氰基衍生苯并嗪树脂的制备及耐热性能研究

doi:10.11949/0438-1157.20250254

摘要/Abstract

摘要：

从生物质原料制备可低温固化的高性能苯并嗪树脂对满足工业领域可持续发展具有重要意义。但制备兼具低固化温度和高性能的苯并嗪树脂是当前领域的难点，为了克服这一困难，以生物质香草醛和对羟基苯甲醛为原料，合成了含氰基基团的生物质单体，采用无溶剂法合成了两种苯并嗪单体HN-fa和VN-fa。通过热分析（DSC）研究了氰基对苯并嗪开环聚合的影响。由于分子内氰基官能团的存在，HN-fa和VN-fa的固化峰值温度分别低至200和206℃，将单体热固化聚合制得poly（HN-fa）和poly（VN-fa），并对其热和阻燃性能进行了测试。制得的树脂具有优异的耐热性，poly（HN-fa）和poly（VN-fa）的玻璃化转变温度（T_g）分别高达247和189℃，此外poly（HN-fa）和poly（VN-fa）还具有优异的阻燃性能。研究结果表明，氰基的引入不仅可以降低树脂的固化温度，对于提高树脂的耐热性和阻燃性也有积极的影响。

关键词: 苯并嗪树脂, 生物质, 合成, 聚合, 制备

Abstract:

It is of great significance to prepare low-temperature curable high-performance benzoxazine resins from biomass raw materials, which can meet the requirements of sustainable development in the industrial field. In this paper, 4-hydroxybenzonitrile and vanillonitrile were synthesized from vanillin and p-hydroxybenzaldehyde. Two new biobased benzoxazine monomers, HN-fa and VN-fa, were synthesized by solvent-free method, and then cured to prepare poly(HN-fa) and poly(VN-fa). The effect of nitrile group on reducing ring-opening polymerization of benzoxazines were studied by DSC. Due to the existence of nitrile functionality, the peak curing temperatures of HN-fa and VN-fa were as low as 200 and 206℃, respectively. In addition, the heat resistance of poly(HN-fa) and poly(VN-fa) was investigated by TGA and MCC. Poly(HN-fa) and poly(VN-fa) exhibited high glass transition temperatures (T_g) of 247 and 189℃, respectively. Moreover, these two thermosets also showed excellent flame retardant properties. These attractive results demonstrate that the newly designed nitrile-containing biobased benzoxazine monomers can be used for preparing high heat resistance and low temperature processed materials.

Key words: benzoxazine resin, biomass, synthesis, polymer, preparation

中图分类号:

TQ 322.4

费正皓, 杨秀芝, 刘总堂, 沙新龙. 氰基衍生苯并嗪树脂的制备及耐热性能研究[J]. 化工学报, 2025, 76(10): 5486-5494.

Zhenghao FEI, Xiuzhi YANG, Zongtang LIU, Xinlong SHA. Preparation and heat resistance of cyanide-derived benzoxazine resins[J]. CIESC Journal, 2025, 76(10): 5486-5494.

图/表 11

图1 苯并嗪单体HN-fa和VN-fa的合成路线示意图

Fig.1 Synthetic routes to the benzoxazine monomers HN-fa and VN-fa

图2 HN-fa和VN-fa的FTIR谱图

Fig.2 FTIR spectra of HN-fa and VN-fa

图3 HN-fa和VN-fa的1H NMR[(a)、(b)],13C NMR[(c)、(d)]和HRMS[(e)、(f)]谱图

Fig.3 1H NMR spectra [(a), (b)], 13C NMR spectra [(c), (d)] and HRMS spectra [(e),(f)] of HN-fa and VN-fa

图4 N2气氛下不同苯并嗪单体的DSC曲线

Fig.4 DSC curves of benzoxazines monomers under N2 atmosphere

图5 poly(HN-fa)和poly(VN-fa)的FTIR谱图

Fig.5 FTIR spectra of poly(HN-fa) and poly(VN-fa)

图6 通过DMA测试得到的poly(HN-fa)和poly(VN-fa)的tanδ随温度的变化

Fig.6 tanδ-temperature plots of poly(HN-fa) and poly(VN-fa) from DMA tests

表1 poly（HN-fa）、poly（VN-fa）和一些结构相似苯并嗪树脂的热性能和阻燃性能

Table 1 Thermal stability and heat release properties of poly（HN-fa）， poly（VN-fa） and typical benzoxazine resins

样品	T_g/℃	T_di/℃	Y_C/%	HRC/(J·g^-1·K^-1)	THR/(kJ·g^-1)
poly(PH-a)	133	292	38	118	13.5
poly(GU-fa)	—	320	56	70.6	6.5
poly(HN-fa)	247	338	63.2	50.6	10.3
poly(VN-fa)	189	313	64.7	62.0	11.1
poly(V-fa)	—	293	56.1	132.2	6.9

