High-reliability polypropylene packing material based on BFS technology and preparation process thereof
Through BFS technology, combined with PET, temperature-resistant composition and hyperbranched polyester modified carbon fiber, a high-efficiency molecular entanglement structure and a dense network are formed, solving the problems of poor impact strength and insufficient barrier properties of polypropylene packaging materials at low temperatures, and achieving high-reliability drug protection effect.
Patent Information
- Application Number
- CN202510576493.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-06
- Publication Date
- 2025-08-08
AI Technical Summary
The existing polypropylene packaging materials have poor impact strength and are brittle and hard at low temperatures, and have insufficient barrier properties to oxygen and water vapor, which affects the stability and safety of the drug.
Using BFS technology, hydrogenated styrene-butadiene-styrene block copolymer, polyether-polyester block copolymer and hyperbranched polyester modified carbon fibers are used to form an efficient molecular entanglement structure, enhancing the flexibility and impact resistance of the material, and forming a dense network structure through hyperbranched polyester modified carbon fibers to improve sealing and barrier properties.
It significantly improves the impact strength and low-temperature drop resistance of polypropylene packaging materials, improves the flexibility and compatibility of the material, ensures that the drug maintains good elasticity and sealing barrier properties under low temperature conditions, and improves the stability and safety of the drug.
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Abstract
Description
Technical Field
[0001] The present application relates to the field of polymer material technology, and in particular to a high-reliability polypropylene packaging material based on BFS technology and a preparation process thereof. Background Art
[0002] Pharmaceutical packaging materials, due to their direct contact with medications, can significantly impact their properties. In particular, large-volume infusion packaging materials, where medications are directly injected into the venous bloodstream, place extremely high demands on the cleanliness and safety of the infusion. A drawback of traditional glass infusion containers is that the glass reacts with the medication, creating debris that, once introduced into the body, can clog capillaries and cause edema and phlebitis.
[0003] Existing infusion packaging materials can be roughly divided into two categories: one is pure polypropylene, and the other is polypropylene modified with elastomers. Since pure polypropylene has high rigidity and poor flexibility, it cannot provide the self-shrinkage function for infusion bags. In addition, it has poor impact strength at low temperatures and becomes brittle and hard. When containing medicines that require low-temperature refrigeration, it is easy to develop slight cracks due to physical impact during low-temperature transportation, causing the medicine to leak out. In addition, polypropylene materials have relatively weak barrier properties to gases such as oxygen and water vapor. During long-term infusion or storage, they provide poor protection for therapeutic and nutritional infusions, resulting in reduced efficacy of the medicines and may even cause the medicines to become damp and oxidized, affecting the quality of the medicines. Therefore, with the continuous improvement of the requirements for medical technology and product safety performance, infusion bags, as an indispensable component of the medical system, must strictly ensure the good sterility and stability of infusion products, minimize the chance of cross-contamination, and ensure the safety of patients' medication. Summary of the Invention
[0004] To address the above issues, this application provides a high-reliability polypropylene packaging material and its preparation process based on BFS technology to produce a polypropylene packaging material with high impact strength, low-temperature drop resistance, sealing barrier and other good properties, so that it has good protection for treatment and nutritional infusion, high adaptability, and ensures the safety of patients' medication.
[0005] In the first aspect, the present application provides a high-reliability polypropylene packaging material based on BFS technology, adopting the following technical solution: a high-reliability polypropylene packaging material based on BFS technology, comprising the following components in parts by weight: 12-15 parts of PET, 15-25 parts of a heat-resistant composition, 30-50 parts of polypropylene, and 1-3 parts of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester modified carbon fiber.
