WO2020113474A1 - Matériau en éponge de polyuréthane, son procédé de préparation, son utilisation et article en éponge de polyuréthane - Google Patents

Matériau en éponge de polyuréthane, son procédé de préparation, son utilisation et article en éponge de polyuréthane Download PDF

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WO2020113474A1
WO2020113474A1 PCT/CN2018/119383 CN2018119383W WO2020113474A1 WO 2020113474 A1 WO2020113474 A1 WO 2020113474A1 CN 2018119383 W CN2018119383 W CN 2018119383W WO 2020113474 A1 WO2020113474 A1 WO 2020113474A1
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polyurethane sponge
sponge material
polyurethane
bioactive glass
boron
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PCT/CN2018/119383
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English (en)
Chinese (zh)
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崔旭
程德林
潘浩波
杨鸿生
黄程程
张朦
吴桐
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中国科学院深圳先进技术研究院
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Priority to PCT/CN2018/119383 priority Critical patent/WO2020113474A1/fr
Publication of WO2020113474A1 publication Critical patent/WO2020113474A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/44—Medicaments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/60—Materials for use in artificial skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers

Definitions

  • the present application relates to the technical field of biological materials, in particular to a polyurethane sponge material, its preparation method, application and polyurethane sponge products.
  • the skin is the largest regenerative organ of the human body and a barrier between the internal and external environment of the human body. It can effectively prevent infections caused by pathogens while maintaining the homeostasis of the body. After a small area of trauma, the skin can repair itself. When suffering large areas of trauma such as natural disasters, mechanical trauma, burns, and diabetic feet, the skin often fails to heal through its own repair function, and even further damages subcutaneous tissues, muscles, ligaments, nerves, blood vessels, and even bones, ultimately harming the patient life. Therefore, wound repair has become a challenging medical hotspot.
  • wound dressings to manage the wounds, using the dressings to cover wounds, absorb exudate and prevent infections, etc., to accelerate wound healing.
  • wound dressings not only need to have good biocompatibility, fluid absorption and retention, suitable mechanical strength and elasticity, but also have a bacteriostatic effect to prevent infection of the wound surface, and can promote wound healing.
  • polyurethane material is currently a type of wound dressing that has been researched and applied at home and abroad.
  • existing polyurethane medical dressings cannot effectively promote the formation of skin blood vessels and induce wound regeneration, and repair skin damage quickly in situ.
  • the existing polyurethane medical dressings are easy to cause adhesion to the wound surface, which is easy to cause secondary trauma.
  • the first object of the present application is to provide a polyurethane sponge material to at least alleviate one of the technical problems in the prior art.
  • the second object of the present application is to provide a method for preparing the above-mentioned polyurethane sponge material.
  • the method is simple and easy to operate, convenient for shaping, low in polymerization temperature, and convenient for application.
  • the third object of the present application is to provide the application of the above-mentioned polyurethane sponge material in the repair of wound tissue engineering.
  • the present application provides a polyurethane sponge material, including polyurethane and strontium boron bioactive glass dispersed in polyurethane.
  • the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 1-30 %.
  • the weight of the strontium boron bioactive glass is 5% to 25%, preferably 10% to 20%.
  • polyurethane is mainly prepared from polyether polyol and isocyanate
  • the polyurethane is mainly prepared from 50-93 parts by weight of polyether polyol and 7-50 parts by weight of isocyanate;
  • the polyurethane is mainly prepared from 55-85 parts by weight of polyether polyol and 10-40 parts by weight of isocyanate;
  • the polyurethane is mainly prepared from 65-75 parts by weight of polyether polyol and 20-30 parts by weight of isocyanate;
  • the number average molecular weight range of the polyether polyol is 500-2000, preferably 800-1500, more preferably 1000-1300;
  • the molecular weight range of the isocyanate is 150-250 g/mol, preferably 160-240 g/mol, and more preferably 180-220 g/mol.
  • the strontium boron bioactive glass is selected from one or at least two of the following compositions: aSrO ⁇ bXO ⁇ cB 2 O 3 ⁇ dP 2 O 5 ⁇ eSiO 2 ⁇ fY 2 O ;
  • a, b, c, d, e and f are mole fractions, a is 2-14, b is 2-22, c is 16-54, d is 2-6, e is 0-36, and f is 6-14; X is Ca and/or Mg, Y is Na and/or K;
  • a is 8-14, b is 10-20, c is 36-54, d is 2-4, e is 0-27, and f is 10-14;
  • the strontium boron bioactive glass is
  • the particle size of the strontium boron bioactive glass is not greater than 500 ⁇ m;
  • the strontium boron bioactive glass further includes one or at least two of ZnO, Ag 2 O, CuO and CeO 2 ;
  • the molar content of ZnO is 0-2%
  • the molar content of Ag 2 O is 0-0.5%
  • the molar content of CuO is 0-0.5%
  • the molar content of CeO 2 is 0-1%.
  • the pore size of the polyurethane sponge material is 20-2000 ⁇ m, preferably 50-1900 ⁇ m, more preferably 100-1800 ⁇ m;
  • the porosity of the polyurethane sponge material is 50-300 ppi, preferably 80-280 ppi, more preferably 100-260 ppi;
  • the moisture content of the polyurethane sponge material is 0-12 wt%, preferably 0-8 wt%, more preferably 0-5 wt%.
  • polyurethane sponge material is loaded with solid phase powder
  • each 1g of polyurethane sponge material is loaded with 10-200mg of solid phase powder, preferably 30-180mg, more preferably 50-150mg;
  • the solid phase powder includes one or at least two of antibiotics, protein powder or vitamins.
