酚醛树脂热裂解反应机理的密度泛函理论研究

doi:10.11949/0438-1157.20221063

摘要/Abstract

摘要：

选取2,2'-亚甲基二酚作为酚醛树脂的模型化合物，采用密度泛函理论（DFT），从原子活性和化学键级的视角预测反应趋势，提出反应路径，结合动力学和热力学分析确定各路径优先顺序和产物生成机理。结果表明：由于酚羟基与亚甲基的高活性，酚醛树脂的裂解首先发生脱水缩合反应；亚甲基桥断裂是主要的初始裂解反应，主要生成苯酚及邻甲酚；高活性的酚羟基易解离成 ^• OH，后续反应中亚甲基被 ^• OH氧化，经脱羰基和羧基反应生成苯酚、CO和CO₂。对于硼改性酚醛树脂的裂解过程，结果显示：硼酸酯结构中的B—O键活性很低，不易断裂，热稳定性增强。亚甲基桥更稳定且脱羰基和羧基的趋势明显减弱，且动力学分析发现其能垒均有增加，表明硼的引入能有效提高其热稳定性和残炭率。

关键词: 酚醛树脂, 热解, DFT, 原子活性, 化学键级

Abstract:

2,2'-Methylene diphenol was selected as the model compound of phenolic resin, and density functional theory (DFT) was used to predict the reaction trend from the perspective of atomic activity and chemical bond level, proposed the reaction path, and combined kinetic and thermodynamic analysis to determine the priority of each pathway and the mechanism of product formation. The results show that: due to the high activity of phenolic hydroxyl groups and methylene groups, the cracking of phenolic resin first occurs by dehydration condensation reaction. Methylene bridge cleavage is the main initial cracking reaction, mainly generating phenol and o-cresol. It is dissociated into ^•OH, and the methylene group is oxidized by ^•OH in the subsequent reaction, and phenol, CO and CO₂ are generated by decarbonylation and carboxyl reaction. For the cracking process of boron-modified phenolic resin, the results show that the B—O bond in the boronate structure has low activity, is not easy to break, and has enhanced thermal stability. The methylene bridge is more stable and the tendency of decarbonylation and carboxyl group is obviously weakened, and the kinetic analysis shows that its energy barrier is increased, indicating that the introduction of boron can effectively improve its thermal stability and carbon residue rate.

Key words: phenolic resin, pyrolysis, DFT, atomic activity, chemical bond order

中图分类号:

TQ 323.1

张娜, 潘鹤林, 牛波, 张亚运, 龙东辉. 酚醛树脂热裂解反应机理的密度泛函理论研究[J]. 化工学报, 2023, 74(2): 843-860.

Na ZHANG, Helin PAN, Bo NIU, Yayun ZHANG, Donghui LONG. Density functional theory study on thermal cracking reaction mechanism of phenolic resin[J]. CIESC Journal, 2023, 74(2): 843-860.

图/表 11

图1 优化后的分子结构以及Fukui函数投影到电子密度等值面图（PR）（左侧是优化后的分子结构，右侧对应的等值面图中绿色区域代表贫电子区，蓝色区域代表富电子区。图下方标示的数值为各反应位点的Fukui函数值，单位为e×100）

Fig.1 Optimized molecular structures and projection of Fukui function to electron density isosurfaces (PR) (on the left is the optimized molecular structures,the green areas in the corresponding isosurfaces on the right represents the electron-poor areas, and the blue areas represents the electron-rich areas, the values marked at the bottom of the figure are the Fukui function values of each reaction site, and the unit is e×100)

图2 PR模型化合物热解反应路径图

Fig.2 Pyrolysis reaction pathway diagram of PR model compound

图3 PR反应路径中涉及断键的化学键的Mayer键级和 Laplacian键级（横坐标中数字“1,2,3,4,5,6”分别表示反应物R的化学键“C3—C25,C16—C25, C4—O21, C15—O23, O21—H22, O23—H24”,“7,8”分别表示水杨醛P4和水杨酸P5中的化学键“C3—C13, C6—C10”,“-1”表示异构化产物1-i1的对应化学键，“-2”表示苯甲酮的对应化学键）

