WO2020113474A1

WO2020113474A1 - Polyurethane sponge material, preparation method therefor, use thereof and polyurethane sponge article

Info

Publication number: WO2020113474A1
Application number: PCT/CN2018/119383
Authority: WO
Inventors: 崔旭; 程德林; 潘浩波; 杨鸿生; 黄程程; 张朦; 吴桐
Original assignee: 中国科学院深圳先进技术研究院
Priority date: 2018-12-05
Filing date: 2018-12-05
Publication date: 2020-06-11

Abstract

The present application provides a polyurethane sponge material, a preparation method therefor, a use thereof and a polyurethane sponge article, and relates to the technical field of biological materials. The polyurethane sponge material provided in the present application comprises strontium-boron bioactive glass and polyurethane. The polyurethane sponge material has good bioactivity, biodegradability and biocompatibility, and can be used as a composite artificial skin for wound repair and treatment integration. Furthermore, wound vascularization and skin regeneration can be effectively induced, skin damage can be quickly repaired in situ, adhesion is not easily caused, and secondary trauma is avoided, thereby achieving better effects in facilitating wound repair. The preparation method for the polyurethane sponge material provided in the present application is simple and easy to operate, can conveniently achieve shaping, has low polymerization temperature, and is easy to apply, and the prepared polyurethane sponge material has good bioactivity, biodegradability and biocompatibility.

Description

聚氨酯海绵材料及其制备方法、应用和聚氨酯海绵制品Polyurethane sponge material, its preparation method, application and polyurethane sponge product

技术领域Technical field

本申请涉及生物材料技术领域，尤其是涉及一种聚氨酯海绵材料及其制备方法、应用和聚氨酯海绵制品。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.

背景技术Background technique

皮肤是人体最大的再生器官，是人体内部与外部环境的屏障，能有效地预防病原体导致的感染，同时维持身体的内稳态。小面积创伤发生后皮肤能够实现自我修复。当遭受自然灾害、机械创伤、烧烫伤以及糖尿病足等大面积创伤时，皮肤通过自身的修复功能往往无法短期愈合，甚至进一步损伤皮下组织、肌肉、韧带、神经、血管甚至骨骼，最终危害患者的生命。因此创伤的修复已经成为一个颇具挑战的医学热点。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.

创面的临床治疗需要医用敷料对创面进行管理，利用敷料覆盖伤口、吸收渗出液和防止感染等，以加速创面愈合。通常，创伤敷料不仅要求具有良好的生物相容性、吸液保液性、适宜的力学强度和弹性，还应具有隔菌作用，以防止创面的感染，而且能够促进创面的愈合。聚氨酯材料因其安全、无毒、无刺激、不致敏、具有一定的渗出液吸收能力、良好的生物相容性和力学性能等特性，是目前国内外研究和应用较多的一类创伤敷料。然而，现有的聚氨酯医用敷料不能有效地促进皮肤血管的生成和诱导创面再生，原位地迅速修复皮肤损伤。且现有的聚氨酯医用敷料容易与创面发生粘连，易造成二次创伤。The clinical treatment of wounds requires medical dressings to manage the wounds, using the dressings to cover wounds, absorb exudate and prevent infections, etc., to accelerate wound healing. In general, 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. Because of its safe, non-toxic, non-irritating, non-allergenic, certain exudate absorption capacity, good biocompatibility and mechanical properties, polyurethane material is currently a type of wound dressing that has been researched and applied at home and abroad. . However, existing polyurethane medical dressings cannot effectively promote the formation of skin blood vessels and induce wound regeneration, and repair skin damage quickly in situ. Moreover, the existing polyurethane medical dressings are easy to cause adhesion to the wound surface, which is easy to cause secondary trauma.

因此，开发一种能够有效地促进皮肤血管的生成和诱导创面再生，原位地迅速修复全层皮肤损伤，且不易造成粘连，避免二次创伤的聚氨酯医用敷料尤为重要。Therefore, it is particularly important to develop a polyurethane medical dressing that can effectively promote the formation of skin blood vessels and induce wound regeneration, quickly repair full-thickness skin damage in situ, and not easily cause adhesion, and avoid secondary trauma.

有鉴于此，特提出本申请。In view of this, this application is hereby submitted.

发明内容Summary of the invention

本申请的第一个目的在于提供一种聚氨酯海绵材料，以至少缓解现有技术中存在的技术问题之一。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.

本申请的第二个目的在于提供上述聚氨酯海绵材料的制备方法，该方法简单易操作，塑形方便，聚合温度低，便于应用。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.

本申请的第三个目的在于提供上述聚氨酯海绵材料在创伤组织工程修复中的应用。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.

本申请提供了一种聚氨酯海绵材料，包括聚氨酯和分散在聚氨酯中的锶硼生物活性玻璃，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为1～30％。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 %.

进一步地，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为5％～25％，优选为10％～20％。Further, based on the weight of the polyurethane sponge material being 100%, the weight of the strontium boron bioactive glass is 5% to 25%, preferably 10% to 20%.

进一步地，其中，聚氨酯主要由聚醚多元醇与异氰酸酯制备得到；Further, wherein, polyurethane is mainly prepared from polyether polyol and isocyanate;

优选地，所述聚氨酯主要由聚醚多元醇50-93重量份和异氰酸酯7-50重量份制备得到；Preferably, the polyurethane is mainly prepared from 50-93 parts by weight of polyether polyol and 7-50 parts by weight of isocyanate;

优选地，所述聚氨酯主要由聚醚多元醇55-85重量份和异氰酸酯10-40重量份制备得到；Preferably, the polyurethane is mainly prepared from 55-85 parts by weight of polyether polyol and 10-40 parts by weight of isocyanate;

优选地，所述聚氨酯主要由聚醚多元醇65-75重量份和异氰酸酯20-30重量份制备得到；Preferably, the polyurethane is mainly prepared from 65-75 parts by weight of polyether polyol and 20-30 parts by weight of isocyanate;

优选地，所述聚醚多元醇的数均分子量范围为500-2000，优选为800-1500，更优选为1000-1300；Preferably, the number average molecular weight range of the polyether polyol is 500-2000, preferably 800-1500, more preferably 1000-1300;

优选地，所述异氰酸酯的分子量范围为150-250g/mol，优选为160-240g/mol，更优选为180-220g/mol。Preferably, the molecular weight range of the isocyanate is 150-250 g/mol, preferably 160-240 g/mol, and more preferably 180-220 g/mol.

进一步地，所述锶硼生物活性玻璃选自具有如下组成的锶硼生物活性玻璃中的一种或者至少两种：aSrO·bXO·cB ₂O ₃·dP ₂O ₅·eSiO ₂·fY ₂O； Further, 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 ;

其中，a、b、c、d、e和f为摩尔份数，a为2-14，b为2-22，c为16-54，d为2-6，e为0-36，f为6-14；X为Ca和/或Mg，Y为Na和/或K；Where 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;

优选地，a为8-14，b为10-20，c为36-54，d为2-4，e为0-27，f为10-14；Preferably, 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;

优选地，所述锶硼生物活性玻璃为Preferably, the strontium boron bioactive glass is

14SrO·8CaO·8MgO·54B ₂O ₃·2P ₂O ₅·0SiO ₂·6Na ₂O·8K ₂O、 14SrO·8CaO·8MgO·54B ₂ O ₃ ·2P ₂ O ₅ ·0SiO ₂ ·6Na ₂ O·8K ₂ O,

8SrO·12CaO·8MgO·27B ₂O ₃·4P ₂O ₅·27SiO ₂·6Na ₂O·8K ₂O或 8SrO·12CaO·8MgO·27B ₂ O ₃ ·4P ₂ O ₅ ·27SiO ₂ ·6Na ₂ O·8K ₂ O or

14SrO·20CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O中的一种或至少两种； One or at least two of 14SrO·20CaO·36B ₂ O ₃ ·2P ₂ O ₅ ·18SiO ₂ ·10Na ₂ O;

优选地，所述锶硼生物活性玻璃的粒径不大于500μm；Preferably, the particle size of the strontium boron bioactive glass is not greater than 500 μm;

优选地，所述锶硼生物活性玻璃还包括ZnO、Ag ₂O、CuO和CeO ₂中的一种或至少两种； Preferably, the strontium boron bioactive glass further includes one or at least two of ZnO, Ag ₂ O, CuO and CeO ₂ ;

优选地，ZnO的摩尔含量为0-2％，Ag ₂O的摩尔含量为0-0.5％，CuO的摩尔含量为0-0.5％，CeO ₂的摩尔含量为0-1％。 Preferably, 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%, and the molar content of CeO ₂ is 0-1%.

进一步地，所述聚氨酯海绵材料的孔尺寸为20-2000μm，优选为50-1900μm，更优选为100-1800μm；Further, the pore size of the polyurethane sponge material is 20-2000 μm, preferably 50-1900 μm, more preferably 100-1800 μm;

优选地，所述聚氨酯海绵材料的孔隙率为50-300ppi，优选为80-280ppi，更优选为100-260ppi；Preferably, the porosity of the polyurethane sponge material is 50-300 ppi, preferably 80-280 ppi, more preferably 100-260 ppi;

优选地，所述聚氨酯海绵材料的湿含量为0-12wt％，优选为0-8wt％，更优选为0-5wt％。Preferably, the moisture content of the polyurethane sponge material is 0-12 wt%, preferably 0-8 wt%, more preferably 0-5 wt%.

