WO2021051902A1 - 一种含硫酸钡能显影的复合生物补片及其制备方法 - Google Patents

一种含硫酸钡能显影的复合生物补片及其制备方法 Download PDF

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WO2021051902A1
WO2021051902A1 PCT/CN2020/096114 CN2020096114W WO2021051902A1 WO 2021051902 A1 WO2021051902 A1 WO 2021051902A1 CN 2020096114 W CN2020096114 W CN 2020096114W WO 2021051902 A1 WO2021051902 A1 WO 2021051902A1
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barium sulfate
polypropylene
composite biological
composite
biological patch
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PCT/CN2020/096114
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English (en)
French (fr)
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杨宇民
王勇军
李鹏
郭其阳
张鲁中
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南通大学
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Priority to AU2020348320A priority Critical patent/AU2020348320B2/en
Publication of WO2021051902A1 publication Critical patent/WO2021051902A1/zh

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00—Preparations for testing in vivo
    • A61K49/04—X-ray contrast preparations
    • A61K49/0404—X-ray contrast preparations containing barium sulfate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/028—Other inorganic materials not covered by A61L31/022 - A61L31/026
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/048—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/18—Materials at least partially X-ray or laser opaque
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces

Definitions

  • the invention relates to the field of biomedical engineering, in particular to a compound biological patch containing barium sulfate capable of being developed and a preparation method thereof.
  • Hernia is one of the common and frequently-occurring diseases in general surgery, and it occurs at all ages. According to relevant data, there are about 20 million hernia repair operations in the world every year, and 80% of the operations require hernia patches. Tension-free hernia repair is currently the most widely used hernia repair operation. Biological patches made of polypropylene and other polymer materials are widely used as hernia patches. The main function of the hernia patch implanted in the human body is to resist the internal pressure of the human body and support the new tissue. Therefore, the patch must have a stable structure, sufficient strength and flexibility. Therefore, the main physical and mechanical properties to measure the quality of repair nets are composed of tensile breaking strength, bursting strength, rigidity and flexibility, and wrinkle recovery.
  • the future hernia patch should have good antibacterial ability, prevent tissue adhesion and hemolytic reaction, have good tissue support and can be completely or partially absorbed by the human body, and reduce the postoperative shrinkage of the patch to the trauma. It can even assist the regeneration of endogenous tissues, repair surgical trauma areas, reduce the generation of postoperative scar tissue, and minimize the pain of patients and improve the prognosis.
  • Polypropylene material has the advantages of stable chemical properties, high physical tensile strength, firm weaving, good hand feeling, resistance to infection and repeated bending.
  • the polypropylene patch woven with it has the characteristics of easy tissue growth and granulation tissue proliferation. And because of its large weaving pore size, it facilitates the entry and exit of white blood cells and macrophages, and kills bacteria in the patch grid. Therefore, this type of patch has an excellent anti-infection effect and is widely used in hernia repair.
  • the low price of polypropylene patch it can stimulate tissue healing, the surgical wound is small, and the postoperative recovery is quicker, it has become the most commonly used synthetic non-absorbable patch in hernia repair.
  • polypropylene patches also have some disadvantages: for example, due to the rough surface of the polypropylene patch, direct contact with abdominal organs will cause more severe abdominal adhesions, and even erode the intestinal wall, leading to intestinal fistula or intestinal fistula. Occurrence of intestinal obstruction.
  • composite hernia repair materials that combine the advantages of the two materials are constantly emerging.
  • the composite hernia patch is generally prepared by overall weaving, suture, bonding, lamination and other methods.
  • Common composite patches can be divided into mechanically reinforced patches, partially degraded patches, and anti-adhesion patches according to their composite applications.
  • According to their materials they can be divided into polypropylene and expanded polytetrafluoroethylene material combined patches, polypropylene and flexible patches.
  • the shrinkage rate can reach 20%-50%) after the hernia repair using the bio-patch made of polymer materials, the polymer bio-patch is distorted, and its irregular surface will be distorted. It irritates and even damages surrounding tissues, causing skin sinus formation and infection. At this time, a second operation should be performed to remove the distorted patch for replacement.
  • Bacterial infection after hernia repair is also one of the more serious complications.
  • a large number of clinical statistics published at home and abroad point out that the incidence of infection after hernia repair is 6%-10%, especially after incisional hernia infection is 40%. about. Severe postoperative infection can lead to prolonged hospital stay, poor prognosis and even require follow-up surgery to clean up the infected site.
  • infection after hernia repair is also one of the more serious complications.
  • a large number of clinical statistics published at home and abroad point out that the incidence of infection after hernia repair is 6% to 10%; the other is due to the occurrence of polymer biopatch Distorted, its irregular surface can irritate or even damage surrounding tissues, causing skin sinus formation and infection.
  • the clinical treatment of these two infections is completely different.
