厚朴酚基环氧树脂防腐涂层的制备及性能评价

doi:10.11949/0438-1157.20230492

摘要/Abstract

摘要：

以环氧氯丙烷和生物基化合物厚朴酚为原料，通过一步反应制得厚朴酚环氧树脂（DGEM），以聚醚胺D230为固化剂制备含云母粉的防腐涂层。采用红外光谱仪、耐磨试验仪、热失重分析仪、差示扫描量热仪、电化学工作站、铅笔硬度、冲击试验器等对涂层进行分析表征和性能测试，研究了云母粉填料用量对涂层的耐腐蚀等相关性能的影响。结果表明：相比于纯DGEM-D230涂层，添加3%（质量）云母粉填料的涂层DGEM-D230-3%表现出更好的力学性能和耐腐蚀性能，其铅笔硬度为4H，冲击强度为30 cm，低频阻抗模值达到8.47×10⁸ Ω∙cm²，氮气氛围下800℃时的残炭率为37.1%，柔韧性达到0.5 mm，附着力达到0级。

关键词: 生物基, 环氧树脂, 厚朴酚, 防腐涂层

Abstract:

Using epichlorohydrin and bio-based compound magnolol as raw materials, magnolol epoxy resin (DGEM) was prepared by one-step reaction, and polyetheramine D230 was used as curing agent to prepare anti-corrosion coating containing mica powder. Comprehensive analyses and characterizations were performed by using multiple techniques, including infrared spectroscopy, wear resistance testing, thermogravimetric analysis, differential scanning calorimetry, electrochemical workstation, pencil hardness testing, and impact testing. The effects of varying mica powder filler content on the corrosion resistance of the coating were investigated. The results revealed that the addition of 3% (mass) mica powder filler significantly enhanced the mechanical and corrosion resistance properties of the DGEM-D230 coating. Specifically, the DGEM-D230-3% exhibited a pencil hardness of 4H, an impact strength of 30 cm, an electrochemical impedance value of 8.47×10⁸ Ω∙cm², a residual carbon yield of 37.1% at 800°C under a nitrogen atmosphere, and a flexibility of 0.5 mm, with 0-level adhesion, surpassing those of the pure DGEM-D230 coating. These findings highlight the potential of DGEM-D230-3% coating as a promising corrosion-resistant coating for various applications.

Key words: bio-based, epoxy resin, magnolol, anti-corrosion coating

中图分类号:

TQ 050.9

赵婧, 顾程文, 蹇锡高, 翁志焕. 厚朴酚基环氧树脂防腐涂层的制备及性能评价[J]. 化工学报, 2023, 74(7): 3010-3017.

Jing ZHAO, Chengwen GU, Xigao JIAN, Zhihuan WENG. Preparation and performance evaluation of magnolol-based epoxy resin anti-corrosion coatings[J]. CIESC Journal, 2023, 74(7): 3010-3017.

图/表 7

图1 DGEM的合成路径及其以D230为固化剂的固化产物

Fig.1 Synthetic route of DGEM and its cured product with D230 as curing agent

图2 DGEM-D230的红外光谱图

Fig.2 FTIR spectra of DGEM-D230

图3 不同组分DGEM-D230涂层在3.5% (质量) NaCl溶液中浸泡1、7、15、30 d时的Nyquist曲线

Fig.3 Nyquist plots of different composite DGEM-D230 coatings immersed in 3.5% (mass) NaCl solution for 1, 7, 15, 30 d

图4 不同组分DGEM-D230涂层在3.5% (质量) NaCl溶液中浸泡1, 7, 15, 30 d时的Bode曲线

Fig.4 Bode plots of different composite DGEM-D230 coatings immersed in 3.5% (mass) NaCl solution for 1, 7, 15, 30 d

图5 涂层在浸泡初期、中期、后期的等效电路模型

Fig.5 Equivalent circuit models for coatings during early, mid, late immersion stages

图6 涂层的力学性能比较

Fig.6 Comparison of mechanical properties of coatings

图7 在N2氛围下DGEM-D230和DGEM-D230-3%云母粉的TGA和DSC曲线

Fig.7 TGA and DSC curves of DGEM-D230 and DGEM-D230-3% mica powder under N2 atmosphere

