the polymer material within the range of 40℃-90℃, thereby enabling the realization of medical in vitro fixation of the polymer material. Simultaneously, the resulting polymer material exhibits excellent mechanical strength, reprocessability, shape memory properties, and biocompatibility.

[0071] In some embodiments, the relative molecular weight of the diol or diamine containing disulfide bonds is ≤500. This facilitates the control of the glass transition temperature of the polymer material within the range of 40°C to 90°C, thereby enabling the medical in vitro fixation of the polymer material. Simultaneously, the resulting polymer material exhibits excellent mechanical strength and reprocessability.

[0072] In some embodiments, the relative molecular weight of polylactic acid diol is 500-2000; for example, it can be, but is not limited to, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, or any range between two of the above values. This facilitates the control of the glass transition temperature of the polymer material within the range of 40℃-90℃, thereby facilitating the realization of medical in vitro fixation of the polymer material. Simultaneously, the resulting polymer material exhibits excellent mechanical strength, reprocessability, shape memory properties, and biocompatibility.

[0073] As one possible implementation, the molar ratio of the diol or diamine containing disulfide bonds to polylactic acid diol is (0.5-2):1; for example, it can be, but is not limited to, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, or any range between two of the above molar ratios. This facilitates the control of the glass transition temperature of the polymer material within the range of 40℃-90℃, thereby facilitating the realization of medical in vitro fixation of polymer materials. Simultaneously, the resulting polymer material exhibits excellent mechanical strength, reprocessability, shape memory properties, and biocompatibility.

[0074] In some embodiments, the ratio of the total molar amount of isocyanate ions in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and the polylactic acid diol is (1-1.2):1. For example, it can be, but is not limited to, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, or any range between two of the above ratios. As a result, the prepared polymer material has high crosslinking density, high tensile strength, high glass transition temperature, and excellent shape stability.

[0075] In some embodiments, the mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, polylactic acid diol, and isocyanate polymer is 0.5 wt%-6 wt%; for example, it can be, but is not limited to, 0.5 wt%, 0.52 wt%, 0.54 wt%, 0.56 wt%, 0.58 wt%, 0.6 wt%, or any range between two of the above values. Thus, the higher the dynamics of the crosslinked network containing urethane groups in the polymer material, the better the reprocessability of the material. Optionally, the mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, polylactic acid diol, and isocyanate polymer is 3 wt%-5 wt%.

[0076] In some embodiments, the diol or diamine containing a disulfide bond includes one or more of 2,2'-diaminodiphenyl disulfide, bis(2-hydroxyethyl) disulfide, 4,4′-dihydroxydiphenyl disulfide, 3,3′-dithiodiphenylphenol, cystamine, 4,4′-diaminodiphenyl disulfide, and 3,3′-dithiodiphenylamine.

[0077] As one possible implementation, the isocyanate polymer includes one or more of polyhexamethylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate trimer, L-lysine triisocyanate, and triphenyl isocyanate thiophosphate.

[0078] In some embodiments, the catalyst includes one or more of organotin catalysts, tin salt catalysts, organozinc catalysts, and zinc salt catalysts.

[0079] In some alternative embodiments, the catalyst includes one or more of dibutyltin dilaurate, zinc acetate, stannous octoate, stannous isooctanoate, and zinc acetylacetonate.

[0080] The second aspect of this application provides a method for preparing a polymeric material, which can be used to prepare the aforementioned polymeric material. The method includes: curing a mixture comprising a diol or diamine containing disulfide bonds, polylactic acid diol, isocyanate polymer, and a catalyst to prepare the polymeric material.

[0081] This preparation method is simple, convenient, and time-saving. The resulting polymer material contains both a disulfide-bonded crosslinked network and a urethane-based crosslinked network, i.e., a dual-dynamic crosslinked network. The disulfide-bonded crosslinked network can achieve network topological rearrangement at lower temperatures (50℃-80℃), giving the polymer material excellent reprocessability; the urethane-based crosslinked network can achieve network topological rearrangement at higher temperatures (120℃-160℃), giving the polymer material excellent creep resistance. Therefore, the presence of these two crosslinked networks makes the polymer material reprocessable and recyclable, as well as having good creep resistance, enabling repair, remodeling, reuse, and recycling. Simultaneously, this material exhibits excellent mechanical strength, X-ray penetration, degradability, biocompatibility, and shape memory properties. When used as a medical surgical fixation material, it can solve the problem that current medical shell fixation materials prepared by chemical crosslinking methods cannot be recycled and processed into new materials, achieving recycling and reuse.