  • the present application also provides a method for preparing the above-mentioned polyurethane sponge material, which adopts a method of in-situ polymerization of polyurethane to disperse strontium-boron bioactive glass in polyurethane to obtain a polyurethane sponge material.
  • a polyurethane sponge slurry is obtained by mixing a solution of strontium boron bioactive glass and polyether polyol and an isocyanate, curing the slurry and drying it to obtain the polyurethane sponge material;
  • the preparation method of the strontium boron bioactive glass includes:
  • the raw materials of the components of the strontium boron bioactive glass are mixed and mixed evenly, and then heated and melted to obtain a mixture material; the mixture material is quenched to obtain a bioactive glass block, and the bioactive glass block is sequentially crushed and ball milled And sieving to obtain the strontium boron bioactive glass;
  • the solution of the polyether polyol is an aqueous solution of polyether polyol
  • the curing time is 1-10 minutes, preferably 2-8 minutes.
  • the present application also provides the above-mentioned polyurethane sponge material, or the application of the polyurethane sponge material prepared by the above-mentioned preparation method in the repair of wound tissue engineering.
  • the present application also provides a polyurethane sponge product comprising the above polyurethane sponge material, or the polyurethane sponge material obtained by applying the above preparation method.
  • the polyurethane sponge material provided by the present application includes polyurethane and strontium boron bioactive glass dispersed in polyurethane.
  • the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 1-30%.
  • the polyurethane sponge material provided by this application by adding strontium boron bioactive glass to promote wound healing on the basis of polyurethane, combines the properties of strontium boron bioactive glass and polyurethane, and the obtained polyurethane sponge material has good biological activity, Biodegradability and biocompatibility, can be used as a composite artificial skin for the integration of wound repair and treatment.
  • the strontium-boron bioactive glass will gradually degrade, forming a calcium phosphorus compound in situ, giving the polyurethane sponge material provided by the present application biological activity and degradability.
  • strontium-boron bioactive glass will release strontium (Sr), calcium (Ca), boron (B), magnesium (Mg) and silicon (Si) and other elements that are conducive to wound regeneration and angiogenesis during the degradation process.
  • the polyurethane sponge material provided by the application can effectively induce wound vascularization and skin regeneration and quickly repair full-thickness skin damage in situ, and it is not easy to cause adhesion and avoid secondary trauma, thus achieving a better effect in promoting wound repair .
  • the polyurethane sponge material provided in this application can form a local slightly alkaline environment, which can effectively resist the invasion of acidophilic bacteria and has a certain antibacterial performance.
  • the preparation method of the polyurethane sponge material provided by the present application adopts the method of in-situ polymerization of polyurethane to uniformly disperse the strontium boron bioactive glass in the polyurethane to obtain the polyurethane sponge material.
  • the method is simple and easy to operate, convenient to shape and convenient to apply, and the prepared polyurethane sponge material has good biological activity, biodegradability and biocompatibility.
  • 1A is a graph showing the size and morphology of strontium boron bioactive glass particles provided in Experimental Example 2 of the present application;
  • 1B is an infrared spectrum of strontium boron bioactive glass particles provided in Experimental Example 2 of the present application;
  • FIG. 3 is a scanning electron micrograph (SEM) of polyurethane sponge material provided in Experimental Example 2 of the present application, in which the white arrow is marked as strontium boron bioactive glass;
  • 5A is the result of the release of strontium (Sr) and boron (B) of the polyurethane sponge material matrix after the polyurethane sponge material with a 15% strontium-boron bioactive glass content provided in Experimental Example 4 of the present application is immersed in a phosphate buffer solution for different times;
  • 5B is the result of the release of strontium (Sr) and boron (B) of the polyurethane sponge material matrix after the polyurethane sponge material with a 45% strontium-boron bioactive glass content provided in Experimental Example 4 of the present application is immersed in a phosphate buffer solution for different times;
  • FIG. 6 is an in vitro drug release curve of the polyurethane sponge material provided by Experimental Example 5 of the present application after loading with gentamicin sulfate.
  • a polyurethane sponge material which includes polyurethane and strontium boron bioactive glass dispersed in polyurethane, and the weight of the polyurethane sponge material is 100%. The weight is 1-30%.
  • the polyurethane sponge material described in this application is a porous material with polyurethane as the matrix, and the strontium-boron bioactive glass is dispersed in the polyurethane matrix, wherein the strontium-boron bioactive glass can be dispersed on the surface of the polyurethane matrix It can also be dispersed in the interior of the polyurethane matrix, for example, in the porous pores, or it can be simultaneously dispersed on the surface of the polyurethane matrix and in the porous pores.
  • strontium boron bioactive glass means a bioactive glass containing "strontium boron" element.
  • the polyurethane sponge material includes polyurethane, strontium boron bioactive glass, optionally other components, and inevitable impurities. Among them, the sum of polyurethane, strontium boron bioactive glass, optionally other components, and the weight of impurities is 100%.
  • other components may be, for example, but not limited to antibiotics, growth factors, small molecule RNA, hyaluronic acid, collagen protein or vitamins, etc., which are helpful for wound healing.
  • the inevitable impurities may be, for example, but not limited to, reactants remaining after the polymerization reaction, or impurities such as potassium, sodium, or aldehyde impurities existing in the raw materials.
