通过与苯乙烯共聚改善含硅芳炔树脂及其复合材料性能

杨娜; 苏韬; 黄锴荻; 王文俊

doi:10.13801/j.cnki.fhclxb.20221219.001

通过与苯乙烯共聚改善含硅芳炔树脂及其复合材料性能

doi: 10.13801/j.cnki.fhclxb.20221219.001

杨娜^1,,
苏韬²,
黄锴荻¹,
王文俊^1, ,

1.
北京理工大学　材料科学与工程学院，北京 100081
2.
中国航空工业集团　济南特种结构研究所，济南 250023

详细信息

通讯作者:
王文俊，博士，副教授，硕士生导师，研究方向为聚合物基复合材料　E-mail: wangwenjun@bit.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-10-18
- 修回日期: 2022-11-17
- 录用日期: 2022-12-06
- 网络出版日期: 2022-12-20
- 刊出日期: 2023-09-15

Modification of silicon-containing arylacetylene resin and its composite properties by copolymerization with styrene

YANG Na^1
,,
SU Tao²,
HUANG Kaidi¹,
WANG Wenjun^{1
, ,}

1.
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
2.
Jinan Institute of Special Structures, Aviation Industry Corporation of China, Jinan 250023, China

摘要

摘要: 含硅芳炔树脂(PSA)/石英纤维(QF)复合材料是极具潜力的新型耐高温透波材料，但由于PSA树脂质脆、极性低，加上石英纤维表面光滑，导致两者间界面粘结弱，突出表现为复合材料层间性能(如层间剪切强度)低。本文采用苯乙烯(ST)对含硅芳炔树脂进行改性，通过ST与PSA分子间发生共聚反应，降低体系的交联密度，均匀化其交联网络结构，提高树脂抗压损伤阻抗，最终达到了改善PSA基复合材料层间剪切强度的目的。通过DSC、TG、DMA等手段测试和表征了改性前后PSA树脂及其复合材料的固化反应性能、流变性能、耐热性能、介电性能和力学性能等，结果表明：添加苯乙烯不会影响PSA树脂的固化规律和工艺。随着ST添加量的增加，改性PSA树脂的耐热性有所下降，但其失重5wt%温度T_d5均接近500℃，远高于应用要求的350℃。改性后复合材料保持了良好的介电性能，介电常数为3.09，损耗因子tanδ为2×10⁻³；在保持较高弯曲强度的同时，改性后复合材料层间剪切强度得到显著提升。当ST质量比为15%时，QF/PSA-15ST在室温下的层间剪切强度提高了53.0%，350℃下提高了98.3%；350℃下层间剪切强度保留率为78.3%，高于改性前的60.4%。
- 含硅芳炔树脂 /
- 复合材料 /
- 苯乙烯 /
- 增韧 /
- 层间剪切强度(ILSS)
Abstract: Quartz fiber (QF) reinforced poly(silica-containing arylacetylene) (PSA) composite is a new type of highly promising new wave-transparent materials with highly heat-resistance. However, the brittleness and low molecular polarity of PSA resins, combined with the smooth surface of quartz fibers, results in a weak interfacial adhesion, and low interlaminar shear strength (ILSS) of the composites. In this paper, silicon-containing arylacetylene resin was modified by copolymerizing with styrene (ST). As a consequence, the crosslinking density was decreased, the crosslinking network got homogenized, and the crack resistance of the resin against load was improved. Finally, the ILSS of Quartz fiber reinforced PSA composites was improved. The properties of the resin and composites were characterized with differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), mechanical property testing, dielectric property testing, rheological property testing. The results showed that the addition of ST didn’t affect the curing process of the resin. With the increase of ST content, the heat resistance of modified PSA resin decreased to some extent, but its mass loss 5wt% temperature T_d5 was still close to 500℃, which was much higher than the expected application temperature of 350℃. The modified composite also maintained the good dielectric properties with dielectric constant of 3.09 and loss factor tanδ of 0.002. The results also showed that the addition of ST significantly improved ILSS. For instance, the ILSS of QF/PSA-15ST increased by 53.0% at room temperature and 98.3% at 350℃. Compared with that at room temperature, the retention rate of interlaminar shear strength at 350℃ was 78.3%, which was much higher than that before modification (60.4% ).
- silicon-containing arylacetylene resin /
- composites /
- styrene /
- toughening /
- interlaminar shear strength (ILSS)

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图 1 添加不同比例ST的甲基二苯乙炔基硅烷(MDPES)树脂的DSC曲线

