Shapeable composite material, preparation method and application thereof, and medical orthopedic external fixation material

Abstract

The invention belongs to the technical field of biomedicine, and provides a moldable composite material, a preparation method and application thereof, and a medical orthopedic external fixation material. The polycaprolactone, the heat-conducting filler powder, the hollow glass beads and the gypsum powder in a specific ratio are combined as main preparation raw materials of the moldable composite material, and the moldable composite material can quickly respond to the temperature, so that the moldable composite material can be quickly softened and molded and quickly cooled, cured and shaped, and is light in weight, high in strength, free of stickiness, brittleness and powder falling, good in pressure resistance and long in service life. Furthermore, the moldable composite material can be used as a medical external fixing material for the orthopedics department, can be molded according to the requirements of different patients, is high in adaptability, high in fitting degree, good in air permeability, high in strength, skin-friendly, good in cold and heat conductivity and low in sensitization, can be worn by a human body for a long time, and can be used for showering in a healing period; x-ray images can pass through, and the temperature range is wide; and the device can be used instantly, and can meet the timely use requirements of external fracture fixation people.

Description

Technical Field

[0001] The present invention relates to the technical field of biomedical materials, and more specifically, to a plastic composite material, a preparation method and application thereof, and a medical orthopedic external fixation material. Background Art

[0002] Medical orthopedic external fixation materials are commonly used in external fixation and correction treatments for long bone fractures of the limbs, pelvic fractures, and various bone diseases. Commonly used materials include plaster, metal splints, and polymer materials (polymer bandages and splints, such as polyester fiber and rubber). These medical orthopedic external fixation materials generally need to meet at least the following criteria: ① They are non-damaging to the soft tissue surrounding the immobilized limb, maintaining normal blood flow to the injured area and not affecting normal healing; ② They can effectively fix the affected area, eliminating rotational, shear, and angulation forces that are detrimental to fracture healing, ensuring relative stability of the fracture ends and creating favorable conditions for fracture healing; ③ They have a high degree of compatibility with the joints of the injured limb and low constraint force, facilitating early functional mobility; and ④ They possess a certain strength and can correct residual displacement after fracture reduction. However, currently used fixation materials each have some drawbacks. Typically, closed fractures are often accompanied by a certain degree of edema. After the edema disappears, the fit of traditional splints decreases, making secondary reshaping difficult and the fixation effect less than expected. Polymer bandages commonly used in clinical practice require special electric saws to disassemble after surgery, which is highly dangerous and cumbersome to operate; polymer splints have poor air permeability and are prone to allergies, requiring multiple replacements; low-temperature thermoforming plates require stretching and pressurization operations, which can easily cause docking and displacement of the affected area; modular protective gear (prefabricated products) is only suitable for large areas, is rigid and uncomfortable, has many specifications, is expensive, and is complex to operate; although 3D printing materials have a high degree of fit, they are expensive, have high equipment costs, cannot be adjusted and shaped secondary, and the printing cycle takes at least 3-4 days, which cannot meet the clinical needs of immediate emergency use. For some fracture patients, callus has already begun to form without docking and fixation, resulting in many usage defects.

[0003] Therefore, there is an urgent need to develop a medical orthopedic external fixation material with high fit, light weight, high strength, easy operation, strong plasticity, secondary reshaping and strong stability, which can handle various fracture conditions and even have a good fixation effect on complex fracture conditions. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a shapeable composite material, a preparation method and application thereof, and a medical orthopedic external fixation material. The shapeable composite material provided by the present invention has the characteristics of high fit, light weight, high strength, strong shapeability, the ability to be reshaped (first heated to soften, then cooled and hardened after shaping), and strong stability. It can be further used as a medical orthopedic external fixation material for various fractures. Even complex fractures can be well fitted, and the operation is simple, which can achieve a reliable fixation effect.

[0005] A first aspect of the present invention provides a shapeable composite material.

