Bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste and preparation method thereof

Abstract

This invention discloses a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste and its preparation method, specifically relating to the field of textile fabrics. The raw materials are as follows (parts by weight): Bio-based biodegradable resin matrix: 50-80 parts poly(butylene adipate / terephthalate), 20-50 parts polylactic acid; Agricultural waste regenerated fiber filler: 5-20 parts micron-sized yew powder; Interface compatibilizer: 0.3-1.2 parts epoxy functionalized chain extender. This invention uses yew residue after paclitaxel extraction as raw material, which is then used as a functional filler after simple physical grinding, avoiding resource waste caused by incineration or composting. This filler originates from medicinal plant waste and is a renewable resource. Its introduction significantly reduces the amount of PBAT / PLA matrix used, reducing dependence on fossil fuels. The resulting fabric can be biodegraded through industrial composting or anaerobic digestion after disposal, and the degradation products can be reabsorbed into the biomass cycle, fully aligning with the sustainable development concept of easy recycling, recyclability, and regeneration.

Description

Technical Field

[0001] This invention relates to the field of textile fabric technology, and more specifically, to a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste and its preparation method. Background Technology

[0003] Polylactic acid (PLA) and polybutylene adipate / terephthalate (PBAT), as typical biodegradable polymers, have significant application value in solving the problem of traditional plastic pollution. PLA possesses excellent mechanical strength and recyclability, but is brittle and lacks toughness; PBAT exhibits good flexibility and ductility, but has a lower modulus. Blending the two can compensate for their respective performance deficiencies, expanding their applications in packaging, agricultural mulch films, and textile fabrics. However, the complex manufacturing processes and high costs of PLA and PBAT limit their large-scale application.

[0004] In existing technologies, there have been attempts to introduce inorganic fillers (such as calcium carbonate and talc) or bio-based fillers (such as bamboo powder and starch) into PLA / PBAT systems to reduce costs. Yew trees are important for extracting the anticancer drug paclitaxel, producing a large amount of plant residue after extraction. This residue is rich in cellulose and lignin, and contains bioactive residues such as taxadiene, which have potential antibacterial activity. Currently, the main methods for treating these residues are incineration and composting, and their potential value is not fully utilized. If they could be used as functional fillers in biodegradable fabrics, it would not only achieve high-value utilization of agricultural waste resources but also endow the fabrics with unique functions such as antibacterial and moisturizing properties. Summary of the Invention

[0005] In order to overcome the above-mentioned defects of the prior art, the embodiments of the present invention provide a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste and its preparation method. The technical problem to be solved by the present invention is: how to solve the technical problems of low resource utilization rate of agricultural and forestry waste, poor interfacial compatibility of bio-based composite materials, deterioration of mechanical properties, lack of antibacterial and moisturizing functions and insufficient recyclability in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste, comprising the following raw materials in parts by weight:

[0007] Bio-based biodegradable resin matrix: 50-80 parts of polybutylene adipate / terephthalate (PBAT), 20-50 parts of polylactic acid (PLA);

[0008] Agricultural waste recycled fiber filler: 5-20 parts of micron-sized yew powder (TP);

[0009] Interface compatibilizer: 0.3-1.2 parts of epoxy functionalized chain extender (ADR);

[0010] Additives: Antioxidant Irganox 1010 0.1-0.5 parts, lubricant pentaerythritol stearate (PETS) 0.1-0.5 parts.

[0011] The yew powder (TP) is a micron-sized powder obtained by drying, ultra-fine grinding, ball milling, and sieving of yew residue after paclitaxel extraction. Its average particle size (D50) is 8-15 μm and the large-end particle size (D90) is 20-30 μm.

[0012] The epoxy functionalized chain extender (ADR) is selected from ADR-4370 (functionality 6) or ADR-4468 (functionality 9), preferably ADR-4468.

[0013] In a preferred embodiment, the mass ratio of PBAT to PLA in the bio-based biodegradable resin matrix is ​​7:3.

