WO2023093737A1 - 可生物降解注射器专用料及采用其制备注射器的方法 - Google Patents

可生物降解注射器专用料及采用其制备注射器的方法 Download PDF

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WO2023093737A1
WO2023093737A1 PCT/CN2022/133592 CN2022133592W WO2023093737A1 WO 2023093737 A1 WO2023093737 A1 WO 2023093737A1 CN 2022133592 W CN2022133592 W CN 2022133592W WO 2023093737 A1 WO2023093737 A1 WO 2023093737A1
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syringe
biodegradable
special material
injection molding
syringes
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PCT/CN2022/133592
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English (en)
French (fr)
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付宇经
张义玲
巩向志
金新杰
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山东兰德英科新材料科技有限公司
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61MDEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
    • A61M5/00Devices for bringing media into the body in a subcutaneous, intra-vascular or intramuscular way; Accessories therefor, e.g. filling or cleaning devices, arm-rests
    • A61M5/178Syringes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17Component parts, details or accessories; Auxiliary operations
    • B29C45/72Heating or cooling
    • B29C45/73Heating or cooling of the mould
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00Layered products having a non-planar shape
    • B32B1/08Tubular products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/29Compounds containing one or more carbon-to-nitrogen double bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/02Applications for biomedical use
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the invention belongs to the technical field of biodegradable materials, and in particular relates to a special material for biodegradable syringes and a method for preparing syringes using the same.
  • the disposable syringe is composed of a jacket, a core rod, a rubber stopper, an awl, a pusher, and an awl.
  • the scope of application of the product is matched with the disposable injection needle for subcutaneous, intramuscular, intravenous injection of liquid medicine, blood drawing or dissolving medicine.
  • the purpose of the present invention is to provide a special material for biodegradable syringes.
  • the syringe prepared by using the special material has high strength, good transparency, can be completely biodegradable, and meets the requirements of disposable syringes;
  • the invention also provides a method for preparing syringes, which is scientific, reasonable, simple and applicable to industrial production.
  • biodegradable syringes of the present invention can be used for parts other than rubber stoppers of disposable syringes.
  • the biodegradable syringe special material according to the present invention is made of the following raw materials in parts by weight:
  • the anti-hydrolysis aid is polycarbodiimide with a molecular weight of 50,000-300,000.
  • the particle size of the fumed silica is above 2000 mesh.
  • the slippery agent is erucamide.
  • the crosslinking agent is an epoxy resin with multiple epoxy groups, and the number of epoxy groups is 5-8. It can be the ADR4370 of BSF in Germany.
  • the method for preparing a syringe using the biodegradable syringe special material comprises the following steps:
  • masterbatch Preparation of masterbatch: mix 10-20 parts of PBS, antioxidant 1010, anti-hydrolysis aid, light stabilizer 944, fumed silica, smoothing agent and crosslinking agent in a mixer, and then The masterbatch is formed by melting, plasticizing and granulating in the twin-screw extruder, and the production temperature is 130-180°C;
  • step 2) Preparation of special material: mix the masterbatch prepared in step 1) with the remaining PBS evenly, then melt, plasticize and granulate in a twin-screw extruder to form special material, and the production temperature is 130-180°C;
  • the injection molding machine is used for injection molding at 180°C, the temperature of the injection molding machine is 150-160-170-180-170-170°C, and the mold temperature is 60°C.
  • the syringe prepared by the present invention is completely biodegradable, which is in line with the general trend.
