木质素/LDH的制备及增强聚氨酯力学性能的研究

doi:10.19964/j.issn.1006-4990.2024-0310

摘要/Abstract

摘要：

为降低聚氨酯涂料的成本及改善其力学性能，采用水热反应法制备了木质素/镁铝型层状双氢氧化物复合材料（Lignin-LDH），并以Lignin-LDH为填料加入到聚氨酯涂料体系中，制备了木质素/镁铝型层状双氢氧化物/聚氨酯复合涂层（Lignin-LDH-PU）。考察了水热反应温度对Lignin-LDH性质和形貌的影响，以及Lignin-LDH添加量对聚氨酯涂层附着力等级、抗冲击强度和铅笔硬度等力学性能的影响。结果表明，随着水热温度的升高，Lignin-LDH的结晶度、复合程度、热稳定性均升高，但过高的水热温度会导致其复合程度和热稳定性的下降，适宜的水热温度为180 ℃。随着Lignin-LDH-180添加量的增加，Lignin-LDH-PU的力学性能会增加，但过高的添加量会导致涂层力学性能的下降。适宜的添加量为10%，此时涂层的力学性能最好，附着力等级为5B，抗冲击强度为115 cm（正面）和105 cm（反面），铅笔硬度为3H。相比LDH填料制备的10%LDH-PU，10%Lignin-LDH-180-PU的力学性能有着显著的增强。因此，水热法制备的Lignin-LDH-180填料在聚氨酯涂层中展示了较好的应用前景。

关键词: 木质素/镁铝型层状双氢氧化物, 水热反应, 聚氨酯

Abstract:

To reduce the cost and improve the mechanical properties of polyurethane coatings，Lignin/Mg-Al layered double hydroxide composites（Lignin-LDH） were prepared by hydrothermal reaction method，which were used as fillers in the polyurethane coating system to prepare Lignin/Mg-Al layered double hydroxide/PU composite coatings（Lignin-LDH-PU）.The effects of hydrothermal temperature on the properties and morphology of Lignin-LDH and the amount of Lignin-LDH on the adhesion grade，impact strength and pencil hardness of polyurethane coatings were investigated.The crystallinity，degree of recombination and thermal stability of Lignin-LDH composite fillers were increased with the increase of hydrothermal temperature.However，the recombination degree and thermal stability of lignin-LDH were decreased at the excessive hydrothermal temperature.Therefore，the optimal hydrothermal temperature was 180 ℃.The mechanical properties of Lignin-LDH-PU were increased with the increase of the addition of Lignin-LDH-180.However，the mechanical properties of lignin-LDH-PU were decreased with the excessive addition.With the optimal addition of 10% Lignin-LDH-180，the coating exhibited the best mechanical properties，including the adhesion grade of 5B，the impact strength of 115 cm（front） and 105 cm（back），and the pencil hardness of 3H.Compared to 10% LDH-PU，mechanical properties of 10%Lignin-LDH-180-PU were obviously enhanced.Therefore，Lignin-LDH-180 composite fillers prepared by hydrothermal reaction method presented good application prospect in polyurethane anticorrosive coating.

Key words: Lignin-LDH composites, hydrothermal reaction, polyurethane

中图分类号:

TB33

邹辽, 马小琳, 李小保, 叶菊娣. 木质素/LDH的制备及增强聚氨酯力学性能的研究[J]. 无机盐工业, 2025, 57(1): 64-70.

ZOU Liao, MA Xiaolin, LI Xiaobao, YE Judi. Study on preparation of Lignin/LDH and improvement of mechanical properties of polyurethane[J]. Inorganic Chemicals Industry, 2025, 57(1): 64-70.