Fig.3 The Mayer bond order and the Laplacian bond order of the chemical bonds involved in the broken bonds in the reaction pathways of PR (the numbers “1, 2, 3, 4, 5, 6” in the abscissa represent the chemical bonds“C3—C25, C16—C25, C4—O21, C15—O23, O21—H22, O23—H24”,“7,8”represent the chemical bonds“C3—C13, C6—C10” in salicylaldehyde P4 and salicylic acid P5 respectively,“-1” represents the corresponding chemical bonds of isomerization product 1-i1,“-2” represents the corresponding chemical bonds of benzophenone)

表1 PR热解反应路径中的反应物、重要的过渡态、中间体和产物的优化几何结构

Table 1 Optimized geometries of reactants， important transition states， intermediates and products in the pyrolysis reaction pathways of PR

R(4,21) 1.3837

R(3,25) 1.5265

R(15,23) 1.4096

R(11,17) 1.0859

A(3,4,21) 123.5698

A(16,15,23) 116.6298

A(3,25,16) 115.1569

A(26,25,27) 106.4195

D(3,4,21,22) 17.5317

D(16,15,23,24) 177.6034

D(8,2,3,25) -0.5943

D(17,11,16,15) 179.8965

TS1a

R(4,21) 1.3313

R(3,25) 1.5717

R(16,25) 1.5149

R(3,22) 1.4548

A(3,4,21) 107.6645

A(3,25,26) 108.2772

A(15,16,25) 120.5249

A(26,25,27) 107.7724

D(2,3,4,21) 146.3908

D(2,3,25,16) 57.0082

D(23,15,16,25) 0.7638

D(22,3,25,26) -31.9241

1-i1

R(4,21) 1.2509

R(3,25) 1.5724

R(15,23) 1.3925

R(11,17) 1.0866

A(3,4,21) 120.1579

A(16,15,23) 116.1152

A(3,25,16) 116.3922

A(26,25,27) 107.2023

D(21,4,3,22) 69.4683

D(16,15,23,24) 178.8148

D(8,2,3,25) 42.8377

D(17,11,16,15) 179.6106

1-i2

R(5,6) 1.433

R(6,13) 1.3991

R(13,14) 1.0799

R(13,15) 1.0825

A(5,11,12) 109.1272

A(1,6,13) 122.1677

A(5,6,13) 121.3617

A(6,13,14) 121.2142

D(6,5,11,12) -180.0119

D(7,1,6,13) -0.0014

D(1,6,13,14) -179.9998

D(1,6,13,15) -0.0012

1-i3

R(3,4) 1.4523

R(4,5) 1.4523

R(5,6) 1.3748

R(4,11) 1.2514

A(4,5,6) 120.9385

A(3,4,5) 116.9288

A(6,5,9) 122.1827

A(5,4,11) 121.5356

D(9,5,6,10) -0.0001

D(9,5,4,11) 0.0001

D(2,3,4,11) 0.0001

D(6,5,4,11) -179.9999

P₁

R(5,6) 1.4045

R(6,13) 1.5095

R(13,14) 1.0973

R(13,15) 1.0973

A(5,11,12) 109.606

A(1,6,13) 121.6233

A(5,6,13) 120.4383

A(6,13,14) 112.0314

D(6,5,11,12) -0.0037

D(7,1,6,13) 0.0006

D(1,6,13,14) 119.5144

D(1,6,13,15) -119.5242

P₃

R(3,4) 1.3967

R(4,5) 1.3963

R(5,6) 1.3934

R(4,12) 1.3671

A(4,5,6) 119.8367

A(3,4,5) 119.9397

A(6,5,10) 120.2222

A(4,12,13) 109.1344

D(3,4,12,13) -179.9897

D(10,5,4,12) -0.001

D(3,4,12,13) 179.9582

D(5,4,12,13) -0.0447

TS1c

R(3,4) 1.4079

R(2,8) 1.0837

R(13,15) 1.3486

R(17,18) 0.9812

A(4,11,12) 111.8752

A(6,5,9) 120.3442

A(3,13,14) 115.9687

A(16,17,18) 122.7612

D(8,2,3,4) -179.5535

D(5,4,11,12) 1.5985

D(2,3,13,14) -158.9475

D(13,16,17,18) 110.7506

表1 PR热解反应路径中的反应物、重要的过渡态、中间体和产物的优化几何结构

Table 1 Optimized geometries of reactants， important transition states， intermediates and products in the pyrolysis reaction pathways of PR

