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)
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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
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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)
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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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目的
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，加工性能良好、介电性能突出，在航空航天、核电等军用民用领域均有广泛应用，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。本文从硅炔杂化树脂(PSA)出发，采用苯并噁嗪PBZ和氨基稀释剂PAD共混改性硅炔杂化树脂PSA，制备了适用于RTM成型工艺的PPA树脂，以提高复合材料的力学性能。
方法以苯并噁嗪树脂(PBZ)和氨基稀释剂(PAD)共混改性PSA树脂，制备三元树脂体系PSA/PBZ/PAD(PPA树脂)，并采用RTM工艺制备复合材料。通过DSC、FTIR分析改性硅炔杂化树脂的结构变化，研究固化过程与反应机理；利用旋转流变仪、旋转黏度计测试改性硅炔杂化树脂黏度及流变特性，分析PPA树脂的RTM成型工艺窗口；采用TGA测定改性硅炔杂化树脂耐热性能变化情况；通过力学试验测试对比PPA树脂复合材料的室温和400 ℃热老化后的力学性能变化；利用DMA及热老化测试研究复合材料的热性能。
结果(1)PPA树脂在常温下是具有一定黏度的液体状树脂，40 ℃黏度降至800 mPa·s以下，且在40 ℃能够长时间保持黏度稳定。(2)PPA树脂在250 ℃附近存在单一的的固化峰，随着PBZ的含量增加，固化峰值温度逐渐降低。固化过程中PSA树脂、PBZ树脂和PAD之间存在相互反应，包括噁嗪环开环、炔基与氨基的氢胺化反应、Si−H与炔基的硅氢加成反应以及炔基之间的Diels-Alder反应和环三聚反应。(3)PPA树脂固化物质量损失5%的温度(T)和质量保留率均低于PSA树脂固化物，并且T和质量保留率均随着PBZ树脂的增加而逐渐下降，其中PPA-1(PSA:PBZ:PAD质量比为5:1:2)树脂在氮气和空气中的T分别为585.4 ℃ 和568.3 ℃，1000 ℃质量保留率分别为88.3% 和26.0%。(4)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，QF/PPA-1复合材料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%。(6)QF/PPA复合材料的储能模量随着温度升高明显提高，玻璃化转变温度均高于500 ℃。(7)QF/PPA复合材料在400 ℃高温下长时间热老化后，整体颜色发白，结构完好，层间结合牢固，其中在热老化10 h后，QF/PPA复合材料质量损失率小于3%，低于QF/PSA复合材料。
结论本文制备了改性硅炔杂化树脂PPA，PPA树脂加工窗口较宽，40 ℃的黏度满足RTM成型工艺的要求，但固化温度高于PSA树脂。PBZ/PAD引入改善了PSA树脂与纤维的界面结合性能，复合材料的力学性能均有大幅提升，室温弯曲强度较QF/PSA复合材料提高了120%以上。PPA树脂和QF/PPA复合材料的耐热性能均非常优异，400 ℃热老化10 h后QF/PPA复合材料质量损失率低于3%，玻璃化转变温度高于500 ℃。
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硅炔杂化树脂是一种兼具优异加工性、介电性能、耐热性能、低密度和低吸水率的有机无机杂化树脂，广泛应用于航空航天及核电等军用民用领域。但硅炔杂化树脂固化之后交联密度过高，脆性大，与纤维界面结合性差，导致复合材料力学性能较差，限制了其在各领域的应用。
本文从硅炔杂化树脂PSA出发，采用含乙炔基苯并噁嗪PBZ和氨基稀释剂PAD共混改性硅炔杂化树脂PSA，得到改性硅炔杂化树脂PPA，并制备石英纤维增强PPA树脂复合材料(QF/PPA)。引入PBZ和PAD后，PPA树脂不仅黏度降低至600 mPa·s且能够保持足够长的时间，满足RTM成型工艺的要求，同时提高了树脂与纤维之间的结合性，改善了复合材料的界面性能，并且PPA树脂中三种组分相互之间可以交联固化，耐热性能优异。因此，PPA树脂可以在40 ℃注射树脂，浸润纤维，注射温度较低，安全环保。所制备的QF/PPA复合材料力学性能明显提高，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 ℃热处理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，高温力学强度保留率超过70%。
QF/PPA复合材料的弯曲强度和层间剪切强度
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