进一步地，所述聚氨酯海绵材料装载有固相粉剂；Further, the polyurethane sponge material is loaded with solid phase powder;

优选地，每1g聚氨酯海绵材料装载有10-200mg的固相粉剂，优选为30-180mg，更优选为50-150mg；Preferably, each 1g of polyurethane sponge material is loaded with 10-200mg of solid phase powder, preferably 30-180mg, more preferably 50-150mg;

优选地，所述固相粉剂包括抗生素、蛋白粉或维生素中的一种或至少两种。Preferably, the solid phase powder includes one or at least two of antibiotics, protein powder or vitamins.

本申请还提供了上述的聚氨酯海绵材料的制备方法，采用聚氨酯原位聚合的方法，使锶硼生物活性玻璃分散在聚氨酯中，得到聚氨酯海绵材料。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.

进一步地，将锶硼生物活性玻璃及聚醚多元醇的溶液和异氰酸酯混合得到聚氨酯海绵浆料，将所述浆料固化后干燥，得到所述聚氨酯海绵材料；Further, 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;

优选地，所述锶硼生物活性玻璃的制备方法包括：Preferably, the preparation method of the strontium boron bioactive glass includes:

按照摩尔比取锶硼生物活性玻璃的各组分原料并混合均匀，然后加热熔融得到混合物物料；将所述混合物物料淬冷得到生物活性玻璃块，所述生物活性玻璃块依次经过粉碎、球磨细碎和筛分，得到所述锶硼生物活性玻璃；According to the molar ratio, 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;

优选地，所述聚醚多元醇的溶液为聚醚多元醇水溶液；Preferably, the solution of the polyether polyol is an aqueous solution of polyether polyol;

优选地，所述固化的时间为1-10分钟，优选为2-8分钟。Preferably, the curing time is 1-10 minutes, preferably 2-8 minutes.

本申请还提供了上述的聚氨酯海绵材料，或应用上述的制备方法制得的聚氨酯海绵材料在创伤组织工程修复中的应用。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.

另外，本申请还提供了包含上述的聚氨酯海绵材料，或应用上述的制备方法制得的聚氨酯海绵材料的聚氨酯海绵制品。In addition, 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.

本申请提供的聚氨酯海绵材料，包括聚氨酯和分散在聚氨酯中的锶硼生物活性玻璃，以聚氨酯海绵材料的重量为100％计，锶硼生物活性玻璃的重量为1～30％。本申请提供的聚氨酯海绵材料，通过在聚氨酯的基础上加入了促进创面愈合的锶硼生物活性玻璃，综合了锶硼生物活性玻璃和聚氨酯的性能，制得的聚氨酯海绵材料具有良好的生物活性、生物降解性和生物相容性，可作为创面修复和治疗一体化的复合人工皮肤。同时，用于创面修复后，锶硼生物活性玻璃会逐渐降解，原位形成钙磷化合物，赋予本申请提供的聚氨酯海绵材料生物活性和降解性。并且，锶硼生物活性玻璃在降解过程中会释放有利于创面再生和成血管的锶(Sr)、钙(Ca)、硼(B)、镁(Mg)和硅(Si)等元素，使得本申请提供的聚氨酯海绵材料能够有效地诱导创面血管化和皮肤再生和原位地迅速修复全层皮肤损伤，且不易造成粘连，避免二次创伤，从而在促进创面修复方面达到了更为良好的效果。此外，由于锶硼生物活性玻璃的引入，与传统的聚氨酯海绵敷料相比，本申请提供的聚氨酯海绵材料能够形成局部微碱性环境，从而可以有效地抵御嗜酸性细菌的入侵，具有一定的抗菌性能。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. At the same time, after being used for wound repair, 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. In addition, 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 . In addition, due to the introduction of strontium boron bioactive glass, compared with the traditional polyurethane sponge dressing, 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.

本申请提供的聚氨酯海绵材料的制备方法，采用聚氨酯原位聚合的方法，使锶硼生物活性玻璃均匀分散在聚氨酯中，得到聚氨酯海绵材料。该方法简单易操作、塑形方便和便于应用，且制备得到的聚氨酯海绵材料具有良好的生物活性、生物降解性和生物相容性。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.

附图说明BRIEF DESCRIPTION

为了更清楚地说明本申请具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly explain the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings required for the specific embodiments or the description of the prior art. Obviously, the appended The drawings are some embodiments of the present application. For those of ordinary skill in the art, without paying any creative labor, other drawings can also be obtained based on these drawings.

图1A为本申请实验例2提供的锶硼生物活性玻璃颗粒的尺寸形貌结果图；1A is a graph showing the size and morphology of strontium boron bioactive glass particles provided in Experimental Example 2 of the present application;

图1B为本申请实验例2提供的锶硼生物活性玻璃颗粒的红外图谱；1B is an infrared spectrum of strontium boron bioactive glass particles provided in Experimental Example 2 of the present application;

图2为本申请实验例2提供的包装并灭菌后的聚氨酯海绵材料；2 is a packaged and sterilized polyurethane sponge material provided in Experimental Example 2 of the present application;

图3为本申请实验例2提供的聚氨酯海绵材料扫描电镜图谱(SEM)，其中白色箭头标记为锶硼生物活性玻璃；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;

图4为本申请实验例3提供的各组分不同配比的聚氨酯海绵材料的细胞相对增殖率结果；4 is the result of the relative cell proliferation rate of polyurethane sponge materials with different proportions of each component provided in Experimental Example 3 of the present application;

图5A为本申请实验例4提供的锶硼生物活性玻璃含量15％的聚氨酯海绵材料浸泡在磷酸盐缓冲溶液不同时间后，聚氨酯海绵材料基体的锶(Sr)和硼(B)的释放结果；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;

图5B为本申请实验例4提供的锶硼生物活性玻璃含量45％的聚氨酯海绵材料浸泡在磷酸盐缓冲溶液不同时间后，聚氨酯海绵材料基体的锶(Sr)和硼(B)的释放结果；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;

图6为本申请实验例5提供的聚氨酯海绵材料负载硫酸庆大霉素后的体外药物释放曲线。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.

具体实施方式detailed description

下面将结合实施例对本申请的技术方案进行清楚且完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The technical solution of the present application will be described clearly and completely in conjunction with the embodiments below. Obviously, the described embodiments are a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

根据本申请的一个方面，提供了一种聚氨酯海绵材料，包括聚氨酯和分散在聚氨酯中的锶硼生物活性玻璃，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为1～30％。According to an aspect of the present application, a polyurethane sponge material is provided, 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%.

在本申请所述的聚氨酯海绵材料，是一种多孔材料，聚氨酯作为基体，所述锶硼生物活性玻璃分散在聚氨酯基体中，其中，所述锶硼生物活性玻璃既可以分散在聚氨酯基体的表面，也可以分散在聚氨酯基体的内部，例如多孔的孔隙中，也可以同时分散在聚氨酯基体的表面和多孔的孔隙中。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.

本申请所述的锶硼生物活性玻璃意指，含有“锶硼”元素的生物活性玻璃。The strontium boron bioactive glass mentioned in the present application means a bioactive glass containing "strontium boron" element.

在本申请中，所述聚氨酯海绵材料包括聚氨酯、锶硼生物活性玻璃、可选地其它组分以及不可避免的杂质。其中，聚氨酯、锶硼生物活性玻璃、可选地其它组分以及杂质重量之和为100％。In the present application, 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%.

其中，可选地其它组分例如可以为，但不限于抗生素、生长因子、小分子RNA、透明质酸、胶原蛋白质或维生素等有助于创伤愈合的物质。Wherein, optionally 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.

不可避免的杂质例如可以为，但不限于聚合反应后剩余的反应物，或原料中存在的杂质如钾、钠或醛类杂质等。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.

锶硼生物活性玻璃，具有优异的生物活性、生物降解性和生物相容性，在人体体液中能降解并释放出锶(Sr)、钙(Ca)、硼(B)、镁(Mg)和硅(Si)等创面再生重要元素，可以刺激内皮细胞的生长，具有较好的皮肤再生效果；降解过程完成后，锶硼生物活性玻璃能够转化为钙磷化合物，能够有效地吸附蛋白和细胞，有利于新生皮肤组织的攀爬和迁移。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.

本申请提供的聚氨酯海绵材料，通过在聚氨酯的基础上加入了促进创面愈合的锶硼生物活性玻璃，综合了锶硼生物活性玻璃和聚氨酯的性能，制得的聚氨酯海绵材料具有良好的生物活性、生物降解性和生物相容性，可作为创面修复和治疗一体化的复合人工皮肤。同时，用于创面修复后，锶硼生物活性玻璃会逐渐降解，原位形成钙磷化合物层，赋予本申请提供的聚氨酯海绵材料生物活性和降解性。并且，锶硼生物活性玻璃在降解过程中会释放有利于创面再生和成血管的锶(Sr)、钙(Ca)、硼(B)、镁(Mg)和硅 (Si)等元素，使得本申请提供的聚氨酯海绵材料能够有效地诱导创面血管化和皮肤再生和原位地迅速修复全层皮肤损伤，且不易造成粘连，避免二次创伤，从而在促进创面修复方面达到了更为良好的效果。此外，由于锶硼生物活性玻璃的引入，与传统的聚氨酯海绵敷料相比，本申请提供的聚氨酯海绵材料能够形成局部微碱性环境，从而可以有效地抵御嗜酸性细菌的入侵，具有一定的抗菌性能。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. At the same time, after being used for wound repair, 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. In addition, 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 . In addition, due to the introduction of strontium boron bioactive glass, compared with the traditional polyurethane sponge dressing, 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.