Species

Structure parameter

Bond length/Å

Bond angle/(°)

Dihedral angle/(°)

R(4,21) 1.3837

R(3,25) 1.5265

R(15,23) 1.4096

R(11,17) 1.0859

A(3,4,21) 123.5698

A(16,15,23) 116.6298

A(3,25,16) 115.1569

A(26,25,27) 106.4195

D(3,4,21,22) 17.5317

D(16,15,23,24) 177.6034

D(8,2,3,25) -0.5943

D(17,11,16,15) 179.8965

TS1a

R(4,21) 1.3313

R(3,25) 1.5717

R(16,25) 1.5149

R(3,22) 1.4548

A(3,4,21) 107.6645

A(3,25,26) 108.2772

A(15,16,25) 120.5249

A(26,25,27) 107.7724

D(2,3,4,21) 146.3908

D(2,3,25,16) 57.0082

D(23,15,16,25) 0.7638

D(22,3,25,26) -31.9241

1-i1

R(4,21) 1.2509

R(3,25) 1.5724

R(15,23) 1.3925

R(11,17) 1.0866

A(3,4,21) 120.1579

A(16,15,23) 116.1152

A(3,25,16) 116.3922

A(26,25,27) 107.2023

D(21,4,3,22) 69.4683

D(16,15,23,24) 178.8148

D(8,2,3,25) 42.8377

D(17,11,16,15) 179.6106

1-i2

R(5,6) 1.433

R(6,13) 1.3991

R(13,14) 1.0799

R(13,15) 1.0825

A(5,11,12) 109.1272

A(1,6,13) 122.1677

A(5,6,13) 121.3617

A(6,13,14) 121.2142

D(6,5,11,12) -180.0119

D(7,1,6,13) -0.0014

D(1,6,13,14) -179.9998

D(1,6,13,15) -0.0012

1-i3

R(3,4) 1.4523

R(4,5) 1.4523

R(5,6) 1.3748

R(4,11) 1.2514

A(4,5,6) 120.9385

A(3,4,5) 116.9288

A(6,5,9) 122.1827

A(5,4,11) 121.5356

D(9,5,6,10) -0.0001

D(9,5,4,11) 0.0001

D(2,3,4,11) 0.0001

D(6,5,4,11) -179.9999

P₁

R(5,6) 1.4045

R(6,13) 1.5095

R(13,14) 1.0973

R(13,15) 1.0973

A(5,11,12) 109.606

A(1,6,13) 121.6233

A(5,6,13) 120.4383

A(6,13,14) 112.0314

D(6,5,11,12) -0.0037

D(7,1,6,13) 0.0006

D(1,6,13,14) 119.5144

D(1,6,13,15) -119.5242

P₃

R(3,4) 1.3967

R(4,5) 1.3963

R(5,6) 1.3934

R(4,12) 1.3671

A(4,5,6) 119.8367

A(3,4,5) 119.9397

A(6,5,10) 120.2222

A(4,12,13) 109.1344

D(3,4,12,13) -179.9897

D(10,5,4,12) -0.001

D(3,4,12,13) 179.9582

D(5,4,12,13) -0.0447

TS1c

R(3,4) 1.4079

R(2,8) 1.0837

R(13,15) 1.3486

R(17,18) 0.9812

A(4,11,12) 111.8752

A(6,5,9) 120.3442

A(3,13,14) 115.9687

A(16,17,18) 122.7612

D(8,2,3,4) -179.5535

D(5,4,11,12) 1.5985

D(2,3,13,14) -158.9475

D(13,16,17,18) 110.7506

图4 PR模型化合物的热解路径势能剖面图

Fig.4 Pyrolysis pathway potential energy profiles of PR model compounds

图5 PR模型化合物热解各路径∆G⊝-T和∆H⊝-T折线图

Fig.5 Line graph of ΔG⊝-T andΔH⊝-T for each pathway of PR model compound pyrolysis

图6 BPR模型化合物热解反应路径图

Fig.6 Pyrolysis reaction pathway diagram of BPR model compound

图7 优化后的分子结构以及Fukui函数投影到电子密度等值面图（BPR）（左侧是优化后的分子结构，右侧对应的等值面图中绿色区域代表贫电子区，蓝色区域代表富电子区。图中间标示的数值为各反应位点的Fukui函数值，单位为e×100）