  • Strontium boron bioactive glass has excellent biological activity, biodegradability and biocompatibility, and can degrade and release strontium (Sr), calcium (Ca), boron (B), magnesium (Mg) and Silicon (Si) and other important elements for wound regeneration can stimulate the growth of endothelial cells and have a good skin regeneration effect; after the degradation process is completed, the strontium-boron bioactive glass can be converted into calcium and phosphorus compounds, which can effectively adsorb proteins and cells. Conducive to climbing and migration of new skin tissue.
  • the polyurethane sponge material provided in this application by adding strontium boron bioactive glass to promote wound healing on the basis of polyurethane, combining the properties of strontium boron bioactive glass and polyurethane, the obtained polyurethane sponge material has good biological activity, Biodegradability and biocompatibility, can be used as a composite artificial skin for the integration of wound repair and treatment.
  • the strontium-boron bioactive glass will gradually degrade, forming a calcium-phosphorus compound layer in situ, giving the polyurethane sponge material provided by the present application biological activity and degradability.
  • strontium-boron bioactive glass releases strontium (Sr), calcium (Ca), boron (B), magnesium (Mg), and silicon (Si) and other elements that are beneficial to wound regeneration and angiogenesis during the degradation process, making this
  • strontium-boron bioactive glass releases strontium (Sr), calcium (Ca), boron (B), magnesium (Mg), and silicon (Si) and other elements that are beneficial to wound regeneration and angiogenesis during the degradation process, making this
  • the polyurethane sponge material provided by the application can effectively induce wound vascularization and skin regeneration and quickly repair full-thickness skin damage in situ, and it is not easy to cause adhesion and avoid secondary trauma, thus achieving a better effect in promoting wound repair .
  • the polyurethane sponge material provided in this application can form a local slightly alkaline environment, which can effectively resist the invasion of acidophilic bacteria and has a certain antibacterial effect performance.
  • strontium boron bioactive glass Although strontium boron bioactive glass has good biological activity, degradability and wound regeneration ability, the amount of strontium-boron bioactive glass is not as much as possible. The amount of its addition only works within a certain range. In the present application, based on the weight of the polyurethane sponge material being 100%, the weight of the strontium-boron bioactive glass is 1-30%, for example, but not limited to 1%, 3%, 5%, 8%, 10% , 12%, 15%, 18%, 20%, 22%, 25%, 28% or 30%. Excessive addition of strontium boron bioactive glass will affect the porous structure and mechanical properties of the polyurethane sponge material, resulting in its inability to be used in the field of wound repair.
  • the amount of strontium-boron bioactive glass added is too small to improve the performance of polyurethane sponge materials to promote angiogenesis, induce wound regeneration and avoid secondary trauma.
  • the polyurethane sponge material provided by this application by adding 1-30% by weight of strontium boron bioactive glass, solves the problem that a single polyurethane sponge has certain exudate absorption capacity, good biocompatibility and mechanical properties, but cannot Effectively promote the formation of skin blood vessels and induce wound regeneration, quickly repair the full-thickness skin damage in situ, and easily adhere to the wound surface, which is easy to cause the shortcomings of secondary trauma, so that the polyurethane sponge material has good biological activity and biological Compatibility, at the same time, it can effectively promote the formation of skin blood vessels and induce the advantages of wound regeneration.
  • the weight of the strontium boron bioactive glass is 5% to 25%, preferably 10% to 20%.
  • the polyurethane sponge material provided by the present application has better biobiological activity and biocompatibility, and at the same time can more effectively promote the formation of skin blood vessels and induce wounds regeneration.
  • the polyurethane is mainly prepared from polyether polyol and isocyanate.
  • the polyurethane is mainly prepared from 48-97 parts by weight of polyether polyol and 2-22 parts by weight of isocyanate.
  • Polyether polyol (referred to as polyether for short) is composed of an initiator (a compound containing an active hydrogen group) and ethylene oxide (EO), propylene oxide (PO) or butylene oxide (BO) in the presence of a catalyst Next, a linear polymer made by ring-opening homopolymerization or copolymerization.
  • a typical but non-limiting polyether polyol may be polyoxypropylene glycol, polytetrahydrofurandiol, or tetrahydrofuran-propylene oxide copolymer diol.
  • the content may be, for example, but not limited to, 48 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, or 97 parts by weight.
  • Typical but non-limiting isocyanates can be toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethyl polyphenyl isocyanate (PAPI).
  • the content may be, for example, but not limited to, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, or 22 parts by weight.
  • the polyurethane is mainly prepared from 55-85 parts by weight of polyether polyol and 5-20 parts by weight of isocyanate.
  • the polyurethane is mainly prepared from 65-75 parts by weight of polyether polyol and 10-15 parts by weight of isocyanate.
  • the polyurethane sponge material provided in this application has better mechanical properties, fatigue properties and micro-porosity, and the pore structure is stable, and it has better biological properties Activity and biocompatibility.
  • the number average molecular weight of the polyether polyol is in the range of 500-2000, such as, but not limited to, 500, 600, 800, 1000, 1200, 1400, 1600, 1800 or 2000, preferably 800-1500, More preferably, it is 1000-1300.
  • the number average molecular weight of the polyether polyol can be measured by means such as GPC.
  • the molecular weight range of the isocyanate is 150-250g/mol, for example, it can be, but not limited to, 150g/mol, 180g/mol, 200g/mol, 220g/mol or 250g/mol, preferably 160-240g/mol, more preferably 180-220g/mol.
  • the polyurethane sponge material provided by the present application has better mechanical properties, fatigue properties and microscopic porosity, and the pore structure is stable, while having Better biological activity and biocompatibility.