锶硼生物活性玻璃虽然具有良好的生物活性、可降解性和诱导创面再生能力，但其加入的量也不是越多越好，其加入的量只有在一定的范围内起作用。在本申请中，以聚氨酯海绵材料的重量为100％计，锶硼生物活性玻璃的重量为1～30％，例如可以为，但不限于1％、3％、5％、8％、10％、12％、15％、18％、20％、22％、25％、28％或30％。锶硼生物活性玻璃加入的量过多会影响聚氨酯海绵材料的多孔结构和力学性能，导致其不能应用于创面修复领域。锶硼生物活性玻璃加入的量过少，无法起到改善聚氨酯海绵材料促进血管生成、诱导创面再生和避免二次创伤等性能。本申请提供的聚氨酯海绵材料，通过添加1-30重量％的锶硼生物活性玻璃，解决了单一聚氨酯海绵虽然具有一定的渗出液吸收能力、良好的生物相容性和力学性能等，但是不能有效地促进皮肤血管的生成和诱导创面再生，原位地迅速修复全层皮肤损伤，且容易与创面发生粘连，易造成二次创伤的缺点，从而使得该聚氨酯海绵材料具有良好的生物活性与生物相容性，同时能有效地促进皮肤血管的生成和诱导创面再生的优点。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.

在一些优选的实施方式中，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为5％～25％，优选为10％～20％。In some preferred embodiments, based on the weight of the polyurethane sponge material being 100%, the weight of the strontium boron bioactive glass is 5% to 25%, preferably 10% to 20%.

通过对锶硼生物活性玻璃的含量进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更良好的生物生物活性与生物相容性，同时能更有效地促进皮肤血管的生成和诱导创面再生。By further adjusting and optimizing the content of strontium boron bioactive glass, 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.

在一些优选的实施方式中，聚氨酯主要由聚醚多元醇与异氰酸酯制备得到。In some preferred embodiments, the polyurethane is mainly prepared from polyether polyol and isocyanate.

优选地，所述聚氨酯主要由聚醚多元醇48-97重量份和异氰酸酯2-22重量份制备得到。Preferably, the polyurethane is mainly prepared from 48-97 parts by weight of polyether polyol and 2-22 parts by weight of isocyanate.

聚醚多元醇(简称聚醚)是由起始剂(含活性氢基团的化合物)与环氧乙烷(EO)、环氧丙烷(PO)或环氧丁烷(BO)等在催化剂存在下，开环均聚或共聚制得的线型聚合物。典型但非限制性的聚醚多元醇可以为聚氧化丙烯二醇、聚四氢呋喃二醇或四氢呋喃-氧化丙烯共聚二醇。其含量例如可以为，但不限于48重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份或97重量份。异氰酸酯是异氰酸的各种酯的总称，包括单异氰酸酯R-N＝C＝O和二异氰酸酯O＝C＝N-R-N＝C＝O及多异氰酸酯等。典型但非限制性的异氰酸酯可以为甲苯二而异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)或多次甲基多苯基异氰酸酯(PAPI)。其含量例如可以为，但不限于2重量份、5重量份、8重量份、10重量份、12重量份、15重量份、18重量份、20重量份或22重量份。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. Isocyanate is the general term for various esters of isocyanate, including monoisocyanate R-N=C=O and diisocyanate O=C=N-R-N=C=O and polyisocyanate. 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.

优选地，所述聚氨酯主要由聚醚多元醇55-85重量份和异氰酸酯5-20重量份制备得到。Preferably, the polyurethane is mainly prepared from 55-85 parts by weight of polyether polyol and 5-20 parts by weight of isocyanate.

优选地，所述聚氨酯主要由聚醚多元醇65-75重量份和异氰酸酯10-15重量份制备得到。Preferably, the polyurethane is mainly prepared from 65-75 parts by weight of polyether polyol and 10-15 parts by weight of isocyanate.

通过对聚醚多元醇和异氰酸酯的配比进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更好的力学性能、疲劳性能及微观孔隙率，且孔隙结构稳定，同时具有更良好的生物活性与生物相容性。By further adjusting and optimizing the ratio of polyether polyol and 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.

优选地，所述聚醚多元醇的数均分子量范围为500-2000，例如可以为，但不限于500、600、800、1000、1200、1400、1600、1800或2000，优选为800-1500，更优选为1000-1300。所述聚醚多元醇的数均分子量可通过例如GPC等手段测得。Preferably, 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.

所述异氰酸酯的分子量范围为150-250g/mol，例如可以为，但不限于150g/mol、180g/mol、200g/mol、220g/mol或250g/mol，优选为160-240g/mol，更优选为180-220g/mol。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.

通过对聚醚多元醇的数均分子量和异氰酸酯的分子量进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更好的力学性能、疲劳性能及微观孔隙率，且孔隙结构稳定，同时具有更良好的生物活性与生物相容性。By further adjusting and optimizing the number average molecular weight of the polyether polyol and the molecular weight of the isocyanate, 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.

在一些优选的实施方式中，所述锶硼生物活性玻璃选自具有如下组成的锶硼生物活性玻璃中的一种或者至少两种：aSrO·bXO·cB ₂O ₃·dP ₂O ₅·eSiO ₂·fY ₂O； In some preferred embodiments, 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;

其中，a、b、c、d、e和f为摩尔份数，a为2-14，b为2-22，c为16-54，d为2-6，e为0-36，f为6-14；X为Ca和/或Mg，Y为Na和/或K。Where 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.

优选地，a为8-14，b为10-20，c为36-54，d为2-4，e为0-27，f为10-14。Preferably, 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.

通过对锶硼生物活性玻璃中各组成成分的配比进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更良好的生物活性与生物相容性，能够有效促进皮肤血管的生成、促进上皮细胞在创面出迁移和爬附、减小疤痕面积和最终诱导创面再生。By further adjusting and optimizing the proportion of each component in the strontium boron bioactive glass, 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.

优选地，所述锶硼生物活性玻璃包括：Preferably, the strontium boron bioactive glass includes:

14SrO·20CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O中的一种或至少两种。 One or at least two of 14SrO·20CaO·36B ₂ O ₃ ·2P ₂ O ₅ ·18SiO ₂ ·10Na ₂ O.

上述优选组分，通过调节锶(Sr)、硼(B)、硅(Si)、钙(Ca)的比例，能够调控锶硼生物活性玻璃的降解，从而更加匹配皮肤再生速度。By adjusting the ratio of strontium (Sr), boron (B), silicon (Si), and calcium (Ca), the above-mentioned preferred components can regulate the degradation of strontium-boron bioactive glass, thereby better matching the rate of skin regeneration.

优选地，所述锶硼生物活性玻璃的粒径不大于500μm，粒径例如可以为，但不限于500μm、450μm、400μm、350μm、300μm、250μm、200μm、150μm、100μm、50μm、40μm、30μm、20μm、10μm或1μm；Preferably, the particle size of the strontium-boron bioactive glass is not greater than 500 μm, and the particle size may be, for example, but not limited to 500 μm, 450 μm, 400 μm, 350 μm, 300 μm, 250 μm, 200 μm, 150 μm, 100 μm, 50 μm, 40 μm, 30 μm, 20μm, 10μm or 1μm;

在一些优选的实施方式中，所述锶硼生物活性玻璃还包括ZnO、Ag ₂O、CuO和CeO ₂中的一种或至少两种。 In some preferred embodiments, the strontium boron bioactive glass further includes one or at least two of ZnO, Ag ₂ O, CuO, and CeO ₂ .

其中，锌元素能够激活体内多种酶，诱导创面愈合；铜元素可以促进体内血管化；银元素具有一定的抗菌作用。在本申请提供的聚氨酯海绵材料中的锶硼生物活性玻璃中添加ZnO、Ag ₂O、CuO和CeO ₂中的一种或至少两种，能够进一步加强聚氨酯海绵材料的多种功能性，比如抗菌抑菌性能和促进血管生成。 Among them, 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.

优选地，ZnO的摩尔含量为0-2％，例如可以为，但不限于0％、0.5％、1％、1.5％或2％，Ag ₂O的摩尔含量为0-0.5％，例如可以为，但不限于0％、0.1％、0.2％、0.3％、0.4％或0.5％，CuO的摩尔含量为0-0.5％，例如可以为，但不限于0％、0.1％、0.2％、0.3％、0.4％或0.5％，CeO ₂的摩尔含量为0-1％，例如可以为，但不限于0％、0.1％、0.2％、0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％或1％； Preferably, 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%;

在一些优选的实施方式中，所述聚氨酯海绵材料的孔尺寸为20-2000μm，例如可以为，但不限于20μm、50μm、100μm、200μm、500μm、800μm、1000μm、1200μm、1500μm、1800μm或2000μm，优选为50-1900μm，更优选为100-1800μm；In some preferred embodiments, the pore size of the polyurethane sponge material is 20-2000 μm, such as, but not limited to, 20 μm, 50 μm, 100 μm, 200 μm, 500 μm, 800 μm, 1000 μm, 1200 μm, 1500 μm, 1800 μm or 2000 μm, It is preferably 50-1900 μm, more preferably 100-1800 μm;

优选地，所述聚氨酯海绵材料的孔隙率为50-300ppi，例如可以为，但不限于50ppi、100ppi、150ppi、200ppi、250ppi或300ppi，优选为80-280ppi，更优选为100-260ppi。Preferably, 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.

