High-oxygen-barrier PET composite material and high-oxygen-barrier medicine packaging bottle
By using composites of organic and inorganic oxygen barriers and modified cellulose nanocrystals, nanoclays, etc. in PET materials, multiple defense lines are formed, which solves the problem of high oxygen transmittance in PET pharmaceutical packaging bottles, and achieves efficient long-term oxygen barrier and mechanical stability.
Patent Information
- Application Number
- CN202510836594.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-21
- Publication Date
- 2025-08-01
AI Technical Summary
The oxygen transmittance of pharmaceutical packaging bottles made of traditional PET materials is high, which is difficult to meet the demand for ultra-high oxygen resistance of high active drugs. The existing methods of coating inorganic barrier layers are costly and have insufficient long-term stability.
Using a composite of organic and inorganic oxygen barrier agents, the formation of tortuous channels in the PET matrix and the capture of oxygen molecules by chemical reactions, combining antioxidants and dispersants, improve barrier properties, and improve compatibility by modifying cellulose nanocrystals and nanoclays to form multiple defense barriers.
Significantly reduce oxygen transmittance, improve the oxygen resistance of PET composite materials, and ensure that the drug packaging bottles maintain high oxygen resistance and mechanical performance stability during long-term use.
Smart Images
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Abstract
Description
Technical Field
[0001] This application relates to the field of PET materials, and more specifically, to a high-oxygen-barrier PET composite material and a high-oxygen-barrier pharmaceutical packaging bottle. Background Art
[0002] With the rapid development of the pharmaceutical industry, the functional requirements for pharmaceutical packaging bottles are becoming increasingly stringent, especially in terms of oxygen barrier performance. Oxygen permeation is one of the key factors leading to the oxidation and deterioration of drugs and the degradation of active ingredients, directly affecting the safety, stability, and shelf life of drugs. Due to the characteristics of PET materials such as high transparency, lightweight, chemical resistance, and easy processing, the oxygen transmission rate of pharmaceutical packaging bottles made of traditional PET materials is relatively high, making it difficult to meet the requirements of highly active drugs for ultra-high oxygen barrier properties.
[0003] In related technologies, in order to improve the oxygen barrier performance of pharmaceutical packaging bottles, inorganic barrier layers such as silicon oxide and diamond-like carbon are coated on the surface of PET materials. Such processes have high equipment costs, the coating is prone to microcracks due to mechanical stress, the long-term oxygen barrier stability is insufficient, and it is difficult to be compatible with high-speed blow molding processes. Summary of the Invention
[0004] In order to improve the oxygen barrier property of pharmaceutical packaging bottles, this application provides a high-oxygen-barrier PET composite material and a high-oxygen-barrier pharmaceutical packaging bottle.
[0005] In the first aspect, this application provides a high-oxygen-barrier PET composite material, which adopts the following technical solution: A high-oxygen-barrier PET composite material, which comprises the following raw materials in parts by weight: 90 - 100 parts of PET resin, 1 - 3 parts of composite oxygen barrier agent, 0.5 - 1 part of antioxidant, 1 - 2 parts of dispersant, and 2 - 4 parts of SEBS; The composite oxygen barrier agent is a composite of an organic oxygen barrier agent and an inorganic oxygen barrier agent.
[0006] By adopting the above scheme, the composite oxygen barrier agent is selected as a composite of an organic oxygen barrier agent and an inorganic oxygen barrier agent, with excellent oxygen barrier performance. The inorganic oxygen barrier agent nanoparticles can form tortuous channels in the PET matrix, thereby extending the diffusion path of oxygen molecules in the material and improving the barrier performance. The organic oxygen barrier agent actively captures or consumes oxygen molecules through chemical reactions, and can more effectively prevent the penetration of oxygen. Therefore, the physical barrier of the inorganic oxygen barrier agent delays the oxygen permeation rate, and the organic oxygen barrier agent further blocks the residual oxygen through chemical adsorption, forming a double defense line, significantly reducing the oxygen transmission rate, and improving the high-oxygen-barrier property of the PET composite material.
[0007] Antioxidants block the oxidation chain reaction by capturing free radicals or decomposing peroxides, reduce the breakage of molecular chains, maintain the molecular weight and mechanical properties of PET composites, and avoid processing instability caused by the decrease in melt viscosity. In addition, antioxidants can also prevent yellowing, embrittlement or degradation of mechanical properties of PET composites during long-term use in light, humid heat or oxidative environments.
