Sulfur-containing degradable plastic orthopedic external fixation material and preparation method thereof

Abstract

The present invention relates to the technical field of polymer materials, and specifically to a sulfur-containing degradable plastic orthopedic external fixation material and a preparation method thereof. The sulfur-containing polymer prepared by copolymerization of elemental sulfur, epoxy monomer and olefin monomer has the advantages of light weight, high strength, damage resistance, fatigue resistance, low shrinkage and high plasticity, which can make up for the shortcomings of insufficient mechanical properties and difficult molding of traditional degradable polymer materials. The rich sulfur content in the material not only gives the material the characteristic of being degradable, but also shows obvious antibacterial effect, preventing secondary infection of the wound. The orthopedic external fixation material prepared by the present invention can show a high degree of plasticity at a temperature suitable for the human body, and can show strong support and stability when cooled to room temperature, which not only meets the fixation needs, but also avoids the physiological discomfort of patients caused by excessively high temperatures. At the same time, the material has the characteristics of antibacterial, degradable, low shrinkage rate, etc., and is a functional polymer orthopedic external fixation material.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a sulfur-containing degradable plastic orthopedic external fixation material and a preparation method thereof. Background Art

[0002] In the construction, transportation, and manufacturing industries, injuries to the limbs and spine caused by accidents are usually fixed with wood boards, splints, plaster, plastic materials, etc. to achieve the effect of trauma repair.

[0003] However, existing orthopedic fixation materials have problems such as poor air permeability, low plasticity, low strength, and heavy weight, which not only slow down the patient's recovery, but also have the risk of causing secondary trauma and secondary infection. For example, low material strength often leads to unstable fixation, and the wound cannot be effectively recuperated and treated; long-term use of orthopedic fixation materials will also cause bacteria to grow near the wound, increasing the possibility of wound lesions in patients; the low plasticity of the material also brings a workload to medical staff. On the other hand, traditional polymer materials have poor compatibility with the natural environment and cannot be degraded in a short time, thus causing environmental pollution.

[0004] Based on the above defects of traditional orthopedic external fixation materials, the use of degradable materials such as polylactic acid and polycaprolactone has certain biocompatibility and degradability, but still has problems such as harsh molding conditions, poor mechanical properties, and low antibacterial ability. Therefore, the development of orthopedic external fixation materials with simple synthesis process, high plasticity, degradability, light weight and high strength has always been a hot spot and difficulty in the polymer medical materials industry. Summary of the invention

[0005] In order to solve the use limitations of existing polymer-based orthopedic external fixation materials, the present invention provides a sulfur-containing degradable plastic orthopedic external fixation material and a preparation method thereof. The polymer orthopedic external fixation material of the present invention has strong antibacterial properties, is degradable and plastic, can be plastically fixed within a temperature range applicable to the human body, and more importantly, the material has extremely strong support and stability, and the preparation method is simple and the molding conditions are mild.

[0006] In order to achieve the above objectives, the present invention is implemented through the following technical solutions:

[0007] The sulfur-containing degradable plastic orthopedic external fixation material is prepared with a polysulfide polymer as a raw material, and the formula composition according to mass percentage is: 90-94wt% of polysulfide polymer, 2-3wt% of sorbitan monopalmitate, 1-2wt% of antistatic agent, 2-3wt% of activated carbon powder filler, and 0.5-2wt% of antioxidant.

[0008] The polysulfide polymer consists of 25-40 wt% elemental sulfur, 30-50 wt% polyether and 25-40 wt% polyolefin.

[0009] The polyolefin component in the polysulfide polymer is one or more of 1,4-butanediol diacrylate (BDDA), polyethylene glycol diacrylate (PEG-DA) or ethylene glycol diacrylate (EGDA);

[0010] The polyether component is one or more of bisphenol A diglycidyl ether (BADGE), epoxidized soybean oil (EO), and polyethylene glycol diglycidyl ether (PEG-GE).

