Method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers

Abstract

The present invention discloses a method for preparing a cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers, wherein the cellulose nanocrystals and cellulose nanofibers are respectively subjected to antibacterial modification to obtain modified cellulose nanocrystals and modified cellulose nanofibers respectively, and then the polycaprolactone, modified cellulose nanocrystals and modified cellulose nanofibers are subjected to solution blending, melt blending, tableting and injection molding to finally prepare a cellulose-based polycaprolactone antibacterial plastic. The present invention utilizes CNC, CNF, anti-CNC and anti-CNF to improve the antibacterial properties of PCL, and finds that the addition of CNC, CNF, anti-CNC and anti-CNF can effectively improve the antibacterial ability of PCL. The addition of CNC, CNF, anti-CNC and anti-CNF can significantly improve the tensile properties of PCL. CNC, CNF, anti-CNC and anti-CNF can promote the nucleation of PCL and shorten the crystallization time of PCL. The addition of CNC, CNF, anti-CNC and anti-CNF can change the microstructure and hydrophilic and hydrophobic properties of PCL.

Description

Technical Field

[0001] The invention relates to a method for preparing cellulose-based polycaprolactone antibacterial plastic by using modified cellulose nanocrystals and modified cellulose nanofibers, belonging to the technical field of polycaprolactone (PCL) antibacterial material preparation. Background Art

[0002] Antimicrobial plastics, a subcategory of antimicrobial materials, are materials with antimicrobial properties. These typically involve adding an antimicrobial agent to plastics, imparting inherent antimicrobial properties. These agents can inhibit or kill bacteria contaminating the plastic within a certain period of time. Compared to conventional chemical and physical methods, antimicrobial plastics offer a longer sterilization timeframe, making them both economical and convenient.

[0003] Polycaprolactone (PCL) is a linear polyester derived from caprolactone and acrylic acid via a ring-opening reaction. It exhibits a rubbery appearance at room temperature, exhibits excellent heat resistance, and exhibits a high cracking temperature. PCL is a novel implantable, controlled-release biomedical material. It can also be used in agricultural films, containers, fishing nets, fishing lines, various nonwoven fabrics, slope collapse prevention nets, adhesives, slow-release fertilizer carriers, packaging materials, and disposable dishes.

[0004] Cellulose nanocrystals (CNC) are a material with a particle size of 5-70nm and a length of 100-500nm. They are mainly derived from wood, cotton, seaweed and microbial cellulose. CNC has been increasingly used in biomedicine, sewage treatment, energy, electronics and other fields.

[0005] Cellulose nanofiber (CNF) is a nanocellulose material made from natural cellulose material, which has excellent properties such as high specific surface area, high mechanical strength, renewability, and biodegradability.

[0006] CNF preparation methods include mechanical refining, acid hydrolysis, oxidation, and other methods. During the preparation process, CNF with different properties and morphologies can be obtained by adjusting parameters and changing processing conditions. As a renewable, low-cost, and environmentally friendly material, CNF has applications in biomedical fields such as biosensors, drug delivery, and tissue engineering. It can also be applied to paper, adhesives, composite materials, transparent materials, and coatings.

[0007] PCL has the advantages of being easy to form and process, and being in a rubbery state at room temperature. It can withstand large deformations, but it cannot be used in high-rigidity materials. Blending and modifying PCL with cellulose nanofibers can improve the strength and dimensional stability of PCL composites. Antibacterial modification of CNC and CNF, and blending the modified and unmodified CNC and CNF with PCL to prepare cellulose-based polycaprolactone antibacterial plastics, can not only improve the mechanical properties of PCL, maintain its biodegradability and environmentally friendly properties, but also enhance its antibacterial properties and broaden its scope of application.

[0008] In order to solve the defect of PCL in the prior art that it does not have antibacterial properties, the present invention provides a method for improving the antibacterial properties of PCL using modified cellulose nanocrystals (anti-CNC) and modified cellulose nanofibers (anti-CNF). Summary of the Invention

[0009] The present invention aims to solve the problems existing in the above-mentioned prior art and provides a method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers. The technical solutions adopted by the present invention are as follows:

[0010] A method for preparing a cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers, comprising: performing antibacterial modification on the cellulose nanocrystals and cellulose nanofibers to obtain modified cellulose nanocrystals and modified cellulose nanofibers respectively; and then solution blending, melt blending, tableting and injection molding the polycaprolactone, modified cellulose nanocrystals and modified cellulose nanofibers to finally prepare the cellulose-based polycaprolactone antibacterial plastic.