  • the syringe material of the present invention cannot be recycled, prevents secondary utilization, prevents the spread of medical waste, and essentially solves the abuse and pollution of medical waste. After use, it cannot be recycled. It contains water during the injection process, and it will decompose after contact with water, so it cannot be reused.
  • the syringe prepared by using the special material of the present invention has high strength and good transparency.
  • the preparation method of the present invention is scientific and reasonable, simple and easy to implement, and is suitable for industrial production.
  • Fig. 1 is the infrared spectrogram of the syringe prepared in Example 1 of the present invention.
  • the PBS is a commercially available product from Xinjiang Lanshan Tunhe Technology Co., Ltd.
  • the polycarbodiimide uses anti-hydrolysis agent s-9000.
  • Described fumed silica adopts Degussa fumed silica.
  • the cross-linking agent is ADR4370 from BSF in Germany.
  • the biodegradable syringe special material is made of the following raw materials in parts by weight:
  • masterbatch Mix 15 parts of PBS, antioxidant 1010, polycarbodiimide, light stabilizer 944, fumed silica, erucamide and cross-linking agent in a mixer, and then The masterbatch is formed by melting, plasticizing and granulating in the screw extruder, and the production temperature is 130, 130, 140, 150, 150, 150, 160, 170, 180, 180, 170, 160°C.
  • Step 2) Preparation of special material: Mix the masterbatch prepared in step 1) with the remaining PBS evenly, then melt, plasticize and granulate in a twin-screw extruder to form special material, the production temperature is 130, 130, 140, 150, 150, 150, 160, 170, 180, 180, 170, 160°C.
  • the injection molding machine is used for injection molding at 180°C, the temperature of the injection molding machine is 150-160-170-180-170-170°C, and the mold temperature is 60°C.
  • the biodegradable syringe special material is made of the following raw materials in parts by weight:
  • masterbatch Mix 10 parts of PBS, antioxidant 1010, polycarbodiimide, light stabilizer 944, fumed silica, erucamide and cross-linking agent in a mixer, and then The masterbatch is formed by melting, plasticizing and granulating in the screw extruder, and the production temperature is 130, 130, 140, 140, 150, 150, 160, 170, 180, 180, 170, 160°C.
  • step 2) Preparation of special material: Mix the masterbatch prepared in step 1) with the remaining PBS evenly, then melt, plasticize and granulate in a twin-screw extruder to form special material, the production temperature is 130, 130, 140, 140, 150, 150, 160, 170, 180, 180, 170, 160°C.
  • the injection molding machine is used for injection molding at 180°C, the temperature of the injection molding machine is 150-160-170-180-170-170°C, and the mold temperature is 60°C.
  • the biodegradable syringe special material is made of the following raw materials in parts by weight:
  • masterbatch Mix 20 parts of PBS, antioxidant 1010, polycarbodiimide, light stabilizer 944, fumed silica, erucamide and cross-linking agent in a mixer, and then The master batch is formed by melting, plasticizing and granulating in the screw extruder, and the production temperature is 130, 130, 140, 140, 150, 160, 160, 170, 180, 180, 170, 160°C.
  • step 2) Preparation of special material: Mix the masterbatch prepared in step 1) with the remaining PBS evenly, then melt, plasticize and granulate in a twin-screw extruder to form special material, the production temperature is 130, 130, 140, 140, 150, 160, 160, 170, 180, 180, 170, 160°C.
  • the injection molding machine is used for injection molding at 180°C, the temperature of the injection molding machine is 150-160-170-180-170-170°C, and the mold temperature is 60°C.
  • Example 3 93.3 33.1 Comparative example 1 0 23.0
  • the tensile strength adopts GB/T 1040-2018.
  • the relative biodegradation rate adopts GB/T 20197-2006.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Anesthesiology (AREA)
  • Vascular Medicine (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Hematology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Infusion, Injection, And Reservoir Apparatuses (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