[0008] The dispersant promotes the uniform dispersion of each raw material in the PET composite, avoids the agglomeration or sedimentation of raw materials, improves the processing fluidity, and thus improves the mechanical properties and oxygen barrier properties of the PET composite.
[0009] SEBS is added as a compatibilizer. By reacting with the terminal hydroxyl or ester groups of PET through polar groups, it enhances the interfacial bonding, forms a more stable blend system, can also reduce the viscosity of the PET melt, improves the fluidity, is more easily processed especially at high shear rates, helps to reduce the surface defects of the pharmaceutical packaging bottle, improves the filling efficiency, and is suitable for the preparation of pharmaceutical packaging bottles.
[0010] Preferably: the weight ratio of the organic oxygen barrier agent to the inorganic oxygen barrier agent is 1:(2 - 3).
[0011] Preferably: the organic oxygen barrier agent is selected from any one or more of sodium ferric ethylenediaminetetraacetate, polyhexamethylene isophthalamide, cellulose nanocrystals and polylactic acid; the inorganic oxygen barrier agent is selected from any one or more of nano-silica, glass flakes, nano-clay, graphene oxide; the antioxidant is selected from any one or more of antioxidant 1010 and antioxidant 168; the dispersant is selected from any one or more of polyethylene wax, polypropylene wax and polyvinylpyrrolidone.
[0012] In this application, when the organic oxygen barrier agent is selected from any one or more of sodium ferric ethylenediaminetetraacetate, polyhexamethylene isophthalamide, cellulose nanocrystals and polylactic acid; the inorganic oxygen barrier agent is selected from any one or more of nano-silica, glass flakes, nano-clay, graphene oxide; the antioxidant is selected from any one or more of antioxidant 1010 and antioxidant 168; the dispersant is selected from any one or more of polyethylene wax, polypropylene wax and polyvinylpyrrolidone, the properties of the PET composite are predictable and all have high oxygen barrier properties.
[0013] Preferably: the organic oxygen barrier agent is cellulose nanocrystals; the cellulose nanocrystals are prepared by modification, specifically: S1. Mix cellulose nanocrystals with deionized water, and ultrasonically disperse them at 200 - 400W for 30 - 50min to obtain a cellulose nanocrystal suspension with a mass concentration of 3% - 5%. S2. Add 4-dimethylaminopyridine and p-toluenesulfonic acid to the cellulose nanocrystal suspension, add succinic anhydride, and stir and react at 75 - 80 °C under nitrogen for 7 - 9 h. Filter, wash, dry, and mix evenly with dibutyltin dilaurate to obtain modified cellulose nanocrystals.
[0014] The dosage of the 4-dimethylaminopyridine is 1% - 3% of the mass of the cellulose nanocrystals; the dosage of the p-toluenesulfonic acid is 3 - 5% of the mass of the cellulose nanocrystals; the dibutyltin dilaurate is 1% - 2% of the mass of the cellulose nanocrystals.
[0015] By adopting the above scheme, the cellulose nanocrystals have a high aspect ratio and a regular nanoscale lamellar structure, can form a dense "labyrinth effect" in the PET composite material, significantly extend the diffusion path of oxygen molecules, and reduce the oxygen permeability.
[0016] Modify the cellulose nanocrystals to reduce the agglomeration of cellulose nanocrystals in the PET composite material, achieve nanoscale dispersion, improve the compatibility between the cellulose nanocrystals and the PET resin, and further improve the oxygen barrier effect of the cellulose nanocrystals. Use 4-dimethylaminopyridine and p-toluenesulfonic acid as two catalysts to catalyze synergistically. Activate the anhydride with p-toluenesulfonic acid, and 4-dimethylaminopyridine neutralizes the by-product acid to promote the reaction equilibrium.
[0017] Mix the acetylated modified cellulose nanocrystals evenly with dibutyltin dilaurate to inhibit the thermal degradation of cellulose nanocrystals at high temperature.
[0018] As a preference: The mass ratio of the cellulose nanocrystals to the succinic anhydride is 1:(1.5 - 3).
[0019] By adopting the above scheme, regulate the mass ratio of the cellulose nanocrystals to the succinic anhydride to further improve the modification effect, thereby enhancing the oxygen barrier effect of the cellulose nanocrystals.
