Polyphenylene ether type phthalonitrile resin and its composite materials
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摘要: 为保留聚苯醚树脂优异介电性能的同时提升其耐溶剂性和热稳定性，拓宽其在高频高速覆铜板领域的应用，本文以K2CO3为缚酸剂，通过4-硝基邻苯二甲腈的亲核取代合成了一种聚苯醚型的邻苯二甲腈树脂(PPOCN)。通过FTIR、DSC、TGA、流变性分析对树脂的结构、固化行为、耐热性以及加工性能进行了综合分析，通过介电分析仪、动态热机械分析及力学性能测试评估了复合材料的各项性能。结果表明，PPOCN具备交联反应活性，固化物的玻璃化转变温度(Tg)为295 ℃，5%热失重温度(Td5%)为419.3 ℃，与聚苯醚原料相比热稳定性显著提高。以PPOCN为基体树脂，二氨基二苯甲烷(DDM)为固化剂制备的纤维增强复合材料具备优异的力学性能和介电性能，弯曲强度为863.9 MPa，层间剪切强度为68.6 MPa，1 GHz频率下的介电常数为3.15，损耗角正切为0.003。PPOCN在保留了聚苯醚树脂优异介电性能的同时，兼具优异的力学性能和优良的热性能。Abstract: In order to preserve the excellent dielectric properties of polyphenylene oxide resin while improving its solvent resistance and thermal stability, and expand its application in the field of high-frequency and high-speed copper clad laminates, this paper synthesized a polyphenylene oxide type phthalonitrile resin (PPOCN) through nucleophilic substitution of 4-nitrophthalonitrile using K2CO3 as a binding agent. A comprehensive analysis was conducted on the structure, curing behavior, heat resistance, and processing performance of the resin through FTIR, DSC, TGA, and rheological analysis. The various properties of the composite material were evaluated through dielectric analyzer, dynamic thermomechanical analysis, and mechanical performance testing. The results showed that PPOCN has crosslinking reaction activity, and the glass transition temperature (Tg) of the cured product is 295 ℃, and the 5% thermal weight loss temperature (Td5%) is 419.3 ℃. Compared with the raw material of polyphenylene oxide, the thermal stability of PPOCN is significantly improved. The fiber reinforced composite material prepared with PPOCN as the matrix resin and diaminodiphenylmethane (DDM) as the curing agent has excellent mechanical and dielectric properties, with a bending strength of 863.9 MPa, interlayer shear strength of 68.6 MPa, dielectric constant of 3.15 at 1 GHz frequency, and loss tangent of 0.003. PPOCN retains the excellent dielectric properties of polyphenylene oxide resin while also possessing excellent mechanical and thermal properties.
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Key words:
- Thermosets /
- Polyphenylene ether /
- Phthalonitrile /
- Copper clad laminate /
- Dielectric properties
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图 2 SA90、4-硝基邻苯二甲腈和PPOCN的红外光谱
Figure 2. Infrared spectra of SA90、4-nitrophthalonitrile and PPOCN
图 5 胺基催化邻苯二甲腈的聚合机制
Figure 5. Mechanism of amine catalyzed polymerization of phthalonitrile
图 7 PHDM/石英纤维布(QF)复合材料的的DMA曲线
Figure 7. DMA curves of PHDM/Quartz fiber cloth (QF) composite materials
图 8 PHDM/QF复合材料的介电性能测试结果(a)介电常数(b)损耗角正切
Figure 8. Test results of dielectric properties of PHDM/QF composite materials(a) Dielectric constant (b) Tan Delta
图 9 PHDM/QF复合材料力学强度(a)弯曲强度(b)层间剪切强度
Figure 9. Mechanical strength of PHDM/QF composite materials(a) flexural strength (b) interlaminar shear strength
图 10 PHDM-1/QF复合材料耐溶剂性测试前(a)后(b)外观变化
Figure 10. Appearance changes of PHDM-1/QF composite materials before(a) and after(b) solvent resistance testing
表 1 不同比例的PHDM树脂配方
Table 1. PHDM resin formula with different proportions
Sample Resin mass ratio PPOCN DDM PPOCN 100 0 PHDM-1 100 1 PHDM-2 100 2 PHDM-3 100 3 Notes: PPOCN−Polyphenylene ether type phthalonitrile resin; DDM—4,4'-diaminodiphenylmethane; PHDM−Blends of PPOCN and DDM 
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表 2 PPO树脂固化物的TGA数据
Table 2. TGA data of PPO resin cured products
Samples Td5% /℃ 800℃ Mass
retention/%N2 Air N2 Air SA90 357.3 349.5 21.4 0.49 PPOCN 417.6 409.9 55.46 0.529 PHDM-1 416.2 401.4 55.77 0.524 PHDM-2 418.5 406.0 54.22 0.536 PHDM-3 419.3 409.6 55.33 0.673 Notes：Td5%−5% weight loss temperature
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