本发明属于生物降解材料技术领域,具体涉及一种可生物降解注射器专用料及采用其制备注射器的方法。所述的可生物降解注射器专用料,由PBS、抗氧剂1010、防水解助剂、光稳定剂944、气相二氧化硅、爽滑剂和交联剂制成;制备方法为:1)母料的制备;2)专用料的制备;3)注射器的生产:采用注塑机注塑成型,注塑机温度:150-160-170-180-170-170℃,模具温度60℃。采用本发明专用料制备的注射器强度高,透明度好,可完全生物降解,满足一次性使用注射器的要求;其制备方法,科学合理、简单易行,适合工业化生产。

Description

可生物降解注射器专用料及采用其制备注射器的方法 技术领域
本发明属于生物降解材料技术领域,具体涉及一种可生物降解注射器专用料及采用其制备注射器的方法。
背景技术
一次性使用注射器由外套、芯杆、胶塞、锥头、按手及锥头等组成。产品适用范围与一次性使用注射针配套用于皮下、肌肉、静脉注射药液、抽血或溶药。
目前,一次性使用注射器大多使用聚丙烯材料制成,具有优越的刚性与抗冲击性平衡最低扭曲性,良好的低温耐冲击性。但是,该材料不能降解,只能作为医疗垃圾进行处理,严重污染环境。此外,有可能会导致二次使用(滥用),存在一定的安全隐患,乙肝、艾滋病等疾病传播很大部分是由注射器的交叉滥用引起的。
发明内容
针对现有技术的不足,本发明的目的是提供一种可生物降解注射器专用料,采用该专用料制备的注射器,强度高,透明度好,可完全生物降解,满足一次性使用注射器的要求;本发明还提供采用其制备注射器的方法,科学合理、简单易行,适合工业化生产。
本发明所述的可生物降解注射器专用料可用于一次性使用注射器胶塞以外的部分。
本发明所述的可生物降解注射器专用料,由如下重量份数的原料制成:
Figure PCTCN2022133592-appb-000001
其中:
所述的防水解助剂为聚碳化二亚胺,其分子量为5万-30万。
所述的气相二氧化硅的粒度在2000目以上。
所述的爽滑剂为芥酸酰胺。
所述的交联剂为多环氧基团的环氧树脂,环氧基团数量为5-8。可以是德国BSF的ADR4370。
采用所述的可生物降解注射器专用料制备注射器的方法,包括以下步骤:
1)母料的制备:将10-20份的PBS、抗氧剂1010、防水解助剂、光稳定剂944、气相二氧化硅、爽滑剂和交联剂在搅拌机中混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成母料,生产温度为130-180℃;
2)专用料的制备:将步骤1)制备的母料与剩余的PBS混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成专用料,生产温度130-180℃;
3)注射器的生产:
采用注塑机180℃下注塑成型,注塑机温度:150-160-170-180-170-170℃,模具温度60℃。
与现有技术相比,本发明的有益效果如下:
1、本发明制备的注射器可完全生物降解,符合大趋势。
2、本发明的注射器材料不能回收使用,杜绝二次利用,防止医疗垃圾的扩散,本质上解决医疗垃圾滥用、污染。用完后,不能回收。注射过程中含水,接触水后即发生分解,不能二次利用。
3、采用本发明专用料制备的注射器强度高,透明度好。
4、本发明所述的制备方法,科学合理、简单易行,适合工业化生产。
附图说明
图1是本发明实施例1制备的注射器的红外光谱图。
具体实施方式
下面结合实施例对本发明做进一步说明,但本发明的保护范围不仅限于此。
实施例中用到的所有原料除特殊说明外,均为市购。
实施例中采用原料:
所述的PBS采用新疆蓝山屯河科技股份有限公司市售产品。
所述的聚碳化二亚胺采用抗水解剂s-9000。
所述的气相二氧化硅采用德固赛气相法二氧化硅。
所述的交联剂为德国BSF的ADR4370。
实施例1
所述的可生物降解注射器专用料,由如下重量份数的原料制成:
Figure PCTCN2022133592-appb-000002
其制备方法,具体步骤如下:
1)母料的制备:将15份的PBS、抗氧剂1010、聚碳化二亚胺、光稳定剂944、气相二氧化硅、芥酸酰胺和交联剂在搅拌机中混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成母料,生产温度为130、130、140、150、150、150、160、170、180、180、170、160℃。
2)专用料的制备:将步骤1)制备的母料与剩余的PBS混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成专用料,生产温度130、130、140、150、150、150、160、170、180、180、170、160℃。
3)注射器的生产:
采用注塑机180℃下注塑成型,注塑机温度:150-160-170-180-170-170℃,模具温度60℃。
实施例2
所述的可生物降解注射器专用料,由如下重量份数的原料制成:
Figure PCTCN2022133592-appb-000003
其制备方法,具体步骤如下:
1)母料的制备:将10份的PBS、抗氧剂1010、聚碳化二亚胺、光稳定剂944、气相二氧化硅、芥酸酰胺和交联剂在搅拌机中混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成母料,生产温度为130、130、140、140、150、150、160、170、180、180、170、160℃。
2)专用料的制备:将步骤1)制备的母料与剩余的PBS混合均匀,然后在双螺杆挤出机 中熔融、塑化造粒形成专用料,生产温度130、130、140、140、150、150、160、170、180、180、170、160℃。
3)注射器的生产:
采用注塑机180℃下注塑成型,注塑机温度:150-160-170-180-170-170℃,模具温度60℃。
实施例3
所述的可生物降解注射器专用料,由如下重量份数的原料制成:
Figure PCTCN2022133592-appb-000004
其制备方法,具体步骤如下:
1)母料的制备:将20份的PBS、抗氧剂1010、聚碳化二亚胺、光稳定剂944、气相二氧化硅、芥酸酰胺和交联剂在搅拌机中混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成母料,生产温度为130、130、140、140、150、160、160、170、180、180、170、160℃。
2)专用料的制备:将步骤1)制备的母料与剩余的PBS混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成专用料,生产温度130、130、140、140、150、160、160、170、180、180、170、160℃。
3)注射器的生产:
采用注塑机180℃下注塑成型,注塑机温度:150-160-170-180-170-170℃,模具温度60℃。
对比例1
市售聚丙烯注射器。
对实施例1-3与对比例1制备的注射器专用料进行性能测试,测试结果见表1。
表1测试结果
  相对生物分解率/% 拉伸强度/MPa
实施例1 94.6 31.3
实施例2 95.9 30.6
实施例3 93.3 33.1
对比例1 0 23.0
上表中涉及的检测,检测标准如下:
拉伸强度采用GB/T 1040-2018。
相对生物分解率采用GB/T 20197-2006。

