侧氰基芳醚硅芳炔树脂的制备与表征

马满平; 戴妮娉; 李传; 刘晓天; 袁荞龙; 黄发荣

doi:10.13801/j.cnki.fhclxb.20200507.003

侧氰基芳醚硅芳炔树脂的制备与表征

doi: 10.13801/j.cnki.fhclxb.20200507.003

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: 中央高校基本科研业务费专项资金(50321042017001)

详细信息

通讯作者:
黄发荣，博士，教授，博士生导师，研究方向为特种聚合物及复合材料　E-mail：fhuanglab@ecust.edu.cn

中图分类号: TB332；TQ323
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出版历程
- 收稿日期: 2020-03-09
- 录用日期: 2020-04-10
- 网络出版日期: 2020-05-07
- 刊出日期: 2020-12-15

Preparation and characterization of a silicon-containing arylacetylene resin with cyano groups

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: 在无水三氟甲磺酸锌催化下通过2,6-双-(4-乙炔基苯氧基)-苯腈和二甲基二氯硅烷室温反应制备了侧氰基芳醚硅芳炔树脂(CNSA)；采用¹H-NMR、FTIR、DSC、TGA等分析测试技术表征了CNSA的结构与性能。结果显示，CNSA树脂具有好的溶解性和宽的加工窗口，可在较低温度(<200℃)下发生固化反应；树脂固化物具有好的热性能，在50~400℃之间无玻璃化转变，在N₂中质量损失5%的温度T_d5达512℃；T300碳纤维平纹布/CNSA(CF/CNSA)复合材料的室温弯曲强度达383.8 MPa，弯曲模量为62.9 GPa。
- 氰基 /
- 含硅芳炔树脂 /
- 催化聚合 /
- 复合材料 /
- 固化反应
Abstract: A silicon-containing arylacetylene resin with cyano groups (CNSA resin) was formed by reaction of 2,6-bis-(4-ethynylphenoxy)-phenylnitrile polymerized with dimethyldichlorosilane by the catalysis of anhydrous zinc trifluoromethane sulfonate at room temperature. The structure and properties of the CNSA resin were characterized by ¹H-NMR, FTIR, DSC and TGA analysis techniques. The results show that the CNSA resin has good solubility and a wide processing window. The curing reactions of the CNSA resin take place at low temperature (<200℃). The cured CNSA resin has good heat resistance. There is no glass transition in the temperature range of 50−400℃. The decomposition temperature of 5% mass loss T_d5 is 512℃ in nitrogen. The flexural strength and the flexural modulus of T300 carbon fiber cloth/CNSA (CF/CNSA) composites are 383.8 MPa and 62.9 GPa at room temperature, respectively.
- cyano group /
- silicon-containing arylacetylene resin /
- catalytic polymerization /
- composite /
- curing reaction

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图 1 2,6-双-(4-乙炔基苯氧基)-苯腈(BEPBN)的合成

Figure 1. Synthesis of 2,6-bis(4-ethynylphenoxy) benzonitrile (BEPBN)

BIPBN-2,6-bis(4-iodophenoxy)benzonitrile；BTEPBN-2,6-bis(4-((trimethylsilyl)ethynyl)phenoxy)benzonitrile

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图 2 侧氰基芳醚硅芳炔树脂(CNSA)的合成

Figure 2. Synthesis of silicon-containing arylacetylene resin with cyano groups (CNSA)

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图 3 CNSA树脂¹H-NMR图谱

Figure 3. ¹H-NMR spectrum of CNSA resin

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图 4 CNSA树脂FTIR图谱

Figure 4. FTIR spectrum of CNSA resin

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图 5 CNSA树脂流变曲线

Figure 5. Rheological curve of CNSA resin (2℃·min⁻¹)

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图 6 CNSA树脂的DSC曲线(10℃·min⁻¹)

Figure 6. DSC curve of CNSA resin(10℃·min⁻¹)

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图 7 不同升温速率的CNSA树脂DSC曲线

Figure 7. DSC curves of CNSA resin at different heating rates

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图 8 CNSA树脂的ln(β/T_p²)、lnβ与1 000/T_p的关系

Figure 8. ln(β/T_p²) vs 1 000/T_p and lnβ vs 1 000/T_p plot of CNSA resin

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图 9 CNSA树脂不同温度下的FTIR图谱

Figure 9. FTIR spectra of CNSA resin at different temperatures

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图 10 CNSA树脂的热交联反应机制

Figure 10. Thermal cross-linking mechanisms of CNSA resin

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图 11 CNSA树脂浇铸体的DMA曲线

Figure 11. DMA curves of CNSA resin casting

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图 12 CNSA树脂固化物的热失重曲线(10℃·min⁻¹, N₂)

Figure 12. Thermogravinmetric curve of cured CNSA resin (10℃·min⁻¹, N₂)

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图 13 T300碳纤维平纹布/CNSA(CF/CNSA)复合材料弯曲性能

Figure 13. Flexural properties of T300 carbon fiber cloth/CNSA (CF/CNSA) composite

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表 1 CNSA室温溶解性

Table 1. Solubility of CNSA at room temperature

Solvent	Solubility	Solvent	Solubility
CHCl₃	++	DMSO	++
THF	++	CH₃CN	+
Toluene	+	EtOH	−
Acetone	++	Hexane	−
DMF	++	PE	−
Notes: THF— Tetrahydrofuran; DMF—N, N-dimethylformamide; DMSO—Dimethyl sulfoxide; EtOH—Ethyl alcohol; PE—Petroleum ether.

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表 2 不同升温速率下CNSA树脂的DSC分析数据

Table 2. DSC data of CNSA resin at different heating rates

Heating rate/ (℃·min⁻¹)	T_i/℃	T_p/℃	T_f/℃	∆H/(J·g⁻¹)
5	168.6	225.7	265.4	351.3
10	180.3	242.1	280.6	287.6
15	194.9	251.6	287.5	249.9
20	193.7	258.2	295.2	246.6
Notes：T_i, T_p and T_f —Initial curing temperature, peak curing temperature and final curing temperature, respectively; ∆H—Exothermic enthalpy change of curing reactions.

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表 3 CNSA树脂的固化反应的DSC分析数据

Table 3. DSC data for treatment of CNSA reaction

β/(℃·min⁻¹)	T_p/K	1 000/T_p/K⁻¹	ln(β/T_p²)	lnβ
5	498.85	2.005	−10.815	1.609
10	515.21	1.941	−10.187	2.303
15	524.76	1.906	−9.818	2.708
20	531.32	1.882	−9.555	2.996
Notes: β—Heating rate; T_p—Peak temperature of curing reactions.

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