单宁/增韧紫胶树脂复合涂膜的制备及其防蚀性能

doi:10.3969/j.issn.0253-2417.2021.04.001

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (4): 1-9.doi: 10.3969/j.issn.0253-2417.2021.04.001

单宁/增韧紫胶树脂复合涂膜的制备及其防蚀性能

李春吟¹^,²(), 李坤¹^,*(), 孙彦琳², 刘义稳³, 张弘¹, 雷福厚⁴

1. 中国林业科学研究院资源昆虫研究所; 国家林业和草原局特色森林资源工程技术研究中心, 云南昆明 650224
2. 昆明理工大学化学工程学院, 云南昆明 650500
3. 五峰赤诚生物科技股份有限公司; 国家林业和草原局五倍子高效培育与精深加工工程技术研究中心, 湖北宜昌 443413
4. 广西民族大学, 广西林产化学与工程重点实验室, 广西林产化学与工程协同创新中心, 广西南宁 530006

收稿日期:2020-09-29 出版日期:2021-08-28 发布日期:2021-08-31
通讯作者: 李坤 E-mail:licy12615@126.com;likunkm@163.com
作者简介:李坤, 助理研究员, 博士, 研究方向为林业生物资源化学与材料; E-mail: likunkm@163.com
李春吟(1994-), 男, 云南昆明人, 硕士生, 研究方向为天然产物及高分子材料; E-mail: licy12615@126.com
基金资助:
国家重点研发计划资助项目(2018YFD0600404)

Preparation and Corrosion Resistance of Tannin Acid/Toughened Shellac Resin Composite Coating

Chunyin LI¹^,²(), Kun LI¹^,*(), Yanlin SUN², Yiwen LIU³, Hong ZHANG¹, Fuhou LEI⁴

1. Research Institute of Resources Insects, Chinese Academy of Forestry; National Forestry and Grassland Bureau Characteristic Forest Resources Engineering Technology Research Center, Kunming 650224, China
2. College of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China
3. Wufeng Chicheng Biotechnology CO., LTD.; Research Centers of Chinese Gall Effective Cultivation and Deep Processing Engineering Technology, National Forestry and Grassland Administration, Yichang 443413, China
4. Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products, Guangxi University for Nationalities, Nanning 530006, China

Received:2020-09-29 Online:2021-08-28 Published:2021-08-31
Contact: Kun LI E-mail:licy12615@126.com;likunkm@163.com

摘要/Abstract

摘要：

为改善紫胶（SHL）树脂韧性，采用桐油酸（EA）以Diels-Alder反应与SHL树脂进行加成，制备得到增韧紫胶（TS）树脂，通过凝胶色谱（GPC）、红外光谱（FT-IR）和核磁共振碳谱（¹³C NMR）对其结构进行解析；向SHL和TS树脂中引入单宁酸（TA），制得SHL-TA和TS-TA复合涂膜，并利用电化学工作站、耐中性盐水和耐中性盐雾测试分析TA、EA对SHL树脂涂膜防蚀性能的影响。研究结果表明：产物TS树脂具有较好韧性，当m（SHL）：m（EA）为1.8：1时制备的TS-3涂膜断裂伸长率高达381.81%；此外，EA改性还增加了SHL树脂膜的疏水性，TS-3涂膜的静态水接触角可达95.01°。TA的引入提高了涂膜在金属基材上的附着力，TA以及EA的共同作用增强了SHL树脂涂膜的防蚀性能。最佳的防蚀体系为TS-3-TA涂膜，在3.5%NaCl中浸泡48 h后，涂膜的极化电阻仍有36.3 kΩ，优于其他涂膜。在碱体系中制备的TS-3-TA涂膜的耐中性盐水时间为120 h，耐中性盐雾时间为168 h。

关键词: 桐油酸, 增韧紫胶树脂, 单宁酸, 涂膜防蚀

Abstract:

