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Application of Deep Eutectic Solvents in Polymer Synthesis

Li Jintao , Zhang Mingzu , He Jinlin , Ni Peihong

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (10) : 2159 -2172.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (10) : 2159-2172 DOI: 10.7536/PC220306
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Application of Deep Eutectic Solvents in Polymer Synthesis
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Abstract

Deep eutectic solvents (DES) are one kind of low-transition-temperature mixture composed of two or several components mixed in a certain ratio. The melting points of DES are significantly lower than that of each pure component, and they can be considered as a new type of ionic liquid. Compared with traditional organic solvents, DES possess the advantages of broad resource of raw materials, low cost, easy preparation, low toxicity and biodegradability. These characteristics make them become a promising green reaction media, which have been widely used in many areas including extraction and separation, inorganic synthesis, organic synthesis and ion gels. In recent years, the applications of DES in polymer chemistry have attracted broad research interests. Starting from a brief description of DES and their applications in organic synthesis, this review mainly focuses on the applications of DES in polymerizations, such as condensation polymerization, free radical polymerization, anionic polymerization, electrochemical polymerization, ring-opening polymerization and oxidative polymerization. In the meantime, the prospects of DES in polymer synthesis are also discussed.

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green chemistry / deep eutectic solvents / polymerization / polymeric materials / reaction media

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Li Jintao, Zhang Mingzu, He Jinlin, Ni Peihong. Application of Deep Eutectic Solvents in Polymer Synthesis. Progress in Chemistry, 2022, 34(10): 2159-2172 DOI:10.7536/PC220306

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Contents

1 Introduction
2 Introduction of DES
3 Applications of DES in organic synthesis
4 Applications of DES in polymer synthesis
4.1 Condensation polymerization
4.2 Free radical polymerization
4.3 Anionic polymerization
4.4 Electrochemical polymerization
4.5 Other polymerizations
5 Conclusion and outlook

1 Introduction

Since the concept of "green chemistry" was put forward in the early 1990s, people have paid more and more attention to the impact of solvents used in chemical reactions on the environment. Most of the traditional organic solvents come from petroleum-based raw materials, which may cause serious environmental problems in the process of use, and there are also some hidden dangers in the long-term safety of these chemicals[1,2]. The development of green solvent system is in line with the national ecological protection strategy and the development of green chemical industry. Over the past two decades, ionic liquids have been used to replace traditional organic solvents in the fields of material chemistry, electrochemistry and catalysis due to their low vapor pressure, high solubility, high thermal stability and easy recovery[3⇓⇓~6]. However, the complex synthesis process and high production cost of ionic liquids lead to their high price, and they also have the disadvantages of potential toxicity and poor biodegradability, which limit their wide application in industry[7,8].
At the beginning of this century, researchers invented a new type of green solvent, Deep eutectic solvents (DES), which can also be called "Deep eutectic solvents" or "eutectic solvents". Although the Chinese names are different, they generally refer to the mixture solvent whose melting point is lower than the ideal eutectic temperature, otherwise it can not be distinguished from other mixtures. To avoid ambiguity, the term "eutectic solvent" is used to describe DES in this paper. It is developed on the basis of ionic liquids, so some people call it a new type of ionic liquid. In addition to the excellent characteristics of ionic liquids, the components used to prepare DES are inexpensive, the preparation method is simple, and 100% atom economy can be achieved without further purification. At the same time, most of the components used to prepare DES are biodegradable and have excellent biocompatibility, which is a good green reaction medium[9⇓~11]. At present, there are many reviews on the physical and chemical properties of DES and its applications in the fields of extraction and separation, inorganic synthesis, organic synthesis and ionic gel, but there are few literatures systematically summarizing the application of DES in polymerization[12,13][14,15][16][17,18][19]. In this paper, DES and their applications in organic synthesis are briefly described, and their applications in polymer synthesis such as condensation polymerization, radical polymerization, anionic polymerization, electrochemical polymerization, ring-opening polymerization and oxidative polymerization are emphatically introduced, and their development trends are prospected.