Fig.7 Optimized molecular structures and projection of Fukui function to electron density isosurfaces (BPR) (on the left is the optimized molecular structures,the green areas in the corresponding isosurfaces on the right represents the electron-poor areas, and the blue areas represents the electron-rich areas, the values marked in the middle of the figure are the Fukui function values of each reaction site, and the unit is e×100)

图8 BPR反应路径中涉及断键的化学键的Mayer键级和 Laplacian键级（横坐标中数字“1,3”分别表示反应物R（PR）的化学键“C3—C25, C4—O21”,“2,4”分别表示反应物R（BPR）的化学键“C3—C24, C4—O20”,“5,7”分别表示PR中P4和P5的化学键“C3—C13,C6—C10”,“-1”表示异构化产物1-i1的对应化学键，“6,6-1”分别表示BPR中P4和P5的化学键“C6—C28”）

Fig.8 The Mayer bond order and the Laplacian bond order of the chemical bonds involved in the broken bonds in the reaction pathways of BPR (The numbers “1,3” in the abscissa represent the chemical bonds “C3—C25,C4—O21” of the reactant R (PR),“2,4”represent the chemical bonds “C3—C24,C4—O20” of the reactant R (BPR), and “5,7” represent the chemical bonds “C3—C13,C6—C10” of P4 and P5 in PR respectively, “-1” represents the corresponding chemical bonds of the isomerized product 1-i1,“6,6-1”represent the chemical bonds “C6—C28” of P4 and P5 in BPR respectively)

表2 BPR热解反应路径中的反应物、重要的过渡态、中间体和产物的优化几何结构

Table 2 Optimized geometries of reactants， important transition states， intermediates and products in the pyrolysis reaction pathways of BPR

	Species	Structure parameter
	Species	Bond length/Å	Bond angle/(°)	Dihedral angle/(°)
R		R(3,4) 1.4129 R(3,24) 1.5263 R(6,10) 1.0856 R(11,16) 1.4053	A(6,1,7) 120.5751 A(2,3,24) 119.9444 A(3,4,20) 123.7277 A(12,11,17) 119.7931	D(7,1,6,10) -0.1032 D(8,2,3,4) -179.5135 D(24,3,4,5) -177.5334 D(4,3,24,25) 37.4906
TS1a		R(1,7) 1.0847 R(2,8) 1.0872 R(3,21) 1.4603 R(11,16) 1.4039	A(3,4,20) 108.8091 A(21,3,24) 89.6951 A(4,5,6) 116.4379 A(12,13,14) 118.4517	D(2,3,4,20) -149.7406 D(4,3,24,26) 90.1564 D(21,4,5,9) -113.5019 D(15,16,24,3) 65.6825
1-i1		R(2,8) 1.0868 R(3,21) 1.1056 R(3,24) 1.5676 R(6,10) 1.087	A(3,2,8) 116.7196 A(4,3,21) 105.3531 A(21,3,24) 104.907 A(12,11,16) 121.5719	D(7,1,2,3) 178.9128 D(8,2,3,4) -174.8452 D(21,3,4,20) -69.4398 D(21,3,24,26) 179.7412
P₄		R(6,28) 1.4711 R(13,15) 1.3738 R(19,23) 1.0851 R(22,24) 1.3993	A(6,1,7) 117.5481 A(2,3,9) 121.2674 A(13,14,17) 125.9009 A(17,18,20) 119.1459	D(7,1,6,28) 0.018 D(9,3,4,5) -179.895 D(5,4,12,13) -179.9181 D(14,17,19,23) -0.5538
P₅		R(4,12) 1.3987 R(6,28) 1.4911 R(13,14) 1.3956 R(22,24) 1.3993	A(6,1,7) 119.0185 A(3,4,12) 125.829 A(17,18,20) 119.1356 A(18,20,25) 119.5079	D(7,1,2,3) -177.9088 D(8,2,3,9) 0.5803 D(4,5,10,11) -1.8132 D(14,13,15,16) -2.0753
P₆		R(3,24) 1.4668 R(11,16) 1.4076 R(14,25) 1.4006 R(26,27) 1.3968	A(5,4,20) 117.4778 A(12,11,16) 121.0413 A(14,15,22) 119.9191 A(26,28,29) 119.5608	D(8,2,3,24) 0.9432 D(5,4,20,21) 177.2876 D(17,11,12,13) 179.3928 D(22,15,16,11) -177.754

