负载型离子液体催化生物基多元酸酯的制备

doi:10.6023/A25110367

摘要/Abstract

本工作以弱酸性离子交换树脂为载体, 以有机胺为修饰剂, 通过简单的酸碱中和反应制备得到了一系列负载型离子液体催化剂, 并将其应用到生物基多元酸酯的制备当中. 以2,5-呋喃二甲醛(DFF)和丙二酸二甲酯(DMM)为底物, 以活性最佳的Pyrrolidine-YLST-3为催化剂时, 生物基多元酸酯的产率可以达到99.2%. 这种制备方法极大地减少了传统氧化过程中氧气等强氧化剂的使用, 安全性更高, 对设备要求较低. 此外, 目标产物选择性较高, 副产物主要为水, 对环境更加友好, 更加符合绿色化学原则. 通过核磁共振(NMR)、红外光谱(FTIR)、X射线衍射(XRD)和X射线光电子能谱(XPS)等方法对催化剂进行了表征, 发现吡咯烷与离子交换树脂之间发生了质子转移, 形成了新的负载型离子液体. 通过对多种底物的Knoevenagel缩合反应进行研究均取得了较高的收率, 说明Pyrrolidine-YLST-3催化剂具有很强的普适性.

关键词: 生物基多元酸酯, 绿色化学, 负载型离子液体, 非均相催化, Knoevenagel缩合反应

Biomass resources, characterized by their wide distribution, carbon neutrality, and renewability, have emerged as ideal alternatives to fossil fuels. Derived from these resources, bio-based platform compounds such as 5-hydroxymethylfur- fural (HMF) and 2,5-diformylfuran (DFF) exhibit diverse application potential. These bio-based platform compounds can be converted into high-value-added chemicals through organic chemical reactions. Bio-based polyacid esters show broad potential for applications in fields such as chemical engineering, polymer materials, and biomedicine, where they can serve as crosslinking agents, lubricants, emulsifiers, among other roles. Conventional methods for synthesizing polybasic acid esters typically involve strong oxidants, intricate processes, and demanding equipment requirements. In this study, we prepared a series of supported ionic liquid catalysts via in-situ acid-base neutralization reaction, employing weak acidic ion exchange resin as the solid support and organic amines as functional modifiers, and used them to the preparation of bio-based polyacid esters. When 2,5-diformylfuran (DFF) and dimethyl malonate (DMM) were employed as substrates, the yield of bio-based polyacid esters can reach 99.2% in the presence of Pyrrolidine-YLST-3. The structural modifications of the resins were comprehensively characterized using multiple analytical techniques, including elemental analysis (EA), nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). These comprehensive analyses provided conclusive evidence for the successful surface modification of YLST-3 resin with pyrrolidine, revealing distinct chemical interactions between the modifier and the resin. Comprehensive characterization of both fresh and deactivated catalysts was performed using EA, FTIR, and XRD to investigate catalyst deactivation mechanisms. Successful regeneration was accomplished through a two-step protocol involving hydrogen peroxide oxidation followed by pyrrolidine re-modification, which substantially improved cycling stability. Substrate scope evaluation demonstrated that the Pyrrolidine-YLST-3 catalyst exhibited excellent activity in Knoevenagel condensation reactions across diverse substrates, confirming its broad applicability.

Key words: bio-based polyacid ester, green chemistry, supported ionic liquids, heterogeneous catalysis, Knoevenagel condensation reaction

引用此文

赵馨雨, 韩燕楠, 徐吉磊, 安庆大, 肖作毅, 苏鑫, 黄家辉. 负载型离子液体催化生物基多元酸酯的制备[J]. 化学学报, 2026, 84(3): 341-352.

Zhao Xinyu, Han Yannan, Xu Jilei, An Qingda, Xiao Zuoyi, Su Xin, Huang Jiahui. Preparation of Bio-based Polyacid Esters Catalyzed by Supported Ionic Liquids[J]. Acta Chimica Sinica, 2026, 84(3): 341-352.

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图/表 18

图式1. DFF和DMM的Knoevenagel缩合反应

Scheme 1. The Knoevenagel condensation reaction of DFF and DMM

Entry	Catalyst	Conversion/%	Yield/%	Selectivity/%
1	Pyrrolidine-YLST-3	100	79.1	79.1
2	Pyrrolidine-D113	100	63.8	63.8
3	Ethanolamine-YLST-3	97.0	60.0	61.5
4	Ethanolamine-D113	99.2	73.4	74.0
5	Diethanolamine-YLST-3	11.6	0	0
6	Diethanolamine-D113	9.9	0	0
7^b	Pyrrolidine-YLST-3	92.7	68.9	74.4
8^b	Ethanolamine-D113	98.7	58.8	59.5
9	YLST-3	18.2	0	0
10	Pyrrolidine	100	19.4	19.4

表1. 不同负载型离子液体催化剂催化DFF和DMM的Knoevenagel缩合反应a

Table 1. The Knoevenagel condensation reaction of DFF and DMM catalyzed by different supported ionic liquid catalysts

图1. (a, b) YLST-3和(c, d) Pyrrolidine-YLST-3的扫描电镜图

Figure 1. (a, b) SEM images of YLST-3 and (c, d) Pyrrolidine-YLST-3

Entry		Catalyst	Elemental content/%
Entry		Catalyst	N	C	H	O
1	YLST-3		1.0	51.3	6.3	41.4
2	Pyrrolidine-YLST-3		7.0	54.6	8.4	30.0