[0006] Specifically, a shapeable composite material comprises the following raw materials in parts by weight:

[0007] Polycaprolactone 7-10 parts,

[0008] 0.5-2 parts of thermal conductive filler powder,

[0009] Hollow glass beads 0.1-1 parts,

[0010] 0.15-0.5 parts of gypsum powder.

[0011] After melting, polycaprolactone (PCL) can coat other components, improving adhesion between them and preventing powder loss. It also imparts free shaping, setting, and memory properties to the material. It is biodegradable and environmentally friendly. However, excessive amounts of PCL can cause the product's surface to become sticky and prolong cooling time, while too little can lead to brittleness, discoloration, and powder loss. Thermally conductive filler powders (such as aluminum powder) conduct heat and cold, allowing the material to absorb temperature changes more quickly and evenly, allowing for rapid softening and shaping, as well as rapid cooling and setting. However, excessive amounts can lead to brittle products, while too little can create a sticky feel, poor heat transfer, and prolonged curing time. Hollow glass beads, as fillers, not only reduce material weight but also improve compressive strength and reduce surface stickiness. However, excessive amounts can lead to brittle products, while too little can result in a sticky surface and insufficient compressive strength. Gypsum powder imparts a high degree of hardness to the material, but excessive amounts can make the product brittle and heavy, while too little can lead to insufficient hardness. The present invention utilizes a combination of polycaprolactone, thermally conductive filler powder, hollow glass beads and gypsum powder in a specific ratio, so that the material not only responds quickly to temperature, thereby achieving rapid softening and shaping as well as rapid cooling and solidification, but also makes the material light in weight, high in strength, non-sticky, non-brittle, non-powder-shedding, and has good pressure resistance, thus meeting the needs of medical fixation materials.

[0012] Preferably, the following raw materials are included in the preparation, based on parts by weight:

[0013] Polycaprolactone 8-9 parts,

[0014] 0.5-1.5 parts of thermal conductive filler powder,

[0015] 0.4-0.6 parts of hollow glass beads,

[0016] 0.23-0.27 parts of gypsum powder.

[0017] More preferably, the following raw materials are included in the preparation, based on parts by weight:

[0018] Polycaprolactone 8.5-9 parts,

[0019] 1-1.5 parts of thermal conductive filler powder,

[0020] 0.5-0.6 parts of hollow glass beads,

[0021] 0.25-0.27 parts of gypsum powder.

[0022] Preferably, the thermally conductive filler powder is at least one of aluminum powder, alumina powder, copper powder, and aluminum nitride powder.

[0023] Further preferably, the thermally conductive filler powder is aluminum powder.

[0024] Preferably, the average particle size of the thermally conductive filler powder is 0.1-0.3 mm.

[0025] More preferably, the average particle size of the thermally conductive filler powder is 0.178-0.2 mm.

[0026] Preferably, the average particle size of the hollow glass beads is 0.0005-0.002 mm.

[0027] More preferably, the average particle size of the hollow glass beads is 0.001-0.002 mm.

[0028] Preferably, the average particle size of the gypsum powder is 0.0005-0.002 mm.

[0029] More preferably, the average particle size of the gypsum powder is 0.001-0.002 mm.

[0030] Preferably, the softening temperature of the shapeable composite material is 55-65° C., and / or the softening time of the shapeable composite material is 15-45 seconds.

[0031] Further preferably, the softening temperature of the shapeable composite material is 55-60° C., and / or the softening time of the shapeable composite material is 15-20 seconds.

[0032] Preferably, the curing temperature of the shapeable composite material is 10-30° C., and / or the curing time of the shapeable composite material is 1-5 minutes.

[0033] Further preferably, the curing temperature of the shapeable composite material is 20-28° C., and / or the curing time of the shapeable composite material is 2-5 minutes.

[0034] After being softened by heating, the moldable composite material can be molded into any shape, and then cooled and hardened to play a good fixing role. Therefore, it can be used as a medical orthopedic external fixation material. According to the location of the fracture, it can be stably fitted to the affected area after secondary shaping.

