不同结构的含硅芳炔树脂共混改性研究

玻璃钢/复合材料 ›› 2016, Vol. 0 ›› Issue (7): 63-68.

不同结构的含硅芳炔树脂共混改性研究

蒋孝杰, 邓诗峰^*, 杜磊

特种功能高分子材料及相关技术教育部重点实验室,华东理工大学,上海200237

收稿日期:2016-01-12 出版日期:2016-07-28 发布日期:2016-07-28
通讯作者: 邓诗峰,男,博士,副教授,主要从事耐高温树脂及薄透材料的研究,sfdeng@ecust.edu.cn。
作者简介:蒋孝杰(1990-),男,硕士研究生,主要从事耐高温树脂的合成及性能研究相关工作。

INVESTIGATION OF BLENDING MODIFIED POLY (SILYLENE-ARYLACETYLENE) WITH DIFFERENT GROUPS

JIANG Xiao-jie, DENG Shi-feng^*, DU Lei

Key Laboratory of Specially Functional Polymeric Materials and Related Technology of the Ministry of Education, East China University of Science and Technology, Shanghai 200237, China

Received:2016-01-12 Online:2016-07-28 Published:2016-07-28

摘要/Abstract

摘要： 含硅芳炔(PSA)树脂是一种新型耐高温树脂,固化后具有优良的力学性能和透波性。PSA树脂一般采用格氏试剂法制备,该方法制备的PSA(PSA-G)树脂固化后交联密度高,脆性较大。锌粉催化法是一种新型、高效的PSA合成方法。该方法合成的PSA(PSA-Zn)树脂末端含有部分烯键,树脂粘度低,交联密度小,脆性相对较小,但耐热性相对PSA-G树脂有所降低。采用PSA-G共混PSA-Zn得到改性树脂,研究了改性树脂的固化工艺、粘度、耐热性以及PSA-Zn质量分数为70%的改性树脂复合材料和树脂浇铸体的力学性能。研究结果表明PSA-Zn含量为70%的共混树脂粘度较低,为122mPa·s;热分解5%时的温度(T_d5)达564℃,耐热性较好;复合材料具有良好的力学性能,浇铸体弯曲强度比PSA-G提高了11%。

关键词: 含硅芳炔, 共混改性, 耐高温, 复合材料

Abstract: Poly(silylene-arylacetylene) (PSA) resin is a new high-temperature resin. The cured resin exhibits excellent mechanical properties and good wave transmission properties. PSA resin usually prepared by Grignard reagent, and the resin (PSA-G) is brittle because of the high crosslink density after being cured. PSA prepared by catalyst zinc is a new method with high efficiency. PSA prepared by zinc (PSA-Zn) is a kind of PSA resin with terminal olefinic bond. PSA-Zn has low viscosity and the flexural properties of the cured resin are better than PAS-G while the thermal property is a little lower than PSA-G. In this paper, PSA-G was used to blend with PSA-Zn to obtain a modified resin. The curing process, the viscosity and the heat resistance of the modified resin was studied. Quartz fiber reinforced composite and casting of the modified resin (PSA-Zn′s content is 70 wt%) were prepared and the mechanical properties of the composite and the casting were tested. The results show that the modified resin (PSA-Zn′s content is 70 wt%) kept a low viscosity, the T_d5 (temperature that the weight decreases 5%) of the resin reached to 564 ℃, the composite has good mechanical properties and the flexural strength of the casting increased by 11% relative to PSA-G.

Key words: poly(silylene-arylacetylene), blending modification, high-temperature resistance, composite

中图分类号:

TB332

蒋孝杰, 邓诗峰, 杜磊. 不同结构的含硅芳炔树脂共混改性研究[J]. 玻璃钢/复合材料, 2016, 0(7): 63-68.

JIANG Xiao-jie, DENG Shi-feng, DU Lei. INVESTIGATION OF BLENDING MODIFIED POLY (SILYLENE-ARYLACETYLENE) WITH DIFFERENT GROUPS[J]. Fiber Reinforced Plastics/Composites, 2016, 0(7): 63-68.