[0082] In some embodiments, the relative molecular weight of polylactic acid diol is 500-2000; for example, it can be, but is not limited to, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, or any range between two of the above values. This facilitates the control of the glass transition temperature of the polymer material within the range of 40℃-90℃, thereby facilitating the realization of medical in vitro fixation of the polymer material. Simultaneously, the resulting polymer material exhibits excellent mechanical strength, reprocessability, shape memory properties, and biocompatibility.

[0083] In some embodiments, the relative molecular weight of the diol or diamine containing disulfide bonds is ≤500. This facilitates the control of the glass transition temperature of the polymer material within the range of 40°C to 90°C, thereby enabling the medical in vitro fixation of the polymer material. Simultaneously, the resulting polymer material exhibits excellent mechanical strength and reprocessability.

[0084] As one possible implementation, the molar ratio of the diol or diamine containing disulfide bonds to polylactic acid diol is (0.5-2):1; for example, it can be, but is not limited to, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, or any range between two of the above molar ratios. This facilitates the control of the glass transition temperature of the polymer material within the range of 40℃-90℃, thereby facilitating the realization of medical in vitro fixation of polymer materials. Simultaneously, the resulting polymer material exhibits excellent mechanical strength, reprocessability, shape memory properties, and biocompatibility.

[0085] In some embodiments, the ratio of the total molar amount of isocyanate ions in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and the polylactic acid diol is (1-1.2):1. For example, it can be, but is not limited to, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, or any range between two of the above ratios. As a result, the prepared polymer material has high crosslinking density, high tensile strength, high glass transition temperature, and excellent shape stability.

[0086] In some embodiments, the mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, polylactic acid diol, and isocyanate polymer is 0.5 wt%-6 wt%; for example, it can be, but is not limited to, 0.5 wt%, 0.52 wt%, 0.54 wt%, 0.56 wt%, 0.58 wt%, 0.6 wt%, or any range between two of the above values. Thus, the higher the dynamics of the crosslinked network containing urethane groups in the polymer material, the better the reprocessability of the material. Optionally, the mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, polylactic acid diol, and isocyanate polymer is 3 wt%-5 wt%.

[0087] In some alternative embodiments, the diol or diamine containing a disulfide bond includes one or more of 2,2'-diaminodiphenyl disulfide, bis(2-hydroxyethyl) disulfide, 4,4′-dihydroxydiphenyl disulfide, 3,3′-dithiodiphenol, cystamine, 4,4′-diaminodiphenyl disulfide, and 3,3′-dithiodiphenylamine.

[0088] In some embodiments, the isocyanate polymer includes one or more of polyhexamethylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate trimer, L-lysine triisocyanate, and triphenyl isocyanate thiophosphate.

[0089] In some embodiments, the catalyst includes one or more of organotin catalysts, tin salt catalysts, organozinc catalysts, and zinc salt catalysts.

[0090] Optionally, the catalyst includes one or more of dibutyltin dilaurate, zinc acetate, stannous octoate, stannous isooctanoate, and zinc acetylacetonate.

[0091] In some embodiments, the curing temperature is 40°C to 140°C. For example, it can be, but is not limited to, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or any range between two of the above temperatures.

[0092] In some optional implementations, the curing time is 1h-12h; for example, it can be, but is not limited to, 1h, 2h, 4h, 6h, 8h, 10h, 12h or any range between the above two times.

[0093] The third aspect of this application provides the application of a polymer material prepared by the preparation method of the polymer material of the first aspect of this application or the polymer material of the second aspect of this application in the preparation of medical surgical fixation materials.

[0094] As a non-limiting example, a method for preparing medical surgical fixation materials using polymer materials includes: using a laser cutting machine to punch holes in the polymer material and cut it into geometric shapes suitable for various parts of the body; heating the polymer material to near its glass transition temperature, causing the polymer material to soften; wrapping the polymer material around the fixation site; and rapidly increasing the modulus of the material after cooling, thus fixing the material and obtaining the medical surgical fixation material.

[0095] The technical solutions of this application will be described in detail below with reference to specific embodiments. It should be understood that these embodiments are only for illustrating this application and are not intended to limit the scope of this application. For experimental methods in the following embodiments where specific conditions are not specified, please refer to the guidelines given in this application first, or follow experimental manuals or conventional conditions in the field, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the field.

