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ARGET ATRP of styrene with low catalyst usage in bio-based solvent γ-valerolactone

  • Qianqian Zhu , Tianchen Song , Jiaxin Zhao , Gang Gao , Yixin Xiang , Jiangang Gao and Xianrong Shen EMAIL logo
Published/Copyright: May 31, 2024
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e-Polymers
From the journal e-Polymers Volume 24 Issue 1

Abstract

The application of bio-based solvents for living radical polymerization has been a hot topic in recent year. In this article, γ-valerolactone (GVL), a bio-based solvent as green media for ARGET atom transfer radical polymerization (ATRP) of styrene (St) were investigated. We first conducted polymerization of St in γ-valerolactone using copper(ii) bromide as the catalyst, tris(2-pyridylmethyl) amine as the ligand, and only sodium ascorbate as reducing agent. The polymerization achieved moderate conversion; however, the controllability of polymerization was not very good, providing a polymer with a broad molecular weight distribution (M w/M n > 1.30). When sodium carbonate is introduced, excellent results were obtained providing high yields and low M w/M n values under very low catalyst usage (∼5 ppm). 1H NMR spectroscopy, chain extension, and MALDI–MS experiments confirmed the final polymer chains with high fidelity. The use of GVL solvent opens a new route for the easy synthesis of PS through ARGET ATRP with low catalyst usage conditions.

Keywords: styrene polymerization; green solvent; ARGET ATRP; γ-valerolactone; living radical polymerization

1 Introduction

Atom transfer radical polymerization (ATRP) is a classic method for the precise design and synthesis of functional polymers with different topologies, such as block, comb, star, ladder, due to its mild reaction conditions, wide range of monomers, and variety of polymerization implementation methods (1,2). ATRP technology employs transition metal catalysts with low redox potential to reversibly regulate the breaking of carbon–halogen bonds in the ATRP initiator and to construct a dynamic equilibrium between the reactive radicals and the dormant species, so that the polymerization system is in good balance (3).

The dynamic equilibrium between active radicals and dormant species is established to keep the concentration of free radicals in the polymerization system low, effectively inhibit the chain transfer and chain termination reactions, and control the quality and structure of polymer molecules. However, the shortcomings of traditional ATRP reaction systems, such as high catalyst toxicity, high cost, and the difficulty of catalyst removal from the products, have seriously restricted the theoretical and applied development of ATRP technology (4), and the development of catalytic systems with high activity, low toxicity, and low cost, and the in-depth study of the reaction process of ATRP are of great significance in accelerating the realization of the industrialization of ATRP technology (5).

For this purpose, new ATRP catalytic systems have been developed to reduce the catalyst concentration to the ppm level, such as electron transfer regeneration activator (ARGET) ATRP (6), continuous activator regeneration initiator ATRP (7), supplemental activator and reducing agent ATRP (8), single electron transfer living radical polymerization (9), electrochemically-mediated ATRP (10), and photochemically-mediated ATRP (11,12).

The ARGET ATRP polymerization process is very similar to conventional free radical polymerization and is very promising for industrialization. The high valence metal catalyst accumulated in the polymerization process can be continuously reduced to low oxidation activator by adding excess reductant, which can effectively reduce the amount of metal catalyst in the system (8,13). At the same time, the excess reductant can consume a small amount of oxygen and oxidant in the system, so the system does not need to be strictly degassed before polymerization, which greatly simplifies the polymerization operation. Currently, the amount of copper catalyst can be reduced to 5 ppm in MA’s ARGET ATRP process, and as low as 10 ppm in styrene’s (St) ARGET ATRP (14). Reducing agents used in the ARGET ATRP, besides Sn (EH)2 and ascorbic acid, other noticeable reducing agents such as thiourea dioxide, guanidine, alcohols, and commodity products such as caffeine also have been reported (15–17). The choice of polymerization conditions, metal catalysts, ligand, and reducing agent types are the key to the successful construction of the system (18).

The use of solvents also plays an important role in ARGET ATRP catalytic systems to promote the solubilization of polymers and catalysts and to improve the controllability of the reaction (19,20). In some ATRP catalytic systems, the action of the solvent on the catalyst or some additives can modulate the equilibrium of the ATRP reaction, thus influencing the amount of catalyst and the rate of polymerization reaction (21). Current regulations are urging industries to use bio-based solvents because they are less toxic, environmentally friendly, and biodegradable. There is a growing area of interest in the green chemistry of bio-based solvents, there are many examples of the sustainability movement in free radical polymerization (22–30).