[0006] By adopting the above technical solution, PET and polypropylene can increase the heat deformation temperature of the material, allowing it to maintain good shape stability even in higher temperature environments, expanding the material's operating temperature range and reducing the risk of cracking or breakage caused by physical impact. The butadiene flexible segments in the hydrogenated styrene-butadiene-styrene block copolymer and the polyether flexible segments in the polyether-polyester block copolymer have good molecular compatibility. The flexible segments form effective molecular entanglements, which significantly enhance the material's flexibility and deformation resistance. Simultaneously, the styrene rigid segments in the hydrogenated styrene-butadiene-styrene block copolymer and the polyester rigid segments in the polyether-polyester block copolymer form a stable framework structure that acts as physical crosslinks to restrict the movement of the flexible segments, thereby improving the material's heat resistance. The flexible segments absorb impact energy through their own deformation, while hindering the relative sliding and breakage of the polypropylene molecular chains, thereby improving the material's impact resistance. This combined rigidity and flexibility in the microstructure enables the material to maintain good impact strength even in low-temperature environments, effectively avoiding the problem of increased brittleness caused by temperature drops. The addition of hyperbranched polyester modified carbon fiber, due to its high specific surface area and rich functional group characteristics, can interact with the rigid segments in hydrogenated styrene-butadiene-styrene block copolymer and polyether-polyester block copolymer through hydrogen bonding and other interactions, thereby forming a dense network structure. Moreover, its network structure can form a strong interface bond with the polypropylene matrix, effectively filling the tiny pores inside the material, thereby greatly improving the sealing and barrier properties of the packaging material, further reducing the diffusion rate of gas molecules, making it difficult for oxygen and water vapor to penetrate, optimizing the overall performance of the material, and making it perform well in resistance to low-temperature drops, sealing and barrier, etc., providing long-term and reliable protection for infusion packaging materials.
[0007] In a specific embodiment, the mass ratio of the hydrogenated styrene-butadiene-styrene block copolymer, the polyether-polyester block copolymer and the hyperbranched polyester modified carbon fiber is (3-5):1:(2-3).
[0008] By adopting the above technical solutions, the hydrogenated styrene-butadiene-styrene block copolymer, polyether-polyester block copolymer and hyperbranched polyester modified carbon fiber within the scope of this application interact with each other, significantly improving the impact strength and low-temperature drop resistance of the polypropylene packaging material, improving the flexibility and compatibility of the material, so that the packaging material can still maintain good elasticity and sealing barrier properties under low temperature conditions. When the content of hydrogenated styrene-butadiene-styrene block copolymer is too low, the flexibility of the material will be insufficient, because the butadiene soft segment in the block copolymer cannot fully form an elastic network structure, thereby affecting the impact resistance of the material. Its content is too high, then the low-temperature drop resistance of the material may be caused to decline. In addition, when the content of hyperbranched polyester modified carbon fiber is too low, due to the insufficient carbon fiber reinforcement effect, the barrier properties and mechanical strength of the material as a whole will be affected, specifically manifested in the weakening of the blocking ability of small molecules such as oxygen and water vapor, making it difficult to meet the high sealing requirements of pharmaceutical packaging. The low content of polyether-polyester block copolymer may cause the material to crack during use, thereby affecting the safety and stability of the drug.
[0009] In a specific embodiment, the preparation method of the hyperbranched polyester modified carbon fiber comprises: (1) slowly adding DMF containing diisopropylcarbodiimide to a NMP solution of citric acid under a N2 atmosphere, stirring and reacting at 40-55°C for 8-12 hours, filtering, and distilling the filtrate under reduced pressure to obtain a hyperbranched polyester; (2) immersing the carbon fiber in an ethanol solution containing 10-15% of a silane coupling agent, stirring and treating at 60-70° C. for 45-60 minutes, separating, washing, and drying to obtain a modified carbon fiber; (3) The hyperbranched polyester obtained in step (1) and the modified carbon fiber obtained in step (2) are added to DMF, stirred evenly at 40-55° C. under a N2 atmosphere, and then diisopropylcarbodiimide and 4-pyrrolidinopyridine are added. The mixture is reacted for 8-12 h, and filtered and dried to obtain a hyperbranched polyester modified carbon fiber.
[0010] The mass ratio of the hyperbranched polyester to the modified carbon fiber is 1:(2-4).
[0011] By adopting the above technical solution, the hyperbranched structure of hyperbranched polyester and modified carbon fiber can effectively enhance the flexibility and cohesive energy of the material, thereby improving the impact resistance of the packaging material. Its rich surface activity improves the overall mechanical properties, barrier properties and low-temperature resistance of the heat-resistant composition, and forms an efficient stress transfer network with the polypropylene matrix, so that the packaging material can still maintain excellent mechanical properties and structural stability when subjected to external forces or low-temperature environments.
[0012] The hyperbranched polyester and modified carbon fiber ratios within this application significantly improve the material's toughness, further enhancing its mechanical strength and impact resistance. Within a specific mass ratio, the two effectively mitigate the brittleness and sealing properties of polypropylene packaging materials at low temperatures, ensuring they are less susceptible to cracking or breakage during transportation and use.
