College of Furnishings and Industrial Design, Nanjing Forestry University, Nanjing 210037, China.
Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing 210042, China.
Int J Biol Macromol. 2023 Dec 31;253(Pt 2):126743. doi: 10.1016/j.ijbiomac.2023.126743. Epub 2023 Sep 7.
Cellulose nanocrystals (CNCs) are green reinforcing materials, and their potential has been evaluated in the preparation of waterborne UV-curable resin composites with high-performance. Herein, we present a novel and scalable approach for preparing surface-modified CNCs with acrylic-based polymers to strengthen the compatibility and interaction between CNCs and UV-curable resins. Using tert-butyl acrylate as the monomer, the nanocellulose grafted copolymer CNC-g-PtBA was successfully synthesized via atom transfer radical polymerization (ATRP) in the presence of a macromolecular initiator. Then, the CNC-g-PtBA is blended into the acrylic resin as a nanofiller to prepare the UV-curable nanocomposite. The results indicated that the contact angle of the CNCs increased from 38.7° to approximately 74.8°, and their thermal stability was significantly improved after graft modification. This contributed to the effective alleviation of the agglomeration phenomenon of nanocomposites due to the high hydrophilicity of pure CNCs. Notably, not only was the UV curing efficiency of the nanocomposites greatly increased but the mechanical properties were also further enhanced. Specifically, with the addition of 0.5 wt% CNC-g-PtBA, the curing time of the nanocomposite was shortened from >30 mins down to approximately 6 mins, and the bending strength was increased from 10 MPa for the original resin and 5 MPa for the addition of pure CNCs to 14.3 MPa, and the bending modulus was also greatly increased (up to approximately 730 MPa). Compared to pure CNCs, they are compatible with the resin, exhibiting high mechanical strength and flexibility, and have virtually no effect on the light transmission of the nanocomposites. Additionally, dielectric analysis (DEA) was used to monitor the dielectric constant and conductivity of the UV-curable nanocomposites in real time to further characterize their curing kinetics. The permittivity of these nanocomposites increased by 125 % compared to pristine resin, which shows potential for applications in high dielectric composites or for improving electrical conductivity. This work provides a feasible method for preparing UV-curable nanocomposites with high curing efficiency and permittivity, realizing a wider application of this high-performance nanocomposite.
纤维素纳米晶(CNC)是绿色增强材料,其在制备高性能水基紫外光固化树脂复合材料方面的潜力已得到评估。本文提出了一种新颖且可扩展的方法,通过原子转移自由基聚合(ATRP),使用叔丁基丙烯酸酯作为单体,在大分子引发剂存在下成功合成了接枝丙烯酸酯的纳米纤维素接枝共聚物 CNC-g-PtBA。然后,将 CNC-g-PtBA 作为纳米填料混入丙烯酸树脂中制备紫外光固化纳米复合材料。结果表明,CNC 的接触角从 38.7°增加到约 74.8°,接枝改性后其热稳定性显著提高。这有助于有效缓解由于纯 CNC 高亲水性而导致的纳米复合材料的团聚现象。值得注意的是,不仅纳米复合材料的紫外光固化效率大大提高,而且机械性能也进一步增强。具体来说,添加 0.5wt%的 CNC-g-PtBA 后,纳米复合材料的固化时间从超过 30 分钟缩短到约 6 分钟,弯曲强度从原始树脂的 10MPa 和添加纯 CNCs 的 5MPa 提高到 14.3MPa,弯曲模量也大大提高(高达约 730MPa)。与纯 CNCs 相比,它们与树脂相容,具有较高的机械强度和柔韧性,对纳米复合材料的透光率几乎没有影响。此外,通过介电分析(DEA)实时监测紫外光固化纳米复合材料的介电常数和电导率,进一步表征其固化动力学。与原始树脂相比,这些纳米复合材料的介电常数增加了 125%,这表明它们在高介电复合材料或提高电导率方面具有应用潜力。这项工作为制备具有高固化效率和介电常数的紫外光固化纳米复合材料提供了一种可行的方法,实现了这种高性能纳米复合材料的更广泛应用。