Study on curing phthalonitrile resin with novel poly(phthalazinone ether nitrile)

doi:10.11949/0438-1157.20221229

Abstract

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

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

CLC Number:

TQ 324.8

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.

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.

Figures/Tables 15

Fig.1 The synthesis route of A-PPEN

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

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

Fig.4 ATR-FTIR spectra of A-PPEN

Fig.5 TGA curves of A-PPEN and DDS

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

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

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

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

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

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

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

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

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

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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