[0035] A second aspect of the present invention provides a method for preparing a shapeable composite material.

[0036] A method for preparing a shapeable composite material comprises the following steps:

[0037] The polycaprolactone, heat-conducting filler powder, hollow glass beads and gypsum powder are mixed, melted, granulated, dried, extruded and cooled to prepare the shapeable composite material.

[0038] The present invention first mixes the raw materials and then melts them to make the components evenly mixed, which is beneficial to improving the shrinkage rate, hardness, strength, toughness and heat and cold conductivity. Then granulation is performed to complete the material modification, and then drying, extrusion and cooling are performed to obtain the finished product.

[0039] Preferably, the melting temperature is 160-190° C., and / or the melting time is 3-8 minutes.

[0040] Preferably, the extrusion is carried out in a screw plastic extruder.

[0041] Further preferably, the extrusion is carried out in a screw plastic extruder, and the temperature of the screw plastic extruder is 160-210° C. During the extrusion heating process, the mixed material is softened.

[0042] More preferably, the temperature of the screw plastic extruder is 170-200°C.

[0043] Preferably, the cooling temperature is 18-25° C., and / or the cooling time is 3-5 minutes.

[0044] A third aspect of the present invention provides an application of a shapeable composite material.

[0045] The invention discloses an application of a shapeable composite material as a medical external fixation material, a decorative material, a packaging material or a building material.

[0046] A fourth aspect of the present invention provides a medical orthopedic external fixation material.

[0047] A medical orthopedic external fixation material is made from the plastic composite material.

[0048] Preferably, the medical orthopedic external fixation material is a medical orthopedic external fixation splint.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The present invention uses a specific ratio of polycaprolactone (PCL), thermal conductive filler powder, hollow glass beads, and gypsum powder as the main raw materials for preparing the plastic composite material, so that the material can not only respond quickly to temperature, thereby achieving rapid softening and shaping as well as rapid cooling and solidification, but also make the material highly conformable, light in weight, high in strength, non-sticky, non-brittle, non-powder-shedding, and have good pressure resistance, thus meeting the needs of medical fixation materials. Furthermore, the shapeable composite material can be used as a fixation material for external use in medical orthopedics. It has unique self-adhesiveness and can be arbitrarily shaped. Its self-adhesiveness can be used to shape the wire or plate into a closed shape or annular structure. It can be shaped according to the individual needs of different patients. Even when dealing with complex fractures, it has high plasticity and can meet the clinical needs of large parts (elbows, wrists, bare bones, limbs, etc.) and small parts (fingers, palms, noses, etc.); it has strong adaptability, good breathability, high strength, skin-friendly, good heat and cold conductivity, and low allergenicity, allowing the human body to wear it for a long time. During the bone healing period, it can be washed and showered without affecting the deformation and strength of the product. It can be imaged by X-rays, has a wide temperature range (for example, it can be softened at a water temperature of 55-65°C), and has a low melting point, which greatly reduces the chance of burns in actual applications. It can soften in seconds at 10-30°C and completely harden and set within 5 minutes after softening, thereby shortening clinical time. It can be used repeatedly without reducing the effectiveness of shaping, does not require prefabrication, and can be used immediately, providing an excellent new material for clinical fracture external fixation, sports rehabilitation and plastic surgery rehabilitation treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 This is a diagram of a process of fixing a hand using the shapeable composite material of Example 1 in Application Example 1 of the present invention;

[0052] Figure 2 This is a diagram showing the use of the shapeable composite material of Example 1 of the present invention for fixing different parts. DETAILED DESCRIPTION

[0053] In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the following examples are given for illustration. It should be noted that the following examples do not limit the scope of protection claimed by the present invention.

[0054] Unless otherwise specified, the raw materials, reagents, or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0055] Example 1

[0056] A shapeable composite material, comprising the following raw materials in parts by weight:

[0057] 8.5 parts of polycaprolactone, 1 part of aluminum powder, 0.5 parts of hollow glass beads, and 0.25 parts of gypsum powder.

