苯并噁嗪-氨基稀释剂改性硅炔杂化树脂及其复合材料性能

束长朋; 王茂源; 周权; 宋宁; 倪礼忠

doi:10.13801/j.cnki.fhclxb.20200224.002

苯并噁嗪-氨基稀释剂改性硅炔杂化树脂及其复合材料性能

doi: 10.13801/j.cnki.fhclxb.20200224.002

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

基金项目: 国家自然科学基金(51573044)

详细信息

通讯作者:
周权，博士，副教授，硕士生导师，研究方向为耐高温树脂基复合材料　E-mail：qzhou@ecust.edu.cn

中图分类号: TB332; TQ322
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出版历程
- 收稿日期: 2019-12-10
- 录用日期: 2020-01-16
- 网络出版日期: 2020-02-25
- 刊出日期: 2020-11-15

Properties of silicone-acetylene resin modified with ethynyl benzoxazine-amino diluent and its composite

Key Laboratory for Special Polymer Materials and Related Technology, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 采用氨基稀释剂(AD)和端乙炔基型聚苯并噁嗪(EB)树脂改性一种具有高力学性能的聚(间二乙炔基苯-二甲基硅烷)(PDMP)树脂。按照质量比PDMP∶EB∶AD=5∶1∶1进行共混后制备PDMP-EB-AD树脂。利用FTIR、DSC、介电分析仪(DEA)、TGA分析改性前后树脂的结构、黏度、固化过程和耐热性能变化。结果表明，AD与EB中的—NH₂和—C≡CH均参与进PDMP固化过程中，共混后PDMP-EB-AD树脂固化温度升高，黏度降低，热分解温度(T_d5)在N₂和空气下分别为539.5℃和518.7℃，1 000℃质量保留率分别为85.1%和18.1%。利用浸渍法将PDMP-EB-AD树脂与石英纤维(QF)制备成预浸料进行模压成型，制备的QF增强PDMP-EB-AD树脂(QF/(PDMP-EB-AD))复合材料力学性能极大提高，且树脂与纤维的黏结性得到改善。常温下QF/(PDMP-EB-AD)复合材料弯曲强度和层间剪切强度(ILSS)分别为694.5 MPa和41.9 MPa，较QF/PDMP复合材料分别提高了176.6%和96.7%，250℃时弯曲强度和ILSS达到319.5 MPa和20.11 MPa。
- 硅炔杂化树脂 /
- 端乙炔基型苯并噁嗪 /
- 氨基稀释剂 /
- 热性能 /
- 力学性能
Abstract: The poly (dimethylsilane-m-diacetylenyl phenyl) (PDMP) resin was modified by amino diluent (AD) and ethynyl benzoxazine (EB) resin. The modified blending PDMP-EB-AD resin was prepared according to PDMP∶EB∶AD mass ratio=5∶1∶1. The FTIR, DSC, dielectric analyzer (DEA), TGA were used to analyze the molecular structure, viscosity, curing process and heat resistance of the resin before and after modification. The test results show that —NH₂ and —C≡CH in the AD and EB participate in the PDMP curing process. The curing temperature of the PDMP-EB-AD resin increases and the viscosity decreases. The thermal decomposition temperatures (T_d5) of the PDMP-EB-AD resin at N₂ and air are 539.5℃ and 518.7℃, respectively. The mass retention rates of the PDMP-EB-AD resin at 1 000℃ are 85.1% and 18.1%, respectively. The quartz fiber (QF)/(PDMP-EB-AD) composites were prepared by PDMP-EB-AD resin and QF by impregnation and compression molding methods. The adhesion between resin and fiber and the mechanical properties greatly improve. The flexural strength and interlaminar shear strength (ILSS) of the QF/(PDMP-EB-AD) composites at room temperature are 694.5 MPa and 41.9 MPa, respectively, which are 176.6% and 96.7% higher than the QF/PDMP composite under the same conditions, the flexural strength and ILSS at 250℃ are 319.5 MPa and 20.11 MPa, respectively.
- silicone-acetylene resin /
- ethynyl benzoxazine /
- amino diluent /
- thermal properties /
- mechanical properties

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图 1 聚(间二乙炔基苯-二甲基硅烷)(PDMP)树脂和端乙炔基型苯并噁嗪(EB)树脂的结构式

Figure 1. Structures of poly(dimethylsilane-m-diacetylenyl phenyl) (PDMP) resin and ethynyl benzoxazine (EB) resin

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图 2 PDMP-EB-氨基稀释剂(AD)树脂固化前后的FTIR图谱

