环氧基倍半硅氧烷修饰的联苯酚醛改性热塑性酚醛树脂性能

doi:10.11949/0438-1157.20240930

摘要/Abstract

摘要：

热塑性酚醛树脂（NR）的性能与其交联网络结构密切相关，多领域应用对NR的性能提出了更高的要求，然而NR的强度、玻璃化转变温度（T_g）与韧性的提升存在着矛盾，同时提高NR的强度、韧性和T_g仍然面临着挑战。通过环氧基低聚倍半硅氧烷（EPOSS）和联苯酚醛树脂（BN）反应制备了改性剂BEP，与树脂构建了具有不均一交联结构的BEP+NR共固化网络，实现了树脂强度和韧性的提升，在此基础上对BEP+NR体系的固化特性进行了动力学研究，通过调控BEP的均聚、BEP和NR的共固化以及NR的固化得到了致密的不均一交联网络。1BEP+NR固化物的T_g、弯曲强度、冲击强度分别达到146.3℃、4.1 kJ/m²、76.5 MPa，相比NR分别提高10.9℃、78.2%、50.9%。随着BEP均聚程度的增加，交联网络的不均一性进一步增加，BEP+NR的力学性能、热稳定性和T_g降低。

关键词: 酚醛树脂, 交联网络, 倍半硅氧烷, 动力学, 增韧

Abstract:

The properties of novolac resins (NR) are closely related to the cross-linked network structure of the cured material, and the applications in various fields place higher demands on the properties of NR. However, there is a contradiction between the improvement of NR's strength, glass transition temperature (T_g) and toughness, and improving NR's strength, toughness and T_g at the same time is still challenging. In this study, the modifier named BEP was prepared by the reaction of epoxy-based polyhedral oligomeric silsesquioxane (EPOSS) and biphenyl phenolic resin (BN). The BEP+NR co-curing network with an inhomogeneous cross-linked structure was established, which improved the strength and toughness of NR. On this basis, the curing kinetics of BEP+NR was studied. Dense inhomogeneous crosslinked networks were obtained by modulating the homopolymerization of BEP, the co-curing of BEP and NR, and the self-curing of NR. Compared to NR, the T_g, flexural strength and impact strength of 1BEP+NR up to 146.3℃, 4.1 kJ/m² and 76.5 MPa, which were improved by 10.9℃, 78.2% and 50.9%, respectively. With the homopolymerization degree of BEP increased, the inhomogeneous of the crosslinked network further increased and the mechanical properties, thermal stability and T_g of BEP+NR decreased.

Key words: phenolic resin, cross-linked network, polyhedral oligosiloxanes, kinetics, toughened

中图分类号:

TQ 323.1

张忠州, 李怡霏, 陈双, 强军锋, 刘育红. 环氧基倍半硅氧烷修饰的联苯酚醛改性热塑性酚醛树脂性能[J]. 化工学报, 2025, 76(4): 1809-1819.

Zhongzhou ZHANG, Yifei LI, Shuang CHEN, Junfeng QIANG, Yuhong LIU. Properties of epoxy polyhedral oligosiloxanes decorative biphenyl phenolics modified novolac resin[J]. CIESC Journal, 2025, 76(4): 1809-1819.

图/表 12

图1 BEP的合成路线

Fig.1 Synthetic formulae for BEP

图2 （a）EPOSS和BEP的1H NMR曲线；（b）BN、BEP和EPOSS的FT-IR曲线；（c）EPOSS和BEP的29Si NMR曲线；（d）EPOSS、BN和BEP的GPC曲线

Fig.2 (a) 1H NMR curves of EPOSS and BEP; (b) FT-IR curves of BN, BEP and EPOSS; (c) 29Si NMR curves of EPOSS and BEP; (d) GPC curves of EPOSS, BN and BEP

图3 NR（a）、1BEP+NR（b）、3BEP+NR（c）和6BEP+NR（d）在不同升温速率下的DSC曲线

Fig.3 DSC curves of NR (a), 1BEP+NR (b), 3BEP+NR (c) and 6BEP+NR (d) under different heating rates

表1 NR、1BEP+NR、3BEP+NR和6BEP+NR在不同升温速率下的DSC特征参数

Table 1 DSC parameters of NR， 1BEP+NR， 3BEP+NR and 6BEP+NR under different heating rates

样品	β/(K/min)	T_i/℃	T_d/℃	ΔT/℃
NR	5	123.7	153.7	30.0
	10	130.2	168.8	38.6
	15	126.7	177.7	51.0
	20	131.6	185.2	53.6
1BEP+NR	5	93.1	180.9	87.8
	10	99.6	188.6	89.0
	15	102.6	197.7	95.1
	20	103.6	211.6	108.0
3BEP+NR	5	91.3	173.5	82.2
	10	97.2	176.8	79.6
	15	102.6	201.3	98.7
	20	104.8	203.2	98.4
6BEP+NR	5	87.6	170.2	82.6
	10	94.1	184.4	90.3
	15	98.7	180.9	82.2
	20	100.5	194.1	93.6

图4 不同升温速率下1BEP+NR的DSC曲线分峰图

Fig.4 Split peaks of DSC curves of 1BEP+NR under different heating rates

图5 1BEP+NR不同升温速率Kissinger方程的线性回归拟合结果

Fig.5 Linear regression fitting results of Kissinger equation for different heating rates of 1BEP+NR

图6 BPR+NR固化过程可能的反应机理

Fig.6 Possible reaction mechanism of BPR+NR curing process

图7 NR和BPR+NR体系固化物的储能模量（a）和损耗因子（b）随温度的变化曲线

Fig.7 Variation curves of energy storage modulus (a) and loss factor (b) with temperature for NR and BPR+NR system cures

表2 NR和BPR+NR体系的DMA数据

Table 2 DMA data for NR and BPR+NR system

样品	E′(40℃)/MP	T_g/℃	E_r/MPa	V_e/（kmol/m³）
NR	7004	135.4	37.1	3.64
1BEP+NR	8409	146.3	129.0	12.33
3BEP+NR	10947	134.6	73.2	7.20
6BEP+NR	9803	137.2	63.1	6.17

图8 NR和BEP+NR体系的TGA（a）和DTG（b）曲线以及弯曲强度（c）和冲击强度（d）

Fig.8 (a) TGA and (b) DTG curves， (c) flexural strength and (d) impact strength of NR and BEP+NR systems

表3 NR和BEP+NR体系的热重数据

Table 3 TGA data of NR and BEP+NR systems

样品	T_5%/℃	800℃残炭率/%(N₂)
NR	338.3	49.8
1BEP+NR	280.1	55.8
3BEP+NR	287.3	52.1
6BEP+NR	258.2	52.6

图9 不同类型树脂的SAXS（a）和Ξ值（b）

Fig.9 SAXS (a) and Ξ values (b) for different types of resins

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