Medical ultra-transparent propylene-butadiene binary co-polypropylene material as well as preparation method and application thereof

Abstract

The invention discloses a medical ultra-transparent propylene-butadiene binary co-polypropylene material as well as a preparation method and application thereof, and belongs to the field of high polymer materials. The invention provides a medical ultra-transparent propylene-butadiene binary co-polypropylene material, which is prepared from the following raw materials in parts by weight: 75 to 85 parts of propylene; 15 to 25 parts of butylene; 0.1 to 0.5 part of a medical transparent nucleating agent; 0.1 to 0.5 part of an antioxidant; and 0.2 to 0.8 part of a biological compatilizer. The haze of the medical ultra-transparent propylene-butadiene binary co-polypropylene material provided by the invention can be as low as 5% or below, the light transmittance is as high as 98% or above, and the medical ultra-transparent propylene-butadiene binary co-polypropylene material has ultra-high transparency so as to accord with the harsh standard of the medical field on the transparency of the material, and has irreplaceable important significance in the aspects of visual operation of medical instruments and the like.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to a medical super-transparent propylene-butylene binary copolymer polypropylene material and a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not be necessarily regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] Transparent polypropylene (PP) material is made transparent by adding a second copolymer monomer to the PP molecular chain, destroying the regularity of the molecular chain segment, reducing the size of the spherulites, or by adding an efficient nucleating agent to increase the crystallization rate of PP to obtain smaller spherulites. When ethylene monomer is used for copolymerization, although the transparency can be improved, the bending modulus of the product will be reduced and the content of n-hexane extract will increase, which cannot meet the high hygiene standards for food and medical product packaging. Therefore, in order to meet the requirements of food and medical packaging, propylene-butene copolymers with high isotacticity, less n-hexane or n-heptane extractables, uniform lamella thickness, high rigidity index (bending modulus), and better rigidity-toughness balance have ushered in development opportunities. The random copolymer of propylene and butene presents unique properties with the change of 1-butene content. When the content is low, it is close to homopolymerized polypropylene. When the content increases, the bending modulus decreases and the impact strength increases. The rigidity-toughness balance is better than that of ethylene-propylene random copolymer polypropylene, and it has less xylene solubles, low n-hexane extract content, and good transparency. It shows broad application prospects in the medical or food packaging industry and film fields.

[0004] In the medical field, there are strict requirements for the transparency, biocompatibility, and mechanical properties of materials. Traditional polypropylene materials have deficiencies in transparency and certain properties, making it difficult to meet the needs of high-end medical applications. Propylene-butadiene binary copolymer polypropylene has improved the performance of polypropylene to a certain extent, but the existing propylene-butadiene binary copolymer polypropylene still has room for improvement in medical applications, especially in meeting the synergy of high transparency, good biocompatibility, and excellent mechanical properties. Summary of the invention

[0005] In order to solve the deficiencies of the prior art, the purpose of the present invention is to provide a medical super-transparent propylene-butylene copolymer polypropylene material and its preparation method and application. The medical super-transparent propylene-butylene copolymer polypropylene material provided by the present invention can have a haze as low as less than 5% and a light transmittance as high as more than 98%, and has ultra-high transparency to meet the strict standards for material transparency in the medical field.

[0006] In order to achieve the above object, the technical solution of the present invention is:

[0007] In a first aspect, the present invention provides a medical super-transparent propylene-butene binary copolymer polypropylene material, comprising the following raw materials in parts by weight: 75-85 parts of propylene; 15-25 parts of butene; 0.1-0.5 parts of a medical transparent nucleating agent; 0.1-0.5 parts of an antioxidant; and 0.2-0.8 parts of a biocompatible agent.

[0008] In a second aspect, the present invention provides a method for preparing the above-mentioned medical super-transparent propylene-butadiene binary copolymer polypropylene material, comprising the following steps:

[0009] Propylene, butene, a medical transparent nucleating agent, an antioxidant and a biocompatible agent are mixed, and a catalyst is added to carry out copolymerization reaction to obtain a medical super-transparent propylene-butene binary copolymer polypropylene material.