[0011] Furthermore, the cellulose nanofibers are extracted from sugarcane bagasse by the following process:

[0012] 11) Mix 10 g of crushed and sieved bagasse with an appropriate amount of deionized water and stir in an 80°C water bath for 2 h to obtain a mixture from which water-soluble components have been removed;

[0013] 12) After the mixture was rinsed with ethanol, the mixture was dispersed in a mixed solution of toluene and anhydrous ethanol and stirred in a water bath at 60° C. for 5 h to remove lipids from the bagasse;

[0014] 13) After degreasing, rinse with deionized water three times, then add nitric acid to the degreased product and stir in an 85°C water bath for 1 hour to remove pectin, then wash the product until neutral and filter out impurities;

[0015] 14) The filtered product and a 4% sodium hydroxide solution were added to a beaker and stirred in an 80°C water bath for 2 hours. The stirred product was washed several times with deionized water and filtered. Then, 0.8% hydrogen peroxide was added to the beaker, and the pH value was adjusted to 4.5-5.0 with a 50% acetic acid solution. The mixture was reacted in an 80°C water bath for 2 hours and then cooled to room temperature. After repeated centrifugation and washing, bagasse cellulose nanofibers were obtained.

[0016] Furthermore, in step 12), the volume ratio of toluene to anhydrous ethanol is 2:1.

[0017] Furthermore, in step 13), 150 mL of 0.1 mol / L nitric acid is added to the defatted product.

[0018] Further, in step 14),

[0019] The weight ratio of the filtered product to 4% sodium hydroxide solution is 20:1;

[0020] The weight ratio of 0.8% hydrogen peroxide to the corresponding filtered product is 20:1.

[0021] Furthermore, the process of performing antibacterial modification on the cellulose nanocrystals to obtain the modified cellulose nanocrystals is as follows:

[0022] 21) Add 10 g of white tea to 100 mL of deionized water, heat to 80°C, and stir for 30 min.

[0023] 22) After cooling to room temperature, filter out the tea and set aside;

[0024] 23) Add 1 g of cellulose nanocrystals to 100 mL of 2% acetic acid solution and stir in a 60°C water bath for 30 min. Then add 1 g of chitosan and continue stirring in a 60°C water bath for 1 h. Then add 10 mL of 10 mmol / L silver nitrate and continue stirring at 60°C for 1 h. Finally, heat to 80°C and add 9 mL of tea dropwise. Continue stirring for 4 h. After cooling to room temperature, the product is centrifuged and washed with deionized water to obtain modified cellulose nanocrystals.

[0025] Furthermore, the process of performing antibacterial modification on cellulose fibers to prepare modified cellulose nanofibers is as follows:

[0026] 21) Add 10 g of white tea to 100 mL of deionized water, heat to 80°C, and stir for 30 min.

[0027] 22) After cooling to room temperature, filter out the tea and set aside;

[0028] 23) Add 1 g of cellulose nanofibers to 100 mL of 2% acetic acid solution and stir in a 60°C water bath for 30 min. Then add 1 g of chitosan and continue stirring in a 60°C water bath for 1 h. Then add 10 mL of 10 mmol / L silver nitrate and stir at 60°C for 1 h. Finally, heat to 80°C and add 9 mL of tea dropwise. Continue stirring for 4 h. After cooling to room temperature, the product is centrifuged and washed with deionized water to obtain modified cellulose nanofibers.

[0029] Furthermore, the concentration of white tea is 0.1 g / mL.

[0030] Furthermore, the process for preparing cellulose-based polycaprolactone antibacterial plastic is as follows:

[0031] 41) Dispersing 1 g of modified cellulose nanocrystals and 5 g of polycaprolactone in chloroform, a PCL / anti-CNC antibacterial masterbatch with a modified cellulose nanocrystal content of 20% was prepared by a solution blending method;

[0032] 44g of polycaprolactone and PCL / anti-CNC antibacterial masterbatch were melt blended, tableted and injection molded to prepare PCL / anti-CNC antibacterial plastic with a modified cellulose nanocrystal concentration of 2%.