[0058] The method for preparing the above-mentioned shapeable composite material comprises the following steps:

[0059] 8.5 parts of polycaprolactone, 1.0 part of aluminum powder, 0.5 parts of hollow glass beads and 0.25 parts of gypsum powder are mixed and poured into a dyeing mixer. The mixture is heated to a constant temperature until the raw materials are hot-melted. The constant melting temperature is 180°C and the hot-melting time is 5 minutes. The mixture is evenly stirred with polycaprolactone; then it enters the granulator for strip granulation to complete the modification of the material. After drying, the modified mixed material particles are poured into a screw plastic extruder. The temperature of the screw plastic extruder is set at 170°C to soften the modified polycaprolactone mixed particles. The screw is rotated and transported to the discharge port, and the modified and softened mixture is extruded from a special mold into a pipe sleeve, thereby forming a multi-layer stacked mesh hollow structure, wherein the width of the extruded mesh is: 520mm, the wire diameter is: 1.0mm; the thickness is 6.0±0.2mm, and the cavitation rate is 0.52g / cm 3 The screen is cooled in a cooling water pool (water temperature: 22°C, cooling time 4 minutes), dried, and then cut again to form a finished product of a shapeable composite material.

[0060] Example 2

[0061] A shapeable composite material, comprising the following raw materials in parts by weight:

[0062] 9 parts of polycaprolactone, 1.5 parts of aluminum powder, 0.6 parts of hollow glass beads, and 0.25 parts of gypsum powder. The preparation method of Example 2 is the same as that of Example 1.

[0063] Compared to Example 1, the moldable composite material produced in Example 2 exhibited enhanced flexural strength, a corresponding increase in raw material weight and conductivity, due to the increased aluminum powder content. However, the filament flowability during extrusion was slightly poor, resulting in a slower extrusion rate. Increasing the amount of polycaprolactone resulted in a longer molding time. By increasing the amounts of polycaprolactone and aluminum powder simultaneously, while maintaining the weights of the insulating glass and gypsum powder constant, the overall viscosity of the raw material increased.

[0064] Example 3

[0065] A shapeable composite material, comprising the following raw materials in parts by weight:

[0066] 8.5 parts of polycaprolactone, 1.0 part of aluminum powder, 0.6 parts of hollow glass beads, and 0.25 parts of gypsum powder. The preparation method of Example 3 is the same as that of Example 1.

[0067] Compared with Example 1, the shapeable composite material prepared in Example 3 has a slightly lower viscosity of the raw material due to the increase in the amount of hollow glass beads, while the other components remain unchanged, and is less likely to stick to hands or utensils during the shaping process; the overall weight is slightly lighter, the surface roughness of the raw material increases, the glossiness decreases, and the fluidity of the filaments during the extrusion preparation process slows down.

[0068] Comparative Example 1

[0069] A composite material, which differs from Example 1 in that polycaprolactone is replaced by polyurethane in equal parts by weight.

[0070] Since polyurethane is used as the raw material, the resulting composite material requires a higher temperature to soften (70-80°C). The rigidity after full fixation is slightly stronger than that of polycaprolactone, making it more difficult to shape during the shaping process. The bends need to be stretched and extended before they can be fitted and covered, which can easily cause displacement or dislocation of the fractured parts that have been reset. After full solidification, the fit with the skin is poor. And because polyurethane is too rigid, patients have poor wearing comfort, and long-term use can easily lead to friction damage to the skin and joints. Therefore, it needs to be used in combination with a soft lining, which greatly reduces the breathability and can easily cause allergies after long-term wear.

[0071] The present invention uses polycaprolactone as a raw material, resulting in a relatively low softening temperature (55-65°C) for the resulting moldable composite material, making it relatively safe to use and less prone to burns. After removing from the warm bath, the material can be applied to the skin after wiping dry, eliminating the need to wait or measure the cooling point, making it safe and convenient to use. Furthermore, polycaprolactone not only provides mechanical support with a certain strength (100N), but also offers flexibility and low friction with the skin, making it more comfortable to wear long-term.