限定聚氨酯海绵材料的孔尺寸和孔隙率，能够进一步保证本申请提供的聚氨酯海绵材料良好的生物活性、生物降解性和生物相容性，同时有效地诱导创面血管化和皮肤再生。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.

优选地，干燥所述的聚氨酯海绵材料至其湿含量为0-12wt％，优选为0-8wt％，更优选为0-5wt％。Preferably, the polyurethane sponge material is dried to a moisture content of 0-12 wt%, preferably 0-8 wt%, more preferably 0-5 wt%.

含湿量过高，会导致聚氨酯海绵材料的吸液能力下降，不利于创伤的愈合。If the moisture content is too high, the liquid absorption capacity of the polyurethane sponge material will decrease, which is not conducive to wound healing.

在一些优选的实施方式中，所述聚氨酯海绵材料装载有固相粉剂。In some preferred embodiments, the polyurethane sponge material is loaded with solid phase powder.

在本申请中，通过装载不同功能的固体粉剂，可以使得聚氨酯海绵材料具有相应的附加功能，例如装载抗生素，能够使聚氨酯海面材料具有更好的杀菌抗菌性能，有效防止创伤感染，又如装载维生素，能够为创口提供营养物质，加速创伤的愈合。In this application, by loading solid powders with different functions, 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.

在本申请中，所述固体粉剂装载于聚氨酯海绵材料的内外表面。In this application, the solid powder is loaded on the inner and outer surfaces of the polyurethane sponge material.

对装载方法不做限定，典型的装载方法可以采用聚氨酯原位聚合的方法，使锶硼生物活性玻璃和固相粉剂分散在聚氨酯中，得到装载有固相粉剂聚氨酯海绵材料；或者利用吸附的方式在聚氨酯海绵材料的孔隙中吸附固相粉剂；或者现有技术中能实现将固体粉剂装在于孔隙中的方法均可。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.

其中，固体粉剂例如可以为，但不限于抗生素、生长因子、小分子RNA、透明质酸粉、胶原蛋白粉或维生素。The solid powder may be, for example, but not limited to antibiotics, growth factors, small molecule RNA, hyaluronic acid powder, collagen powder, or vitamins.

优选地，每1g聚氨酯海绵材料装载有10-200mg的固相粉剂，例如可以为，但不限于10mg、20mg、50mg、80mg、100mg、120mg、150mg、180mg或200mg；优选为30-180mg，更优选为50-150mg。Preferably, 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.

优选地，所述固相粉剂为抗生素，典型的抗生素可以为硫酸庆大霉素或利福平。Preferably, the solid phase powder is an antibiotic, and a typical antibiotic may be gentamicin sulfate or rifampicin.

该方法简单易操作，塑形方便，便于应用，且制备得到的聚氨酯海绵材料具有良好的生物活性、生物降解性和生物相容性。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.

在一些优选的实施方式中，将锶硼生物活性玻璃及聚醚多元醇的溶液和异氰酸酯混合得到聚氨酯海绵浆料，将所述浆料固化后干燥，得到所述聚氨酯海绵材料。In some preferred embodiments, 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.

在本申请提供的制备方法中，锶硼生物活性玻璃和聚醚的溶液及异氰酸酯在混合初期，得到的为糊状浆体，这种糊状浆体具有可塑性，会进行自由基聚合反应，得到聚氨酯海绵的聚合体；所述糊状浆体可在几分钟内便自我固化，形成具有一定力学强度和皮肤修复能力的固态物，所述固态物是以聚氨酯为基体，所述锶硼生物活性玻璃均匀地分散于所述基体的内部和表面，即得到聚氨酯海绵材料。In the preparation method provided by the present application, 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.

在一些优选的实施方式中，所述锶硼生物活性玻璃的制备方法包括：In some preferred embodiments, the preparation method of the strontium boron bioactive glass includes:

按照摩尔比取锶硼生物活性玻璃的各组分原料并混合均匀，然后加热熔融得到混合物物料；将所述混合物物料淬冷得到生物活性玻璃块，所述生物活性玻璃块依次经过粉碎、球磨细碎和筛分，得到所述锶硼生物活性玻璃。According to the molar ratio, 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.

其中，锶硼生物活性玻璃包括aSrO·bXO·cB ₂O ₃·dP ₂O ₅·eSiO ₂·fY ₂O；a、b、c、d、e和f为摩尔份数，a为2-14，b为2-22，c为16-54，d为2-6，e为0-36，f为6-14；X为Ca和/或Mg，Y为Na和/或K。 Among them, 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.

按照摩尔比取锶硼生物活性玻璃的各组分原料即按照摩尔分数取SrO、XO、B ₂O ₃、P ₂O ₅、SiO ₂和Y ₂O作为原料混合均匀。 According to the molar ratio, 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.

对加热熔融的温度不做限定，只要能够达到熔融目的即可。优选加热温度为1100-1250℃，例如可以为，但不限于1100℃、1150℃、1180℃、1200℃、1220℃或1250℃。The temperature for heating and melting is not limited, as long as it can achieve the purpose of melting. Preferably, 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.

对熔制的时间不做限定，只要能够达到熔融目的即可。优选加热时间为2-5h，例如可以为，但不限于2h、3h、4h或5h。The melting time is not limited as long as it can achieve the purpose of melting. Preferably, the heating time is 2-5h, for example, it can be, but not limited to, 2h, 3h, 4h or 5h.

优选地，所述聚氨酯溶液为聚氨酯水溶液，其中聚氨酯的质量百分含量不做限定，只要能够使制备得到的聚氨酯海绵材料的孔尺寸为20-2000μm且孔隙率为50-300ppi即可；Preferably, 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 μm and the porosity is 50-300 ppi;

优选地，所述固化的时间为1-10分钟，例如可以为，但不限于1分钟、2分钟、5分钟、8分钟或10分钟；优选为2-8分钟；Preferably, 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;

典型的聚氨酯海绵制品可以为将聚氨酯海绵材料通过固定尺寸、包装或灭菌等操作进行处理后得到的。A typical polyurethane sponge product can be obtained by processing the polyurethane sponge material through operations such as fixed size, packaging, or sterilization.

在一个具体的实施方式中，将制得的聚氨酯海绵材料根据需要剪裁为适当大小后，包装于包装袋中并封口，然后利用辐照灭菌，即制得无菌的生物活性聚氨酯海绵敷料制品。In a specific embodiment, after 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 .

下面结合具体实施例和对比例，对本申请作进一步说明。The following further describes the present application in conjunction with specific embodiments and comparative examples.

实施例1Example 1

本实施例提供了一种聚氨酯海绵材料，包括聚氨酯和分散在聚氨酯中的锶硼生物活性玻璃，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为1％。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% .

其中，锶硼生物活性玻璃具有如下组成：Among them, strontium boron bioactive glass has the following composition:

14SrO·8CaO·8MgO·54B ₂O ₃·2P ₂O ₅·0SiO ₂·6Na ₂O·8K ₂O。 14SrO·8CaO·8MgO·54B ₂ O ₃ ·2P ₂ O ₅ ·0SiO ₂ ·6Na ₂ O·8K ₂ O.

实施例2Example 2

本实施例提供了一种聚氨酯海绵材料，与实施例1的不同之处在于，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为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 30%.

实施例3Example 3

本实施例提供了一种聚氨酯海绵材料，与实施例1的不同之处在于，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为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 5%.

实施例4Example 4

本实施例提供了一种聚氨酯海绵材料，与实施例1的不同之处在于，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为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 25%.

实施例5Example 5

本实施例提供了一种聚氨酯海绵材料，与实施例1的不同之处在于，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为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 10%.

实施例6Example 6

本实施例提供了一种聚氨酯海绵材料，与实施例1的不同之处在于，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为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 20%.

实施例7Example 7

本实施例提供了一种聚氨酯海绵材料，与实施例1的不同之处在于，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为15％。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%.

实施例8Example 8

本实施例提供了一种聚氨酯海绵材料，与实施例7的不同之处在于，锶硼生物活性玻璃具有如下组成：This example provides a polyurethane sponge material. The difference from Example 7 is that the strontium boron bioactive glass has the following composition:

8SrO·12CaO·8MgO·27B ₂O ₃·4P ₂O ₅·27SiO ₂·6Na ₂O·8K ₂O。 8SrO·12CaO·8MgO·27B ₂ O ₃ ·4P ₂ O ₅ ·27SiO ₂ ·6Na ₂ O·8K ₂ O.

实施例9Example 9

14SrO·20CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O。 14SrO·20CaO·36B ₂ O ₃ ·2P ₂ O ₅ ·18SiO ₂ ·10Na ₂ O.

实施例10Example 10

本实施例提供了一种聚氨酯海绵材料，与实施例7的不同之处在于，锶硼生物活性玻璃具有如下组成：This embodiment provides a polyurethane sponge material, which differs from Embodiment 7 in that the strontium boron bioactive glass has the following composition:

2SrO·22CaO·20B ₂O ₃·6P ₂O ₅·36SiO ₂·14Na ₂O。 _{_{2SrO · 22CaO · 20B 2 O 3}} · 6P 2 O 5 · 36SiO 2 · 14Na 2 O.