2 Introduction to Eutectic Solvent

In 2003, Abbott et al. First mixed choline chloride (ChCl, m. P. 302 ℃) and Urea (Urea, m. P. 133 ℃) at a molar ratio of 1 ∶ 2 and heated them to prepare a mixture with a melting point (12 ℃) much lower than that of the two components, and defined this mixture as a eutectic solvent (DES)[20]. They suggested that this was due to the hydrogen bonding formed between the hydrogen bond donor (Urea) and the hydrogen bond acceptor (ChCl), which inhibited the precipitation of the solid. In 2014, Smith and Abbott et al. Proposed the general formula :Cat+X-zY for DES, in principle Cat+ can be any ammonium, phosphonium, or sulfonium cation, X is a Lewis base (usually a halogen anion), Y is usually a Lewis acid or a Brønsted acid, and Z is the number of Y molecules interacting with the X- anion[21]. At the same time, they divided DES into four types according to the nature of the selected components (Table 1). Recently, Coutinho et al. Reported a new type of nonionic DES composed of thymol and menthol, and classified it into the fifth category of DES, expanding the category of DES[22].
At present, type III DES is the most widely studied, which is prepared by mixing hydrogen bond acceptors (HBA, such as quaternary ammonium salt, betaine, etc.) With hydrogen bond donors (HBD, such as carboxylic acid, polyol, amide, etc.). The chemical structural formulas of common components are shown in Figure 1[17][23]. There are four preparation methods of DES: (1) heating method[24]; (2) grinding method[25]; (3) evaporation method[26]; (4) Freeze-drying[27]. Among them, the heating method is the most widely used method because of its simple operation.
Freezing point is a typical physical characteristic of eutectic solvents, most of which are in the range of-69 ~ 149 ℃. The freezing point of DES is much lower than that of HBA and HBD, which are mainly affected by ion symmetry, alkane chain length, hydrogen bond forming ability and preparation methods[28][29]. Compared with traditional organic solvents, the most significant physical property of DES system is its higher viscosity (mostly in the range of 10 ~ 5000 cP)[30]. The abundant hydrogen bond network in DES leads to the low mobility of free species in its structure, which leads to its high viscosity, so the structure of HBA and HBD has an important impact on the viscosity of DES. In addition, similar to traditional solvents, the viscosity of DES is temperature-dependent[31]. This high viscosity has great advantages in some areas of polymer synthesis, such as supramolecular gels. Most DES systems exhibit higher densities than water, with densities at 298 K in the 1.04~1.63 g/cm3 and varying with the nature and molar ratio of HBA and HBD, while hydrophobic DES has a lower density than water[25]. In addition, the density of some DES is temperature-dependent and decreases linearly with the increase of temperature, and the presence of moisture in DES usually has little effect on its density[32]. The ionic conductivity of DESs has been a hot topic in electrochemical applications, such as their potential applications in electrolytes for batteries[33]. Although most DESs are based on ionic components, they tend to exhibit relatively low ionic conductivities (< 2 mS/cm at room temperature)[25]. On the one hand, it can be attributed to the size of the ion itself, which may migrate in pairs after interacting with HBD, so it is larger than the size of the ion itself, limiting the free motion of the ion. On the other hand, conductivity has a strong correlation with viscosity, and the high viscosity of DES limits the flow of ions. When the temperature increases, the viscosity decreases and the ionic conductivity increases. In addition, DES has good solubility, high surface tension and certain polarity. By selecting different combinations of HBA and HBD, DES with different physical and chemical properties can be prepared, which provides a variety of possibilities for its application in chemical reactions.

3 Application of DES in Organic Synthesis

In the field of organic synthesis, due to the problems of potential toxicity, low safety and high price of commonly used organic solvents, the greening of solvents has become a research hotspot in the field of synthetic chemistry. The emergence of DES provides a new choice for the study of green and cheap solvents in organic synthesis[17,18]. In 2002, Davies' group first reported the Diels-Alder reaction in which the product was obtained in high yield (85% – 94%) in a solvent composed of ChCl/MCl2(1∶2,M=Zn,Sn)[34]. In 2004, Jenkins et al. Reported a one-pot Fischer indole synthesis in ChCl/ZnCl2 type DES to synthesize indole derivatives in high yields (∼ 91%)[35]. Subsequently, K König et al. Reported a Suzuki reaction based on sugar/urea derivative/salt-type DES, which provided a new idea for the cross-coupling reaction[36]. In 2014, Garc García-Álvarez et al. introduced ChCl/Urea type DES into the cycloisomerization reaction of γ-alkynoic acid, which can prepare cycloenol lactone under the catalysis of Au (I) complex. The catalytic system can still maintain a yield of more than 90% after four cycles, and the reaction conditions are mild, reflecting the good compatibility of DES for the reaction[37]. Recently, Wang Yinglei et al. Used ChCl/lactic acid DES as reaction medium and catalyst to synthesize chromene. The research results showed that chromene and its derivatives could be prepared in high yield of 85% ~ 93% through condensation reaction. DES could be recycled at least five times without significant decrease in yield[38].
Polar organometallic reagents (such as Grignard reagents and organolithium reagents) are sensitive to air and water, which greatly limits their application in laboratory and industrial production. It has been the goal of researchers to find a kind of organometallic reaction with polar metal reagents under mild conditions. In 2014, Hevia and Garc García-Álvarez et al. Jointly reported the first chemoselective addition reaction of ketones in air using Grignard reagents and organolithium reagents at room temperature using ChCl-based DES as a green reaction medium[39]. The reaction can be completed in 2 – 3 s and gives tertiary alcohols in up to 90% yield, and the substrates of the reaction can be aliphatic ketones or aromatic ketones, and the polar metal reagent can also be alkyl or aryl substitution (Figure 2A). In the same year, Capriati's team used butyl lithium to regioselectively lithiate diphenyltetrahydrofuran, and then added electrophilic reagents to DES at room temperature to obtain ortho-substituted products in high yields[40]. These reports open a new frontier in organometallic chemistry, broadening the practical applications of polar metal reagents under environmentally benign conditions (DES green solvent, air, room temperature). Subsequently, Garc García-Álvarez et al. Extended the reaction system to non-reactive imine and nitrile substrates[41,42]. For example, they used ChCl/glycerol (Gly) type DES as solvent to carry out nucleophilic addition reaction of organolithium to imine at room temperature in air to obtain secondary amine in 73% -95% yield. Organolithium can also be used to carry out ultra-fast selective addition reaction to benzonitrile substrates, and the obtained imine can be hydrolyzed to obtain aromatic ketones (Figure 2b). With the development of gas-moisture compatible polar organometallic reactions, in 2020, they reported the ultra-fast selective amidation of esters mediated by lithium amide in DES and other sustainable solvents.A new sustainable access to formamide has been established by using green solvents to cleave the carbon-oxygen bond of a range of esters in air[43]. In 2021, Capriati et al. Used the nucleophilic addition of Grignard and organolithium reagents to esters in ChCl/Urea DES to prepare tertiary alcohols. This method showed a wide substrate range, and the addition reaction proceeded rapidly (20 s) and completely at room temperature in air, with a yield of 98% (Fig. 2C)[44]. These reactions can be carried out smoothly in the strong hydrogen-bonded DES medium under heterogeneous conditions (considered to occur at the interface between the organic and DES), which is of great significance for organic synthesis under environmentally friendly conditions[45⇓~47].