[0020] As a preference: The inorganic oxygen barrier agent is nano-clay; the nano-clay is prepared by modification, specifically: S1. Add the nano-clay to deionized water and disperse it ultrasonically to obtain a nano-clay suspension with a mass concentration of 4 - 6%. S2. Add cetyltrimethylammonium bromide to deionized water, stir and dissolve it to obtain a cetyltrimethylammonium bromide solution with a mass concentration of 2 - 4%. Add the cetyltrimethylammonium bromide solution to the nano-clay suspension, continuously stir at 50 - 70 °C for 2 - 4 h, filter, wash, dry, grind and sieve to obtain modified nano-clay.
[0021] By adopting the above-mentioned scheme, cetyltrimethylammonium bromide is used to modify nano-clay, replacing the inorganic cations between nano-clays, which can improve the dispersibility of nano-clay in the PET composite material, effectively avoid the agglomeration of nano-clay, and thus improve the oxygen barrier effect of nano-clay in the PET composite material.
[0022] Preferably, the mass ratio of cetyltrimethylammonium bromide to nano-clay is 1:(5 - 10).
[0023] By adopting the above-mentioned scheme, adjusting the mass ratio of cetyltrimethylammonium bromide to nano-clay can improve the modification effect of nano-clay, and thus improve the oxygen barrier property of the PET composite material.
[0024] Preferably, the raw materials of the high-oxygen-barrier PET composite material further include 10 - 20 parts by weight of polyamide.
[0025] By adopting the above-mentioned scheme, polyamide has excellent oxygen barrier performance. When added to the PET composite material, it reduces the diffusion channels of oxygen molecules inside the PET composite material, and can further improve the oxygen barrier property of the PET material. Moreover, the amide groups of polyamide can form hydrogen bonds with the ester groups of PET, improving the compatibility and reducing the interfacial defects, thereby improving the oxygen barrier property of the PET composite material.
[0026] In addition, polyamide can also form a complementary multiple barrier mechanism with nano-clay and cellulose nanocrystals, further enhancing the oxygen barrier effect. Moreover, nano-clay and cellulose nanocrystals can also improve the compatibility between polyamide and PET resin, further reducing the oxygen permeation channels and improving the oxygen barrier property of the PET composite material.
[0027] In the second aspect, the present application provides a high-oxygen-barrier medicine packaging bottle prepared from the high-oxygen-barrier PET composite material according to any one of claims 1 - 7, which is specifically realized through the following technical scheme: A high-oxygen-barrier medicine packaging bottle prepared from the high-oxygen-barrier PET composite material according to any one of claims 1 - 7 is prepared by the following steps: Extruding and pelletizing the high-oxygen-barrier PET composite material according to any one of claims 1 - 5 at 260 - 270 °C, injection molding to form a preform, heating, cooling, placing the preform in a mold, preliminarily blowing the preform into the bottle cavity of a beverage bottle with gas, stretching the preform, blowing high-pressure air into the pre-stretched and blown preform to form a packaging bottle, cooling and shaping, and demolding to obtain the high-oxygen-barrier medicine packaging bottle.
[0028] 1. By controlling the types and dosages of each raw material in the high-oxygen-barrier PET composite material, the present application makes the oxygen concentration inside the high-oxygen-barrier medicine packaging bottle be 0% before 68 days, and the oxygen concentrations inside the bottle at 92 days and 125 days are 0.009% and 0.097 - 0. O99% respectively, improving the oxygen barrier property of the medicine packaging bottle.
[0029] 2. By modifying the cellulose nanocrystals in the high oxygen barrier PET composite material and controlling the mass ratio of cellulose nanocrystals to succinic anhydride, the oxygen concentration in the high oxygen barrier pharmaceutical packaging bottles at 92 days and 125 days is 0.006 - 0.007% and 0.079 - 0.080% respectively, which can further improve the oxygen barrier property of the pharmaceutical packaging bottles.
[0030] 3. By modifying the nanoclay in the high oxygen barrier PET composite material and controlling the mass ratio of cetyltrimethylammonium bromide to nanoclay, the oxygen concentration in the high oxygen barrier pharmaceutical packaging bottles at 92 days and 125 days is 0.004% and 0.070 - 0.073% respectively, which can further improve the oxygen barrier property of the pharmaceutical packaging bottles.