[0033] 42) Dispersing 1 g of modified cellulose nanofibers and 5 g of polycaprolactone in chloroform, a PCL / anti-CNF antibacterial masterbatch with a modified cellulose nanofiber concentration of 20% was prepared by a solution blending method;

[0034] 44g of polycaprolactone was melt-blended, tableted and injection-molded with PCL / anti-CNF antibacterial masterbatch to produce PCL / anti-CNF antibacterial plastic with a modified cellulose nanofiber concentration of 2%.

[0035] The present invention has the following beneficial effects:

[0036] 1) The present invention utilizes CNC, CNF, anti-CNC and anti-CNF to improve the antibacterial properties of PCL. It is found that the addition of CNC, CNF, anti-CNC and anti-CNF can effectively improve the antibacterial ability of PCL.

[0037] 2) The addition of CNC, CNF, anti-CNC and anti-CNF can significantly improve the tensile properties of PCL.

[0038] 3) CNC, CNF, anti-CNC and anti-CNF can promote the nucleation of PCL and shorten the crystallization time of PCL.

[0039] 4) The addition of CNC, CNF, anti-CNC and anti-CNF can change the microstructure and hydrophilic and hydrophobic properties of PCL. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 These are the infrared spectra of sample 1 and sample 2.

[0041] Figure 2 is the scanning electron microscope image of sample 1.

[0042] Figure 3 This is the scanning electron microscope image of sample 2.

[0043] Figure 4 These are the UV spectra of samples 3 and 4.

[0044] Figure 5 The infrared spectra of the comparative example and embodiments 1, 2, 3 and 4 are shown.

[0045] Figure 6 The thermogravimetric curves of the comparative example and examples 1, 2, 3, and 4 are shown.

[0046] Figure 7 The DSC curves of the comparative example and embodiments 1, 2, 3, and 4 are shown.

[0047] Figure 8 Relative crystallinity curves of comparative example and examples 1, 2, 3, and 4.

[0048] Figure 9 The contact angles of the comparative example and examples 1, 2, 3, and 4 are shown.

[0049] Figure 10 The stress-strain curves of the comparative example and embodiments 1, 2, 3, and 4 are shown.

[0050] Figure 11a-Figure 11e Graph showing the relationship between storage modulus, loss modulus and complex viscosity of the corresponding control and Examples 1, 2, 3 and 4 as a function of angular frequency.

[0051] Figure 12a-12e The compliance and recovery compliance of the corresponding control and Examples 1, 2, 3, and 4 are shown.

[0052] Figure 13 The antibacterial test results of Staphylococcus aureus of the comparative example and Examples 1, 2, 3, and 4 are shown. DETAILED DESCRIPTION

[0053] The following is combined with Figure 1-13 The present invention will be further described.

[0054] 1. Preparation of surface-modified nanocellulose samples

[0055] Sample 1: Cellulose nanocrystals (CNC) were vacuum dried for 6 hours and recorded as Sample 1.

[0056] Sample 2: 10 g of bagasse was mixed with an appropriate amount of deionized water and stirred at 80°C for 2 hours to remove water-soluble components. After rinsing with ethanol, the mixture was dispersed in a mixture of toluene and anhydrous ethanol (toluene:anhydrous ethanol, 2:1, by volume) and stirred at 60°C for 5 hours to remove lipids. After defatting, the product was rinsed three times with deionized water. 150 mL of 0.1 mol / L nitric acid was then added to the defatted product. The product was stirred at 85°C for 1 hour to remove pectin. The product was then washed to neutrality and filtered. The filtered product and 4% sodium hydroxide solution (weight ratio of alkaline solution to filtered product, 20:1) were added to a beaker and stirred at 80°C for 2 hours. The soaked product was washed several times with deionized water. 0.8% hydrogen peroxide (weight ratio of hydrogen peroxide to filtered product, 20:1) was then added to the beaker. The pH of the system was adjusted to 4.5-5.0 using 50% acetic acid solution. After reacting at 80°C for 2 hours, the system was cooled to room temperature. After repeated centrifugation and washing, bagasse nanocellulose fibers (CNFs) were obtained and recorded as sample 2.