  • the strontium-boron bioactive glass is selected from one or at least two of the following compositions: aSrO ⁇ bXO ⁇ cB 2 O 3 ⁇ dP 2 O 5 ⁇ eSiO 2 ⁇ fY 2 O;
  • a, b, c, d, e and f are mole fractions, a is 2-14, b is 2-22, c is 16-54, d is 2-6, e is 0-36, and f is 6-14; X is Ca and/or Mg, and Y is Na and/or K.
  • a is 8-14
  • b is 10-20
  • c is 36-54
  • d is 2-4
  • e is 0-27
  • f is 10-14.
  • the polyurethane sponge material provided by the present application has better biological activity and biocompatibility, and can effectively promote the formation and promotion of skin blood vessels Epithelial cells migrate and crawl on the wound surface, reduce the scar area and eventually induce wound regeneration.
  • the strontium boron bioactive glass includes:
  • the above-mentioned preferred components can regulate the degradation of strontium-boron bioactive glass, thereby better matching the rate of skin regeneration.
  • the particle size of the strontium-boron bioactive glass is not greater than 500 ⁇ m, and the particle size may be, for example, but not limited to 500 ⁇ m, 450 ⁇ m, 400 ⁇ m, 350 ⁇ m, 300 ⁇ m, 250 ⁇ m, 200 ⁇ m, 150 ⁇ m, 100 ⁇ m, 50 ⁇ m, 40 ⁇ m, 30 ⁇ m, 20 ⁇ m, 10 ⁇ m or 1 ⁇ m;
  • the strontium boron bioactive glass further includes one or at least two of ZnO, Ag 2 O, CuO, and CeO 2 .
  • zinc element can activate various enzymes in the body and induce wound healing; copper element can promote vascularization in the body; silver element has a certain antibacterial effect.
  • Adding one or at least two of ZnO, Ag 2 O, CuO, and CeO 2 to the strontium boron bioactive glass in the polyurethane sponge material provided by this application can further enhance the various functions of the polyurethane sponge material, such as antibacterial Antibacterial properties and promote angiogenesis.
  • the molar content of ZnO is 0-2%, for example, it can be, but not limited to, 0%, 0.5%, 1%, 1.5%, or 2%, and the molar content of Ag 2 O is 0-0.5%, for example, it can be , But not limited to 0%, 0.1%, 0.2%, 0.3%, 0.4% or 0.5%, the molar content of CuO is 0-0.5%, for example may be, but not limited to 0%, 0.1%, 0.2%, 0.3% , 0.4% or 0.5%, the molar content of CeO 2 is 0-1%, such as, but not limited to, 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8 %, 0.9% or 1%;
  • the pore size of the polyurethane sponge material is 20-2000 ⁇ m, such as, but not limited to, 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, 200 ⁇ m, 500 ⁇ m, 800 ⁇ m, 1000 ⁇ m, 1200 ⁇ m, 1500 ⁇ m, 1800 ⁇ m or 2000 ⁇ m, It is preferably 50-1900 ⁇ m, more preferably 100-1800 ⁇ m;
  • the porosity of the polyurethane sponge material is 50-300 ppi, for example, but not limited to 50 ppi, 100 ppi, 150 ppi, 200 ppi, 250 ppi or 300 ppi, preferably 80-280 ppi, more preferably 100-260 ppi.
  • Limiting the pore size and porosity of the polyurethane sponge material can further ensure the good biological activity, biodegradability and biocompatibility of the polyurethane sponge material provided by the present application, while effectively inducing vascularization of the wound surface and skin regeneration.
  • the polyurethane sponge material is dried to a moisture content of 0-12 wt%, preferably 0-8 wt%, more preferably 0-5 wt%.
  • the liquid absorption capacity of the polyurethane sponge material will decrease, which is not conducive to wound healing.
  • the polyurethane sponge material is loaded with solid phase powder.
  • polyurethane sponge materials can have corresponding additional functions, such as loading antibiotics, which can make polyurethane sea surface materials have better sterilization and antibacterial properties, effectively preventing wound infections, and loading vitamins. , Can provide nutrients for wounds, accelerate wound healing.
  • the solid powder is loaded on the inner and outer surfaces of the polyurethane sponge material.
  • the loading method is not limited, and the typical loading method may adopt the method of in-situ polymerization of polyurethane to disperse the strontium boron bioactive glass and the solid phase powder in the polyurethane to obtain the polyurethane sponge material loaded with the solid phase powder; or use the adsorption method
  • the solid phase powder can be adsorbed in the pores of the polyurethane sponge material; or in the prior art, a method for loading the solid powder in the pores may be used.
  • the solid powder may be, for example, but not limited to antibiotics, growth factors, small molecule RNA, hyaluronic acid powder, collagen powder, or vitamins.
  • each 1 g of polyurethane sponge material is loaded with 10-200 mg of solid phase powder, for example, but not limited to 10 mg, 20 mg, 50 mg, 80 mg, 100 mg, 120 mg, 150 mg, 180 mg or 200 mg; preferably 30-180 mg, more It is preferably 50-150 mg.
  • the solid phase powder is an antibiotic
  • a typical antibiotic may be gentamicin sulfate or rifampicin.
  • the present application also provides a method for preparing the above-mentioned polyurethane sponge material, which adopts a method of in-situ polymerization of polyurethane to disperse strontium-boron bioactive glass in polyurethane to obtain a polyurethane sponge material.
  • the method is simple and easy to operate, convenient to shape, and convenient to apply, and the prepared polyurethane sponge material has good biological activity, biodegradability and biocompatibility.