参考文献 34

1	Matthiesen J E, Carraher J M, Vasiliu M, et al. Electrochemical conversion of muconic acid to biobased diacid monomers[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(6): 3575-3585.
2	Wang W L, Xue L W, Zhang T S, et al. The influence of MgO/ZrO₂/Al₂O₃ refractories on the refining process of Ti-containing steel based on kinetic study[J]. Ceramics International, 2020, 46(11): 17561-17568.
3	Chen B, Wu Q, Li J, et al. A novel and green method to synthesize a epoxidized biomass eucommia gum as the nanofiller in the epoxy composite coating with excellent anticorrosive performance[J]. Chemical Engineering Journal, 2020, 379: 122323.
4	Nabipour H, Wang X, Song L, et al. Facile synthesis of a novel zinc-triazole complex for simultaneous improvement in fire safety and mechanical properties of epoxy resins[J]. Composites Part A: Applied Science and Manufacturing, 2021, 143: 106284.
5	Waśkiewicz S, Zenkner K, Langer E W, et al. Organic coatings based on new Schiff base epoxy resins[J]. Progress in Organic Coatings, 2013, 76(7/8): 1040-1045.
6	Wan J T, Zhao J Q, Gan B, et al. Ultrastiff biobased epoxy resin with high T_g and low permittivity: from synthesis to properties[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(5): 2869-2880.
7	Xin J N, Li M, Li R, et al. Green epoxy resin system based on lignin and tung oil and its application in epoxy asphalt[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(5): 2754-2761.
8	Dai J Y, Teng N, Shen X B, et al. Synthesis of biobased benzoxazines suitable for vacuum-assisted resin transfer molding process via introduction of soft silicon segment[J]. Industrial & Engineering Chemistry Research, 2018, 57(8): 3091-3102.
9	Wang X, Leng W Q, Oshani Nayanathara R M, et al. Anticorrosive epoxy coatings from direct epoxidation of bioethanol fractionated lignin[J]. International Journal of Biological Macromolecules, 2022, 221: 268-277.
10	Li M L, Hao X H, Hu M L, et al. Synthesis of vanillin-based flame retardant epoxy coating on wood surface[J]. Progress in Organic Coatings, 2022, 172: 107161.
11	Zheng S L, Bellido-Aguilar D A, Hu J, et al. Waterborne bio-based epoxy coatings for the corrosion protection of metallic substrates[J]. Progress in Organic Coatings, 2019, 136: 105265.
12	Wang X, Nabipour H, Kan Y C, et al. A fully bio-based, anti-flammable and non-toxic epoxy thermosetting network for flame-retardant coating applications[J]. Progress in Organic Coatings, 2022, 172: 107095.
13	Huang J, Zhang J S, Zhu G Q, et al. Self-healing, high-performance, and high-biobased-content UV-curable coatings derived from rubber seed oil and itaconic acid[J]. Progress in Organic Coatings, 2021, 159: 106391.
14	Jiang H, Sun L, Zhang Y R, et al. Novel biobased epoxy resin thermosets derived from eugenol and vanillin[J]. Polymer Degradation and Stability, 2019, 160: 45-52.
15	Zhang Y T, Pang H, Wei D D, et al. Preparation and characterization of chemical grouting derived from lignin epoxy resin[J]. European Polymer Journal, 2019, 118: 290-305.
16	Ammar S, Iling A W M, Ramesh K, et al. Development of fully organic coating system modified with epoxidized soybean oil with superior corrosion protection performance[J]. Progress in Organic Coatings, 2020, 140: 105523.
17	何吉喆, 刘明言, 徐杨书函. 环氧豆油树脂涂层的防腐性能研究[J]. 化工学报, 2021, 72(2): 1067-1077.
	He J Z, Liu M Y, Xu Y S H. Study on anticorrosive properties of epoxy soybean oil resin coating[J]. CIESC Journal, 2021, 72(2): 1067-1077.
18	赵晓磊, 侯桂香, 于守武. 植物酚型生物基环氧树脂研究进展[J]. 高分子材料科学与工程, 2022, 38(9): 167-175.
