PET (Polyethylene Terephthalate) solid medicinal hard sheet and preparation method thereof

Abstract

The invention discloses a PET solid medicinal hard sheet and a preparation method thereof, the PET solid medicinal hard sheet comprises PET, a stabilizer, a plasticizer, a lubricant and an antioxidant, the stabilizer comprises a modified nano titanium carbide sheet, hydroxymethyl cellulose and a stability regulator, the modified nano titanium carbide sheet contains Ti3C2A, and A is an oxygen-containing or fluorine-containing functional group. According to the invention, the interaction between the modified nano titanium carbide sheet and hydroxymethyl cellulose is utilized to form a sheet-line combined structure with a limiting effect on the plasticizer, so that the emigration rate of the plasticizer is greatly reduced, and meanwhile, the stability of the material is also well promoted.

Description

Technical Field

[0001] This invention belongs to the field of pharmaceutical packaging technology, specifically relating to a PET solid pharmaceutical rigid sheet and its preparation method. Background Technology

[0002] Pharmaceutical packaging materials can protect tablets from contamination by bacteria and other microorganisms, making pharmaceutical packaging of immeasurable importance.

[0003] Existing packaging materials for tablet-type pharmaceuticals are mainly composite rigid sheet structures, including PVC (polyvinyl chloride) and PVC / PE. These packaging materials need to have good barrier properties against water vapor and oxygen. However, PVC has limited barrier properties against water vapor and oxygen, and PVC packaging materials are also not stable enough under high temperature and light conditions, making them unable to meet the increasingly harsh external environment.

[0004] PET, or polyethylene terephthalate, is a thermoplastic polyester. Due to its excellent mechanical properties, high rigidity, and good toughness, it is widely used in pharmaceutical packaging. For example, patent document CN104527160A discloses a hot-molded composite aluminum rigid sheet, in which the PET layer is composited with PBT, glass fiber, plasticizer, lubricant, etc. The plasticizer used is polyethylene glycol with a molecular weight of 800-1500. Since plasticizing is required during the preparation of pharmaceutical rigid sheets, the plasticizer can improve the plasticizing effect. However, the polyethylene glycol plasticizer used is prone to migration due to its polarity, leading to deformation of the rigid sheet during use and storage, which is detrimental to drug preservation. Furthermore, plasticizer migration may weaken the barrier properties and high-temperature stability of the pharmaceutical rigid sheet, affecting the quality of drug preservation. Therefore, it is necessary to research and develop a pharmaceutical PET rigid sheet with minimal plasticizer migration, good high-temperature stability, and excellent barrier properties.

[0005] Therefore, this patent application is filed. Summary of the Invention

[0006] To address the above issues, the purpose of this patent application is to provide a PET solid pharmaceutical rigid sheet and its preparation method, which restricts the plasticizer, reduces the migration of the plasticizer, and significantly improves its performance.

[0007] This invention is achieved through the following technical solution: The first objective of this invention is to provide a PET solid pharmaceutical rigid sheet, comprising PET, a stabilizer, a plasticizer, a lubricant, and an antioxidant. The stabilizer comprises modified nano-titanium carbide sheets, hydroxymethyl cellulose, and a stabilizing regulator. The modified nano-titanium carbide sheets contain Ti3C2A, wherein A is an oxygen-containing or fluorine-containing functional group.

[0008] In this invention, the stabilizer contains two-dimensional modified titanium carbide nanosheets. The Ti3C2A contained in these nanosheets has oxygen-containing or fluorine-containing groups, where the oxygen-containing groups can be -OH, =O, -O, etc., and the fluorine-containing groups can be -F. The preferred oxygen-containing group is -OH. Hydroxymethyl cellulose has a linear structure with numerous oxygen-containing groups, which can form a linear-sheet interlaced structure with the two-dimensional modified titanium carbide nanosheets. This linear-sheet combined structure can restrict the plasticizer, greatly promoting its non-migration. Simultaneously, this two-dimensional spatial structure also stabilizes the stabilizer, giving the pharmaceutical hard tablets excellent stability under light, high temperature, and humidity conditions, significantly improving the material's preservation stability.

[0009] In this invention, hydroxymethyl cellulose is chosen because it improves the toughness of the material and helps with subsequent plasticizing and molding, preventing material fracture during the molding process. Titanium carbide can improve the material's thermal stability, chemical stability, and strength.

[0010] As a preferred design, the mass ratio of PET, stabilizer, plasticizer, lubricant and antioxidant is (70~80):(6~15):(40~60):(0.3~0.8):(5~10).