  • the former should be treated with anti-infective treatment, and the latter should be treated with a second operation.
  • the clinical distinction between these two types of lesions still depends on the doctor's clinical experience. Sometimes it is really impossible to distinguish, and only surgical exploration can be performed, which brings additional pain and burden to the patient. Therefore, if non-surgical methods are used to explore the cause of postoperative infection and provide a basis for clinical diagnosis and treatment, it has become an urgent problem to be solved.
  • the purpose of the present invention is to provide a composite biological patch containing barium sulfate that can be developed and a preparation method thereof.
  • the composite biological patch prepared by the preparation method provided by the present invention has better mechanical properties and development strength.
  • the present invention provides a composite biological patch containing barium sulfate that can be developed.
  • the composition of the composite biological patch according to mass percentage is: polypropylene 65-85%, nano-barium sulfate 15-35% .
  • the thickness of the composite biological patch is 0.6 mm, and the aperture of the composite biological patch is 2 mm.
  • the polypropylene is medical grade isotactic polypropylene with a melting point of 164-170°C and an isotactic index ⁇ 96%.
  • the particle size of the nano barium sulfate ranges from 30 to 70 nm.
  • the present invention also provides a method for preparing the above-mentioned compound biological patch containing barium sulfate capable of being developed, which includes the following steps:
  • step (2) The polypropylene/nano barium sulfate solution obtained in step (1) is added to an equal volume of coagulation bath for phase inversion curing, and after curing is completed, it is taken out for washing and vacuum drying to obtain a polypropylene/nano barium sulfate composite material;
  • the composite biological patch material is extruded and spun through a single screw extruder to obtain composite fibers, and the composite fiber is woven to obtain a developable composite biological patch containing barium sulfate.
  • the organic solvent in step (1) is one or more of toluene, xylene and decalin.
  • the temperature at which polypropylene is dissolved in the organic solvent in step (1) is 100-120° C.; the concentration of polypropylene in the polypropylene solution is 100-125 g/L; and the stirring time is 2-4 h.
  • the coagulation bath in step (2) includes one of absolute ethanol or acetone.
  • the extrusion temperature in step (3) is 150-200°C; the screw speed is 60-120 r/min.
  • the extrusion temperature in step (4) is 150-220°C.
  • the present invention adds a certain amount (15%-35%) of barium sulfate that can be developed into the raw material of the polymer biological patch to ensure the tensile strength of the biological patch and can be inspected by X-ray. It can determine whether the biological patch is distorted, so as to provide a basis for clinical diagnosis and treatment.
  • the invention provides a developable composite biological patch containing barium sulfate.
  • the composition of the composite biological patch according to mass percentages is 65-85% of polypropylene and 15-35% of nano-barium sulfate.
  • the thickness of the composite biological patch is preferably 0.6 mm, and the pore diameter of the composite biological patch is preferably 2 mm.
  • the polypropylene in the present invention is medical grade isotactic polypropylene, with a melting point of 164-170°C, and an isotactic index ⁇ 96%.
  • the composite biological patch provided by the present invention contains polypropylene and nano barium sulfate.
  • Polypropylene material has the advantages of stable chemical properties, high physical tensile strength, firm weaving, good hand feeling, resistance to infection and repeated bending.
  • the polypropylene patch woven with it has the characteristics of easy tissue growth and granulation tissue proliferation. And because of its large weaving pore size, it facilitates the entry and exit of white blood cells and macrophages, and kills bacteria in the patch grid. Therefore, this type of patch has excellent anti-infection effect, and can stimulate tissue healing and has surgical wounds. The advantages of small, quicker recovery after surgery.
  • the content of polypropylene is 65-85% by mass percentage, so that the tensile strength of the composite biological patch can meet the strength requirements of the biological patch for hernia surgery.
  • Barium sulfate is a white loose powder and is a double X-ray contrast agent.
  • the fine and uniform barium agent is mostly synthetic barium, the particles are fine and uniform, mostly round, light in specific gravity, slow and consistent sedimentation, widely used in single and double contrast of esophagus, stomach, duodenum, small intestine, and colon Radiography check.
  • the content of barium sulfate affects the imaging effect and the mechanical properties of the composite biological patch. As the content of barium sulfate increases, the mechanical properties of the biological patch decrease. But if the content of barium sulfate is too low, the development strength of the biological patch is not strong enough. After testing, the patch with barium sulfate content between 15% and 35% can meet the requirements of developing strength and mechanical properties.
  • the particle size range of nano barium sulfate is preferably 30-70 nm.
  • Nano-barium sulfate with a particle size of 30-70nm has a large specific surface area, and the greater the possibility of physical or chemical interaction with polymer materials, the stronger the ability to adsorb on polypropylene and other melts, and the enhanced interfacial adhesion.
  • the layer is relatively thin, with better strength and stretchability.
