Preparation of Bio-based Polyacid Esters Catalyzed by Supported Ionic Liquids

doi:10.6023/A25110367

Abstract

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

Cite this article

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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Fig. & Tab. 18

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

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

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

Table 2. Element analysis

Scheme 2. Preparation of Pyrrolidine-YLST-3

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

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

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

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

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

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.

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.

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

Table 4. Element analysis

Figure 9. XRD spectra of fresh and regenerated catalysts

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

Table 5. Substrate expansion

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

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