Properties of cyanate ester resin for hot melt prepreg
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摘要: 采用聚醚砜(PES)对氰酸酯树脂改性，制备出PM915树脂。对PM915树脂的工艺性能和固化物性能进行了系统研究，该树脂成膜性和贮存稳定性良好，适用于热熔法预浸料工艺。研究了PM915树脂的流变性能及凝胶时间，树脂在70℃时的黏度为20 Pa·s左右，在120℃条件下可保持黏度稳定时间达115 min，160℃时凝胶时间为40 min。PM915树脂制备过程中部分反应热已释放，其拥有较低的固化放热焓，固化温度为220℃。通过引入热塑性组分PES，PM915树脂的固化收缩率低至0.16%。PM915树脂固化物具有优良的热性能，热失重5%时的温度Td5=423℃，玻璃化转变温度Tg=276℃，热膨胀系数为4.4×10−5/℃。通过热塑性树脂的改性，引入了柔性基团，进而提高了树脂固化物的韧性，PM915树脂固化物的弯曲强度和弯曲模量分别为139.3 MPa和4.2 GPa，拉伸强度和拉伸模量分别为75.8 MPa和3.8 GPa；扫描电子显微镜（SEM）表征显示PM915树脂固化物为韧性断裂。结果表明，PM915树脂是一种适用于热熔法预浸料的氰酸酯树脂基体，且具有低固化收缩率、高尺寸稳定性和优良耐热性，可应用于卫星等航天器结构件。Abstract: PM915 resin was prepared by modifying cyanate ester resin with polyethersulfone (PES). The processability and cured resin properties of PM915 resin were investigated systematically. The PM915 resin has excellent process performance, good film-forming property and better storage stability, and could be used to prepare prepreg by hot melting method. The process properties such as rheological property and gel time of PM915 resin were measured. The results show that the viscosity of PM915 resin at 70℃ is about 20 Pa·s, the viscosity of the resin can keep stable for 115 min at 120℃, and the gelation time is 40 min at 160℃. Due to the release of some reaction heat in the preparation process, the curing exothermic enthalpy of PM915 resin decreases, and the curing temperature of PM915 resin is 220℃. The curing shrinkage of PM915 resin is as low as 0.16% due to the introduction of PES. The temperature at 5% thermal weight loss Td5, glass transition temperature Tg and thermal expansion coefficient of cured PM915 resin are 423℃, 276℃ and 4.4×10−5/℃, respectively, which indicates that the cured PM915 resin possesses excellent thermal properties. After modification, the toughness of the cured resin has been greatly improved owing to the introduction of flexible groups. The flexural strength and modulus of the cured PM915 resin are 139.3 MPa and 4.2 GPa, the tensile strength and modulus of the cured PM915 resin are 75.8 MPa and 3.8 GPa respectively. What’s more, the investigation of fracture surface by scanning electron microscope (SEM) indicates that the cured PM915 resin exhibits toughness fracture. Therefore, the PM915 resin is a kind of ideal resin matrix for fiber reinforced prepregs by hot melting process, and possesses low curing shrinkage, high dimensional stability and heat resistance, which can be used in satellites and other spacecraft.
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Keywords:
- cyanate ester resin /
- hot melt processing /
- prepreg /
- rheology /
- heat resistance
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图 1 双酚A型氰酸酯单体(BACy)和聚醚砜(PES)的结构式
Figure 1. Structures of bisphenol A cyanate monomer (BACy) and polyethersulfone (PES)
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图 2 PES改性氰酸酯树脂(PM915树脂)的流变性能
Figure 2. Rheological properties of cyanate ester resin modified by PES (PM915) resin
表 1 PM915树脂凝胶时间
Table 1 Gelation time of PM915 resin
Sample Gelation time t/min 130℃ 140℃ 150℃ 160℃ PM915 151 115 75 40 
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表 2 BACy及PM915树脂的DSC数据
Table 2 DSC date of BACy and PM915 resin
Sample Ti/℃ Tp/℃ Tf/℃ ΔH/(J·g-1) BACy 216.2 305.9 361.5 703.8 PM915 142.6 222.9 288.3 387.2 Notes: Ti, Tp and Tf —Initial curing temperature, peak curing temperature and final curing temperature, respectively; ΔH—Curing exothermic enthalpy.
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表 3 BACy及PM915树脂的固化收缩率
Table 3 Shrinkage of BACy and PM915
Sample ρ1/(g·mL−1) ρ2/(g·mL−1) Vs/% BACy 1.208 1.234 2.11 PM915 1.218 1.220 0.16 Notes: ρ1—Density of uncured resin; ρ2—Density of cured resin; Vs—Cure shrinkage rate.
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表 4 BACy-C及PM915-C的力学性能
Table 4 Mechanical properties of BACy-C and PM915-C
Property BACy-C PM915-C Flexural strength/MPa 97.2 139.3 Flexural modulus/GPa 3.7 4.2 Tensile strength/MPa − 75.8 Tensile modulus/GPa − 3.8 Elongation/% − 2.1
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