参考文献

[1] Buvat P, Jousse F, Delnaud L, et al. Synthesis and properties of new processable type polyarylacetylenes[J]. A materials and processes odyssey, 2001, 134-144.
[2] 张玲玲, 高飞, 周围, 等. 含硅氢基团甲基芳炔树脂的合成及表征[J]. 过程工程学报, 2009, 9(3): 574-579.
[3] Itoh M, Inoue K, Hirayama N, et al. Fiber reinforced plastics using a new heat-resistant silicon based polymer[J]. Journal of materials science, 2002, 37(17): 3795-3801.
[4] Zhang J, Huang J, Du W, et al. Thermal stability of the copolymers of silicon-containing arylacetylene resin and acetylene-functional benzoxazine[J]. Polymer Degradation and Stability, 2011, 96(12): 2276-2283.
[5] Jiang Z, Zhou Y, Du L. Characterization of a modified silicon-containing arylacetylene resin with POSS functionality[J]. Chinese Journal of Polymer Science, 2011, 29(6): 726-731.
[6] Itoh M, Inoue K, Iwata K, et al. New highly heat-resistant polymers containing silicon: poly (silyleneethynylenephenyleneethynylene) s[J]. Macromolecules, 1997, 30(4): 694-701.
[7] Itoh M, Mitsuzuka M, Iwata K, et al. A novel synthesis and extremely high thermal stability of poly [(phenylsilylene) ethynylene-1, 3-phenyleneethynylene][J]. Macromolecules, 1994, 27(26): 7917-7919.
[8] Itoh M, Mitsuzuka M, Iwata K, et al. Poly (silyleneethynylene phenyleneethynylenes), method for preparing same and hardened product thereof: U.S. Patent 5,420,238[P]. 1995-5-30.
[9] Itoh M. A novel synthesis of a highly heat-resistant organosilicon polymer using base catalysts[J]. Catalysis Surveys from Asia, 1999, 3(1): 61-69.
[10] Liu H Q, Harrod J F. Copper (I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes[J]. Canadian Journal of Chemistry, 1990, 68(7): 1100-1105.
[11] Meorg U, Viirlaid S, Hagu H, et al. On the in situ trimethylsilylation of zinc acetylides[J]. Journal of Organometallic Chemistry, 2000, 601(2): 341-342.
[12] 严浩, 齐会民, 黄发荣. 新颖含硅芳基多炔树脂的合成与性能[J]. 石油化工, 2004, 33(9): 880-884.
[13] 张健, 周围, 黄健翔, 等. 新型含硅芳炔树脂及其复合材料的性能:复合材料——基础、创新、高效:第十四届全国复合材料学术会议论文集(上)[C]. 北京: 中国导航出版社, 2006.
[14] Xu J F, Wang C Y, Lai G Q, et al. Synthesis and characterization of phenylacetylene-terminated poly (silyleneethynylene-4, 4′-phenylethereneethynylene) s[J]. European polymer journal, 2007, 43(2): 668-672.
[15] 沈浩, 蒋孝杰, 周燕, 等. 锌粉催化合成含硅芳炔树脂[J]. 过程工程学报, 2014(2): 024.
[16] Wang M C, Zhao T. Polyarylacetylene blends with improved processability and high thermal stability[J]. Journal of applied polymer science, 2007, 105(5): 2939-2946.
[17] Wang S, Li M, Gu Y, et al. Experimental study on crack defects formation in polyarylacetylene composites and modification improvement of resin[J]. Journal of composite materials, 2010, 44(25): 3017-3032.
[18] Huang J X, Du W, Zhang J, et al. Study on the copolymers of silicon-containing arylacetylene resin and acetylene-functional benzoxazine[J]. Polymer bulletin, 2009, 62(2): 127-138.
[19] 汤乐旻, 周燕, 田鑫, 等. 改性含硅芳炔树脂及其复合材料性能研究[J]. 玻璃钢/复合材料, 2012 (6).
[20] 齐会民, 王光后, 张健, 等. 含硅芳炔树脂的改性及其性能研究[C]. 第十五届全国复合材料学术会议论文集 (上册), 2008.
[21] 李晓杰, 陈会高, 袁荞龙, 等. 端乙炔基聚醚酰亚胺改性含硅芳炔树脂的性能[J]. 石油化工, 2015, 44(9): 1115-1120.
[22] 刘海帆, 邓诗峰, 黄发荣, 等. 乙酰丙酮镍催化含硅芳炔树脂的固化反应行为[J]. 过程工程学报, 2012, 12(1): 154-159.
[23] 孙赛, 刘木金, 王海, 等. RTM 成型工艺及其派生工艺[J]. 宇航材料工艺, 2010 (6).