图/表 9

图1

图2

图3

图4

图5

图6

图7

图8

表1

参考文献 25

1	于国玲，符英，赵万赛，等.国内聚氨酯涂料的研究进展［J］.弹性体，2022，32（5）：98-102.
	YU Guoling， FU Ying， ZHAO Wansai，et al.Research progress of polyurethane coatings in China［J］.China Elastomerics，2022，32（5）：98-102.
2	汪雷，黄磊.生物基聚氨酯胶黏剂的研究进展［J］.聚氨酯工业，2024，39（3）：6-10.
	WANG Lei， HUANG Lei.Research progress of bio-based polyurethane adhesives［J］.Polyurethane Industry，2024，39（3）：6-10.
3	ABIL E， AREFINIA R.The influence of talc particles on corrosion protecting properties of polyurethane coating on carbon steel in 3.5% NaCl solution［J］.Progress in Organic Coatings，2022，172：107067.
4	CAO Yanhui， ZHENG Dajiang， LIN Changjian.Construction of ecofriendly anticorrosive composite film ZnAl-LDH by modification of lignin on AA 7075 surface［J］.Materials and Corrosion，2021，72（10）：1595-1606.
5	MUKKE A P， MORE A P.Custard apple seed oil-based polyesteramide polyol-a precursor for layered double hydroxide（LDH）-modified polyurethane coatings［J］.Industrial Crops and Products，2024，214：118606.
6	STARUKH G， BUDZINSKA V， BRYCHKA S Y.Structural characterization，thermal and mechanical properties of polyurethane-MgAl-layered double hydroxide nanocomposites prepared via physical dispersion［J］.Applied Nanoscience，2019，9（5）：987- 996.
7	MA Ruoyu， TANG Pinggui， FENG Yongjun，et al.UV absorber co-intercalated layered double hydroxides as efficient hybrid UV-shielding materials for polypropylene［J］.Dalton Transactions，2019，48（8）：2750-2759.
8	WANG Dengfeng， SHAN Yaotao， LIU Lin，et al.Lignin demethylation enabled robust and reprocessable bio-polyurethane elastomer with adaptable cross-linking network［J］.Industrial Crops and Products，2024，208：117905.
9	WU Liran， LIU Shanshan， WANG Qiang，et al.High strength and multifunctional polyurethane film incorporated with lignin nano-particles［J］.Industrial Crops and Products，2022，177：114526.
10	WANG Yunyan， SCHEIDEMANTLE B， WYMAN C E，et al.Polyurethanes based on unmodified and refined technical lignins：Correlation between molecular structure and material properties［J］.Biomacromolecules，2021，22（5）：2129-2136.
11	DING Jingyuan， LI Xiaobao， REN Yuyang，et al.Preparation of PLA/Lignin-CaCO₃ composites by carbon dioxide carbonization and subsequent melt blending method［J］.Materials Letters， 2023（336）：133883.
12	李金鑫.Fe基水滑石固体碱制备过程调控及其催化解聚木质素磺酸钙性能研究［D］.大庆：东北石油大学，2019.
	LI Jinxin.Regulation on preparation process of Iron based hydrotalcites solid alkali oxides and its catalytic performance for the depolymerization of calcium lignosulfonate［D］.Daqing：Northeast Petroleum University，2019.
13	邢颖，李殿卿，郭灿雄，等.Zn-Al-CO₃水滑石晶粒尺寸控制与光屏蔽作用研究［J］.精细化工，2003，20（1）：1-4，7.
	XING Ying， LI Dianqing， GUO Canxiong，et al.Preparation of Zn-Al-CO₃ LDHs with controllable particle size and variation of their light attenuating properties with particle size［J］.Fine Che-micals，2003，20（1）：1-4，7.
14	WU Tao， LI Xiaobao， MA Xiaolin，et al.Modification of lignin by hexamethylene diisocyanate to synthesize lignin-based polyurethane as an organic polymer for marine polyurethane anticorrosive coatings［J］.Materials Research Express，2022，9（10）：105302.
15	ORTIZ CASTILLO R， DOUMER M E， CARBAJAL ARÍZAGA G G，et al.Spectroscopic study of copper adsorption by chitosan and lignin composites containing layered double hydroxides［J］.Journal of Electron Spectroscopy and Related Phenomena，2018，226：1-8.
16	HE Bianyang， XIAO Yao， LI Yanfang，et al.Preparation and characterization of lignin grafted layered double hydroxides for sustainable service of bitumen under ultraviolet light［J］.Journal of Cleaner Production，2022，350：131536.
17	TANG Yan， WU Fang， FANG Liang，et al.A comparative study and optimization of corrosion resistance of ZnAl layered double hydroxides films intercalated with different anions on AZ31 Mg alloys［J］.Surface and Coatings Technology，2019，358：594-603.
18	薛峰.固体碱催化解聚木质素制取芳香基化合物的研究［D］.大庆：东北石油大学，2018.
	XUE Feng.Catalytic depolymerization of lignin by solid base for preparation of aromatic compounds［D］.Daqing：Northeast Petroleum University，2018.
19	KAMEDA T， FUBASAMI Y， UCHIYAMA N，et al.Elimination behavior of nitrogen oxides from a NO₃ ^--intercalated Mg-Al layered double hydroxide during thermal decomposition［J］.Thermochimica Acta，2010，499（1/2）：106-110.
20	武继来.典型木质素结构分析及催化热解制备芳烃研究［D］.青岛：青岛科技大学，2020.
	WU Jilai.Structural analysis of typical lignin and study on the preparation of aromatics by catalytic pyrolysis［D］.Qingdao：Qingdao University of Science & Technology，2020.
21	ZHAO Wenjing， SUI Zhihui， ZHANG Qi，et al.Hydrophobic and mechanical strength enhancement of hemp fabric and paper enabled by waterborne polyurethane-derived functional coating［J］.Cellulose，2024，31（3）：1687-1703.
22	李杏，秦军，吕晴，等. α/γ-氧化铝对合成镁铝水滑石结构性能的影响［J］.无机盐工业，2022，54（12）：51-59.
	LI Xing， QIN Jun， Qing LÜ，et al.Effect of α/γ-alumina on structure and properties of synthesized Mg-Al hydrotalcite［J］.Inorganic Chemicals Industry，2022，54（12）：51-59.
23	XIE Huihui， ZHANG Hui， LIU Xinxin，et al.Ag immobilized lignin-based PU coating：A promising candidate to promote the mechanical properties，thermal stability，and antibacterial property of paper packaging［J］.International Journal of Biological Macromolecules，2021，189：690-697.
24	AVELINO F， ALMEIDA S L， DUARTE E B，et al.Thermal and mechanical properties of coconut shell lignin-based polyurethanes synthesized by solvent-free polymerization［J］.Journal of Materials Science，2018，53（2）：1470-1486.
25	CAO Yiding， LIU Zhenzhen， ZHENG Bixia，et al.Synthesis of lignin-based polyols via thiol-ene chemistry for high-performance polyurethane anticorrosive coating［J］.Composites Part B：Engineering，2020，200：108295.