[0013] In a specific embodiment, the polypropylene is maleic anhydride grafted polypropylene.
[0014] The mass ratio of the PET to the polypropylene is 1:(1.5-2).
[0015] By adopting the above technical solution, after polypropylene is modified with maleic anhydride, its compatibility with PET and other components is significantly improved, and extensive hydrogen bonding is produced with a large number of polar groups in the highly branched structure of the packaging material, so that the maleic anhydride grafted polypropylene molecular chains can be entangled on the carbon fiber surface, thereby improving the interfacial bonding strength and impact strength of the packaging material.
[0016] A certain ratio of PET to polypropylene improves the strength and heat resistance of the overall material. If the polypropylene content is too low, the rigidity of the polypropylene packaging material will be insufficient, affecting the stability of the overall structure. Too low a PET content will reduce the heat resistance of the packaging material, making it prone to deformation in high-temperature environments, thereby affecting the sealing and barrier properties of the infusion packaging material, and increasing the risk of moisture and oxidation of the drug.
[0017] In the second aspect, the present application provides a preparation process for high-reliability polypropylene packaging materials based on BFS technology, which adopts the following technical solution: comprising the following steps: adding PET, a heat-resistant composition, polypropylene and an antioxidant into a mixer in sequence, mixing them evenly at a speed of 500-1000 rpm, and then extruding the mixed materials into granules through a twin-screw extruder underwater.
[0018] The granulation melting temperature is 220-240°C.
[0019] In summary, this application includes at least one of the following beneficial technical effects: 1. The heat deformation temperature of the material can be increased by combining PET and polypropylene, allowing it to maintain good shape stability even in higher temperature environments, expanding the material's operating temperature range and reducing the risk of cracks or breakage caused by physical impact. The heat-resistant composition is a combination of hydrogenated styrene-butadiene-styrene block copolymer, polyether-polyester block copolymer, and hyperbranched polyester-modified carbon fiber. The optimized ratio significantly improves the impact strength and low-temperature drop resistance of the polypropylene packaging material, while enhancing the overall toughness of the material, thereby effectively avoiding cracks caused by physical impact during low-temperature transportation. In addition, the sealing barrier properties of the packaging material are further improved, enhancing the protection of therapeutic and nutritional infusions, and ensuring the stability and safety of drugs during long-term storage or infusion.
[0020] 2. After being modified with maleic anhydride, polypropylene significantly improves its compatibility with PET and other components, and produces extensive hydrogen bonding with a large number of polar groups in the highly branched structure of the packaging material, allowing the maleic anhydride-grafted polypropylene molecular chains to entangle on the carbon fiber surface, thereby improving the interfacial bonding strength and impact strength of the packaging material. DETAILED DESCRIPTION
[0021] The carbon fiber model in this application is T700 purchased from Toray Industries, Japan; the silane coupling agent is KH560; the polypropylene is copolymer polypropylene: model R530 from Hyosung, South Korea; the antioxidant is antioxidant 1010; the hydrogenated styrene-butadiene-styrene block copolymer is brand G1657 from Kraton, USA; the polyether-polyester block copolymer model is D150-152 purchased from Keheng Polymer (Guangdong) Co., Ltd.; the maleic anhydride grafted polypropylene is model QB510 from Mitsui, Japan; the PET brand is BL8450 from SK, South Korea; other raw materials can be obtained commercially.
[0022] Preparation Example 1 The preparation method of hyperbranched polyester modified carbon fiber is as follows: (1) under N2 atmosphere, 15 ml of DMF containing 1.8 g of diisopropylcarbodiimide is slowly added dropwise to 20 ml of NMP solution containing 4.2 g of citric acid, stirred at 40 ° C for 12 h, filtered, and the filtrate is vacuum distilled to obtain hyperbranched polyester; (2) 10 g of carbon fiber was immersed in 100 ml of ethanol solution containing 15% silane coupling agent, stirred at 60° C. for 60 min, separated, washed, and dried to obtain modified carbon fiber; (3) 4 g of the hyperbranched polyester obtained in step (1) and 10 g of the modified carbon fiber obtained in step (2) were added to 30 ml of DMF, stirred evenly at 40 ° C under N2 atmosphere, and then 5 g of diisopropylcarbodiimide and 0.3 g of 4-pyrrolidinopyridine were added. The mixture was reacted for 8 h, filtered, and dried at 60 ° C to obtain hyperbranched polyester modified carbon fiber.