[0096] In the specific embodiments described below, the measurement parameters involving raw material components may have slight deviations within the weighing accuracy range unless otherwise specified. Temperature and time parameters are subject to acceptable deviations due to instrument testing accuracy or operational precision.

[0097] I. Preparation of Polymer Materials

[0098] Example 1

[0099] Weigh 12.4 g of 2,2'-diaminodiphenyl disulfide, 12.5 g of polylactic acid diol with a relative molecular weight of 500, and 0.52 g of dibutyltin dilaurate, and dissolve them in 60 g of toluene. Stir magnetically until homogeneous. Weigh 26.2 g of polyhexamethylene diisocyanate and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene plastic mold. Place the mold in an electric heating drying oven and heat to 80°C for 12 hours to cure. After curing, vacuum dry at 80°C for 12 hours to obtain the sample. The molar ratio of 2,2'-diaminodiphenyl disulfide to polylactic acid diol is 2:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diols or diamines containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0100] Example 2

[0101] Weigh 11.25g of 4,4′-dihydroxydiphenyl disulfide, 15g of polylactic acid diol with a relative molecular weight of 500, and 0.52g of zinc acetylacetonate, and dissolve them in 65g of toluene. Stir magnetically until homogeneous. Weigh 33.1g of isophorone diisocyanate trimer and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour into a polytetrafluoroethylene plastic mold. Place the mold in an electric heating drying oven and heat to 80℃ for 12 hours to cure. After curing, vacuum dry at 80℃ for 12 hours to obtain the sample. The molar ratio of 4,4′-dihydroxydiphenyl disulfide to polylactic acid diol is 1.5:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diols or diamines containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0102] Example 3

[0103] Weigh 9.3 g of 4,4′-diaminodiphenyl disulfide, 18.75 g of polylactic acid diol with a relative molecular weight of 500, 0.34 g of zinc acetate, and 0.20 g of stannous octoate, and dissolve them in 65 g of toluene. Stir magnetically until homogeneous. Weigh 26.2 g of polyhexamethylene diisocyanate and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene plastic mold. Place the mold in an electric heating drying oven and heat to 80°C for 12 hours to cure. After curing, vacuum dry at 80°C for 12 hours to obtain the sample. The molar ratio of 4,4′-diaminodiphenyl disulfide to polylactic acid diol is 1:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diols or diamines containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0104] Example 4

[0105] Weigh 3.85g of bis(2-hydroxyethyl) disulfide, 25g of polylactic acid diol with a relative molecular weight of 500, 0.34g of dibutyltin dilaurate, and 0.22g of stannous octoate, and dissolve them in 70g of toluene. Stir magnetically until homogeneous. Weigh 19.1g of triphenylmethane triisocyanate and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene (PTFE) plastic mold. Place the mold in an electric heating drying oven and heat to 80℃ for 12 hours to cure. After curing, vacuum dry at 80℃ for 12 hours to obtain the sample. The molar ratio of bis(2-hydroxyethyl) disulfide to polylactic acid diol is 0.5:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and polylactic acid diol is 1:1.

[0106] Example 5

[0107] Weigh 12.5g of 3,3′-dithiodiphenol, 25g of polylactic acid diol with a relative molecular weight of 1000, 0.32g of dibutyltin dilaurate, and 0.32g of stannous isooctanoate, and dissolve them in 75g of toluene. Stir magnetically until homogeneous. Weigh 19.1g of triphenylmethane triisocyanate and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene (PTFE) plastic mold. Place the mold in an electric heating drying oven and heat to 80℃ for 12 hours to cure. After curing, vacuum dry at 80℃ for 12 hours to obtain the sample. The molar ratio of 3,3′-dithiodiphenol to polylactic acid diol is 2:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diols or diamines containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0108] Example 6

[0109] Weigh 6.84g of cystamine, 30g of polylactic acid diol with a relative molecular weight of 1000, and 0.66g of zinc acetate, and dissolve them in 80g of toluene. Stir magnetically until homogeneous. Weigh 13.9g of L-lysine triisocyanate and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene (PTFE) plastic mold. Place the mold in an electric heating drying oven and heat to 80℃ for 12 hours to cure. After curing, vacuum dry at 80℃ for 12 hours to obtain the sample. The molar ratio of cystamine to polylactic acid diol is 1.5:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diols or diamines containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0110] Example 7

