Toward a Greener Tomorrow: Sustainable Synthesis of Well-defined Polymers in Ionic Liquids via Recyclable Nanocatalyst-Mediated Photopolymerization

Abstract

The widespread use of ionic liquids (ILs) in reversible deactivation radical polymerization (RDRP) procedures has opened new pathways to address the problems caused by hazardous solvents. Additionally, photoinduced RDRP (photoRDRP) of methacrylate monomers in recyclable ILs has been developed, which is catalyzed by magnetic nano zero-valent iron (nZVI), enabling incredible control over M _n and Đ _s during the polymerization of methyl methacrylate (MMA) by simply turning the UVA radiation (λ _max ≈ 352 nm) “ON” and “OFF”. This allows for good temporal control. Furthermore, the chain end fidelity was determined through the synthesis of many distinct diblock copolymers with acceptable Đ _s values (≤1.20).

Keywords

Recyclable ionic liquid - Nano zero-valent iron - PhotoRDRP - Diblock copolymer - Sustainable method

Significance

• Recyclable ionic liquids are used as solvents for polymerization, instead of conventional hazardous organic solvents.

• Recyclable nanocatalysts enabled excellent control over polymerization.

• Remarkable temporal control was achieved through “ON–OFF” experiments.

• Well-defined narrow dispersed polymers and diblock copolymers were synthesized.

Introduction

The overutilization of organic solvents raises concerning environmental issues. Inhalation or exposure to high concentrations of organic solvents can result in many health problems, and these solvents are also extremely combustible, toxic, and irritating. The disposal of organic solvents contributes to air pollution [1], and burning these dangerous solvents poses major problems. Therefore, reducing the use of organic solvents is necessary although different processes rely on different solvents. A sustainable approach can be achieved through the use of recyclable ionic liquids (ILs) as solvents [2]. The presence of a range of anions and cations is a defining characteristic of ionic liquids. Among the most commonly employed organic cations in ILs that contain nitrogen are pyridinium and imidazolium. Bromides, tetrafluoroborate, chloride, iodide, and hexafluoro phosphate are some common anions [3]. These organic equivalents have a number of peculiar features, such as low volatility, effective dissolution, high flash point, non-volatility, extreme heat stability, and high polarity [4], [5]. These features of ILs have gained their interest recently and may serve as alternative solvents in various reactions. It is remarkable that the ILs can be recycled and used as green solvents to develop circularity in the system [6]. Significantly, ILs have emerged in several fields, including catalysis [7], organic synthesis [8], electrochemistry [9], analysis [10], material chemistry [11], and polymerization.

Although there is a wide variety of polymerization techniques accessible, reversible deactivation radical polymerization (RDRP) technologies have greatly improved over the last several decades [12]. They have functioned as a possible technique for the development of stimuli-responsive polymers [13], [14] and have amazing command over molecular mass, architecture, and functions [15]. The various RDRP techniques comprise atom transfer radical polymerization (ATRP) [16] and many more [17] [18] [19] [20].

Zero-valent transition metal-catalyzed RDRP procedures are well-proven methods for achieving effective control over molecular mass and chain end fidelities [21]. Designing externally triggered RDRP has expanded the application of standard RDRP procedures, and it has lately received attention from photo-irradiation [22] [23] [24], electrochemistry [25], and pressure [26]. Interestingly, photoinduced RDRP methods are appealing as they offer spatiotemporal control, lower polymerization temperature, and tolerance to functional moieties and hence are favored over other polymerization techniques [27], [28]. Although the RDRP procedures are well recognized, certain aspects still need to be developed. Lately, an emphasis has been given to circular processes. Some areas of interest include recoverable, reusable catalysts and reducing the usage of conventional transition metal catalysts, as it impart coloration [29].

It is also essential to select a suitable solvent. Recently, Cu(II) was used as a catalyst for ATRP of methyl acrylate (MA), which produced a well-defined polymer after 120 min at 60 °C in dimethyl formamide (DMF) as the solvent [30]. Another report depicts the synthesis of PMA using copper-mediated RDRP in a series of solvents, including acetone, DMF, and DMSO at 110 °C, yet the conversion was found to be 82% [31]. Various organic solvents, including acetone and DMF, have been utilized in these reported techniques at increased temperatures. These conditions are not economically sustainable and require various conditions thus making the method costly. Reusable solvent and catalyst-mediated photoRDRP are potent solutions to these problems. Reusing reaction components will help improve process competency and pave the way for a circular economy. This can be easily achieved by IL as a solvent in transformations including polymerization [32].