  • a solution of strontium boron bioactive glass and polyether polyol and isocyanate are mixed to obtain a polyurethane sponge slurry, which is cured and dried to obtain the polyurethane sponge material.
  • the solution of strontium boron bioactive glass and polyether and isocyanate at the initial stage of mixing are obtained as a paste-like paste, which has plasticity and undergoes free radical polymerization to obtain A polymer of polyurethane sponge; the paste-like slurry can self-solidify within a few minutes to form a solid substance with certain mechanical strength and skin repair ability, the solid substance is based on polyurethane, and the strontium boron is biologically active
  • the glass is evenly dispersed on the inside and the surface of the substrate to obtain a polyurethane sponge material.
  • the preparation method of the strontium boron bioactive glass includes:
  • the raw materials of the components of the strontium boron bioactive glass are mixed and mixed evenly, and then heated and melted to obtain a mixture material; the mixture material is quenched to obtain a bioactive glass block, and the bioactive glass block is sequentially crushed and ball milled And sieving to obtain the strontium boron bioactive glass.
  • strontium boron bioactive glass includes aSrO ⁇ bXO ⁇ cB 2 O 3 ⁇ dP 2 O 5 ⁇ eSiO 2 ⁇ fY 2 O; a, b, c, d, e and f are mole fractions, a is 2-14 , B is 2-22, c is 16-54, d is 2-6, e is 0-36, f is 6-14; X is Ca and/or Mg, Y is Na and/or K.
  • the raw materials of the components of the strontium-boron bioactive glass are taken, that is, SrO, XO, B 2 O 3 , P 2 O 5 , SiO 2 and Y 2 O are taken as raw materials and mixed uniformly according to the molar fraction.
  • the temperature for heating and melting is not limited, as long as it can achieve the purpose of melting.
  • the heating temperature is 1100-1250°C, which may be, for example, but not limited to 1100°C, 1150°C, 1180°C, 1200°C, 1220°C or 1250°C.
  • the melting time is not limited as long as it can achieve the purpose of melting.
  • the heating time is 2-5h, for example, it can be, but not limited to, 2h, 3h, 4h or 5h.
  • the polyurethane solution is an aqueous polyurethane solution, wherein the mass percentage of polyurethane is not limited, as long as the pore size of the prepared polyurethane sponge material is 20-2000 ⁇ m and the porosity is 50-300 ppi;
  • the curing time is 1-10 minutes, such as, but not limited to, 1 minute, 2 minutes, 5 minutes, 8 minutes or 10 minutes; preferably 2-8 minutes;
  • the present application also provides the above-mentioned polyurethane sponge material, or the application of the polyurethane sponge material prepared by the above-mentioned preparation method in the repair of wound tissue engineering.
  • the present application also provides a polyurethane sponge product comprising the above polyurethane sponge material, or the polyurethane sponge material obtained by applying the above preparation method.
  • a typical polyurethane sponge product can be obtained by processing the polyurethane sponge material through operations such as fixed size, packaging, or sterilization.
  • the prepared polyurethane sponge material is cut to an appropriate size as needed, it is packaged in a packaging bag and sealed, and then sterilized by irradiation, that is, a sterile biologically active polyurethane sponge dressing is prepared .
  • This embodiment provides a polyurethane sponge material, including polyurethane and strontium boron bioactive glass dispersed in polyurethane.
  • the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 1% .
  • strontium boron bioactive glass has the following composition:
  • This embodiment provides a polyurethane sponge material.
  • the difference from Embodiment 1 is that the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 30%.
  • This embodiment provides a polyurethane sponge material.
  • the difference from Embodiment 1 is that the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 5%.
  • This embodiment provides a polyurethane sponge material.
  • the difference from Embodiment 1 is that the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 25%.
  • This embodiment provides a polyurethane sponge material.
  • the difference from Embodiment 1 is that the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 10%.
  • This embodiment provides a polyurethane sponge material.
  • the difference from Embodiment 1 is that the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 20%.
  • This embodiment provides a polyurethane sponge material.
  • the difference from Embodiment 1 is that the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 15%.
  • This example provides a polyurethane sponge material.
  • the difference from Example 7 is that the strontium boron bioactive glass has the following composition:
  • This example provides a polyurethane sponge material.
  • the difference from Example 7 is that the strontium boron bioactive glass has the following composition:
  • This embodiment provides a polyurethane sponge material, which differs from Embodiment 7 in that the strontium boron bioactive glass has the following composition:
  • This example provides a polyurethane sponge material.
  • the difference from Example 7 is that the strontium boron bioactive glass has the following composition:
  • This example provides a polyurethane sponge material.
  • the difference from Example 7 is that the strontium boron bioactive glass has the following composition:
  • This example provides a polyurethane sponge material.
  • the difference from Example 7 is that the strontium boron bioactive glass has the following composition:
  • polyurethane sponge material.
  • polyurethane is mainly prepared from 48 parts by weight of polyoxypropylene glycol and 22 parts by weight of toluene diisocyanate.
  • polyurethane sponge material.
  • polyurethane is mainly prepared from 97 parts by weight of polytetrahydrofurandiol and 2 parts by weight of diphenylmethane diisocyanate.
  • polyurethane sponge material.
  • polyurethane is mainly prepared from 70 parts by weight of tetrahydrofuran-propylene oxide copolymer diol and 12 parts by weight of polymethyl polyphenyl isocyanate.