[0023] Preparation Example 2 The preparation method of hyperbranched polyester modified carbon fiber is as follows: (1) under N2 atmosphere, 15 ml of DMF containing 1.8 g of diisopropylcarbodiimide is slowly added dropwise to 20 ml of NMP solution containing 4.2 g of citric acid, stirred at 40 ° C for 12 h, filtered, and the filtrate is vacuum distilled to obtain hyperbranched polyester; (2) 10 g of carbon fiber was immersed in 100 ml of ethanol solution containing 15% silane coupling agent, stirred at 60° C. for 60 min, separated, washed, and dried to obtain modified carbon fiber; (3) 4 g of the hyperbranched polyester obtained in step (1) and 20 g of the modified carbon fiber obtained in step (2) were added to 30 ml of DMF, stirred evenly at 40 ° C under N2 atmosphere, and then 5 g of diisopropylcarbodiimide and 0.3 g of 4-pyrrolidinopyridine were added. The mixture was reacted for 8 h, filtered, and dried at 60 ° C to obtain hyperbranched polyester modified carbon fiber.
[0024] Preparation Example 3 The preparation method of the modified carbon fiber is as follows: 10g of carbon fiber is immersed in 100ml of ethanol solution containing 10-15% of a silane coupling agent, stirred at 60°C for 60min, separated, washed, and dried to obtain the modified carbon fiber.
[0025] Preparation Example 4 The preparation method of hyperbranched polyester modified carbon fiber is as follows: (1) under N2 atmosphere, 15 ml of DMF containing 1.8 g of diisopropylcarbodiimide is slowly added dropwise to 20 ml of NMP solution containing 4.2 g of citric acid, stirred at 40 ° C for 12 h, filtered, and the filtrate is vacuum distilled to obtain hyperbranched polyester; (2) 10 g of carbon fiber was treated with 100 ml of nitric acid / sulfuric acid mixture (volume ratio 1:3) at 60 °C for 30 min and dried to obtain modified carbon fiber; (3) 4 g of the hyperbranched polyester obtained in step (1) and 10 g of the modified carbon fiber obtained in step (2) were added to 30 ml of DMF, stirred uniformly at 40° C. under a nitrogen atmosphere, and then 5 g of diisopropylcarbodiimide and 0.3 g of 4-pyrrolidinopyridine were added. The mixture was reacted for 8 h and filtered. The mixture was dried at 60° C. to obtain a hyperbranched polyester-modified carbon fiber.
[0026] Example 1 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1 in a mass ratio of 4:1:2.
[0027] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0028] Example 2 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 15 g of PET, 15 g of a heat-resistant composition, 45 g of polypropylene, and 3 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1 in a mass ratio of 4:1:2.
[0029] PET, heat-resistant composition, polypropylene and antioxidant were added to the mixer in sequence and mixed evenly at a speed of 1000 rpm. The mixed materials were then extruded and granulated underwater through a twin-screw extruder at a granulation melting temperature of 220°C.
[0030] Example 3 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1 in a mass ratio of 5:1:3.
[0031] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0032] Example 4 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1 in a mass ratio of 2:1:2.
[0033] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0034] Example 5 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1 in a mass ratio of 4:2:1.
[0035] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0036] Example 6 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of maleic anhydride-grafted polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1 in a mass ratio of 4:1:2.
[0037] PET, heat-resistant composition, maleic anhydride grafted polypropylene and antioxidant were added to the mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0038] Example 7 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 15 g of PET, 23 g of a heat-resistant composition, 30 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1 in a mass ratio of 4:1:2.
[0039] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0040] Example 8 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 2 in a mass ratio of 4:1:2.
[0041] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0042] Example 9 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 4 in a mass ratio of 4:1:2.
[0043] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0044] Comparative Example 1 The high-reliability polypropylene packaging material based on BFS technology includes the following components by weight: 12g PET, 21g heat-resistant composition, 35g polypropylene, and 1g antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer and a polyether-polyester block copolymer in a mass ratio of 4:3.
[0045] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0046] Comparative Example 2 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a polyether-polyester block copolymer in a mass ratio of 5:2 and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1.