  • the present invention also provides a method for preparing the above-mentioned compound biological patch containing barium sulfate capable of being developed, which includes the following steps:
  • step (2) The polypropylene/nano barium sulfate solution obtained in step (1) is added to an equal volume of coagulation bath for phase inversion curing, and after curing is completed, it is taken out for washing and vacuum drying to obtain a polypropylene/nano barium sulfate composite material;
  • the composite biological patch material is extruded and spun through a single screw extruder to obtain composite fibers, and the composite fiber is woven to obtain a developable composite biological patch containing barium sulfate.
  • the present invention adopts a solution blending method for granulation. Specifically, firstly, polypropylene is dissolved in an organic solvent to obtain a polypropylene solution, and nano-barium sulfate is added to the polypropylene solution and stirred until it is uniformly mixed to obtain a polypropylene/nano-barium sulfate solution.
  • a solution blending method for granulation Specifically, firstly, polypropylene is dissolved in an organic solvent to obtain a polypropylene solution, and nano-barium sulfate is added to the polypropylene solution and stirred until it is uniformly mixed to obtain a polypropylene/nano-barium sulfate solution.
  • the source of polypropylene there is no special restriction on the source of polypropylene, as long as the polypropylene well known to those skilled in the art can be used.
  • the organic solvent is preferably one or more selected from toluene, xylene and decalin.
  • the temperature at which polypropylene is dissolved in the organic solvent is preferably 100 to 120°C; the concentration of polypropylene in the polypropylene solution is preferably 100 to 125 g/L; the stirring time is preferably 2 to 4 hours.
  • the purpose of the stirring in the present invention It is to make the components mix uniformly.
  • the polypropylene/nano barium sulfate solution is obtained, the polypropylene/nano barium sulfate solution is added to an equal volume of coagulation bath for phase inversion curing, and after curing is completed, it is taken out for washing and vacuum drying to obtain a polypropylene/nano barium sulfate composite material.
  • the coagulation bath is preferably selected from one of absolute ethanol or acetone.
  • the polypropylene/nano barium sulfate composite material is extruded and pelletized by a co-rotating twin-screw extruder to obtain a composite biological patch raw material; in the present invention, the co-rotating twin-screw extruder
  • the output temperature is preferably 150 to 200°C
  • the screw rotation speed is preferably 60 to 120 r/min, more preferably 60 r/min.
  • the composite biological patch material is extruded and spun through a single screw extruder to obtain a composite fiber, and the composite fiber is woven to obtain a developable composite biological patch containing barium sulfate.
  • the extrusion temperature of the single-screw extruder is preferably 150 to 220°C, and more preferably 220°C.
  • the polypropylene/nano barium sulfate solution was slowly poured into the 80 mL absolute ethanol coagulation bath, and the stirring rate of the coagulation bath was 30 r/min.
  • the polypropylene/nano barium sulfate composite material is extruded and pelletized by a twin screw to obtain a composite biological patch raw material, the temperature range of the extruder is 150-200°C, and the screw speed is 60r/min.
  • the raw material particles are melt-spun by a single screw to obtain composite fibers, and the spinning temperature is 220°C.
  • the composite fiber is woven and processed to obtain a biological patch with a thickness of 0.6 mm and a pore of 2 mm.
  • the weight of the patch is 82g/m 2 , and the tensile strength is 1275mmHg; after X-ray inspection, the composite biological patch is clearly visible.
  • the polypropylene/nano barium sulfate solution was slowly poured into a 90 mL absolute ethanol coagulation bath, and the stirring rate of the coagulation bath was 30 r/min.
  • the polypropylene/nano barium sulfate composite material is extruded and pelletized by a twin screw to obtain a composite biological patch raw material, the temperature range of the extruder is 150-200 DEG C, and the screw speed is 60r/min.
  • the raw material particles are melt-spun by a single screw to obtain composite fibers, and the spinning temperature is 220°C.
  • the composite fiber is woven and processed to obtain a biological patch with a thickness of 0.6 mm and a pore of 2 mm.
  • the weight of the patch is 84g/m 2 , and the tensile strength is 1065mmHg; after X-ray inspection, the composite biological patch is clearly visible.
  • the polypropylene/nano barium sulfate solution was slowly poured into a 100 mL absolute ethanol coagulation bath, and the stirring rate of the coagulation bath was 30 r/min.
  • the polypropylene/nano barium sulfate composite material was extruded and pelletized by a twin-screw to obtain the composite biological patch raw material, the temperature range of the extruder was 150-200°C, and the screw speed was 60r/min.
  • the raw material particles are melt-spun by a single screw to obtain composite fibers, and the spinning temperature is 220°C.
  • the composite fiber is woven and processed to obtain a biological patch with a thickness of 0.6 mm and a pore of 2 mm.
  • the weight of the patch is 86g/m 2 , and the tensile strength is 820mmHg; after X-ray inspection, the composite biological patch is clearly visible.