  • This embodiment provides a polyurethane sponge material, which is prepared by the following method:
  • the strontium boron bioactive glass 14SrO ⁇ 8CaO ⁇ 8MgO ⁇ 54B 2 O 3 ⁇ 2P 2 O 5 ⁇ 6Na 2 O ⁇ 8K 2 O raw materials after mixing, put the original ingredients in platinum kumquat Placed in the pot and placed in a silicon key furnace at 1100 °C, smelted for 5h, after taking out, the resulting clear glass liquid was poured on the preheated steel plate to obtain a strontium boron bioactive glass block.
  • the obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 1-10 ⁇ m is selected.
  • the mixture of the strontium boron bioactive glass and polyether polyol solution prepared above and the multiple methyl polyphenyl isocyanate is mixed to form a polyurethane sponge slurry, which is cured after 10 minutes A polyurethane sponge material is obtained.
  • This embodiment provides a polyurethane sponge material, which is prepared by the following method:
  • Strontium boron bioactive glass 8SrO ⁇ 12CaO ⁇ 8MgO ⁇ 54B 2 O 3 ⁇ 4P 2 O 5 ⁇ 6Na 2 O ⁇ 8K 2 O was weighed according to the molar ratio, after mixing, the original ingredients were put in platinum kumquat Place in the pot and put in a silicon key furnace at 1250°C, melt for 2h, and after taking out, pour the obtained clear glass liquid on the preheated steel plate to obtain a strontium boron bioactive glass block.
  • the obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 300-500 ⁇ m is selected.
  • the mixture of the strontium boron bioactive glass and polyether polyol solution prepared above and toluene diisocyanate is mixed to form a polyurethane sponge slurry, and the polyurethane sponge material is obtained after curing for 1 minute .
  • This embodiment provides a polyurethane sponge material, which is prepared by the following method:
  • strontium-boron bioactive glass 14SrO ⁇ 20CaO ⁇ 36B 2 O 3 ⁇ 2P 2 O 5 ⁇ 18SiO 2 ⁇ 10Na 2 O according to the molar ratio after mixing, put the original ingredients in the platinum kumquat pot and Placed in a silicon key furnace at 1200°C, melted for 3.5 hours, and after taking out, the obtained clear glass liquid was poured on a preheated steel plate to obtain a strontium boron bioactive glass block.
  • the obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 200-300 ⁇ m is selected.
  • the mixture of the strontium boron bioactive glass and polyether polyol solution prepared above and diphenylmethane diisocyanate is mixed to form a polyurethane sponge slurry, and the polyurethane is obtained after curing for 5 minutes Sponge material.
  • This embodiment provides a polyurethane sponge material, which is prepared by the following method:
  • strontium-boron bioactive glass 14SrO ⁇ 20CaO ⁇ 36B 2 O 3 ⁇ 2P 2 O 5 ⁇ 18SiO 2 ⁇ 10Na 2 O according to the molar ratio after mixing, put the original ingredients in the platinum kumquat pot and Placed in a silicon key furnace at 1200°C, melted for 3.5 hours, and after taking out, the obtained clear glass liquid was poured on a preheated steel plate to obtain a strontium boron bioactive glass block.
  • the obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 50-100 ⁇ m is selected.
  • This embodiment provides a polyurethane sponge material, which is prepared by the following method:
  • strontium-boron bioactive glass 14SrO ⁇ 19CaO ⁇ 36B 2 O 3 ⁇ 2P 2 O 5 ⁇ 18SiO 2 ⁇ 10Na 2 O ⁇ 1ZnO according to the molar ratio, after mixing, put the original ingredients in the platinum kumquat pot Inside and placed in a silicon key furnace at 1200 °C, melting for 3.5h, after taking out, the resulting clear glass liquid was poured on the preheated steel plate to obtain a strontium boron bioactive glass block.
  • the obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 20-50 ⁇ m is selected.
  • the mixture of the strontium boron bioactive glass and polyether polyol solution prepared above and diphenylmethane diisocyanate is mixed to form a polyurethane sponge slurry, and the polyurethane is obtained after curing for 5 minutes Sponge material.
  • polyurethane sponge material.
  • polyurethane is mainly prepared from 100 parts by weight of polytetrahydrofurandiol and 1 part by weight of diphenylmethane diisocyanate.
  • the present embodiment provides a polyurethane sponge material, different from Example 7 in that the bioactive glass comprises a boron strontium 1SrO ⁇ 22CaO ⁇ 15B 2 O 3 ⁇ 10P 2 O 5 ⁇ 12Na 2 O.
  • This embodiment provides a polyurethane sponge material, which is prepared by the following method:
  • strontium-boron bioactive glass 14SrO ⁇ 20CaO ⁇ 36B 2 O 3 ⁇ 2P 2 O 5 ⁇ 18SiO 2 ⁇ 10Na 2 O according to the molar ratio after mixing, put the original ingredients in the platinum kumquat pot and Placed in a silicon key furnace at 1000°C, melted for 1 h, and after taking out, the obtained clear glass liquid was poured on a preheated steel plate to obtain a strontium boron bioactive glass block.
  • the obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 10-20 ⁇ m is selected.
  • the mixture of the strontium boron bioactive glass and polyether solution prepared above and diphenylmethane diisocyanate is mixed to form a polyurethane sponge slurry, and the polyurethane sponge material is obtained after 15 minutes of curing .
  • the polyurethane sponge material prepared above is dried in an oven at 60°C until its moisture content is 15% by weight to obtain a polyurethane sponge material product.
  • This comparative example provides a polyurethane sponge material, which includes polyurethane and strontium boron bioactive glass dispersed in polyurethane.
  • the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 40% .