The adaptability of the photoRDRP system and the use of ILs as a solvent are highlighted in this study, opening new possibilities for polymerization with greater temporal control. Our group has been working in the field of photoRDRP, and in some of our previous work, we have limited to only a single type of ionic liquid system [33], [34]. This work additionally focuses on the IL-enabled recyclable catalyst-aided polymerization of MMA and illustrates the impact of chain length in imidazolium-based ILs. We have synthesized and investigated a variety of ILs with diverse chain lengths, ranging from ethyl to decyl, in the photoRDRP of MMA. Remarkably, even after numerous cycles of photoRDRP, the catalyst maintained its activity with respect to controlling molecular mass and dispersity. Moreover, well-defined diblock copolymers are produced by using the synthesized poly(methyl methacrylate) (PMMA) homopolymer. The poly(methyl methacrylate)-block-poly(methyl methacrylate) (PMMA-b-PMMA), poly(methyl methacrylate)-block-poly(tert-butyl acrylate) (PMMA-b-PTBA), and poly(methyl methacrylate)-block-poly(tert-butyl methacrylate) (PMMA-b-PTBMA) are the diblock copolymers with lower Đ values (≤1.20). Additional features of photoRDRP, like temporal control, have also been investigated through “ON” and “OFF” studies. These experiments demonstrate remarkable control over polymerization and have produced a new, environmentally friendly way of polymerization.

Results and Discussion

The effect of substituted alkyl chains on the activity of IL as a solvent in polymerization was studied, and a variety of ILs have been produced following the reported method [35]. In this study, the alkyl chain of ILs varied from ethyl (C₂) to decyl (C₁₀) and resulted in ILs named 1-ethyl-3-methylimidazolium bromide (EMIMBr), 1-butyl-3-methylimidazolium bromide (BMIMBr), 1-hexyl-3-methylimidazolium bromide (HMIMBr), 1-octyl-3-methylimidazolium bromide (OMIMBr), and 1-decyl-3-methylimidazolium bromide (DMIMBr), respectively (Figure S2), and characterized via IR, ¹H, ¹³C, HSQC and HMBC NMR spectrum along with LCMS spectra (Figure S3–S11, S13, respectively). Initially, all ILs, that is, EMIMBr, BMIMBr, HMIMBr, OMIMBr, and DMIMBr, were used in photoRDRP (UVA light-induced λ _max ≈ 352 nm) of nZVI mediated RDRP of MMA ([Figure 1]). The produced ILs were viscous with rising chain length, leading to an increase in polymerization time from 45 to 240 min in the case of EMIMBr to DMIMBr, respectively (P1–P5, Table S1). Another interesting observation was that when the carbon in the alkyl chain was <4, it resulted in poor control over polymerization (P1–P5, Table S1).

Figure 1 Representative scheme of the polymerization of nZVI-catalyzed photoRDRP of MMA in IL and synthesis of the diblock copolymer.

A preliminary optimization of the nZVI-catalyzed photoRDRP of MMA in BMIMBr was carried out considering the above observations, using a UVA light (λ _max ≈ 352 nm) photoreactor (P2, Table S1). The photoRDRP in the BMIMBr system was found to produce controlled and well-defined PMMA. So, taking this observation into account, further well-defined PMMA is achieved using Me₆TREN and EBiB as ligand and initiating units respectively ([Figure 1]). The synthesized homopolymer was characterized using ¹H NMR ([Figure 4A]) and ATR-IR (Figure S14), respectively, which also validates the formation of PMMA. The linear dependence of ln([M][M]₀/[M]) vs. time ([Figure 2A]) confirms that the nZVI-induced polymerization possesses all the features of the RDRP approach, as is obvious from the kinetics investigation. It is evident from the linear rise of M _n vs conversion ([Figure 2B]) that successful synthesis of narrow dispersed PMMAs (≤1.20) with varying M _n (from 1600 to 11,000 g mol⁻¹, Figure S1, P11–P15, Table S2) was achieved.

Figure 2 Kinetic plots of (A) conversion vs. time, ln([M]₀/[M]) vs time, and (B) evolution of molar mass (M _n) and dispersity (Đ) with monomer conversion.

