Easily processable high toughness cyclic olefin polymer material, method of preparation and cyclic olefin polymer pharmaceutical packaging bottle

Abstract

This application relates to the field of pharmaceutical packaging technology, specifically disclosing an easily processable, high-toughness cyclic olefin polymer material, its preparation method, and a cyclic olefin polymer pharmaceutical packaging bottle. The easily processable, high-toughness cyclic olefin polymer material comprises the following raw materials: a cyclic olefin polymer, a maleic anhydride-grafted polyolefin elastomer, an organic nano-silicate, an antioxidant, and a lubricant. Pharmaceutical packaging bottles made from the cyclic olefin polymer material obtained in this application have a light transmittance ≥92%, high oxygen and carbon dioxide barrier properties, can withstand autoclaving, can package drugs with a pH greater than 9, exhibit strong acid and alkali resistance, and have a water vapor permeability of only 0.03 g·m³. 2 / 24h, and the highest impact strength and elongation at break of the simply supported beam were 38.6kJ / m 2 With a strength of 26%, it has high toughness and is more suitable for packaging high-end pharmaceuticals such as lymphocyte antigens, hormone drugs, anesthetic drugs, protein-based biopharmaceuticals, and vaccines.

Description

Technical Field

[0001] This application relates to the field of pharmaceutical packaging, and more specifically, it relates to an easily processable, high-toughness cyclic olefin polymer material, a preparation method thereof, and a cyclic olefin polymer pharmaceutical packaging bottle. Background Technology

[0002] In the rapid development of the pharmaceutical industry, drug packaging, as a key link in ensuring drug quality, stability and medication safety, has increasingly higher performance requirements with the emergence of new high-end drugs such as biologics, gene drugs and cell drugs.

[0003] Currently, the mainstream pharmaceutical packaging materials mainly include glass, polyethylene, polypropylene, and polyethylene terephthalate. However, all of these materials have certain limitations in practical use. For example, glass is prone to breakage during ultra-low temperature storage or transportation, and its acid and alkali resistance is poor. When the pH value of the drug is greater than 9, inorganic substances may leach from the glass packaging, potentially causing tablet detachment. The detached glass fragments can then enter the liquid medication, affecting the safety of intravenous and intramuscular injection products. Polyethylene materials have low oxygen barrier properties, low carbon dioxide barrier properties, and low transparency, allowing external oxygen to easily penetrate the packaging, potentially leading to issues with products such as vitamins and antibiotics. Drugs such as steroids and biological agents that are sensitive to oxygen undergo oxidative degradation, destroying the active ingredients, reducing efficacy, and even producing harmful substances. Poor carbon dioxide barrier properties can lead to gas leakage from carbon dioxide-containing drug solutions, damaging the original properties and efficacy of the drug solution. Low transparency makes it difficult to observe whether the drug solution has abnormal states such as turbidity or precipitation, making it difficult to detect drug deterioration in advance. Furthermore, polyethylene is not suitable for high-temperature steam sterilization, making it difficult to ensure sterility through this efficient sterilization method. Polypropylene and polyethylene terephthalate also have low oxygen and carbon dioxide barrier properties, and polyethylene terephthalate is also not suitable for high-temperature steam sterilization.

[0004] Therefore, developing a pharmaceutical packaging material that can overcome the shortcomings of existing materials such as glass, polyethylene, polypropylene, and polyethylene terephthalate when used as pharmaceutical packaging is of great significance for promoting high-end pharmaceutical packaging materials, ensuring the safety of drug storage and transportation, and promoting the development of high-end pharmaceutical industries such as biopharmaceuticals. This has become a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In order to obtain a pharmaceutical packaging material that can overcome the defects of existing materials such as glass, polyethylene, polypropylene and polyethylene terephthalate, this application provides an easy-to-process, high-toughness cyclic olefin polymer material, a preparation method and a cyclic olefin polymer pharmaceutical packaging bottle.

[0006] In a first aspect, this application provides an easily processable, high-toughness cyclic olefin polymer material, which adopts the following technical solution: An easily processable, high-toughness cyclic olefin polymer material comprises the following raw materials in parts by weight: 80-90 parts of cyclic olefin polymer, 5-10 parts of maleic anhydride-grafted polyolefin elastomer, 1-3 parts of organic nano-silicate, 0.3-0.5 parts of antioxidant, and 0.2-0.5 parts of lubricant.

