Preparation method of 3D printing wound dressing
Technical Field
The invention belongs to the technical field of high molecular functional materials and biomedical materials, and particularly relates to a preparation method of a 3D printing wound dressing.
Background
The wound dressing can shorten the healing time of the wound surface, reduce the waste of resources, greatly reduce the medical workload and meet the requirements of patients. The gauze dressing is made of cotton or artificially synthesized, has a simple manufacturing process and is the dressing with the widest application so far. However, the traditional gauze dressing has many defects, such as easy bacteria breeding, easy formation of crust skin after wound exudate is adhered to dry dermal tissue, obstruction of epithelization process and the like; after the wound surface is adhered to the gauze, severe pain is easily caused when dressing change is carried out and even secondary wound is caused; the fiber of the gauze dressing is easy to fall off, which causes foreign body reaction and influences healing. Modern wound dressing is mainly characterized in that a moist environment is created around the wound surface to accelerate the healing of the wound surface.
Polyurethane-based hydrogels absorb and retain wound exudate, promote fibroblast proliferation and keratinocyte migration, which are essential for the intact epithelialization and healing of the wound. The hydrogel is soft and elastic, is convenient to use, has no damage after wound healing, can reduce the temperature of skin wounds, plays a role in relieving and cooling, has no irritation, no reaction to biological tissues, no permeability to metabolites, and good mechanical properties, and can support the use of the hydrogel as a wound dressing.
Polyacrylic acid gel is widely used in medical fields such as wound dressing, scar repairing gel, antipyretic patch and the like. Zinc has protective effect on cell injury caused by toxic substances such as biotoxin, heavy metal, H2O2 and alcohol. In 1967, Boris proposed that zinc has the effect of stimulating surgical wounds of people to promote healing, and oral administration of zinc sulfate of 600mg/d can accelerate granulation wounds of young patients to heal by 43% compared with a control group. Fox reported in 1976 that sulfadiazine zinc has a significant effect on external treatment of burn wounds, indicating that zinc ions accelerate burn wound healing.
The 3D printing technology can customize products in a personalized way, and particularly, the application of the 3D printing technology in medical materials such as dental materials and orthopedic materials is mature day by day, so that a very valuable direction is provided for solving personalized medical requirements.
In view of the above, the invention provides a wound dressing pad prepared by printing Thermoplastic Polyurethane (TPU), zinc polyacrylate ionomer, polyvinyl alcohol, polyvinyl pyrrolidone (PVP), zinc oxide and calcium carbonate microspheres into the wound dressing pad by using a 3D printing technology and adopting technical means such as surface treatment and the like to accelerate wound healing.
Disclosure of Invention
The invention aims to provide a preparation method of a 3D printing wound dressing, and the method provided by the invention solves the technical problem that the dressing can be customized according to the type of a wound and the size of the wound surface.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a 3D printing wound dressing comprises the following steps:
(1) mixing Thermoplastic Polyurethane (TPU) and a zinc polyacrylate ionomer, polyvinyl alcohol, polyvinyl pyrrolidone (PVP), zinc oxide and calcium carbonate microspheres according to a proportion, and preparing into a 3D printing consumable through melting, extruding and wire drawing;
(2) printing the consumables in the step (1) into a gasket by adopting a 3D printer;
(3) soaking the pad in dilute hydrochloric acid or dilute acetic acid, soaking the pad in dilute chitosan solution, taking out, soaking in dilute chondroitin sulfate solution, repeating the process for several times, taking out the pad, and naturally drying at room temperature to obtain the wound dressing for wound repair.
Preferably, step (2), the consumable material of step (1) is printed into a pad with a thickness of 2-5mm by a 3D printer at 135-200 ℃.
Preferably, in step (2), the gasket has a circular, square, oval or irregular shape.
Preferably, in the step (1), the thermoplastic polyurethane TPU, the zinc polyacrylate ionomer, the polyvinyl alcohol, the polyvinyl pyrrolidone (PVP), the zinc oxide and the calcium carbonate microspheres are mixed according to the mass fraction ratio of 20-60: 25-45: 5-15: 1-10: 0.1-0.5: 5-25 and mixing.
