WO2017028528A1 - 制备聚氨酯复合材料的方法及该方法获得的复合材料 - Google Patents

制备聚氨酯复合材料的方法及该方法获得的复合材料 Download PDF

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WO2017028528A1
WO2017028528A1 PCT/CN2016/076819 CN2016076819W WO2017028528A1 WO 2017028528 A1 WO2017028528 A1 WO 2017028528A1 CN 2016076819 W CN2016076819 W CN 2016076819W WO 2017028528 A1 WO2017028528 A1 WO 2017028528A1
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polyurethane
preparing
polyurethane composite
composite material
layer
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French (fr)
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欧阳晨曦
严拓
张会平
刘思诗
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欧阳晨曦
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28Polysaccharides or their derivatives

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  • the invention relates to a method for preparing a polyurethane composite material and a composite material obtained by the method.
  • the composite material has high water absorption property and is used for protecting a wound portion of a medium and mild burn, and is suitable for a wound with a large amount of wound exudate.
  • the skin is the barrier for the human body to maintain its internal environment and resist external microbial invasion.
  • Wound healing is a biological process involving tissue regeneration, including stages of hemostasis, infection, cell migration, cell proliferation, and remodeling.
  • the traditional polyurethane composite materials used for wound healing such as gauze, cotton, etc., are easy to breed bacteria.
  • the wound exudate easily forms suede together with the dried dermal tissue, which hinders epithelialization.
  • the wound is easy to dress and adhere, and the dressing is caused by lifting. Pain, causing secondary trauma.
  • wet theory it is generally believed that maintaining proper moistness of the wound can contribute to the healing of the wound.
  • the present invention provides a method for preparing a polyurethane composite material and the complex obtained by the method
  • the polyurethane composite In combination with the material, the polyurethane composite not only maintains a moderately moist environment for the wound, but also ensures a certain breathability, so that the wound is in an optimal healing environment.
  • the method for preparing a polyurethane composite material provided by the present invention has the following specific steps:
  • the polyurethane solution obtained in the step 1) is formed by casting, after the completion of the casting, it is air-dried at room temperature, and finally dried and shaped to obtain an absorption layer;
  • a polyurethane solution for preparing a carrier layer Preparing a polyurethane solution for preparing a carrier layer: mixing the polyurethane material with an organic solvent according to a mass fraction of 10 to 40%, stirring until the two are uniformly mixed, and then adding the polysaccharide in a ratio of 1 to 10% by mass. After uniformly stirring, defoaming to obtain a polyurethane solution for preparing a carrier layer;
  • the polyurethane solution obtained in the step 3) is prepared by a spinning method to be laid on the absorption layer, and after drying, the polyurethane composite material is obtained after cooling.
  • the organic solvent is selected from N, N-dimethylformamide, acetone or alcohol.
  • the defoaming pressure is -0.1 to 0.8 MPa, and the defoaming time is 0.5 to 6 hours.
  • the casting thickness is 0.015 to 0.030 mm, and the casting speed is The degree is 5 to 30 mm/min, and the flow elongation is 0.5 to 1.5 m.
  • the polysaccharide is selected from the group consisting of chitin, chitosan or seaweed polysaccharide.
  • the organic solvent is a mixture of N,N-dimethylformamide, acetone and an alcohol having a mass of 1:0.5:2, and in the step 3), the polysaccharide is a carapace.
  • the mixture of the prime and seaweed polysaccharides has a mass ratio of 1:0.35.
  • the spinning speed is 0.5 to 10 cm 3 /h, and the spinning time is 2 to 6 hours.
  • the present invention also provides a polyurethane composite prepared by the above method.
  • the polyurethane composite obtained by the above method has a thickness of 0.020 to 0.040 mm, and comprises an absorption layer which is a superabsorbent polyurethane film, and a carrier layer which is a polysaccharide-containing film having a microporous structure;
  • the micropore diameter is 20 to 150 ⁇ m.
  • the invention provides a method for preparing a polyurethane composite material and a composite material obtained by the method, which adopts an ultra-thin film formed by polyurethane which is excellent in water permeability and water absorption and is used as an absorption layer of a polyurethane composite material, and uses an electrospinning technology.
  • the polyurethane is made into a carrier layer having a microporous structure and can be loaded with a drug, thereby preparing a polyurethane composite.
  • the thickness of the absorbing layer is thin and has good moisturizing property; the carrier layer has a microporous structure, has good gas permeability, and carries a drug, and can directly contact the wound.
  • the polyurethane composite is capable of keeping the wound in a moderately moist and ventilated environment, and the drug it carries also promotes wound healing.
