Preparation and anticorrosion properties of bio-based polybenzoxazine/cellulose nanocrystals superhydrophobic coating

doi:10.11949/0438-1157.20210820

Abstract

Abstract:

A bio-based benzoxazine monomer was synthesized by using cardanol, stearylamine and paraformaldehyde as raw materials. Differential scanning calorimetry and infrared spectroscopy were employed to investigate the thermal curing behavior of benzoxazine with tannic acid acting as the curing agent. The results show that tannic acid can effectively reduce the ring-opening curing temperature of benzoxazine. The polybenzoxazine primer was prepared on the surface of carbon steel sheet, and then the topcoat was obtained by adding amino-modified cellulose nanocrystalline. The bio-based superhydrophobic coating (PBTC) was constructed with static water contact angle of 161.1°±2.9°. The superhydrophobic coating exhibits good temperature resistance and scratch resistance. Moreover, the electrochemical measurement results indicated that the PBTC coating could still exhibit excellent corrosion resistance after immersion in NaCl aqueous solution for 30 days.

Key words: polybenzoxazine, nanoparticles, superhydrophobic coating, corrosion, composites

摘要：

以腰果酚、十八胺和多聚甲醛为原料合成出生物基苯并嗪单体，以单宁酸为固化剂，采用差示扫描量热分析技术和红外光谱考察了苯并嗪单体的热固化行为，结果表明单宁酸可以有效降低苯并嗪的开环固化温度。在钢片表面首先制备聚苯并嗪涂层作为底漆，再通过在涂层中掺杂氨基修饰纤维素纳米晶制备面漆，构建出静态水接触角为161.1°±2.9°的生物基超疏水防腐蚀涂层（PBTC）。该超疏水涂层表现出良好的耐高低温性能和耐刮擦性。电化学测试结果表明PBTC涂层在NaCl水溶液中浸泡30天后仍然具有良好的防腐蚀性能。

关键词: 聚苯并嗪, 纳米粒子, 超疏水涂层, 腐蚀, 复合材料

CLC Number:

TG 178

Yuzhu CAO,Xin LU,Litong WANG,Manlin YUAN,Zhong XIN. Preparation and anticorrosion properties of bio-based polybenzoxazine/cellulose nanocrystals superhydrophobic coating[J]. CIESC Journal, 2021, 72(11): 5717-5725.

曹玉柱,陆馨,王立通,袁满林,辛忠. 生物基聚苯并嗪/纤维素纳米晶超疏水防腐蚀涂层的制备及性能[J]. 化工学报, 2021, 72(11): 5717-5725.

Figures/Tables 14

Fig.1 Synthesis of benzoxazine monomers

Fig.2 DSC curves of Bz and Bz/TA mixtures

Fig.3 DSC curves of PBT-150, PBz-200 and PBz-150

Fig.4 FTIR spectra of Bz, Bz/TA-10 and PBT

Fig.5 Ring-opening reaction mechanism of Bz with TA

Fig.6 SEM images of the coating surface(The inset is the corresponding static WCA image)

Fig.7 TGA curves of PBz, PBT and PBTC coatings

Table 1 Thermal stability of PBz， PBT and PBTC coatings

Sample	T_1%/℃	T_5%/℃	T_10%/℃	Char yield at 800℃/%
PBz	269	315	341	6.33
PBT	250	305	334	7.40
PBTC	252	306	334	22.39

Fig.8 The mechanically durable test of superhydrophobic PBTC coating

Fig.9 The temperature resistance of PBTC coating at -20℃ (a) and 100℃ (b)

Fig.10 Bode impedance plots and phase angle plots of PBT (a1，a2) and PBTC (b1,b2) coatings during 30 days immersion in 3.5% NaCl solution

Fig.11 The equivalent circuit models for fitting the EIS results

Table 2 Values of electrochemical parameters fitted from EIS results of PBT and PBTC coatings