Figure 2. FTIR spectra of PDMP-EB-amino diluent(AD) resin before and after curing

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图 3 PDMP和PDMP-EB-AD树脂的DSC曲线

Figure 3. DSC curves of PDMP and PDMP-EB-AD resins

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图 4 PDMP和PDMP-EB-AD树脂的动态黏度曲线

Figure 4. Viscosity curves of PDMP and PDMP-EB-AD resins

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图 5 PDMP和PDMP-EB-AD树脂的固化转化率曲线

Figure 5. Cure conversion curves of PDMP and PDMP-EB-AD resins

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图 6 PDMP和PDMP-EB-AD树脂的介电分析(DEA)曲线

Figure 6. Dielectric analysis(DEA) curves of PDMP and PDMP-EB-AD resins

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图 7 PDMP和PDMP-EB-AD树脂固化物的TGA曲线

Figure 7. TGA curves of cured PDMP and PDMP-EB-AD resins

T_d5—Thermal decomposition temperature

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图 8 石英纤维(QF)/(PDMP-EB-AD)复合材料在室温和250℃时的弯曲强度和层间剪切强度

Figure 8. Flexual strength and interlaminar shear strength of quartz fiber(QF)/(PDMP-EB-AD) composites at room temperature and 250°C

RT—Room temperature

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图 9 QF/PDMP和QF/(PDMP-EB-AD)复合材料弯曲载荷-位移曲线

Figure 9. Flexural load-displacement curves of QF/PDMP and QF/(PDMP-EB-AD) composites

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图 10 QF/PDMP和QF/(PDMP-EB-AD)复合材料在断裂面和层间破坏面的SEM图像

Figure 10. SEM images of QF/PDMP and QF/(PDMP-EB-AD) composites on fracture surface and interlayer surface

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参考文献(21)