[0031] 4. By adding polyamide to the high oxygen barrier PET composite material and controlling its dosage, the oxygen concentration in the high oxygen barrier pharmaceutical packaging bottles at 92 days and 125 days is 0.003% and 0.068% respectively, which can further improve the oxygen barrier property of the pharmaceutical packaging bottles. Specific Embodiments
[0032] The following further elaborates on the present application with specific embodiments. The following raw materials in the present application are all commercially available products. To fully disclose the raw materials of the present application, it should not be construed as a limitation on the source of the raw materials. Specifically: PET resin, food grade, brand DuPont of the United States, with an active ingredient content of 96%; antioxidant, antioxidant 1010 is selected; dispersant, polyethylene wax is selected; SEBS, brand Xindongyi, 400PE wax; organic oxygen barrier agent, cellulose nanocrystals are selected, with a diameter of 10 - 50 nm, a length of 100 - 500 nm, and an aspect ratio of 1 - 100; inorganic oxygen barrier agent, nanoclay is selected, with a particle size of 50 nm; deionized water, with an active ingredient content of 99%; 4-dimethylaminopyridine, with an active ingredient content of 99%; p-toluenesulfonic acid, with an active ingredient content of 99%; succinic anhydride, with an active ingredient content of 99%; dibutyltin dilaurate, with a tin content of 18.6% and an active ingredient content of 99%; cetyltrimethylammonium bromide, with an active ingredient content of 99%; polyamide, model PA66.
[0033] The following is a preparation example of modified cellulose nanocrystals Preparation Example 1 The modified cellulose nanocrystals of Preparation Example 1 are specifically as follows: S1. Mix 1 kg of cellulose nanocrystals with 25 L of deionized water and ultrasonically disperse for 40 min at 300 W to obtain a cellulose nanocrystal suspension; S2. Add 20 g of 4-dimethylaminopyridine and 40 g of p-toluenesulfonic acid to the cellulose nanocrystal suspension, then add 1 kg of succinic anhydride. Stir and react at 75 - 80 °C under nitrogen for 7 - 9 h, filter, wash, dry, and mix evenly with 15 g of dibutyltin dilaurate to obtain modified cellulose nanocrystals.
[0034] Preparation Examples 2 - 5 The modified cellulose nanocrystals of Preparation Examples 2 - 5 have the same types of raw materials and preparation methods as those of Preparation Example 1, with the difference being the different dosages of succinic anhydride, specifically 1.5 kg, 2 kg, 3 kg, and 3.5 kg. The remaining steps are the same as those of Preparation Example 1.
[0035] The following are the preparation examples of modified nanoclays Preparation Example 6 The modified nanoclay of Preparation Example 6 is specifically as follows: S1. Add 1 kg of nanoclay to 20 L of deionized water and disperse it by ultrasonic treatment to obtain a nanoclay suspension; S2. Add 0.25 kg of cetyltrimethylammonium bromide to 8.33 L of deionized water, stir and dissolve it to obtain a cetyltrimethylammonium bromide solution. Add the cetyltrimethylammonium bromide solution to the nanoclay suspension, continuously stir at 60 °C for 3 h, filter, wash, dry, grind, and sieve to obtain modified nanoclay.
[0036] Preparation Examples 7 - 10 The modified cellulose nanocrystals of Preparation Examples 7 - 10 have the same types of raw materials and preparation methods as those of Preparation Example 1, with the difference being the different dosages of cetyltrimethylammonium bromide, specifically 0.2 kg, 0.14 kg, 0.1 kg, and 0.09 kg. The remaining steps are the same as those of Preparation Example 1.
[0037] Example 1 The high-oxygen-barrier pharmaceutical packaging bottle of Example 1 is prepared through the following operating steps: According to the dosages in Table 1, extrude and pelletize the high-oxygen-barrier PET composite material at 260 °C, injection mold it into a preform, heat it, cool it, place the preform in a mold, preliminarily blow the preform into the bottle cavity of a beverage bottle with gas, stretch the preform, blow high-pressure air into the pre-stretched and blown preform to form a packaging bottle, cool and shape it, and demold it to obtain the high-oxygen-barrier pharmaceutical packaging bottle. Among them, the organic oxygen barrier agent is cellulose nanocrystals, and the inorganic oxygen barrier agent is nanoclay.
[0038] Examples 2 - 5 The high-oxygen-barrier pharmaceutical packaging bottles of Examples 2 - 5 have the same preparation methods and types of raw materials as those of Example 1, with the difference being the different dosages of each raw material, as specifically shown in Table 1.
[0039] Table 1 Dosage of each raw material of the high oxygen barrier PET composite materials in Examples 1 - 5 (unit: kg) Examples 6 - 10 The preparation method of the high oxygen barrier pharmaceutical packaging bottles in Examples 6 - 10 is the same as that in Example 3, except that the cellulose nanocrystals are the modified cellulose nanocrystals prepared in Preparation Examples 1 - 5, and the types and dosages of the remaining raw materials are the same as those in Example 3.
