Intrinsic Flame Retardant Mechanism of Bio⁃Based Epoxy Resin Containing Pyridazinone Structure

doi:10.12422/j.issn.1006-396X.2023.01.001

Abstract

Abstract:

The intrinsic flame retardant mechanism of bio?based epoxy resin containing pyridazinone structure was explored through resin ablation experiment, scanning electron microscope,X?ray photoelectron spectrometer,thermogravimetry?infrared simultaneous thermal analyzer,and other characterization methods.The results show that compared with the most commonly used petroleum?based bisphenol A epoxy resin, the resultant bio?based epoxy resin is more likely to form a large amount of intumescent carbon layer structure during combustion and release a large amount of non?combustible gases such as CO₂ and NH₃ with less combustible gases.The intrinsic flame retardant bio?based epoxy resin containing pyridazinone structure exhibits a condensed phase?gas phase synergistic flame retardant mechanism. This study provides new ideas for constructing high?performance intrinsic flame retardant epoxy resin.

Key words: Bio?based, Epoxy resin, Intrinsic flame retardant, Pyridazinone, High?performance

摘要：

通过树脂烧蚀实验和扫描电子显微镜、X射线光电子能谱仪、热重?红外同步热分析仪等表征手段探究了含哒嗪酮结构的生物基环氧树脂的本征阻燃机制。结果表明，相对于目前最常用的石油基双酚A型环氧树脂，所制备的生物基环氧树脂在燃烧时更易形成大量膨胀型的炭层结构，同时释放出大量CO₂和NH₃等不可燃性气体和更少的可燃性气体；含哒嗪酮结构的本征阻燃生物基环氧树脂呈现出凝聚相?气相协同阻燃机理。本研究为构筑高性能的本征阻燃环氧树脂提供了新的思路。

关键词: 生物基, 环氧树脂, 本征阻燃, 哒嗪酮结构, 高性能

CLC Number:

TQ323.5

Yu Qi, Qi Cao, Jiahui Li, Xigao Jian, Zhihuan Weng. Intrinsic Flame Retardant Mechanism of Bio⁃Based Epoxy Resin Containing Pyridazinone Structure[J]. Journal of Petrochemical Universities, 2023, 36(1): 1-7.

戚裕, 曹旗, 李佳惠, 蹇锡高, 翁志焕. 含哒嗪酮结构生物基环氧树脂本征阻燃机制研究[J]. 石油化工高等学校学报, 2023, 36(1): 1-7.

Figures/Tables 7

Fig.1 Chemical structures of epoxy precursors and curing agent

Fig.2 Morphological changes of epoxy before and after calcination

Fig.3 SEM images of the outer and inner layers of carbon in the epoxy with different magnification

Fig.4 XPS spectrum of char residues formed from eposy after UL?94 test

Table 1 The mass fraction of each element in the char residues of epoxy

元素	质量分数/%
元素	GSPZ⁃EP/DDM	DGEBA/DDM
C	78.93	88.18
N	8.71	3.80
O	12.36	8.02

Fig.5 Meteorological 3D infrared spetrum of eposy during the whole degradation process and FT?IR spectrum of maximum pyrolysis rate