  • the polypropylene/nano barium sulfate solution was slowly poured into the 80 mL absolute ethanol coagulation bath, and the stirring rate of the coagulation bath was 30 r/min.
  • the polypropylene/nano barium sulfate composite material is extruded and pelletized by a twin screw to obtain a composite biological patch raw material, the temperature range of the extruder is 150-200 DEG C, and the screw speed is 60r/min.
  • the raw material particles are melt-spun by a single screw to obtain composite fibers, and the spinning temperature is 220°C.
  • the composite fiber is woven and processed to obtain a biological patch with a thickness of 0.6 mm and a pore of 2 mm.
  • the patch weight is 81g/m 2 , and the tensile strength is 1340mmHg; after X-ray inspection, the composite biological patch is not clearly visible.
  • the polypropylene/nano barium sulfate solution was slowly poured into a 100 mL absolute ethanol coagulation bath, and the stirring rate of the coagulation bath was 30 r/min.
  • the polypropylene/nano barium sulfate composite material is extruded and pelletized by a twin-screw to obtain the composite biological patch raw material, the temperature range of the extruder is 150-200 DEG C, and the screw speed is 60r/min.
  • the raw material particles are melt-spun by a single screw to obtain composite fibers, and the spinning temperature is 220°C.
  • the composite fiber is woven and processed to obtain a biological patch with a thickness of 0.6 mm and a pore of 2 mm.
  • the weight of the patch is 90g/m 2 , and the tensile strength is 530mmHg; after X-ray inspection, the composite biological patch is clearly visible.
  • Table 1 shows the barium sulfate content, patch weight, thickness, porosity, tensile strength and development strength of the composite biological patch material in Examples 1-3 and Comparative Example 1-2. It can be seen from the examples and comparative examples that when the mass percentage of barium sulfate is less than 15%, the development strength of the material is not clear, and when the mass percentage of sulfuric acid is higher than 35%, the mechanical properties of the material are significantly reduced.
