煤沥青基吸水树脂的制备与性能

doi:10.16085/j.issn.1000-6613.2020-2105

摘要/Abstract

摘要：

以煤沥青为原料、空气为氧化剂、碱性水溶液为介质，考察了液固比、固碱比及反应时间等对煤沥青氧化率的影响。在此基础上，本文将煤沥青氧化液体产物（LP）直接与丙烯酸（AA）通过溶液聚合法制备出高吸水树脂。通过单因素与正交设计实验确定各因素对树脂吸水性能的影响，进而确定出合成树脂的最佳反应条件。同时，对合成树脂进行了结构表征与反应机理分析。结果表明，LP同丙烯酸、过硫酸铵和N-N′-亚甲基双丙烯酰胺在温度为75℃、时间为30min的最佳反应条件下合成的树脂具有最大吸水值，而红外吸收光谱证实合成的树脂含有LP中芳香组分的芳环特征吸收峰。其中，在去离子水与0.9%（质量分数）NaCl水溶液中最大吸水倍率分别为613.3g/g与42.2g/g，而合成树脂的机理是LP中的苯多酸与AA和N,N′-亚甲基双丙烯酰胺通过酯基联结而成。该研究为高效利用煤沥青探索出一条可供选择的新途径。

关键词: 煤沥青, 氧化, 吸水树脂, 聚合, 反应机理

Abstract:

With coal pitch as a raw material, air as an oxidant, and alkaline aqueous solution as the reaction medium, the effects of liquid-solid ratio, solid-alkali ratio and reaction time on the oxidation rate of coal pitch were investigated. On this basis, a super absorbent resin was directly prepared by solution polymerization with the liquid product of coal oxidation (LP) and acrylic acid (AA) in water. In order to determine the optimal reaction conditions, the influence of the water absorbency performance of each factor through single factor and orthogonal design experiments were discussed. At the same time, the synthetic resin was characterized and the reaction mechanism was analyzed. Results showed that the resin synthesized by LP with acrylic acid, ammonium persulfate and N,N′-methylenebisacrylamide under the optimal reaction conditions of 75℃ and 30min had the maximum water absorption value. The infrared absorption spectrum confirmed that the synthesized resin contained the characteristic absorption peak of the aromatic ring of the aromatic component in LP. Among them, the water absorption rate in deionized water and 0.9% NaCl aqueous solution can reach the maximum of 613.3g/g and 42.2g/g, respectively. The mechanism of the synthetic resin was that the benzene polyacid in LP was connected with AA and N,N′-methylenebisacrylamide through ester group. This research explored a new alternative way for the efficient use of coal pitch.

Key words: coal pitch, oxidation, superabsorbent, polymerization, reaction mechanism

中图分类号:

TQ32

马欣如, 郭涛, 王群, 李俊美, 张振楠, 曹青. 煤沥青基吸水树脂的制备与性能[J]. 化工进展, 2021, 40(10): 5634-5641.

MA Xinru, GUO Tao, WANG Qun, LI Junmei, ZHANG Zhennan, CAO Qing. Preparation and properties of coal pitch-based water-absorbing resin[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5634-5641.

图/表 13

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影响因素	固液比 /g·mL^-1	温度 /℃	时间 /h	固碱比 /g·g^-1	氧化率 /%
煤沥青∶H₂O	10∶200	240	2	1∶2	30.3
	20∶200	240	2	1∶2	29.5
	30∶200	240	2	1∶2	31.3
反应温度	30∶200	220	2	1∶2	26.4
	30∶200	230	2	1∶2	27.7
	30∶200	240	2	1∶2	31.3
反应时间	30∶200	240	1	1∶2	24.0
	30∶200	240	2	1∶2	31.3
	30∶200	240	3	1∶2	30.1
煤沥青∶碱	30∶200	240	2	1∶1	19.2
	30∶200	240	2	1∶2	31.3
	30∶200	240	2	1∶3	31.1

影响因素	固液比 /g·mL^-1	温度 /℃	时间 /h	固碱比 /g·g^-1	氧化率 /%
煤沥青∶H₂O	10∶200	240	2	1∶2	30.3
	20∶200	240	2	1∶2	29.5
	30∶200	240	2	1∶2	31.3
反应温度	30∶200	220	2	1∶2	26.4
	30∶200	230	2	1∶2	27.7
	30∶200	240	2	1∶2	31.3
反应时间	30∶200	240	1	1∶2	24.0
	30∶200	240	2	1∶2	31.3
	30∶200	240	3	1∶2	30.1
煤沥青∶碱	30∶200	240	2	1∶1	19.2
	30∶200	240	2	1∶2	31.3
	30∶200	240	2	1∶3	31.1

编号	A：APS^①/%	B：MBA^①/%	C：T/℃	D：P/%	Q/g·g^-1
1	3.6	0.08	65	50	349.8
2	3.6	0.10	75	60	542.4
3	3.6	0.12	85	70	308.9
4	3.8	0.08	75	70	463.8
5	3.8	0.10	85	50	303.9
6	3.8	0.12	65	60	554.7
7	4.0	0.08	85	60	324.9
8	4.0	0.10	65	70	455.1
9	4.0	0.12	75	50	402.5
均值1	400.367	379.500	453.200	352.067	—
均值2	440.800	433.800	469.567	474.000	—
均值3	394.167	422.033	312.567	409.267	—
极差	46.633	54.300	157.000	121.933	—

编号	A：APS^①/%	B：MBA^①/%	C：T/℃	D：P/%	Q/g·g^-1
1	3.6	0.08	65	50	349.8
2	3.6	0.10	75	60	542.4
3	3.6	0.12	85	70	308.9
4	3.8	0.08	75	70	463.8
5	3.8	0.10	85	50	303.9
6	3.8	0.12	65	60	554.7
7	4.0	0.08	85	60	324.9
8	4.0	0.10	65	70	455.1
9	4.0	0.12	75	50	402.5
均值1	400.367	379.500	453.200	352.067	—
均值2	440.800	433.800	469.567	474.000	—
均值3	394.167	422.033	312.567	409.267	—
极差	46.633	54.300	157.000	121.933	—

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