实施例11Example 11

14SrO·10MgO·54B ₂O ₃·2P ₂O ₅·14SiO ₂·6K ₂O。 14SrO·10MgO·54B ₂ O ₃ ·2P ₂ O ₅ ·14SiO ₂ ·6K ₂ O.

实施例12Example 12

8SrO·20CaO·36B ₂O ₃·4P ₂O ₅·18SiO ₂·14Na ₂O。 8SrO·20CaO·36B ₂ O ₃ ·4P ₂ O ₅ ·18SiO ₂ ·14Na ₂ O.

实施例13Example 13

14SrO·10MgO·46B ₂O ₃·2P ₂O ₅·18SiO ₂·10K ₂O。 14SrO·10MgO·46B ₂ O ₃ ·2P ₂ O ₅ ·18SiO ₂ ·10K ₂ O.

实施例14Example 14

本实施例提供了一种聚氨酯海绵材料，与实施例7的不同之处在于，聚氨酯主要由聚氧化丙烯二醇48重量份和甲苯二而异氰酸酯22重量份制备得到。This example provides a polyurethane sponge material. The difference from Example 7 is that polyurethane is mainly prepared from 48 parts by weight of polyoxypropylene glycol and 22 parts by weight of toluene diisocyanate.

实施例15Example 15

本实施例提供了一种聚氨酯海绵材料，与实施例7的不同之处在于，聚氨酯主要由聚四氢呋喃二醇97重量份和二苯基甲烷二异氰酸酯2重量份制备得到。This example provides a polyurethane sponge material. The difference from Example 7 is that polyurethane is mainly prepared from 97 parts by weight of polytetrahydrofurandiol and 2 parts by weight of diphenylmethane diisocyanate.

实施例16Example 16

本实施例提供了一种聚氨酯海绵材料，与实施例7的不同之处在于，聚氨酯主要由四氢呋喃-氧化丙烯共聚二醇70重量份和多次甲基多苯基异氰酸酯12重量份制备得到。This example provides a polyurethane sponge material. The difference from Example 7 is that polyurethane is mainly prepared from 70 parts by weight of tetrahydrofuran-propylene oxide copolymer diol and 12 parts by weight of polymethyl polyphenyl isocyanate.

实施例17Example 17

本实施例提供了一种聚氨酯海绵材料，由如下方法制备得到：This embodiment provides a polyurethane sponge material, which is prepared by the following method:

(a)锶硼生物活性玻璃的制备：(a) Preparation of strontium boron bioactive glass:

按照摩尔比称取锶硼生物活性玻璃14SrO·8CaO·8MgO·54B ₂O ₃·2P ₂O ₅·6Na ₂O·8K ₂O的各组分原料，混合均匀后，将原始配料放于铂金柑锅内并放置在1100℃的硅钥炉中，熔制5h，取出后将所得的澄清玻璃液倒在已预热的钢板上得到锶硼生物活性玻璃块。将所得锶硼生物活性玻璃块利用粉碎设备依次经过粉碎、球磨细碎并筛分，选取颗粒直径位于1-10μm的锶硼生物活性玻璃粉。 According to the molar ratio, weigh 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 ℃, 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 μm is selected.

(b)聚醚多元醇溶液的制备：(b) Preparation of polyether polyol solution:

将聚氧化丙烯二醇溶解于水中，混合均匀，得到30％的聚醚多元醇溶液；Dissolve the polyoxypropylene glycol in water and mix well to obtain a 30% polyether polyol solution;

(c)聚氨酯海绵材料的制备：(c) Preparation of polyurethane sponge material:

按照1％：99％的质量百分比，将上述制得的锶硼生物活性玻璃和聚醚多元醇溶液与多次甲基多苯基异氰酸酯的混合物进行混合，形成聚氨酯海绵浆料，固化10分钟后得到聚氨酯海绵材料。According to the mass percentage of 1%:99%, 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.

(d)将上述制得的聚氨酯海绵材料在60℃的烘箱中干燥，直至其湿含量为12wt％，得到聚氨酯海绵材料制品。(d) The polyurethane sponge material prepared above is dried in an oven at 60°C until its moisture content is 12% by weight to obtain a polyurethane sponge material product.

实施例18Example 18

按照摩尔比称取锶硼生物活性玻璃8SrO·12CaO·8MgO·54B ₂O ₃·4P ₂O ₅·6Na ₂O·8K ₂O的各组分原料，混合均匀后，将原始配料放于铂金柑锅内并放置在1250℃的硅钥炉中，熔制2h，取出后将所得的澄清玻璃液倒在已预热的钢板上得到锶硼生物活性玻璃块。将所得锶硼生物活性玻璃块利用粉碎设备依次经过粉碎、球磨细碎并筛分，选取颗粒直径位于300-500μm的锶硼生物活性玻璃粉。 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 μm is selected.

将聚四氢呋喃二醇溶解于水中，混合均匀，得到20％的聚醚多元醇溶液；Dissolve polytetrahydrofurandiol in water and mix well to obtain a 20% polyether polyol solution;

按照30％：70％的质量百分比，将上述制得的锶硼生物活性玻璃和聚醚多元醇溶液与甲苯二而异氰酸酯的混合物进行混合，形成聚氨酯海绵浆料，固化1分钟后得到聚氨酯海绵材料。According to a mass percentage of 30%:70%, 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 .

(d)将上述制得的聚氨酯海绵材料在60℃的烘箱中干燥，直至其湿含量为8wt％，得到聚氨酯海绵材料制品。(d) The polyurethane sponge material prepared above is dried in an oven at 60°C until its moisture content is 8 wt%, to obtain a polyurethane sponge material product.

实施例19Example 19

按照摩尔比称取锶硼生物活性玻璃14SrO·20CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O的各组分原料，混合均匀后，将原始配料放于铂金柑锅内并放置在1200℃的硅钥炉中，熔制3.5h，取出后将所得的澄清玻璃液倒在已预热的钢板上得到锶硼生物活性玻璃块。将所得锶硼生物活性玻璃块利用粉碎设备依次经过粉碎、球磨细碎并筛分，选取颗粒直径位于200-300μm的锶硼生物活性玻璃粉。 Weigh the 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 μm is selected.

将四氢呋喃-氧化丙烯共聚二醇溶解于水中，混合均匀，得到60％的聚醚多元醇溶液；Dissolve the tetrahydrofuran-propylene oxide copolymer glycol in water and mix well to obtain a 60% polyether polyol solution;

按照25％：75％的质量百分比，将上述制得的锶硼生物活性玻璃和聚醚多元醇溶液与二苯基甲烷二异氰酸酯的混合物进行混合，形成聚氨酯海绵浆料，固化5分钟后得到聚氨酯海绵材料。According to the mass percentage of 25%:75%, 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.

(d)将上述制得的聚氨酯海绵材料在60℃的烘箱中干燥，直至其湿含量为5wt％，得到聚氨酯海绵材料制品。(d) The polyurethane sponge material prepared above is dried in an oven at 60°C until its moisture content is 5 wt% to obtain a polyurethane sponge material product.

实施例20Example 20

按照摩尔比称取锶硼生物活性玻璃14SrO·20CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O的各组分原料，混合均匀后，将原始配料放于铂金柑锅内并放置在1200℃的硅钥炉中，熔制3.5h，取出后将所得的澄清玻璃液倒在已预热的钢板上得到锶硼生物活性玻璃块。将所得锶硼生物活性玻璃块利用粉碎设备依次经过粉碎、球磨细碎并筛分，选取颗粒直径位于50-100μm的锶硼生物活性玻璃粉。 Weigh the 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 μm is selected.

将聚氧化丙烯二醇溶解于水中，混合均匀，得到60％的聚醚多元醇溶液；Dissolve the polyoxypropylene glycol in water and mix well to obtain a 60% polyether polyol solution;

按照25％：74.9％：0.1％的质量百分比，将上述制得的锶硼生物活性玻璃、聚醚多元醇溶液与甲苯二而异氰酸酯的混合物和庆大霉素进行混合，形成含有抗生素的聚氨酯海绵浆料，固化5分钟后得到聚氨酯海绵材料。According to the mass percentage of 25%: 74.9%: 0.1%, the mixture of the above-prepared strontium boron bioactive glass, polyether polyol solution, toluene diisocyanate and gentamicin are mixed to form a polyurethane sponge containing antibiotics After the slurry was cured for 5 minutes, a polyurethane sponge material was obtained.

实施例21Example 21

按照摩尔比称取锶硼生物活性玻璃14SrO·19CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O·1ZnO的各组分原料，混合均匀后，将原始配料放于铂金柑锅内并放置在1200℃的硅钥炉中，熔制3.5h，取出后将所得的澄清玻璃液倒在已预热的钢板上得到锶硼生物活性玻璃块。将所得锶硼生物活性玻璃块利用粉碎设备依次经过粉碎、球磨细碎并筛分，选取颗粒直径位于20-50μm的锶硼生物活性玻璃粉。 Weigh the 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 ℃, 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 μm is selected.

实施例22Example 22

本实施例提供了一种聚氨酯海绵材料，与实施例7的不同之处在于，聚氨酯主要由聚四氢呋喃二醇 100重量份和二苯基甲烷二异氰酸酯1重量份制备得到。This example provides a polyurethane sponge material. The difference from Example 7 is that polyurethane is mainly prepared from 100 parts by weight of polytetrahydrofurandiol and 1 part by weight of diphenylmethane diisocyanate.

