粗甘油生物基聚氨酯材料的制备及吸附性能研究

doi:10.11949/0438-1157.20211800

化工学报 ›› 2022, Vol. 73 ›› Issue (5): 2270-2278.DOI: 10.11949/0438-1157.20211800

• 材料化学工程与纳米技术 • 上一篇下一篇

粗甘油生物基聚氨酯材料的制备及吸附性能研究

李梦雨¹(),王冬祥²,郑晓阳³,徐桂转²,杜朝军⁴,常春¹()

^1.郑州大学化工学院，河南郑州 450001
^2.河南农业大学机电工程学院，河南郑州 450001
^3.焦作华康糖醇科技有限公司，河南焦作 454150
^4.南阳理工学院郑州大学南阳研究院，河南南阳 473004

收稿日期:2021-12-22 修回日期:2022-02-16 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 常春
作者简介:李梦雨(1996—)，女，硕士研究生，1162213315@qq.com
基金资助:
国家自然科学基金项目(22178328);南阳市协同创新重大专项 (郑州大学南阳研究院)(NRIZU2020CIP0006)

Preparation and adsorption properties of crude glycerol bio-based polyurethane material

Mengyu LI¹(),Dongxiang WANG²,Xiaoyang ZHENG³,Guizhuan XU²,Chaojun DU⁴,Chun CHANG¹()

^1.School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^2.College of Mechanical and Electrical Engineering, Henan Agricultural University, Zhengzhou 450001, Henan, China
^3.Henan Jiaozuo Huakang Sugar Alcohol Technology Co. Ltd. , Jiaozuo 454150, Henan, China
^4.Nanyang Research Institute of Zhengzhou University, Nanyang Institute of Technology, Nanyang 473004, Henan, China

Received:2021-12-22 Revised:2022-02-16 Online:2022-05-05 Published:2022-05-24
Contact: Chun CHANG

摘要/Abstract

摘要：

以生物质基粗甘油为主要原料，采用一锅法合成粗甘油基多元醇，进一步发泡制备了聚氨酯泡沫材料。在此基础上，利用甲基三氯硅烷对泡沫材料进行疏水改性，制备出改性聚氨酯吸油材料。采用傅里叶红外光谱仪、扫描电镜和热重分析对改性前后泡沫的结构形貌、热稳定性和接触角进行表征，测试了改性聚氨酯吸油材料吸油性能。结果表明：经疏水改性后在泡沫表面合成了聚硅氧烷，水接触角由130°增大至140°，提高了吸油材料疏水性能。改性聚氨酯吸油材料对乙醇、甲醇、氯仿等8种有机物的吸附量范围为16.7～45.2 g/g。经循环使用50次后，吸油材料对柴油和大豆油的吸附量分别为最高吸附量的95.8%和97.6%，表现出优异的吸油性能。

关键词: 生物质, 粗甘油, 聚氨酯, 泡沫, 复合材料, 疏水改性

Abstract:

Using biomass-based crude glycerol as the main raw material, a one-pot method was used to synthesize crude glycerol-based polyol, and the polyurethane foam material was prepared by further foaming. On the basis, the modified polyurethane oil absorption material was prepared by hydrophobic modification with methyl trichlorosilane. The morphology, thermal stability and the contact angel of the polyurethane foam before and after modification were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The oil absorption properties of the modified polyurethane oil absorption material were also tested. The results showed that polysiloxane was successfully synthesized on the foam surface after the modification of methyl trichlorosilane. The water contact angle increased from 130° to 140°, indicating that the hydrophobicity of the oil absorption material was improved. The adsorption capacity of modified polyurethane oil absorption material for eight kinds of organic substances such as ethanol, methanol and chloroform, etc., ranges from 16.7 g/g to 45.2 g/g. After 50 cycles, the adsorption capacity of the oil absorption material for diesel and soybean oil was 95.8% and 97.6% of the maximum adsorption capacity, respectively, showing excellent oil absorption performance.

Key words: biomass, crude glycerol, polyurethane, foam, composite material, hydrophobic modification

中图分类号:

TQ 328.3

李梦雨, 王冬祥, 郑晓阳, 徐桂转, 杜朝军, 常春. 粗甘油生物基聚氨酯材料的制备及吸附性能研究[J]. 化工学报, 2022, 73(5): 2270-2278.

Mengyu LI, Dongxiang WANG, Xiaoyang ZHENG, Guizhuan XU, Chaojun DU, Chun CHANG. Preparation and adsorption properties of crude glycerol bio-based polyurethane material[J]. CIESC Journal, 2022, 73(5): 2270-2278.