[0047] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0048] Comparative Example 3 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer in a mass ratio of 5:2 and a hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1.
[0049] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0050] Comparative Example 4 A high-reliability polypropylene packaging material based on BFS technology includes the following components by weight: 12g PET, 21g heat-resistant composition, 35g polypropylene, and 1g antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer.
[0051] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0052] Comparative Example 5 A high-reliability polypropylene packaging material based on BFS technology includes the following components by weight: 12g of PET, 21g of a heat-resistant composition, 35g of polypropylene, and 1g of an antioxidant; the heat-resistant composition is a polyether-polyester block copolymer.
[0053] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0054] Comparative Example 6 A high-reliability polypropylene packaging material based on BFS technology includes the following components by weight: 12g PET, 21g heat-resistant composition, 35g polypropylene, and 1g antioxidant; the heat-resistant composition is the hyperbranched polyester-modified carbon fiber prepared in Preparation Example 1.
[0055] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0056] Comparative Example 7 A high-reliability polypropylene packaging material based on BFS technology includes the following components in parts by weight: 12 g of PET, 21 g of a heat-resistant composition, 35 g of polypropylene, and 1 g of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and the modified carbon fiber prepared in Preparation Example 3 in a mass ratio of 4:1:2.
[0057] PET, heat-resistant composition, polypropylene and antioxidant were added into a mixer in sequence and mixed evenly at a speed of 800 rpm. The mixed materials were then extruded into granules through a twin-screw extruder underwater, and the granulation melting temperature was 230°C.
[0058] Performance testing The high-reliability polypropylene packaging materials produced in the Examples and Comparative Examples using BFS technology were used in the production of polypropylene soft bottles using the blow-fill-seal process. The performance test technical indicators were measured using the following methods: a. Refer to the "National Standard Gas Permeation Measurement Method for Pharmaceutical Packaging Materials" (YBB00082003) to test the oxygen and nitrogen permeation rates [cm 3 / (m 2 ·24h·0.1MPa)].
[0059] b. Impact strength (KJ / m 2 ): Reference standard ISO 180-2000; c. Tensile strength (MPa): Reference standard GB / T1040.2-2006; d. Brittle temperature (°C): Refer to the standard GB / T5470-2008; e. Drop resistance: Refer to the YBB00022002-2015 standard and test the cracking and leakage when dropped from a height of 1m. The product is qualified if there is no cracking or leakage. The results are shown in Table 1.
[0060] As shown in Table 1, the high-reliability polypropylene packaging material based on BFS technology obtained in the above embodiment has higher impact strength, low-temperature drop resistance, sealing and barrier properties than the comparative example. The qualified rate of polypropylene soft bottles produced by the blow-fill-seal (BFS) process is higher, making it more protective and adaptable for therapeutic and nutritional infusion, thereby ensuring the safety of patients' medication.
[0061] Comparison of Examples 1-5 and Comparative Examples 1-6 shows that the high-reliability polypropylene packaging material based on BFS technology prepared in Example 1 has better comprehensive performance indicators such as oxygen and nitrogen sealing barrier properties, impact strength, tensile strength, brittle temperature, and drop resistance than the comparative example. Analysis shows that the heat-resistant composition is a combination of hydrogenated styrene-butadiene-styrene block copolymer, polyether-polyester block copolymer, and hyperbranched polyester modified carbon fiber. The optimized ratio significantly improves the impact strength and low-temperature drop resistance of the polypropylene packaging material, while enhancing the overall toughness of the material, further improving the sealing barrier properties of the packaging material, and enhancing the protection of therapeutic and nutritional infusions, ensuring the stability and safety of drugs during long-term storage or infusion. When the content of hyperbranched polyester modified carbon fiber is too low, the overall barrier properties and mechanical strength of the material will be affected due to insufficient carbon fiber reinforcement. Specifically, the barrier ability to small molecules such as oxygen and water vapor is weakened, making it difficult to meet the high sealing requirements of drug packaging. Too low a content of polyether-polyester block copolymer may cause the material to crack during use, thereby affecting the safety and stability of the drug.
[0062] By comparing Example 1 and Example 6, it can be seen that after propylene is modified with maleic anhydride, extensive hydrogen bonding occurs with a large number of polar groups in the highly branched structure of the packaging material, allowing the maleic anhydride-grafted polypropylene molecular chains to entangle on the carbon fiber surface, thereby improving the interfacial bonding strength and impact strength of the packaging material.