[0057] according to Figure 1 It can be seen that in the infrared spectrum, 3338 cm -1 The stretching vibration absorption peak of OH in cellulose is 2902 cm -1 The stretching vibration absorption peak of methylene CH in cellulose is 1652 cm -1 The stretching vibration absorption peak of C=O in cellulose is 1023 cm -1 The peak at 40° is the stretching vibration absorption peak of CO in cellulose. The infrared spectroscopy data showed that CNF was successfully extracted from sugarcane bagasse.

[0058] according to Figure 2 and Figure 3 It can be seen that CNC has a nanorod-like structure and CNF has a nanofiber-like structure. From the sample morphology, it can be seen that the aspect ratio of CNF is higher than that of CNC.

[0059] Sample 3: Add white tea leaves to an appropriate amount of distilled water, heat to 80°C, and stir for 30 minutes. After cooling to room temperature, filter out the tea and set aside. Add 1g of CNC to 100ml of 2% acetic acid solution, place in a water bath at 60°C and stir for 30 minutes, then add 1g of chitosan, stir at 60°C for 1h, then add 10ml of 10mmol / L silver nitrate, stir at 60°C for 1h, finally heat to 80°C, add 9ml of tea dropwise and stir for 4h, then cool to room temperature and centrifuge with distilled water to obtain the product modified cellulose nanocrystals (anti-CNC), recorded as sample 3.

[0060] Sample 4: Add white tea leaves to an appropriate amount of distilled water, heat to 80°C, and stir for 30 minutes. After cooling to room temperature, filter out the tea and set aside. Add 1g of CNF to 100ml of 2% acetic acid solution, place in a water bath at 60°C and stir for 30 minutes, then add 1g of chitosan, stir at 60°C for 1h, then add 10ml of 10mmol / L silver nitrate, stir at 60°C for 1h, finally heat to 80°C, add 9ml of tea dropwise and stir for 4h, then cool to room temperature and centrifuge with distilled water to obtain the product modified cellulose nanofiber (anti-CNF), recorded as sample 4.

[0061] according to Figure 4 UV spectrum, Figure 4 The characteristic peaks of nanosilver appeared in the pores, indicating that nanosilver had been successfully loaded on CNC and CNF.

[0062] 2. Preparation of Cellulose-based Polycaprolactone Antibacterial Plastics

[0063] Comparative Example

[0064] Pure PCL was prepared by melt blending, tableting and injection molding to obtain PCL materials with the same thermal history as other samples.

[0065] Example 1

[0066] A PCL / CNC masterbatch containing a high CNC concentration (20%) was prepared by uniformly dispersing 5g of PCL and 1g of CNC in chloroform. After complete solvent evaporation, the PCL / CNC masterbatch was mixed with 44g of PCL. A PCL / CNC composite with a CNC content of 2wt% was prepared through melt blending, tableting, and injection molding.

[0067] Example 2

[0068] A PCL / CNF masterbatch containing a high CNF concentration (20%) was prepared by uniformly dispersing 5g of PCL and 1g of CNF in chloroform. After complete solvent evaporation, the PCL / CNF masterbatch was mixed with 44g of PCL. A PCL / CNF composite with a CNF content of 2wt% was prepared through melt blending, tableting, and injection molding.

[0069] Example 3

[0070] A PCL / anti-CNC masterbatch containing a high concentration of anti-CNC (20%) was prepared by uniformly dispersing 5g of PCL and 1g of anti-CNC in chloroform. After complete solvent evaporation, the PCL / anti-CNC masterbatch was mixed with 44g of PCL. A PCL / anti-CNC composite with a 2wt% anti-CNC content was prepared through melt blending, tableting, and injection molding.

[0071] Example 4

[0072] A PCL / anti-CNF masterbatch containing a high concentration of anti-CNF (20%) was prepared by uniformly dispersing 5g of PCL and 1g of anti-CNF in chloroform. After complete solvent evaporation, the PCL / anti-CNF masterbatch was mixed with 44g of PCL. A PCL / anti-CNF composite with a 2wt% anti-CNF content was prepared through melt blending, tableting, and injection molding.

