PING Chenhui^1;2; YAN Hongqiang²; GUO Zhenghong²; LI Juan²; TONG Zaizai¹; FANG Zhengping²;

Abstract：

Aiming at poor carbonization of ABS resin, different structures of benzoxazine monomers (BOZ) were blended with ABS resin compounded with the flame retardant bisphenol A diphenyl phosphate (BDP) and the synergist zinc borate (ZB), and the effects of different structures of BOZ monomers and its formulation with BDP and ZB on the flame retardant and mechanical properties of ABS were also studied in order to achieve efficient halogen-free flame retardancy of ABS resin. The experimental results showed that the combination of BOZ, BDP, and ZB could effectively improve the carbonization of ABS resin and demonstrate excellent synergy in flame retardant modification of ABS resin. The LOI of ABS/10C/15B/2ZB reached 34.4%, and PHRR, THR, AEHC, TOC, and TSR decreased by 45.4%, 22.8%, 23.2%, 21.9%, and 7.7%, respectively, finally FPI and FGI also showed significant improvement. At the same time, its tensile strength also increased to 40.2 MPa, which was slightly higher than that of pure ABS resin (39.9 MPa). Therefore, the combination of BOZ with BDP and ZB can achieve a synergistic improvement in flame retardancy and mechanical properties of ABS resin.

Key Words： ABS;benzoxazine;carbonization;flame retardant;mechanical property

Abstract:

Keywords:

Foundation: 国家自然科学基金资助项目(51991355).

Authors: PING Chenhui^1;2; YAN Hongqiang²; GUO Zhenghong²; LI Juan²; TONG Zaizai¹; FANG Zhengping²;

References：

• [1] 高顺, 郭正虹. PC/ABS合金的气相/凝聚相协同阻燃作用[J]. 浙江大学学报(工学版), 2020, 54(12): 2321-2328. GAO S, GUO Z H. Synergistic flame retardancy of gas phase and condensed phase of PC/ABS alloy[J].Journal of Zhejiang University (Engineering Science), 2020, 54(12): 2321-2328.
  [2] SINI N K, ENDO T. Toward elucidating the role of number of oxazine rings and intermediates in the benzoxazine backbone on their thermal characteristics[J].Macromolecules, 2016, 49(22): 8466-8478.
  [3] ZHANG S, RAN Q C, GU Y. Polymerization mechanism of 1,3-benzoxazine catalyzed by PCl₅ and rearrangement of chemical structures[J].European Polymer Journal, 2021, 142: 110133.
  [4] 殷平, 闫红强, 程捷, 等. 新型生物基苯并口��嗪的合成及性能[J]. 高等学校化学学报, 2019, 40(5): 1071-1079. YIN P, YAN H Q, CHENG J, et al. Synthesis and properties of a novel bio-based benzoxazine[J].Chemical Journal of Chinese Universities, 2019, 40(5): 1071-1079.
  [5] RIGOUSSEN A, RAQUEZ J M, DUBOIS P, et al. A dual approach to compatibilize PLA/ABS immiscible blends with epoxidized cardanol derivatives[J].European Polymer Journal, 2019, 114: 118-126.
  [6] RIGOUSSEN A, VERGE P, RAQUEZ J M, et al. In-depth investigation on the effect and role of cardanol in the compatibilization of PLA/ABS immiscible blends by reactive extrusion[J].European PolymerJournal, 2017, 93: 272-283.
  [7] 王光开, 林晓丹, 杨兵, 等. 苯并噁嗪树脂用于ABS阻燃的研究[J]. 塑料工业, 2011, 39(5): 121-123. WANG G K, LIN X D, YANG B, et al. Research on flame retardance of ABS by benzoxazines[J].China Plastics Industry,2011, 39(5): 121-123.
  [8] YAN H Q, SUN C, FANG Z P, et al. Synthesis of an intrinsically flame retardant bio-based benzoxazine resin[J].Polymer, 2016, 97: 418-427.
  [9] ZHAN Z M, YAN H Q, YIN P, et al. Synthesis and properties of a novel bio-based benzoxazine resin with excellent low-temperature curing ability[J].Polymer International, 2019, 69(4): 355-362.
  [10] ZHAN Z M, YAN H Q, WANG H Q, et al. Novel full bio-based phloroglucinol benzoxazine resin: Synthesis, curing reaction and thermal stability[J].Polymer, 2020, 200: 122534.
  [11] YAN H Q, ZHAN Z M, WANG H Q, et al. Synthesis, curing, and thermal stability of low-temperature-cured benzoxazine resins based on natural renewable resources[J].ACS Applied Polymer Materials, 2021, 3(7): 3392-3401.
  [12] HAUBOLD T S, WOLTER N, SANDINGE A, et al. How phosphorous flame retardant additives affect benzoxazine-based monomer and polymer properties[J].Macromolecular Materials and Engineering, 2023, 308(11): 2300132.
  [13] KARRASCH A, WAWRZYN E, SCHARTEL B, et al. Solid-state NMR on thermal and fire residues of bisphenol A polycarbonate/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate)/(PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB)-Part I: PC charring and the impact of BDP and ZnB[J].Polymer Degradation and Stability, 2010, 95(12): 2525-2533.