[0014] In a preferred embodiment, the content of the agricultural waste recycled fiber filler (TP) is 6-9 parts by weight.

[0015] In a preferred embodiment, the content of the epoxy functionalized chain extender (ADR) is 0.6-0.9 parts by weight.

[0016] This invention also includes a method for preparing a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste, comprising the following steps:

[0017] S1. Preparation of agricultural waste recycled fiber filler: The residue after extracting paclitaxel from yew was dried at 40-50℃ for 24h, and then preliminarily ground by an ultra-micro pulverizer and passed through a 100-mesh sieve; the obtained powder was placed in a planetary ball mill for secondary grinding. The ball milling parameters were 100 zirconium beads / tank, and the ratio of large, medium and small zirconium beads was 2:2:6. After continuous grinding for 20min, the grinding was paused for 10min, and the grinding was carried out for a total of 4h to obtain micron-sized yew powder (TP).

[0018] S2. Raw material drying: Place PBAT, PLA and TP in a constant temperature drying oven at 60-80℃ and dry for 24 hours;

[0019] S3. Melt blending: Weigh the dried PBAT, PLA, TP, ADR and additives according to the weight ratio, mix them evenly at room temperature, and then put them into an internal mixer for melt blending. The processing parameters are set as follows: temperature 180-200℃, speed 60-100r / min, and mixing time 8-10min.

[0020] S4. Calendering film formation: The molten blend is transferred to a flat vulcanizing machine and molded at 180-200℃ and 10-20MPa pressure. After cooling, a composite film is obtained.

[0021] S5. Cutting and post-processing: Cut the obtained composite film to the required size to obtain the antibacterial and moisturizing fabric.

[0022] In a preferred embodiment, in step S3, the internal mixer processing temperature is 190°C and the rotation speed is 80 r / min.

[0023] In a preferred embodiment, in step S4, the molding conditions are: temperature 190°C, pressure 15MPa, and holding time 2min.

[0024] The technical effects and advantages of this invention are as follows:

[0025] 1. This invention uses the residue of Taxus chinensis after paclitaxel extraction as raw material. After ultrafine grinding and ball milling to reach a certain particle size, it can be used as a functional filler, avoiding the waste of resources caused by incineration or composting. The filler is derived from medicinal plant waste and is a renewable resource. Its introduction significantly reduces the amount of PBAT / PLA matrix used and reduces dependence on fossil energy. At the same time, the resulting fabric can be biodegraded into carbon dioxide and water through industrial composting or anaerobic digestion after disposal. The water produced by degradation can be reabsorbed into the biomass cycle, which fully conforms to the sustainable development concept of easy recycling, recyclability, and renewability.

[0026] 2. This invention makes the main active ingredient in yew, taxanes, more easily exposed and released on the surface of the composite material after ultrafine grinding; the antibacterial performance of the PBAT / PLA / TP composite material against Escherichia coli and Staphylococcus aureus is significantly enhanced compared with the PBAT / PLA blend without TP; making the fabric particularly suitable for fields with high antibacterial requirements such as medical protective, maternity and baby products and underwear.

[0027] 3. This invention effectively improves the interfacial compatibility between PBAT, PLA, and TP by introducing an epoxy functionalized chain extender (ADR). The epoxy groups in the ADR molecule can chemically react with the carboxyl and hydroxyl groups at the ends of the PBAT / PLA molecular chains and the hydroxyl groups abundant on the surface of TP, constructing a stable chemical connection network in the interfacial region. The tensile strength and elongation at break of the composite material are significantly improved. At the same time, due to the enhanced interfacial bonding, the TP particles are transformed from easily detached fillers into stable hydrophilic nodes embedded in the matrix, which is conducive to the diffusion of water and microorganisms into the material interior. Unlike the understanding that some traditional compatibilizers inhibit degradation, this invention achieves synergistic optimization of mechanical properties and degradation performance.