  • the invention provides a composite biological patch and a preparation method of its raw materials, which can determine whether the biological patch is distorted by X-ray inspection, simplifies the method for discriminating lesions after hernia repair, improves the discriminating efficiency, reduces the suffering of patients, and meets clinical practice application.

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Abstract

一种含硫酸钡能显影的复合生物补片及其制备方法。复合生物补片中硫酸钡的质量百分比为15～35％，具有较好的力学性能和显影强度。该复合生物补片的制备方法，包括：(1)制备聚丙烯溶液，加入纳米硫酸钡搅拌均匀，得聚丙烯/纳米硫酸钡溶液；(2)将聚丙烯/纳米硫酸钡溶液加入凝固浴中进行相转化固化，取出洗涤、真空干燥，得到聚丙烯/纳米硫酸钡复合材料；(3)将聚丙烯/纳米硫酸钡复合材料经同向双螺杆挤出机挤出造粒，得到复合生物补片原料；(4)再经单螺杆挤出机挤出纺丝制得复合纤维，编织加工制得含硫酸钡能显影的复合生物补片。制备方法简单，适合工业化生产。

Description

一种含硫酸钡能显影的复合生物补片及其制备方法 技术领域
本发明涉及生物医学工程领域，尤其涉及一种含硫酸钡能显影的复合生物补片及其制备方法。
背景技术
疝气是普外科的常见病和多发病之一，且在各年龄阶段均有发生。据相关资料显示：世界上每年约有2000万例疝修补手术，其中80％的手术需要用到疝气补片。无张力疝修补术是目前应用最广泛的疝修复手术方式，由聚丙烯等高分子材料制备的生物补片被广泛用作疝气补片。疝气补片植入人体内的主要作用是抵抗人体内部压强，支撑新生组织，所以补片必须具有稳定的结构、足够的强度和柔软度。因此衡量修补网质量的主要物理机械性能由拉伸断裂强度、顶破强度、刚柔性能、折皱回复性等指标组成。
根据临床手术的需求，未来疝气补片应该向着具有良好的抗菌能力、防止组织黏连和溶血反应、具有良好的组织支撑性且可以被人体完全或部分吸收、降低术后补片收缩对创伤处的影响等方向研究和发展，甚至能辅助内源组织的再生，修复手术创伤区域，减少术后疤痕组织的生成，以最大程度地减轻患者的痛苦和改善预后。
聚丙烯材料具有化学性质稳定、物理张力强度较高、编织牢固、手感好、可耐受感染和可反复弯曲等优点，使用其编织的聚丙烯补片具有易于组织长入和肉芽组织增殖的特点，且由于其编织孔径较大，利于白细胞与巨噬细胞进出，对补片网格中的细菌进行杀灭，因此这类补片具有优异的抗感染作用，在疝气修补术中得到广泛应用。同时由于聚丙烯补片价格低廉，可刺激组织愈合，手术创口小，术后恢复较快等优点，成为疝气修补术中最常使用的人工合成不可吸收补片。但是在目前使用过程中，发现聚丙烯补片也具有一些缺点：如由于聚丙烯补片表面粗糙，直接与腹腔脏器接触会导致较为严重的腹腔黏连，甚至侵蚀肠壁从而导致肠瘘或肠梗堵的发生。
单一材质补片往往有生物力学性能不相容和不稳固，重量型和黏连现象严重的问题。为解决上述问题，结合两种材料优势的复合疝气修补材料不断涌现。复合疝气补片一般通过整体编织、缝合、黏合、层压等方式制备。常见的复合补片按复合用途可分为力学加强补片、部分降解补片、抗黏连补片，按材料可分为聚丙烯与膨体聚四氟乙烯材料结合补片、聚丙烯与可吸收材料结合补片和聚丙烯与可吸收材料相结合的多层补片等。
临床使用发现，由于使用高分子材料制备的生物补片进行疝气修补术后期疤痕明显收缩(收缩率可达20％～50％)，高分子材料生物补片发生扭曲，其不规则的表面会刺激甚至损伤周围组织，从而引起皮肤窦道形成和感染的发生。这时应该进行二次手术取出已经发生扭曲的补片进行置换。
疝气修补术后细菌感染也是较为严重的并发症之一，国内外发表的大量临床统计数据指出，疝气修补术后感染发生率为6％～10％，尤其是切口疝术后感染率为40％左右。严重的术后感染可以导致患者的住院时间延长，预后不佳甚至需要后续手术对感染部位进行清理。
由此可见，疝气修补术后感染也是较为严重的并发症之一。而感染的因素有两种，一种是细菌感染，国内外发表的大量临床统计数据指出，疝气修补术后感染发生率为6％～10％；另一种是因为高分子材料生物补片发生扭曲，其不规则的表面会刺激甚至损伤周围组织，从而引起皮肤窦道形成和感染的发生。这两种感染的临床治疗截然不同。前一种进行抗感染治疗，后一种应该进行二次手术。目前临床上区分这两种病变还是靠医生的临床经验，有时实在无法分辨，只能够进行手术探查，给病人带来额外的痛苦和负担。因此，如果通过非手术方式探查术后感染原因并为临床诊断和治疗提供依据成为亟需解决的问题。