[0011] The material forming process of the sulfur-containing biodegradable plastic orthopedic external fixation material is as follows:

[0012] A. Mix and extrude the dried polysulfide polymer, sorbitan monopalmitate, antistatic agent, activated carbon powder filler and antioxidant in an open mill at a certain temperature:

[0013] The refining temperature is 70-90℃ and the refining time is 10-30min.

[0014] B. Hot-pressing the formed mixture with medical polymer non-woven fabric to obtain sulfur-containing biodegradable plastic orthopedic external fixation material.

[0015] The hot pressing temperature is 90-120°C and the hot pressing time is 5-10 minutes.

[0016] Beneficial technical effects:

[0017] The sulfur-containing degradable plastic orthopedic external fixation material of the present invention has a double-crosslinked network structure that provides the material with strong mechanical properties. The material has excellent supporting properties and can effectively prevent patients from suffering secondary injuries.

[0018] The sulfur-containing degradable plastic orthopedic external fixation material prepared by the present invention can effectively inhibit bacterial growth and prevent external bacteria from causing wound infection due to its rich sulfur content.

[0019] The sulfur-containing degradable plastic orthopedic external fixation material prepared by the present invention can dynamically exchange SS bonds in the material at a relatively low temperature, and can exhibit high plasticity within the applicable range of the human body. On the other hand, the SS weak bonds and ester bonds in the material can be broken under certain conditions, which is specifically manifested in the degradation performance of the material, and is an environmentally friendly material.

[0020] The orthopedic external fixation material of the present invention has a simple preparation method, low raw material price, short production cycle, and greatly reduces the production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 1 and 2 are DSC curves of the orthopedic external fixation materials obtained in Examples 2 and 4.

[0022] Figure 2 The relaxation curves of the orthopedic external fixation materials obtained in Example 1, Example 2, Example 3, and Example 4 at 70°C.

[0023] Figure 3 The following are actual pictures of the unpackaged products of Example 2, Example 5, and Example 6 (from left to right).

[0024] Figure 4 This is the degradation of the products obtained in Example 2, Example 5, and Example 7 in a pH=1 aqueous solution. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present invention will be described clearly and completely below in combination with the embodiments and drawings. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Example 1

[0027] A method for preparing a sulfur-containing degradable plastic orthopedic external fixation material:

[0028] Take 90.13g of a polysulfide polymer containing 50wt% of polyether (BADGE), 25wt% of polyolefin (BDDA), and 25wt% of sulfur after impurity removal and drying, 2.53g of sorbitan monopalmitate, 1.22g of an antistatic agent, 2.81g of activated carbon powder, and 1.31g of an antioxidant, mix them in an open mill at 80°C for 20min, and hot-press the product with a medical polypropylene non-woven fabric at 100°C for 10min in a predetermined mold to obtain a sulfur-containing degradable and plastic orthopedic external fixation material.

[0029] The preparation method of the polysulfide polymer is as follows: the selected polyolefin, polyether and elemental sulfur are added into a reaction bottle according to the mass ratio, 0.5wt% of the total monomer amount of 1,8-diazabicycloundec-7-ene (DBU) catalyst is added, the sample is placed in an ethanol solution and stirred for 1h after reacting at 30°C for 6h, the step is repeated twice, and finally the sample is dried and stored dry.

[0030] Example 2

[0031] A method for preparing a sulfur-containing degradable plastic orthopedic external fixation material:

[0032] Take 182.72 g of a polysulfide polymer (prepared by the same method as in Example 1) containing 50 wt% of polyether (BADGE), 25 wt% of polyolefin (BDDA), and 25 wt% of sulfur after impurity removal and drying, 5.01 g of sorbitan monopalmitate, 2.52 g of an antistatic agent, 2.24 g of activated carbon powder, and 1.01 g of an antioxidant, mix and refine in a 90° C. mill for 10 min, and hot-press the product with a medical polypropylene non-woven fabric at 120° C. for 5 min in a predetermined mold to obtain a sulfur-containing degradable and plastic orthopedic external fixation material.