图9 BPR模型化合物的热解路径势能剖面图

Fig.9 Pyrolysis pathway potential energy profiles of BPR model compounds

参考文献 30

1	闫联生, 姚冬梅, 杨学军. 新型耐烧蚀材料研究[J]. 宇航材料工艺, 2002, 32(2): 29-31.
	Yan L S, Yao D M, Yang X J. A study of new ablation resistant materials[J]. Aerospace Materials ＆ Technology, 2002, 32(2): 29-31.
2	王子龙, 邢素丽, 尹昌平, 等. 高残炭耐烧蚀树脂基体研究进展[J]. 工程塑料应用, 2018, 46(8): 131-137.
	Wang Z L, Xing S L, Yin C P, et al. Research progress of ablative resistant resin matrix with high carbonization rate[J]. Engineering Plastics Application, 2018, 46(8): 131-137.
3	陈鸯飞, 陈智琴, 肖绍懿, 等. 酚醛树脂热降解过程中的结构变化[J]. 热固性树脂, 2008, 23(4): 4-8, 12.
	Chen Y F, Chen Z Q, Xiao S Y, et al. The structural changes of phenolic resin during thermal degradation[J]. Thermosetting Resin, 2008, 23(4): 4-8, 12.
4	王亚楠, 李兆, 曹静, 等. 酚醛树脂及含硼酚醛树脂热裂解和碳化研究进展[J]. 当代化工, 2021, 50(9): 2235-2241.
	Wang Y N, Li Z, Cao J, et al. Research progress of pyrolysis and carbonization of phenolic resin and boron-containing phenolic resin[J]. Contemporary Chemical Industry, 2021, 50(9): 2235-2241.
5	高南, 张亚峰, 邝健政, 等. 改性酚醛树脂及其在防腐涂料中的应用[J]. 新型建筑材料, 2011, 38(2): 11-14, 18.
	Gao N, Zhang Y F, Kuang J Z, et al. Modified phenolic resin and its application in anticorrosive paint[J]. New Building Materials, 2011, 38(2): 11-14, 18.
6	张力, 张以河, 姚亚琳, 等. 硼酚醛树脂及其复合材料的研究进展[J]. 玻璃钢/复合材料, 2018(3): 107-120.
	Zhang L, Zhang Y H, Yao Y L, et al. Research progress in boron modified phenolic resin and its composites[J]. Fiber Reinforced Plastics/Composites, 2018(3): 107-120.
7	Jiang H Y, Wang J G, Wu S Q, et al. The pyrolysis mechanism of phenol formaldehyde resin[J]. Polymer Degradation and Stability, 2012, 97(8): 1527-1533.
8	陈治宇, 胡宏林, 余瑞莲, 等. 一种酚醛树脂模型化合物热解反应的密度泛函理论研究及实验验证[J]. 宇航材料工艺, 2018, 48(1): 30-36.
	Chen Z Y, Hu H L, Yu R L, et al. Pyrolysis reactions of one model compound of phenolic resin using density functional theory and experimental validation[J]. Aerospace Materials ＆ Technology, 2018, 48(1): 30-36.
9	Abdalla M O, Ludwick A, Mitchell T. Boron-modified phenolic resins for high performance applications[J]. Polymer, 2003, 44(24): 7353-7359.
10	Lu T, Chen F W. Multiwfn: a multifunctional wavefunction analyzer[J]. Journal of Computational Chemistry, 2012, 33(5): 580-592.
11	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.
12	Chen Z Q, Chen Y F, Liu H B. Pyrolysis of phenolic resin by TG-MS and FTIR analysis[C]//Materials Engineering for Advanced Technologies. Trans Tech Publications, 2012:102-107.
13	Wong H W, Peck J, Bonomi R E, et al. Quantitative determination of species production from phenol-formaldehyde resin pyrolysis[J]. Polymer Degradation and Stability, 2015, 112: 122-131.
14	Bennett A, Payne D R, Court R W. Pyrolytic and elemental analysis of decomposition products from a phenolic resin[J]. Macromolecular Symposia, 2014, 339(1): 38-47.
15	Fitzer E, Schaefer W, Yamada S. The formation of glasslike carbon by pyrolysis of polyfurfuryl alcohol and phenolic resin[J]. Carbon, 1969, 7(6): 643-648.