[0011] As a preferred design, the stabilizer is a calcium-zinc heat stabilizer and / or a tin heat stabilizer.

[0012] As a preferred design, the calcium-zinc stabilizer is at least one of zinc octanoate, zinc stearate, and polyvinyl alcohol; The tin heat stabilizer is dimethyltin dithioacetate isooctyl ester.

[0013] As a preferred design, the weight ratio of modified nano-titanium carbide sheets, hydroxymethyl cellulose, and stabilizer in the stabilizer is (5~9):(2~4):(1~3).

[0014] This invention rationally designs the proportions of each component in the stabilizer to achieve an overall improvement and balance in plasticizer migration and material toughness.

[0015] As a preferred design, the plasticizer is a complex of trioctyl trimellitate and tributyl citrate, wherein the mass ratio of tributyl citrate to trioctyl trimellitate is 1:(0.5~2).

[0016] In this invention, trioctyl trimellitate and tributyl citrate are used as a plasticizer. Polyethylene terephthalate (PET) contains both ester and hydroxyl groups. Trioctyl trimellitate primarily interacts with the hydroxyl groups in PET, while tributyl citrate contains both hydroxyl and ester groups and has multiple alkyl chains, which primarily interact with the ester groups in PET. Furthermore, the multiple alkyl chains increase the spacing between PET esters, thus improving plasticizing performance. Simultaneously, the linear and sheet-like structure formed by the interaction of two-dimensional titanium carbide nanosheets and hydroxymethyl cellulose also provides a certain spacing effect between PET esters, further enhancing the plasticizing properties of PET. Therefore, this invention, through the ingenious design of the trioctyl trimellitate and tributyl citrate compound, and the synergistic linear-sheet structure formed by the interaction of two-dimensional titanium carbide nanosheets and hydroxymethyl cellulose, significantly improves the plasticizing performance of PET materials.

[0017] As a preferred design, the lubricant is a composite of oxidized polyethylene wax and acrylate copolymer, wherein the mass ratio of oxidized polyethylene wax to acrylate copolymer is (2~5):(1~5).

[0018] In this invention, oxidized polyethylene wax and acrylate copolymers are used as a lubricant. The oxidized polyethylene wax provides lubrication, while the acrylate copolymers, with their core-shell microstructure, exhibit good compatibility with the oxidized polyethylene wax. Furthermore, the use of oxidized polyethylene wax improves the dispersibility of the acrylate copolymers, thereby enhancing the compatibility between the acrylate copolymers and PET, which is beneficial for improving the impact resistance of PET, the main component. The oxidized polyethylene wax and the core-shell acrylate copolymers are embedded between trioctyl trimellitate and tributyl citrate. The carbon-carbon double bonds in the acrylate copolymers' structure, together with the modified nano-titanium carbide flakes and hydroxymethyl cellulose in the stabilizer, form a multi-dimensional network structure. This multi-dimensional network structure can resist various external impacts, forming an elastic buffer and collectively improving the impact resistance of the pharmaceutical hard tablets.

[0019] As a preferred design, the antioxidant is a triphosphite.

[0020] A second objective of this invention is to provide a method for preparing a PET solid pharmaceutical hard sheet as described in any of the above claims, comprising the following steps: (1) Dry the PET, then weigh the dried PET according to the ratio, add stabilizer, plasticizer, lubricant and antioxidant to it, and then mix it thoroughly by high-speed stirring; (2) The mixed material is fed through the feed port of the twin-screw extruder, and then the extruded material is cooled, air-dried, pelletized and dried. (3) The product obtained in (2) is placed into a calender for calendering. The calendered hard sheet is then rolled up and cut to obtain the PET solid pharmaceutical hard sheet.

[0021] As a preferred design, the preparation process of the modified nano-titanium carbide sheet is as follows: After etching the aluminum phase with acid, titanium aluminum carbide powder is centrifuged and ultrasonically peeled to remove the precipitate. The supernatant is then taken to obtain a suspension of modified nano-titanium carbide sheets containing Ti3C2A. The acid solution is any one of hydrochloric acid, sulfuric acid, and hydrofluoric acid; The stabilizer is prepared by mixing the modified nano-titanium carbide sheet suspension with hydroxymethyl cellulose and a stabilizer.