  • FIG. 1 is a schematic cross-sectional structural view of a polyurethane composite material.
  • the polyurethane composite material in this embodiment is composed of the absorbent layer 1 and the carrier layer 2 as shown in FIG. 1.
  • the absorbent layer 1 is a highly water-absorptive polyurethane having a thickness of 0.015 to 0.030 mm; and the carrier layer 2 has micropores.
  • the structured film has a micropore diameter of 20 to 150 ⁇ m, and the carrier layer 2 carries a polysaccharide or a drug component such as chitin, chitosan or alginate.
  • the preparation method of polyurethane composite is as follows:
  • the organic solvent may be N, N-dimethylformamide, acetone or alcohol, and the obtained mixture is 20-100 rpm at normal temperature.
  • the polyurethane solution for preparing the absorbent layer 1 is placed in the barrel of the casting machine.
  • the setting parameters of the casting machine are as follows: the casting thickness is 0.015 to 0.030 mm, the casting speed is 5 to 30 mm/min, and the flow elongation is 0.5 to 1.5. m. After the casting is completed, it is air-dried at room temperature for 2 to 6 hours, and then annealed in an oven at 40 to 60 ° C for 30 to 150 minutes to obtain an absorbent layer 1.
  • the organic solvent may be alcohol, and the obtained mixture is stirred at a temperature of 20-100 rpm at room temperature, and stirred for 2 hours until the polyurethane material is completely dissolved.
  • the seaweed polysaccharide is added at a mass ratio of 10% by mass, stirred at a temperature of 10 to 50 rpm at room temperature for 15 to 60 minutes, uniformly mixed, placed in a vacuum defoaming box, and the pressure is adjusted. -0.1 MPa to 0.8 MPa, defoaming for 0.5 to 6 hours, and a polyurethane solution for preparing the carrier layer 2 after defoaming is obtained.
  • the polyurethane solution prepared for the carrier layer 2 is placed in a reservoir of the raw material solution of the electrospinning machine, and the absorbent layer 1 is placed on the receiving device of the electrospinning machine, and the receiving device may be in the form of a flat plate or a drum, and the electrospinning is set.
  • the wire machine parameters were spinning speed of 10 cm 3 /h and spinning for 2 hours. After the end of the spinning, the absorbent layer 1 and the carrier layer 2 on the spinning machine receiving device were placed in an oven set to a temperature of 40 ° C for 4 hours, and the product was taken out and naturally cooled to obtain a polyurethane composite.
  • the polyurethane composite has a thickness of 0.040 mm and a water absorption rate of 600 to 650%.
  • the preparation method of the polyurethane composite material in this embodiment is substantially the same as that in the first embodiment, and the difference is that the polyurethane material is mixed with dimethylformamide (DMF) in a proportion of 15% by mass, stirred at room temperature for 4 hours, and the flow is adopted.
  • the film was formed by a delay, and the parameters of the casting machine were adjusted.
  • the film thickness was 0.030 mm, and it was taken out and dried at 40 ° C for 4 hours, and then taken out to obtain a polyurethane absorbent layer 1.
  • the polyurethane material is mixed with acetone at a mass fraction of 20%, stirred at room temperature for 3 hours until it is completely dissolved, and then mixed with chitosan at a mass ratio of 8.5%, and stirred at room temperature for 30 minutes to make it uniformly mixed.
  • a chitosan-containing polyurethane solution was prepared.
  • the chitosan-containing polyurethane solution was placed in an electrospinning machine, the spinning speed was adjusted to 1 cm 3 /h, and the solution was spun on the absorbent layer 1. After spinning for 6 hours, the electrospinning machine was turned off. The sample was placed in an oven and heated to 60 ° C for 2 hours to obtain a double-layer composite polyurethane dressing with chitosan on its surface.
  • the polyurethane composite material in this embodiment has a thickness of 0.035 mm and a water absorption rate of 700 to 750%.
  • the preparation method of the polyurethane composite material in this embodiment is substantially the same as that in the first embodiment, and the difference is that the polyurethane material has a mass fraction of 40% and the mass of N, N-dimethylformamide, acetone and alcohol is 1:0.5.
  • the mixture of 2 was mixed and stirred at normal temperature for 4 hours.
  • the film was formed by a casting method, and the parameters of the casting machine were adjusted to a thickness of 0.025 mm. After being dried at 40 ° C for 4 hours, the film was taken out to obtain a polyurethane absorbent layer 1.
  • the above polyurethane solution containing chitin and seaweed polysaccharide was placed in an electrospinning machine, the spinning speed was adjusted to 2 cm 3 /h, the solution was spun on the absorbent layer 1, and after spinning for 3 hours, the electrospinning was turned off.
  • the sample was placed in an oven and heated to 60 ° C for 2.5 hours to obtain a double-layer composite polyurethane dressing.
  • the polyurethane composite material has a thickness of 0.028 to 0.030 mm and a water absorption rate of 800 to 900%.
  • the present invention relates to product performance Omiderm TM contrast, the specific comparison of Table 1.