[0010] In a third aspect, the present invention provides the application of the above-mentioned medical super-transparent propylene-butadiene binary copolymer polypropylene material in the medical field.

[0011] One or some of the above technical solutions have the following advantages or beneficial effects:

[0012] 1. The medical super-transparent propylene-butylene binary copolymer polypropylene of the present invention exhibits excellent ultra-high transparency, with a haze value as low as 5% or less and a light transmittance of more than 98%. It can accurately meet the stringent requirements of the medical field for material transparency and has irreplaceable significance in the visual operation of medical devices. The core of the present invention lies in the unique formula design. By accurately adjusting the proportions of propylene, butylene, medical transparent nucleating agent, antioxidant and polylactic acid as a biocompatible agent, the transparency, mechanical properties and biocompatibility of the material are synergistically improved to meet the high-standard requirements of the ever-changing medical field.

[0013] 2. The addition of medical transparent nucleating agent can effectively optimize the crystallization morphology of polypropylene, making the material form a finer and more uniform spherulite structure, thereby greatly improving the transparency. In addition, while significantly improving the transparency of the material, it can also enhance the rigidity and heat resistance of the material, giving the material better comprehensive performance. It provides an ideal nucleation site in the crystallization process of polypropylene, making the crystallization process more orderly and efficient, thereby improving the physical and mechanical properties of the material.

[0014] 3. The addition of antioxidants provides a solid guarantee for the stability of the material of the present invention, which can greatly improve the antioxidant properties of the material, effectively extend the service life of the material in a complex medical environment, and reduce the risk of material aging and performance degradation.

[0015] 4. The use of polylactic acid as a biocompatibility agent is the core element to ensure the safety of materials. It makes the material have good biocompatibility and can effectively avoid adverse phenomena such as cytotoxicity and allergic reactions during contact with the human body, providing a reliable material basis for medical applications.

[0016] 5. The preparation method of the present invention has the significant advantage of being simple and easy to implement. It does not require complicated process equipment and cumbersome operating procedures. It is highly suitable for large-scale industrial production and can efficiently and stably provide high-quality, high-performance materials for the medical field, which will effectively promote the development of the medical materials industry. DETAILED DESCRIPTION

[0017] Existing medical polypropylene materials generally have limited transparency, high haze, and low transmittance, which cannot meet the strict requirements for high transparency such as visual operation of medical devices. Some materials also have biocompatibility issues, which may cause cytotoxicity, allergic reactions, etc., posing a potential threat to human health. In addition, it is difficult to achieve a good balance between the comprehensive mechanical properties and transparency of the material, and strength and other properties are often sacrificed when improving transparency. In view of this, the present invention proposes a medical super-transparent propylene-butyl binary copolymer polypropylene material, the haze can be as low as less than 5%, the transmittance is as high as more than 98%, and it has ultra-high transparency to meet the strict standards for material transparency in the medical field. By adding specific 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol as a medical transparent nucleating agent, the polypropylene crystal morphology is optimized, and the rigidity and heat resistance of the material are enhanced while significantly improving the transparency. The introduction of antioxidant 1010 improves the antioxidant performance of the material and extends its service life in the medical environment. Polylactic acid PLA is used as a biocompatible agent to ensure the safety of the material when it comes into contact with the human body. The preparation method of the invention is simple and easy to implement, suitable for large-scale industrial production, and provides a high-performance material solution for the medical field, achieving the coordinated optimization of transparency, mechanical properties and biocompatibility.

[0018] A typical embodiment of the present invention provides a medical super-transparent propylene-butene binary copolymer polypropylene material, which comprises the following raw materials in parts by weight: 75-85 parts of propylene; 15-25 parts of butene; 0.1-0.5 parts of a medical transparent nucleating agent; 0.1-0.5 parts of an antioxidant; and 0.2-0.8 parts of a biocompatible agent.