[0111] Weigh 9.3 g of 3,3′-dithiodiphenylamine, 37.5 g of polylactic acid diol with a relative molecular weight of 1000, and 0.72 g of dibutyltin dilaurate, and dissolve them in 85 g of toluene. Stir magnetically until homogeneous. Weigh 24.2 g of triphenyl isocyanate thiophosphate and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene (PTFE) plastic mold. Place the mold in an electric heating drying oven and heat to 80°C for 12 hours to cure. After curing, vacuum dry at 80°C for 12 hours to obtain the sample. The molar ratio of 3,3′-dithiodiphenylamine to polylactic acid diol is 1:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diols or diamines containing disulfide bonds and the hydroxyl and amino groups in polylactic acid diol is 1:1.

[0112] Example 8

[0113] Weigh 9.3 g of 2,2'-diaminodiphenyl disulfide, 50 g of polylactic acid diol with a relative molecular weight of 1000, and 0.82 g of dibutyltin dilaurate, and dissolve them in 95 g of toluene. Stir magnetically until homogeneous. Weigh 26.2 g of polyhexamethylene diisocyanate and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene plastic mold. Place the mold in an electric heating drying oven and heat to 80°C for 12 hours to cure. After curing, vacuum dry at 80°C for 12 hours to obtain the sample. The molar ratio of 2,2'-diaminodiphenyl disulfide to polylactic acid diol is 0.5:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diols or diamines containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0114] Example 9

[0115] Weigh 12.4 g of 4,4′-dihydroxydiphenyl disulfide, 50 g of polylactic acid diol with a relative molecular weight of 2000, and 0.88 g of dibutyltin dilaurate, and dissolve them in 100 g of toluene. Stir magnetically until homogeneous. Weigh 26.2 g of isophorone diisocyanate trimer and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour into a polytetrafluoroethylene plastic mold. Place the mold in an electric heating drying oven and heat to 80°C for 12 h to cure. After curing, vacuum dry at 80°C for 12 h to obtain the sample. The molar ratio of 4,4′-dihydroxydiphenyl disulfide to polylactic acid diol is 2:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diol or diamine containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0116] Example 10

[0117] Weigh 2.79 g of 4,4′-diaminodiphenyl disulfide, 2.79 g of 2,2′-diaminodiphenyl disulfide, 30 g of polylactic acid diol with a relative molecular weight of 2000, and 0.49 g of dibutyltin dilaurate, and dissolve them in 50 g of toluene. Stir magnetically until homogeneous. Weigh 13.1 g of isophorone diisocyanate trimer and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene (PTFE) plastic mold. Place the mold in an electric heating drying oven and heat to 80°C for 12 hours to cure. After curing, vacuum dry at 80°C for 12 hours to obtain the sample. The total molar ratio of 4,4′-diaminodiphenyl disulfide and 2,2′-diaminodiphenyl disulfide to the molar ratio of polylactic acid diol is 1.5:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and polylactic acid diol is 1:1.

[0118] Example 11

[0119] Weigh 2.325 g of 4,4′-diaminodiphenyl disulfide, 2.325 g of 3,3′-disulfide diphenylamine, 37.5 g of polylactic acid diol with a relative molecular weight of 2000, and 0.56 g of dibutyltin dilaurate, and dissolve them in 70 g of toluene. Stir magnetically until homogeneous. Weigh 6.55 g of polyhexamethylene diisocyanate and 8.28 g of isophorone diisocyanate trimer and add them to the above mixed solution. Stir rapidly until homogeneous, place in a vacuum drying oven, turn on the vacuum pump to remove air bubbles, and then quickly pour into a polytetrafluoroethylene plastic mold. Place the mold in an electric heating drying oven, heat to 80°C, and cure for 12 h. After curing, vacuum dry at 80°C for 12 h to obtain the sample. The total molar ratio of 4,4′-diaminodiphenyl disulfide and 3,3′-disulfide diphenylamine to the molar ratio of polylactic acid diol is 1:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and polylactic acid diol is 1:1.