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Abstract

一种制备聚氨酯复合材料的方法及该方法获得的复合材料,通过采用透水透气和吸水性优良的聚氨酯成型超薄薄膜作为聚氨酯复合材料的吸收层,利用静电纺丝技术将聚氨酯制成具有微孔结构可以载药的载体层,进而制备出聚氨酯复合材料。吸收层厚度较薄,并且具有良好的保湿性;载体层有微孔结构,具备良好的透气性,同时承载药物,可以与伤口直接接触。该聚氨酯复合材料能够保持伤口处于适度的湿润和透气的环境,其承载的药物对伤口的愈合也有促进作用。

Description

制备聚氨酯复合材料的方法及该方法获得的复合材料 技术领域
本发明涉及一种制备聚氨酯复合材料的方法及该方法获得的复合材料,该复合材料具有高吸水性,用于保护中、轻度烧伤的伤口部位,适用于创面渗液较多的伤口,属于生物材料领域。
背景技术
皮肤是人体维持内环境稳定和抵御外界微生物入侵的屏障。伤口愈合是一个涉及组织再生的生物学过程,包括止血、感染、细胞迁移、细胞增殖和重塑等阶段。传统的用于创面愈合的聚氨酯复合材料如纱布、棉花等,易滋生细菌,创面渗出液易与干燥真皮组织一起形成痂皮,妨碍上皮化;同时创面易于敷料粘连,换药揭起时引起疼痛,带来二次创伤。近几十年随着生物材料的发展以及“湿润理论”的创立,普遍认为保持伤口适当的湿润能够更加有助于伤口的愈合。2008年8月美国FDA在其发布的创面医疗用品《外用药和敷料》指南中特别强调,保持创面的湿润环境是标准的处理方法。但是过度的湿润又会导致皮肤因浸渍而受损,因此保持创面适当的湿润环境是作为创面敷料要考虑的重要因素之一。为了解决传统聚氨酯复合材料具备的问题,同时遵循伤口愈合的湿润理论,一种具有高吸水性的聚氨酯复合材料就显得十分重要。
发明内容
为了克服传统聚氨酯复合材料保湿透气性差、容易与伤口粘连等缺点,本发明提供一种制备聚氨酯复合材料的方法及该方法获得的复 合材料,该聚氨酯复合材料不仅能保持伤口适度的湿润环境,而且能保证一定的透气性,使伤口处于最佳的愈合环境。
为实现上述目的,本发明提供的制备聚氨酯复合材料的方法,具体步骤如下:
1)配制制备吸收层的聚氨酯溶液:称取聚氨酯材料与有机溶剂按照质量分数为10~40%的比例混合,搅拌至二者混合均匀,混合物经过脱泡得到制备吸收层的聚氨酯溶液;
2)吸收层的成型:将步骤1)得到的聚氨酯溶液通过流延的方法成型,流延完成后置于室温条件下风干,最后烘干定型,得到吸收层;
3)配制制备载体层的聚氨酯溶液:称取聚氨酯材料与有机溶剂按照质量分数为10~40%的比例混合,搅拌至二者混合均匀,再以质量分数为1~10%的比例加入多糖,搅拌均匀后脱泡得到制备载体层的聚氨酯溶液;
4)聚氨酯复合材料的成型:将步骤3)得到的聚氨酯溶液以纺丝方法制备成载体层铺设于所述吸收层上,纺丝结束后烘干定型,冷却后得到聚氨酯复合材料。
可选地,所述步骤1)和步骤3)中,有机溶剂均选自于N,N-二甲基甲酰胺,丙酮或酒精。
可选地,所述步骤1)和步骤3)中,脱泡压力为-0.1~0.8MPa,脱泡时间为0.5~6小时。
优选地,所述步骤2)中,流延厚度为0.015~0.030mm,流延速 度为5~30mm/min,流延长度为0.5~1.5m。
可选地,所述步骤3)中,多糖选自于甲壳素,壳聚糖或海藻多糖。
优选地,所述步骤1)和步骤3)中,有机溶剂为N,N-二甲基甲酰胺、丙酮及酒精质量为1:0.5:2的混合物,所述步骤3)中,多糖为甲壳素和海藻多糖质量比为1:0.35的混合物。
优选地,所述步骤4)中,纺丝速度为0.5~10cm3/h,纺丝时间为2~6小时。
本发明还提供一种由上述方法制备的聚氨酯复合材料。
由上述方法得到的聚氨酯复合材料的厚度为0.020~0.040mm,包括吸收层和载体层,所述吸收层为高吸水性聚氨酯薄膜,所述载体层为具有微孔结构的含有多糖的薄膜;其微孔孔径为20~150μm。
本发明的有益效果:提供一种制备聚氨酯复合材料的方法及该方法获得的复合材料,通过采用透水透气和吸水性优良的聚氨酯成型超薄薄膜作为聚氨酯复合材料的吸收层,利用静电纺丝技术将聚氨酯制成具有微孔结构可以载药的载体层,进而制备出聚氨酯复合材料。吸收层厚度较薄,并且具有良好的保湿性;载体层有微孔结构,具备良好的透气性,同时承载药物,可以与伤口直接接触。该聚氨酯复合材料能够保持伤口处于适度的湿润和透气的环境,其承载的药物对伤口的愈合也有促进作用。