Samples	Time/d	Chi-Squared/%	CPE_c		R_c/ (Ω·cm²)	CPE_dl		R_ct/ (Ω·cm²)
Samples	Time/d	Chi-Squared/%	Y₀/(Ω^-1·cm^-2·sⁿ)	n	R_c/ (Ω·cm²)	Y₀/(Ω^-1·cm^-2·sⁿ)	n	R_ct/ (Ω·cm²)
PBT	0	0.06	1.42×10^-10	0.98	1.11×10¹¹	—	—	—
	10	0.07	1.42×10^-10	0.98	1.19×10⁷	5.65×10^-8	0.65	8.64×10⁷
	20	0.46	1.67×10^-10	0.97	4.33×10⁶	3.99×10^-7	0.51	6.20×10⁶
	30	0.36	1.84×10^-10	0.95	7.89×10⁵	1.78×10^-7	0.58	1.06×10⁶
PBTC	0	0.67	9.78×10^-11	0.98	2.06×10¹²	—	—	—
	10	0.95	7.81×10^-11	0.98	4.00×10¹⁰	1.97×10^-11	0.62	4.31×10¹¹
	20	0.85	1.42×10^-10	0.98	3.27×10¹⁰	1.37×10^-10	0.58	7.02×10⁹
	30	0.12	1.93×10^-10	0.98	6.78×10⁹	4.34×10^-9	0.58	1.24×10⁹

