P3ht composite material, preparation method and application thereof

Abstract

The application discloses a P3HT composite material and a preparation method and application thereof, and the raw material of the P3HT composite material comprises polyolefin and P3HT, wherein the regularity of the P3HT is 88-92%. The P3HT is stably present in the form of nanometer size in the composite material by adding the P3HT with the regularity of 88-92% into the polyolefin, and then high-efficiency and long-lasting antibacterial effect based on a mechanism of photodynamic therapy is obtained.

Description

Technical Field

[0001] This invention belongs to the field of P3HT composite material technology, and particularly relates to a P3HT composite material, its preparation method and application. Background Technology

[0002] Polyolefin materials (such as polyethylene and polypropylene) have outstanding advantages such as low cost, good mechanical properties, chemical inertness, and ease of processing and molding, making them a common matrix for the preparation of medical films, catheters, implants, and food packaging. However, polyolefins themselves do not possess antibacterial activity, and their polarity is extremely low, making it difficult for common photosensitizers to be uniformly dispersed at the nanoscale within them. This results in limited photosensitization efficiency and low reactive oxygen species yield, making it difficult to meet the requirements for highly efficient antibacterial properties.

[0003] Polythiophene is a typical conjugated conductive polymer with excellent light absorption, good photostability and tunable band structure, and has attracted much attention in the fields of optoelectronic devices and biomedicine.

[0004] The basic principle of photodynamic therapy (PDT) is that when a photosensitizer is irradiated with light of a specific wavelength, it transfers energy to surrounding oxygen molecules, generating reactive oxygen species (such as singlet oxygen and superoxide anions). These strong oxidizing substances can indiscriminately attack the cell membrane, proteins, and nucleic acids of bacteria, thereby rapidly killing pathogens and minimizing the likelihood of inducing drug resistance. Therefore, antibacterial products based on photodynamic therapy have become a research hotspot.

[0005] Therefore, how to provide a P3HT composite material in which polythiophene exists stably in a nanoscale form and can achieve a highly efficient and long-lasting antibacterial effect based on the photodynamic therapy mechanism is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] To address the shortcomings of the existing technology, a P3HT composite material, its preparation method, and its application are provided. By adding P3HT with a regularity of 88-92% to polyolefin, P3HT is stably present in the composite material in a nanoscale form, thereby obtaining a highly efficient and long-lasting antibacterial effect based on the photodynamic therapy mechanism.

[0007] The purpose of this invention is to provide a P3HT composite material, the raw materials of which include polyolefin and P3HT, wherein the regularity of the P3HT is 88-92%.

[0008] This invention, by adding P3HT of the aforementioned regularity to polyolefins, enables P3HT to exist stably in the composite material at the nanoscale, thereby achieving a highly efficient and long-lasting antibacterial effect based on the photodynamic therapy mechanism. Specifically, the aforementioned regularity of P3HT in polyolefins facilitates self-assembly into nanoscale regions and simultaneously undergoes co-crystallization with the polyolefin matrix to achieve the formation of uniform and stable nanoscale regions within the polyolefin.

[0009] In addition, in some specific embodiments, the regularity of the P3HT can be 88.5%, 89%, 89.5%, 90%, 90.5%, 91% or 91.5%.

[0010] Furthermore, the nanoscale refers to a size less than 100 nm. In some specific embodiments, the nanoscale is 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, or 90 nm.

[0011] In some embodiments of the present invention, the P3HT is 0.008-3 wt%, preferably 0.01-1 wt%, based on 100 wt% of the raw material. In some specific embodiments, it may be 0.009 wt%, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.4 wt%, 2.6 wt%, or 2.8 wt%.

[0012] In some embodiments of the present invention, the number-average molecular weight of the thiophene copolymer is 10-40 kDa, and the molecular weight distribution is 1.1-3.0.