发明内容
有鉴于此，本发明的目的在于提供一种含硫酸钡能显影的复合生物补片及其制备方法，本发明提供的制备方法制备得到的复合生物补片具有较好的力学性能和显影强度。
为解决上述技术问题，本发明提供了一种含硫酸钡能显影的复合生物补片，所述复合生物补片的组成按照质量百分比为：聚丙烯65～85％，纳米硫酸钡15～35％。
优选的，所述复合生物补片的厚度为0.6mm，所述复合生物补片的孔径为2mm。
优选的，所述聚丙烯为医用级等规聚丙烯，熔点为164～170℃，等规指数≥96％。
优选的，所述纳米硫酸钡的粒径范围为30～70nm。
本发明还提供了一种上述含硫酸钡能显影的复合生物补片的制备方法，包括以下步骤：
(1)将聚丙烯溶于有机溶剂得到聚丙烯溶液，向所述聚丙烯溶液中加入纳米硫酸钡搅拌至混合均匀，得到聚丙烯/纳米硫酸钡溶液；
(2)将步骤(1)得到的聚丙烯/纳米硫酸钡溶液加入等体积的凝固浴中进行相转化固化，固化结束后取出洗涤、真空干燥，得到聚丙烯/纳米硫酸钡复合材料；
(3)将所述聚丙烯/纳米硫酸钡复合材料经同向双螺杆挤出机挤出造粒，得到复合生物补片原料；
(4)将所述复合生物补片原料经单螺杆挤出机挤出纺丝制得复合纤维，将所述复合纤维经编织加工制得含硫酸钡能显影的复合生物补片。
优选的，步骤(1)中所述有机溶剂为甲苯、二甲苯和十氢化萘中的一种或几种。
优选的，步骤(1)中将聚丙烯溶于有机溶剂的温度为100～120℃；所述聚丙烯溶液中聚丙烯的浓度为100～125g/L；所述搅拌时间为2～4h。
优选的，步骤(2)中所述凝固浴包括无水乙醇或丙酮中的一种。
优选的，步骤(3)中所述挤出温度150～200℃；螺杆转速60～120r/min。
优选的，步骤(4)中所述挤出温度150～220℃。
本发明与现有技术相比，通过在高分子生物补片的原材料中里添加一定量(15％-35％)能够显影的硫酸钡，保证生物补片的抗张强度且可以通过X射线检查就能够判别是否生物补片是否发生扭曲，从而为临床诊断和治疗提供依据。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为了进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
本发明所有原料，对其来源没有特别限制，在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。
本发明提供了一种含硫酸钡能显影的复合生物补片，复合生物补片的组成按照质量百分比为：聚丙烯65～85％，纳米硫酸钡15～35％。
本发明中，复合生物补片的厚度优选为0.6mm，复合生物补片的孔径优选为2mm。
本发明中聚丙烯为医用级等规聚丙烯，熔点为164～170℃，等规指数≥96％。
本发明提供的复合生物补片，包含聚丙烯和纳米硫酸钡。聚丙烯材料具有化学性质稳定、物理张力强度较高、编织牢固、手感好、可耐受感染和可反复弯曲等优点，使用其编织的聚丙烯补片具有易于组织长入和肉芽组织增殖的特点，且由于其编织孔径较大，利于白细胞与巨噬细胞进出，对补片网格中的细菌进行杀灭，因此这类补片具有优异的抗感染作用，且可刺激组织愈合，具有手术创口小，术后恢复较快等优点。本发明中，按质量百分比，聚丙烯的含量为65～85％，从而使复合生物补片的抗张强度满足疝气手术生物补片强度需求。硫酸钡为白色疏松的细粉，为X线双重造影剂。细而均匀型钡剂多为合成钡，颗粒细而均匀，多为圆形，比重较轻，沉降慢且一致，广泛适用于食道、胃、十二指肠、小肠、结肠的单、双对比造影检查。硫酸钡含量影响显影效果以及复合生物补片的力学性能。随着硫酸钡含量的增加，生物补片的力学性能下降。但如果硫酸钡含量的过低，生物补片显影强度又不够强。经过试验，硫酸钡含量在15％～35％的的补片能够满足显影强度和力学性能的要求。
本发明中，纳米硫酸钡的粒径范围优选为30～70nm。粒径为30～70nm的纳米硫酸钡比表面积大，与高分子材料发生物理或化学作用的可能性越大，吸附在聚丙烯等熔体上的能力就越强，界面粘结力增强，界面层相对比较薄，强度和可拉伸性能较好。
本发明还提供了一种上述含硫酸钡能显影的复合生物补片的制备方法，包括以下步骤：
(1)将聚丙烯溶于有机溶剂得到聚丙烯溶液，向所述聚丙烯溶液中加入纳米硫酸钡搅拌至混合均匀，得到聚丙烯/纳米硫酸钡溶液；
(2)将步骤(1)得到的聚丙烯/纳米硫酸钡溶液加入等体积的凝固浴中进行相转化固化，固化结束后取出洗涤、真空干燥，得到聚丙烯/纳米硫酸钡复合材料；
(3)将所述聚丙烯/纳米硫酸钡复合材料经同向双螺杆挤出机挤出造粒，得到复合生物补片原料；