[0007] Among them, the organic nano-silicate is attapulgite; the antioxidant is any one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-p-cresol, bis(2,2,6,6-tetramethylpiperidinyl) sebacate, tris(2,4-di-tert-butylphenyl) phosphite, and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; and the lubricant is any one of vinyl bis-stearamide, erucamide, calcium stearate, and polydimethylsiloxane.

[0008] By adopting the above technical solution, cyclic olefin polymers possess high oxygen barrier properties, high carbon dioxide barrier properties, and high transparency, enabling visual detection of drug clarity, foreign matter, and precipitation. This effectively prevents drug oxidative degradation and gas leakage from carbon dioxide-containing drug solutions. Furthermore, they exhibit excellent chemical stability, showing no interaction with protein-based or peptide-based biologics. Cyclic olefin polymers do not precipitate inorganic substances and are free of heavy metals, residual monomers, and harmful additives, thus avoiding adsorption of active proteins in biologics and ensuring drug potency. They are particularly suitable for high-value biologics such as monoclonal antibodies, insulin, and vaccines. They can withstand 121°C autoclaving and have strong acid-base resistance, allowing packaging of drugs with a pH greater than 9. This approach comprehensively overcomes the shortcomings of materials such as glass, polyethylene, polypropylene, and polyethylene terephthalate, making them more suitable for packaging high-end pharmaceuticals such as lymphocyte antigens, hormones, anesthetics, protein-based biopharmaceuticals, and vaccines.

[0009] However, packaging bottles made from cyclic olefin polymers generally have low toughness. Simply adding maleic anhydride-grafted polyolefin elastomer improves the toughness of the cyclic olefin polymer material but reduces its rigidity, leading to softening of the bottle opening and poor sealing. Adding organic nano-silicates in conjunction with maleic anhydride-grafted polyolefin elastomers can synergistically improve the toughness of the cyclic olefin polymer. The maleic anhydride-grafted polyolefin elastomer, as the soft phase of the elastomer, is dispersed within the cyclic olefin polymer. When the cyclic olefin polymer material is impacted, the elastomer particles undergo plastic deformation and elastic rebound, absorbing the impact energy. However, microcracks can occur at the interface between the maleic anhydride-grafted polyolefin elastomer and the cyclic olefin polymer. The organic nano-silicates, dispersed in a two-dimensional sheet-like structure within the cyclic olefin polymer, significantly increase the crack propagation path and energy consumption when these microcracks extend to the sheet-like locations, thus terminating crack propagation and improving the toughness of the cyclic olefin polymer material.

[0010] Antioxidants inhibit the oxidative degradation of cyclic olefin polymer materials, ensuring long-term material stability and preventing oxidative damage to pharmaceutical bottles during 121°C autoclaving. Lubricants reduce inter-chain friction, improve melt flow, and are suitable for injection molding of thin-walled pharmaceutical bottles, preventing defects such as material shortages, shrinkage marks, and weld lines. They also reduce friction between the cyclic olefin polymer material and the mold, minimizing the risk of melt adhesion to equipment, enabling rapid demolding, and improving production efficiency. Simultaneously, they ensure a smooth bottle surface, preventing scratches and pitting, and meeting the appearance requirements of pharmaceutical packaging.

[0011] As a preferred option: an easily processable, high-toughness cyclic olefin polymer material, comprising 84-88 parts of cyclic olefin polymer, 7-9 parts of maleic anhydride-grafted polyolefin elastomer, 1.5-2.5 parts of organic nano-silicate, 0.35-0.45 parts of antioxidant, and 0.3-0.4 parts of lubricant.

[0012] When the raw materials for the cyclic olefin polymer material of this application are selected from any one of the following values: 84-88 parts of cyclic olefin polymer, 7-9 parts of maleic anhydride-grafted polyolefin elastomer, 1.5-2.5 parts of organic nano-silicate, 0.35-0.45 parts of antioxidant, and 0.3-0.4 parts of lubricant, they can overcome the defects of existing materials such as glass, polyethylene, polypropylene, and polyethylene terephthalate. They all have high oxygen barrier rate, carbon dioxide barrier rate, and transparency, strong acid and alkali resistance, can package drugs with pH greater than 9, and have high toughness, can withstand 121℃ high-pressure steam sterilization, meeting the actual use requirements of high-end pharmaceutical packaging such as lymphocyte antigens, hormone drugs, anesthetic drugs, protein-based biopharmaceuticals, and vaccines.