[0013] In some embodiments of the present invention, the polyolefin is selected from at least one of polyethylene, polypropylene, polybutene, binary polypropylene, ternary polypropylene, poly(4-methyl-1-pentene), and polyolefin elastomers (such as ethylene-octene elastomers). Furthermore, based on 100 wt% of the raw material, the polyolefin comprises 95 to 99.992 wt%. Additionally, the binary polypropylene is a binary propylene copolymer obtained by copolymerizing propylene with another olefin monomer, such as a common ethylene-propylene copolymer, specifically a random copolymer polypropylene or a block copolymer polypropylene obtained by copolymerizing ethylene and propylene; the ternary polypropylene is a ternary propylene copolymer obtained by copolymerizing propylene with two other olefin monomers, such as a common propylene-ethylene-butene copolymer, propylene-ethylene-hexene copolymer, or propylene-ethylene-diene copolymer.

[0014] In some embodiments of the present invention, the raw materials may also include some processing aids, such as antioxidants, light stabilizers, heat stabilizers, compatibilizers, dispersants, etc.

[0015] Another object of the present invention is to provide a method for preparing the above-mentioned P3HT composite material, which includes the following steps:

[0016] S1. Take a portion of the polyolefin and prepare a polyolefin solution;

[0017] S2. Take P3HT and prepare a P3HT solution;

[0018] S3. After mixing the polyolefin solution obtained in S1 with the P3HT solution obtained in S2 to form a homogeneous solution, add a poor solvent and precipitate to obtain the matrix material;

[0019] S4. Blend the matrix material obtained in S3 with the remaining polyolefin and melt extrude to obtain the P3HT composite material.

[0020] In some embodiments of the present invention, the preparation method includes the following specific steps:

[0021] S1. Crush the polyolefin into powder, take a portion of the polyolefin powder and mix it with an organic solvent, heat until dissolved, and obtain a polyolefin solution;

[0022] S2. Mix P3HT with an organic solvent and heat until dissolved to obtain a P3HT solution;

[0023] S3. Mix the polyolefin solution obtained in S1 and the P3HT solution obtained in S2 into a homogeneous solution, add a poor solvent, precipitate, and obtain the matrix material;

[0024] S4. The matrix material obtained in S3 is blended with the remaining polyolefin powder and melt-extruded to obtain the P3HT composite material.

[0025] In some embodiments of the present invention, the amount of the polyolefin in S1 does not exceed 1 wt% of the total amount of polyolefin.

[0026] In some embodiments of the present invention, at least one of toluene, xylene, tetrahydrofuran, chloroform, tetrachloroethane, and dichloroethane is used to prepare the polyolefin solution in S1.

[0027] In some embodiments of the present invention, at least one of toluene, xylene, tetrahydrofuran, chloroform, tetrachloroethane, and dichloroethane is used in step S2 to prepare the P3HT solution.

[0028] In some embodiments of the present invention, the undesirable solvent in S3 is selected from at least one of methanol and its aqueous solution, and ethanol and its aqueous solution.

[0029] In some embodiments of the present invention, the temperature of the melt extrusion in S4 is 180~230°C.

[0030] Another object of the present invention is to provide the application of the above-mentioned P3HT composite material in the preparation of antibacterial products.

[0031] Another object of the present invention is to provide an antibacterial article comprising the above-mentioned P3HT composite material.

[0032] In some embodiments of the present invention, the antibacterial product may be a medical antibacterial product or a food antibacterial product.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] The P3HT composite material of the present invention has a highly efficient and long-lasting antibacterial effect and can be widely used in medical antibacterial products and food antibacterial products, such as medical films, medical catheters, medical implants and food packaging materials.

[0035] The P3HT composite material of this invention has low preparation cost, simple process, and is easy to industrialize. Attached Figure Description

[0036] Figure 1 The ultraviolet-visible absorption spectrum and fluorescence emission spectrum of the P3HT composite materials obtained in Examples 1 and 6 were analyzed.