[0028] 4. The cellulose and hemicellulose molecular chains in TP in this invention contain a large number of hydroxyl groups. As the TP content increases, the static water contact angle of the composite material decreases, realizing the transformation from hydrophobic to hydrophilic. This is beneficial for the fabric to absorb and retain moisture, giving the fabric good moisturizing properties and improving wearing comfort. It is especially suitable for use in fields such as underwear, sportswear and medical dressings where moisturizing is required. Detailed Implementation

[0029] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1:

[0031] This invention provides a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste, the raw material composition (by weight) of which is: 70 parts PBAT, 30 parts PLA, 3 parts TP, and 0.3 parts ADR-4370;

[0032] Preparation methods include:

[0033] S1. Preparation of agricultural waste recycled fiber filler: The residue after extracting paclitaxel from yew was dried at 50℃ for 24h, and then preliminarily ground by an ultra-micro pulverizer and passed through a 100-mesh sieve; the obtained powder was placed in a planetary ball mill for secondary grinding. The ball milling parameters were 100 zirconium beads / tank, and the ratio of large, medium and small zirconium beads was 2:2:6. After continuous grinding for 20min, the grinding was paused for 10min, and the grinding was carried out for a total of 4h to obtain micron-sized yew powder (TP) with an average particle size D50 of 10.63μm and D90 of 27.51μm;

[0034] S2. Raw material drying: Place PBAT, PLA and TP in a 60℃ constant temperature drying oven and dry for 24 hours;

[0035] S3. Melt blending: Weigh the dried PBAT, PLA, TP, ADR-4370 and additives according to the weight ratio, mix them evenly at room temperature, and then put them into an internal mixer for melt blending. The processing parameters are set as follows: temperature 190℃, speed 80r / min, and mixing time 8min.

[0036] S4. Calendering film formation: The molten blend is transferred to a flat vulcanizing machine and molded at 190°C and 15MPa pressure. After cooling, a composite film is obtained.

[0037] S5. Cutting and post-processing: Cut the obtained composite film into strips of 150mm×20mm×0.3mm and square sheets of 10mm×10mm×0.3mm to obtain the antibacterial and moisturizing fabric.

[0038] Example 2:

[0039] This embodiment provides a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste, the raw material composition (by weight parts) of which is: 70 parts PBAT, 30 parts PLA, 6 parts TP, and 0.9 parts ADR-4468.

[0040] Preparation methods include:

[0041] S1. Preparation of agricultural waste recycled fiber filler: The residue after extracting paclitaxel from yew was dried at 50℃ for 24h, and then preliminarily ground by an ultra-micro pulverizer and passed through a 100-mesh sieve; the obtained powder was placed in a planetary ball mill for secondary grinding. The ball milling parameters were 100 zirconium beads / tank, and the ratio of large, medium and small zirconium beads was 2:2:6. After continuous grinding for 20min, the grinding was paused for 10min, and the grinding was carried out for a total of 4h to obtain micron-sized yew powder (TP) with an average particle size D50 of 10.63μm and D90 of 27.51μm;

[0042] S2. Raw material drying: Place PBAT, PLA and TP in a 60℃ constant temperature drying oven and dry for 24 hours;

[0043] S3. Melt blending: Weigh the dried PBAT, PLA, TP, ADR-4468 and additives according to the weight ratio, mix them evenly at room temperature, and then put them into an internal mixer for melt blending. The processing parameters are set as follows: temperature 190℃, speed 80r / min, and mixing time 8min.

[0044] S4. Calendering film formation: The molten blend is transferred to a flat vulcanizing machine and molded at 190°C and 15MPa pressure. After cooling, a composite film is obtained.

[0045] S5. Cutting and post-processing: Cut the obtained composite film into strips of 150mm×20mm×0.3mm and square sheets of 10mm×10mm×0.3mm to obtain the antibacterial and moisturizing fabric.

[0046] Example 3:

[0047] This embodiment provides a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste, the raw material composition (by weight parts) of which is: 70 parts PBAT, 30 parts PLA, 9 parts TP, and 0.9 parts ADR-4468.