实施例23Example 23

本实施例提供了一种聚氨酯海绵材料，与实施例7的不同之处在于，锶硼生物活性玻璃包括1SrO·22CaO·15B ₂O ₃·10P ₂O ₅·12Na ₂O。 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.

实施例24Example 24

按照摩尔比称取锶硼生物活性玻璃14SrO·20CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O的各组分原料，混合均匀后，将原始配料放于铂金柑锅内并放置在1000℃的硅钥炉中，熔制1h，取出后将所得的澄清玻璃液倒在已预热的钢板上得到锶硼生物活性玻璃块。将所得锶硼生物活性玻璃块利用粉碎设备依次经过粉碎、球磨细碎并筛分，选取颗粒直径位于10-20μm的锶硼生物活性玻璃粉。 Weigh the 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 μm is selected.

(2)聚醚多元醇溶液的制备：(2) Preparation of polyether polyol solution:

将聚氧化丙烯二醇溶解于水中，混合均匀，得到80％的聚醚多元醇溶液；Dissolve polyoxypropylene glycol in water and mix evenly to obtain 80% polyether polyol solution;

(3)聚氨酯海绵材料的制备：(3) Preparation of polyurethane sponge material:

按照25％：75％的质量百分比，将上述制得的锶硼生物活性玻璃和聚醚溶液与二苯基甲烷二异氰酸酯的混合物进行混合，形成聚氨酯海绵浆料，固化15分钟后得到聚氨酯海绵材料。According to the mass percentage of 25%:75%, 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 .

(4)将上述制得的聚氨酯海绵材料在60℃的烘箱中干燥，直至其湿含量为15wt％，得到聚氨酯海绵材料制品。(4) 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.

对比例1Comparative Example 1

市售医用聚氨酯(驻马店康丰医疗)。Commercially available medical polyurethane (Zhumadian Kangfeng Medical).

对比例2Comparative Example 2

本对比例提供了一种聚氨酯海绵材料，包括聚氨酯和分散在聚氨酯中的锶硼生物活性玻璃，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为40％。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% .

14SrO·2CaO·8MgO·54B ₂O ₃·2P ₂O ₅·8SiO ₂·6Na ₂O·6K ₂O。 14SrO·2CaO·8MgO·54B ₂ O ₃ ·2P ₂ O ₅ ·8SiO ₂ ·6Na ₂ O·6K ₂ O.

对比例3Comparative Example 3

本对比例提供了一种聚氨酯海绵材料，包括聚氨酯和分散在聚氨酯中的锶硼生物活性玻璃，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为0.45％。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% .

实验例1Experimental Example 1

取30只实验家兔(雄性/雌性；2.0-2.5kg)，随机分为15组，每组两只。将30只实验家兔进行皮肤挫伤处理，具体为：Thirty experimental rabbits (male/female; 2.0-2.5 kg) were randomly divided into 15 groups, two in each group. 30 experimental rabbits were treated with skin contusion, specifically:

在家兔双侧背部剃毛，使用锉刀制造皮肤挫伤(20×50mm，0.2mm深度)。造模后分别应用本申请实施例1-11及对比例1-3提供的聚氨酯海绵材料覆盖损伤部位，剩余1组不覆盖材料，作为对照组。Shave the back of both sides of the rabbit and use a file to create a skin contusion (20×50mm, 0.2mm depth). After modeling, the polyurethane sponge materials provided in Examples 1-11 of the present application and Comparative Examples 1-3 were used to cover the damaged parts, and the remaining one group was not covered with the material as a control group.

从第二天起每3天更换覆盖材料并记录，结果如下表所示：Replace the cover material and record every 3 days from the next day. The results are shown in the following table:

从上述结果中可以看出，本申请实施例1-24提供的聚氨酯海绵材料，通过特定含量锶硼生物活性玻璃和聚氨酯之间的协同配合，使得本申请提供的聚氨酯海绵材料具有良好的生物活性、生物降解性和生物相容性，能够有效地诱导创面血管化和皮肤再生和原位地迅速修复全层皮肤损伤，且不易造成粘连，避免二次创伤，在促进创面修复方面达到了更为良好的效果。而对比例1-3提供的聚氨酯海绵材料，无论在创面修复、抗炎作用或防止粘连的方面，其效果均不及本申请实施例的水平。As can be seen from the above results, 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. However, 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.

其中，实施例1-7提供的聚氨酯海绵材料，其组成相同，仅配比不同。但实施例3-7提供的聚氨酯海绵材料在创面修复的方面优于实施例1和2的水平，实施例5-7提供的聚氨酯海绵材料在创面修复的方面优于实施例3和4的水平，实施例7提供的聚氨酯海绵材料在创面修复的方面优于实施例1和2的水平。说明在添加的锶硼生物活性玻璃相同的情况下，通过对所加入的锶硼生物活性玻璃的含量进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。Among them, the polyurethane sponge materials provided in Examples 1-7 have the same composition but only different proportions. However, the polyurethane sponge materials provided in Examples 3-7 are superior to those in Examples 1 and 2 in terms of wound repair, and 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.

实施例7-13提供的聚氨酯海绵材料，其中锶硼生物活性玻璃的含量相同，但锶硼生物活性玻璃的组成原料及配比不同。但实施例7-9提供的聚氨酯海绵材料在创面修复的方面优于实施例10-13的水平，实施例12和13提供的聚氨酯海绵材料在创面修复的方面优于实施例10和11的水平。说明通过对锶硼生物活性玻璃各组分及配比进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。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. However, the polyurethane sponge materials provided in Examples 7-9 are superior to those in Examples 10-13 in terms of wound repair, and 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.

实施例14-16提供的聚氨酯海绵材料，其中锶硼生物活性玻璃的组分配比及含量均相同，但制备聚氨酯的聚醚多元醇和异氰酸酯的配比不同。实施例16提供的聚氨酯海绵材料在创面修复的方面优于实施例14和15的水平。说明通过对聚氨酯各原料的配比进行进一步的调整和优化，能够使得本申请提供的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。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.

实施例7与实施例19，分别采用了相同的原料，但实施例19应用本申请提供的制备方法对聚氨酯海绵材料进行制备，实施例19提供的聚氨酯海绵材料无论在创面修复、抗炎作用和防止粘连的方面均分别优于实施例7的水平。说明在原料相同的条件下，应用本申请提供的制备方法制备得到的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。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.

实施例17-19，均分别采用了相同的原料和相同的制备方法进行制备，仅制备的条件参数不同。但实施例19提供的聚氨酯海绵材料无论在创面修复、抗炎作用和防止粘连的方面均分别优于实施例17和 18的水平。说明在原料和方法相同的条件下，应用本申请提供的优选制备方法制备得到的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。In Examples 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. However, 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.

实施例19和20均采用相同制备方法及原料，但实施例20中加载了抗生素，实施例20提供的聚氨酯海绵材料相比于实施例19，具有更好的抗炎作用。Both Examples 19 and 20 use 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.

实施例19和21均采用相同制备方法及原料，但实施例21中的锶硼生物活性玻璃中添加了ZnO，实施例21提供的聚氨酯海绵材料相比于实施例19，具有更好的诱导创面愈合的作用。Both 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.

实施例7与对比例2和对比例3提供的聚氨酯海绵材料，其组成完全相同，仅锶硼生物活性玻璃的含量不同。但实施例7提供的聚氨酯海绵材料无论在创面修复、抗炎作用和防止粘连的方面均优于对比例2和对比例3的水平。说明通过对锶硼生物活性玻璃的含量进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。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. However, 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.

实施例7与实施例23提供的聚氨酯海绵材料，其组成相同，但实施例23中的锶硼生物活性玻璃组分不在本申请优选范围内，其无论在创面修复、抗炎作用和防止粘连的方面均逊色于实施例7的水平。说明通过对锶硼生物活性玻璃中各组分的配比进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。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.

实施例19与实施例24供的聚氨酯海绵材料，均分别采用了相同的组成和相同的制备方法进行制备，仅制备的条件参数不同，实施例24提供的制备方法的条件参数不在本申请优选范围内。其无论在创面修复、抗炎作用和防止粘连的方面均逊色于实施例19的水平。说明通过对条件参数进行进一步的调整和优化，使得本申请提供的聚氨酯海绵材料具有更好的创面修复、抗炎作用和防止粘连的效果。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.

实验例2Experimental Example 2

为节约成本，本实验例选择效果较好的实施例9提供的聚氨酯海绵材料进行试验。In order to save costs, the polyurethane sponge material provided in Example 9 with better effect is selected for the experiment.

一、将实施例9所得的锶硼生物活性玻璃粉进行微观外貌及红外图谱检测。其微观形貌和红外图谱分别如图1A及图1B所示。如图1A可知，制备的锶硼生物活性玻璃为不规则的颗粒形貌，粒径范围约为几个微米。红外结果图1B有显示，锶硼生物活性玻璃显示出典型的硅-氧和硼-氧的振动峰。1. The microscopic appearance and infrared spectrum detection of the strontium boron bioactive glass powder obtained in Example 9. The microscopic morphology and infrared spectrum are shown in Figure 1A and Figure 1B, respectively. As shown in FIG. 1A, 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.

二、将实施例9制得的聚氨酯海绵材料包装于包装袋中并封口，然后利用辐照灭菌，即制得无菌的聚氨酯海绵材料制品，如图2。2. 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.

