对苯二甲醛酚醛树脂的制备及其固化动力学研究

doi:10.11949/0438-1157.20211801

摘要/Abstract

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

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

中图分类号:

TB 332

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.

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.

图/表 15

图1 对苯二甲醛酚醛树脂合成过程中0 h和4 h的核磁图以及可能的预聚物结构(a)；反应过程中参与反应的对苯二甲醛的量(b)

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)

图2 对苯二甲醛酚醛树脂不同合成阶段的红外光谱图

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

图3 对苯二甲醛酚醛树脂的GPC谱图

Fig.3 GPC spectrogram of terephthalaldehyde phenolic resin

图4 不同二茂铁甲醛含量(0%、7%、15%)的对苯二甲醛酚醛树脂在升温过程中(80~170℃)的表观黏度曲线

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

图5 0%-二茂铁甲醛(a)、7%-二茂铁甲醛(b)、15%-二茂铁甲醛(c)改性对苯二甲醛酚醛树脂的DSC图及树脂固化过程中的FTIR图(d)

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)

图6 对苯二甲醛酚醛树脂(a)和二茂铁甲醛改性对苯二甲醛酚醛树脂(b)的固化机理图(R:H或其取代物)

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

表1 不同二茂铁甲醛含量（0%、7%、15%）的对苯二甲醛酚醛树脂两个固化峰的峰值温度

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

图7 0%-二茂铁甲醛[(a)、(b)]、7%-二茂铁甲醛[(c)、(d)]、15%-二茂铁甲醛[(e)、(f)]改性对苯二甲醛酚醛树脂的拟合曲线

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

表2 不同二茂铁甲醛含量（0%、7%、15%）的对苯二甲醛酚醛树脂的活化能

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

图8 不同二茂铁甲醛含量(0%、7%、15%)的对苯二甲醛酚醛树脂峰1(a)和峰2(b)活化能

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

图9 0%-二茂铁甲醛[(a)、(b)]、7%-二茂铁甲醛[(c)、(d)]、15%-二茂铁甲醛[(e)、(f)]改性对苯二甲醛酚醛树脂固化度与温度曲线

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

表3 不同含量的二茂铁甲醛（0%、7%、15%）改性对苯二甲醛酚醛树脂的固化动力学参数

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

图10 0%-二茂铁甲醛[(a)、(b)]、7%-二茂铁甲醛[(c)、(d)]、15%-二茂铁甲醛[(e)、(f)]改性对苯二甲醛酚醛树脂的拟合曲线(实线为模拟数据所得，散点为实验数据所得)

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)

图11 不同含量的二茂铁甲醛(0%、7%、15%)改性对苯二甲醛酚醛树脂固化物的MDSC曲线

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

图12 不同含量的二茂铁甲醛 (0%、7%、15%)改性对苯二甲醛酚醛树脂的TG(a)和DTG(b)曲线(N2气氛)