Temporal control and catalyst recyclability are the two areas of interest in heterogeneous photocatalysis; in this case, the polymerization method also shows IL recyclability. To achieve this, the investigation of temporal control involved turning “ON” and “OFF” the UV irradiation to either activate or deactivate the polymerization ([Figure 3A]), and there was a linear rise in ln([M]₀/[M]) vs. total UVA light exposure over the period. It was discovered that the polymerization stopped when the UVA radiation was turned “OFF” ([Figure 3A]). All the traits of photoRDRP processes are exhibited by this system, this system exhibits remarkable temporal control ([Figure 3B]). Additionally, the green IL is separable and reusable in the reaction mixture. Concerning control and molecular mass in polymerization, (P19–P22, Table S4) show that the process was continued for up to three cycles without any evident loss in activity. Furthermore, in the above processes, nZVI, the magnetically separable catalyst, was used. It is noteworthy to mention that there has been no decrease in the catalytic activity (regarding control and molecular mass during polymerization (P23–P26, Table S5)).

Figure 3 Represents temporal control with sequential “irradiation ON” (blue area) and “irradiation OFF” (white area) for polymerization of MMA: (A) ln([M]₀/[M]) vs radiation time of UVA-light and (B) M _n and Đ vs monomer conversion.

Polymerization did not occur in the reactions performed in the absence of the ligand (Me₆TREN), catalyst (nZVI), or initiator (EBiB) (P8–P10, Table S1). This emphasizes that the polymerization process requires the presence of all components, i.e., the catalyst, ligand, and initiator. Interestingly, a different set of investigations using 2,2′-bipyridine (bpy) or N,N,N′,N″,N″-pentamethyl diethylenetriamine (PMDETA) produced an ill-defined polymer and a sluggish polymerization (P6–P7, Table S1). Concurrently, the temporal control investigation demonstrates that UVA irradiation (λ _max ≈ 352 nm) is an additional essential factor for polymerization. The mechanistic study depicts ([Scheme 1]) that iron gets oxidized to Fe(II) and forms Fe(II)Br/L _n complex. The introduction of MMA results in excellent control over polymerization, which is attributed to the complex Fe(II)(Me₆TREN)Br₂. The mechanistic study was confirmed by the theoretical study was reported in our earlier work [34].

Scheme 1 Proposed mechanism for the nZVI-catalyzed photoRDRP in IL.

A variety of block copolymers have also been synthesized to further illustrate the active chain end of the produced homopolymer as a macroinitiator. The produced block copolymers are namely PMMA₂₅-b-PTBMA₅₀-Br, PMMA₂₅-b-PTBA₅₀-Br, and PMMA₂₅-b-PMMA₅₀-Br diblock copolymers ([Figure 1], Table S3). Using ¹H NMR, the synthesized PMMA₂₅-b-PMMA₅₀-Br copolymer was characterized [36] ([Figure 4B]) and the ATR-IR spectra (Figure S14) depict the formation of block copolymers.

Figure 4 ¹H NMR spectra of PMMA₂₅-Br (A), PMMA₂₅-b-PMMA₅₀-Br (B), PMMA₂₅-b-PTBA₅₀-Br (C), and PMMA₂₅-b-PTBMA₅₀-Br (D).

The obtained PMMA₂₅-b-PTBA₅₀-Br copolymer was characterized through ¹H NMR [37] ([Figure 4C]), and the ATR-IR spectra diblock copolymer shows characteristic signals (Figure S14). This also validates the synthesis of PMMA₂₅-b-PTBA₅₀-Br. The prepared PMMA₂₅-b-PTBMA₅₀-Br copolymer was characterized through ¹H NMR spectra [36] ([Figure 4D]), and the ATR-IR spectra (Figure S14) depict the formation of copolymers. The ¹H NMR spectra of block copolymers show peak broadening and merging due to the randomness of polymeric chain arrangement and a wide range of local chemical environments for each proton [38]. The synthesis of several diblock copolymers demonstrates that the chain end is active. It has been demonstrated that the BMIMBr system is capable of synthesizing well-defined diblock copolymers.

Conclusions

In summary, we emphasize the widespread use of ILs in reversible-deactivation radical polymerization (RDRP) methods to address the problems caused by hazardous solvents, hence creating new opportunities for polymerization. Furthermore, nZVI-catalyzed polymerization of MMA in the IL system has been described here; to investigate in detail, the ILs have various alkyl substitutions ranging from ethyl to decyl. Surprisingly, The IL with butyl substituent has been found to be promising in terms of control and molecular mass. Another peculiar feature depicted by IL systems is recyclability, which is achieved here, along with the reuse of magnetically separable nZVI catalysts. Moreover, the polymerization showed a notable ability to regulate time by merely turning “ON” and “OFF” the UVA radiation. We have effectively demonstrated the chain end fidelity through the preparation of different diblock copolymers, i.e., PMMA₂₅-b-PMMA₅₀-Br, PMMA₂₅-b-PTBMA₅₀-Br, and PMMA₂₅-b-PTBA₅₀-Br. This simple IL-mediated method enables photo-controlled precision in the manufacturing of customized polymers through a sustainable system inducing circularity.

