Modified silicone alkyne hybrid resin for RTM and its composite
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摘要: 树脂传递模塑(RTM)成型工艺是一种液体闭模成型工艺，成品表面光滑、安全环保、成本较低，极具发展潜力。硅炔杂化树脂是一种耐高温性能优异的有机无机杂化树脂，在航空航天领域均有广泛应用，但其与纤维的结合性能较差，复合材料力学性能不佳，成为制约其发展应用的主要因素。本文以苯并噁嗪树脂(PBZ)和氨基稀释剂(PAD)共混改性聚(间二乙炔基苯-甲基氢硅烷)树脂(PSA)，制备了适用于RTM成型工艺的改性硅炔杂化树脂(PPA)。通过DSC、FTIR、流变仪、旋转黏度计和热重等方法对PPA树脂的RTM成型工艺、固化行为及耐热性能进行分析。结果表明：PPA树脂的加工窗口宽，可以实现RTM成型的目标，但固化温度高于PSA树脂；PPA树脂的耐热性能优异，其中PPA-1 (PSA∶PBZ∶PAD质量比为5∶1∶2)树脂在氮气和空气中质量损失5%的温度(Td5)分别为585.4℃和568.3℃，1000℃质量保留率分别为88.3% 和26.0%。复合材料力学性能测试表明，石英纤维增强PPA树脂复合材料(QF/PPA)力学性能随PBZ含量的增加而逐渐升高，其中QF/PPA-1常温下弯曲强度为346.2 MPa，层间剪切强度为21.4 MPa，较QF/PSA复合材料分别提高了120.6%和72.6%，400℃热老化2 h后的弯曲强度和层间剪切强度分别为256.5 MPa和17.1 MPa，400℃热老化2 h后的力学性能保留率超过70%。Abstract: Resin transfer molding (RTM) forming process is a liquid closed mold forming process, which has a smooth surface of the finished product, safety and environmentally friendly, low cost, and has great development potential. Silicone alkyne hybrid resin is an organic-inorganic hybrid resin with excellent high-temperature resistance, widely used in aerospace field, but its poor bonding performance with fibers and poor mechanical properties of composites have become the main factors restricting its development and application. Poly(m-diacetylbenzene-methylhydrosilane) resin (PSA) was modified by blending benzoxazine resin (PBZ) and amino diluent (PAD) to prepare modified silicone alkyne hybrid resin (PPA) suitable for RTM molding process. The RTM molding process, curing behavior, and heat resistance of PPA resin were analyzed by DSC, FTIR, rheometer, rotational viscometer, and thermogravimetry. The results show that the processing window of PPA resin is wide, which can achieve the goal of RTM molding, but the curing temperature is higher than that of PSA resin. The heat resistance of PPA resin is excellent, and the temperature of 5% mass loss (Td5) of PPA-1 resin (PSA∶PBZ∶PAD mass ratio 5∶1∶2) resin is 585.4℃ and 568.3℃, respectively. The mass retention rates at 1000℃ is 88.3% and 26.0%, respectively. The mechanical property tests show that the mechanical properties of quartz fiber reinforced PPA resin composites (QF/PPA) gradually increase with the increase of PBZ content. The flexural strength of QF/PPA-1 at room temperature is 346.2 MPa, and the interlaminar shear strength is 21.4 MPa, which is 120.6% and 72.6% higher than that of QF/PSA composites, respectively. After thermal aging at 400℃ for 2 h, the flexural strength and interlaminar shear strength are 256.5 MPa and 17.1 MPa, respectively, and the retention rate of mechanical properties after thermal aging at 400℃ for 2 h exceeds 70%.
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图 1 聚(间二乙炔基苯-甲基氢硅烷)树脂(PSA)和含乙炔基苯并噁嗪树脂(PBZ)的结构式
Figure 1. Structures of poly(m-diacetylbenzene-methylhydrosilane) resin (PSA) and benzoxazine resin (PBZ)
图 5 不同固化温度的PPA-2树脂红外图谱
Figure 5. Infrared spectra of PPA-2 resin at different curing temperatures
图 8 石英纤维增强PPA树脂复合材料(QF/PPA)的弯曲强度与层间剪切强度
RT—Room temperature
Figure 8. Flexural strength and interlaminar shear strength of quartz fiber reinforced PPA resin composites (QF/PPA)
图 10 QF/PPA复合材料热老化10 h前后外观变化
Figure 10. Appearance change of QF/PPA composites before and after thermal aging
表 1 不同比例的改性硅炔杂化树脂(PPA)配方
Table 1. Modified silicone alkyne hybrid resin (PPA) formula with different proportions
Sample Resin mass ratio PSA PBZ PAD PPA-1 5 1 2 PPA-2 5 2 2 PPA-3 5 3 2 Note: PAD—Amino diluent. 
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表 2 PPA树脂的黏度
Table 2. Viscosity of PPA resin
Sample Viscosity/(mPa·s) 25℃ 30℃ 40℃ PSA 740 350 100 PPA-1 1000 610 230 PPA-2 1700 1000 400 PPA-3 4000 1800 640
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表 3 PPA树脂的凝胶时间
Table 3. Gelation time of PPA resin
Sample Gel time/min 160℃ 180℃ 200℃ PPA-1 23.5 11.0 5.1 PPA-2 20.1 9.3 4.0 PPA-3 18.2 8.1 3.0
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表 4 PPA树脂的TGA数据
Table 4. TGA data of PPA resin
Sample Td5/℃ Mass retention/% Air N2 Air N2 PSA 563.1 689.8 31.26 91.36 PPA-1 568.3 613.7 26.01 89.13 PPA-2 555.4 601.8 23.04 88.78 PPA-3 538.6 595.9 21.66 88.74 Note: Td5—Temperature of 5% mass loss.
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表 5 QF/PPA复合材料热老化10 h质量损失
Table 5. Mass loss of QF/PPA composites thermal aging
Sample Mass loss/wt% QF/PSA 4.28 QF/PPA-1 2.06 QF/PPA-2 2.50 QF/PPA-3 2.80
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