[0040] Examples 11 - 15 The preparation method of the high oxygen barrier pharmaceutical packaging bottles in Examples 11 - 15 is the same as that in Example 8, except that the nano - clay is the modified nano - clay prepared in Preparation Examples 6 - 10, and the types and dosages of the remaining raw materials are the same as those in Example 8.
[0041] Example 16 The preparation method of the high oxygen barrier pharmaceutical packaging bottles in Example 16 is the same as that in Example 13, except that the raw materials of the high oxygen barrier PET composite material further include 15 kg of polyamide.
[0042] Comparative Example 1 The preparation method of the high oxygen barrier pharmaceutical packaging bottles in Comparative Example 1 is exactly the same as that in Example 1, except that the composite oxygen barrier agent is replaced with nano - clay in equal amount, and the remaining raw materials and dosages are the same as those in Example 1.
[0043] Comparative Example 2 The preparation method of the high oxygen barrier pharmaceutical packaging bottles in Comparative Example 2 is exactly the same as that in Example 1, except that the composite oxygen barrier agent is replaced with cellulose nanocrystals in equal amount, and the remaining raw materials and dosages are the same as those in Example 1.
[0044] Comparative Example 3 The preparation method of the high oxygen barrier pharmaceutical packaging bottles in Comparative Example 3 is exactly the same as that in Example 1, except that the composite oxygen barrier agent is not added to the high oxygen barrier PET composite material, and the remaining raw materials and dosages are the same as those in Example 1.
[0045] Performance Detection (I) The high oxygen barrier pharmaceutical packaging bottles obtained from different Examples 1 - 16 and Comparative Examples 1 - 2 were respectively subjected to performance detection using the following detection standards or methods. The detection results are shown in Table 2.
[0046] Oxygen concentration inside the bottle: Detected using an oxygen content instrument.
[0047] Table 2 Performance Detection Results of Different High Oxygen Barrier Pharmaceutical Packaging Bottles The test results in Table 2 show that the oxygen concentration inside the high-oxygen-barrier pharmaceutical packaging bottle obtained in this application was 0% before 68 days, and the lowest oxygen concentrations inside the bottle at 92 days and 125 days were only 0.003% and 0.068% respectively, improving the oxygen barrier property of the pharmaceutical packaging bottle.
[0048] Combined with the performance test data of the high-oxygen-barrier pharmaceutical packaging bottles in Examples 1-5, it was found that the oxygen concentrations inside the bottles of the high-oxygen-barrier pharmaceutical packaging bottles in Examples 2-4 at 92 days and 125 days were 0.009% and 0.097 - 0.099% respectively, which were lower than those in Example 1 and Example 5. This indicates that when the weight ratio of the organic oxygen barrier agent to the inorganic oxygen barrier agent in the high-oxygen-barrier PET composite material is 1:(2 - 3), it is more appropriate, improving the oxygen barrier property of the pharmaceutical packaging bottle.
[0049] Combined with the performance test data of the high-oxygen-barrier pharmaceutical packaging bottles in Examples 6-10, it was found that the oxygen concentrations inside the bottles of the high-oxygen-barrier pharmaceutical packaging bottles in Examples 7-9 at 92 days and 125 days were 0.006 - 0.007% and 0.079 - 0.080% respectively, which were lower than those in Example 6 and Example 10. This indicates that modifying the cellulose nanocrystals in the high-oxygen-barrier PET composite material and controlling the mass ratio of cellulose nanocrystals to succinic anhydride to be 1:(1.5 - 3) can further improve the oxygen barrier property of the pharmaceutical packaging bottle.
[0050] Combined with the performance test data of the high-oxygen-barrier pharmaceutical packaging bottles in Examples 11-15, it was found that the oxygen concentrations inside the bottles of the high-oxygen-barrier pharmaceutical packaging bottles in Examples 7-9 at 92 days and 125 days were 0.004% and 0.070 - 0.073% respectively, which were lower than those in Example 6 and Example 10. This indicates that modifying the nanoclay in the high-oxygen-barrier PET composite material and controlling the mass ratio of cetyltrimethylammonium bromide to nanoclay to be 1:(5 - 10) can further improve the oxygen barrier property of the pharmaceutical packaging bottle.