16	马伟. 酚醛树脂的热解研究[D]. 重庆: 重庆大学, 2007.
	Ma W. Study on the pyrolysis of phenolic resin[D]. Chongqing: Chongqing University, 2007.
17	Chattaraj P K, Sarkar U, Roy D R. Electrophilicity index[J]. Chemical Reviews, 2006, 106(6): 2065-2091.
18	张晨. 类煤模型化合物热解过程中脱羧反应和C—C/C—O断键规律研究[D]. 徐州: 中国矿业大学, 2020.
	Zhang C. Research on decarboxylation reaction and C—C/C—O breaking law of coal-like model compounds during pyrolysis[D]. Xuzhou: China University of Mining and Technology, 2020.
19	Li M, Mo C H, Luo X, et al. Exploring key reaction sites and deep degradation mechanism of perfluorooctane sulfonate via peroxymonosulfate activation under electrocoagulation process[J]. Water Research, 2021, 207: 117849.
20	渠艳飞, 关泽宇, 马邕文, 等. 基于硫酸自由基氧化降解邻苯二甲酸二丁酯的密度泛函理论研究[J]. 环境化学, 2017, 36(9): 1896-1905.
	Qu Y F, Guan Z Y, Ma Y W, et al. A theoretical investigation on the degradation of dibutyl phthalate based on sulfate radicals oxidation: a DFT study[J]. Environmental Chemistry, 2017, 36(9): 1896-1905.
21	Shen Q R, Fu Z W, Li R, et al. A study on the pyrolysis mechanism of a β-O-4 lignin dimer model compound using DFT combined with Py-GC/MS[J]. Journal of Thermal Analysis and Calorimetry, 2021, 146(4): 1751-1761.
22	张洋, 陈世荣. 羟基自由基与苯酚反应机理的量子化学研究[J]. 陕西师范大学学报(自然科学版), 2008, 36(5): 58-61.
	Zhang Y, Chen S R. Theoretical study on the reaction of hydroxyl radical with phenol[J]. Journal of Shaanxi Normal University (Natural Science Edition), 2008, 36(5): 58-61.
23	Ouchi K, Honda H. Pyrolysis of coal(Ⅰ): Thermal cracking of phenolformaldehyde resins taken as coal models[J]. Fuel, 1959, 38:429-443.
24	Jackson W M, Conley R T. High temperature oxidative degradation of phenol-formaldehyde polycondensates[J]. Journal of Applied Polymer Science, 1964, 8(5): 2163-2193.
25	姚灿, 田红, 黄章俊, 等. 基于量子化学的玉米秸秆热解机理的模拟计算[J]. 西北大学学报(自然科学版), 2019, 49(1): 122-131.
	Yao C, Tian H, Huang Z J, et al. Theoretical study on pyrolysis mechanism of corn stalk based on quantum chemistry[J]. Journal of Northwest University (Natural Science Edition), 2019, 49(1): 122-131.
26	Tang B, Wang Y T, Peng X L, et al. Efficient predictions of Gibbs free energy for the gases CO, BF, and gaseous BBr[J]. Journal of Molecular Structure, 2020, 1199: 126958.
27	梁韬. 基于Py-GC/MS的半纤维素热裂解机理研究[D]. 杭州: 浙江大学, 2013.
	Liang T. Mechanism research of hemicellulose pvrolvsis based on Py-GC/MS[D]. Hangzhou: Zhejiang University, 2013.
28	张亚运. 木质纤维素热化学转化机理及裂解气体CO₂和H₂吸附分离的分子模拟研究[D]. 重庆: 重庆大学, 2017.
	Zhang Y Y. The mechanism of lignin cellulose thermal conversion and adsorption and separation of pyrolytic gases CO₂ and H₂ by molecular simulation[D]. Chongqing: Chongqing University, 2017.
29	Costa L, di Montelera L R, Camino G, et al. Structure-charring relationship in phenol-formaldehyde type resins[J]. Polymer Degradation and Stability, 1997, 56(1): 23-35.
30	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.

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