[0073] Figure 5 The infrared spectra of the comparative example and Examples 1, 2, 3, and 4 are shown. No new peaks appear in the infrared spectra of Examples 1, 2, 3, and 4, and no characteristic peaks shift, indicating that the addition of CNC, CNF, anti-CNC, and anti-CNF does not destroy the structure of PCL.

[0074] Figure 6 Thermogravimetric curves of the comparative example and examples 1, 2, 3, and 4 are shown in the figure. As can be seen from the data in the figure, the thermal decomposition temperatures of the comparative example and examples 1, 2, 3, and 4 are not much different, indicating that the addition of CNC, CNF, anti-CNC, and anti-CNF has no effect on the thermal stability of PCL.

[0075] Figure 7 The DSC curves of the comparative example and Examples 1, 2, 3, and 4 are shown in the figure. As can be seen from the data in the figure, the crystallization temperatures of Examples 1, 2, 3, and 4 are higher than those of the comparative example, indicating that CNC, CNF, anti-CNC, and anti-CNF play a role in heterogeneous nucleation during the crystallization of PCL, thereby promoting the crystallization of PCL.

[0076] Figure 8 Relative crystallinity curves of the comparative example and examples 1, 2, 3, and 4. From the half-crystallization time in the figure, it can be seen that the addition of CNC, CNF, anti-CNC, and anti-CNF shortens the half-crystallization time of PCL and accelerates the crystallization process of PCL.

[0077] Figure 9The contact angles of the comparative example and Examples 1, 2, 3, and 4 are shown in the figure. As can be seen from the data in the figure, the contact angles of Examples 1, 2, 3, and 4 are all greater than those of the comparative example, indicating that the addition of CNC, CNF, anti-CNC, and anti-CNF improves the hydrophobicity of PCL. Since the added cellulose and antibacterial cellulose are both nanoscale, the nanostructures can change the hydrophilic and hydrophobic properties of the material surface by increasing the roughness of the material surface. The nanostructures on the hydrophobic surface are usually layered or staggered. These structures can increase the roughness of the surface, thereby increasing the contact area between the surface and the air, making it more difficult for water droplets to penetrate and infiltrate.

[0078] Figure 10 The stress-strain curves for the comparative example and Examples 1, 2, 3, and 4 are shown in the figure. As can be clearly seen from the curves in the figure, the tensile strength of Examples 1, 2, 3, and 4 is higher than that of the comparative example. Cellulose is a high-molecular polymer formed by cellulose molecular chains through hydrogen and covalent bonds, and possesses high strength and stiffness. Modifying PCL with cellulose materials can improve its strength.

[0079] Figure 11a-Figure 11e Figure 2 shows the relationship between the storage modulus, loss modulus, and complex viscosity of the comparative example and Examples 1, 2, 3, and 4 as a function of angular frequency. As can be seen from the data in the figure, at a frequency of 0.1 Hz, the storage modulus of Examples 1, 2, 3, and 4 is lower than that of the comparative example, while the viscosity of Example 4 is higher than that of the comparative example. This indicates that the addition of CNC, CNF, anti-CNC, and anti-CNF affects the microstructure of PCL.

[0080] Figure 12a-12e The compliance and recovery compliance of the comparative example and Examples 1, 2, 3, and 4 are shown in the figure. As can be seen from the data in the figure, Examples 2 and 4 show higher compliance, indicating that CNF and anti-CNF increase the elasticity of the PCL viscous system.

[0081] Figure 13 The figures show the antibacterial test results against Staphylococcus aureus for the comparative example and Examples 1, 2, 3, and 4. As can be seen from the figures, under identical experimental conditions, the comparative example had a colony count of 152, while Example 1 had a colony count of 72, Example 2 had a colony count of 49, Example 3 had a colony count of 45, and Example 4 had a colony count of 16. The antibacterial properties of Examples 1, 2, 3, and 4 were significantly superior to those of the comparative example, demonstrating the successful preparation of the cellulose-based polycaprolactone antibacterial plastic.