Fig.6 The flame retardancy mechanism of eposy system

References 36

1	Jin F L，Li X，Park S J.Synthesis and application of epoxy resins：A review［J］.Journal of Industrial and Engineering Chemistry，2015，29：1⁃11.
2	Gioia C，Lo Re G，Lawoko M，et al.Tunable thermosetting epoxies based on fractionated and well⁃characterized lignins［J］.Journal of the American Chemical Society，2018，140（11）：4054⁃4061.
3	Auvergne R，Caillol S，David G，et al.Biobased thermosetting epoxy：Present and future［J］.Chemical Reviews，2014，114（2）：1082⁃1115.
4	Hernandez N，Williams R C，Cochran E W.The battle for the "green" polymer.Different approaches for biopolymer synthesis：Bioadvantaged vs. bioreplacement［J］.Organic & Biomolecular Chemistry，2014，12（18）：2834⁃2849.
5	牛浩鑫，王鑫，宋磊，等.本征阻燃生物基环氧树脂研究进展［J］.高分子学报，2022，53（8）：894⁃904.
	Niu H X，Wang X，Song L，et al.Progress on intrinsically flame⁃retardant bio⁃based epoxy thermosets［J］.Acta Polymerica Sinica，2022，53（8）：894⁃904.
6	Hillmyer M A.The promise of plastics from plants plant⁃derived feedstocks are increasingly competitive in plastics production［J］.Science，2017，358（6365）：868⁃870.
7	Schneiderman D K，Hillmyer M A.50th anniversary perspective：There is a great future in sustainable polymers［J］.Macromolecules，2017，50（10）：3733⁃3749.
8	Wang X L，Chen L，Wu J N，et al.Flame⁃retardant pressure⁃sensitive adhesives derived from epoxidized soybean oil and phosphorus⁃containing dicarboxylic acids［J］.ACS Sustainable Chemistry & Engineering，2017，5（4）：3353⁃3361.
9	Gao T Y，Wang F D，Xu Y，et al.Luteolin⁃based epoxy resin with exceptional heat resistance，mechanical and flame retardant properties［J］.Chemical Engineering Journal，2022，428：131173.
10	Wang X，Niu H，Guo W，et al.Cardanol as a versatile platform for fabrication of bio⁃based flame⁃retardant epoxy thermosets as DGEBA substitutes［J］.Chemical Engineering Journal，2021，421：129738.
11	Meng J，Zeng Y，Zhu G，et al.Sustainable bio⁃based furan epoxy resin with flame retardancy［J］.Polymer Chemistry，2019，10（19）：2370⁃2375.
12	Wang S，Ma S，Xu C，et al.Vanillin⁃derived high⁃performance flame retardant epoxy resins：Facile synthesis and properties［J］.Macromolecules，2017，50（5）：1892⁃1901.
13	Liu J，Dai J，Wang S，et al.Facile synthesis of bio⁃based reactive flame retardant from vanillin and guaiacol for epoxy resin［J］.Composites Part B⁃Engineering，2020，190：107926.
14	Yu B，Xing W，Guo W，et al.Thermal exfoliation of hexagonal boron nitride for effective enhancements on thermal stability，flame retardancy and smoke suppression of epoxy resin nanocomposites via sol⁃gel process［J］.Journal of Materials Chemistry A，2016，4（19）：7330⁃7340.
15	Levchik S V，Weil E D.Thermal decomposition，combustion and flame⁃retardancy of epoxy resins：A review of the recent literature［J］.Polymer International，2004，53（12）：1901⁃1929.
16	Chen L，Ruan C，Yang R，et al.Phosphorus⁃containing thermotropic liquid crystalline polymers：A class of efficient polymeric flame retardants［J］.Polymer Chemistry，2014，5（12）：3737⁃3749.
17	Wang X，Guo W，Song L，et al.Intrinsically flame retardant bio⁃based epoxy thermosets：A review［J］.Composites Part B⁃Engineering，2019，179：107487.
18	Liu B W，Zhao H B，Wang Y Z.Advanced flame⁃retardant methods for polymeric materials［J］.Advance Materials，2022，34：2107905.
19	Liu B，Chen L，Guo D，et al.Fire⁃safe polyesters enabled by end⁃group capturing chemistry［J］.Angewandte Chemie.International Ed，2019，58：9188⁃9193.
20	Miao J，Yuan L，Guan Q，et al.Biobased epoxy resin derived from eugenol with excellent integrated performance and high renewable carbon content［J］.Polymer International，2018，67（9）：1194⁃1202.
21	Li J，Weng Z，Cao Q，et al.Synthesis of an aromatic amine derived from biomass and its use as a feedstock for versatile epoxy thermoset［J］.Chemical Engineering Journal，2022，433：134512.
22	Qi Y，Weng Z，Kou Y，et al.Synthesize and introduce bio⁃based aromatics⁃triazine in epoxy resin： Enabling extremely high thermal stability，mechanical properties，and flame retardancy to achieve high⁃performance sustainable polymers［J］.Chemical Engineering Journal，2021，406：126881.
23	Cao Q，Weng Z，Qi Y，et al.Achieving higher performances without an external curing agent in natural magnolol⁃based epoxy resin［J］.Chinese Chemical Letters，2022，33（4）：2195⁃2199.
24	Qi Y，Wang J，Kou Y，et al.Synthesis of an aromatic N⁃heterocycle derived from biomass and its use as a polymer feedstock［J］.Nature Communications，2019，10：2107.
25	Dong X，Chen L，Duan R T，et al.Phenylmaleimide⁃containing PET⁃based copolyester：Cross⁃linking from 2π+π cycloaddition toward flame retardance and anti⁃dripping［J］.Polymer Chemistry，2016，7（15）：2698⁃2708.
26	Pels J R，Kapteijn F，Moulijn J A，et al.Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis［J］.Carbon，1995，33（11）：1641⁃1653.
27	朱志成，王洪国，廖克俭，等.膨胀型阻燃体系在沥青中协同阻燃作用的研究［J］.石油化工高等学校学报，2015，28（3）：37⁃40.
	Zhu Z C，Wang H G，Liao K J，et al.Study on synergistic effect of intumescent flame retardant for road asphalt［J］.Journal of Petrochemical Universities，2015，28（3）：37⁃40.
28	Guan Y，Huang J，Yang J，et al.An effective way to flame⁃retard biocomposite with ethanolamine modified ammonium polyphosphate and its flame retardant mechanisms［J］.Industrial & Engineering Chemistry Research，2015，54（13）：3524⁃3531.
29	Zhao H B，Liu B W，Wang X L，et al.A flame⁃retardant⁃free and thermo⁃cross⁃linkable copolyester：Flame⁃retardant and anti⁃dripping mode of action［J］.Polymer，2014，55（10）：2394⁃2403.
30	Weidenthaler C，Lu A H，Schmidt W，et al.X⁃ray photoelectron spectroscopic studies of PAN⁃based ordered mesoporous carbons （OMC）［J］.Microporous and Mesoporous Materials，2006，88（1⁃3）：238⁃243.
31	Bourbigot S，Bras M L，Delobel R，et al.XPS study of an intumescent coating.II.Application to the ammonium polyphosphate/pentaerythritol/ethylenic terpolymer fire retardant system with and without synergistic agent［J］.Applied Surface Science，1997，120（1）：15⁃29.
32	Tan Y，Shao Z B，Yu L X，et al.Piperazine⁃modified ammonium polyphosphate as monocomponent flame⁃retardant hardener for epoxy resin：Flame retardance，curing behavior and mechanical property［J］.Polymer Chemistry，2016，7（17）：3003⁃3012.
33	Wu J，Chen L，Fu T，et al.New application for aromatic schiff base：High efficient flame⁃retardant and anti⁃dripping action for polyesters［J］.Chemical Engineering Journal，2018，336：622⁃632.
34	Zhu Y，Yuan L，Liang G，et al.Green flame retarding bismaleimide resin with simultaneously good processing characteristics，high toughness and outstanding thermal stability based on a multi⁃functional organic boron compound［J］.Polymer Degradation and Stability，2015，118：33⁃44.
35	Liu C，Yao Q.Design and synthesis of efficient phosphorus flame retardant for polycarbonate［J］.Industrial & Engineering Chemistry Research，2017，56（31）：8789⁃8796.
36	Ding H，Huang K，Li S，et al.Flame retardancy and thermal degradation of halogen⁃free flame⁃retardant biobased polyurethane composites based on ammonium polyphosphate and aluminium hypophosphite［J］.Polymer Testing，2017，62：325⁃334.