  • strontium boron bioactive glass has the following composition:
  • This comparative example provides a polyurethane sponge material, including polyurethane and strontium boron bioactive glass dispersed in polyurethane.
  • the weight of the polyurethane sponge material is 100%, and the weight of the strontium boron bioactive glass is 0.45% .
  • strontium boron bioactive glass has the following composition:
  • the polyurethane sponge materials provided in Examples 1-24 of the present application through the synergistic coordination between the bioactive glass with a specific content of strontium boron and polyurethane, make the polyurethane sponge materials provided by the present application have good biological activity , Biodegradability and biocompatibility, can effectively induce wound vascularization and skin regeneration and quickly repair full-thickness skin damage in situ, and it is not easy to cause adhesion, avoid secondary trauma, and achieve more in terms of promoting wound repair good effect.
  • the polyurethane sponge materials provided in Comparative Examples 1-3 are not as effective as the examples of the present application in terms of wound repair, anti-inflammatory effect, or prevention of adhesion.
  • the polyurethane sponge materials provided in Examples 1-7 have the same composition but only different proportions.
  • the polyurethane sponge materials provided in Examples 3-7 are superior to those in Examples 1 and 2 in terms of wound repair
  • the polyurethane sponge materials provided in Examples 5-7 are superior to those in Examples 3 and 4 in terms of wound repair.
  • the polyurethane sponge material provided in Example 7 is superior to that of Examples 1 and 2 in terms of wound repair. It means that under the same condition of the added strontium boron bioactive glass, by further adjusting and optimizing the content of the added strontium boron bioactive glass, the polyurethane sponge material provided by this application has better wound repair and anti-inflammatory Effect and prevent adhesion.
  • the polyurethane sponge material provided in Example 7-13 wherein the content of the strontium-boron bioactive glass is the same, but the composition raw materials and the ratio of the strontium-boron bioactive glass are different.
  • the polyurethane sponge materials provided in Examples 7-9 are superior to those in Examples 10-13 in terms of wound repair
  • the polyurethane sponge materials provided in Examples 12 and 13 are superior to those in Examples 10 and 11 in terms of wound repair. . It indicates that by further adjusting and optimizing the components and proportion of the strontium boron bioactive glass, the polyurethane sponge material provided by the present application has better wound repair, anti-inflammatory effect and prevention of adhesion.
  • the polyurethane sponge materials provided in Examples 14-16 wherein the composition ratio and content of the strontium boron bioactive glass are the same, but the ratio of the polyether polyol and isocyanate used to prepare the polyurethane is different.
  • the polyurethane sponge material provided in Example 16 is superior to Examples 14 and 15 in terms of wound healing. It shows that by further adjusting and optimizing the ratio of each raw material of polyurethane, the polyurethane sponge material provided in this application can have better wound repair, anti-inflammatory effect and prevention of adhesion.
  • Example 7 and Example 19 use the same raw materials, but Example 19 uses the preparation method provided in this application to prepare polyurethane sponge materials.
  • the polyurethane sponge materials provided in Example 19 no matter in wound repair, anti-inflammatory effects and The prevention of blocking was superior to that of Example 7 respectively. It shows that under the same conditions of raw materials, the polyurethane sponge material prepared by the preparation method provided by the present application has better wound repair, anti-inflammatory effect and prevention of adhesion.
  • Example 17-19 the same raw materials and the same preparation method were used for preparation, respectively, except that the preparation conditions and parameters were different.
  • the polyurethane sponge material provided in Example 19 is superior to Examples 17 and 18 in terms of wound repair, anti-inflammatory effect, and prevention of adhesion, respectively. It shows that under the same conditions of raw materials and methods, the polyurethane sponge material prepared by using the preferred preparation method provided by the present application has better wound repair, anti-inflammatory effect and prevention of adhesion.
  • Example 19 uses the same preparation method and raw materials, but antibiotics are loaded in Example 20.
  • the polyurethane sponge material provided in Example 20 has a better anti-inflammatory effect than Example 19.
  • Examples 19 and 21 use the same preparation method and raw materials, but ZnO is added to the strontium-boron bioactive glass in Example 21, and the polyurethane sponge material provided in Example 21 has a better induced wound surface than Example 19 The role of healing.
  • the polyurethane sponge materials provided in Example 7 and Comparative Example 2 and Comparative Example 3 have the same composition except for the content of strontium boron bioactive glass.
  • the polyurethane sponge material provided in Example 7 is superior to Comparative Example 2 and Comparative Example 3 in terms of wound repair, anti-inflammatory effect, and prevention of adhesion. It indicates that by further adjusting and optimizing the content of strontium-boron bioactive glass, the polyurethane sponge material provided by the present application has better wound repair, anti-inflammatory effect and prevention of adhesion.
  • Example 7 has the same composition as the polyurethane sponge material provided in Example 23, but the strontium-boron bioactive glass component in Example 23 is not within the preferred scope of this application, regardless of its role in wound repair, anti-inflammatory effect and adhesion prevention All aspects are inferior to the level of Example 7. It shows that the polyurethane sponge material provided by this application has better wound repair, anti-inflammatory effect and prevention of adhesion by further adjusting and optimizing the proportion of each component in the strontium boron bioactive glass.
  • the polyurethane sponge materials provided in Example 19 and Example 24 are prepared with the same composition and the same preparation method, respectively, only the preparation conditions are different, and the condition parameters of the preparation method provided in Example 24 are not within the scope of this application. Inside. It is inferior to Example 19 in terms of wound repair, anti-inflammatory effect and prevention of adhesion. It indicates that the polyurethane sponge material provided by this application has better wound repair, anti-inflammatory effect and prevention of adhesion by further adjusting and optimizing the condition parameters.