[0120] Example 12

[0121] Weigh 3.1 g of 4,4′-diaminodiphenyl disulfide, 50 g of polylactic acid diol with a relative molecular weight of 2000, and 0.66 g of dibutyltin dilaurate, and dissolve them in 80 g of toluene. Stir magnetically until homogeneous. Weigh 13.1 g of isophorone diisocyanate trimer and add it to the above mixture. Stir rapidly until homogeneous, then place in a vacuum drying oven. Turn on the vacuum pump to remove air bubbles, and then quickly pour the mixture into a polytetrafluoroethylene plastic mold. Place the mold in an electric heating drying oven and heat to 80°C for 12 hours to cure. After curing, vacuum dry at 80°C for 12 hours to obtain the sample. The molar ratio of 4,4′-diaminodiphenyl disulfide to polylactic acid diol is 0.5:1. The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of diol or diamine containing disulfide bonds and hydroxyl and amino groups in polylactic acid diol is 1:1.

[0122] Example 13

[0123] The preparation method of Example 13 is similar to that of Example 1, except that the relative molecular weight of polylactic acid diol in Example 13 is 2000 and the amount added is 50g; all other aspects are the same.

[0124] Example 14

[0125] The preparation method of Example 14 is similar to that of Example 1, except that the relative molecular weight of polylactic acid diol in Example 14 is 2500 and the amount added is 62.5g; all other aspects are the same.

[0126] Example 15

[0127] The preparation method of Example 15 is similar to that of Example 1, except that: the amount of 2,2'-diaminodiphenyl disulfide added in Example 15 is 3.1g, and the molar ratio of 2,2'-diaminodiphenyl disulfide to polylactic acid diol is 0.5:1; all other aspects are the same.

[0128] Example 16

[0129] The preparation method of Example 16 is similar to that of Example 1, except that: the amount of 2,2'-diaminodiphenyl disulfide added in Example 16 is 6.2g, and the molar ratio of 2,2'-diaminodiphenyl disulfide to polylactic acid diol is 1:1; all other aspects are the same.

[0130] Comparative Example 1

[0131] The preparation method of Comparative Example 1 is similar to that of Example 1, except that polylactic acid diol was not added during the preparation of Comparative Example 1; all other aspects are the same.

[0132] Comparative Example 2

[0133] The preparation method of Comparative Example 2 is similar to that of Example 1, except that 2,2'-diaminodiphenyl disulfide was not added during the preparation of Comparative Example 2; all other aspects are the same.

[0134] The main differences between the above embodiments and comparative examples are shown in Table 1.

[0135] Table 1

[0136]

[0137] The molar ratio refers to the molar ratio of diols or diamines containing disulfide bonds to polylactic acid diols.

[0138] It should be noted that other differences between the various embodiments are referred to in the above embodiment settings section, and will not be repeated here.

[0139] II. Performance Testing

[0140] The polymer material samples from Examples 1-16 and Comparative Examples 1-2 were tested as follows:

[0141] 1. Static Mechanical Property Testing: The stress-strain curves of the samples were analyzed using an Instron 5567 universal tensile testing machine (Instron Corporation, USA). Testing was conducted according to ASTM (American Society for Testing and Materials) standards. The tensile speed was 5 mm / min, and five tests were performed for each test data point.

[0142] 2. Dynamic Thermomechanical Analysis (DMA): A DMA Q800 dynamic thermomechanical analyzer (TA Instruments, USA) was used. The material was cut into standard rectangular strips with dimensions of 15×4×1 mm. The DMA thin film tensile multi-frequency strain mode was employed, using a temperature ramp / frequency scan. The test amplitude was 20 μm, force tracking was 125%, the frequency was 1 Hz, the prestress was 0.001 N, and the heating rate was 3°C / min. The test temperature range was -50 to 150°C, with a hold time of 3 min at -50°C. The glass transition temperature (Tg) of the material was determined. g The temperature corresponding to the peak value of the loss factor tan δ.

[0143] 3. Shape Memory Recovery Rate and Fixation Rate Test: The shape memory performance was measured using a DMA Q800 instrument and the control force mode in the static test program. A typical test cycle for the shape memory process is as follows: A 30 mm × 5 mm × 1 mm specimen is mounted in the tensile fixture of the DMA cavity, and the specimen is heated to T at a heating rate of 5°C / min. d = T g +15 °C, and held at that temperature for 5 minutes, recorded as ε. n Then, by gradually increasing the stress until the spline is stretched to a fixed strain ε, the spline is stretched to a fixed strain. m Cool to shape-fixed temperature T at a cooling rate of 5°C / min. f =T g -30°C, hold at that temperature for 5 minutes; then unload the stress to 0.001 N, the specimen undergoes a small deformation recovery, and the strain ε at this point is recorded. u At this point, the shape is fixed. Maintaining the fixture stress at 0.001 N, the temperature is increased again to the recovery temperature T at a heating rate of 5°C / min. r =T d = T g +15°C, and held at this temperature for 20 min until the internal stress of the material is completely released and the material undergoes significant deformation recovery. The deformation after recovery is recorded as ε. p .