[0037] Figure 2 The images show SEM images of the P3HT composite materials obtained in Examples 6 and 8. Detailed Implementation

[0038] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0039] The following is the P3HT used in specific embodiments of the present invention:

[0040] P3HT-1: Regularity is 91.7%, number-average molecular weight is approximately 35.3 kDa, and molecular weight distribution is approximately 1.63;

[0041] P3HT-2: Regularity is 90.2%, number-average molecular weight is approximately 29.1 kDa, and molecular weight distribution is approximately 1.45;

[0042] P3HT-3: regularity is 89.4%, number-average molecular weight is approximately 36.5 kDa, and molecular weight distribution is approximately 1.77;

[0043] P3HT-4: regularity is 88.1%, number-average molecular weight is approximately 24.9 kDa, and molecular weight distribution is approximately 1.52;

[0044] P3HT-5: regularity is 86.7%, number-average molecular weight is approximately 27.4 kDa, and molecular weight distribution is approximately 1.70;

[0045] P3HT-6: regularity is 92.5%, number-average molecular weight is approximately 32.5 kDa, and molecular weight distribution is approximately 1.3.

[0046] Example 1

[0047] This embodiment provides a P3HT composite material, which, by mass percentage, comprises 99.99% polyethylene and 0.01% P3HT-1, and its preparation steps are as follows:

[0048] S1. Pulverize polypropylene into powder, take 0.5 wt% of polypropylene powder relative to the total amount of polypropylene powder, mix with tetrachloroethane, heat to about 140°C to dissolve, and obtain a polypropylene solution;

[0049] S2. Mix P3HT-1 and tetrachloroethane, heat to 140℃ to dissolve, and obtain P3HT solution;

[0050] S3. Mix the polypropylene solution obtained in S1 and the P3HT solution obtained in S2 into a homogeneous solution, add methanol, the volume ratio of the homogeneous solution to methanol is about 1:100, precipitate, filter, and dry to obtain the matrix material.

[0051] S4. Blend the matrix material obtained in S3 with the remaining polypropylene powder, and melt-extrude the mixture while controlling the temperature of the extruder within the range of 180~230℃ to obtain the P3HT composite material.

[0052] Examples 2-4 and Comparative Examples 1-2

[0053] The only difference between this embodiment / comparative example and Example 1 is the type of P3HT used; everything else remains the same. See Table 1 for details.

[0054] Table 1: Raw material composition of P3HT composite materials in Examples 1-4 and Comparative Examples 1-2

[0055]

[0056] Examples 5-12

[0057] The only difference between the above embodiments and Embodiment 2 is the mass percentage of P3HT in the P3HT composite material or the type of polyolefin; otherwise, they remain the same as Embodiment 2. See Table 2 for details.

[0058] Table 2: Raw material composition of P3HT composite materials in Examples 2, 5-12

[0059]

[0060] Performance testing:

[0061] 1. The P3HT composite materials obtained in Examples 1 and 6 were subjected to ultraviolet-visible absorption and fluorescence emission analysis, and the results are as follows: Figure 1 As shown. By Figure 1 It is known that the above-mentioned P3HT composite material has absorption in the ultraviolet-visible light range and can emit fluorescence with a maximum wavelength of about 672nm, which has optical responsiveness. This is the basis for realizing the antibacterial effect of photodynamic therapy.

[0062] 2. SEM analysis of the P3HT composite materials obtained in Examples 6 and 8 yielded the following results: Figure 2 As shown. By Figure 2 It can be seen that the above P3HT composite material does not exhibit phase separation, has good compatibility and dispersion, and no agglomerated particles were observed at the micron level. In other words, P3HT can be uniformly dispersed in the composite material and is basically dispersed in the polyolefin matrix at the nanoscale.

[0063] 3. The P3HT composite materials obtained in Examples 1-12 and Comparative Examples 1-2 were subjected to photodynamic antibacterial tests. The concentration of the inoculum for *Escherichia coli* ATCC 8739 was 8.1 × 10⁻⁶. 6The inoculum concentration of Staphylococcus aureus ATCC6538 was 4.2 × 10⁻⁶ CFU / mL, the inoculum volume was 2 mL, and the concentration of the inoculum was 4.2 × 10⁻⁶ CFU / mL. 6 The inoculum was 2 mL with CFU / mL. After incubation in the dark for 60 min, it was moved to light conditions (LED light with λ=395nm) for 20 min, and then incubated in the dark for 24 h. After contact, the colony count was performed per square centimeter. The logarithmic reduction value and the percentage reduction in bacterial count relative to the blank control (polyolefin without P3HT) were calculated to evaluate the antibacterial adhesion value and antibacterial adhesion rate. The results are shown in Table 3.