	Zhao X L, Hou G X, Yu S W. Progress on research of plant phenolic bio-based epoxy resin[J]. Polymer Materials Science & Engineering, 2022, 38(9): 167-175.
19	翁志焕, 李佳惠, 戚裕, 等. 生物基环氧树脂高性能化和功能化的研究进展[J]. 中国材料进展, 2019, 38(10): 999-1008, 1016.
	Weng Z H, Li J H, Qi Y, et al. Progress on high performance and functionalization of bio-based epoxy resins[J]. Materials China, 2019, 38(10): 999-1008, 1016.
20	宋乐群, 戚裕, 曹旗, 等. 高性能和厚朴酚生物基环氧树脂的性能调控[J]. 高分子材料科学与工程, 2022, 38(2): 1-7, 16.
	Song L Q, Qi Y, Cao Q, et al. Rational regulation of performance on high-performance bio-based epoxy resin bearing honokiol moiety[J]. Polymer Materials Science & Engineering, 2022, 38(2): 1-7, 16.
21	戚裕. 耐高温本征阻燃高性能生物基环氧树脂的制备及性能研究[D]. 大连: 大连理工大学, 2021.
	Qi Y. Preparation and properties of high-temperature resistant intrinsic flame retardant high-performance bio-based epoxy resin[D]. Dalian: Dalian University of Technology, 2021.
22	Qi Y, Weng Z H, Zhang K W, et al. Magnolol-based bio-epoxy resin with acceptable glass transition temperature, processability and flame retardancy[J]. Chemical Engineering Journal, 2020, 387: 124115.
23	Xu M Z, Lei Y X, Ren D X, et al. Thermal stability of allyl-functional phthalonitriles-containing benzoxazine/bismaleimide copolymers and their improved mechanical properties[J]. Polymers, 2018, 10(6): 596.
24	刘立立. 颜填料的特性及其对隔热涂料性能的影响[D]. 武汉: 武汉科技大学, 2015.
	Liu L L. Characteristics of fillers and its effect on the properties of thermal insulation coatings[D]. Wuhan: Wuhan University of Science and Technology, 2015.
25	da Silva L R R, Carvalho B A, Pereira R C S, et al. Bio-based one-component epoxy resin: novel high-performance anticorrosive coating from agro-industrial byproduct[J]. Progress in Organic Coatings, 2022, 167: 106861.
26	Zhang Y Y, Chu L Y, Dai Z S, et al. Synergistically enhancing the performance of cardanol-rich epoxy anticorrosive coatings using cardanol-based reactive diluent and its functionalized graphene oxide[J]. Progress in Organic Coatings, 2022, 171: 107060.
27	Margarit-Mattos I C P. EIS and organic coatings performance: revisiting some key points[J]. Electrochimica Acta, 2020, 354: 136725.
28	Xing C, Wang W, Qu S, et al. Degradation of zinc-rich epoxy coating in 3.5% NaCl solution and evolution of its EIS parameters[J]. Journal of Coatings Technology and Research, 2021, 18(3): 843-860.
29	陈绪蕾, 彭强, 邓志强, 等. 氟化石墨烯硅烷功能化对环氧复合涂层耐腐蚀性的影响[J]. 涂料工业, 2022, 52(12): 1-8.
	Chen X L, Peng Q, Deng Z Q, et al. Effect of fluorinated graphene silane functionalization on the corrosion resistance of epoxy composite coatings[J]. Paint & Coatings Industry, 2022, 52(12): 1-8.
30	莫梦婷. 聚氨酯/石墨烯复合涂层的制备及其防腐耐磨性能[D]. 北京: 中国科学院大学, 2016.
	Mo M T. Preparation of polyurethane/graphene composite coating and its corrosion and wear resistance[D]. Beijing: University of Chinese Academy of Sciences, 2016.
31	刘雷, 徐萍. 跑合试验对螺杆变幅机构的必要性的实例分析[J]. 内燃机与配件, 2021(12): 57-58.
	Liu L, Xu P. Example analysis of the necessity of running-in test for screw luffing mechanism[J]. Internal Combustion Engine & Parts, 2021(12): 57-58.
32	姜秀杰, 冷晓飞, 白杨, 等. 高耐划伤性航空耐磨涂料的研制[J]. 涂料工业, 2021, 51(6): 69-74.
	Jiang X J, Leng X F, Bai Y, et al. Development of highly scratch resistant aviation wear-resistant coatings[J]. Paint & Coatings Industry, 2021, 51(6): 69-74.
33	李鹏. 基于衣康酸和大豆油的环保型光固化涂料的研究[D]. 太原: 中北大学, 2016.
	Li P. Environment friendly UV-cured coatings based on itaconic acid and soybean oil[D]. Taiyuan: North University of China, 2016.
34	冯江波. 基于PANI/SiO₂环氧防防腐涂层的制备及性能的研究[D]. 西安: 陕西科技大学, 2021.
	Feng J B. Research on preparation and performance of epoxy anticorrosive coating based on PANI/SiO₂ [D]. Xi'an: Shaanxi University of Science & Technology, 2021.