Claims (6)

  1. 一种可生物降解注射器专用料,其特征在于:由如下重量份数的原料制成:
    Figure PCTCN2022133592-appb-100001
  2. 根据权利要求1所述的可生物降解注射器专用料,其特征在于:防水解助剂为聚碳化二亚胺,其分子量为5万-30万。
  3. 根据权利要求1所述的可生物降解注射器专用料,其特征在于:气相二氧化硅的粒度在2000目以上。
  4. 根据权利要求1所述的可生物降解注射器专用料,其特征在于:爽滑剂为芥酸酰胺。
  5. 根据权利要求1所述的可生物降解注射器专用料,其特征在于:交联剂为多环氧基团的环氧树脂,环氧基团数量为5-8。
  6. 一种采用权利要求1-5任一所述的可生物降解注射器专用料制备注射器的方法,其特征在于:包括以下步骤:
    1)母料的制备:将10-20份的PBS、抗氧剂1010、防水解助剂、光稳定剂944、气相二氧化硅、爽滑剂和交联剂在搅拌机中混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成母料,生产温度为130-180℃;
    2)专用料的制备:将步骤1)制备的母料与剩余的PBS混合均匀,然后在双螺杆挤出机中熔融、塑化造粒形成专用料,生产温度130-180℃;
    3)注射器的生产:
    采用注塑机180℃下注塑成型,注塑机温度:150-160-170-180-170-170℃,模具温度60℃。
PCT/CN2022/133592 2021-11-25 2022-11-23 可生物降解注射器专用料及采用其制备注射器的方法 WO2023093737A1 (zh)

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