[0013] Preferably, the weight ratio of the organic nano-silicate to the maleic anhydride-grafted polyolefin elastomer is 1:(3-5).

[0014] By adopting the above scheme and adjusting the weight ratio of organic nano-silicate to maleic anhydride-grafted polyolefin elastomer, the toughness of cyclic olefin polymer materials can be further improved.

[0015] Preferably, the organosilicone nanoparticles are modified to obtain the following: Organic nano-silicates were added to deionized water and ultrasonically dispersed to obtain an organic nano-silicate suspension. Octadecyl phosphate was added to an ethanol solution, heated to 50-60℃, and stirred until completely dissolved. Triethanolamine was added to adjust the pH of the solution to 7.0-7.5. The organic nano silicate suspension was then added dropwise to obtain the modified organic nano silicate.

[0016] By adopting the above scheme, the organic nano-silicate is hydrophobically modified with octadecyl phosphate, which improves the compatibility with maleic anhydride-grafted polyolefin elastomers and cyclic olefin polymers, thereby further improving the toughness of cyclic olefin polymer materials.

[0017] Preferably, the mass ratio of the octadecyl phosphate to the organic nano silicate is 1:(5-8).

[0018] By adopting the above technical solution and adjusting the mass ratio of octadecyl phosphate to organic nano-silicate, the toughness of cyclic olefin polymer materials can be further improved.

[0019] Preferably, the cyclic olefin polymer material further includes the following raw materials in parts by weight: 0.3-0.5 parts of tributyl citrate and 0.1-0.3 parts of di(p-methylbenzyl)sorbitol.

[0020] By employing the above technical solutions, the addition of tributyl citrate can disrupt the van der Waals forces and hydrogen bonds between cyclic olefin polymer chains, increase the interchain spacing, reduce the resistance to chain movement, weaken the interchain forces, and improve toughness while reducing rigidity. The addition of di(p-methylbenzyl)sorbitol refines the cyclic olefin polymer grains, strengthens the rigidity of the cyclic olefin polymer, and can also regulate the nucleation rate of tributyl citrate, resulting in more uniform and finer grains. Tributyl citrate can also assist in the dispersion of di(p-methylbenzyl)sorbitol in the cyclic olefin polymer matrix, preventing di(p-methylbenzyl)sorbitol agglomeration, which is more conducive to improving the toughness and rigidity of the cyclic olefin polymer material.

[0021] Preferably, the weight ratio of di(p-methylbenzyl)sorbitol to tributyl citrate is 1:(2-4).

[0022] By adopting the above technical solution and adjusting the weight ratio of di(p-methylbenzyl)sorbitol to tributyl citrate to 1:(2-4), the toughness of cyclic olefin polymer materials can be further improved.

[0023] Secondly, this application provides a method for preparing any of the above-mentioned easily processable high-toughness cyclic olefin polymer materials, specifically achieved through the following technical solution: A method for preparing an easily processable high-toughness cyclic olefin polymer material includes the following steps: melt-blending a cyclic olefin polymer and a maleic anhydride-grafted polyolefin elastomer, adding other raw materials, and extruding and granulating to obtain an easily processable high-toughness cyclic olefin polymer material.

[0024] Thirdly, this application provides a cyclic olefin polymer pharmaceutical packaging bottle prepared from any of the above-mentioned easily processable high-toughness cyclic olefin polymer materials, specifically achieved through the following technical solution: A pharmaceutical packaging bottle made from an easily processable, high-toughness cyclic olefin polymer material is prepared by the following steps: The cyclic olefin polymer material is dried; the dried cyclic olefin polymer material is placed in the heating cylinder of a molding equipment and heated to molten state at 210-320°C; the molten cyclic olefin polymer material is fed into a mold and injection molded at a pressure of 2-15 MPa and a temperature of 220-80°C to obtain a preform; the preform is heated to 160-360°C and stretched axially; then compressed air is introduced into the preform through a mold core for radial inflation to obtain the cyclic olefin polymer pharmaceutical packaging bottle.