[0019] In some examples of this embodiment, propylene is 75-80 parts; butene is 20-25 parts; medical transparent nucleating agent is 0.3-0.5 parts; antioxidant is 0.3-0.5 parts; biocompatible agent is 0.5-0.8 parts.

[0020] In some embodiments of this embodiment, the medical transparent nucleating agent is 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol, also known as Meiken 8000, CAS No. 882073-43-0, is commercially available.

[0021] Among them, the mechanism of action of 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol in propane-butane copolymer polypropylene is as follows: 1. Promote crystallization nucleation: As a heterogeneous nucleating agent, it provides preferential nucleation sites for polypropylene molecular chains, reduces crystallization activation energy, accelerates crystallization rate and improves crystallinity, shortens crystallization time to improve production efficiency. 2. Refine grain size: Restrict grain growth, and distribute it evenly in the matrix with good dispersion, promote the formation of many small and uniform grains, which is conducive to improving optical and mechanical properties. 3. Improve transparency: Refining grains can reduce light scattering, improve crystal morphology, make light easier to propagate in a straight line, reduce scattering to enhance transparency. 4. Enhance mechanical properties: Improve crystallinity and refine grains, enhance rigidity, and improve stress transmission and deformation resistance when subjected to force; it can also improve toughness to a certain extent, refine the structure to prevent crack propagation, and improve impact resistance.

[0022] In some examples of this embodiment, the antioxidant is antioxidant 1010, and its chemical name is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0023] In some examples of this embodiment, the biocompatible agent is polylactic acid (PLA).

[0024] Another embodiment of the present invention provides a method for preparing the above-mentioned medical super-transparent propylene-butadiene binary copolymer polypropylene material, comprising the following steps:

[0025] Propylene, butene, a medical transparent nucleating agent, an antioxidant and a biocompatible agent are mixed, and a catalyst is added to carry out copolymerization reaction to obtain a medical super-transparent propylene-butene binary copolymer polypropylene material.

[0026] In some examples of this embodiment, the catalyst is a medical grade catalyst, and the medical grade catalyst is a polypropylene SP catalyst or a Ziegler-Natta catalyst. Among them, the polypropylene SP catalyst used in the present invention is purchased from Lihe Technology, which is a new type of diether polypropylene catalyst, suitable for the polypropylene catalyst of the Spheripol / Spherizone process. The main components of the Ziegler-Natta catalyst are triethylaluminum and titanium tetrachloride.

[0027] In some examples of this embodiment, in the copolymerization reaction, the reaction temperature is 50-80° C., the reaction pressure is 1-3 MPa, and the reaction time is 2-4 hours.

[0028] In some examples of this implementation manner, after the copolymerization reaction is completed, the product is subjected to devolatilization and drying treatment to obtain medical super-transparent propylene-butane binary copolymer polypropylene.

[0029] A third embodiment of the present invention provides an application of the above-mentioned medical super-transparent propylene-butadiene binary copolymer polypropylene material in the medical field.

[0030] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0031] Example 1

[0032] Raw material composition: 75 parts of propylene; 20 parts of butene; 0.3 parts of medical transparent nucleating agent (Millad NX8000); 0.3 parts of antioxidant (1010); 0.5 parts of biocompatibility agent (polylactic acid PLA).

[0033] Preparation method: Propylene, butene, medical transparent nucleating agent, antioxidant and biocompatible agent are added to a polymerization reactor, and copolymerization is carried out under the action of a medical-grade catalyst, the reaction temperature is 65°C, the reaction pressure is 2MPa, and the reaction time is 3 hours. After the reaction is completed, the product is devolatilized and dried to obtain medical super-transparent propylene-butene binary copolymer polypropylene.

[0034] Embodiment 2:

[0035] Raw material composition: 78 parts of propylene; 22 parts of butene; 0.4 parts of medical transparent nucleating agent (Millad NX8000); 0.4 parts of antioxidant (1010); 0.6 parts of biocompatibility agent (polylactic acid PLA).