图7 poly(V-fa)、poly(HN-fa)和poly(VN-fa)在N2气氛下的热重曲线

Fig.7 TGA curves of poly(V-fa), poly(HN-fa) and poly(VN-fa) under a N2 atmosphere

图8 poly(V-fa)、poly(HN-fa)和poly(VN-fa)在N2气氛下的DTG曲线

Fig.8 DTG curves of poly(V-fa), poly(HN-fa) and poly(VN-fa)under a N2 atmosphere

图9 poly(V-fa)、poly(HN-fa)和poly(VN-fa)的热释放率

Fig.9 Heat release rate for poly(V-fa), poly(HN-fa) and poly(VN-fa)

图10 poly(V-fa)、poly(HN-fa)和poly(VN-fa)的总热量释放

Fig.10 Total heat release for poly(V-fa), poly(HN-fa) and poly(VN-fa)

参考文献 36

[1]	Zhang C Q, Xue J Q, Yang X Y, et al. From plant phenols to novel bio-based polymers[J]. Progress in Polymer Science, 2022, 125: 101473.
[2]	Adjaoud A, Marcolini B, Dieden R, et al. Deciphering the self-catalytic mechanisms of polymerization and transesterification in polybenzoxazine vitrimers[J]. Journal of the American Chemical Society, 2024, 146(19): 13367-13376.
[3]	Zhang S J, Yi J J, Chen J M, et al. Weldable, reprocessable, and water-resistant polybenzoxazine vitrimer crosslinked by dynamic imine bonds[J]. ChemSusChem, 2024, 17(14): e202301708.
[4]	Yang M Y, Wang T C, Tian Y Z, et al. Nature's empowerment: unraveling superior performance and green degradation closed-loop in self-curing fully bio-based benzoxazines[J]. Green Chemistry, 2024, 26(8): 4771-4784.
[5]	Li N, Yang S F, Zhang K. Thiophene-rich benzoxazines with an amide moiety: integration of structural and hydrogen bonding influence on the polymerization mechanism by experimental and computational studies[J]. Macromolecules, 2023, 56(17): 6667-6678.
[6]	Zhou X, Shen M G, Fu F, et al. High strength, self-healing and hydrophobic fully bio-based polybenzoxazine reinforced pine oleoresin-based vitrimer and its application in carbon fiber reinforced polymers[J]. Chemical Engineering Journal, 2024, 484: 149585.
[7]	Yadav S, Amarnath N, et al. Advancing renewable amines: furan-derived polybenzoxazines[J]. ACS Applied Polymer Materials, 2024, 6(24): 15281-15292.
[8]	Seychal G, Van Renterghem L, Ocando C, et al. Towards sustainable reprocessable structural composites: Benzoxazines as biobased matrices for natural fibers[J]. Composites Part B: Engineering, 2024, 272: 111201.
[9]	Madesh P, Krishnasamy B, Arumugam H, et al. Bio-based benzoxazine composites derived from magnolol: promising solution for sustainable alternatives for dielectric and superhydrophobic applications[J]. Polymer Composites, 2024, 45(8): 7137-7149.
[10]	Yang R, Li N, Evans C J, et al. Phosphaphenanthrene-functionalized benzoxazines bearing intramolecularly hydrogen-bonded phenolic hydroxyl: synthesis, structural characterization, polymerization mechanism, and property investigation[J]. Macromolecules, 2023, 56(4): 1311-1323.
[11]	Mohamed Mydeen K, Krishnasamy B, Arumugam H, et al. Sustainable strategies for fully biobased polybenzoxazine composites from trifunctional thymol and biocarbons: advancements in high-dielectric and antibacterial corrosion implementations[J]. ACS Sustainable Chemistry & Engineering, 2024, 12(6): 2225-2240.
[12]	Mohamed Mydeen K, Arumugam H, Krishnasamy B, et al. Nonylphenol-based polybenzoxazine composites: hydrophobic coating, ultra-low-k and anticorrosion applications[J]. Journal of Materials Science, 2023, 58(25): 10340-10358.
[13]	Lochab B, Monisha M, Amarnath N, et al. Review on the accelerated and low-temperature polymerization of benzoxazine resins: addition polymerizable sustainable polymers[J]. Polymers, 2021, 13(8): 1260.
[14]	Zhang K, Yu X Y, Wang Y T, et al. Thermally activated structural changes of a norbornene-benzoxazine-phthalonitrile thermosetting system: simple synthesis, self-catalyzed polymerization, and outstanding flame retardancy[J]. ACS Applied Polymer Materials, 2019, 1(10): 2713-2722.
[15]	Ren D X, Xu M Z, Chen S J, et al. Curing reaction and properties of a kind of fluorinated phthalonitrile containing benzoxazine[J]. European Polymer Journal, 2021, 159: 110715.
[16]	Wang T, Shi C Y, Qadeer Dayo A, et al. Synthesis and properties of novel self-catalytic phthalonitrile monomers with aliphatic chain and their copolymerization with multi-functional fluorene-based benzoxazine monomers[J]. European Polymer Journal, 2021, 161: 110862.