(4)将所述复合生物补片原料经单螺杆挤出机挤出纺丝制得复合纤维，将所述复合纤维经编织加工制得含硫酸钡能显影的复合生物补片。
为了增大硫酸钡的加入量，并制备均匀的硫酸钡高分子共混材料，本发明采用溶液共混法进行造粒。具体的，首先将聚丙烯溶于有机溶剂得到聚丙烯溶液，向所述聚丙烯溶液中加入纳米硫酸钡搅拌至混合均匀，得到聚丙烯/纳米硫酸钡溶液。本发明对聚丙烯的来源没有特殊限制，采用本领域技术人员所熟知的聚丙烯即可。在本发明中有机溶剂优选选自甲苯、二甲苯和十氢化萘中的一种或几种。在本发明中，聚丙烯溶于有机溶剂的温度优选为100～120℃；聚丙烯溶液中聚丙烯的浓度优选为100～125g/L；搅拌时间优选为2～4h，本发明中搅拌的目的是使各组分混合均匀。
得到聚丙烯/纳米硫酸钡溶液后，将聚丙烯/纳米硫酸钡溶液加入等体积的凝固浴中进行相转化固化，固化结束后取出洗涤、真空干燥，得到聚丙烯/纳米硫酸钡复合材料。本发明中凝固浴优选选自无水乙醇或丙酮中的一种。
得到聚丙烯/纳米硫酸钡复合材料后，将聚丙烯/纳米硫酸钡复合材料经同向双螺杆挤出机挤出造粒，得到复合生物补片原料；本发明中，同向双螺杆的挤出温度优选为150～200℃，螺杆转速优选为60～120r/min，更优选为60r/min。
得到复合生物补片原料后，将复合生物补片原料经单螺杆挤出机挤出纺丝制得复合纤维，将所述复合纤维经编织加工制得含硫酸钡能显影的复合生物补片。本发明中，单螺杆挤出机的挤出温度优选为150～220℃，更优选为220℃。
为了进一步理解本发明，下面结合实施例对本发明提供的一种含硫酸钡能显影的复合生物补片及其制备方法进行详细说明，本发明的保护范围不受以下实施例的限制。
实施例1：
向反应釜中加入80mL甲苯和10g聚丙烯(占聚丙烯/纳米硫酸钡复合材料的质量百分比为85％)进行搅拌溶解，反应釜搅拌速率为200r/min，同时将反应釜升温至100℃。待聚丙烯完全溶解后，向反应釜内加入1.7647g纳米硫酸钡粉末(占聚丙烯/纳米硫酸钡复合材料的质量百分比为15％)，纳米硫酸钡粉末的平均粒径为70nm。加料完毕后继续搅拌2h，直至纳米硫酸钡粉末与聚丙烯充分混合均匀。随后将聚丙烯/纳米硫酸钡溶液缓慢倒入80mL无水乙醇凝固浴中，凝固浴的搅拌速率为30r/min。随后将聚丙烯/纳米硫酸钡复合材料经双螺杆挤出造粒得到复合生物补片原料，挤出机温度区间为150～200℃，螺杆转速为60r/min。原材料颗粒经单螺杆熔融纺丝得到复合纤维，纺丝温度为220℃。复合纤维经编织加工后得到厚度为0.6mm、孔隙为2mm的生物补片。
经测试，补片重量为82g/m 2，抗张强度为1275mmHg；经X射线检查，复合生物补片显影清晰。
实施例2：
向反应釜中加入90mL甲苯和10g聚丙烯(占聚丙烯/纳米硫酸钡复合材料的质量百分比为75％)进行搅拌溶解，反应釜搅拌速率为200r/min，同时将反应釜升温至100℃。待聚丙烯完全溶解后，向反应釜内加入3.3333g纳米硫酸钡粉末(占聚丙烯/纳米硫酸钡复合材料的质量百分比为25％)，纳米硫酸钡粉末的平均粒径为70nm。加料完毕后继续搅拌2h，直至纳米硫酸钡粉末与聚丙烯充分混合均匀。随后将聚丙烯/纳米硫酸钡溶液缓慢倒入90mL无水乙醇凝固浴中，凝固浴的搅拌速率为30r/min。随后将聚丙烯/纳米硫酸钡复合材料经双螺杆挤出造粒得到复合生物补片原料，挤出机温度区间为150～200℃，螺杆转速为60r/min。原材料颗粒经单螺杆熔融纺丝得到复合纤维，纺丝温度为220℃。复合纤维经编织加工后得到厚度为0.6mm、孔隙为2mm的生物补片。
经测试，补片重量为84g/m 2，抗张强度为1065mmHg；经X射线检查，复合生物补片显影清晰。
实施例3：
向反应釜中加入100mL甲苯和10g聚丙烯(占聚丙烯/纳米硫酸钡复合材料的质量百分比为65％)进行搅拌溶解，反应釜搅拌速率为200r/min，同时将反应釜升温至100℃。待聚丙烯完全溶解后，向反应釜内加入5.3846g纳米硫酸钡粉末(占聚丙烯/纳米硫酸钡复合材料的质量百分比为35％)，纳米硫酸钡粉末的平均粒径为70nm。加料完毕后继续搅拌2h，直至纳米硫酸钡粉末与聚丙烯充分混合均匀。随后将聚丙烯/纳米硫酸钡溶液缓慢倒入100mL无水乙醇凝固浴中，凝固浴的搅拌速率为30r/min。随后将聚丙烯/纳米硫酸钡复 合材料经双螺杆挤出造粒得到复合生物补片原料，挤出机温度区间为150～200℃，螺杆转速为60r/min。原材料颗粒经单螺杆熔融纺丝得到复合纤维，纺丝温度为220℃。复合纤维经编织加工后得到厚度为0.6mm、孔隙为2mm的生物补片。
经测试，补片重量为86g/m 2，抗张强度为820mmHg；经X射线检查，复合生物补片显影清晰。
对比例1：