[0036] Preparation method: The difference from Example 1 is that the reaction temperature is 70°C, the reaction pressure is 2.5 MPa, the reaction time is 3.5 hours, and the other conditions are the same.

[0037] Embodiment 3:

[0038] Raw material composition: 80 parts of propylene; 20 parts of butene; 0.4 parts of medical transparent nucleating agent (Millad NX8000); 0.4 parts of antioxidant (1010); 0.6 parts of biocompatibility agent (polylactic acid PLA).

[0039] Preparation method: The difference from Example 1 is that the reaction temperature is 70°C, the reaction pressure is 1.0 MPa, the reaction time is 2 hours, and the other conditions are the same.

[0040] Embodiment 4:

[0041] Raw material composition: 83 parts of propylene; 17 parts of butene; 0.4 parts of medical transparent nucleating agent (Millad NX8000); 0.4 parts of antioxidant (1010); 0.6 parts of biocompatibility agent (polylactic acid PLA).

[0042] Preparation method: The difference from Example 1 is that the reaction temperature is 75°C, the reaction pressure is 2.5 MPa, the reaction time is 2.5 hours, and the other conditions are the same.

[0043] Embodiment 5:

[0044] Raw material composition: 85 parts of propylene; 15 parts of butene; 0.5 parts of medical transparent nucleating agent (Millad NX8000); 0.5 parts of antioxidant (1010); 0.8 parts of (polylactic acid PLA).

[0045] Preparation method: The difference from Example 1 is that the reaction temperature is 70°C, the reaction pressure is 2.5 MPa, the reaction time is 4 hours, and the other conditions are the same.

[0046] Comparative Example 1:

[0047] The difference from Example 1 is that in the raw material composition, propylene is 100 parts, butene is not added, and the other conditions are the same.

[0048] This comparative example aims to compare the performance differences between propylene-butane binary copolymer and homopolymer polypropylene. The results show that the haze of homopolymer polypropylene increased significantly to 12%, the transmittance decreased, the nominal strain at break was only 506%, the tensile yield stress was 24.8 MPa, and the bending modulus was 800 MPa, indicating the importance of propylene-butane copolymer in improving the comprehensive performance of the material.

[0049] Comparative Example 2:

[0050] The difference from Example 1 is that in the raw material composition, butene is replaced by ethylene, and the other conditions are the same.

[0051] This comparative example is used to reflect the difference in medical properties between propylene-butane copolymer and ethylene-propylene copolymer. It was found that its haze was 10% and although its cytotoxicity was level 0, other properties such as bending modulus (1120MPa) were different from those of propylene-butane copolymer, highlighting the advantages of propylene-butane copolymer in meeting medical hygiene requirements and balancing performance.

[0052] Comparative Example 3:

[0053] The difference from Example 1 is that no transparent nucleating agent (Meiliken) is added to the raw material composition. 8000), and the other conditions are the same.

[0054] This comparative example is used to explore the effect of nucleating agent on material performance. The test results show that the haze increases to 12%, the transmittance decreases significantly, and the bending modulus decreases to 1134MPa, indicating that Meiliken 8000 plays a key role in improving transparency and rigidity.

[0055] Comparative Example 4:

[0056] The difference from Example 1 is that no biocompatible agent (polylactic acid PLA) is added to the raw material composition, and the other conditions are the same.

[0057] This comparative example mainly examines the role of biocompatibility agents. The experiment found that although the cytotoxicity was still at level 0, the cell adhesion and proliferation rate were slightly reduced in the long-term cell culture experiment, indicating that polylactic acid PLA helps to improve the biocompatibility and cell affinity of the material.

