Synthesis and curing kinetics of terephthalaldehyde phenolic resin

doi:10.11949/0438-1157.20211801

Abstract

Abstract:

Due to the detriment and non-renewable of formaldehyde in phenolic resin, a novel phenolic resin, terephthalaldehyde phenolic thermosets, was synthesized by using a safe and renewable terephthalaldehyde instead of formaldehyde. NMR, IR, GPC and rheometer were utilized to explore the structure and properties of the resin. To further improve the thermal properties of the resin, ferrocenecarboxaldehyde was choosed to modify the resin. The curing mechanism of the modified resin was systematically clarified according to the curing kinetics of resin by Kissinger, isoconversion and autocatalytic kinetic model. Finally, the thermal properties of the cured resin were studied by MDSC and TG. When adding 15% ferrocenecarboxaldehyde, the modified resin presents excellent thermal properties whose glass transition temperature and initial decomposition temperature was 319.3℃ and 397.7℃ respectively, and the weight retention rate was as high as 76.07% under 800℃ nitrogen atmosphere.

Key words: terephthalaldehyde phenolic resin, structure and properties, curing kinetics, activation energy, thermal properties

摘要：

基于酚醛树脂原料中甲醛的危害性与不可再生性，使用安全、可再生的对苯二甲醛代替甲醛，合成了一种新型的酚醛树脂——对苯二甲醛酚醛树脂。采用核磁、红外、GPC和流变仪等分析手段对此类树脂的结构与性能进行了表征。为了进一步提高该树脂的热性能，使用二茂铁甲醛对其进行改性。采用Kissinger方程、等转换法及双参数自催化模型对改性前后树脂的固化动力学进行了研究，明确了二茂铁甲醛在树脂固化中的作用机理。最后通过MDSC和TG研究了改性前后树脂固化物的热性能，结果表明：在加入15%的二茂铁甲醛后，改性树脂呈现出优异的热性能，其玻璃化转变温度为319.3℃，起始分解温度为397.7℃，在800℃氮气气氛下质量保持率高达76.07%。

关键词: 对苯二甲醛酚醛树脂, 结构与性能, 固化动力学, 活化能, 热性能

CLC Number:

TB 332

Jian WANG, Zixuan LEI, Jiayu YAO, Jian LI, Yuhong LIU. Synthesis and curing kinetics of terephthalaldehyde phenolic resin[J]. CIESC Journal, 2022, 73(3): 1403-1415.

王建, 雷子萱, 姚家钰, 李建, 刘育红. 对苯二甲醛酚醛树脂的制备及其固化动力学研究[J]. 化工学报, 2022, 73(3): 1403-1415.

Figures/Tables 15

Fig.1 NMR images at 0 h and 4 h during the synthesis of terephthalaldehyde phenolic resin and possible prepolymer structure(a); The amount of terephthalaldehyde involved in the reaction process(b)

Fig.2 FTIR spectra of terephthalaldehyde phenolic resin at different synthesis stages

Fig.3 GPC spectrogram of terephthalaldehyde phenolic resin

Fig.4 Rheological viscosity diagrams of terephthalaldehyde phenolic resins with different contents of ferrocenecarboxaldehyde (0%, 7%, 15%) during heating (80—170℃)

Fig.5 DSC of 0%-ferrocenecarboxaldehyde (a), 7%-ferrocenecarboxaldehyde (b), 15%-ferrocenecarboxaldehyde (c) modified terephthalaldehyde phenolic resin and FTIR diagram during resin curing process(d)

Fig.6 Curing mechanism diagram of terephthalaldehyde phenolic resin (a) and ferrocenecarboxaldehyde modified terephthalaldehyde phenolic resin (b) (R:H or its substitute)

Table 1 Peak temperatures of two curing peaks of terephthalaldehyde phenolic resin with different contents of ferrocenecarboxaldehyde （0%， 7%， 15%）

β/(℃/min)	0%		7%		15%
β/(℃/min)	T_p1/℃	T_p2/℃	T_p1/℃	T_p2/℃	T_p1/℃	T_p2/℃
5	142.1	222.8	141.3	218.8	142.8	218.4
10	148.6	235.7	147.5	230.6	148.7	228.8
15	152.5	242.7	152.0	238.8	153.2	236.0
20	156.5	250.4	155.9	246.1	156.6	240.6

Fig.7 Fitting curves of 0%- ferrocenecarboxaldehyde [(a)，(b)], 7%- ferrocenecarboxaldehyde [(c)，(d)], 15%-ferrocenecarboxaldehyde [(e)，(f)] modified terephthalaldehyde phenolic resin

Table 2 Activation energy of terephthalaldehyde phenolic resin with different contents of ferrocenecarboxaldehyde （0%， 7%， 15%）

Peak	E_a/(kJ/mol)
Peak	0%	7%	15%
peak 1	137.82	134.07	143.14
peak 2	101.81	100.16	121.89
total	239.63	234.23	265.03

Fig.8 Activation energy of peak 1(a) and peak 2(b) of terephthalaldehyde phenolic resin with different contents of ferrocenecarboxaldehyde (0%, 7%, 15%)

Fig.9 Curves of curing degree and temperature of 0%- ferrocenecarboxaldehyde [(a)，(b)], 7%- ferrocenecarboxaldehyde [(c)，(d)], 15%- ferrocenecarboxaldehyde [(e)，(f)] modified terephthalaldehyde phenolic resin

Table 3 Curing kinetic parameters of terephthalaldehyde phenolic resin with different contents of ferrocenecarboxaldehyde （0%， 7%， 15%）

Sample	β/(℃/min)	lnA₁	m₁	n₁	m₁/n₁	lnA₂	m₂	n₂	m₂/n₂
0%	5	39.39	0.75	0.08	7.90	23.94	0.78	0.28	3.53
	10	39.37	0.73	0.04		23.86	0.78	0.25
	15	39.56	0.79	0.11		23.77	0.76	0.17
	20	39.48	0.81	0.16		23.60	0.75	0.17
7%	5	38.36	0.87	0.08	5.38	23.46	0.78	0.19	3.54
	10	38.37	0.76	0.07		23.89	0.84	0.30
	15	38.80	0.85	0.35		23.78	0.78	0.19
	20	38.37	0.93	0.14		23.63	0.76	0.22
15%	5	40.88	0.80	0.03	5.20	28.77	0.75	0.02	9.70
	10	41.00	0.79	0.12		28.92	0.80	0.15
	15	41.05	0.85	0.30		28.88	0.83	0.15
	20	40.86	0.80	0.17		28.81	0.78	0.01

Fig.10 Fitting curves of 0%- ferrocenecarboxaldehyde[(a),(b)], 7%- ferrocenecarboxaldehyde[(c),(d)], 15%- ferrocenecarboxaldehyde[ (e),(f) ] modified terephthalaldehyde phenolic resin (the solid line is the curve obtained from simulated data, and the scattered point is the curve obtained from experimental data)

Fig.11 MDSC curves of cured terephthalaldehyde phenolic resin modified by different contents of ferrocenecarboxaldehyde(0%,7%,15%)

Fig.12 TG(a) and DTG(b) curves of terephthalaldehyde phenolic resin modified with different contents of ferrocenecarboxaldehyde (0%, 7%, 15%) in N2 atmosphere

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