  • Example 9 the polyurethane sponge material provided in Example 9 with better effect is selected for the experiment.
  • the microscopic morphology and infrared spectrum are shown in Figure 1A and Figure 1B, respectively.
  • the prepared strontium-boron bioactive glass has irregular particle morphology and a particle size range of about several microns.
  • the infrared results shown in Fig. 1B show that the strontium-boron bioactive glass shows typical vibration peaks of silicon-oxygen and boron-oxygen.
  • the polyurethane sponge material obtained in Example 9 is packaged in a packaging bag and sealed, and then sterilized by irradiation to produce a sterile polyurethane sponge material product, as shown in FIG. 2.
  • Strontium boron bioactive glass 8SrO ⁇ 12CaO ⁇ 8MgO ⁇ 54B 2 O 3 ⁇ 4P 2 O 5 ⁇ 6Na 2 O ⁇ 8K 2 O was weighed according to the molar ratio, after mixing, the original ingredients were put in platinum kumquat Place it in a silicon key furnace at 1100-1200°C and melt for 5h. After taking it out, pour the obtained clear glass liquid on the preheated steel plate to obtain a strontium-boron bioactive glass block. The obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 100-200 ⁇ m is selected.
  • strontium-boron bioactive glass and polyurethane solution prepared above are mixed to prepare polyurethane sponge slurry with strontium-boron bioactive glass content of 10%, 20% and 30%. After curing for 10 minutes, the strontium-boron bioactive glass content is 10 %, 20% and 30% polyurethane sponge materials are named 10SrBG/JAZ, 20SrBG/JAZ and 30SrBG/JAZ respectively.
  • the polyurethane sponge material prepared above is dried in an oven at 60°C until its moisture content is 10% by weight to obtain a polyurethane sponge material product.
  • the samples of the experimental group and the control group used in the cytotoxicity test are 2cm*2cm square samples. All cytotoxicity tests are based on GB/T16886.5-2003.
  • the test method for the extract is selected, and the test is performed according to the recommended MTT method in GB/T14233.2-2005 "Cytotoxicity Test". The specific process is as follows:
  • Cell culture first take frozen L929 fibroblasts for recovery-culture-passage-culture process, when the cells are passed to the third generation (5-6 days under normal conditions), digest the cells use.
  • the relative proliferation rate (RGR) was calculated, and the cytotoxicity levels of the samples in the experimental group and the control group were determined according to the RGR.
  • the results of the cytotoxicity test at 3 and 7 days are shown in Figure 4.
  • the cell survival rate of the experimental group and the control group is higher than 80%, which shows that all components of the polyurethane sponge material have good biological compatibility.
  • Strontium boron bioactive glass 8SrO ⁇ 12CaO ⁇ 8MgO ⁇ 54B 2 O 3 ⁇ 4P 2 O 5 ⁇ 6Na 2 O ⁇ 8K 2 O was weighed according to the molar ratio, after mixing, the original ingredients were put in platinum kumquat Place it in a silicon key furnace at 1100-1200°C and melt for 5h. After taking it out, pour the obtained clear glass liquid on the preheated steel plate to obtain a strontium-boron bioactive glass block. The obtained strontium-boron bioactive glass block is crushed, ball-milled and sieved in sequence using a crushing device, and strontium-boron bioactive glass powder with a particle diameter of 100-200 ⁇ m is selected.
  • the polyurethane sponge materials are named 15SrBG/JAZ and 45SrBG/JAZ respectively.
  • the polyurethane sponge material prepared above is dried in an oven at 60°C until its moisture content is 10% by weight to obtain a polyurethane sponge material product.
  • the initial release rate of boron (B) and strontium (Sr) is relatively slow, and within 14-30 days, the release rate increases significantly.
  • the concentration of boron (B) and strontium (Sr) released after soaking is also higher.
  • the polyurethane sponge material can also be used as a drug carrier, the drug release rate is moderate, and meets the clinical requirements, thereby achieving a better effect in promoting its skin repair.

Abstract

La présente invention concerne un matériau en éponge de polyuréthane, son procédé de préparation, son utilisation et un article en éponge de polyuréthane, et concerne le domaine technique des matériaux biologiques. Le matériau en éponge de polyuréthane de la présente invention comprend du verre bioactif de strontium-bore et du polyuréthane. Le matériau en éponge de polyuréthane présente de bonnes activité biologique, biodégradabilité et biocompatibilité, et peut être utilisé en tant que peau artificielle composite de réparation des plaies et d'intégration de traitement. En outre, la vascularisation des plaies et la régénération de la peau peuvent être efficacement induites, les dégâts à la peau peuvent être rapidement réparés in situ, l'adhésion n'apparaît pas facilement, et un traumatisme secondaire est évité, ce qui permet d'atteindre de meilleurs effets de facilitation de la réparation des plaies. Le procédé de préparation pour le matériau en éponge de polyuréthane de la présente invention est simple et facile à faire fonctionner, peut atteindre de manière pratique un façonnage, présente une bonne température de polymérisation, et est facile à appliquer, et le matériau en éponge de polyuréthane préparé présente de bonnes activité biologique, biodégradabilité et biocompatibilité.
PCT/CN2018/119383 2018-12-05 2018-12-05 Matériau en éponge de polyuréthane, son procédé de préparation, son utilisation et article en éponge de polyuréthane WO2020113474A1 (fr)

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