[0051] Combined with the performance test data of the high-oxygen-barrier pharmaceutical packaging bottles in Example 16 and Example 13, it was found that the oxygen concentrations inside the bottles of the high-oxygen-barrier pharmaceutical packaging bottle in Example 16 at 92 days and 125 days were 0.003% and 0.068% respectively, which were lower than those in Example 13. This indicates that adding polyamide to the high-oxygen-barrier PET composite material can further improve the oxygen barrier property. Combined with the performance test data of the high-oxygen-barrier pharmaceutical packaging bottles in Example 1 and Comparative Examples 1-2, it was found that adding nanoclay and cellulose nanocrystals to the raw materials of the high-oxygen-barrier PET composite material can improve the oxygen barrier property of the pharmaceutical packaging bottle to varying degrees.
[0052] This specific embodiment is only an explanation of this application and not a limitation. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of this application, it is protected by the patent law.
Claims
1. A high oxygen barrier PET composite material, characterized in that, It comprises the following raw materials in parts by weight: 90 - 100 parts of PET resin, 1 - 3 parts of composite oxygen barrier agent, 0.5 - 1 part of antioxidant, 1 - 2 parts of dispersant, and 2 - 4 parts of SEBS; The composite oxygen barrier agent is a composite of an organic oxygen barrier agent and an inorganic oxygen barrier agent.
2. The high-barrier oxygen PET composite material according to claim 1, wherein The weight ratio of the organic oxygen barrier agent to the inorganic oxygen barrier agent is 1:(2 - 3).
3. The high-barrier oxygen PET composite material according to claim 1, wherein The organic oxygen barrier agent is selected from any one or more of sodium iron ethylenediaminetetraacetate, polyhexamethylene adipamide, cellulose nanocrystals, and polylactic acid; the inorganic oxygen barrier agent is selected from any one or more of nano - silica, glass flakes, nano - clay, and graphene oxide; the antioxidant is selected from any one or more of antioxidant 1010 and antioxidant 168; the dispersant is selected from any one or more of polyethylene wax, polypropylene wax, and polyvinylpyrrolidone.
4. The high-barrier oxygen PET composite material according to claim 1, wherein The organic oxygen barrier agent is cellulose nanocrystals; the cellulose nanocrystals are prepared by modification, specifically: S1. Mix cellulose nanocrystals with deionized water, and perform ultrasonic dispersion at 200 - 400W for 30 - 50min to obtain a cellulose nanocrystal suspension with a mass concentration of 3% - 5%; S2. Add 4 - dimethylaminopyridine and p - toluenesulfonic acid to the cellulose nanocrystal suspension, add succinic anhydride, and stir and react at 75 - 80°C under nitrogen for 7 - 9h. Filter, wash, dry, and mix evenly with dibutyltin dilaurate to obtain modified cellulose nanocrystals.
5. The high-barrier oxygen PET composite material according to claim 4, wherein The mass ratio of the cellulose nanocrystals to succinic anhydride is 1:(1.5 - 3).
6. The high-barrier oxygen PET composite material according to claim 1, wherein The inorganic oxygen barrier agent is nano - clay; the nano - clay is prepared by modification, specifically: S1. Add nano - clay to deionized water and perform ultrasonic dispersion to obtain a nano - clay suspension with a mass concentration of 4% - 6%; S2. Add cetyltrimethylammonium bromide to deionized water, stir and dissolve to obtain a cetyltrimethylammonium bromide solution with a mass concentration of 2% - 4%. Add the cetyltrimethylammonium bromide solution to the nano - clay suspension, continuously stir at 50 - 70°C for 2 - 4h, filter, wash, dry, pulverize, and sieve to obtain modified nano - clay.
7. The high-barrier oxygen PET composite material according to claim 6, wherein, The mass ratio of the cetyltrimethylammonium bromide to the nano - clay is 1:(5 - 10).
8. The high-barrier oxygen PET composite material according to claim 1, characterized in that, The high - oxygen - barrier PET composite material raw materials also include 10 - 20 parts by weight of polyamide.
9. A high-oxygen-barrier pharmaceutical packaging bottle prepared from the high-oxygen-barrier PET composite material according to any one of claims 1-8, characterized in that, It is prepared by the following steps: Extrude and pelletize the high - oxygen - barrier PET composite material according to any one of claims 1 - 5 at 260 - 270°C, injection - mold to form a preform, heat, cool, place the preform in a mold, preliminarily blow the preform into the cavity of a beverage bottle with gas, stretch the preform, blow high - pressure air into the pre - blown and stretched preform to form a packaging bottle, cool and shape, and demold to obtain a high - oxygen - barrier pharmaceutical packaging bottle.