[0082] The above description is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements can be made without departing from the principles of the present invention. These improvements should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers, characterized in that: Carrying out antibacterial modification on cellulose nanocrystals and cellulose nanofibers respectively, and obtaining modified cellulose nanocrystals and modified cellulose nanofibers respectively; Cellulose-based polycaprolactone antibacterial plastics are prepared by solution blending, melt blending, tableting and injection molding of polycaprolactone and modified cellulose nanocrystals; Alternatively, polycaprolactone and modified cellulose nanofibers are solution blended, melt blended, tableted, and injection molded to prepare cellulose-based polycaprolactone antibacterial plastics; The cellulose nanofibers are extracted from sugarcane bagasse by the following process: 11) Mix 10 g of crushed and sieved bagasse with an appropriate amount of deionized water and stir in an 80°C water bath for 2 h to obtain a mixture from which water-soluble components have been removed. 12) After rinsing the mixture with ethanol, the mixture was dispersed in a mixed solution of toluene and anhydrous ethanol and stirred in a 60 °C water bath for 5 h to remove lipids from the bagasse. 13) After degreasing, rinse with deionized water three times, then add nitric acid to the degreased product and stir in an 85°C water bath for 1 hour to remove pectin. Then wash the product until it is neutral and filter out impurities. 14) The filtered product and 4% sodium hydroxide solution were added to a beaker and stirred in an 80°C water bath for 2 hours. The stirred product was washed several times with deionized water and filtered. Then, 0.8% hydrogen peroxide was added to the beaker, and the pH value was adjusted to 4.5-5.0 with 50% acetic acid solution. The product was reacted in an 80°C water bath for 2 hours, then cooled to room temperature, and repeatedly centrifuged and washed to obtain bagasse cellulose nanofibers. The antibacterial modification of cellulose nanocrystals and cellulose nanofibers is carried out, and the corresponding process for preparing modified cellulose nanocrystals and modified cellulose nanofibers is as follows: 21) Add 10 g of white tea to 100 mL of deionized water, heat to 80°C, and stir for 30 min. 22) After cooling to room temperature, filter out the tea and set aside; 23) Add 1 g of cellulose nanocrystals or 1 g of cellulose nanofibers to 100 mL of 2% acetic acid solution and stir in a 60 °C water bath for 30 min. Then add 1 g of chitosan and continue stirring at 60 °C for 1 h. Then add 10 mL of 10 mmol / L silver nitrate and continue stirring at 60 °C for 1 h. Finally, heat to 80 °C and add 9 mL of tea dropwise. Continue stirring for 4 h. After cooling to room temperature, wash the product with deionized water by centrifugation to obtain modified cellulose nanocrystals or modified cellulose nanofibers.

2. The method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers according to claim 1, characterized in that: In step 12), the volume ratio of toluene to anhydrous ethanol is 2:

1.

3. The method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers according to claim 1, characterized in that: In step 13), 150 mL of 0.1 mol / L nitric acid was added to the defatted product.

4. The method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers according to claim 1, wherein: In step 14), The weight ratio of the filtered product to 4% sodium hydroxide solution is 20:1; The weight ratio of 0.8% hydrogen peroxide to the corresponding filtered product is 20:

1.

5. The method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers according to claim 1, characterized in that: The concentration of white tea was 0.1 g / mL.

6. The method for preparing cellulose-based polycaprolactone antibacterial plastic using modified cellulose nanocrystals and modified cellulose nanofibers according to claim 1, wherein: The process of preparing cellulose-based polycaprolactone antibacterial plastic is: 41) Modified cellulose nanocrystals and polycaprolactone were dispersed in chloroform, and a PCL / anti-CNC antibacterial masterbatch with a modified cellulose nanocrystal concentration of 20% was prepared by solution blending. Polycaprolactone and PCL / anti-CNC antibacterial masterbatch were melt blended, tableted and injection molded to prepare PCL / anti-CNC antibacterial plastic with a modified cellulose nanocrystal concentration of 2%. 42) Modified cellulose nanofibers and polycaprolactone were dispersed in chloroform, and a PCL / anti-CNF antibacterial masterbatch with a modified cellulose nanofiber concentration of 20% was prepared by solution blending. Polycaprolactone and PCL / anti-CNF antibacterial masterbatch were melt blended, tableted and injection molded to produce PCL / anti-CNF antibacterial plastic with a modified cellulose nanofiber concentration of 2%.

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