[1]	王帅, 杨富凯, 徐新宇. 阻燃型全生物基多元醇聚氨酯泡沫的制备及性能研究[J]. 化工学报, 2023, 74(3): 1399-1408.
[2]	郑杰元, 张先伟, 万金涛, 范宏. 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.
[3]	王哲, 祖愿, 胡方圆, 蹇锡高. 含杂萘联苯结构的环氧树脂固化动力学分析[J]. 化工学报, 2022, 73(2): 681-688.
[4]	韩维辰, 王佳铭, 贺曼罗, 贺高红, 焉晓明, 阮雪华. 潜伏型环氧固化剂甲基异丁基酮二亚胺的合成及工艺优化[J]. 化工学报, 2021, 72(7): 3832-3838.
[5]	金晶, 安秋凤, 杨博文, 史书源, 田华鹏. 环氧基POSS改性环氧树脂的研制与性能研究[J]. 化工学报, 2020, 71(5): 2432-2439.
[6]	徐彦芹, 杨锡智, 罗若诗, 黄玉红, 霍锋, 王丹. 合成生物学在生物基塑料制造中的应用[J]. 化工学报, 2020, 71(10): 4520-4531.
[7]	于守武, 肖淑娟, 赵泽文, 霍晓文, 魏俊富. 蜜胺-环氧树脂双层包覆聚磷酸铵及其阻燃PP的研究[J]. 化工学报, 2019, 70(6): 2370-2376.
[8]	张继宗, 常厚春, 常建民, 龙金星, 李雪辉. 生物油对生物油基淀粉胶黏剂性能的影响[J]. 化工学报, 2018, 69(S1): 123-128.
[9]	倪卓, 林煜豪, 黄苇颖, 林丽蓉. 环氧树脂微胶囊合成及其反应动力学[J]. 化工学报, 2018, 69(4): 1790-1798.
[10]	张继宗, 常厚春, 常建民, 龙金星, 李雪辉. 生物油淀粉胶黏剂固化特性研究[J]. 化工学报, 2018, 69(12): 5309-5315.
[11]	陈杨, 史铁钧, 钱莹, 何涛. 新型含硼苯并噁嗪的合成及其与环氧树脂共混热性能[J]. 化工学报, 2017, 68(6): 2604-2610.
[12]	杜朋亚, 边锋, 姚蒙蒙, 常达, 唐二军. 高阻尼性涂层用环氧-丙烯酸酯复合乳液的合成[J]. 化工学报, 2016, 67(10): 4508-4513.
[13]	俞坚, Pradeep Munasinghe, 康世民. 基于二氧化碳、水、太阳能的绿色化工精炼[J]. 化工学报, 2015, 66(8): 3225-3232.
[14]	王权, 史铁钧, 张焱, 虞伕, 刘建华. 聚双胍/环氧树脂体系潜伏性固化过程[J]. 化工学报, 2015, 66(1): 464-470.
[15]	王权, 史铁钧, 虞伕, 刘建华, 周讯. 新型潜伏性固化剂的合成及性能[J]. 化工学报, 2014, 65(9): 0-0.