4 Application of DES in Polymer Synthesis

Ionic liquids have been used as polymerization solvents to eliminate or reduce the hazards of volatile organic solvents[48]. However, it also has some problems, such as toxicity, high price and difficult preparation, which limit its wide use in polymerization. As a new type of ionic liquid, DES not only retains the advantages of ionic liquids, but also has the characteristics of low price, simple preparation, good biocompatibility and so on. In recent years, DES has been widely used in different types of polymerization as a new green reaction medium, and the research progress of its application in the field of polymer synthesis will be introduced in detail below.

4.1 Condensation polymerization

In 2010, del Monte and Guti Gutiérrez first used DES as a solvent for the polycondensation reaction. ChCl/ethylene glycol (EG) DES was used as a solvent for the polycondensation reaction of resorcinol and formaldehyde, and it was found that the condensation degree of the resin prepared in DES with excellent solvating ability was higher than that prepared in aqueous solution[49]. Subsequently, they designed different types of DESs for the polycondensation reaction, including resorcinol/ChCl type, resorcinol/3-hydroxypyridine/ChCl type, resorcinol-4-hexylresorcinol-p-nitrophenol/ChCl-type, resorcinol-2-cyanophenol or 4-cyanophenol/ChCl-type, etc[50][51][52][53]. The prepared DES plays multiple roles (solvent, structure-directing agent, etc.) during the polycondensation reaction, and further carbonization of the obtained resin can obtain hierarchical porous carbon materials, which have large pore surface area, excellent CO2 adsorption capacity, and electrical conductivity[51][54][55]. In 2012, del Monte and Serrano et al. First prepared DES based on 1,8-octanediol and local anesthetic lidocaine, and then added citric acid for polycondensation to prepare biodegradable poly (octanediol-co-citrate) (POC) elastomer loaded with lidocaine, and the obtained elastomer copolymer had high drug loading and controlled drug release properties[56]. DES plays multiple key roles in this process, which not only provides most of the raw materials needed for the synthesis of elastomers, but also improves the solubility of citric acid so that the polycondensation reaction can proceed smoothly. Subsequently, as shown in Figure 3, they replaced lidocaine with quaternary ammonium salt or quaternary phosphonium salt for the preparation of DES, and used a similar polycondensation method to synthesize POC polyester elastomer[57]. The elastomer not only has good cytocompatibility, biodegradability and mechanical properties, but also has excellent antibacterial properties due to the introduction of quaternary ammonium salt.
In 2018, Rajan et al. Prepared a new amphiphilic polyester poly (ε-cp-co-CA) by polycondensation of ε-caprolactone and citric acid using DES composed of choline chloride and citric acid as solvent, and used it for the delivery of hydrophobic anti-tumor drug camptothecin[58]. In 2020, Mota-Morales and Lian et al. Used DES composed of ZnCl2 and acetamide to dissolve lignin[59]. Both the lignin solution and its regenerated fraction in DES can be used to replace part of the phenol in the condensation polymerization of phenol and formaldehyde to introduce biomass in the resulting phenolic resin. The mixed solution of DES and lignin has multiple functions, including as a source of natural polyphenols, as a component and filler for polycondensation with formaldehyde, and as a source of zinc to accelerate the polycondensation reaction. This work is expected to further expand the application value of lignin. Recently, Wu et al. Used a new type of amino acid-based DES based on L-aspartic acid and urea to polycondense with formaldehyde. The DES component is not only a polycondensation monomer, but also a solvent and dopant to prepare hierarchical porous carbon materials with high heteroatom doping content and apply them to high-performance supercapacitors[60]. Sousa et al. Reported the design of a urea/zinc acetate-type DES system for innovative chemical recycling of bio-based poly (vinyl 2,5-furandicarboxylate) (PEF)[61]. PEF can be efficiently recovered by glycolysis in DES, and the monomer can be re-prepared by polycondensation in DES with a yield of 91%. The DES has the ability to catalyze glycolysis and esterification reactions, and can also be extended to other polyester applications.