[0022] Compared with the prior art, the present invention has the following advantages and beneficial effects: 1. The present invention provides a PET solid pharmaceutical hard sheet and its preparation method. The two-dimensional modified nano-titanium carbide sheet and the linear interlaced structure formed by hydroxymethyl cellulose form a limiting effect on plasticizer, which greatly promotes the non-migration of plasticizer. At the same time, it also has a stabilizing effect on the stabilizer, so that the pharmaceutical hard sheet has good stability under light, high temperature and humidity conditions, and greatly improves the stability of material storage.

[0023] 2. The PET solid pharmaceutical hard sheet and its preparation method provided in the embodiments of the present invention have a reasonable design of compound plasticizers, which greatly improves the plasticizing performance of PET materials.

[0024] 3. The PET solid pharmaceutical hard sheet and its preparation method provided in the embodiments of the present invention have a rationally designed compounded lubricant, especially the core-shell microstructure of acrylate copolymers, which, together with modified nano-titanium carbide sheets and hydroxymethyl cellulose, form a multi-dimensional network structure that can resist external impacts from multiple aspects, form elastic buffering force, and jointly improve the impact resistance and toughness of the pharmaceutical hard sheet, and increase the elongation at break. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The illustrative embodiments and descriptions of this invention are only used to explain this invention and are not intended to limit this invention.

[0026] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60–120 and 80–110 are listed for a specific parameter, it is understood that ranges of 60–110 and 80–120 are also expected. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1–3, 1–4, 1–5, 2–3, 2–4, and 2–5. In this application, unless otherwise stated, the numerical range "a–b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0027] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0028] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0029] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. The process is performed sequentially. For example, the method includes steps (a) and (b), indicating that the method may include step (a) performed sequentially. (b) may also include steps (b) and (a) performed sequentially. For example, the method may also include step (c). This indicates that step (c) can be added to the method in any order; for example, the method may include steps (a), (b), and (c). It may also include steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0030] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0031] Example 1: A PET solid pharmaceutical rigid sheet, by weight, comprises the following components: 70 parts PET, 8 parts stabilizer, 45 parts plasticizer, 0.6 parts lubricant, and 8 parts antioxidant.

[0032] The stabilizer includes modified nano-titanium carbide sheets, hydroxymethyl cellulose, and a stabilizer in a mass ratio of 5:2:3. The stabilizer is polyvinyl alcohol.

[0033] The plasticizer is a compound of trioctyl trimellitate and tributyl citrate, with a mass ratio of 1:2.

[0034] The lubricant is a complex of oxidized polyethylene wax and acrylate copolymer, with a mass ratio of 5:2.

[0035] The antioxidant is triphosphite.

[0036] Prepared using the following process: 1. Dry the PET at 120℃ for 3 hours, then set aside for use; 2. Weigh the dried PET according to the formula, add stabilizer, plasticizer, lubricant and antioxidant, and then mix thoroughly by high-speed stirring; 3. The mixed material is fed into the feed port of the twin-screw extruder. The extrusion temperature of the twin-screw extruder is 120℃. The extruded material is then cooled, air-dried, pelletized, and dried to form masterbatch. 4. Place the masterbatch into a calender for calendering. Set the calendering temperature to 180℃. Then, roll the calendered hard sheet and cut it into the required shape and size to obtain PET solid pharmaceutical hard sheets for packaging.

[0037] The preparation process of modified nano-titanium carbide sheets is as follows: 1. Take 10 mL of a solution with a concentration of 5 mol·L⁻¹ -1 Hydrochloric acid and 0.5g of lithium fluoride were placed in a reactor and mixed evenly. 2.5g of 350-mesh precursor titanium aluminum carbide (Ti3AlC2) powder was slowly added, and the mixture was heated to 80℃ to perform acid etching of the aluminum phase.

[0038] 2. After the reaction is completed, centrifuge to obtain the etched solid phase, then centrifuge again and ultrasonically peel off at 200W power for 1 hour to remove the precipitate, thus obtaining a suspension of modified nano-titanium carbide sheets containing Ti3C2A.

[0039] The stabilizer is prepared by uniformly mixing the modified nano-titanium carbide sheet suspension with hydroxymethyl cellulose and a stabilizer.

[0040] The plasticizer is prepared by mixing trioctyl trimellitate and tributyl citrate evenly.

[0041] The lubricant is prepared by uniformly mixing oxidized polyethylene wax with acrylate copolymer.

[0042] Example 2: A PET solid pharmaceutical rigid sheet, by weight, comprises the following components: 80 parts PET, 6 parts stabilizer, 40 parts plasticizer, 0.8 parts lubricant, and 10 parts antioxidant.