Figure 1. DSC curves of methyldiphenylacetylidene-silane (MDPES) resin with different ratio of ST

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图 2 PSA-0ST和PSA-15ST的流变行为

Figure 2. Rheology behaviors of PSA-0ST and PSA-15ST

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图 3 添加不同比例ST的MDPES树脂固化物在N₂中的TGA (a) 和DTG (b) 曲线；分别在空气 (c) 和在N₂ (d) 中350℃下恒温30 min的TG曲线

Figure 3. TGA (a) and DTG (b) curves of the cured MDPES resin adding with different ratio of ST in N₂; Thermostatic TG at 350℃ for 30 min in air (c) and N₂ (d)

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图 4 石英纤维(QF)/PSA复合材料改性前后的DMA曲线

Figure 4. DMA curves of quartz fiber (QF)/PSA composites before and after modification

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图 5 QF/PSA复合材料改性前后的DSC曲线

Figure 5. DSC curves of QF/PSA composites before and after modification

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图 6 QF/PSA复合材料改性前后的力学性能

Figure 6. Mechanical properties of QF/PSA composites before and after modification

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图 7 改性前 (a) 后 (b) 树脂浇注体断面的SEM图像

Figure 7. SEM images of resin castings before (a) and after (b) modification

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图 8 短梁弯曲实验后复合材料层合板的CT图像

Figure 8. CT image of composite laminate after short beam bending test

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图 9 短梁弯曲载荷示意图

Figure 9. Illustration of short beam shear loading

P—Load; Span between supports is fixed for any one test

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表 1 含硅芳炔树脂(PSA)-苯乙烯(ST)树脂浇注体的命名

Table 1. Naming of poly(silica-containing arylacetylene) (PSA)-styrene (ST) resin castable

Sample	Mass ratio of ST/%	Mass ratio of MDPES/%
PSA-0ST	0	100
PSA-10ST	10	90
PSA-15ST	15	85
PSA-20ST	20	80
Note: MDPES—Methyldiphenylacetylidene-silane.

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表 2 添加不同比例ST的MDPES树脂的DSC数据

Table 2. DSC data of MDPES resin adding with different ratio of styrene

	T_i/℃	T_p/℃	T_f/℃	ΔH/(J·g⁻¹)
PSA-0ST	210.6	257.7	334.7	196.5
PSA-10ST	206.1	257.9	316.4	191.3
PSA-15ST	205.7	247.6	317.4	191.7
PSA-20ST	201.9	245.9	318.9	196.9
Notes: T_i, T_p and T_f—Initial temperature, peak temperature and final temperature of cure exotherm; ΔH—Enthalpy of cure exotherm.

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表 3 添加不同比例ST的MDPES固化树脂的热重数据

Table 3. TGA data of the cured MDPES resin adding with different ratio of Styrene

	T_onset/℃	T_d5/℃	T_max/℃	Y_350℃/%
PSA-0ST	424	504	547	100.0
PSA-10ST	375	497	551	99.6
PSA-15ST	377	494	551	99.6
PSA-20ST	374	480	552	99.6
Notes: T_onset, T_d5 and T_max—Starting decomposition temperature, the temperature at 5wt% mass decomposition and the temperature corresponding to the maximum decomposition rate; Y_350℃—Mass residual rate at 350°C.

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表 4 QF/PSA复合材料改性前后的力学性能和介电性能

Table 4. Mechanical and dielectric properties of QF/PSA compsites before and after modification

	Flexural strength/MPa		ILSS/MPa		Dielectric properties
	RT	350℃	RT	350℃	ε	tanδ
Before modification	66.38 ±6.33	40.22±5.00	5.02± 1.07	3.03±0.22	3.05±0.02	0.004± 0.001
After modification	83.83 ±8.96	58.68 ±2.54	7.68 ±0.73	6.01±1.15	3.09±0.01	0.003± 0.001
Notes: ILSS—Interlaminar shear strength; RT—Room temperature; ε—Dielectric constant; tanδ—Loss factor.

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表 5 改性前后树脂浇注体薄片的洛氏硬度测试结果

Table 5. Rockwell hardness values of flake resin casts before and after modification

	HDR/Damage to specimens’ surface					Average of HDR
Before modification	78.5/SV	69.1/SV	62.0/SV	−/SV	−/SV	69.9
After modification	94.4/IT	94.3/IT	92.9/IT	88.6/SL	68.3/SV	87.7
Notes: HDR—Rockwell hardness values; SV—Severe damage; SL—Slight damage; IT—Intact.

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