A Novel Zirconium Modified Arylacetylene Resin: Preparation, Thermal Properties and Ceramifiable Mechanism

With the rapid development of thermal protection systems for the aerospace industry and power electronics, polyarylacetylene (PAA) resin plays an important role because of its good mechanical properties, high glass transition temperature (Tg), low water absorption, high char yield (Yc), and the fact that there is no byproduct released in the curing process. In order to further improve the thermal property of PAA based FRP for the thermal protection field, the introduction of a zirconium element into arylacetylene is promising. In this paper, zirconium modified arylacetylene (ZAA) resin was prepared by two-step synthesis. The FTIR analysis characterized its molecular structure and confirmed the products. The viscosity of ZAA was about 6.5 Pa·s when the temperature was above 120 °C. The DSC analysis showed that the ZAA had a low curing temperature, and its apparent activation energy was 103.86 kJ/mol in the Kissinger method and 106.46 kJ/mol in the Ozawa method. The dielectric constant at 1 MHz of poly(zirconium modified arylacetylene) (PZAA) was 3.4. The TG analysis showed that the temperatures of a weight loss of 5% (Td5) and char yield (Yc) at 800 °C of PZAA were 407.5 °C and 61.4%, respectively. The XRD results showed the presence of SiO2 and ZrO2 in the PZAA residue after ablation. The XRF results showed that the contents of SiO2 and ZrO2 in PZAA residual after ablation were, respectively, 15.3% and 12.4%. The SEM showed that the surface of PZAA after ablation had been covered with a dense and rigid ceramic phase composed of ZrO2 and SiO2. Therefore, the introduction of Zr into arylacetylene greatly improved the densification of the surface after ablation, and improved the heat resistant property.

[1]  Y. Qin,et al.  Effects of Zirconium Silicide on the Vulcanization, Mechanical and Ablation Resistance Properties of Ceramifiable Silicone Rubber Composites , 2020, Polymers.

[2]  M. Barczewski,et al.  Mechanically robust and thermally stable abrasive tools from phenolic resins reinforced with diazonium-modified zeolites , 2018, Polymer Composites.

[3]  Tao Yang,et al.  Thermal stability and ablation resistance, and ablation mechanism of carbon–phenolic composites with different zirconium silicide particle loadings , 2018, Composites Part B: Engineering.

[4]  Emmanuel O. Ogunsona,et al.  Thermally Stable Pyrolytic Biocarbon as an Effective and Sustainable Reinforcing Filler for Polyamide Bio-composites Fabrication , 2018, Journal of Polymers and the Environment.

[5]  Ping Li,et al.  Thermal curing and degradation behaviour of silicon-containing arylacetylene resins , 2016 .

[6]  S. R. Kumar,et al.  Epoxy benzoxazine based ternary systems of improved thermo-mechanical behavior for structural composite applications , 2015 .

[7]  C. Hong,et al.  The effects of zirconium diboride particles on the ablation performance of carbon–phenolic composites under an oxyacetylene flame , 2013 .

[8]  D. Hui,et al.  Improved ablation resistance of carbon–phenolic composites by introducing zirconium diboride particles , 2013 .

[9]  C. Xu,et al.  Liquid poly(silylacetylene)siloxane resin as a novel precursor of silicon carbide and silicon oxycarbide ceramics , 2012 .

[10]  Z. Zhang,et al.  Experimental Study on Crack Defects Formation in Polyarylacetylene Composites and Modification Improvement of Resin , 2010 .

[11]  F. Huang,et al.  A New Silicon-Containing Arylacetylene Resin With Amine Groups as Precursor to Si−C−N Ceramic , 2009 .

[12]  Liwu Liu,et al.  Influence of coupling agent chain lengths on interfacial performances of carbon fiber and polyarylacetylene resin composites , 2009 .

[13]  Sabu Thomas,et al.  Effect of chemical modifications on the thermal stability and degradation of banana fiber and banana fiber-reinforced phenol formaldehyde composites , 2008 .

[14]  F. Huang,et al.  Synthesis and characterization of a novel arylacetylene oligomer containing POSS units in main chains , 2008 .

[15]  F. Huang,et al.  Fiber reinforced silicon-containing arylacetylene resin composites , 2007 .

[16]  浄治 大下,et al.  パターン化可能なセラミックス前駆体としてのポリ[(シアノフェニル)シリレン-p-フェニレン] 類の合成 , 2006 .

[17]  S. Kuo,et al.  Influence of PMMA-Chain-End Tethered Polyhedral Oligomeric Silsesquioxanes on the Miscibility and Specific Interaction with Phenolic Blends , 2006 .

[18]  L. Matějka,et al.  Epoxy Networks Reinforced with Polyhedral Oligomeric Silsesquioxanes (POSS). Thermomechanical Properties , 2004 .

[19]  L. Matějka,et al.  Epoxy Networks Reinforced with Polyhedral Oligomeric Silsesquioxanes (POSS). Structure and Morphology , 2004 .

[20]  P. Hergenrother,et al.  Aryl Ethynyl Terminated Imide Oligomers and Their Cured Polymers , 2002 .

[21]  Craig L. Homrighausen,et al.  High‐temperature elastomers from silarylene‐siloxane‐diacetylene linear polymers , 2002 .

[22]  Joseph G. Smith,et al.  Phenylethynyl containing imide oligomers , 2000 .

[23]  M. Ding,et al.  Study on a novel polyimide precursor prepared by a modified polymerization of monomeric reactants (MPMR) procedure , 2000 .

[24]  J. Ohshita,et al.  Synthesis of Poly{[bis(ethynylphenyl)silylene]phenylene}s with Highly Heat-Resistant Properties , 1999 .

[25]  Junichi Ishikawa,et al.  Thermosetting Mechanism Study of Poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene] by Solid-State NMR Spectroscopy and Computational Chemistry , 1998 .