[0043] The stabilizer includes modified nano-titanium carbide sheets, hydroxymethyl cellulose, and a stabilizer in a mass ratio of 9:3:2. The stabilizer is polyvinyl alcohol.

[0044] The plasticizer is a compound of trioctyl trimellitate and tributyl citrate, with a mass ratio of 1:1.

[0045] The lubricant is a complex of oxidized polyethylene wax and acrylate copolymer, with a mass ratio of 4:3.

[0046] The antioxidant is triphosphite.

[0047] Prepared using the following process: 1. Dry the PET at 120℃ for 3 hours, then set aside for use; 2. Weigh the dried PET according to the formula, add stabilizer, plasticizer, lubricant and antioxidant, and then mix thoroughly by high-speed stirring; 3. The mixed material is fed into the feed port of the twin-screw extruder. The extrusion temperature of the twin-screw extruder is 120℃. The extruded material is then cooled, air-dried, pelletized, and dried to form masterbatch. 4. Place the masterbatch into a calender for calendering. Set the calendering temperature to 180℃. Then, roll the calendered hard sheet and cut it into the required shape and size to obtain PET solid pharmaceutical hard sheets for packaging.

[0048] The preparation process of modified nano-titanium carbide sheets is as follows: 1. Take 10 mL of a solution with a concentration of 5 mol·L⁻¹ -1 Hydrochloric acid and 0.5g of lithium fluoride were placed in a reactor and mixed evenly. 2.5g of 350-mesh precursor titanium aluminum carbide (Ti3AlC2) powder was slowly added, and the mixture was heated to 80℃ to perform acid etching of the aluminum phase.

[0049] 2. After the reaction is completed, centrifuge to obtain the etched solid phase, then centrifuge again and ultrasonically peel off at 200W power for 1 hour to remove the precipitate, thus obtaining a suspension of modified nano-titanium carbide sheets containing Ti3C2A.

[0050] The stabilizer is prepared by uniformly mixing the modified nano-titanium carbide sheet suspension with hydroxymethyl cellulose and a stabilizer.

[0051] The plasticizer is prepared by mixing trioctyl trimellitate and tributyl citrate evenly.

[0052] The lubricant is prepared by uniformly mixing oxidized polyethylene wax with acrylate copolymer.

[0053] Example 3: A PET solid pharmaceutical rigid sheet, by weight, comprises the following components: 70 parts PET, 15 parts stabilizer, 60 parts plasticizer, 0.3 parts lubricant, and 5 parts antioxidant.

[0054] The stabilizer includes modified nano-titanium carbide sheets, hydroxymethyl cellulose, and a stabilizer in a mass ratio of 8:3:1. The stabilizer is isooctyl dithioacetate dimethyltin.

[0055] The plasticizer is a complex of trioctyl trimellitate and tributyl citrate, with a mass ratio of 1:0.5.

[0056] The lubricant is a complex of oxidized polyethylene wax and acrylate copolymer, with a mass ratio of 2:5.

[0057] The antioxidant is triphosphite.

[0058] The preparation process is the same as in Example 1.

[0059] Example 4: A PET solid pharmaceutical rigid sheet, by weight, comprises the following components: 78 parts PET, 9 parts stabilizer, 55 parts plasticizer, 0.7 parts lubricant, and 5 parts antioxidant.

[0060] The stabilizer includes modified nano-titanium carbide sheets, hydroxymethyl cellulose, and a stabilizer in a mass ratio of 9:3.5:2. The stabilizer is a composite of dimethyltin dithioacetate and zinc stearate.

[0061] The plasticizer is a complex of trioctyl trimellitate and tributyl citrate, with a mass ratio of 1:1.2.

[0062] The lubricant is a complex of oxidized polyethylene wax and acrylate copolymer, with a mass ratio of 4:2.

[0063] The antioxidant is triphosphite.

[0064] The preparation process is the same as in Example 1.

[0065] Comparative Example 1: A PET solid pharmaceutical rigid sheet, by weight, comprises the following components: 70 parts PET, 8 parts stabilizer, 45 parts plasticizer, 0.6 parts lubricant, and 8 parts antioxidant.

[0066] The stabilizer includes modified nano-titanium carbide sheets and a stabilizer in a mass ratio of 5:3. The stabilizer is polyvinyl alcohol.

[0067] Everything else is the same as in Example 1.