[0025] In summary, this application includes at least one of the following beneficial technical effects: (1) The cyclic olefin polymer pharmaceutical packaging bottle obtained in this application has a light transmittance of ≥92%, which enables the visual detection of drug clarity, foreign matter, and precipitation, and the oxygen transport rate and carbon dioxide transport rate are as low as 0.025 cm⁻¹. 3 / (bottle·d·bar) and 0.08cm 3 This packaging material ( / (bottle·d·bar)) has a high oxygen and carbon dioxide barrier rate, effectively preventing drug oxidative degradation and gas leakage of carbon dioxide-containing drug solutions. It does not release inorganic substances, contains no heavy metals, residual monomers, or harmful additives, and avoids adsorption of active proteins in biological agents, ensuring drug potency. It is particularly suitable for high-value biological drugs such as monoclonal antibodies, insulin, and vaccines. It can withstand 121°C autoclaving and has strong acid and alkali resistance, allowing packaging of drugs with a pH greater than 9. The lowest water vapor permeability is only 0.03 g·m³. 2 The packaging provides 24-hour protection to prevent the drug from degrading due to moisture and to ensure its chemical stability. Furthermore, the cyclic olefin polymer drug packaging bottle obtained in this application exhibits the highest simply supported beam impact strength and elongation at break of 38.6 kJ / m². 2With a strength of 26% and a flexural strength and flexural modulus of up to 59.0 MPa and 2120 MPa respectively, it possesses high toughness and rigidity, comprehensively compensating for the defects of materials such as glass, polyethylene, polypropylene, and polyethylene terephthalate. It is more suitable for packaging high-end pharmaceuticals such as lymphocyte antigens, hormone drugs, anesthetic drugs, protein-based biopharmaceuticals, and vaccines.

[0026] (2) This application achieves an impact strength and elongation at break of 28.4-28.8 kJ / m for the simply supported beam of the cyclic olefin polymer pharmaceutical packaging bottle by adjusting the type and dosage of the raw materials. 2 With a strength of 13-15%, it exhibits high toughness.

[0027] (3) This application modifies the organic nano-silicate and adjusts the amount of octadecyl phosphate to achieve a simple beam impact strength and elongation at break of 31.2-33.3 kJ / m for the cyclic olefin polymer pharmaceutical packaging bottle. 2 And 19-21%, further improving the toughness of cyclic olefin polymer materials.

[0028] (4) This application achieves a simple beam impact strength and elongation at break of 36.8-38.6 kJ / m for cyclic olefin polymer pharmaceutical packaging bottles by adding di(p-methylbenzyl)sorbitol and tributyl citrate to the original raw materials of olefin polymer materials and controlling the ratio of the two. 2 And 24-26%, further improving the toughness of cyclic olefin polymer materials. Detailed Implementation

[0029] The following detailed description, in conjunction with specific embodiments, further illustrates this application. All the raw materials used in this application are commercially available products and are intended to fully disclose the raw materials used in this application; they should not be construed as limiting the source of the raw materials. Specifically: cyclic olefin polymer, brand Zeon (Japan), medical grade, model COP 690R; maleic anhydride grafted polyolefin elastomer, brand POE, model YSF-W1; organic nano-silicate, selected from organoprothiolane, particle size 325 mesh; antioxidant, selected from antioxidant 1010; lubricant, selected from calcium stearate; octadecyl phosphate, active ingredient content 98%; triethanolamine, pharmaceutical grade, active ingredient content 99%; tributyl citrate, active ingredient content 99%; di(p-methylbenzyl)sorbitol, active ingredient content 99%.

[0030] The following are examples of the preparation of modified organosilica nanoparticles: Preparation Example 1 The modified organosilicon nanoparticles of Example 1 were prepared by the following steps: 1 kg of organic nano-silicate was added to 4 L of deionized water and ultrasonically dispersed at 300 W for 20 min to obtain an organic nano-silicate suspension. Add 40g of octadecyl phosphate to 1L of 70% ethanol solution, heat to 50℃, stir until completely dissolved, add triethanolamine to adjust the pH of the solution to 7.0-7.5, add the organic nano silicate suspension dropwise at a rate of 5mL / min, stir for 1-2h, centrifuge, wash and dry to obtain modified organic nano silicate.

[0031] Preparation Examples 2-5 The modified organic nano-silicates prepared in Examples 2-5 were prepared using the same method as those prepared in Example 1, except that the amount of octadecyl phosphate used was different, at 50g, 70g, 100g and 110g respectively. The other raw materials were the same as those in Example 1.