[0048] Preparation methods include:

[0049] S1. Preparation of agricultural waste recycled fiber filler: The residue after extracting paclitaxel from yew was dried at 50℃ for 24h, and then preliminarily ground by an ultra-micro pulverizer and passed through a 100-mesh sieve; the obtained powder was placed in a planetary ball mill for secondary grinding. The ball milling parameters were 100 zirconium beads / tank, and the ratio of large, medium and small zirconium beads was 2:2:6. After continuous grinding for 20min, the grinding was paused for 10min, and the grinding was carried out for a total of 4h to obtain micron-sized yew powder (TP) with an average particle size D50 of 10.63μm and D90 of 27.51μm;

[0050] S2. Raw material drying: Place PBAT, PLA and TP in a 60℃ constant temperature drying oven and dry for 24 hours;

[0051] S3. Melt blending: Weigh the dried PBAT, PLA, TP, ADR-4468 and additives according to the weight ratio, mix them evenly at room temperature, and then put them into an internal mixer for melt blending. The processing parameters are set as follows: temperature 190℃, speed 80r / min, and mixing time 8min.

[0052] S4. Calendering film formation: The molten blend is transferred to a flat vulcanizing machine and molded at 190°C and 15MPa pressure. After cooling, a composite film is obtained.

[0053] S5. Cutting and post-processing: Cut the obtained composite film into strips of 150mm×20mm×0.3mm and square sheets of 10mm×10mm×0.3mm to obtain the antibacterial and moisturizing fabric.

[0054] Example 4:

[0055] This embodiment provides a bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste, the raw material composition (by weight parts) of which is: 70 parts PBAT, 30 parts PLA, 6 parts TP, and 0.9 parts ADR-4370.

[0056] Preparation methods include:

[0057] S1. Preparation of agricultural waste recycled fiber filler: The residue after extracting paclitaxel from yew was dried at 50℃ for 24h, and then preliminarily ground by an ultra-micro pulverizer and passed through a 100-mesh sieve; the obtained powder was placed in a planetary ball mill for secondary grinding. The ball milling parameters were 100 zirconium beads / tank, and the ratio of large, medium and small zirconium beads was 2:2:6. After continuous grinding for 20min, the grinding was paused for 10min, and the grinding was carried out for a total of 4h to obtain micron-sized yew powder (TP) with an average particle size D50 of 10.63μm and D90 of 27.51μm;

[0058] S2. Raw material drying: Place PBAT, PLA and TP in a 60℃ constant temperature drying oven and dry for 24 hours;

[0059] S3. Melt blending: Weigh the dried PBAT, PLA, TP, ADR-4370 and additives according to the weight ratio, mix them evenly at room temperature, and then put them into an internal mixer for melt blending. The processing parameters are set as follows: temperature 190℃, speed 80r / min, and mixing time 8min.

[0060] S4. Calendering film formation: The molten blend is transferred to a flat vulcanizing machine and molded at 190°C and 15MPa pressure. After cooling, a composite film is obtained.

[0061] S5. Cutting and post-processing: Cut the obtained composite film into strips of 150mm×20mm×0.3mm and square sheets of 10mm×10mm×0.3mm to obtain the antibacterial and moisturizing fabric.

[0062] The fabrics prepared in Examples 1-4 above, as well as the control sample (PBAT / PLA 7:3) without added TP and ADR, were subjected to performance tests. The test methods and results are as follows:

[0063] Mechanical property testing: In accordance with Chinese standard GB / T 1040.3-2006, an electronic tensile testing machine was used with a tensile speed of 100 mm / min and a gauge length of 50 mm to test tensile strength and elongation at break.

[0064] Antibacterial performance test: The inhibition rate against *Escherichia coli* and *Staphylococcus aureus* was tested using the standardized shaking method according to ASTM E 2149-20 standard. The bacterial reduction rate was calculated using formula (1):

[0065] (1)

[0066] Where A is the bacterial concentration (cfu / mL) 24 hours after sample contact, and B is the bacterial concentration (cfu / mL) 24 hours after sample absence.