Fig.12 Corrosion protection mechanism of superhydrophobic PBTC coating

References 30

1	Nuruddin M, Chowdhury R A, Szeto R, et al. Structure–property relationship of cellulose nanocrystal–polyvinyl alcohol thin films for high barrier coating applications[J]. ACS Applied Materials & Interfaces, 2021, 13(10): 12472-12482.
2	徐峻, 高艺, 吴祺祺, 等. 纤维素纳米晶的改性对其晶体结构及性能的影响[J]. 高分子材料科学与工程, 2021, 37(3): 66-71, 78.
	Xu J, Gao Y, Wu Q Q, et al. Effect of modification of cellulose nanocrystals on crystal structure and properties[J]. Polymer Materials Science & Engineering, 2021, 37(3): 66-71, 78.
3	吴开丽, 韩陈晓, 于娟娟. 纤维素纳米晶的制备及应用研究进展[J]. 造纸科学与技术, 2020, 39(4): 9-13.
	Wu K L, Han C X, Yu J J. Research progress on the preparation and application of cellulose nanocrystals[J]. Paper Science & Technology, 2020, 39(4): 9-13.
4	汤浩, 陈照峰, 邱宇航, 等. KH550改性纳米晶纤维素增强三元乙丙橡胶[J]. 宇航材料工艺, 2020, 50(4): 44-48.
	Tang H, Chen Z F, Qiu Y H, et al. Reinforcement of ethylene propylene diene monomer by nanocrystalline cellulose modified KH550[J]. Aerospace Materials & Technology, 2020, 50(4): 44-48.
5	Lee Y, Park S, Ha K. Preparation and properties of eco-friendly polyurethane nanocomposites using cellulose nanocrystals with amino group as fillers[J]. Polymer Korea, 2020, 44(3): 397-407.
6	Wang X F, Gou X L, Guo Z G. Robust superhydrophobic polyurea@cellulose nanocrystal coating[J]. New Journal of Chemistry, 2020, 44(27): 11739-11745.
7	Huang J D, Lyu S Y, Fu F, et al. Green preparation of a cellulose nanocrystals/polyvinyl alcohol composite superhydrophobic coating[J]. RSC Advances, 2017, 7(33): 20152-20159.
8	Lyu Y, Ishida H. Natural-sourced benzoxazine resins, homopolymers, blends and composites: a review of their synthesis, manufacturing and applications[J]. Progress in Polymer Science, 2019, 99: 101168.
9	Yagci Y, Kiskan B, Ghosh N N. Recent advancement on polybenzoxazine—A newly developed high performance thermoset[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2009, 47(21): 5565-5576.
10	Li X Y, Zhao S P, Hu W H, et al. Robust superhydrophobic surface with excellent adhesive properties based on benzoxazine/epoxy/mesoporous SiO₂[J]. Applied Surface Science, 2019, 481: 374-378.
11	Zachariah S, Chuo T W, Liu Y L. Crosslinked polybenzoxazine coatings with hierarchical surface structures from a biomimicking process exhibiting high robustness and anticorrosion performance[J]. Polymer, 2018, 155: 168-176.
12	Huang J, Lou C, Xu D, et al. Cardanol-based polybenzoxazine superhydrophobic coating with improved corrosion resistance on mild steel[J]. Progress in Organic Coatings, 2019, 136: 105191.
13	Lou C, Zhang R, Lu X, et al. Facile fabrication of epoxy/polybenzoxazine based superhydrophobic coating with enhanced corrosion resistance and high thermal stability[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 562: 8-15.
14	朱慧斌. 高性能苯并嗪超疏水复合材料制备与性能研究[D]. 太原: 中北大学, 2018.
	Zhu H B. Preparation and properties of superhydrophobic composite materials with high performance of benzoxazine[D]. Taiyuan: North University of China, 2018.
15	张心湄. 腰果酚型苯并嗪聚合物的制备及其性能研究[D]. 福州: 福建师范大学, 2019.
	Zhang X M. Preparation and properties of cardanol benzoxazine polymers[D]. Fuzhou: Fujian Normal University, 2019.
16	Renaud A, Bonnaud L, Dumas L, et al. A benzoxazine/substituted borazine composite coating: a new resin for improving the corrosion resistance of the pristine benzoxazine coating applied on aluminum[J]. European Polymer Journal, 2018, 109: 460-472.
17	Caldona E B, de Leon A C C, Thomas P G, et al. Superhydrophobic rubber-modified polybenzoxazine/SiO₂ nanocomposite coating with anticorrosion, anti-ice, and superoleophilicity properties[J]. Industrial & Engineering Chemistry Research, 2017, 56(6): 1485-1497.
18	Bai W B, Lin H M, Chen K H, et al. Eco-friendly stable cardanol-based benzoxazine modified superhydrophobic cotton fabrics for oil-water separation[J]. Separation and Purification Technology, 2020, 253: 117545.
19	Zhang W Z, Jiang N, Zhang T T. Synthesis and properties of corresponding polymers of urushiol-based benzoxazine monomers modified by silane[J]. International Journal of Polymer Analysis and Characterization, 2021, 26(3): 265-276.
20	Appavoo D, Amarnath N, Lochab B. Cardanol and eugenol sourced sustainable non-halogen flame retardants for enhanced stability of renewable polybenzoxazines[J]. Frontiers in Chemistry, 2020, 8: 711.
21	Zhang L, Zhu Y J, Li D, et al. Preparation and characterization of fully renewable polybenzoxazines from monomers containing multi-oxazine rings[J]. RSC Advances, 2015, 5(117): 96879-96887.
22	Gnanapragasam S, Krishnan S, Arumugam H, et al. Synthesis and characterization of a novel high-performance benzoxazine from benzaldehyde-based bisphenol[J]. Advances in Polymer Technology, 2018, 37(8): 3056-3065.
23	Sharma P, Kumar D, Roy P K. Enhancing the processibility of high temperature polymerizing cardanol derived benzoxazines using eco-friendly curing accelerators[J]. Polymer, 2018, 138: 343-351.
24	Zhang L, Mao J L, Wang S, et al. Meta-phenylenediamine formaldehyde oligomer: a new accelerator for benzoxazine resin[J]. Reactive and Functional Polymers, 2017, 121: 51-57.
25	Espinosa M A, Cádiz V, Galià M. Synthesis and characterization of benzoxazine-based phenolic resins: crosslinking study[J]. Journal of Applied Polymer Science, 2003, 90(2): 470-481.
26	Thirukumaran P, Sathiyamoorthi R, Shakila Parveen A, et al. New benzoxazines from renewable resources for green composite applications[J]. Polymer Composites, 2016, 37(2): 573-582.
27	Kotzebue L R V, Ribeiro F W M, Sombra V G, et al. Spectral and thermal studies on the synthesis and catalyzed oligomerization of novel cardanol-based benzoxazines[J]. Polymer, 2016, 92: 189-200.
28	Yee Low H, Ishida H. Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazines[J]. Polymer, 1999, 40(15): 4365-4376.
29	Pan C C, Wang X Z, Behnamian Y, et al. Monododecyl phosphate film on LY12 aluminum alloy: pH-controlled self-assembly and corrosion resistance[J]. Journal of the Electrochemical Society, 2020, 167(16): 161510.
30	Jiang D, Xia X C, Hou J, et al. A novel coating system with self-reparable slippery surface and active corrosion inhibition for reliable protection of Mg alloy[J]. Chemical Engineering Journal, 2019, 373: 285-297.