[0032] Example 1 Example 1: Easily processable high-toughness cyclic olefin polymer material, comprising the following steps: According to the raw material dosages of the cyclic olefin polymer material shown in Table 1, the cyclic olefin polymer and maleic anhydride grafted polyolefin elastomer are melt-blended at 220°C, other raw materials are added and mixed evenly, and then melted, extruded, and granulated using a twin-screw extruder with a length-to-diameter ratio of 40:1 and a screw diameter of 16.0 mm. The temperatures of each section in the extruder are set sequentially from the feed section to the die at 220°C, 225°C, 230°C, 235°C, 240°C, 240°C, and 235°C. After water cooling, pelletizing, and drying, the easily processable high-toughness cyclic olefin polymer material is obtained.

[0033] Examples 2-5 The easy-to-process, high-toughness cyclic olefin polymer materials of Examples 2-5 are prepared in the same way as those of Example 1, using the same raw material types. The difference lies in the different amounts of each raw material, as detailed in Table 1.

[0034] Table 1. Raw material dosage (kg) for cyclic olefin polymer materials in Examples 1-5

[0035] Examples 6-10 The easily processed, high-toughness cyclic olefin polymer materials of Examples 6-10 are prepared in the same way as those of Example 3 in terms of preparation method and raw material type and dosage. The difference is that the modified organic nano-silicates prepared in Examples 1-5 are used respectively, and the dosage of other raw materials is the same as that of Example 3.

[0036] Examples 11-15 The easy-to-process, high-toughness cyclic olefin polymer materials of Examples 11-15 are prepared in exactly the same way as those of Example 8. The difference is that the raw materials of the cyclic olefin polymer materials also include tributyl citrate and di(p-methylbenzyl)sorbitol, with specific dosages of 0.3 kg and 0.3 kg, 0.2 kg and 0.4 kg, 0.1 kg and 0.3 kg, 0.1 kg and 0.4 kg, and 0.1 kg and 0.5 kg, respectively. The dosages of the remaining raw materials are the same as those of Example 8.

[0037] Comparative Example 1 The easy-to-process, high-toughness cyclic olefin polymer material of Comparative Example 1 was prepared in the same way as that of Example 1, except that no organic nano-silicates were added to the raw materials of the cyclic olefin polymer material, while the other raw materials and dosages were the same as those of Example 1.

[0038] Comparative Example 2 The easy-to-process, high-toughness cyclic olefin polymer material of Comparative Example 2 was prepared in the same way as that of Example 1, except that maleic anhydride-grafted polyolefin elastomer was not added to the raw materials of the cyclic olefin polymer material, while the other raw materials and dosages were the same as those of Example 1.

[0039] The following are applications of cyclic olefin polymer materials in pharmaceutical packaging bottles. Application Example 1 Application Example 1: Application of cyclic olefin polymer materials in pharmaceutical packaging bottles. Specifically, the process was carried out in a Class C cleanroom with a temperature of 18-22°C and a humidity of 37-43%. The cyclic olefin polymer material obtained in Example 1 was dried at 100°C for 4 hours. The dried cyclic olefin polymer material was then placed in the heating cylinder of the molding equipment and heated to 255°C and subjected to shearing friction until melted. The molten cyclic olefin polymer material was injected into the mold cavity through the nozzle and hot runner by the screw. After injection molding at an injection speed of 10-15%, a pressure of 12 MPa, and a temperature of 245°C, a preform was obtained. The core mold temperature was set to 120°C, the injection mold temperature to 110°C, and the blow mold temperature to 90°C. The preform was then transferred to the heating station for temperature adjustment. The preform was adjusted to the temperature suitable for stretch blow molding by setting the heating tank temperature to 345°C. The preform after temperature adjustment is transferred to the stretch blow molding station, where the preform is stretched axially using mechanical means, and compressed air is introduced into the preform through the mold core for radial inflation. The preform is then cooled and shaped using a blow molding die. The blow molding time is 3 seconds, resulting in a cyclic olefin polymer pharmaceutical packaging bottle.

[0040] Application Example 2-15 The application methods of the cyclic olefin polymer material in pharmaceutical packaging bottles in Application Examples 2-15 are the same as those in Application Example 1, except that the cyclic olefin polymer material prepared in Example 2-15 is used. The remaining steps are the same as in Application Example 1.