三、取实施例9制得的聚氨酯海绵材料，将其冷冻干燥后表面喷金，利用环境扫描电子显微镜观察宏观和微观形貌，如图3。结果显示制得的聚氨酯海绵材料具有多孔结构；微观结构显示其孔径分布为50-150微米；锶硼生物活性玻璃(图3中白色箭头指示为锶硼生物活性玻璃)分散于聚氨酯海绵材料的基体。3. Take the polyurethane sponge material prepared in Example 9 and spray gold on the surface after freeze drying, and observe the macro and micro morphology using an environmental scanning electron microscope, as shown in FIG. 3. The results show that the prepared polyurethane sponge material has a porous structure; the microstructure shows that the pore size distribution is 50-150 microns; the strontium boron bioactive glass (the white arrow in FIG. 3 indicates strontium boron bioactive glass) is dispersed in the matrix of the polyurethane sponge material .

实验例3细胞毒性测试Experimental Example 3 Cytotoxicity Test

(1)锶硼生物活性玻璃的制备：(1) Preparation of strontium boron bioactive glass:

按照摩尔比称取锶硼生物活性玻璃8SrO·12CaO·8MgO·54B ₂O ₃·4P ₂O ₅·6Na ₂O·8K ₂O的各组分原料，混合均匀后，将原始配料放于铂金柑锅内并放置在1100-1200℃的硅钥炉中，熔制5h，取出后将所得的澄清玻璃液倒在已预热的钢板上得到锶硼生物活性玻璃块。将所得锶硼生物活性玻璃块利用粉碎设备依次经过粉碎、球磨细碎并筛分，选取颗粒直径位于100-200μm的锶硼生物活性玻璃粉。 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 μm is selected.

(2)聚氨酯溶液的制备：(2) Preparation of polyurethane solution:

将聚氨酯溶解于水中，混合均匀，得到60％的聚醚溶液；Dissolve polyurethane in water and mix well to obtain 60% polyether solution;

将上述制得的锶硼生物活性玻璃和聚氨酯溶液进行混合，制得锶硼生物活性玻璃含量10％、20％和30％的聚氨酯海绵浆体，固化10分钟后得到锶硼生物活性玻璃含量10％、20％和30％的聚氨酯海绵材料，分别命名为10SrBG/JAZ、20SrBG/JAZ和30SrBG/JAZ。The 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.

(4)将上述制得的聚氨酯海绵材料在60℃的烘箱中干燥，直至其湿含量为10wt％，得到聚氨酯海绵材料制品。(4) 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.

细胞毒性测试中所用到的实验组和对照组样品均为2cm*2cm正方形样品。所有细胞毒性测试都根据GB/T16886.5-2003选择浸提液试验方法，按照GB/T14233.2-2005《细胞毒性试验》中推荐的MTT法进行试验。具体过程如下：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:

(1)首先进行细胞培养：取冻存的L929成纤维细胞进行复苏—培养—传代—培养的过程，当细胞传至第三代时(正常状态下需5-6天)，对细胞消化待用。(1) 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.

(2)其次是浸提液准备：采用浸提液试验方法，计算实验组和对照组骨水泥样品重量与表面积的转换关系，采用DMEM细胞培养液(含15％胎牛血清)，以浸提比例6cm ²/ml，37℃，24h制备实验组、对照组的浸提液。 (2) Followed by the preparation of the extraction solution: using the extraction solution test method, the conversion relationship between the weight and surface area of the bone cement samples of the experimental group and the control group was calculated, and the DMEM cell culture solution (containing 15% fetal bovine serum) was used to extract The ratio of 6cm ² /ml, 37℃, 24h was used to prepare the extract of the experimental group and the control group.

将配制好的密度为1×10 ⁴/ml的细胞悬液接种于96孔板中，每孔100μl，设置空白组(只有细胞培养液，不加浸提液)、实验组和对照组，每组至少接种3个孔，在含5％二氧化碳条件下，37℃培养24h后，弃去培养液，空白组用细胞培养液交换，实验组和对照组分别用各自浸提液交换。置于5％二氧化碳培养箱中37℃培养72h后，加MTT继续培养4h，在酶标仪570nm和630nm处测定吸光度。以空白组的吸光度为标准，计算相对增殖率(RGR)，根据RGR判断实验组和对照组样品的细胞毒性反应级别。3天和7天的细胞毒性的测试结果如图4，与空白组相比，实验组和对照组的细胞存活率均高于80％，这说明所有组分的聚氨酯海绵材料都具有良好的生物相容性。 Inoculate the prepared cell suspension with a density of 1×10 ⁴ /ml in a 96-well plate, 100 μl per well, set up a blank group (only cell culture fluid, no extract), experimental group and control group, each The group was inoculated with at least 3 wells. After culturing at 37°C for 24h under 5% carbon dioxide, the culture solution was discarded, the blank group was exchanged with cell culture solution, and the experimental group and control group were exchanged with their respective extracts. After being cultured in a 5% carbon dioxide incubator at 37°C for 72h, MTT was added to continue the cultivation for 4h, and the absorbance was measured at 570nm and 630nm with a microplate reader. Using the absorbance of the blank group as the standard, 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. Compared with the blank group, 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.

实验例4聚氨酯海绵材料的活性离子析出Experimental Example 4 Active ion precipitation of polyurethane sponge material

(2)聚氨酯溶液的制备：(2) Preparation of polyurethane solution:

将上述制得的锶硼生物活性玻璃和聚氨酯溶液进行混合，形成锶硼生物活性玻璃含量15％和45％的聚氨酯海绵浆料，固化10分钟后得到锶硼生物活性玻璃含量15％和45％的聚氨酯海绵材料，分别命名为15SrBG/JAZ和45SrBG/JAZ。Mix the strontium boron bioactive glass and polyurethane solution prepared above to form a polyurethane sponge slurry with strontium boron bioactive glass content of 15% and 45%, and after curing for 10 minutes, obtain strontium boron bioactive glass content of 15% and 45% The polyurethane sponge materials are named 15SrBG/JAZ and 45SrBG/JAZ respectively.

(5)将上述制得的15SrBG/JAZ和45SrBG/JAZ组聚氨酯海绵材料(尺寸为1cm*1cm)(平行实验)浸泡于10ml的磷酸盐缓冲溶液(PBS)，并置于37℃且湿度为99％的恒温恒湿箱。随着浸泡时间的延长，聚氨酯海绵材料中的锶(Sr)和硼(B)离子会逐渐释放到PBS中，利用电感耦合等离子体光谱仪(ICP)测定PBS中的(Sr)和硼(B)的累计释放含量，结果如图5A和图5B所示。(5) Immerse the 15SrBG/JAZ and 45SrBG/JAZ group polyurethane sponge materials (size 1cm*1cm) prepared in the above (parallel experiment) in 10ml of phosphate buffer solution (PBS), and place at 37 ℃ and humidity is 99% constant temperature and humidity box. With the extension of the soaking time, the strontium (Sr) and boron (B) ions in the polyurethane sponge material will be gradually released into the PBS, and the inductively coupled plasma spectrometer (ICP) is used to determine the (Sr) and boron (B) in the PBS. The cumulative release content is shown in Figures 5A and 5B.

从图5A和图5B可以看出，浸泡初期，硼(B)和锶(Sr)的释放速度相对较慢，而在14-30天内，释放速度明显增加。随着聚氨酯海绵材料基体中锶硼生物活性玻璃含量的增加，浸泡后释放的硼(B)和锶(Sr)浓度也更高。As can be seen from FIGS. 5A and 5B, the initial release rate of boron (B) and strontium (Sr) is relatively slow, and within 14-30 days, the release rate increases significantly. As the content of strontium-boron bioactive glass in the polyurethane sponge material matrix increases, the concentration of boron (B) and strontium (Sr) released after soaking is also higher.

实验例5聚氨酯海绵材料的载药性能Experimental Example 5 Drug loading properties of polyurethane sponge material

将4件发明实施例10提供的载药的聚氨酯海绵材料(尺寸为1cm*1cm)(平行实验)浸泡于10ml的磷酸盐缓冲溶液(PBS)，并置于37℃且湿度为99％的恒温恒湿箱。随着浸泡时间的延长，载药的聚氨酯海绵材料中的抗生素药物-硫酸庆大霉素会逐渐释放到PBS中，利用高性能液相色谱(HPLC)测定PBS中的药物的累计释放含量，药物释放的结果如图6所示。4 pieces of drug-loaded polyurethane sponge material (size 1cm*1cm) (parallel experiment) provided in Inventive Example 10 were soaked in 10ml of phosphate buffer solution (PBS) and placed at a constant temperature of 37°C and a humidity of 99% Constant humidity box. With the extension of the immersion time, the antibiotic drug gentamicin sulfate in the drug-loaded polyurethane sponge material will be gradually released into the PBS, and the cumulative release content of the drug in the PBS is determined by high performance liquid chromatography (HPLC). The result of the release is shown in Figure 6.

从图6可以看出，在浸泡初期，药物的释放较快，浸泡1天后，药物释放了初始载药总量的约46.6％，7天后小时后释放量约为83％。随后，药物释放速率逐渐减小。药物释放时间持续达19天，药物总的累积释放率为99.8％。因此，聚氨酯海绵材料还能作为药物载体，药物释放速率适中，满足临床要求，从而在促进其在皮肤修复方面达到了更为良好的效果。It can be seen from Fig. 6 that in the early stage of immersion, the drug is released faster. After 1 day of immersion, the drug releases about 46.6% of the initial total drug load, and after 7 days, the release amount is about 83%. Subsequently, the drug release rate gradually decreases. The drug release time lasted up to 19 days, and the total cumulative release rate of the drug was 99.8%. Therefore, 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.