[1]	徐彬, 周权, 倪礼忠. 硅炔杂化树脂改性有机硅树脂及其复合材料的性能[J]. 功能高分子学报, 2012, 25(2):148-151, 158. XU Bin, ZHOU Quan, NI Lizhong. Properties of silicone resin modified silicone resin and its composites[J]. Journal of Functional Polymers,2012,25(2):148-151, 158(in Chinese).
[2]	胡永彬, 王帆, 朱亚平, 等. SiO₂中空微球改性含硅芳炔树脂及其复合材料的结构与性能[J]. 复合材料学报, 2019, 36(3):592-601. HU Yongbin, WANG Fan, ZHU Yaping, et al. Structure and properties of SiO₂ hollow microspheres modified Si-containing arylacetylene resin and their composites[J]. Acta Materiae Compositae Sinica,2019,36(3):592-601(in Chinese).
[3]	周围, 张健 ,尹国光, 等. 氯化含硅芳炔树脂的合成[J]. 石油化工, 2007, 36(6):618-622. ZHOU W, ZHANG J, YIN G G, et al. Synthesis of chlorinated silicon-containing aryne resin[J]. Petrochemical Technology,2007,36(6):618-622(in Chinese).
[4]	成滨, 扈艳红, 邓诗峰, 等. 一种含腈基的硅烷偶联剂改性石英纤维/含硅芳炔复合材料[J]. 复合材料学报, 2019, 36(3):545-554. CHENG Bin, HU Yanhong, DENG Shifeng, et al. Interfacial modification of quartz fiber/silicon-containing arylacetylene composites using novel dicyanide-containing silane coupling agent[J]. Acta Materiae Compositae Sinica,2019,36(3):545-554(in Chinese).
[5]	王林靖, 扈艳红, 杜磊, 等. 乙炔基芳酰胺酸硅烷改进石英纤维/含硅芳炔复合材料高温界面性能[J]. 复合材料学报, 2016, 33(2):287-296. WANG Linjing, HU Yanhong, DU Lei, et al. High-temperature interfacial property of quartz fiber/silicon-containing arylacetylene composites with aromatic amic acid-containing alkyne-terminated silane[J]. Acta Materiae Compositae Sinica,2016,33(2):287-296(in Chinese).
[6]	LASKOSKI M, DOMINGUEZ D D, KELLER T M. Alkyne-containing phthalonitrile resins: Controlling mechanical properties by selective curing[J]. Journal of Polymer Science Part A: Polymer Chemistry,2013,51(22):4774-4778. doi: 10.1002/pola.26899
[7]	贾坤, 徐明珍, 潘海, 等. 耐高温腈基聚合物及复合材料研究进展[J]. 中国材料进展, 2015, 34(12):897-905. JIA K, XU M Z, PAN H, et al. Research progress of high temperature resistant phthalonitrile-based polymers and composites[J]. Materials China,2015,34(12):897-905(in Chinese).
[8]	LANGE N, DIETRICH P M, LIPPITZ A, et al. New azidation methods for the functionalization of silicon nitride and application in copper-catalyzed azide-alkyne cycloaddition (CuAAC)[J]. Surface and Interface Analysis,2016,48(7):621-625. doi: 10.1002/sia.5950
[9]	卢丹, 束长朋, 周权, 等. 聚(间二乙炔基苯-甲基氢硅烷)/含乙炔基苯并噁嗪树脂共混体系固化行为及其耐热性能研究[J]. 北京化工大学学报(自然科学版), 2019, 46(3):54-60. LU Dan, SHU Changpeng, ZHOU Quan, et al. Curing behavior and heat resistance of poly(m-diethynylbenzenemethylsilane)/acetylene-functional benzoxazine blended resins[J]. Journal of Beijing University of Chemical Technology (Natural Science Edition),2019,46(3):54-60(in Chinese).
[10]	SHEN Y, YUAN Q, HUANG F, et al. Effect of neutral nickel catalyst on cure process of silicon-containing polyarylacetylene[J]. Thermochimica Acta,2014,590:66-72. doi: 10.1016/j.tca.2014.06.002
[11]	LAM J W Y, TANG B Z. Functional polyacetylenes[J]. Accounts of Chemical Research,2005,38(9):745-754.
[12]	ITOH M, MITSUZUKA M, IWATA K, et al. A novel synthesis and extremely high thermal stability of poly[(phenyl-silylene)ethynylene-1,3-phenyleneethyny-lene][J]. Macromolecules,1994,27(26):7917-7919. doi: 10.1021/ma00104a056
[13]	ITOH M, INOUE K, IWATA K, et al. New highly heat-resistant polymers containing silicon: Poly(silylene-ethynylenephenyleneethynylene)s[J]. Macromolecules,1997,30(4):694-701.
[14]	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. doi: 10.1023/A:1016538014803
[15]	OGASAWARA T, ISHIKAWA T, ITOH M, et al. Carbon fiber reinforced composites with newly developed silicon containing polymer MSP[J]. Advanced Composite Materials,2001,10(4):319-327. doi: 10.1163/156855101753415346
[16]	OGASAWARA T, ISHIKAWA T, YAMADA T, et al. Thermal response and ablation characteristics of carbon fiber reinforced composite with novel silicon containing polymer MSP[J]. Journal of Composite Materials,2002,36(2):143-157. doi: 10.1177/0021998302036002554
[17]	陈麒, 李扬, 戴泽亮, 等. 甲基二苯乙炔基硅烷及其网络聚合物的合成与表征[J]. 化学学报, 2005, 63(3):254-258. doi: 10.3321/j.issn:0567-7351.2005.03.015 CHEN Qi, LI Yang, DAI Zeliang, et al. Synthesis and characterization of methyl-di(phenylethynyl)silane and its network polymer[J]. Journal of Chemistry,2005,63(3):254-258(in Chinese). doi: 10.3321/j.issn:0567-7351.2005.03.015
[18]	DAI Z L, CHEN Q, NI L Z, et al. Curing kinetics and structural changes of a of di[(N-m-acetenylphenyl) phthalimidel ether/[(methyl) diphenylacetylene] silane copolymer[J]. Journal of Applied Polymer Science,2006,100(3):2126-2130. doi: 10.1002/app.23596
[19]	ZHOU Q, NI L Z. Bismaleimide-modified methyl-di(phe-nylethynyl)silane blends and composites: Cure characteristics, thermal stability, and mechanical property[J]. Journal of Applied Polymer Science,2009,112(6):3721-3727. doi: 10.1002/app.29541
[20]	中国国家标准化管理委员会. 纤维增强塑料弯曲性能试验方法: GB/T 1449—2005[S]. 北京: 中国标准出版社, 2005. Standardization Administration of the People’s Republic of China. Fiber-reinforced plastic composites: Determination of flexural properties: GB/T 1449—2005[S]. Beijing: China Standards Press, 2005(in Chinese).
[21]	中国国家标准化管理委员会. 纤维增强塑料层间剪切强度试验方法: GB/T 1450.1—2005[S]. 北京: 中国标准出版社, 2005. Standardization Administration of the People’s Republic of China. Fiber-reinforced plastic composites: Determination of interlaminar shear strength: GB/T 1450.1—2005[S]. Beijing: China Standards Press, 2005(in Chinese).