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

参考文献 30

1	Reghunadhan Nair C P, Bindu R L, Ninan K N. Thermal characteristics of addition-cure phenolic resins[J]. Polymer Degradation and Stability, 2001, 73(2): 251-257.
2	Yang W S, Jiao L, Wang X, et al. Formaldehyde-free self-polymerization of lignin-derived monomers for synthesis of renewable phenolic resin[J]. International Journal of Biological Macromolecules, 2021, 166: 1312-1319.
3	Sarika P R, Nancarrow P, Khansaheb A, et al. Bio-based alternatives to phenol and formaldehyde for the production of resins[J]. Polymers, 2020, 12(10): 2237.
4	Rivero G, Fasce L A, Ceré S M, et al. Furan resins as replacement of phenolic protective coatings: structural, mechanical and functional characterization[J]. Progress in Organic Coatings, 2014, 77(1): 247-256.
5	Younesi-Kordkheili H. Ionic liquid modified lignin-phenol-glyoxal resin: a green alternative resin for production of particleboards[J]. The Journal of Adhesion, 2019, 95(12): 1075-1087.
6	Foyer G, Chanfi B H, Virieux D, et al. Aromatic dialdehyde precursors from lignin derivatives for the synthesis of formaldehyde-free and high char yield phenolic resins[J]. European Polymer Journal, 2016, 77: 65-74.
7	朱其仁, 李锦春, 王丽娟, 等. 苯酚-亚联苯型酚醛树脂的合成与表征[J]. 化工学报, 2009, 60(4): 1052-1056.
	Zhu Q R, Li J C, Wang L J, et al. Synthesis and characterization of phenol-biphenylene resin[J]. CIESC Journal, 2009, 60(4): 1052-1056.
8	Yun J, Chen L X, Zhang X F, et al. The effects of silicon and ferrocene on the char formation of modified novolac resin with high char yield[J]. Polymer Degradation and Stability, 2017, 139: 97-106.
9	Xu S H, Zhang F Y, Kang Q, et al. The effect of magnetic field on the catalytic graphitization of phenolic resin in the presence of Fe-Ni[J]. Carbon, 2009, 47(14): 3233-3237.
10	Zhang Y, Shen S H, Liu Y J. The effect of titanium incorporation on the thermal stability of phenol-formaldehyde resin and its carbonization microstructure[J]. Polymer Degradation and Stability, 2013, 98(2): 514-518.
11	Naderi A, Mazinani S, Javad Ahmadi S, et al. Modified thermo-physical properties of phenolic resin/carbon fiber composite with nano zirconium dioxide[J]. Journal of Thermal Analysis and Calorimetry, 2014, 117(1): 393-401.
12	Zhou J, Li X G, Du J Z, et al. Conversion of phenolic mixture to refractory resins: a resourcezation strategy for phenolic distillation residues[J]. Journal of Hazardous Materials, 2021, 414: 125357.
13	Granado L, Tavernier R, Foyer G, et al. Catalysis for highly thermostable phenol-terephthalaldehyde polymer networks[J]. Chemical Engineering Journal, 2020, 379: 122237.
14	Yi C, Rostron P, Vahdati N, et al. Curing kinetics and mechanical properties of epoxy based coatings: the influence of added solvent[J]. Progress in Organic Coatings, 2018, 124: 165-174.
15	Granado L, Tavernier R, Foyer G, et al. Comparative curing kinetics study of high char yield formaldehyde- and terephthalaldehyde-phenolic thermosets[J]. Thermochimica Acta, 2018, 667: 42-49.
16	张西莹, 刘育红. 酚醛树脂/碳化硼/聚硼氮烷复合物的固化行为及其热解性能[J]. 化工学报, 2014, 65(8): 3268-3276.
	Zhang X Y, Liu Y H. Curing and pyrolysis behavior of PF/B₄C/PBZ composite[J]. CIESC Journal, 2014, 65(8): 3268-3276.
17	代洁, 李鹏程, 朱蓉琪, 等. 一种高残炭新型苯并𫫇嗪树脂的固化及热解动力学[J]. 功能高分子学报, 2018, 31(2): 114-120.
	Dai J, Li P C, Zhu R Q, et al. Curing and pyrolysis kinetics of a new benzoxazine resin with high char yield[J]. Journal of Functional Polymers, 2018, 31(2): 114-120.
18	Gao J G, Huo L, Du Y G. Nonisothermal cure kinetics and diffusion effect of liquid-crystalline epoxy sulfonyl bis(1, 4-phenylene)bis[4-(2, 3-epoxypropyloxy)benzoate]resin with aromatic diamine[J]. Journal of Applied Polymer Science, 2012, 125(5): 3329-3334.
19	Xu M Z, Luo Y S, Lei Y X, et al. Phthalonitrile-based resin for advanced composite materials: curing behavior studies[J]. Polymer Testing, 2016, 55: 38-43.
20	Li C, Ma Z Z, Zhang X W, et al. Silicone-modified phenolic resin: relationships between molecular structure and curing behavior[J]. Thermochimica Acta, 2016, 639: 53-65.
21	Lei Z X, Jiang X, Lv Y, et al. Time-temperature-transformation diagram of modified resol phenolic resin and the thermomechanical performance of resol phenolic resin/glass fabric composite[J]. Polymers for Advanced Technologies, 2018, 29(11): 2827-2837.
22	Asaro L, Manfredi L B, Pellice S, et al. Innovative ablative fire resistant composites based on phenolic resins modified with mesoporous silica particles[J]. Polymer Degradation and Stability, 2017, 144: 7-16.
23	Wang S J, Jia Q X, Liu Y H, et al. An investigation on the effect of phenylboronic acid on the processibilities and thermal properties of bis-benzoxazine resins[J]. Reactive and Functional Polymers, 2015, 93: 111-119.
24	Wang S J, Jing X L, Wang Y, et al. Synthesis and characterization of novel phenolic resins containing aryl-boron backbone and their utilization in polymeric composites with improved thermal and mechanical properties[J]. Polymers for Advanced Technologies, 2014, 25(2): 152-159.
25	Fox T G, Loshaek S. Influence of molecular weight and degree of crosslinking on the specific volume and glass temperature of polymers[J]. Journal of Polymer Science, 1955, 15(80): 371-390.
26	Trick K A, Saliba T E. Mechanisms of the pyrolysis of phenolic resin in a carbon/phenolic composite[J]. Carbon, 1995, 33(11): 1509-1515.
27	Xing X L, Zhang P, Zhao Y H, et al. Pyrolysis mechanism of phenylboronic acid modified phenolic resin[J]. Polymer Degradation and Stability, 2021, 191: 109672.
28	Wang S J, Wang Y, Bian C, et al. The thermal stability and pyrolysis mechanism of boron-containing phenolic resins: the effect of phenyl borates on the char formation[J]. Applied Surface Science, 2015, 331: 519-529.
29	Amer W A, Wang L, Amin A M, et al. Study on the electrochemical, thermal, and liquid crystalline properties of poly(diethyleneglycol 1, 1'-ferrocene dicarboxylate)[J]. Designed Monomers and Polymers, 2013, 16(2): 160-169.
30	Talabi S I, Luz A P, Pandolfelli V C, et al. Synthesis and graphitization of resole resins by ferrocene[J]. Progress in Natural Science: Materials International, 2019, 29(1): 71-80.

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