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低共熔溶剂辅助交联协同增强明胶基可生物降解缓冲材料的制备与性能

Preparation and Properties of Deep Eutectic Solvent-assisted Crosslinking Synergistically Reinforced Gelatin-based Biodegradable Buffering Materials

  • 摘要:
    目的 开发可生物降解缓冲材料,替代石油基产品,缓解“白色污染”。
    方法 以明胶为基体,双(2-二甲氨基乙基)醚(BDMAEE)为交联剂,在低共熔溶剂(DES)辅助下,协同稻草纤维制备生物基缓冲包装材料(BCMP),采用差示扫描量热仪、红外光谱仪及扫描电镜对其进行表征,并对材料压缩回弹性能与土壤降解行为进行系统评估。
    结果 研究结果表明,在DES作用下,BDMAEE与明胶的氨基、羧基发生共价交联,形成致密网络结构,使材料变性温度由73.1 ℃提升至85.8 ℃,疏水性增强,微观形貌更均匀。该材料在应变<60%时表现出类似石油基材料的缓冲性能,三次压缩回弹率分别为79%、76%和74%,符合传统标准;经120 d土壤降解实验,降解率达91.3%。
    结论 BCMP兼具良好的实用性与环境友好性,为绿色包装提供了可行途径。

     

    Abstract:
    Objective A high-performance, biodegradable bio-based cushioning packaging material (BCMP) was developed as a sustainable alternative to non-degradable petroleum-based materials such as expanded polystyrene (EPS) and expanded polyethylene (EPE). The primary goal was to leverage natural biopolymers and agricultural waste to create a material that combines excellent cushioning performance with environmental benefits, specifically addressing the issue of “white pollution”. The research focused on enhancing the properties of gelatin, a natural protein, through a novel deep eutectic solvent (DES)-assisted crosslinking strategy, and integrating it with rice straw fiber for reinforcement.
    Methods Gelatin was selected as the matrix and modified using a DES system composed of sodium acetate trihydrate and urea (molar ratio of 1∶2). Bis(2-dimethylaminoethyl) ether (BDMAEE) served as the crosslinking agent within this DES medium to facilitate its covalent bonding with gelatin's functional groups. The crosslinked gelatin product (GBDES) was characterized against a control sample (G-F, prepared in pure water) using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR), contact angle measurements, and scanning electron microscopy (SEM). The BCMP was then fabricated by hot-pressing GBDES with alkali-pretreated rice straw fibers and calcium carbonate filler. The final material's performance was systematically characterized through static compression tests (according to GB/T 8168-2008), rebound rate measurements after three compression cycles, and a 120-day soil burial degradation test to assess its biodegradability.
    Results The DES-assisted crosslinking strategy was proved highly effective. DSC analysis showed that the denaturation temperature of the crosslinked film (GBDES-F) increased significantly to 85.8 ℃ from 73.1 ℃ for the control (G-F), indicating the enhanced thermal stability and crosslinking density Fig.1. FT-IR spectra confirmed the successful covalent crosslinking, with the formation of new amide bonds evidenced by a stronger peak at 1403 cm−1 Fig.2. Contact angle measurements demonstrated the improved hydrophobicity for GBDES-F (initial angle~99.3°) compared to G-F (~92.8°), which decreased slowly over time, suggesting a more water-resistant and stable network structure Tab.2. SEM images revealed that the crosslinked film possessed a smoother surface and a more uniform, less porous cross-section than the control Fig.3. The resulting BCMP exhibited promising cushioning properties. Its stress-strain behavior was comparable to that of traditional EPE and EPS materials at strains below 60% Fig.4. The material demonstrated good elastic recovery, with rebound rates of 79%, 76%, and 74% over three consecutive compression cycles, meeting the practical standards for cushioning packaging Fig.5. Most importantly, the BCMP showed excellent biodegradability, achieving a degradation rate of 91.3% after 120 days of soil burial. The degradation profile followed a three-stage process, initially slowed by the antimicrobial effect of urea from the DES, then accelerated as microorganisms metabolized the gelatin and hemicellulose components, and finally plateaued during the slower degradation of crystalline cellulose Fig.6.
    Conclusions A novel bio-based cushioning material was successfully developed through DES-assisted crosslinking of gelatin with BDMAEE and reinforcement with rice straw fibers. This approach significantly improved the thermal stability, hydrophobicity, and structural integrity of the gelatin matrix. The final BCMP composite demonstrated cushioning and elastic recovery performance on par with conventional petroleum-based materials. Coupled with its high biodegradability (91.3% of degradation rate in 120 days), the BCMP presents a viable and environmentally friendly alternative for sustainable packaging. This work provides a new strategy for valorizing biomass resources and offers a practical solution for developing high-performance, fully biodegradable materials to mitigate plastic pollution.

     

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