[0144] Shape memory performance is determined by the shape fixation rate (R). f ) and shape recovery rate (R r ) to quantify:

[0145]

[0146] .

[0147] 4. Cytotoxicity Test: In vitro cytotoxicity tests were conducted according to ISO 10993-5:2009. Samples were sterilized by UV irradiation for 30 min; L929 cells were used. The sterilized samples were immersed in an immersion solution with a concentration of 3 cm⁻¹. 2 mL -1 Cells were extracted from the culture medium. Next, the samples were incubated at 37°C and 5% CO2 for 24 hours to prepare the extraction solution for use. Cells were seeded in 96-well plates with 6 replicates per group. After cell adhesion in complete culture medium for 24 hours, cells were transferred to the extraction medium and cultured for 4 days. Cells cultured in complete culture medium served as a negative control, and the complete culture medium served as a blank control. Cytotoxicity was comprehensively assessed at each time point using a CCK-8 assay kit.

[0148] 5. Stress relaxation test: The shape memory performance was measured using a DMA Q800 instrument and the stress relaxation mode in the static test program. The relaxation strain was 10%, the isothermal time was 3 minutes, and relaxation continued until the stress approached zero.

[0149] The test results of the above embodiments and comparative examples are shown in Table 2. The stress-strain curves of Examples 1-12 are shown in Table 2. Figure 2 As shown. The energy storage modulus-temperature curves for Examples 1-12 are as follows. Figure 3 As shown. The loss factor-temperature curves for Examples 1-12 are shown below. Figure 4 As shown. The shape memory cycle curves of Examples 1-6 are as follows. Figure 5 As shown. The shape memory cycle curves of Examples 7-12 are as follows. Figure 6 As shown. The stress relaxation curves of Examples 1-12 at different temperatures are shown in the figure. Figure 7 As shown. The stress relaxation curves of Comparative Example 1 at different temperatures are shown in Figure 1. Figure 8 As shown. The stress relaxation curves of Comparative Example 2 at different temperatures are shown in Figure 2. Figure 9 As shown. The calculation of the activation energy of network topology rearrangement in Examples 1-12 is as follows. Figure 10 As shown. Images of the samples prepared in Examples 1-4 and the reprocessing process are shown below. Figure 11 As shown. Images of the samples prepared in Examples 5-8 and the reprocessing process are shown below. Figure 12 As shown. Images of the samples prepared in Examples 9-12 and the reprocessing process are shown below. Figure 13 As shown. The stress-strain curves of the materials prepared in Examples 1-12 after reprocessing are shown in the figure. Figure 14 As shown. Cell color photographs of the materials prepared in Examples 1-12 for cytotoxicity testing are shown below. Figure 15 As shown.

[0150] Table 2

[0151]

[0152] A comparison of the results from Examples 1-16 and Comparative Examples 1-2 shows that the polymer material prepared by simultaneously using diols or diamines containing disulfide bonds and polylactic acid diols with isocyanate polymers to undergo a crosslinking reaction contains a dual dynamic crosslinking network. This polymer material exhibits reprocessability and recyclability, as well as good creep resistance, enabling repair, remodeling, reuse, and recycling. Furthermore, this material demonstrates excellent degradability, biocompatibility, and shape memory properties.

[0153] Comparison of the results of Examples 1 and 13-14, and comparison of the results of Examples 1 and 15-16, shows that by controlling the relative molecular weight of polylactic acid diol in the range of 100-2000, and the molar ratio of diol or diamine containing disulfide bonds to polylactic acid diol in the range of (0.5-2):1, it is beneficial to make the glass transition temperature of the prepared polymer material in the range of 40℃-90℃, thereby facilitating the medical in vitro fixation of the polymer material; at the same time, the prepared polymer material has excellent mechanical strength, shape memory properties and biocompatibility.