表2. 元素分析

Table 2. Element analysis

图式2. Pyrrolidine-YLST-3的制备

Scheme 2. Preparation of Pyrrolidine-YLST-3

图2. YLST-3和Pyrrolidine-YLST-3的红外光谱图

Figure 2. FTIR spectra of YLST-3 and Pyrrolidine-YLST-3

图3. YLST-3和Pyrrolidine-YLST-3的XRD谱图

Figure 3. XRD spectra of YLST-3 and Pyrrolidine-YLST-3

图4. (a) YLST-3和Pyrrolidine-YLST-3的XPS全谱, (b) YLST-3和Pyrrolidine-YLST-3的C1s光谱, (c) YLST-3和Pyrrolidine-YLST-3的N1s光谱, 和(d) YLST-3和Pyrrolidine-YLST-3的O1s光谱

Figure 4. (a) XPS survey spectrum of YLST-3 and Pyrrolidine-YLST-3, (b) C1s spectra of YLST-3 and Pyrrolidine-YLST-3, (c) N1s spectra of YLST-3 and Pyrrolidine-YLST-3, and (d) O1s spectra of YLST-3 and Pyrrolidine-YLST-3

图5. YLST-3 and Pyrrolidine-YLST-3的TG-DTG曲线

Figure 5. Thermogravimetric curve of YLST-3 and Pyrrolidine-YLST-3

Entry	Solvent	Conversion/%	Yield/%	Selectivity/%
1	ethyl acetate	100	89.9	89.9
2	tetrahydrofuran	99.3	81.1	81.7
3	dichloromethane	100	82.3	82.3
4	chloroform	100	61.9	61.9
5	acetonitrile	100	79.1	79.1
6	methanol	100	44.8	44.8
7	ethanol	100	54.5	54.5
8	isopropanol	100	54.8	54.8
9	DMSO	100	6.8	6.80
10	DMF	100	17.5	17.5

表3. 溶剂对DFF和DMM的Knoevenagel缩合反应的影响a

Table 3. The influence of solvent on the Knoevenagel condensation reaction of DFF and DMM

图6. 反应条件对DFF和DMM的缩合反应的影响

Figure 6. The influence of reaction conditions on the condensation reaction of DFF and DMM Reaction condition: (a) DFF: 1 mmol, DMM: 3 mmol, catalyst 6% (w), ethyl acetate 0.5 g, t=180 min. (b) DFF: 1 mmol, DMM: 3 mmol, catalyst 6% (w), ethyl acetate 0.5 g, T=80 ℃. (c) DFF: 1 mmol, DMM: 3 mmol, ethyl acetate 0.5 g, T=80 ℃, t=90 min. (d) DFF: 1 mmol, catalyst 6% (w), ethyl acetate 0.5 g, T=80 ℃, t=90 min. (e) DFF: 1 mmol, DMM: 3 mmol, catalyst 6% (w), T=80 ℃, t=90 min.

图7. (a)使用后催化剂的循环性能和(b)再生催化剂的循环性能

Figure 7. (a) Recycling of used catalyst and (b) recycling of regenerated catalyst Reaction condition: DFF: 1 mmol, DMM: 3 mmol, catalyst 6% (w), Ethyl acetate 0.5 g, T=80 ℃, t=60 min.

图8. 新制备、使用后和再生后催化剂的红外光谱图

Figure 8. FTIR spectra of fresh, used and regenerated catalysts

Entry		Catalyst	Elemental content/%
Entry		Catalyst	N	C	H	O
1	Pyrrolidine-YLST-3		7.0	54.6	8.4	30.0
2	used catalyst		4.8	54.5	7.2	33.5
3	regenerated catalyst		5.9	52.1	7.6	34.4

表4. 元素分析

Table 4. Element analysis

图9. 新制备和再生后催化剂的XRD谱图

Figure 9. XRD spectra of fresh and regenerated catalysts

图10. (a)使用后催化剂的扫描电镜图, (b)再生后催化剂的扫描电镜图, 和(c)新制备、使用后和再生后催化剂的N1s光谱

Figure 10. (a) SEM image of used catalysts, (b) SEM image of regenerated catalysts, and (c) N1s spectra of fresh, used and regenerated catalysts

Entry	Temp./℃	Time/min	Conversion/%	Yield/%	Selectivity/%
1^a	80	90	100	99.2	99.2
2^a	60	120	100	65.3	65.3
3^a	80	30	100	61.9	61.9
4^a	100	180	98.2	77.3	78.8
5^b	50	120	100	96.7	96.7
6^b	70	120	100	82.6	82.6
7^b	70	120	99.8	94.3	94.5
8^b	70	120	94.5	92.1	97.5
9^c	80	300	91.9	83.4	90.7
10^b	80	300	95.5	76.3	80.3
11^b	80	300	90.2	86.6	96.1
12^c	40	120	97.9	76.9	78.5
13^b	40	120	100	97.0	97.0

表5. 底物拓展a

Table 5. Substrate expansion

图式3. DFF和DMM的Knoevenagel缩合反应的可能机理

Scheme 3. Possible mechanism of the Knoevenagel condensation reaction between DFF and DMM

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