尹红¹,柳琳¹,袁慎峰¹,陈志荣¹,李沃源²,邓杭军²

• 1:浙江省化工高效制造技术重点实验室，浙江大学 化学工程与生物工程学院，浙江 杭州 310027
• 2:浙江新和成特种材料有限公司，浙江 上虞 312369

摘要(Abstract)：

为了研究羧基封端聚苯硫醚（PPS）结构对其反应活性和热学性能的影响，合成3种羧基封端PPS并通过红外（FTIR）、端基含量测定、裂解气质联用（py-GC/MS）、高温凝胶渗透色谱（HTGPC）、热重（TGA）、差示扫描量热（DSC）等方法，获得改性样品的端基转化率、裂解机理、反应活性和熔点等参数。结果表明，羧基对PPS原有巯基端基的置换率约为50%。裂解过程中改性样品发生更多的环化、重排和次级反应，生成含氧标志性裂解产物。改性PPS的反应活性提高、热稳定性略有下降，起始分解温度和最高分解速率温度均有所降低，熔点升高，结晶度增大。

关键词(KeyWords)： 聚苯硫醚;端基改性;羧基;热性能

Abstract:

Keywords:

基金项目(Foundation):

作者(Author): 尹红¹,柳琳¹,袁慎峰¹,陈志荣¹,李沃源²,邓杭军²

DOI: 10.3969/j.issn.1003-9015.2021.01.006

参考文献(References)：

• [1] 张声春, 杭祖圣, 李栋, 等. 非等温热重法研究聚苯硫醚热分解动力学[J]. 应用化工, 2011, 40(12):2189-2192.ZHANG S C, HANG Z S, LI D, et al. Study on the thermal decomposition kinetics of polyphenylene sulfide (PPS) by non-isothermal thermogravimetry[J]. Applied Chemical Industry, 2011, 40(12):2189-2192.
  [2] GU J, DU J, DANG J. Thermal conductivities, mechanical and thermal properties of graphite nanoplatelets/polyphenylene sulfide composites[J]. RSC Advances, 2014, 4(42):22101-22105.
  [3] DÍEZ-PASCUAL A M, GUAN J, SIMARD B, et al. Poly (phenylene sulphide) and poly (ether ether ketone) composites reinforced with single-walled carbon nanotube buckypaper:II-Mechanical properties, electrical and thermal conductivity[J]. Composites Part A:Applied Science and Manufacturing, 2012, 43(6):1007-1015.
  [4] ZHU C, ZHANG J, Xu J, et al. Aramid nanofibers/polyphenylene sulfide nonwoven composite separator fabricated through a facile papermaking method for lithium ion battery[J]. Journal of Membrane Science, 2019, 588:117169.
  [5] KOUTRAS N, AMIRDINE J, BOYARD N, et al. Characterisation of crystallinity at the interface of ultrasonically welded carbon fibre PPS joints[J]. Composites Part A:Applied Science and Manufacturing, 2019, 125:105574.
  [6] LOHR C, BECK B, HENNING F, et al. Mechanical properties of foamed long glass fiber reinforced polyphenylene sulfide integral sandwich structures manufactured by direct thermoplastic foam injection molding[J]. Composite Structures, 2019, 220:371-385.
  [7] LI X, XU D, GONG N, et al. Improving the strength of injection molded aluminum/polyphenylene sulfide lap joints dependence on surface microstructure and composition[J]. Materials & Design, 2019, 179:107875.
  [8] YANG C, HAN N, ZHANG W, et al. Adhesive-free in situ synthesis of a coral-like titanium dioxide@poly(phenylene sulfide) microporous membrane for visible-light photocatalysis[J]. Chemical Engineering Journal, 2019, 374:1382-1393.
  [9] YU Z, MIAO G, WU Q, et al. Synthesis of thiol- and carboxyl-terminated poly(p-phenylene sulfide) oligomers[J]. Macromolecular Chemistry & Physics, 1996, 197(12):4061-4068.
  [10] 胡泽旭, 孟思, 周哲. 纳米填料改性聚苯硫醚及其纤维研究进展[J]. 中国材料进展, 2014(8):484-491.HU Z X, MENG S, ZHOU Z. Research progress on polyphenylene sulfide (PPS) nanocomposites materials and fibers[J]. Materials China, 2014(8):484-491.
  [11] YANG Y, DUAN H, ZHANG S, et al. Morphology control of nanofillers in poly (phenylene sulfide):A novel method to realize the exfoliation of nanoclay by SiO₂ via melt shear flow[J]. Composites Science and Technology, 2013, 75:28-34.
  [12] STOEFFLER K, ANDJELIC S, LEGROS N, et al. Polyphenylene sulfide (PPS) composites reinforced with recycled carbon fiber[J]. Composites Science and Technology, 2013, 84:65-71.
  [13] ZHOU S, ZHANG Q, WU C, et al. Effect of carbon fiber reinforcement on the mechanical and tribological properties of polyamide6/polyphenylene sulfide composites[J]. Materials & Design, 2013, 44:493-499.
  [14] 赵建青, 李志光, 陈元武. 玻纤增强PPS/Al₂O₃复合材料导热性能的研究[J]. 塑料工业, 2014(10):87-90.ZHAO J Q, LI Z G, CHEN Y W. Thermal conductivity of PPS/Al₂O₃ composites strengthened with glass fiber[J]. China Plastics Industry, 2014(10):87-90.
  [15] GUI H, ZHOU T, LI L, et al. Structure, properties, and mechanism of reactive compatibilization of epoxy to polyphenylene sulfide/polyamide elastomer[J]. Journal of Applied Polymer Science, 2013, 130(5):3411-3420.
  [16] 唐元鑫, 张马亮, 李振环. 聚苯硫醚填充与共混改性研究进展[J]. 合成纤维, 2014, 43(3):27-32.TANG Y X, ZHANG M L, LI Z H. Research progress on filling and blending modification of polyphenylene sulfide[J]. Synthetic Fiber in China, 2014, 43(3):27-32.
  [17] YANG S, ZHANG J, BO Q, et al. Synthesis and characterization of poly(phenylene sulfide):I. Studies on the synthesis and the property differences of poly(phenylene sulfide) with terminal chloro groups and poly(phenylene sulfide) with terminal thiohydroxy groups[J]. Journal of Applied Polymer Science, 1993, 50(11):1883-1889.
  [18] LI K, WU Q, YU Z, et al. Study on the synthesis and property differences of two kinds of terminated poly(phenylene sulfide) oligomers[J]. European Polymer Journal, 1996, 32(12):1371-1375.
  [19] BUDGELL D R, DAY M, COONEY J D. Thermal degradation of poly (phenylene sulfide) as monitored by pyrolysis-GC/MS[J]. Polymer Degradation and Stability, 1994, 43(1):109-115.
  [20] PERNG L H. Thermal decomposition characteristics of poly (phenylene sulfide) by stepwise Py-GC/MS and TG/MS techniques[J]. Polymer Degradation and Stability, 2000, 69(3):323-332.
  [21] CHENG S Z D, WUNDERLICH B. Thermal analysis of thermoplastic polymers[J]. Thermochimica Acta, 1988, 134:161-166.