[0154] The design of a medical surgical fixation brace using the polymer material prepared in Example 3 is shown in the figure below. Figure 16 As shown; its application in surgical fixation is as follows. Figure 17 As shown; digital X-ray examination after human body is worn, such as Figure 18 As shown. By Figure 16-18 It is known that polymer materials have excellent X-ray penetrability.

[0155] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0156] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A polymer material, characterized in that, The raw materials for preparing the polymeric material include diols or diamines containing disulfide bonds, polylactic acid diols, isocyanate polymers, and catalysts; the polymeric material includes cross-linked networks containing disulfide bonds and cross-linked networks containing urethane groups.

2. The polymer material as described in claim 1, characterized in that, The glass transition temperature of the polymer material is 40℃-90℃; and / or, The relative molecular weight of the polylactic acid segments in the polymer material is 500-2000; and / or, The relative molecular weight of the diol or diamine containing disulfide bonds is ≤500.

3. The polymer material as described in claim 1, characterized in that, The polylactic acid diol has a relative molecular weight of 500-2000; and / or, The molar ratio of the diol or diamine containing disulfide bonds to the polylactic acid diol is (0.5-2):1; and / or, The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and the polylactic acid diol is (1-1.2):1; and / or, The mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, the polylactic acid diol, and the isocyanate polymer is 0.5wt%-6wt%.

4. The polymer material according to any one of claims 1 to 3, characterized in that, The diol or diamine containing a disulfide bond includes one or more of 2,2'-diaminodiphenyl disulfide, bis(2-hydroxyethyl) disulfide, 4,4′-dihydroxydiphenyl disulfide, 3,3′-dithiodiphenylphenol, cystamine, 4,4′-diaminodiphenyl disulfide, and 3,3′-dithiodiphenylamine; and / or, The isocyanate polymer includes one or more of polyhexamethylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate trimer, L-lysine triisocyanate, and triphenyl isocyanate thiophosphate; and / or, The catalyst includes one or more of organotin catalysts, tin salt catalysts, organozinc catalysts, and zinc salt catalysts; Optionally, the catalyst comprises one or more of dibutyltin dilaurate, zinc acetate, stannous octoate, stannous isooctanoate, and zinc acetylacetonate.

5. A method for preparing a polymer material, characterized in that, Includes the following steps: The polymer material is prepared by curing a mixture comprising a diol or diamine containing disulfide bonds, polylactic acid diol, isocyanate polymer, and a catalyst.

6. The method for preparing the polymer material as described in claim 5, characterized in that, The polylactic acid diol has a relative molecular weight of 500-2000; and / or, The relative molecular weight of the diol or diamine containing a disulfide bond is ≤500; and / or, The molar ratio of the diol or diamine containing disulfide bonds to the polylactic acid diol is (0.5-2):1; and / or, The ratio of the total molar amount of isocyanate in the isocyanate polymer to the total molar amount of hydroxyl and amino groups in the diol or diamine containing disulfide bonds and the polylactic acid diol is (1-1.2):1; and / or, The mass percentage of the catalyst relative to the total mass of the diol or diamine containing disulfide bonds, the polylactic acid diol, and the isocyanate polymer is 0.5wt%-6wt%.

7. The method for preparing the polymer material as described in claim 5 or 6, characterized in that, The diol or diamine containing a disulfide bond includes one or more of 2,2'-diaminodiphenyl disulfide, bis(2-hydroxyethyl) disulfide, 4,4′-dihydroxydiphenyl disulfide, 3,3′-dithiodiphenylphenol, cystamine, 4,4′-diaminodiphenyl disulfide, and 3,3′-dithiodiphenylamine.

8. The method for preparing the polymer material as described in claim 5 or 6, characterized in that, The isocyanate polymers include one or more of polyhexamethylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate trimer, L-lysine triisocyanate, and triphenyl isocyanate thiophosphate.

9. The method for preparing the polymer material as described in claim 5 or 6, characterized in that, The catalyst includes one or more of organotin catalysts, tin salt catalysts, organozinc catalysts, and zinc salt catalysts; Optionally, the catalyst comprises one or more of dibutyltin dilaurate, zinc acetate, stannous octoate, stannous isooctanoate, and zinc acetylacetonate.

10. The use of a polymer material prepared by any one of claims 1 to 4 or by any one of claims 5 to 9 in the preparation of medical surgical fixation materials.

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