[0072] Comparative Example 2

[0073] A composite material, which differs from Example 1 in that the hollow glass beads are replaced with glass fibers in equal parts by weight.

[0074] Comparative Example 2 replaces the hollow glass beads with an equal weight of glass fiber. Although the chemical composition of glass fiber is consistent with that of hollow glass beads, it is highly brittle and has poor wear resistance. Moreover, due to its filamentous structure, glass fiber is difficult to mix evenly with other raw material components. The raw material has poor fluidity, and the filament diameter is uneven, making it difficult to extrude. It may even completely block the filament outlet and prevent production.

[0075] The present invention utilizes hollow glass beads, whose hollow structure contributes to the overall lightweight product. Furthermore, after the hollow glass beads are mixed and interwoven with other components, some remain embedded in the raw material surface. Because the hollow glass beads are non-sticky, they reduce the viscosity of the surface of the moldable composite material, thereby offsetting the stickiness of the polycaprolactone and making the moldable composite material less likely to adhere to the heating container or the doctor's hand after softening. Furthermore, the circular structure of the hollow glass beads virtually unaffects the raw material's fluidity during the extrusion process, resulting in smooth extrusion, uniform wire diameter, and a high yield rate.

[0076] Comparative Example 3

[0077] A composite material, which differs from Example 1 in that the amount of hollow glass beads is increased to 3 parts.

[0078] The material prepared in Comparative Example 3 has lower toughness than that in Example 1, is more likely to break after shaping, and has lower self-adhesion of the raw material; during the extrusion preparation process, the flow rate of the raw material is reduced.

[0079] Comparative Example 4

[0080] A composite material, which differs from Example 1 in that the amount of polycaprolactone is increased to 13 parts.

[0081] Compared with Example 1, the elongation of the softened mesh or perforated plate of the material prepared in Comparative Example 4 is greatly increased, resulting in the product being too heavy after clamping and deforming, making the overall thickness of the product thinner or uneven, failing to achieve the expected strength and rigidity, and the deformation during the shaping process cannot meet the use requirements; at the same time, it is easier to adhere to the surface of the instrument or the hand than in Example 1, making it difficult to perform external fixation operations.

[0082] Comparative Example 5

[0083] A composite material, which differs from Example 1 in that the amount of aluminum powder is reduced to 0.2 parts.

[0084] The material prepared in Comparative Example 5 has a significantly lower thermal conductivity coefficient than that of Example 1, weaker bending strength, and overall decreased mechanical properties. The elongation of the material after softening (1.36%) is too large, causing deformation before use and making it unusable. At the same time, the softening time and hardening time are both significantly prolonged, from the original hardening time of 4.5 minutes to 6.5 minutes. On the one hand, this increases the difficulty of fixing the body position from softening to hardening, and on the other hand, it reduces the work efficiency of medical staff.

[0085] Application Example 1

[0086] The hand fixation test was carried out using the shapeable composite material prepared in Example 1. Figure 1As shown, the shapeable composite material of Example 1 is first soaked in hot water to soften ( Figure 1 A), softening temperature: 60℃, softening time: 20 seconds. Take it out after softening, wipe off the moisture, cover the affected area of the hand, manually shape it, and adjust the shape to fit the affected area completely. The shaping time is within 2 minutes after softening ( Figure 1 B), after 2 minutes (after the shaping time), the composite material begins to gradually harden and form at a hardening temperature of 24°C, and the complete hardening time is 2.5 minutes. Finally, trim the excess part and smooth it before covering it. You can also fix it with Velcro or elastic bandage ( Figure 1 C).

[0087] The shapeable composite material of the present invention is also suitable for external fixation of various other parts, such as Figure 2 As shown, such as wrists, noses, fingers, arms, backs of hands, elbows, palms, ankles, they can all fit securely.