附图说明
图1为聚氨酯复合材料的剖视结构示意图。
图中:1.吸收层;2.载体层。
具体实施方式
以下结合附图和具体实施例对本发明作进一步的详细描述。
实施例1
本实施例中的聚氨酯复合材料如图1所示,由吸收层1和载体层2聚合而成,吸收层1为高吸水性的聚氨酯,厚度为0.015~0.030mm;载体层2为具有微孔结构的薄膜,微孔孔径为20~150μm,载体层2承载有多糖或药物组分,如甲壳素、壳聚糖、海藻酸盐。
聚氨酯复合材料制备方法如下:
称取一定的质量聚氨酯材料与有机溶剂按照质量分数10%混合,有机溶剂可以是N,N-二甲基甲酰胺,丙酮或酒精,将得到的混合物在常温下以20~100转/min的速度搅拌,搅拌2小时,待聚氨酯材料完全溶解后置于真空脱泡箱中,调节压力为-0.1MPa~0.8MPa,脱泡0.5~6小时,得到脱泡后的制备吸收层1的聚氨酯溶液。
将制备吸收层1的聚氨酯溶液置于流延机的料筒中,流延机设置参数如下:流延厚度为0.015~0.030mm,流延速度为5~30mm/min,流延长度为0.5~1.5m。流延完成后,室温下放置风干2~6小时,再置于40~60℃烘箱内30~150min退火定型,得到吸收层1。
称取一定的质量聚氨酯材料与有机溶剂按照质量分数40%混合,有机溶剂可以是酒精,将得到的混合物在常温下以20~100转/min的速度搅拌,搅拌2小时,待聚氨酯材料完全溶于有机溶剂之后,再以质量分数10%的质量比加入海藻多糖,常温下以10~50转/min的速度,搅拌15~60min,混合均匀后置于真空脱泡箱中,调节压力为 -0.1MPa~0.8MPa,脱泡0.5~6小时,得到脱泡后的制备载体层2的聚氨酯溶液。
将制备载体层2的聚氨酯溶液置于静电纺丝机的原料溶液的储存器中,将吸收层1置于静电纺丝机的接收装置上,接收装置可以是平板状或滚筒状,设置静电纺丝机参数为纺丝速度为10cm3/h,纺丝2小时。纺丝结束后,将纺丝机接收装置上的吸收层1和载体层2放入到温度设定为40℃的烘箱中定型4h,将产品取出后自然冷却,得到聚氨酯复合材料。
本实施例中,聚氨酯复合材料的厚度为0.040mm,水吸收率为600~650%。
实施例2
本实施例中的聚氨酯复合材料制备方法与实施例1大致相同,其区别在于:聚氨酯材料以质量分数为15%的比例与二甲基甲酰胺(DMF)混合,常温下搅拌4小时,采用流延法成型薄膜,调节流延机参数,薄膜厚度为0.030mm,放置于40℃下烘干4小时后取出,得到聚氨酯吸收层1。
将聚氨酯材料以质量分数为20%的比例与丙酮混合,常温下搅拌3小时至其完全溶解,再与壳聚糖按照质量比为8.5%的比例进行混合,常温下搅拌30分钟使其混合均匀,制得含壳聚糖的聚氨酯溶液。
将上述含壳聚糖的聚氨酯溶液置于静电纺丝机中,调节纺丝速度为1cm3/h,将上述溶液纺丝于吸收层1上,纺丝6小时后,关闭静电 纺丝机,样品放入烘箱中升温至60℃保温2小时取出,得到表面载有壳聚糖的双层复合聚氨酯敷料。
本实施例中聚氨酯复合材料的厚度为0.035mm,水吸收率为700~750%。
实施例3
本实施例中的聚氨酯复合材料制备方法与实施例1大致相同,其区别在于:聚氨酯材料以质量分数为40%的比例与N,N-二甲基甲酰胺、丙酮及酒精质量为1:0.5:2的混合物混合,常温下搅拌4小时,采用流延法成型薄膜,调节流延机参数,薄膜厚度为0.025mm,放置于40℃下烘干4小时后取出,得到聚氨酯吸收层1。
将聚氨酯材料以质量分数为25%的比例与N,N-二甲基甲酰胺、丙酮及酒精质量为1:0.5:2的混合物混合,常温下搅拌3小时至其完全溶解,再与甲壳素和海藻多糖质量比为1:0.35的混合物按照质量比为4.5%的比例进行混合,常温下搅拌30分钟使其混合均匀,制得含有甲壳素和海藻多糖的聚氨酯溶液。
将上述含甲壳素和海藻多糖的聚氨酯溶液置于静电纺丝机中,调节纺丝速度为2cm3/h,将上述溶液纺丝于吸收层1上,纺丝3小时后,关闭静电纺丝机,样品放入烘箱中升温至60℃保温2.5小时取出,得到双层复合聚氨酯敷料。
本实施例中聚氨酯复合材料的厚度为0.028~0.030mm,水吸收率为800~900%。
对照例4
本发明产品与OmidermTM的性能对比,具体对比情况如表1。
表1
Figure PCTCN2016076819-appb-000001