最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features in them can be equivalently replaced; and these modifications or replacements do not deviate from the essence of the corresponding technical solutions in the technical solutions of the embodiments of the present application. range.

Claims

一种聚氨酯海绵材料，其特征在于，包括聚氨酯和分散在所述聚氨酯中的锶硼生物活性玻璃，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为1～30％。A polyurethane sponge material, characterized by comprising polyurethane and strontium boron bioactive glass dispersed in the polyurethane, the weight of the polyurethane sponge material is 100%, the weight of the strontium boron bioactive glass is 1 ~30%.
根据权利要求1所述的聚氨酯海绵材料，其特征在于，以所述聚氨酯海绵材料的重量为100％计，所述锶硼生物活性玻璃的重量为5％～25％，优选为10％～20％。The polyurethane sponge material according to claim 1, characterized in that the weight of the polyurethane sponge material is 100%, the weight of the strontium boron bioactive glass is 5% to 25%, preferably 10% to 20 %.
根据权利要求1所述的聚氨酯海绵材料，其特征在于，其中，所述聚氨酯主要由聚醚多元醇与异氰酸酯制备得到；The polyurethane sponge material according to claim 1, wherein the polyurethane is mainly prepared from polyether polyol and isocyanate;

优选地，所述聚氨酯主要由聚醚多元醇50-93重量份和异氰酸酯7-50重量份制备得到；Preferably, the polyurethane is mainly prepared from 50-93 parts by weight of polyether polyol and 7-50 parts by weight of isocyanate;

优选地，所述聚氨酯主要由聚醚多元醇55-85重量份和异氰酸酯10-40重量份制备得到；Preferably, the polyurethane is mainly prepared from 55-85 parts by weight of polyether polyol and 10-40 parts by weight of isocyanate;

优选地，所述聚氨酯主要由聚醚多元醇65-75重量份和异氰酸酯20-30重量份制备得到；Preferably, the polyurethane is mainly prepared from 65-75 parts by weight of polyether polyol and 20-30 parts by weight of isocyanate;

优选地，所述聚醚多元醇的数均分子量范围为500-2000，优选为800-1500，更优选为1000-1300；Preferably, the number average molecular weight range of the polyether polyol is 500-2000, preferably 800-1500, more preferably 1000-1300;

优选地，所述异氰酸酯的分子量范围为150-250g/mol，优选为160-240g/mol，更优选为180-220g/mol。Preferably, the molecular weight range of the isocyanate is 150-250 g/mol, preferably 160-240 g/mol, and more preferably 180-220 g/mol.
根据权利要求1所述的聚氨酯海绵材料，其特征在于，所述锶硼生物活性玻璃选自具有如下组成的锶硼生物活性玻璃中的一种或者至少两种：aSrO·bXO·cB ₂O ₃·dP ₂O ₅·eSiO ₂·fY ₂O； The polyurethane sponge material according to claim 1, wherein 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;

其中，a、b、c、d、e和f为摩尔份数，a为2-14，b为2-22，c为16-54，d为2-6，e为0-36，f为6-14；X为Ca和/或Mg，Y为Na和/或K；Where 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;

优选地，a为8-14，b为10-20，c为36-54，d为2-4，e为0-27，f为10-14；Preferably, 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;

优选地，所述锶硼生物活性玻璃为Preferably, the strontium boron bioactive glass is

14SrO·8CaO·8MgO·54B ₂O ₃·2P ₂O ₅·0SiO ₂·6Na ₂O·8K ₂O、 14SrO·8CaO·8MgO·54B ₂ O ₃ ·2P ₂ O ₅ ·0SiO ₂ ·6Na ₂ O·8K ₂ O,

8SrO·12CaO·8MgO·27B ₂O ₃·4P ₂O ₅·27SiO ₂·6Na ₂O·8K ₂O或 8SrO·12CaO·8MgO·27B ₂ O ₃ ·4P ₂ O ₅ ·27SiO ₂ ·6Na ₂ O·8K ₂ O or

14SrO·20CaO·36B ₂O ₃·2P ₂O ₅·18SiO ₂·10Na ₂O中的一种或至少两种； One or at least two of 14SrO·20CaO·36B ₂ O ₃ ·2P ₂ O ₅ ·18SiO ₂ ·10Na ₂ O;

优选地，所述锶硼生物活性玻璃的粒径不大于500μm；Preferably, the particle size of the strontium boron bioactive glass is not greater than 500 μm;

优选地，所述锶硼生物活性玻璃还包括ZnO、Ag ₂O、CuO和CeO ₂中的一种或至少两种； Preferably, the strontium boron bioactive glass further includes one or at least two of ZnO, Ag ₂ O, CuO and CeO ₂ ;

优选地，ZnO的摩尔含量为0-2％，Ag ₂O的摩尔含量为0-0.5％，CuO的摩尔含量为0-0.5％，CeO ₂的摩尔含量为0-1％。 Preferably, 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%, and the molar content of CeO ₂ is 0-1%.
根据权利要求1所述的聚氨酯海绵材料，其特征在于，所述聚氨酯海绵材料的孔尺寸为20-2000μm，优选为50-1900μm，更优选为100-1800μm；The polyurethane sponge material according to claim 1, wherein the pore size of the polyurethane sponge material is 20-2000 μm, preferably 50-1900 μm, more preferably 100-1800 μm;

优选地，所述聚氨酯海绵材料的孔隙率为50-300ppi，优选为80-280ppi，更优选为100-260ppi；Preferably, the porosity of the polyurethane sponge material is 50-300 ppi, preferably 80-280 ppi, more preferably 100-260 ppi;

优选地，所述聚氨酯海绵材料的湿含量为0-12wt％，优选为0-8wt％，更优选为0-5wt％。Preferably, the moisture content of the polyurethane sponge material is 0-12 wt%, preferably 0-8 wt%, more preferably 0-5 wt%.
根据权利要求1-5任一项所述的聚氨酯海绵材料，其特征在于，所述聚氨酯海绵材料装载有固相粉剂；The polyurethane sponge material according to any one of claims 1 to 5, wherein the polyurethane sponge material is loaded with a solid powder;

优选地，每1g所述聚氨酯海绵材料装载有10-200mg的固相粉剂，优选为30-180mg，更优选为50-150mg；Preferably, each 1g of the polyurethane sponge material is loaded with 10-200mg of solid phase powder, preferably 30-180mg, more preferably 50-150mg;

优选地，所述固相粉剂包括抗生素、蛋白粉或维生素中的一种或至少两种。Preferably, the solid phase powder includes one or at least two of antibiotics, protein powder or vitamins.
如权利要求1-6任一项所述的聚氨酯海绵材料的制备方法，其特征在于，采用聚氨酯原位聚合的方法，使所述锶硼生物活性玻璃分散在所述聚氨酯中，得到所述聚氨酯海绵材料。The method for preparing a polyurethane sponge material according to any one of claims 1 to 6, characterized in that the in-situ polymerization of polyurethane is used to disperse the strontium boron bioactive glass in the polyurethane to obtain the polyurethane Sponge material.
根据权利要求7所述的制备方法，其特征在于，将所述锶硼生物活性玻璃及所述聚醚多元醇的溶液和所述异氰酸酯混合得到聚氨酯海绵浆料，将所述浆料固化后干燥，得到所述聚氨酯海绵材料；The preparation method according to claim 7, characterized in that the solution of the strontium boron bioactive glass and the polyether polyol and the isocyanate are mixed to obtain a polyurethane sponge slurry, which is cured and dried To obtain the polyurethane sponge material;

优选地，所述锶硼生物活性玻璃的制备方法包括：Preferably, the preparation method of the strontium boron bioactive glass includes:

按照摩尔比取所述锶硼生物活性玻璃的各组分原料并混合均匀，然后加热熔融得到混合物物料；将所述混合物物料淬冷得到生物活性玻璃块，所述生物活性玻璃块依次经过粉碎、球磨细碎和筛分，得到所述锶硼生物活性玻璃；According to the molar ratio, 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 crushed, Ball milling and sieving to obtain the strontium boron bioactive glass;

优选地，所述聚醚多元醇的溶液为聚醚多元醇水溶液；Preferably, the solution of the polyether polyol is an aqueous solution of polyether polyol;

优选地，所述固化的时间为1-10分钟，优选为2-8分钟。Preferably, the curing time is 1-10 minutes, preferably 2-8 minutes.
如权利要求1-6任一项所述的聚氨酯海绵材料，或应用权利要求7或8所述的制备方法制得的聚氨酯海绵材料在创伤组织工程修复中的应用。The polyurethane sponge material according to any one of claims 1-6, or the application of the polyurethane sponge material obtained by applying the preparation method according to claim 7 or 8 in wound tissue engineering repair.
包含权利要求1-6任一项所述的聚氨酯海绵材料，或应用权利要求7或8所述的制备方法制得的聚氨酯海绵材料的聚氨酯海绵制品。A polyurethane sponge product comprising the polyurethane sponge material according to any one of claims 1 to 6, or the polyurethane sponge material obtained by applying the preparation method according to claim 7 or 8.