4.2 Free radical polymerization

4.2.1 Thermal initiation

In order to carry out homogeneous traditional free radical polymerization in DES, the first thing is to ensure that DES and monomers have good compatibility. Considering the ionic characteristics of DES, the most commonly used monomers are acrylic acid (AA) or methacrylic acid (MAA).The carboxyl group in the monomer will participate in the formation of DES, and the double bond can participate in the polymerization. This kind of DES containing Polymerizable groups is usually called Polymerizable DES (PDES)[62]. In 2011, del Monte and Luna-B Bírcenas first reported the radical polymerization of PDES, that is, the preparation of gel materials by front-end polymerization of ChCl/AA and ChCl/MAA-type PDES in the presence of thermal initiator dibenzoyl peroxide and crosslinking agent ethylene glycol dimethacrylate[63]. The gel obtained by this method is more transparent and homogeneous, and can achieve a higher conversion rate (~ 85%) than the gel obtained in the organic solvent dimethyl sulfoxide (DMSO). In addition, the results showed that the front-end polymerization could not be successfully achieved by using talc, lauric acid and stearic acid instead of ChCl, which indicated that ChCl-based PDES had a significant role in promoting the polymerization[64]. In 2013, Luna-B Bírcenas and del Monte et al. Uniformly dispersed nitrogen-doped multi-walled carbon nanotubes into ChCl/AA-type PDES, and then obtained PAA-CNxMWCNT composites with macroporous structure by free radical polymerization[65]. The introduction of DES can avoid the use of organic solvents, reduce the reaction temperature and improve the conversion. In addition, DES can be recycled and reused, showing a "green" cycle. Mota-Morales and Luna-B Bírcenas used lidocaine as a hydrogen bond acceptor to form PDES with acrylic acid or methacrylic acid, and then added thermal initiator and crosslinking agent to carry out free radical front-end polymerization to prepare polymer-drug complexes with drug delivery effect in one pot[66]. The introduction of DES makes lidocaine uniformly dispersed in the complex, and the introduction of carboxyl-containing components endows the complex with obvious pH responsiveness. The experimental results show that lidocaine can respond to different pH values and ionic strengths and sustain release in a controlled manner. Recently, Yan et al. Successfully prepared a conductive composite hydrogel by front-end polymerization after mixing ternary PDES (ChCl/AA/AAM) and starch[67]. Due to the good solubility and dispersibility of PDES to starch granules, there is a strong interfacial interaction between starch and polymer hydrogel network, which significantly improves the mechanical properties and electrical conductivity of the composite hydrogel.

4.2.2 Photoinitiation

Compared with thermally initiated polymerization, photo-initiated polymerization has the advantages of environmental friendliness, high production efficiency, low energy consumption, mild reaction conditions, and patterning. The polymerization of PDES can also be carried out under photoinitiation, and the Mecerreyes team first reported the polymerization of PDES initiated by ultraviolet light in 2016, and the prepared polymer was used for the capture of CO2[68]. Subsequently, Pojman's group used real-time Fourier transform infrared spectroscopy to study the photopolymerization kinetics of ChCl/AA and ChCl/MAA-type PDES, as well as methyl methacrylate (MMA) monomer in ChCl/isobutyric acid-type DES in detail[69]. It was found that the polymerization rate was greatly improved in both DES and PDES systems compared with the organic solvent system, and they attributed the polymerization acceleration to the high viscosity, hydrogen bonding and polarity of the DES system. He Minghui and his collaborators have developed a series of conductive polymer materials using photoinitiated polymerization of PDES for flexible and stretchable electronic devices such as sensors, flexible electrodes and wearable devices[70⇓⇓~73]. In 2017, they first mixed ChCl/AA-type PDES with photoinitiator 2959 and crosslinker polyethylene glycol diacrylate, and then exposed to 365 nm UV light for 30 s through a pre-designed mask to prepare patterned transparent conductive elastomers by in-situ photopolymerization (Figure 4A, B). This transparent PDES is used as an ink to prepare conductive paper with the help of a traditional screen printing process (Figure 4 C). In addition, they also sprayed PDES through a syringe or solution spinning, and prepared highly transparent piezoresistive spheres (Fig. 4D) or wearable transparent conductive fibers (Fig. 4E) by rapid in-situ polymerization under UV light irradiation for the construction of optoelectronic devices. Because PDES has the triple functions of reaction medium, precursor and conductive filler, it can be quickly cured under UV irradiation, which provides a new path for the production of highly transparent conductive materials, and can be considered as a fast, VOC-free green manufacturing process. Conductive materials based on PDES can maintain long-term stability, and have good frost resistance, thermal stability and solvent resistance, which have broad application prospects in human motion, medical monitoring, robotics and other fields.
In 2020, they introduced multiple hydrogen bonds into PDES to construct self-healing materials containing dynamic bond networks. Firstly, two kinds of PDES monomers, ChCl/acrylamide and ChCl/maleic acid (Figure 5), were designed and synthesized, and the supramolecular network structure was constructed by multiple intramolecular and intermolecular hydrogen bonds of hydroxyl, carboxyl and amino groups, and the transparent conductive elastomer was prepared by in-situ copolymerization initiated by UV light[74]. The material combines high transparency (95.1%), good tensile properties (∼ 450%), high ionic conductivity (4.0×10-4S/cm), and good self-healing ability (94% self-healing efficiency at room temperature and 73% self-healing efficiency at − 23 ° C). More importantly, the elastomer can still maintain excellent transparency, mechanical properties, electrical conductivity and self-healing properties in the temperature range of -23 ~ 60 ℃, based on which researchers have manufactured deformation sensors that can work in a wide temperature range (-40 ~ 60 ℃). This construction method is expected to be extended to the field of stretchable electronics and flexible optoelectronic devices in various extreme temperature environments.
In addition, He Minghui et al. Introduced natural phytic acid molecules (PA) with high hydrogen bond density into ChCl/AA-type PDES, and prepared transparent conductive elastomers with high transparency (93%), excellent tensile properties (∼ 1300%), high ionic conductivity (7.8×10-4S/cm) and excellent self-healing ability (91.5% self-healing efficiency at room temperature) by using the supramolecular dynamic network formed by the high-density hydrogen bonds present in the system (Figure 6A)[75]. The deformation sensor prepared by the elastomer can be used for monitoring human activities, and the elastomer can still work normally after self-repair. They also replaced ChCl with tetramethylammonium chloride (TMAC), added an appropriate amount of PA as a hydrogen-bonding crosslinking agent to form a TMAC/AA/PA type PDES monomer, and then prepared a conductive elastomer with high mechanical strength (31.21 MPa) and excellent tensile properties (~ 3645%) through rapid and efficient in-situ photopolymerization (Fig. 6B)[76].
The elastomer also exhibits high transparency (> 94%), good electrical conductivity (7.0×10-5~4.0×10-4S/cm), and fast self-healing ability (electrical healing efficiency of 99% in 0. 26 s), which can be used as a strain sensor for monitoring human motion and has broad application prospects in stretchable electronic devices.
Recently, He Minghui et al. Designed choline dihydrogen citrate/AA type PDES, and prepared a self-adhesive dry ionic conductor with a maximum adhesive strength of 3.5 MPa through a supramolecular eutectic polymer obtained by in situ photopolymerization[77]. The ionic conductive elastomer with high mechanical strength and fast self-healing ability was prepared by the copolymerization of ChCl/AA type PDES and 2-acrylamide-2-methylpropanesulfonic acid[78]. In addition, You Yezi et al. Made PDES from diethylaminoethyl methacrylate and (3-aminopropyl) trimethoxysilane as HBA and lauric acid as HBD, and successfully developed an underwater adhesive with dynamic adhesion, self-healing properties and recyclability[79]. Inspired by chameleon skin, Tian et al. Embedded cellulose nanocrystals into ChCl/AA/PA PDES through in situ polymerization to form a highly scalable artificial skin with strain-induced dynamic optical and electrical properties, excellent adhesion and self-healing ability[80].