[0063] By comparing Example 1 and Example 7, it can be seen that a certain ratio of PET to polypropylene improves the strength and heat resistance of the overall material. If the polypropylene content is too low, the rigidity of the polypropylene packaging material will be insufficient, affecting the stability of the overall structure. If the PET content is too low, the heat resistance of the packaging material will decrease, deformation will occur easily, and the low-temperature drop resistance will be poor, thereby affecting the sealing and barrier properties of the infusion packaging material, thereby increasing the risk of moisture and oxidation of the drug.
[0064] By comparing Example 1 with Examples 8-9 and Comparative Example 7, it can be seen that the comprehensive performance indicators of the high-reliability polypropylene packaging material based on BFS technology prepared in Example 1, such as oxygen and nitrogen sealing barrier, impact strength, tensile strength, brittle temperature and drop resistance, are better than those in Comparative Example 7. Analysis shows that this may be because the epoxy groups in the silane coupling agent molecules are retained on the surface of the carbon fiber. The epoxy groups have high reactivity, which hinders the gas from passing through the pores and the diffusion channels of the gas, thereby achieving efficient barrier. Compared with Comparative Example 7, the surface roughness of the modified carbon fiber is higher, so that the gas molecules have more diffusion paths on its surface, and there are a large number of pores and gaps. The gas molecules penetrate through these channels, and the barrier effect is limited.
[0065] The above are all preferred embodiments of the present application, and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application should be included in the scope of protection of the present application.
Claims
1. High reliability polypropylene packaging material based on BFS technology, characterized by: The invention comprises the following components in parts by weight: 12-15 parts of PET, 15-25 parts of a heat-resistant composition, 30-50 parts of polypropylene, and 1-3 parts of an antioxidant; the heat-resistant composition is a hydrogenated styrene-butadiene-styrene block copolymer, a polyether-polyester block copolymer, and a hyperbranched polyester-modified carbon fiber.
2. The high-reliability polypropylene packaging material based on BFS technology according to claim 1, characterized in that: The mass ratio of the hydrogenated styrene-butadiene-styrene block copolymer, the polyether-polyester block copolymer and the hyperbranched polyester modified carbon fiber is (3-5):1:(2-3).
3. The high-reliability polypropylene packaging material based on BFS technology according to claim 1, characterized in that: The preparation method of the hyperbranched polyester modified carbon fiber comprises: (1) slowly dropping DMF containing diisopropylcarbodiimide into a NMP solution of citric acid under a nitrogen atmosphere, stirring and reacting at 40-55° C. for 8-12 hours, filtering, and distilling the filtrate under reduced pressure to obtain a hyperbranched polyester; (2) Immersing the carbon fiber in an ethanol solution containing 10-15% of a silane coupling agent, stirring at 60-70°C for 45-60 minutes, separating, washing, and drying to obtain the modified carbon fiber; (3) The hyperbranched polyester obtained in step (1) and the modified carbon fiber obtained in step (2) are added to DMF, stirred evenly at 40-55°C under N2 atmosphere, and then diisopropylcarbodiimide and 4-pyrrolidinopyridine are added. The mixture is reacted for 8-12 hours, filtered and dried to obtain hyperbranched polyester modified carbon fiber.
4. The high-reliability polypropylene packaging material based on BFS technology according to claim 3, characterized in that: The mass ratio of the hyperbranched polyester to the modified carbon fiber is 1:(2-4).
5. The high-reliability polypropylene packaging material based on BFS technology according to claim 1, characterized in that: The polypropylene is maleic anhydride grafted polypropylene.
6. The high-reliability polypropylene packaging material based on BFS technology according to claim 1, characterized in that: The mass ratio of the PET to the polypropylene is 1:(1.5-2).
7. The process for preparing a high-reliability polypropylene packaging material based on BFS technology according to claims 1-6, characterized in that: The following steps are involved: PET, heat-resistant composition, polypropylene and antioxidant are added into a mixer in sequence, mixed evenly at a speed of 500-1000 rpm, and then the mixed materials are extruded and granulated underwater through a twin-screw extruder.
8. The process for preparing a high-reliability polypropylene packaging material based on BFS technology according to claim 7, characterized in that: The granulation melting temperature is 220-240°C.