Experimental Section

Materials and methods

The monomers were procured from sigma Aldrich. Methyl methacrylate (MMA, 99%), tert-butyl methacrylate (TBMA, 98%), tert-butyl acrylate (TBA, 99%) were passed through the basic column. The precursors 1-methylimidazole (C₄H₆N₂, 99%), 1-bromoethane (C₂H₅Br, 98%), 1-bromobutane (C₄H₉Br, 99%), 1-bromohexane (C₆H₁₃Br, 98%), 1-bromooctane (C₈H₁₇Br, 99%), 1-bromodecane (C₁₀H₂₁Br, 98%), ethyl α-bromoisobutyrate (EBiB, 98%), and deuterated chloroform (CDCl₃, >99.8%) were utilized as obtained. Tris [2-(dimethylamino)ethyl]-amine (Me₆TREN, >98%, TCI Chemicals), along with methanol (CH₃OH, Merck), tetrahydrofuran (THF, 99%), chloroform (CHCl₃, Merck), and diethyl ether (C₄H₁₀O, Merck), were used as received. The nZVI catalyst is synthesized through a previously reported method [39]. ¹H NMR spectra were recorded using Bruker 600 MHz NMR spectrometer. IR spectra were performed using the Perkin Elmer Spectrum 100 instrument in ATR mode. Molar masses (M _ns) and dispersities (Ð _s) of the prepared polymers were assessed with triple-detection GPC, in DMF (comprising 0.1 wt % of LiCl), which is used as the eluent and narrow linear poly(methyl methacrylate) standards are used for instrument calibration.

General procedure for synthesis of ionic liquids

The ILs were synthesized following an earlier reported procedure [35]. In this procedure, 1-methyl imidazole and respective alkyl halide namely 1-bromoethane to 1-bromodecane were added in equimolar proportion in a round bottom flask. The system is refluxed at 70 °C for 36 h. After this, a thick viscous liquid is obtained and is purified using diethyl ether to obtain pale yellowish thick liquids. 1-ethyl-3-methylimidazolium bromide (EMIMBr), 1-butyl-3-methylimidazolium bromide (BMIMBr), 1-hexyl-3-methylimidazolium bromide (HMIMBr), 1-octyl-3-methylimidazolium bromide (OMIMBr), 1-decyl-3 methylimidazolium bromide (DMIMBr) are the IL synthesized. The characteristics of BMIMBr are mentioned as follows.

IR: 3650–3300, 3200–3000, 3000–2700, 1660–1400, 1640–1580, 1460–1330, 1190–1160 cm⁻¹.

¹H NMR: 10.25–9.85, 7.61, 7.49, 4.37–4.32, 4.15, 1.96–1.86, 1.43–1.36, 0.99–0.94 ppm.

¹³C NMR: 137, 124, 122, 50–47, 38–35, 33–30, 21–19, 14–11 ppm.

LCMS: 140  m/z (molecular ion peak + H⁺).

General procedure for homopolymerization and block polymerization

In an nZVI-mediated photoRDRP of MMA (P2, Table S1), a vessel containing nZVI (12 mg, 0.11 mmol), Me₆TREN (30 μL, 0.11 mmol), BMIMBr (445 mg, 2.17 mmol) EBiB (16 μL, 0.11 mmol), and purged MMA (1 mL, 11.03 mmol) were sealed under inert atmosphere. The reaction mixture was irradiated under a UVA photoreactor (λ _max ≈ 352 nm). Upon completion of the reaction, the mixture is diluted with THF, and the catalyst is recovered using a bar magnet. The polymer was isolated by precipitation in chilled methanol and dried under a vacuum. A similar procedure is followed with EMIMBr, HMIMBr, OMIMBr, and DMIMBr.

Synthesis of PMMA₂₅-Br homopolymer was carried out via nZVI-mediated photoRDRP according to the above-described method using EBiB (P2, Table S1) as the initiator. After the completion of the reaction, nZVI was removed by a bar magnet, and the pure polymer was obtained by precipitation into methanol and dried under a vacuum. The GPC profile of the prepared PMMA and block copolymers (Figure S15) also shows the narrow dispersity.

IR: 2954, 1730, and 1139 cm⁻¹.

¹H NMR: 3.6–4.1, 2.2–2.4 and 1.6–2.0 ppm.