[0058] Comparative Example 5:

[0059] The difference from Example 1 is that the raw material composition includes a medical transparent nucleating agent (Meiliken 8000) was replaced with a common sorbitol nucleating agent, and the addition amount was 0.3 parts. The results showed that the haze was 8%, the transmittance was 92%, and the bending modulus was 1050MPa. In comparison, the Meiliken selected in the present invention 8000 performs better in improving transparency and rigidity, indicating that the type of nucleating agent has a significant impact on material properties.

[0060] Comparative Example 6:

[0061] The difference from Example 1 is that the raw material composition is a transparent nucleating agent for Chinese medicine (Meiliken The addition amount of the nucleating agent is 0.05 parts. The test results show that the haze is 6%, the transmittance is 95%, and the bending modulus is 1100MPa. When the addition amount is increased to 0.3 parts (such as Example 1), the haze can be reduced to 3.5%, the transmittance is increased to 98%, and the bending modulus is increased to 1250MPa, indicating that the addition amount of the nucleating agent is positively correlated with the transparency and strength of the material within a certain range.

[0062] The performance test results are shown in Table 1.

[0063] Table 1

[0064]

[0065]

[0066] As can be seen from Table 1, the super-transparent propylene-butadiene binary copolymer polypropylene obtained by the scheme of the present invention has excellent mechanical properties, and its tensile fracture nominal strain is 600-611%, the tensile yield stress is 34.0-36.1MPa, and the simply supported beam notched impact strength is 5.0-7.0KJ / m 2 , haze 3.5-4.5% (1mm), cytotoxicity level 0. The polymer has good rigidity and toughness balance and good transparency, and has good application prospects in the medical or food packaging industry and film fields.

[0067] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A medical super-transparent propylene-butadiene binary copolymer polypropylene material, characterized in that: The invention comprises the following raw materials in parts by weight: 75-85 parts of propylene; 15-25 parts of butene; 0.1-0.5 parts of medical transparent nucleating agent; 0.1-0.5 parts of antioxidant; and 0.2-0.8 parts of biocompatible agent.

2. The medical super-transparent acrylic and butylene copolymer polypropylene material according to claim 1, characterized in that: Propylene 75-80 parts; butene 20-25 parts; medical transparent nucleating agent 0.3-0.5 parts; antioxidant 0.3-0.5 parts; biocompatible agent 0.5-0.8 parts.

3. The medical super-transparent acrylic and butylene copolymer polypropylene material according to claim 1 or 2, characterized in that: The medical transparent nucleating agent is 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol.

4. The medical super-transparent acrylic and butylene copolymer polypropylene material according to claim 1 or 2, characterized in that: The antioxidant is antioxidant 1010.

5. The medical super-transparent propylene-butadiene binary copolymer polypropylene material according to claim 1 or 2, characterized in that: The biocompatible agent is polylactic acid.

6. A method for preparing the medical super-transparent propylene-butadiene binary copolymer polypropylene material as claimed in any one of claims 1 to 5, characterized in that: The following steps are involved: Propylene, butene, a medical transparent nucleating agent, an antioxidant and a biocompatible agent are mixed, and a catalyst is added to carry out copolymerization reaction to obtain a medical super-transparent propylene-butene binary copolymer polypropylene material.

7. The preparation method according to claim 6, characterized in that: The catalyst is a medical grade catalyst. Preferably, the medical grade catalyst is a polypropylene SP catalyst or a Ziegler-Natta catalyst.

8. The preparation method according to claim 6, characterized in that: In the copolymerization reaction, the reaction temperature is 50-80°C, the reaction pressure is 1-3MPa, and the reaction time is 2-4 hours.

9. The preparation method according to claim 6, characterized in that: It also includes the following steps: after the copolymerization reaction is completed, the product is subjected to devolatilization and drying treatment to obtain medical super-transparent propylene-butane binary copolymer polypropylene.

10. Use of the medical super-transparent propylene-butadiene copolymer polypropylene material as claimed in any one of claims 1 to 5 or the medical super-transparent propylene-butadiene copolymer polypropylene material obtained by the preparation method as claimed in any one of claims 6 to 9 in the field of medicine.

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