Preferably, in the step (1), the thermoplastic polyurethane TPU is medical grade, and the selectable brand is one or more of German Baschiv 1185A, German Bayer/255U or German Bayer/795U. The zinc polyacrylate ionomer can be selected from DuPont Surlyn9910 and Surlyn9020 resin or can be made by self. The polyvinyl pyrrolidone (PVP) has one or more of the molecular weights of 600000-1300000.
Preferably, the alcoholysis degree of the polyvinyl alcohol is 60-88%, and the molecular weight is 12-15 ten thousand. The particle size of the calcium carbonate microspheres is 0.5-15 μm.
Preferably, in the step (1), the melting temperature of melting, extruding and drawing is 120-155 ℃, and the diameter of the extruded and drawn wire is 1.75 mm.
Preferably, in the step (3), the concentration of the dilute hydrochloric acid or the dilute acetic acid is 0.5-2% (W/V). The soaking time of the dilute hydrochloric acid or the dilute acetic acid is 0.5 to 4 hours.
Preferably, in the step (3), the concentration of the dilute chitosan solution is 0.2-4% (W/V). The chitosan has molecular weight of 20-40 ten thousand daltons and deacetylation degree of 70-85%. Soaking in dilute chitosan solution for 5-25 min.
Preferably, in the step (3), the concentration of the dilute chondroitin sulfate solution is 0.1-4% (W/V). The molecular weight of the chondroitin sulfate used is 20000-50000. The soaking time in the chondroitin sulfate is 10-30 minutes.
Preferably, in the step (3), repeating for a plurality of times means repeating the process for 3 to 6 times in order.
Compared with the prior art, the invention has the beneficial effects that: the dressing gasket for treating the wound has controllable size, shape, thickness, pore diameter and porosity by adopting a 3D printing method, and the dressing can be customized according to the wound surface. The post-treatment 3D printing pad enables the dressing to obtain a surface with higher biocompatibility, and is beneficial to better healing of a wound surface.
The preparation method is simple in preparation process, high in yield and easy to industrialize, can be used for customizing the dressing pad in a personalized way according to the size and type of the wound surface, and can be widely applied to the wound surfaces which are difficult to heal, such as wounds, scalds, chemical burns, diabetic complications and the like.
The 3D printing wound dressing prepared by the invention can avoid pain caused by gauze replacement, and has a good wound repair effect. The 3D printing wound dressing prepared by the method has the advantages of high mechanical strength, good air permeability, easiness in promoting wound repair and the like, and can be used in the field of skin repair of wounds, scalds, diabetic ulcer skin wound surfaces and the like.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention, specific embodiments will be described below. It is obvious that the following description is only of some embodiments of the invention and that other embodiments can be obtained by those skilled in the art from these descriptions without inventive step.
Example 1:
a preparation method of a 3D printing wound dressing comprises the following steps:
(1) thermoplastic Polyurethane (TPU), zinc polyacrylate ionomer, polyvinyl alcohol, polyvinyl pyrrolidone (PVP), zinc oxide and calcium carbonate microspheres in a mass fraction ratio of 40: 25: 5: 5: 0.2: 8, mixing, melting, extruding and drawing to prepare the 3D printing consumable. The melting temperature is 120 ℃, and the diameter of the extrusion wire drawing is 1.75 mm.
In this step, the thermoplastic polyurethane TPU is medical grade, and german basf 1185A may be selected. The zinc polyacrylate ionomer can be DuPont Surlyn 9910. Polyvinylpyrrolidone (PVP) has a molecular weight of 600000. The alcoholysis degree of the polyvinyl alcohol is 60 percent, and the molecular weight is 12 ten thousand; the particle size of the calcium carbonate microspheres is 0.5 μm.
(2) Printing the consumables (1) into an elliptical gasket with the thickness of 3mm by adopting an FDM type 3D printer at 165 ℃;
(3) soaking the gasket in 2% (W/V) dilute hydrochloric acid for 2 hours, soaking the gasket in 1% (W/V) chitosan dilute solution for 15min, taking out the gasket, and soaking the gasket in 2% (W/V) chondroitin sulfate dilute solution for 15 min. The concentration of the chitosan dilute solution is 0.2 percent; the molecular weight of the chitosan is 20 kilodaltons, and the deacetylation degree is 70%. The concentration of the dilute solution of chondroitin sulfate is 0.1%, and the molecular weight of the chondroitin sulfate is 20000. The pad is taken out after the process is repeated for 5 times, and the pad is naturally dried at room temperature, so that the wound dressing for wound repair is prepared.