[0033] The preparation method of the polysulfide polymer is the same as that of Example 1.

[0034] Example 3

[0035] A method for preparing a sulfur-containing degradable plastic orthopedic external fixation material:

[0036] Take 190.51g of a polysulfide polymer (prepared by the same method as in Example 1) containing 40wt% of polyether (BAD-GE), 35wt% of polyolefin (EGDA) and 25wt% of sulfur after impurity removal and drying, 4.32g of sorbitan monopalmitate, 2.21g of an antistatic agent, 2.10g of activated carbon powder and 1.82g of an antioxidant, mix and refine in a 90°C mill for 15min, and hot-press the product with a medical polypropylene non-woven fabric at 120°C in a predetermined mold for 5min to obtain a sulfur-containing degradable and plastic orthopedic external fixation material.

[0037] Example 4

[0038] A method for preparing a sulfur-containing degradable plastic orthopedic external fixation material:

[0039] 227.51 g of a polysulfide polymer (prepared by the same method as in Example 1) containing 40 wt% of polyether (EO), 30 wt% of polyolefin (PEG-DA) and 30 wt% of sulfur after impurity removal and drying, 6.62 g of sorbitan monopalmitate, 3.32 g of an antistatic agent, 3.05 g of activated carbon powder and 2.82 g of an antioxidant were mixed and milled in an open mill at 80° C. for 15 min. The product was hot-pressed with a medical polypropylene non-woven fabric at 110° C. for 8 min in a predetermined mold to obtain a sulfur-containing degradable and plastic orthopedic external fixation material.

[0040] Example 5

[0041] A method for preparing a sulfur-containing degradable plastic orthopedic external fixation material:

[0042] 187.89 g of a polysulfide polymer (prepared by the same method as in Example 1) containing 30 wt% of polyether (EO), 35 wt% of polyolefin (EGDA) and 35 wt% of sulfur after impurity removal and drying, 4.21 g of sorbitan monopalmitate, 2.82 g of an antistatic agent, 2.51 g of activated carbon powder and 1.98 g of an antioxidant were mixed and milled in an open mill at 70° C. for 30 min. The product was hot-pressed with a medical polypropylene non-woven fabric at 90° C. for 10 min in a predetermined mold to obtain a sulfur-containing degradable and plastic orthopedic external fixation material.

[0043] Example 6

[0044] A method for preparing a sulfur-containing degradable plastic orthopedic external fixation material:

[0045] Take 221.09 g of a polysulfide polymer (prepared by the same method as in Example 1) containing 30 wt% of polyether (PEG-GE), 35 wt% of olefin (BDDA), and 35 wt% of sulfur after impurity removal and drying, 6.43 g of sorbitan monopalmitate, 3.32 g of an antistatic agent, 3.28 g of activated carbon powder, and 3.23 g of an antioxidant, mix and refine in a 90° C. mill for 30 min, and hot-press the product with a medical polypropylene non-woven fabric at 120° C. for 10 min in a predetermined mold to obtain a sulfur-containing degradable and plastic orthopedic external fixation material.

[0046] Example 7

[0047] A method for preparing a sulfur-containing degradable plastic orthopedic external fixation material:

[0048] 189.3 g of a polysulfide polymer (prepared by the same method as in Example 1) containing 30 wt% of polyether (EO), 35 wt% of polyolefin (PEG-DA) and 35 wt% of sulfur after impurity removal and drying, 6.21 g of sorbitan monopalmitate, 2.89 g of an antistatic agent, 3.56 g of activated carbon powder and 2.23 g of an antioxidant were mixed and milled in an open mill at 80° C. for 20 min. The product was hot-pressed with a medical polypropylene non-woven fabric at 110° C. for 10 min in a predetermined mold to obtain a sulfur-containing degradable and plastic orthopedic external fixation material.

