新型聚芳醚腈固化邻苯二甲腈树脂的研究

doi:10.11949/0438-1157.20221229

摘要/Abstract

摘要：

通过两步一锅法制备了氨基封端的新型杂萘联苯聚芳醚腈（A-PPEN），其具有比常用的芳香二胺固化剂4,4′-二氨基二苯砜（DDS）更为优异的热稳定性。采用差示扫描量热法（DSC）研究了A-PPEN对间苯二酚基邻苯二甲腈树脂前体（DPPH）的固化过程，结果显示该固化体系具有自催化固化的特征，A-PPEN的投料比会影响体系的固化活性。另外研究了该固化体系的流变特性和热稳定性，结果表明树脂的5%热失重温度（T_d5%）最高可达552.9℃，800℃时残炭率（C_y800）为78.6%，最低黏度可至0.06 Pa·s，具有优异的热稳定性和较宽的加工温度窗口。

关键词: 聚芳醚腈, 邻苯二甲腈, 耐高温, 动力学, 聚合物, 化学过程

Abstract:

A amino-terminated poly(phthalazinone ether nitrile) (A-PPEN) was prepared by a two-step one-pot method. It had better thermal stability than the commonly used aromatic diamine curing agent 4,4'- diaminodiphenylsulfoxide (DDS). The curing process of A-PPEN for resorcinole-based phthalonitrile resin precursor (DPPH) was studied by differential scanning calorimetry (DSC). The results showed that the curing system had the characteristics of autocatalytic curing, and the feeding ratio of A-PPEN would affect the curing activity of the system. In addition, the rheological properties and thermal stability of the curing system were studied. The results showed that the resin had a maximum 5% mass loss temperature (T_d5%) of 552.9℃, a char yield (C_y800) of 78.6% at 800℃, and a minimum viscosity of 0.06 Pa·s. The resin had excellent thermal stability and a wide processing temperature window.

Key words: poly(phthalazinone ether nitrile), phthalonitrile, high-temperature resistant, kinetics, polymers, chemical processes

中图分类号:

TQ 324.8

胡月, 马守骏, 蹇锡高, 翁志焕. 新型聚芳醚腈固化邻苯二甲腈树脂的研究[J]. 化工学报, 2023, 74(2): 871-882.

Yue HU, Shoujun MA, Xigao JIAN, Zhihuan WENG. Study on curing phthalonitrile resin with novel poly(phthalazinone ether nitrile)[J]. CIESC Journal, 2023, 74(2): 871-882.

图/表 15

图1 A-PPEN的合成路线

Fig.1 The synthesis route of A-PPEN

图2 DHPZ、4-氨基苯酚和A-PPEN的核磁氢谱图

Fig.2 1H NMR spectra of DHPZ, p-aminophenol and A-PPEN

图3 A-PPEN的核磁氢谱积分面积比

Fig.3 1H NMR spectrum integral area ratio of A-PPEN

图4 A-PPEN的全反射红外光谱

Fig.4 ATR-FTIR spectra of A-PPEN

图5 A-PPEN和DDS的热失重曲线

Fig.5 TGA curves of A-PPEN and DDS

图6 不同升温速率下不同含量A-PPEN固化DPPH树脂的动力学曲线

Fig.6 DSC curing kinetics curves for DPPH resins cured with different ratios of A-PPEN at different heating rates

图7 不同含量A-PPEN固化DPPH树脂的峰值温度对应升温速率的拟合曲线

Fig.7 Temperature as a function of heating rates for DPPH phthalonitrile resins cured with different ratios of A-PPEN

表1 不同含量A-PPEN固化DPPH的固化动力学参数

Table 1 Curing kinetic parameters of DPPH resins cured with different ratios of A-PPEN

固化剂	初始固化温度/℃	Kissinger E_a/(kJ/mol)	Ozawa E_a/(kJ/mol)	A/s^-1	N	k/s^-1
5%A-PPEN	201.4	66.7	71.3	2.72✕10⁶	0.89	0.173
10%A-PPEN	195.0	76.5	80.5	4.88✕10⁷	0.90	0.201
20%A-PPEN	190.8	86.1	89.5	8.00✕10⁸	0.91	0.232
30%A-PPEN	191.1	93.1	96.1	5.15✕10⁹	0.92	0.250

图8 不同升温速率下不同含量A-PPEN固化DPPH树脂的转化率对应温度曲线

Fig.8 Conversion as function of temperature for DPPH resins cured with different ratios of A-PPEN at various heating rates

图9 不同转化率下不同含量A-PPEN固化 DPPH 树脂的Starink曲线

Fig.9 Starink plots at various degrees of conversion for DPPH resins cured with different ratios of A-PPEN

图10 Starink法下不同含量A-PPEN固化DPPH树脂的活化能对应转化率曲线

Fig.10 Variation of Eaversusα for DPPH resins cured with different ratios of A-PPEN(Starink method)

图11 不同含量A-PPEN固化DPPH树脂的黏度对应温度和时间的流变曲线

Fig.11 Complex viscosity(η* ) as a function of temperature and time for DPPH phthalonitrile resins cured with different ratios of A-PPEN

表2 不同含量 A-PPEN 固化 DPPH 树脂的流变学参数

Table 2 Rheological parameters of DPPH reins cured with different ratios of A-PPEN

A-PPEN含量/%	最低黏度/(Pa·s)	T_η_<50/℃	T_gel/℃	加工窗口/℃	加工时间/min
10	0.060	167.5	350.4	182.9	23.1
20	0.098	181.9	233.9	42.0	17.7
30	0.218	179.2	213.4	34.2	9.8
40	0.443	178.9	206.9	28.0	6.9

图12 不同后固化温度下不同含量A-PPEN固化DPPH树脂的热失重曲线和微分热失重曲线

Fig.12 TGA and DTG traces of DPPH resins cured with different ratios of A-PPEN under nitrogen

表3 不同后固化温度下不同含量A-PPEN固化DPPH树脂的热稳定性

Table 3 Thermal properties of DPPH resins cured with different ratios of A-PPEN under different post-curing temperature

A-PPEN含量	400℃		350℃		300℃
A-PPEN含量	T_d5%^①/℃	C_y800^②/%	T_d5%/℃	C_y800/%	T_d5%/℃	C_y800/%
5%	546.2	73.1	484.8	72.6	400.2	57.7
10%	552.9	78.6	507.6	75.0	428.7	68.5
20%	544.0	79.6	496.4	75.1	464.2	74.1
30%	536.0	80.3	499.7	75.8	465.4	74.2

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