Example 2:
the preparation method of the 3D printing wound dressing comprises the following steps:
(1) thermoplastic Polyurethane (TPU), zinc polyacrylate ionomer, polyvinyl alcohol, polyvinyl pyrrolidone (PVP), zinc oxide and calcium carbonate microspheres in a mass fraction ratio of 45: 30: 8: 2: 0.1: and 5, mixing, melting, extruding and drawing to prepare the 3D printing consumable. The melting temperature is 155 ℃, and the diameter of the extrusion wire drawing is 1.75 mm.
In the step, the thermoplastic polyurethane TPU is medical grade, and German Bayer/795U can be selected. The zinc polyacrylate ionomer can be DuPont Surlyn9020 resin. Polyvinylpyrrolidone (PVP) has a molecular weight of 1300000. The alcoholysis degree of the polyvinyl alcohol is 88 percent, and the molecular weight is 15 ten thousand; the particle size of the calcium carbonate microspheres is 15 μm.
(2) Printing the consumables (1) into a rectangular gasket with the thickness of 2mm by adopting an FDM type 3D printer at 150 ℃;
(3) soaking the gasket in 2% (W/V) dilute acetic acid for 4 hours, then soaking the gasket in 1% (W/V) chitosan dilute solution for 20min, taking out the gasket, and then soaking the gasket in 1% (W/V) chondroitin sulfate dilute solution for 20 min. The concentration of the chitosan dilute solution is 4 percent; the molecular weight of the chitosan is 40 kilodaltons, and the deacetylation degree is 85%. The concentration of the dilute solution of chondroitin sulfate is 4%, and the molecular weight of the chondroitin sulfate is 50000. The pad is taken out after the process is repeated for 6 times, and the pad is naturally dried at room temperature, so that the wound dressing for wound repair is prepared.
Example 3:
the preparation method of the 3D printing wound dressing comprises the following steps:
(1) thermoplastic Polyurethane (TPU), zinc polyacrylate ionomer, polyvinyl alcohol, polyvinyl pyrrolidone (PVP), zinc oxide and calcium carbonate microspheres in a mass fraction ratio of 30: 25: 5: 2: 0.1: 15 mixing, melting, extruding and drawing to prepare the 3D printing consumable. The melting temperature is 135 ℃, and the diameter of the extrusion wire drawing is 1.75 mm.
In the step, the thermoplastic polyurethane TPU is medical grade, and German Bayer/255U can be selected. The zinc polyacrylate ionomer can be prepared by self. Polyvinylpyrrolidone (PVP) has a molecular weight of 1300000. The alcoholysis degree of the polyvinyl alcohol is 70 percent, and the molecular weight is 13 ten thousand; the particle size of the calcium carbonate microspheres is 7 μm.
(2) Printing the consumables (1) into irregular-shaped gaskets with the thickness of 4mm by adopting an FDM type 3D printer at 175 ℃;
(3) soaking the gasket in 2% (W/V) dilute hydrochloric acid for 1 hour, soaking the gasket in 0.2% (W/V) dilute chitosan solution for 25min, taking out the gasket, and soaking the gasket in 0.2% (W/V) dilute chondroitin sulfate solution for 25 min. The concentration of the chitosan dilute solution is 2 percent; the molecular weight of the chitosan is 30 kilodaltons, and the deacetylation degree is 78%. The concentration of the dilute solution of chondroitin sulfate is 2%, and the molecular weight of the chondroitin sulfate is 30000. Repeating the process for 3 times, taking out the gasket, and naturally drying at room temperature to prepare the wound dressing for wound repair.
The invention relates to a wound dressing which is constructed by using Thermoplastic Polyurethane (TPU) and a zinc polyacrylate ionomer as main materials through a 3D printing technology, pores are formed by adopting the reaction of calcium carbonate and acid, and a hydrophilic surface is obtained by dipping chitosan and a dilute chondroitin sulfate solution to obtain a personalized medical dressing with the function of accelerating healing. The method has simple manufacturing process, high yield and easy industrialization.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.