Synthesis of PMMA₂₅-b-PTBMA₅₀-Br diblock copolymer was carried out via nZVI-catalyzed photoRDRP according to the previously described method using PMMA-Br (P16, Table S3) as the macroinitiator. After the completion of the reaction, nZVI was recovered using a bar magnet, and the pure polymer was obtained by precipitation into methanol and dried under a vacuum.

IR: 2954, 1730, and 1139 cm⁻¹.

¹H NMR: 3.6–4.1, 2.2–2.4 and 1.6–2.0 ppm.

Synthesis of PMMA₂₅-b-PTBA₅₀-Br diblock copolymer was carried out via nZVI-catalyzed photoRDRP according to the above-described method using PMMA-Br (P17, Table S3) as the macroinitiator. After the completion of the reaction, nZVI was recovered using a bar magnet, and the pure polymer was obtained by precipitation into methanol and dried under a vacuum.

IR: 2954, 1730, and 1139 cm⁻¹.

¹H NMR: 3.6–4.1, 2.2–2.4 and 1.6–2.0 ppm.

Synthesis of PMMA₂₅-b-PMMA₅₀-Br diblock copolymer was carried out via nZVI-catalyzed photoRDRP according to the above-described method using PMMA-Br (P18, Table S3) as the macroinitiator. After the completion of the reaction, nZVI was recovered using a bar magnet, and the pure polymer was obtained by precipitation into methanol and dried under a vacuum.

IR: 2954, 1730, and 1139 cm⁻¹.

¹H NMR: 3.6–4.1, 2.2–2.4 and 1.6–2.0 ppm.

General procedure for kinetics and ON/OFF

The polymerization reaction was carried out following the above-mentioned procedure under UVA irradiation (λ _max ≈ 352 nm), to validate the kinetics of the polymerization, aliquots were withdrawn using a degassed syringe at periodic time intervals (5 – 60 min) during the course of the reaction and diluted with THF to assess the evolution of (i) the conversion of monomer and (ii) molar masses (M _ns) and dispersity values (Đ_s ) by gravimetry and SEC, respectively. Keeping the other components (nZVI, Me₆TREN, IL) constant and altering the [MMA]₀/[EBiB]₀ feed ratio, a series of PMMAs of various molar masses (DP = 15 –100) were synthesized and precipitated in methanol. The UVA irradiation was turned “ON/OFF” (the reaction mixture was held in the dark phase (OFF state), after which UVA irradiation was again turned ON) for every 5 min in the initial 15 min of photoRDRP, followed by an interval of 15 min. The “ON/OFF” experiments were performed over many cycles, with aliquots being removed from each “ON” and “OFF” cycle to determine the monomer conversion as well as the molecular mass and dispersity.

General procedure for recyclability studies

Under consistent reaction conditions as used for homopolymerization, the recycled ILs were utilized for subsequent reactions. The ILs were removed by dissolving the reaction mixture in methanol, after the first reaction of the photoRDRP. The PMMA-free IL (500 mg) was then used for the subsequent photoRDRP of MMA for multiple cycles and the purity of IL is confirmed through ¹H NMR (Figure S12). The crude product was dissolved in THF, and the catalyst was isolated by simply holding it against a bar magnet after the first set of photoRDRP of MMA in ILs. The recovered catalyst (approx. 2 mg) was washed with methanol and THF twice, dried, and then employed as a catalyst for the following series of photoRDRP of MMA.

Contributorsʼ Statement

Amul Jain: conception and design of the work, data collection, analysis and interpretation of the data, statistical analysis, drafting the manuscript, critical revision of the manuscript; Bhanendra Sahu: data collection, analysis and interpretation of the data, statistical analysis, critical revision of the manuscript; Nikhil Ingale: data collection, analysis and interpretation of the data, statistical analysis, critical revision of the manuscript; Dr. Sanjib Banerjee: conception and design of the work, analysis and interpretation of the data, statistical analysis, critical revision of the manuscript, supervision, resources.

Conflict of Interest

The authors declare that they have no conflict of interest.

Acknowledgment

The study was funded by The Defence Research and Development Organisation, Government of India (No. ERIP/ER/202311001/M/01/1850). The authors acknowledge equipment facilities provided by the Central Instrument Facility, IIT Bhilai. BS acknowledges University Grants Commission, Government of India, for the fellowship.

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Publication History

Received: 06 October 2024

Accepted after revision: 28 January 2025

Accepted Manuscript online:
30 January 2025

Article published online:
17 April 2025