样品	表干时间/min	附着力等级	抗冲击强度/cm		铅笔硬度
样品	表干时间/min	附着力等级	正面	反面	铅笔硬度
PU	6~7	5B	115	100	H
10%LDH-PU	7~8	3B	85	70	2H
2%Lignin-LDH-180-PU	7~8	5B	115	100	H
5%Lignin-LDH-180-PU	7~8	5B	115	100	2H
10%Lignin-LDH-180-PU	7~8	5B	115	105	3H
15%Lignin-LDH-180-PU	7~8	4B	100	80	3H
20%Lignin-LDH-180-PU	8~9	2B	80	65	2H

[1]	刘新龙, 杨振宇, 郝赫, 刘姝昕, 武晨阳, 王兴利, 马清清. 粉煤灰提铝残渣制备体型化4A分子筛的研究[J]. 无机盐工业, 2025, 57(3): 78-85.
[2]	董雄伟, 韩凤兰, 华炜, 李茂辉, 安长聪, 黄玉才. 硅锰渣基沸石的合成及其表征[J]. 无机盐工业, 2023, 55(12): 128-132.
[3]	滕家阳, 冯庆革, 张璇, 覃方红, 冯靖航, 胡嘉文, 陈超宏. 铝灰资源化制备拟薄水铝石的研究[J]. 无机盐工业, 2023, 55(11): 130-138.
[4]	李森, 王进, 王莹莹, 蔡铭放. NaA分子筛的合成和改性及其在聚氨酯体系中的应用[J]. 无机盐工业, 2023, 55(10): 78-85.
[5]	周敏. PANI/TIO复合材料的制备及其在聚氨酯涂料中的应用[J]. 无机盐工业, 2023, 55(1): 112-117.
[6]	谷和云, 李昇, 李二锐, 王凯, 徐江生. 镁离子掺杂磷酸铁锂的制备及其电化学性能[J]. 无机盐工业, 2016, 48(1): 64-.
[7]	孙雨, 高恩双, 潘旭杰, 宗俊. 水热法合成高分散易过滤高阻燃氢氧化镁[J]. 无机盐工业, 2013, 45(4): 29-.
[8]	张祖亮, 张磊, 吕建平. 棒状形貌纳米氧化锌的合成及其应用[J]. 无机盐工业, 2011, 43(4): 30-.
[9]	赵华;闪俊杰;刘润静;刘忻瑜;胡永琪;杜振雷. 氢氧化镁在强碱水热体系中的晶体生长研究[J]. 无机盐工业, 2009, 0(10): 0-0.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会