4.2.3 Enzyme catalysis

As early as 1994, Gill and Vulfson found that proteases could remain active in heterogeneous eutectic media and could be used to catalyze the synthesis of oligomeric peptides[81]. But it was not until 2008 that Kazlauskas and Srienc reported the first case of enzyme-catalyzed transesterification in DES[82]. They found that Candida antartica could maintain excellent catalytic activity in ChCl-based DES, showing better catalytic effect than conventional organic solvents, and that substances such as urea and alcohols in DES would not affect the activity of the enzyme. Since then, DES has been widely used in biocatalytic organic reactions, including transesterification, aminolysis, hydrolysis, alcoholysis, etc[83]. In addition, Housaindokht and Monhemi et al. Used molecular dynamics simulation to reveal why Candida Antarctica lipase B could remain stable in DES with high concentration of urea, but rapidly denature in aqueous system[84]. Unlike urea, which directly disrupts the internal hydrogen bonds of protein molecules in aqueous phase and causes their denaturation, they found that urea and ChCl can form stable hydrogen bonds, which reduces the diffusion coefficient of urea and prevents it from approaching the protein region. More importantly, urea and ChCl can also form hydrogen bonds with protein surface residues, further improving the stability of the enzyme. However, there are few reports on the use of DES in enzyme-catalyzed polymerization. It was not until 2016 that Mota-Morales and Luna-B Bírcenas et al. First reported the enzyme-catalyzed radical polymerization of acrylamide monomer in two DESs, ChCl/Urea and ChCl/Gly, with a catalytic system consisting of horseradish peroxidase (HRP), H2O2, and 2,4-pentanedione[85]. Although the urea in DES can denature the protein and the activity of HRP is slightly reduced, it can still catalyze monomer polymerization at room temperature and 50 ℃, and the monomer conversion rate at room temperature is close to 100%. Compared with the polymerization system in pure water, the molecular weight of the polymer obtained in ChCl/Urea is close to that in pure water, while the molecular weight distribution is narrower. With the help of ChCl/Gly system, which has a low freezing point, polyacrylamide can be successfully synthesized at a low temperature of 4 ℃, which can not be achieved in pure water. These results suggest that the introduction of DES provides more possibilities for enzyme-catalyzed polymerization at low temperature. Recently, Taka Takaç et al. Reported the laccase-catalyzed oxidative polymerization of aniline with DES as a template for the preparation of polyaniline[86]. They screened a variety of DES and found that D, L-menthol/n-decanoic acid had the best effect. Although DES and aniline have adverse effects on the activity of laccase, the synthesis of polyaniline can be achieved by reducing the concentration of reactants. In addition, the pH and temperature of the reaction medium, the concentration of aniline and the stirring speed have great influence on the polymerization. This study opens up a new way to synthesize polymers by using the template effect of DES, but the mechanism of DES in the polymerization process needs further study.