图/表 15

图1 泡沫的油接触角

Fig.1 Oil contact angle of foam

图2 泡沫的水接触角

Fig.2 Water contact angle of foam

图3 泡沫的FT-IR光谱a—PU-25;b—PU-MTS

Fig.3 FT-IR spectra of foams

图4 PU-MTS表面的XPS谱图:(a) 全谱图；(b) C 1s谱图；(c) O 1s谱图；(d) Si 2p谱图

Fig.4 XPS spectra for the surface of PU-MTS: (a) survey spectrum；(b) C1s spectra；(c) O1s spectra；(d) Si 2p spectra

图5 泡沫的TG(a)和DTG(b)曲线a—PU-25;b—PU-MTS

Fig.5 TG (a) and DTG (b) curves of foams

表1 PU-25和PU-MTS的TG分析

Table 1 TG analysis of PU-25 and PU-MTS

样品	T_5%/℃	T_50%/℃	T_max/℃	残炭率/%
PU-25	265	399	389	7.03
PU-MTS	260	400	403	9.06

图6 PU-25和PU-MTS扫描电镜图：(a)~(c) PU-25在不同放大倍数下的SEM图；(d)~(f) PU-MTS在不同放大倍数下的SEM图(d)—(f) SEM images of PU-MTS at different magnifications

Fig.6 SEM images of PU-25 and PU-MTS: (a)—(c) SEM images of PU-25 at different magnification;

表2 PU-25和PU-MTS的吸附性能对比

Table 2 Comparison of adsorption properties between PU-25 and PU-MTS

溶剂	PU-25吸附量/ (g/g)	PU-MTS吸附量/ (g/g)	提高比例/%
乙醇	15.1	16.7	10.60
甲醇	14.7	18.7	27.21
氯仿	40.9	45.2	10.51
二氯甲烷	43.7	44.9	2.75
丙酮	18.0	23.7	31.67
甲苯	19.2	24.3	26.56
大豆油	9.0	16.9	87.78
柴油	11.2	18.1	61.61
煤油	12.0	19.1	59.17

图7 PU-MTS的油水分离性能

Fig.7 Oil/water separation performance of PU-MTS

图8 PU-MTS吸附去除水中有机物(苏丹红Ⅲ染色)：(a)~(c)氯仿；(d)~(f)甲苯

Fig.8 Adsorptive removal of organics (dyed by Sudan Ⅲ) from water by PU-MTS: (a)—(c) chloroform; (d)—(f) toluene

图9 PU-MTS的循环吸附性能

Fig.9 Cyclic adsorption properties of PU-MTS

图10 PU-MTS的水接触角变化

Fig.10 Changes of water contact angle of PU-MTS

图11 PU-MTS循环吸附后扫描电镜图：(a)~(c)循环10次后PU-MTS在不同放大倍数下的SEM图；(d)~(f)循环30次后PU-MTS在不同放大倍数下的SEM图；(g)~(i)循环50次后PU-MTS在不同放大倍数下的SEM图

Fig.11 SEM images of PU-MTS after cyclic adsorption: (a)—(c) SEM images of PU-MTS at different magnification after 10 cycles; (d)—(f) SEM images of PU-MTS at different magnifications after 30 cycles; (g)—(i) SEM images of PU-MTS at different magnifications after 50 cycles

图12 PU-MTS制备示意图

Fig.12 Scheme for fabrication of the PU-MTS

表3 不同改性泡沫吸附性能对比

Table.3 Comparison of adsorption properties of different modified foams

改性试剂	水接触角/(°)	吸附溶剂	吸附性能/ （g/g）	文献
KH-570处理过的氧化石墨烯分散液	161	大豆油、柴油、泵油	35～39	[32]
甲基三氯硅烷-正己烷	157	润滑油、豆油、汽油、原油、正辛烷、十二烷、癸烷	15～25	[28]
纤维素纳米晶须的石墨烯悬浮液	152	丙酮、乙醇、乙二醇、橄榄油、大豆油、润滑油、甲苯	28～47	[33]
凹凸棒石和十八烷基三氯硅烷	160	氯仿、正己烷、石油醚、柴油、甲苯、煤油、菜籽油	17～45	[34]
碳纳米纤维的乙醇分散液	146	正己烷、庚烷、甲苯、二甲苯、汽油	26～50	[22]
甲基三氯硅烷-正己烷	140	乙醇、甲醇、丙酮、氯仿、二氯甲烷、甲苯、柴油、煤油、大豆油	16.67～45.15	本研究

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粗甘油生物基聚氨酯材料的制备及吸附性能研究

Preparation and adsorption properties of crude glycerol bio-based polyurethane material

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