[1]	LI Hui,LI Yu-jian. Effect of Technological Factors on OMMT/E-51 Composite Modification for Waterborne Polyurethane [J]. Journal of Petrochemical Universities, 2012, 25(1): 18-21.
[2]	LI Hui. Preparation and Performance Study of Epoxy Resin E-51 Modified Waterborne Polyurethane Adhesive [J]. Journal of Petrochemical Universities, 2010, 23(2): 37-39.
[3]	YANG Ming-shan, HE Jie, LIU Zheng. The Preparation and Curing Kinetics of the Silicon － Containing Epoxy Resin [J]. Journal of Petrochemical Universities, 2009, 22(2): 1-4.
[4]	YIN Wen－hua, WU Bi-yao*. Cationic Photocuring Reaction of TMPE/Bisphenol-A Epoxy Resin [J]. Journal of Petrochemical Universities, 2008, 21(1): 30-33.
[5]	YIN Wen－hua， CHEN Yao， WU Bi-yao*. Synthetic Process of Tungoil Modified Phenolic Epoxy Resin and the Performance of Room Temperature Cured [J]. Journal of Petrochemical Universities, 2007, 20(2): 40-42.
[6]	WU Bi-yao， ZHANG Jun-heng， CHEN Yao， YIN Wen -hua. Preparation of Hyperbranched Epoxy Resin and Its Performance [J]. Journal of Petrochemical Universities, 2007, 20(1): 56-59.