[0064] For Escherichia coli ATCC 8739, the logarithmic colony count of blank control sample 1 (polypropylene used in Examples 1-9 and Comparative Examples 1-2) was 4.463, the logarithmic colony count of blank control sample 2 (polyethylene used in Example 10) was 4.471, the logarithmic colony count of blank control sample 3 (binary polypropylene used in Example 11) was 4.468, and the logarithmic colony count of blank control sample 4 (ethylene-octene elastomer used in Example 12) was 4.475. For Staphylococcus aureus ATCC 6538, the logarithmic colony count of blank control sample 1 was 4.693, the logarithmic colony count of blank control sample 2 was 4.685, the logarithmic colony count of blank control sample 3 was 4.691, and the logarithmic colony count of blank control sample 4 was 4.698.

[0065] Table 3: Photodynamic antibacterial properties of P3HT composite materials in Examples 1-12 and Comparative Examples 1-2

[0066]

[0067] Furthermore, a non-photodynamic antibacterial test was conducted on the P3HT composite material of Example 2. The only difference between this test and the aforementioned photodynamic antibacterial test was that the material was incubated in a dark environment throughout. The results showed that for Escherichia coli ATCC 8739, the logarithmic colony count was 4.402, and the antibacterial adhesion value was 0.061; for Staphylococcus aureus ATCC 6538, the logarithmic colony count was 4.455, and the antibacterial adhesion value was 0.238.

[0068] It is evident that P3HT with a regularity of 88-92% is beneficial for dispersing in polyolefins to form stable nanoscale regions, thereby achieving a highly efficient and long-lasting antibacterial effect based on photodynamic mechanisms.

[0069] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that after reading this application specification, they can still modify or make equivalent substitutions to the specific implementation of the present invention, but these modifications or changes do not depart from the protection scope of the pending claims of the present invention.

Claims

1. A P3HT composite material, characterized in that, The raw materials include polyolefins and P3HT, wherein the regularity of the P3HT is 88-92%.

2. The P3HT composite material according to claim 1, characterized in that, Based on the raw material being 100 wt%, the P3HT is 0.008~3 wt%.

3. The P3HT composite material according to claim 2, characterized in that, Based on the raw material being 100 wt%, the P3HT is 0.01~1 wt%.

4. The P3HT composite material according to claims 1-3, characterized in that, The number-average molecular weight of the P3HT is 4~40 kDa.

5. The P3HT composite material according to any one of claims 1 to 3, characterized in that, The polyolefin is selected from at least one of polyethylene, polypropylene, polybutene, binary polypropylene, ternary polypropylene, poly(4-methyl-1-pentene), and polyolefin elastomers.

6. The method for preparing the P3HT composite material according to any one of claims 1 to 5, characterized in that, The steps include the following: S1. Take a portion of the polyolefin and prepare a polyolefin solution; S2. Take P3HT and prepare a P3HT solution; S3. After mixing the polyolefin solution obtained in S1 with the P3HT solution obtained in S2 to form a homogeneous solution, add a poor solvent and precipitate to obtain the matrix material; S4. Blend the matrix material obtained in S3 with the remaining polyolefin and melt extrude to obtain the P3HT composite material.

7. The method for preparing the P3HT composite material as described in claim 6, characterized in that, The amount of polyolefin powder used in S1 shall not exceed 1 wt% of the total amount of polyolefin powder.

8. The method for preparing the P3HT composite material as described in claim 6, characterized in that, The solvents used in preparing the polyolefin solution in S1 and / or preparing the P3HT solution in S2 are selected from at least one of toluene, xylene, tetrahydrofuran, chloroform, tetrachloroethane, and dichloroethane. And / or, the undesirable solvent mentioned in S3 is selected from at least one of methanol and its aqueous solution, ethanol and its aqueous solution; And / or, the melt extrusion temperature described in S4 is 180~230°C.

9. The use of the P3HT composite material according to any one of claims 1 to 5 in the preparation of antibacterial products.

10. An antibacterial product, characterized in that, Includes the P3HT composite material as described in any one of claims 1 to 5.

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