Claims (9)

  1. 一种制备聚氨酯复合材料的方法,其特征在于,所述方法具体步骤如下:
    1)配制制备吸收层的聚氨酯溶液:称取聚氨酯材料与有机溶剂按照质量分数为10~40%的比例混合,搅拌至二者混合均匀,混合物经过脱泡得到制备吸收层的聚氨酯溶液;
    2)吸收层的成型:将步骤1)得到的聚氨酯溶液通过流延的方法成型,流延完成后置于室温条件下风干,最后烘干定型,得到吸收层;
    3)配制制备载体层的聚氨酯溶液:称取聚氨酯材料与有机溶剂按照质量分数为10~40%的比例混合,搅拌至二者混合均匀,再以质量分数为1~10%的比例加入多糖,搅拌均匀后脱泡得到制备载体层的聚氨酯溶液;
    4)聚氨酯复合材料的成型:将步骤3)得到的聚氨酯溶液以纺丝方法制备成载体层铺设于所述吸收层上,纺丝结束后烘干定型,冷却后得到聚氨酯复合材料。
  2. 根据权利要求1所述制备聚氨酯复合材料的方法,其特征在于:所述步骤1)和步骤3)中,有机溶剂均选自于N,N-二甲基甲酰胺,丙酮或酒精。
  3. 根据权利要求1所述制备聚氨酯复合材料的方法,其特征在于:所述步骤1)和步骤3)中,脱泡压力为-0.1~0.8MPa,脱泡时间为0.5~6小时。
  4. 根据权利要求1所述制备聚氨酯复合材料的方法,其特征在于:所述步骤2)中,流延厚度为0.015~0.030mm,流延速度为5~30mm/min,流延长度为0.5~1.5m。
  5. 根据权利要求1所述制备聚氨酯复合材料的方法,其特征在于:所述步骤3)中,多糖选自于甲壳素,壳聚糖或海藻多糖。
  6. 根据权利要求1所述制备聚氨酯复合材料的方法,其特征在于:所述步骤1)和步骤3)中,有机溶剂为N,N-二甲基甲酰胺、丙酮及酒精质量为1:0.5:2的混合物,所述步骤3)中,多糖为甲壳素和海藻多糖质量比为1:0.35的混合物。
  7. 根据权利要求1所述制备聚氨酯复合材料的方法,其特征在于:在步骤4)中,纺丝速度为0.5~10cm3/h,纺丝时间为2~6小时。
  8. 一种由权利要求1所述方法制备的聚氨酯复合材料。
  9. 根据权利要求8所述的聚氨酯复合材料,其特征在于,所述聚氨酯复合材料的厚度为0.020~0.040mm,包括吸收层和载体层,所述吸收层为高吸水性聚氨酯薄膜,所述载体层为具有微孔结构的含有多糖的薄膜;其微孔孔径为20~150μm。
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