4.2.4 Reversible Deactivation Radical Polymerization (RDRP)

Reversible deactivation radical polymerization (RDRP) has the advantages of both traditional radical polymerization and living polymerization. It can prepare polymers with controllable molecular weight and molecular weight distribution, and can precisely design the structure and sequence of polymers[87⇓⇓~90]. RDRP methods mainly include Iniferter polymerization, nitroxide stabilized radical polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, etc. Traditionally, organic solvents are usually used to carry out RDRP, and in recent years, there have been many studies on the use of DES instead of organic solvents for RDRP.
In 2016, the Coelho team first reported the use of DES composed of ethanol, ChCl, and Urea for the SARA ATRP reaction of methyl acrylate (MA)[91]. The results showed that the addition of ethanol made this DES a good solvent for the polymerization system, and the kinetic results showed that the polymerization was controllable. The prepared PMA has low dispersity (-D < 1.2), and can be used for chain extension reaction to prepare diblock copolymer (fig. 7). In addition, the catalyst in the system can be recovered from the final reaction solution (recovery rate of 62%) and reused for at least two ATRP reactions. Subsequently, they also reported the SARA ATRP polymerization of three hydrophilic monomers in DES, including 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), and (3-acrylamidopropyl) trimethylammonium chloride (AMPTMA)[92]. Polymerization was carried out at 30 ° C with Na2S2O4 as the reducing reagent and only ChCl/Urea type DES as the solvent. The polymerization system shows the characteristics of rapid polymerization and good control of the molecular weight of the polymer, and the polymer shows good low dispersity (-D < 1.2) in the reaction process, and can also be used for chain extension reaction to prepare a diblock copolymer. In 2017, Xue Zhigang et al. Successfully carried out the ATRP reaction of MMA without adding additional ligands, using FeBr2 as catalyst, DES as solvent and ligand[93]. Compared with the conventional iron-catalyzed ATRP system, the system is more environmentally friendly, does not need additional ligands, and also has the characteristics of controlled polymerization (narrower molecular weight distribution and successful chain extension reaction). Then, they used glycerol/1,3-dimethyl-2-imidazolidinone DES for the AGET ATRP reaction of MMA[94]. Under the catalysis of iron salt, the polymerization system shows high reaction rate, good controllability and "activity" characteristics. This iron-catalyzed ATRP system is expected to be used in the synthesis of biomedical polymer materials due to the avoidance of the use of toxic copper catalysts and organic solvents.
In 2019, Presa Soto and Garc García-Álvarez jointly reported the successful occurrence of the ARGET ATRP reaction of MMA under air atmosphere in ChCl/Gly type DES[95]. Tin isooctanoate was used as reductant and CuCl2 as catalyst in homogeneous system, while tin isooctanoate was used as reductant and MOF material containing Cu (Ⅱ) as catalyst in heterogeneous system. Polymerization kinetics and chain extension experiments showed that the molecular weight of the polymer increased linearly, and PMMA had a low dispersion (-D ≤ 1.2). In addition, both DES and Cu (Ⅱ) -MOF catalysts could be recovered and reused after polymerization, and could still effectively catalyze the polymerization reaction in six consecutive cycles. However, the polymerization controllability of the catalytic system for other hydrophobic monomers (styrene, 4-vinylpyridine, 2-vinylpyridine) is poor, which is manifested by the large difference between the theoretical molecular weight and the actual molecular weight and the wide molecular weight distribution. In 2020, Mahyari et al. Designed and synthesized a carbon nitride nanosheet photocatalyst (Cu-ACES@g-C3N4) that could be highly stably dispersed in ChCl/Urea-type DES and chelated with Cu (II) on the surface, and used it to catalyze the ATRP reaction of styrene and MMA under visible light, obtaining a polymer with low dispersion (-D < 1.45), and both DES and catalyst could be recycled, but the conversion of monomer was low (< 43%)[96].
Compared with the ATRP reaction, the research on the use of DES in RAFT polymerization system started late. It was not until 2019 that Singha's team reported the RAFT polymerization of HEMA monomer in ChCl/Urea-type DES using 4-cyano-4- [ [ (dodecylthio) thione methyl] thio] valeric acid (CDCPA) as the RAFT reagent and 4,4 ′ -azobis (4-cyanovaleric acid) (ACVA) as the thermal initiator (Figure 8 a)[97]. Differential scanning calorimetry was used to study the polymerization kinetics. It was found that the polymerization rate of HEMA could be accelerated in DES, the reaction conversion could reach more than 90%, and the molecular weight distribution of the polymer was moderate (-D = 1.40). In addition, they also successfully realized the block copolymerization of HEMA and MMA in DES (Fig. 8B). Interestingly, PHEMA-b-PMMA was assembled into vesicles in DES due to the large solubility difference between the two polymer chains in DES, which also indicated that DES was expected to be a new solvent for polymerization-induced self-assembly (PISA). In 2020, Serra et al. Realized the RAFT polymerization of six hydrophobic monomers (MMA, St, MA, n-butyl acrylate n-BA, vinyl chloride VC, vinyl acetate VAc) in hydrophobic DES (D, L-menthol/myristyl alcohol) based entirely on natural compounds[98]. The experimental results showed that the conversion of all monomers was not lower than that of conventional RAFT polymerization, except for St and VC systems (the highest conversion was 80% and 38%, respectively). The polymerization reaction showed controllable characteristics, except for PVC (-D = 1.33), the other polymers had low dispersion (-D < 1.13). In addition, the activity of the obtained homopolymer chain end to continue initiating polymerization was unambiguously confirmed by the preparation of a narrowly distributed PMMA-b-PMA block copolymer (-D = 1.07). Recently, Yu et al. Successfully realized DES-mediated visible-light-driven RAFT polymerization in air environment[99]. DES composed of tetrabutylammonium chloride and ethylene glycol was used as a reaction solvent for a variety of monomers. Photopolymerization was carried out in DES with trithiocarbonate as a chain transfer agent. Compared with the reaction in DMSO, the apparent polymerization rate constants of most monomers were increased and the dispersion was lower. This study shows that DES is expected to be a green medium for promoting photoinduced RAFT polymerization under conditions that do not require additives and degassing processes.