[0049] Performance Test:

[0050] Tensile properties (GB / T 1040.1-2006)

[0051] Impact resistance (GB / T 1043.1-2008)

[0052] Shrinkage performance (GB / T 5471-2008) test

[0053] See Table 1 for data.

[0054] Table 1 Tensile, impact and shrinkage properties of orthopedic fixation materials in the examples

[0055]

[0056] Note: Mechanical properties test was performed before packaging; three groups of control experiments were established for each test example.

[0057] As shown in Table 1, the sulfur-containing biodegradable plastic orthopedic external fixation material synthesized by the present invention has excellent tensile properties, impact resistance, strong support and low shrinkage. It can meet the basic requirements of orthopedic external fixation materials. At the same time, the material can adjust its performance by changing the monomer feed and monomer type, and it also has a wide range of adaptability for fixation materials with special requirements.

[0058] The antibacterial properties of the sulfur-containing degradable plastic orthopedic external fixation material are shown in Table 2. According to the GB / T4789.2-2010 test standard, it can be seen that the sulfur-containing degradable plastic orthopedic external fixation material has excellent antibacterial properties.

[0059] Table 2 Antibacterial properties of sulfur-containing biodegradable plastic orthopedic external fixation materials

[0060]

[0061] The present invention prepares a sulfur-containing orthopedic external fixation material with low-temperature plasticity, high antibacterial properties, high strength and degradability in one step. The sulfur-containing degradable plastic orthopedic external fixation material prepared by the present invention can be quickly softened and plasticized within 5 minutes under a 50°C environment. When cooled to the surface temperature of human skin, it exhibits strong rigidity and toughness, playing a supporting and protective role. The rich sulfur content in the material provides excellent antibacterial properties, reducing the risk of external bacterial infection in patients. At the same time, the material can be successfully degraded in an alkaline aqueous solution, greatly reducing environmental pollution.

[0062] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A sulfur-containing degradable plastic orthopedic external fixation material, characterized in that: The orthopedic external fixation material is composed of: 90-94 wt% of polysulfide polymer, 2-3 wt% of sorbitan monopalmitate, 1-2 wt% of antistatic agent, 2-3 wt% of activated carbon powder filler, and 0.5-2 wt% of antioxidant in terms of mass percentage; The polysulfide polymer comprises, by weight percentage, 25-40 wt% of elemental sulfur, 30-50 wt% of polyether and 25-40 wt% of polyolefin; Wherein, the polyolefin is one or more of: 1,4-butanediol diacrylate BDDA, polyethylene glycol diacrylate PEG-DA or ethylene glycol diacrylate EGDA; The polyether is one or more of bisphenol A diglycidyl ether BADGE, epoxidized soybean oil EO or polyethylene glycol diglycidyl ether PEG-GE.

2. A method for preparing the sulfur-containing degradable plastic orthopedic external fixation material according to claim 1, characterized in that: The preparation method steps are as follows: A. Mix and extrude the dried polysulfide polymer, sorbitan monopalmitate, antistatic agent, activated carbon powder and antioxidant in an open mill according to the mass ratio; B. Hot-pressing the formed mixture with medical polymer non-woven fabric to obtain sulfur-containing biodegradable plastic orthopedic external fixation material.

3. The method for preparing the sulfur-containing degradable plastic orthopedic external fixation material according to claim 2, characterized in that: The refining temperature in step A is 70-90° C. and the refining time is 10-30 min.

4. The method for preparing the sulfur-containing degradable plastic orthopedic external fixation material according to claim 2, characterized in that: The hot pressing temperature in step B is 90-120° C., and the hot pressing time is 5-10 min. The sulfur-containing degradable plastic orthopedic external fixation material according to claim 1 is used as an orthopedic external fixation material.

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