[1]	Fei KANG, Weiguang LYU, Feng JU, Zhi SUN. Research on discharge path and evaluation of spent lithium-ion batteries [J]. CIESC Journal, 2023, 74(9): 3903-3911.
[2]	Rubin ZENG, Zhongjie SHEN, Qinfeng LIANG, Jianliang XU, Zhenghua DAI, Haifeng LIU. Study of the sintering mechanism of Fe₂O₃ nanoparticles based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3353-3365.
[3]	Xingzhi HU, Haoyan ZHANG, Jingkun ZHUANG, Yuqing FAN, Kaiyin ZHANG, Jun XIANG. Preparation and microwave absorption properties of carbon nanofibers embedded with ultra-small CeO₂ nanoparticles [J]. CIESC Journal, 2023, 74(8): 3584-3596.
[4]	Jiaqi CHEN, Wanyu ZHAO, Ruichong YAO, Daolin HOU, Sheying DONG. Synthesis of pistachio shell-based carbon dots and their corrosion inhibition behavior on Q235 carbon steel [J]. CIESC Journal, 2023, 74(8): 3446-3456.
[5]	Ao ZHANG, Yingwu LUO. Low modulus, high elasticity and high peel adhesion acrylate pressure sensitive adhesives [J]. CIESC Journal, 2023, 74(7): 3079-3092.
[6]	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.
[7]	Bin CAI, Xiaolin ZHANG, Qian LUO, Jiangtao DANG, Liyuan ZUO, Xinmei LIU. Research progress of conductive thin film materials [J]. CIESC Journal, 2023, 74(6): 2308-2321.
[8]	Yanhui LI, Shaoming DING, Zhouyang BAI, Yinan ZHANG, Zhihong YU, Limei XING, Pengfei GAO, Yongzhen WANG. Corrosion micro-nano scale kinetics model development and application in non-conventional supercritical boilers [J]. CIESC Journal, 2023, 74(6): 2436-2446.
[9]	Yong LI, Jiaqi GAO, Chao DU, Yali ZHAO, Boqiong LI, Qianqian SHEN, Husheng JIA, Jinbo XUE. Construction of Ni@C@TiO₂ core-shell dual-heterojunctions for advanced photo-thermal catalytic hydrogen generation [J]. CIESC Journal, 2023, 74(6): 2458-2467.
[10]	Juhui CHEN, Qian ZHANG, Lingfeng SHU, Dan LI, Xin XU, Xiaogang LIU, Chenxi ZHAO, Xifeng CAO. Study on flow characteristics of nanoparticles in a rotating fluidized bed based on DEM method [J]. CIESC Journal, 2023, 74(6): 2374-2381.
[11]	Shaoyun CHEN, Dong XU, Long CHEN, Yu ZHANG, Yuanfang ZHANG, Qingliang YOU, Chenglong HU, Jian CHEN. Preparation and adsorption properties of monolayer polyaniline microsphere arrays [J]. CIESC Journal, 2023, 74(5): 2228-2238.
[12]	Jialin DAI, Weidong BI, Yumei YONG, Wenqiang CHEN, Hanyang MO, Bing SUN, Chao YANG. Effect of thermophysical properties on the heat transfer characteristics of solid-liquid phase change for composite PCMs [J]. CIESC Journal, 2023, 74(5): 1914-1927.
[13]	Ruiqi LIU, Xitong ZHOU, Yue ZHANG, Ying HE, Jing GAO, Li MA. The construction and application of biosensor based on gold nanoparticles loaded SiO₂-nanoflowers [J]. CIESC Journal, 2023, 74(3): 1247-1259.
[14]	Dong XU, Du TIAN, Long CHEN, Yu ZHANG, Qingliang YOU, Chenglong HU, Shaoyun CHEN, Jian CHEN. Preparation and electrochemical energy storage of polyaniline/manganese dioxide/polypyrrole composite nanospheres [J]. CIESC Journal, 2023, 74(3): 1379-1389.
[15]	Ruizhe CHEN, Leilei CHENG, Jing GU, Haoran YUAN, Yong CHEN. Research progress in chemical recovery technology of fiber-reinforced polymer composites [J]. CIESC Journal, 2023, 74(3): 981-994.