4.3 Anionic polymerization

Since 1956, Professor Szwarc first reported the anionic polymerization of styrene and proposed the concept of living polymerization, the research on living anionic polymerization has been gradually deepened[100]. Living anionic polymerization can efficiently prepare polymers with well-defined molecular weight and very narrow molecular weight distribution, and precisely design their topology[101]. However, impurities such as water, oxygen and carbon dioxide in the air can easily deactivate the active center of anionic polymerization, which usually requires harsh reaction conditions (anhydrous, oxygen-free and low temperature) and the use of highly toxic organic solvents. At present, the main methods of living anionic polymerization are inert gas protection and high vacuum experimental technology[102]. These methods are highly demanding for operators, so it is a challenge to explore anionic polymerization under environmentally friendly conditions and reduce the difficulty of experimental operation.
As mentioned above, researchers have successfully used organometallic reagents (Grignard reagents, organolithium reagents) to alkylate or arylate unsaturated substrates in an air atmosphere at room temperature using DES as a solvent[39⇓⇓⇓⇓~44]. Based on this, Hevia and Garc García-Álvarez et al. First attempted to initiate anionic polymerization of vinyl monomers with organolithium reagents in DES in 2019[103]. First, they introduced ChCl-based DES (ChCl/EG, ChCl/Gly, ChCl/Urea, etc.) as a polymerization medium to initiate the homopolymerization of various vinyl monomers (St, para-substituted styrene, 2-VP, 4-VP) with organolithium reagents (n-BuLi, sec-BuLi, tert-BuLi, etc.) in air atmosphere. By adjusting the experimental conditions, it was found that the ultrasonic dispersion and the concentration of the reaction solution had great influence on the reaction. Among the polymers synthesized, polystyrene has the highest conversion (< 90%), low dispersion (-D of 1.1 ~ 1.3), but low molecular weight (2.0 ~ 4.0 kg/mol) (Fig. 9a). In addition, they found that the synthesized polystyrene lithium active chain showed hydrolysis resistance up to 1.5 H in ChCl/Gly. Based on this stability of the living chain, the authors then explored the possibility of preparing copolymers in DES, and successfully prepared random copolymer PS-co-P2VP (Figure 9B) and block copolymer PS-b-P2VP (Figure 9C) according to the optimized optimal reaction conditions. This work breaks the recognition that anionic polymerization can only be carried out under traditional harsh conditions, and initially explores the application of DES in the field of green and sustainable polymerization. However, it should be noted that unlike the rapid organometallic reaction, anionic polymerization requires a longer reaction time, during which DES will react with the active center, resulting in a lower molecular weight and a broader molecular weight distribution of the polymer. In addition, the polymerization kinetics of vinyl monomers initiated by organolithium reagents in DES and the difference between the anionic polymerization behavior in traditional solvents need to be further studied.

4.4 Electrochemical polymerization

Ionic liquids have been used as alternative solvents for the synthesis of conducting polymers, but their high price, tedious synthesis and non-biodegradable disadvantages have greatly limited their application[23]. DES has the same characteristics as ionic liquids, such as wide working temperature range, wide electrochemical window and good chemical stability, but it is easier to prepare, cheaper and biodegradable[104][105]. Therefore, in previous electrochemical studies, DES has been used as an electrolyte to promote cell efficiency, as a solvent to synthesize electrode materials with special functions, and as an electrodeposition agent for metals, alloys and semiconductors[106⇓~108]. Subsequently, the research on electrochemical polymerization in DES has gradually increased.
In 2012, Silva et al. First explored the synthesis of conductive polymer polyaniline in DES (ChCl/EG, ChCl/Gly, ChCl/Urea) as the reaction medium, and the results showed that the polyaniline film synthesized in DES had good electrical activity, and the conductivity was significantly increased (σ ≈ 63 S/cm)[109]. They suggested that this may be due to the choline and HBD in DES breaking the interpolymer hydrogen bond network, resulting in the increase of more random conformations. In addition, the viscosity and conductivity of the solvent also affect the electrochemical polymerization. At the same time, they also tried to synthesize polyaniline in ChCl/1,2-propanediol type DES[110]. The formation of polyaniline was verified by cyclic voltammetry, and the polymer was characterized by scanning electron microscopy and ultraviolet-visible absorption spectroscopy. These studies have initially proved that electrochemical polymerization can be carried out in environmentally friendly DES, and there are still more reports on the synthesis of conductive polymers in DES. For example, Brett et al. Carried out electrochemical experiments using a three-electrode cell, and for the first time realized the electrochemical polymerization of 3,4-ethylenedioxythiophene (EDOT) to prepare PEDOT in a variety of DESs[111,112]. It was found that the electrochemical polymerization in pure DES was not effective, and a certain amount of perchloric acid was needed to make the polymerization effective. Ascorbic acid was also used as a model molecule to study the sensing performance of the PEDOT film modified electrode, and the PEDOT film prepared in ChCl/Gly DES had the best electrocatalytic performance and sensing characteristics, with a sensitivity of 245μA/cm2/mmol/L and a detection limit of 0. 9 μmol/L. Furthermore, they continued to expand the electrochemical polymerization in DES to synthesize poly (methylene blue) with different nanostructures, and compounded it with carbon nanotubes to form new nanomaterials to construct highly sensitive electrochemical sensors[113⇓~115].
Similarly, Woi et al. Studied the electrochemical polymerization of melamine in different ChCl-based DESs, and successfully prepared a new type of DES-functionalized electroactive polymelamine (PME) film, in which the ChCl/EG-type DES-functionalized PME film showed superior performance[116]. The sensing performance of the PME membrane synthesized in DES is better than that of the PME membrane synthesized by the traditional electrolyte, and the composite material prepared by combining the PME film with the functionalized multi-walled carbon nanotube modified by the glassy carbon electrode can be used for selectively detecting dopamine. In addition, Yavuz team reported the occurrence of electrochemical polymerization of pyrrole in ChCl/Urea-type DES, and the polymerization mechanism is shown in Fig. 10[117]. The results show that polypyrrole is uniformly deposited on the surface of the graphite composite electrode to form a bubble-like structure, and the composite electrode material exhibits a specific capacitance as high as 535 F/G, and the capacitance retention rate does not decrease significantly after 1000 cycles, which is a potential material for supercapacitors. Brett et al. First realized the electrochemical polymerization of neutral red in ChCl/EG-type DES, and generated a film with nanostructure morphology on a polymer-modified glassy carbon electrode[118]. It was found that the polymer film prepared in DES medium was more stable and resistant to corrosion than that obtained in water medium, and showed higher sensitivity when H2O2 and ascorbic acid were used as standard analytes.