In order to improve the toughness of shellac(SHL) resin, eleostearic acid(EA) was added to shellac resin through Diels-Alder reaction to prepare toughened shellac(TS) resin, and its structure was analyzed by gel chromatography(GPC), infrared spectroscopy(FT-IR) and ¹³C nuclear magnetic resonance(¹³C NMR). And then, tannic acid(TA) was added to prepare SHL-TA, and TS-TA composite coating. The effects of TA and EA on the anti-corrosion properties of shellac resin coating were analyzed by electrochemical workstation, neutral salt water resistance and neutral salt spray(NSS) resistance tests. The results showed that the TS modified by EA through the Diels-Alder reaction exhibited good toughness. When the weight ratio of SHL and EA was 1.8:1, the elongation at break of TS-3 coating was as high as 381.81%. In addition, the hydrophobicity of shellac coating was increased by the modification of EA, and its static water contact angle reached 95.01°.The addition of TA could improve the adhesion of the coating on the metal substrate, and the combined action of TA and EA could enhance the anti-corrosion of SHL coating. The best corrosion protection system was TS-3-TA coating. After immersion in 3.5% NaCl for 48 h, the polarization resistance of the coating was still 36.3 kΩ, far more higher than that of other coatings. And the time of neutral salt water resistance and neutral salt spray(NSS) resistance tests of TS-3-TA, which was prepared in alkali system, was 120 h and 168 h.

Key words: eleostearic acid, toughened shellac resin, tannin acid, anticorrosion coating

中图分类号:

TQ351
TQ941

李春吟, 李坤, 孙彦琳, 刘义稳, 张弘, 雷福厚. 单宁/增韧紫胶树脂复合涂膜的制备及其防蚀性能[J]. 林产化学与工业, 2021, 41(4): 1-9.

Chunyin LI, Kun LI, Yanlin SUN, Yiwen LIU, Hong ZHANG, Fuhou LEI. Preparation and Corrosion Resistance of Tannin Acid/Toughened Shellac Resin Composite Coating[J]. Chemistry and Industry of Forest Products, 2021, 41(4): 1-9.

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样品 sample	m(SHL)∶ m(EA)	断裂强度/MPa breaking strength	断裂伸长率/% breaking elongation	静态接触角/° static contact angle
SHL		8.78±0.73	1.40±0.26	79.60±0.5
TS-1	6∶1	4.28±0.50	8.10±1.70	70.99±2.2
TS-2	3∶1	1.40±0.14	61.80±0.45	93.55±2.1
TS-3	1.8∶1	0.21±0.03	381.81±2.55	95.01±1.1

样品 sample	附着力/MPa adhesion	样品 sample	附着力/MPa adhesion
SHL	6.39±0.38	SHL-TA	10.43±0.21
TS-1	7.72±0.25	TS-1-TA	8.99±0.19
TS-2	8.28±0.15	TS-2-TA	9.03±0.30
TS-3	8.48±0.45	TS-3-TA	9.16±0.27

浸泡时间/h soak time	TS-3涂膜TS-3 coating			TS-3-TA涂膜TS-3-TA coating
浸泡时间/h soak time	E_corr/V	I_corr/A	R_p/kΩ	E_corr/V	I_corr/A	R_p/kΩ
0	-0.32	5.02×10^-7	889.0	-0.09	2.00×10^-7	1873.4
24	-0.71	14.9×10^-7	44.9	-0.65	17.1×10^-7	44.3
48	-0.62	41.2×10^-7	29.8	-0.65	34.5×10^-7	36.3

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单宁/增韧紫胶树脂复合涂膜的制备及其防蚀性能

Preparation and Corrosion Resistance of Tannin Acid/Toughened Shellac Resin Composite Coating

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样品 sample	醇体系ethanol system		碱体系alkaline system
样品 sample	t_NSS/h	t_SRS/h	t_NSS/h	t_SRS/h
SHL	72	168	—	—
TS-1	72	168	48	24
TS-2	72	168	96	< 24
TS-3	72	120	168	120
SHL-TA	72	168	—	—
TS-1-TA	72	168	48	24
TS-2-TA	72	168	72	< 24
TS-3-TA	72	120	168	120