向反应釜中加入80mL甲苯和10g聚丙烯(占聚丙烯/纳米硫酸钡复合材料的质量百分比为90％)进行搅拌溶解，反应釜搅拌速率为200r/min，同时将反应釜升温至100℃。待聚丙烯完全溶解后，向反应釜内加入1.1111g纳米硫酸钡粉末(占聚丙烯/纳米硫酸钡复合材料的质量百分比为10％)，纳米硫酸钡粉末的平均粒径为70nm。加料完毕后继续搅拌2h，直至纳米硫酸钡粉末与聚丙烯充分混合均匀。随后将聚丙烯/纳米硫酸钡溶液缓慢倒入80mL无水乙醇凝固浴中，凝固浴的搅拌速率为30r/min。随后将聚丙烯/纳米硫酸钡复合材料经双螺杆挤出造粒得到复合生物补片原料，挤出机温度区间为150～200℃，螺杆转速为60r/min。原材料颗粒经单螺杆熔融纺丝得到复合纤维，纺丝温度为220℃。复合纤维经编织加工后得到厚度为0.6mm、孔隙为2mm的生物补片。
经测试，补片重量为81g/m 2，抗张强度为1340mmHg；经X射线检查，复合生物补片显影不清晰。
对比例2：
向反应釜中加入100mL甲苯和10g聚丙烯(占聚丙烯/纳米硫酸钡复合材料的质量百分比为60％)进行搅拌溶解，反应釜搅拌速率为200r/min，同时将反应釜升温至100℃。待聚丙烯完全溶解后，向反应釜内加入6.6666g纳米硫酸钡粉末(占聚丙烯/纳米硫酸钡复合材料的质量百分比为40％)，纳米硫酸钡粉末的平均粒径为70nm。加料完毕后继续搅拌2h，直至纳米硫酸钡粉末与聚丙烯充分混合均匀。随后将聚丙烯/纳米硫酸钡溶液缓慢倒入100mL无水乙醇凝固浴中，凝固浴的搅拌速率为30r/min。随后将聚丙烯/纳米硫酸钡复合材料经双螺杆挤出造粒得到复合生物补片原料，挤出机温度区间为150～200℃，螺杆转速为60r/min。原材料颗粒经单螺杆熔融纺丝得到复合纤维，纺丝温度为220℃。复合纤维经编织加工后得到厚度为0.6mm、孔隙为2mm的生物补片。
经测试，补片重量为90g/m 2，抗张强度为530mmHg；经X射线检查，复合生物补片显影清晰。
实施例1-3和对比例1-2中复合生物补片材料内硫酸钡含量、补片重量、厚度、孔隙、抗张强度和显影强度如表1所示。由实施例和对比例可知，当硫酸钡质量百分比低于15％时，材料的显影强度不清晰，而当硫酸质量百分比高于35％时，材料的力学性能明显下降。
表1
Figure PCTCN2020096114-appb-000001
本发明提供了一种复合生物补片及其原材料制备方法，可以经X射线检查判别生物补片是否发生扭曲，简化了疝气修补术后病变判别方法，提高判别效率，减轻患者痛苦，满足临床实际应用。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点，对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (10)

  1. 一种含硫酸钡能显影的复合生物补片，其特征在于，所述复合生物补片的组成按照质量百分比为：聚丙烯65～85％，纳米硫酸钡15～35％。
  2. 根据权利要求1所述的含硫酸钡能显影的复合生物补片，其特征在于，所述复合生物补片的厚度为0.6mm，所述复合生物补片的孔径为2mm。
  3. 根据权利要求1所述的含硫酸钡能显影的复合生物补片，其特征在于，所述聚丙烯为医用级等规聚丙烯，熔点为164～170℃，等规指数≥96％。
  4. 如权利要求1所述的含硫酸钡能显影的复合生物补片，其特征在于，所述纳米硫酸钡的粒径范围为30～70nm。
  5. 一种权利要求1至4中任一项所述含硫酸钡能显影的复合生物补片的制备方法，其特征在于，包括以下步骤：
    (1)将聚丙烯溶于有机溶剂得到聚丙烯溶液，向所述聚丙烯溶液中加入纳米硫酸钡搅拌至混合均匀，得到聚丙烯/纳米硫酸钡溶液；
    (2)将步骤(1)得到的聚丙烯/纳米硫酸钡溶液加入等体积的凝固浴中进行相转化固化，固化结束后取出洗涤、真空干燥，得到聚丙烯/纳米硫酸钡复合材料；
    (3)将所述聚丙烯/纳米硫酸钡复合材料经同向双螺杆挤出机挤出造粒，得到复合生物补片原料；
    (4)将所述复合生物补片原料经单螺杆挤出机挤出纺丝制得复合纤维，将所述复合纤维经编织加工制得含硫酸钡能显影的复合生物补片。
  6. 根据权利要求5所述的含硫酸钡能显影的复合生物补片的制备方法，其特征在于，步骤(1)中所述有机溶剂为甲苯、二甲苯和十氢化萘中的一种或几种。
  7. 根据权利要求5所述的含硫酸钡能显影的复合生物补片的制备方法，其特征在于，步骤(1)中将聚丙烯溶于有机溶剂的温度为100～120℃；所述聚丙烯溶液中聚丙烯的浓度为100～125g/L；所述搅拌时间为2～4h。
  8. 根据权利要求5所述的含硫酸钡能显影的复合生物补片的制备方法，其特征在于，步骤(2)中所述凝固浴包括无水乙醇或丙酮中的一种。
  9. 根据权利要求5所述的含硫酸钡能显影的复合生物补片的制备方法，其特征在于，步骤(3)中所述挤出温度150～200℃；螺杆转速60～120r/min。
  10. 根据权利要求5所述的含硫酸钡能显影的复合生物补片的制备方法，其特征在于，步骤(4)中所述挤出温度150～220℃。
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