[17]	Chen Y P, Dayo A Q, Zhang H Y, et al. Synthesis of cardanol-based phthalonitrile monomer and its copolymerization with phenol–aniline-based benzoxazine[J]. Journal of Applied Polymer Science, 2019, 136(20): 47505.
[18]	Dayo A Q, Wang A R, Derradji M, et al. Copolymerization of mono and difunctional benzoxazine monomers with bio-based phthalonitrile monomer: curing behaviour, thermal, and mechanical properties[J]. Reactive and Functional Polymers, 2018, 131: 156-163.
[19]	Bonjour O, Nederstedt H, Arcos-Hernandez M V, et al. Lignin-inspired polymers with high glass transition temperature and solvent resistance from 4-hydroxybenzonitrile, vanillonitrile, and syringonitrile methacrylates[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(50): 16874-16880.
[20]	郑杰元, 张先伟, 万金涛, 等. 丁香酚环氧有机硅树脂的制备及其固化动力学研究[J]. 化工学报, 2023, 74(2): 924-932.
	Zheng J Y, Zhang X W, Wan J T, et al. Synthesis and curing kinetic analysis of eugenol-based siloxane epoxy resin[J]. CIESC Journal, 2023, 74(2): 924-932.
[21]	Andreu R, Reina J A, Ronda J C. Studies on the thermal polymerization of substituted benzoxazine monomers: electronic effects[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2008, 46(10): 3353-3366.
[22]	Sini N K, Bijwe J, Varma I K. Renewable benzoxazine monomer from vanillin: synthesis, characterization, and studies on curing behavior[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2014, 52(1): 7-11.
[23]	Guan L J, Guo Z Q, Zhou Q, et al. A highly proton conductive perfluorinated covalent triazine framework via low-temperature synthesis[J]. Nature Communications, 2023, 14(1): 8114.
[24]	Xu M Z, Ren D X, Chen L, et al. Understanding of the polymerization mechanism of the phthalonitrile-based resins containing benzoxazine and their thermal stability[J]. Polymer, 2018, 143: 28-39.
[25]	Zhang S, Li Q S, Ye J J, et al. Probing the copolymerization of alkynyl and cyano groups using monocyclic benzoxazine as model compound[J]. Polymer, 2022, 252: 124932.
[26]	Lu Y, Yang Y, Wang J Q, et al. Development of intrinsically flame-retardant bio-thermosets with further enhanced thermal stability through a photo-thermal dual polymerization strategy[J]. Polymer Degradation and Stability, 2024, 229: 110948.
[27]	Lu Y, Liu J M, Zhao W Q, et al. Bio-benzoxazine structural design strategy toward highly thermally stable and intrinsically flame-retardant thermosets[J]. Chemical Engineering Journal, 2023, 457: 141232.
[28]	Muraoka M, Goto M, Minami M, et al. Ethynylene-linked multifunctional benzoxazines: the effect of the ethynylene group and packing on thermal behavior[J]. Polymer Chemistry, 2022, 13(39): 5590-5596.
[29]	胡月, 马守骏, 蹇锡高, 等. 新型聚芳醚腈固化邻苯二甲腈树脂的研究[J]. 化工学报, 2023, 74(2): 871-882.
	Hu Y, Ma S J, Jian X G. Study on curing phthalonitrile resin with novel poly(phthalazinone ether nitrile)[J]. CIESC Journal, 2023, 74(2): 871-882.
[30]	Yang R, Han M C, Hao B R, et al. Biobased high-performance tri-furan functional bis-benzoxazine resin derived from renewable guaiacol, furfural and furfurylamine[J]. European Polymer Journal, 2020, 131: 109706.
[31]	Lu Y, Yu X Y, Evans C J, et al. Elucidating the role of acetylene in ortho-phthalimide functional benzoxazines: design, synthesis, and structure–property investigations[J]. Polymer Chemistry, 2021, 12(35): 5059-5068.
[32]	van Krevelen D W. Some basic aspects of flame resistance of polymeric materials[J]. Polymer, 1975, 16(8): 615-620.
[33]	Spontón M, Ronda J C, Galià M, et al. Studies on thermal and flame retardant behaviour of mixtures of bis(m-aminophenyl)methylphosphine oxide based benzoxazine and glycidylether or benzoxazine of Bisphenol A[J]. Polymer Degradation and Stability, 2008, 93(12): 2158-2165.
[34]	Chen M J, Wang X, Tao M C, et al. Full substitution of petroleum-based polyols by phosphorus-containing soy-based polyols for fabricating highly flame-retardant polyisocyanurate foams[J]. Polymer Degradation and Stability, 2018, 154: 312-322.
[35]	Bourbigot S, Flambard X. Heat resistance and flammability of high performance fibres: a review[J]. Fire and Materials, 2002, 26(4/5): 155-168.
[36]	Walters R N, Lyon R E. Molar group contributions to polymer flammability[J]. Journal of Applied Polymer Science, 2003, 87(3): 548-563.