[0041] Application Comparative Example 1-2 The application methods of the cyclic olefin polymer material in Comparative Examples 1-2 and Application Example 1 are the same as those in Application Example 1, except that the cyclic olefin polymer material prepared in Comparative Examples 1-2 is used. The remaining steps are the same as in Application Example 1.

[0042] Performance testing The performance of cyclic olefin polymer pharmaceutical packaging bottles obtained from different application examples 1-15 and application comparison examples 1-2 was tested using the following testing standards or methods. The test results are detailed in Table 2-3.

[0043] Transparency: The transmittance was obtained by molding cyclic olefin polymer materials into discs with a diameter of 25 mm and a thickness of 1 mm and testing them under a standard C light source of 380-780 nm.

[0044] Oxygen transmission rate: The oxygen transmission rate was tested according to the GB / T1038-2000 test standard.

[0045] Carbon dioxide transport rate: The carbon dioxide transport rate was tested according to the GB / T1038-2000 test standard.

[0046] Water vapor transmission rate: The water vapor transmission rate was tested according to the GB / T 26253-2010 test standard.

[0047] Impact strength of simply supported beams: The impact strength of simply supported beams was tested according to ISO 179 test standard. The test temperature was -20℃, and the sample size was 80mm×6mm×4mm.

[0048] Elongation at break: The elongation at break is tested according to the DIN 53455 test standard.

[0049] Flexural strength: The flexural strength of cyclic olefin polymer materials at 100℃ is tested.

[0050] Flexural modulus: Measure the flexural modulus of cyclic olefin polymer materials at 100°C. Table 2 Performance test results of pharmaceutical packaging bottles with different cyclic olefin polymers

[0051] Table 3 Performance test results of pharmaceutical packaging bottles with different cyclic olefin polymers

[0052] The test results in Tables 2 and 3 show that the cyclic olefin polymer pharmaceutical packaging bottle obtained in this application has a light transmittance of ≥92%, enabling visual detection of drug clarity, foreign matter, and precipitation. Furthermore, the oxygen and carbon dioxide transport rates are as low as 0.025 cm⁻¹. 3 / (bottle·d·bar) and 0.08cm 3 This packaging material ( / (bottle·d·bar)) has a high oxygen and carbon dioxide barrier rate, effectively preventing drug oxidative degradation and gas leakage of carbon dioxide-containing drug solutions. It does not release inorganic substances, contains no heavy metals, residual monomers, or harmful additives, and avoids adsorption of active proteins in biological agents, ensuring drug potency. It is particularly suitable for high-value biological drugs such as monoclonal antibodies, insulin, and vaccines. It can withstand 121°C autoclaving and has strong acid and alkali resistance, allowing packaging of drugs with a pH greater than 9. The lowest water vapor permeability is only 0.03 g·m³. 2 The packaging provides 24-hour protection to prevent the drug from degrading due to moisture and to ensure its chemical stability. Furthermore, the cyclic olefin polymer drug packaging bottle obtained in this application exhibits the highest simply supported beam impact strength and elongation at break of 38.6 kJ / m². 2 With a strength of 26% and a flexural strength and flexural modulus of up to 59.0 MPa and 2120 MPa respectively, it possesses high toughness and rigidity, comprehensively compensating for the defects of materials such as glass, polyethylene, polypropylene, and polyethylene terephthalate. It is more suitable for packaging high-end pharmaceuticals such as lymphocyte antigens, hormone drugs, anesthetic drugs, protein-based biopharmaceuticals, and vaccines.

[0053] In Application Examples 1-5, the simply supported beam impact strength and elongation at break of the cyclic olefin polymer pharmaceutical packaging bottles in Application Examples 2-4 are 28.4-28.8 kJ / m, respectively. 2 The toughness of the cyclic olefin polymer material was 13-15%, which was higher than that of Application Example 1 and Application Example 5. This indicates that adjusting the type and amount of raw materials and controlling the weight ratio of organic nano-silicate to maleic anhydride grafted polyolefin elastomer significantly improved the toughness of the cyclic olefin polymer material.

[0054] In Application Examples 6-10, the simply supported beam impact strength and elongation at break of the cycloolefin polymer pharmaceutical packaging bottles in Application Examples 7-9 were 31.2-33.3 kJ / m, respectively. 2 The values ​​of 19-21% were higher than those of Application Example 6 and Application Example 10, indicating that modifying the organic nano-silicate and adjusting the amount of octadecyl phosphate can further improve the toughness of the cyclic olefin polymer material.