[0067] Biodegradation performance test: A 90-day degradation experiment was conducted using a fully automated biodegradation testing system under anaerobic conditions in a 52℃ water bath, according to Chinese standard GB / T 33797-2017. The degradation rate was calculated using formula (2):

[0068] (2)

[0069] in, The amount of carbon gas released from the container (g). The amount of gaseous carbon released (g) is the blank. The initial carbon content (g) of the test material.

[0070] Water contact angle test: Using a contact angle measuring instrument, droplets are placed at three different locations on the material surface, the droplet angles are measured, and the average value is taken.

[0071] Test Results

[0072] Table 1 Mechanical property data of fabrics in different embodiments

[0073]

[0074] As shown in Table 1, compared with the control sample, the tensile strength of the fabric in Example 2 increased from 12.555 MPa to 20.718 MPa, an increase of 65.0%. Although the elongation at break was lower than that of the control sample, compared with Examples 1, 3, and 4, the elongation at break was the highest (314.75%) when 0.9% ADR-4468 (Example 2) was added at a 6% TP content, achieving the best balance between strength and toughness. This demonstrates that the high-functionality chain extender ADR-4468 can more effectively construct the interfacial bonding network at a higher TP content, achieving effective stress transfer between the matrix and the filler.

[0075] Table 2 Antibacterial performance data of fabrics from different embodiments

[0076]

[0077] As shown in Table 2, the antibacterial properties of the fabric were significantly improved after the introduction of TP. The antibacterial rate increased with increasing TP content, reaching a peak at 6% TP content (Example 2). Further increases in TP content (Example 3) resulted in a slight decrease in the antibacterial rate, possibly due to filler agglomeration affecting the release of active substances. Comparing Examples 2 and 4, at the same TP content, the antibacterial performance of the fabric modified with ADR-4468 was superior to that of ADR-4370, which may be related to the better interfacial dispersion promoting effect of ADR-4468.

[0078] Table 3. Biodegradability data of fabrics from different embodiments

[0079]

[0080] As shown in Table 3, the fabric of Example 2 exhibited the highest biodegradability rate after 90 days, reaching 17.18%, significantly higher than the control sample's 5.63%. This indicates that the synergistic effect of appropriate amounts of TP and ADR not only did not inhibit degradation but also accelerated the degradation process by constructing hydrophilic interfacial channels and increasing the exposure of easily degradable components (cellulose in TP). This result overturns the conventional wisdom that chain extenders inhibit degradation by increasing molecular weight.

[0081] Table 4 Surface wetting performance data of fabrics from different embodiments

[0082]

[0083] As shown in Table 4, with the increase of TP content and ADR addition, the water contact angle of the fabric gradually decreases, and the hydrophilicity increases. The contact angles of Examples 2 and 3 are both less than 90°, achieving a transition from hydrophobic to hydrophilic. This is due to the introduction of a large number of hydroxyl groups on the TP surface and the interfacial reconstruction promoted by ADR, resulting in the enrichment of hydrophilic groups on the material surface. This enhanced hydrophilicity endows the fabric with good moisturizing properties, which is beneficial to improving wearing comfort.

[0084] Based on the data in Tables 1-4 above, the fabric prepared in Example 2 exhibits optimal or near-optimal performance in terms of tensile strength (20.718 MPa), elongation at break (314.75%), antibacterial properties (59.46% inhibition rate against Staphylococcus aureus), biodegradability (17.18% degradation rate after 90 days), and hydrophilicity (contact angle 84.49°). It achieves a synergistic improvement in mechanical properties, functionality, and environmental friendliness, and is the best technical solution of this invention.

[0085] The TP used in this invention is derived from the residue after extracting paclitaxel from the medicinal plant Taxus chinensis, which is a typical agricultural and forestry waste, and its raw material source complies with the principle of renewable resources. The preparation of TP involves only physical grinding and does not require the use of strong acids, strong alkalis, or organic solvents, thus avoiding secondary pollution.