[0068] Comparative Example 2: A PET solid pharmaceutical rigid sheet, by weight, comprises the following components: 70 parts PET, 8 parts stabilizer, 45 parts plasticizer, 0.6 parts lubricant, and 8 parts antioxidant.

[0069] The stabilizer includes hydroxymethyl cellulose and a stabilizer in a mass ratio of 2:3. The stabilizer is polyvinyl alcohol.

[0070] Everything else is the same as in Example 1.

[0071] Comparative Example 3: The difference from Example 1 is that the plasticizer used is trioctyl trimellitate, while the rest are the same as in Example 1.

[0072] Comparative Example 4: The difference from Example 1 is that the plasticizer used is tributyl citrate, while the rest are the same as in Example 1.

[0073] Comparative Example 5: The difference from Example 1 is that the lubricant is oxidized polyethylene wax, while the rest are the same as in Example 1.

[0074] Comparative Example 6: The difference from Example 1 is that the lubricant is an acrylate copolymer, while the rest are the same as in Example 1.

[0075] Comparative Example 7: The plasticizer is polyethylene glycol, and everything else is the same as in Example 1.

[0076] Comparative Example 8: The lubricant was polyethylene wax, and everything else was the same as in Example 1.

[0077] Results test: 1. Barrier performance test The pharmaceutical hard sheets obtained in each embodiment and comparative example were subjected to oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) tests using standard barrier performance testing methods. The results are shown in Table 1.

[0078] Table 1

[0079] As shown in Table 1, the barrier properties against oxygen and water vapor were good in all embodiments. However, in Comparative Example 1, the absence of hydroxymethyl cellulose in the stabilizer resulted in the failure to form an interlacing structure, reducing the stability of the rigid sheet and negatively impacting its barrier properties against oxygen and water vapor. Similarly, in Comparative Example 2, the lack of an interlacing structure also reduced the overall stability of the rigid sheet, leading to a certain degree of reduction in its barrier properties against oxygen and water vapor. In Comparative Examples 3, 4, and 7, changing the plasticizer composition had little impact on the barrier properties of the rigid sheet; in Comparative Examples 5, 6, and 8, changing the lubricant composition also resulted in good barrier properties.

[0080] The inventors conducted plasticizer migration tests on the pharmaceutical hard tablets obtained in each embodiment and comparative example. The specific test method was as follows: a certain amount of pharmaceutical hard tablets was weighed, placed in 60 mL of water at 50°C, pressurized to 100 kPa, soaked for 3 hours, removed, evaporated to dryness in a water bath, dried at 100°C ± 5°C for 2 hours, cooled in a desiccator for 0.5 hours, weighed, dried again at 100°C ± 5°C for 1 hour, removed, cooled in a desiccator for 0.5 hours, weighed, and a blank test was performed simultaneously to calculate the migration amount (‰). The results are shown in Table 2.

[0081] Table 2

[0082] As shown in Table 2, the amount of plasticizer migration in each of the embodiments of the present invention is relatively small. However, in Comparative Example 1, where hydroxymethyl cellulose is absent, the amount of plasticizer migration increases. In Comparative Example 2, where modified nano-titanium carbide sheets are absent, the amount of plasticizer migration continues to increase. This is mainly because a sheet-line bond structure is not formed, and the modified nano-titanium carbide sheets form a good bond with the plasticizer, resulting in a larger amount of migration. The amount of plasticizer migration in Comparative Examples 3-7 is not large, but it is still somewhat increased compared to the embodiments, indicating that the composition of the plasticizer and the lubricant both have a certain influence on the amount of migration.

[0083] The inventors continued to test the tensile strength, impact resistance, and elongation at break of the plasticized films obtained in each embodiment and comparative example. Conventional methods were used for the specific testing, and the results are shown in Table 3.

[0084] Table 3

[0085] As shown in Table 3, the tensile strength of the pharmaceutical hard sheets in all embodiments of the present invention is relatively high. In Comparative Example 1, the absence of hydroxymethyl cellulose has a certain but not significant impact on the tensile strength. In Comparative Example 2, the absence of modified nano-titanium carbide sheets leads to a significant decrease in tensile strength. The tensile strength of Comparative Examples 3-8 remains at a generally good level.

[0086] As can be seen from the comparison of impact resistance, the various embodiments of the present invention have excellent impact resistance. However, the lack of hydroxymethyl cellulose in Comparative Example 1 resulted in a decrease in impact resistance. The impact resistance in Comparative Example 2 was not significantly affected. The impact resistance in Comparative Examples 3 and 4 remained good. However, the lack of the compound of oxidized polyethylene wax and acrylate copolymer as a lubricant in Comparative Examples 5 and 6 resulted in a significant decrease in impact resistance.