[0055] In Application Examples 11-15, the simply supported beam impact strength and elongation at break of the cycloolefin polymer pharmaceutical packaging bottles in Application Examples 12-14 are 36.8-38.6 kJ / m, respectively. 2 The values ​​of 24-26% were higher than those of Application Examples 11 and 15, indicating that adding di(p-methylbenzyl)sorbitol and tributyl citrate to the original raw materials of olefin polymer materials and controlling their ratio can further improve the toughness of cyclic olefin polymer materials.

[0056] Furthermore, by combining the various performance data of the cyclic olefin polymer pharmaceutical packaging bottles from Comparative Examples 1-2 and Application Example 1, it was found that the addition of organic nano-silicates and maleic anhydride-grafted polyolefin elastomers to the raw materials of the cyclic olefin polymer pharmaceutical packaging bottles in this application can improve the toughness of the cyclic olefin polymer materials to varying degrees.

[0057] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A processable, high-toughness cyclic olefin polymer material, characterized in that, It comprises the following raw materials in parts by weight: 80-90 parts of cyclic olefin polymer, 5-10 parts of maleic anhydride grafted polyolefin elastomer, 1-3 parts of organic nano silicate, 0.3-0.5 parts of antioxidant, and 0.2-0.5 parts of lubricant.

2. The easily processable, high-toughness cyclic olefin polymer material according to claim 1, characterized in that, It comprises the following raw materials in parts by weight: 84-88 parts of cyclic olefin polymer, 7-9 parts of maleic anhydride grafted polyolefin elastomer, 1.5-2.5 parts of organic nano silicate, 0.35-0.45 parts of antioxidant, and 0.3-0.4 parts of lubricant.

3. The easily processable, high-toughness cyclic olefin polymer material according to claim 1, characterized in that, The weight ratio of the organic nano-silicate to the maleic anhydride-grafted polyolefin elastomer is 1:(2-8).

4. The easily processable, high-toughness cyclic olefin polymer material according to claim 1, characterized in that, The organic nano-silicate was modified to obtain the following: Organic nano-silicates were added to deionized water and ultrasonically dispersed to obtain an organic nano-silicate suspension. Octadecyl phosphate was added to an ethanol solution, heated to 50-60℃, and stirred until completely dissolved. Triethanolamine was added to adjust the pH of the solution to 7.0-7.

5. The organic nano silicate suspension was added dropwise, stirred, centrifuged, washed and dried to obtain the modified organic nano silicate.

5. The easily processable, high-toughness cyclic olefin polymer material according to claim 4, characterized in that, The amount of the octadecyl phosphate used is 5%-10% of the mass of the organic nano silicate.

6. The easily processable, high-toughness cyclic olefin polymer material according to claim 1, characterized in that, The cyclic olefin polymer material further includes the following raw materials in parts by weight: 0.3-0.5 parts of tributyl citrate and 0.1-0.3 parts of di(p-methylbenzyl)sorbitol.

7. The easily processable, high-toughness cyclic olefin polymer material according to claim 6, characterized in that, The weight ratio of di(p-methylbenzyl)sorbitol to tributyl citrate is 1:(2-4).

8. A method for preparing the easily processable, high-toughness cyclic olefin polymer material according to any one of claims 1-7, characterized in that, The process includes the following steps: melt-blending cyclic olefin polymers and maleic anhydride-grafted polyolefin elastomers, adding other raw materials, and extruding and granulating to obtain easily processable, high-toughness cyclic olefin polymer materials.

9. A cyclic olefin polymer pharmaceutical packaging bottle prepared from the easily processable, high-toughness cyclic olefin polymer material according to any one of claims 1-7, characterized in that, It is prepared by the following steps: the cyclic olefin polymer material is dried, the dried cyclic olefin polymer material is placed in the heating cylinder of the molding equipment and heated to melt at 210-320℃, the molten cyclic olefin polymer material is fed into the mold, and injection molding is performed under the conditions of pressure of 2-15MPa and temperature of 220-280℃ to obtain a preform, the preform is heated to 160-360℃ and stretched axially, and then compressed air is introduced into the preform through the mold core for radial inflation to obtain a cyclic olefin polymer pharmaceutical packaging bottle.

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