[0086] The fabric substrates prepared by this invention are PBAT and PLA, both of which are biodegradable materials. Testing showed that the fabric of Example 2 achieved a degradation rate of 17.18% after 90 days under anaerobic composting conditions, far exceeding that of traditional plastics. The degradation products (CO2, CH4, H2O, and biomass) can be absorbed by the environment and reintroduce into the natural carbon cycle. Scrap materials or waste products generated during production can be crushed and used as fillers to be blended with new materials, achieving recycling in the processing process and reducing resource waste.

[0087] In conclusion, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A bio-based regenerated fiber antibacterial and moisturizing fabric based on agricultural waste, characterized in that, The raw materials include the following by weight: A biobased degradable resin matrix: 50-80 parts of polybutylene adipate terephthalate and 20-50 parts of polylactic acid; A farm waste regenerated fiber filler: 5-20 parts of micron-level taxus powder; An interfacial compatibilizer: 0.3-1.2 parts of an epoxy-functionalized chain extender; The micron-level taxus powder is a powder obtained by drying, ultrafine grinding, ball milling secondary grinding and sieving of taxus residues after extraction of paclitaxel, with an average particle size D50 of 8-15 μm and a large end particle size D90 of 20-30 μm.

2. The bio-based, regenerative, fiber, antibacterial, moisturizing fabric based on agricultural waste according to claim 1, characterized in that: The mass ratio of polybutylene adipate terephthalate to polylactic acid in the biobased degradable resin matrix is 7:

3.

3. The bio-based, regenerative, fiber, antibacterial, moisturizing fabric based on agricultural waste according to claim 1, characterized in that: The epoxy-functionalized chain extender is selected from one of ADR-4370 or ADR-4468.

4. The bio-based, regenerative, fiber, antibacterial, moisturizing fabric based on agricultural waste according to claim 1, characterized in that: The raw materials further include the following by weight of auxiliary agents: 0.1-0.5 parts of an antioxidant and 0.1-0.5 parts of a lubricant; wherein the antioxidant is Irganox 1010 and the lubricant is pentaerythritol stearate.

5. A method of preparing an agricultural waste-based bio-based regenerated fiber antibacterial moisturizing fabric according to any one of claims 1 to 4, characterized by, The method includes the following steps: S1. Preparation of a farm waste regenerated fiber filler: dry taxus residues after extraction of paclitaxel at 40-50 °C for 24 h, and then preliminarily grind the residues with an ultrafine grinder and sieve the ground residues through a 100-mesh sieve; place the obtained powder in a planetary ball mill for secondary grinding to obtain micron-level taxus powder; S2. Drying of raw materials: place polybutylene adipate terephthalate, polylactic acid and the micron-level taxus powder prepared in step S1 in a constant-temperature drying oven at 60-80 °C for drying for 24 h; S3. Melt blending: weigh the dried polybutylene adipate terephthalate, polylactic acid, micron-level taxus powder, epoxy-functionalized chain extender and auxiliary agents according to the proportions by weight, mix them uniformly at room temperature, and then put them into an internal mixer for melt blending; S4. Calendering to form a film: transfer the melt blend to a flat vulcanizing machine for molding, and obtain a composite film after cooling; S5. Cutting and post-processing: cut the obtained composite film to the required size to obtain the antibacterial and moisturizing fabric.

6. The method of claim 5, wherein the method is characterized by: In step S1, the parameters for secondary ball milling are as follows: 100 zirconium beads per jar, a ratio of large, medium and small zirconium beads of 2:2:6, continuous grinding for 20 min, pause for 10 min, and a total grinding time of 4 h.

7. The method of making an agricultural waste based bio-based regenerative fiber, antibacterial, moisturizing fabric of claim 5, wherein: In step S3, the parameters for melt blending are as follows: a temperature of 180-200 °C, a rotation speed of 60-100 r / min, and a mixing time of 8-10 min.

8. The method of claim 5, wherein the method is characterized by: In step S4, the parameters for molding are as follows: a temperature of 180-200 °C, a pressure of 10-20 MPa, and a holding time of 1-3 min.

Images