[0087] Regarding elongation at break, the elongation at break in all embodiments was higher than 250%. However, the absence of hydroxymethyl cellulose in Comparative Example 1 significantly impacted the material's toughness, resulting in a marked decrease in elongation at break. Similarly, the absence of modified nano-titanium carbide sheets in Comparative Example 2 also affected the material's toughness to some extent. In Comparative Examples 3 and 4, the lack of a combination of trioctyl trimellitate and tributyl citrate as plasticizers reduced plasticizing properties, leading to a decrease in elongation at break. In Comparative Examples 5 and 6, the use of a single lubricant also significantly reduced the material's toughness. In particular, Comparative Example 6, lacking a core-shell microstructure acrylate copolymer, failed to form a multi-dimensional network structure, thus failing to provide elastic buffering force, resulting in reduced impact resistance and elongation at break. Comparative Example 7 used conventional polyethylene glycol as a plasticizer, which had a very limited effect on improving the material's plasticizing properties, far less effective than the plasticizer of this invention.

[0088] The above specific embodiments further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above are merely specific embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A PET solid pharmaceutical rigid sheet, characterized in that, It includes PET, stabilizers, plasticizers, lubricants, and antioxidants. The stabilizers include modified nano-titanium carbide sheets, hydroxymethyl cellulose, and stabilizer modifiers. The modified nano-titanium carbide sheets contain Ti3C2A, where A is an oxygen- or fluorine-containing functional group.

2. The PET solid pharmaceutical rigid sheet according to claim 1, characterized in that, The mass ratio of PET, stabilizer, plasticizer, lubricant and antioxidant is (70~80): (6~15): (40~60): (0.3~0.8): (5~10).

3. The PET solid pharmaceutical rigid sheet according to claim 1, characterized in that, The stabilizer is a calcium-zinc heat stabilizer and / or a tin heat stabilizer.

4. The PET solid pharmaceutical rigid sheet according to claim 3, characterized in that, The calcium-zinc stabilizer is at least one of zinc octanoate, zinc stearate, and polyvinyl alcohol. The tin heat stabilizer is dimethyltin dithioacetate isooctyl ester.

5. A PET solid pharmaceutical rigid sheet according to claim 1, characterized in that, In the stabilizer, the weight ratio of modified nano-titanium carbide sheets, hydroxymethyl cellulose, and stabilizer is (5~9):(2~4):(1~3).

6. A PET solid pharmaceutical rigid sheet according to claim 1, characterized in that, The plasticizer is a complex of trioctyl trimellitate and tributyl citrate, wherein the mass ratio of tributyl citrate to trioctyl trimellitate is 1:(0.5~2).

7. A PET solid pharmaceutical rigid sheet according to claim 1, characterized in that, The lubricant is a composite of oxidized polyethylene wax and acrylate copolymer, wherein the mass ratio of oxidized polyethylene wax to acrylate copolymer is (2~5):(1~5).

8. A PET solid pharmaceutical rigid sheet according to claim 1, characterized in that, The antioxidant is triphosphite.

9. A method for preparing a PET solid pharmaceutical hard sheet according to any one of claims 1 to 8, characterized in that, Includes the following steps: (1) Dry the PET, then weigh the dried PET according to the ratio, add stabilizer, plasticizer, lubricant and antioxidant to it, and then mix it thoroughly by high-speed stirring; (2) The mixed material is fed through the feed port of the twin-screw extruder, and then the extruded material is cooled, air-dried, pelletized and dried. (3) The product obtained in (2) is placed into a calender for calendering. The calendered hard sheet is then rolled up and cut to obtain the PET solid pharmaceutical hard sheet.

10. A method for preparing a PET solid pharmaceutical hard sheet according to claim 9, characterized in that, The preparation process of the modified nano-titanium carbide sheet is as follows: After etching the aluminum phase with acid, titanium aluminum carbide powder is centrifuged and ultrasonically peeled to remove the precipitate. The supernatant is then taken to obtain a suspension of modified nano-titanium carbide sheets containing Ti3C2A. The acid solution is any one of hydrochloric acid, sulfuric acid, and hydrofluoric acid; The stabilizer is prepared by mixing the modified nano-titanium carbide sheet suspension with hydroxymethyl cellulose and a stabilizer.

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