4.5 Other polymerization

In addition to the polymerization reactions mentioned above, DES is also used in ring-opening polymerization and oxidative polymerization. In 2012, Coulembier et al. First introduced the concept of DES into ring-opening polymerization[119]. They found that L-lactide (L-LA) could be mixed with trimethylene carbonate (TMC) to form a eutectic at room temperature, and the bulk ring-opening polymerization of monomers could be catalyzed by adding initiator benzyl alcohol and organic base catalyst 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU). PLLA homopolymer can be obtained at room temperature due to the nucleation and gradual crystallization of PLLA chains in the eutectic. If the polymerization system is heated to 60 ℃ or a small amount of good solvent CH2Cl2,TMC is added at room temperature, it will begin to participate in the polymerization, thus obtaining gradient copolymer P (LA-g-TMC). In 2015, del Monte et al. Used the eutectic mixture formed by methanesulfonic acid and 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) as a bifunctional catalyst to catalyze the ring-opening polymerization of ε-caprolactone (ε-CL)[120]. In the absence of initiator and solvent, the ring-opening polymerization can be completed at a low temperature (37 ℃) for 2 H, and the obtained PCL has a moderate molecular weight (6. 1-9. 9 kg/mol), a moderate dispersion (-D = 1. 5-1. 6), and a high crystallinity (98%). Subsequently, they also found that the eutectic mixture could also be formed by mixing L-LA and ε-CL at a molar ratio of 30:70[121]. PLA/PCL macroporous materials for oil-water separation were prepared by ring-opening polymerization of the eutectic mixture using benzyl alcohol as initiator, methanesulfonic acid and DBU as catalyst.
In 2017, Lee and collaborators first reported the oxidative polymerization of 3-octylthiophene catalyzed by FeCl3 in a variety of DES[122]. Studies have shown that the polymerization rate is much higher with ChCl/Urea-type DES than with ionic liquids or traditional organic solvents. For example, 100% conversion can be achieved in DES at 25 ° C for 10 H, while only 87% conversion can be achieved in CHCl3 at 25 ° C for 48 H. Recently, Tashkhourian et al. Investigated the oxidative polymerization of dopamine into PDA particles in two different DES, ChCl/EG and ZnCl2/EG[123]. The experimental results show that DES has the potential to be used to synthesize PDA particles with stable shapes (porous capsules, sponges, and flower-like structures), composition, and size. DES-assisted dopamine polymerization as well as PDA particles in powder state will have many uses in advancing innovative functional materials and devices.

5 Conclusion and prospect

Since its inception in 2003, DES has been widely used in many fields, including extraction separation, organic synthesis, polymerization and so on. In addition to some common properties with ionic liquids, DES has its own unique advantages, such as cheap and widely available raw materials, simple preparation, low toxicity, biodegradable and so on, which has become a very potential green reaction medium. There is a wide variety of DESs, and different components can be designed on demand to prepare specific solvents with different physicochemical properties. As an alternative to traditional organic solvents, DES has been used in condensation polymerization, radical polymerization, anionic polymerization, electrochemical polymerization, ring-opening polymerization and oxidative polymerization, which provides a new idea for the sustainable synthesis of more functional polymer materials. In addition, polymerizable eutectic solvents (PDES) can be prepared by introducing reactive chemical groups into DES, and a variety of functional materials can be obtained by in-situ polymerization under mild conditions, which has great potential in the fields of optoelectronic devices, self-healing materials and conductive elastomers.
However, up to now, there are few studies on the polymerization mechanism in DES. In view of the obvious differences in physical and chemical properties between DES and traditional organic solvents, the study of polymerization mechanism will be of great significance to clarify the role of DES in the polymerization process. On the other hand, the controllability of molecular weight and molecular weight distribution of polymers prepared in DES is not comparable to that of traditional organic solvents, which still needs further exploration. In addition, the recyclability and recycling of DES are also very important for the greening of the reaction process. Finally, although the composition of DES is mostly derived from natural renewable molecules, the monomers currently used are still mainly of petrochemical origin. If DES can be combined with monomers from biomass, the synthesis route of polymer materials will be more in line with the development strategy of "carbon peak, carbon neutralization" actively advocated by our country[124][125⇓~127]. To sum up, in recent years, DES has made important progress in polymerization and the synthesis of functional polymer materials, and has gradually shown new vitality with the intersection of disciplines. It can be predicted that with the deepening of research on green chemistry, the application of DES in the field of polymer synthesis will enter a new stage, and make new contributions to the development of sustainable, efficient, economical and environmentally friendly polymer synthesis processes.

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Funding

National Natural Science Foundation of China(21774081)

Natural Science Foundation of the Jiangsu Higher Education Institutions of China(20KJA150009)

Beijing Key Lab of Special Elastomeric Composite Materials, and the Priority Academic Development of Jiangsu Higher Education Institutions.

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