[0088] Product effect testing

[0089] 1. Performance Testing

[0090] Test method:

[0091] 1. Strength test method: When the product is in the cured state at room temperature, a load of 100N is pressed into the material surface for 5 minutes. The concave amount should not be greater than 30mm; after the load is removed, the residual concave amount should be less than 3mm (GB / T 6569-2006 Fine Ceramics Bending Strength Test Method).

[0092] 2. Thermal conductivity test method: A material sample with a shape and size similar to a coin was selected for thermal conductivity measurement. A heat pulse was applied uniformly to one surface of the sample and maintained for 20 milliseconds (GB / T 22588-2008 Flash Method for Measurement of Thermal Diffusivity or Thermal Conductivity).

[0093] 3. Test method for elongation after softening: Cut samples with a length of 10 cm and equal diameter or thickness (cylinder diameter:

[0094] 5mm), put the sample into a constant temperature water bath at 60℃, and after 120 seconds, immediately take out the sample and place it on a table 30cm above the ground, fix one end and let it fall naturally. After 60 seconds, measure the changed length.

[0095] The results showed that the strength of the moldable composite material prepared in Example 1 was 100N, the thermal conductivity was 0.267, and the elongation after softening was 1.04%.

[0096] 2. Performance comparison with existing products

[0097] The performance of the shaped composite material obtained in Example 1 was compared with that of existing products, and the results were as follows:

[0098] Table 1 Performance results of the shaped composite material obtained in Example 1 and existing products

[0099]

[0100] In the table, ⊙ indicates excellent, ○ indicates good, △ indicates average, and × indicates completely unfeasible.

[0101] As can be seen from the above table, the moldable composite material provided in Example 1 of the present invention has multiple advantages over existing medical orthopedic external fixation materials, such as being easy to mold and re-moldable, not shrinking after molding, having no stickiness during use, having good air permeability, washability, good thermal conductivity, being able to be cold-applied, being able to be cut, and having X-ray penetrability.

Claims

1. A shapeable composite material, characterized in that: According to parts by weight, the following raw materials are included: Polycaprolactone 7-10 parts, 0.5-2 parts of thermal conductive filler powder, Hollow glass beads 0.1-1 parts, 0.15-0.5 parts of gypsum powder.

2. The shapeable composite material according to claim 1, characterized in that According to parts by weight, the following raw materials are included: Polycaprolactone 8-9 parts, 0.5-1.5 parts of thermal conductive filler powder, 0.4-0.6 parts of hollow glass beads, 0.23-0.27 parts of gypsum powder.

3. The shapeable composite material according to claim 1, characterized in that The average particle size of the thermally conductive filler powder is 0.1-0.3 mm, and / or the average particle size of the hollow glass beads is 0.0005-0.002 mm, and / or the average particle size of the gypsum powder is 0.0005-0.002 mm.

4. The shapeable composite material according to claim 1, characterized in that The softening temperature of the shapeable composite material is 55-65° C., and / or the softening time of the shapeable composite material is 15-45 seconds.

5. The shapeable composite material according to claim 1, characterized in that: The curing temperature of the shapeable composite material is 10-30° C., and / or the curing time of the shapeable composite material is 1-5 minutes.

6. The method for preparing the shapeable composite material according to any one of claims 1 to 5, characterized in that: The steps include: The polycaprolactone, heat-conducting filler powder, hollow glass beads and gypsum powder are mixed, melted, granulated, dried, extruded and cooled to prepare the shapeable composite material.

7. The method for preparing a shapeable composite material according to claim 6, wherein: The melting temperature is 160-190°C.

8. The method for preparing a shapeable composite material according to claim 7, wherein: The extrusion is carried out in a screw plastic extruder.

9. Use of the shapeable composite material according to any one of claims 1 to 5 as a medical external fixation material, decorative material, packaging material or building material.

10. A medical orthopedic external fixation material, characterized in that: It is made from the shapeable composite material according to any one of claims 1 to 5.

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