It is worth to notice that the ATRP of acrylates, methacrylates, has been successfully performed in bio-based solvents such as 2‐methyltetrahydrofuran, bio-based dl-menthol/1-tetradecanol eutectic mixture (23,29). Recently, our research group has demonstrated the possibility of using the ethyl lactate and γ-valerolactone (GVL) as green solvents for the preparation of acrylates, methacrylates resin by ATRP (24,27). However, attempts to apply these solvents mentioned above to the living radical polymerization of St have struggled to achieve satisfactory results. Yu et al. attempted St polymerization in biomass deep eutectic solvent by visible-light-driven RAFT polymerization, but unsatisfactory results were obtained due to low solubility of polystyene and low propagation rate (31). The living radical polymerization of (meth)acrylates was examined in detail in the biomass solvents ethyl lactate and pinene, but the polymerization of St was not discussed.

Since St polymers and their copolymers generated with acrylate monomers account for a certain percentage of epoxy-based powder coating and chain extender materials, aromatic hydrocarbon solvents such as xylene are generally used in the preparation of the above polymers (32–34), the gradual replacement of all fossil resources with biomass in the production of carbon-based consumer products should greatly reduce carbon dioxide emission. So it will be very interesting to develop ATRP of St in biomass solvents.

GVL has been previously suggested as a sustainable liquid for the production of chemical materials. GVL has desirable properties as a sustainable liquid, including a remarkably low vapor pressure, does not form hazardous peroxides under air and currently used by the food industry as food additive (35). GVL is directly obtainable in high yields by hydrogenation of levulinic acid (LA). The latter is the main platform chemical obtained from the chemical transformation (acidic digestion) of cellulose and hemicelluloses (36). Processes for LA production has already exhibited mid-level environmental factors (kilograms of waste per kilogram of product) (37).

Based on the above advantages, the ATRP of St in γ-pentolactone is of great significance and meets the requirements in green chemistry. Unfortunately experimental results showed that both bimolecular coupling and β-H elimination reactions lead to reducing the functionality of PSt prepared by normal ATRP (38). Among these, the β-H elimination reaction induced by the deactivator Cu(ii) is the main mechanism, leading to a significant decrease in the proportion of halogen-capped polymer chains. Lowering the concentration of the catalyst not only leads to a “greener” polymerization process, but also reduces catalyst-induced side reactions in ATRP (39). For this reason, various approaches have been taken to reduce the amount of catalyst used for St ARGET ATRP polymerization, among which the addition of inorganic bases has received considerable attention due to its convenience and effectiveness (40–44).

In this work, we report for the first time that ARGET ATRP for St using GVL as a solvent can be carried out with ppm catalyst usage under the condition of using sodium ascorbate (AsAc-Na) and sodium carbonate (Na2CO3) as regeneration activators. The reported system afforded higher polymer yield and an excellent control over the polymers molecular weight. The feeding of Na2CO3 in the polymerization allowed better control under ppm level catalyst, with polymers showing M w/M n < 1.3 throughout the reaction time.

2 Materials and methods

2.1 Materials

St (Sinopharm Chemical Reagent Co. Ltd, SCRC, AR) was passed through a basic alumina column before use in order to remove the radical inhibitor, GVL (SCRC, AR), AsAc-Na (SCRC, AR), copper(ii) bromide (CuBr2) (Alfa Aesar, 98%), tris(2-pyridylmethyl) amine (TPMA, Alfa Aesar, 98%), and ethyl bromophenylacetate (EBPA, Alfa Aesar, 98%) were used as received. Tetrahydrofuran (THF) (HPLC grade) was filtered under reduced pressure before use. Other solvents and reagents were used without further purification except as noted.

2.2 Typical procedure for the ARGET ATRP of St in GVL

In a typical ARGET ATRP experiment, CuBr2 (14.5 mg, 0.07 mmol) was dissolved in 1.5 mL of GVL in a dry glass tube. Then 26 mg of AsAc-Na (0.13 mmol), TPMA (46.5 mg, 0.16 mmol), and 3 mL of degassed St (26.0 mmol) were added and the mixture was bubbled with nitrogen for 15 min, and then sealed with a rubber septum. EBPA (21.0 μL, 0.13 mmol) was subsequently introduced via a syringe, then immersed in a thermostatic oil bath at designed temperature. After an expected time, the tube was opened to stop the reaction. The product PS was obtained after precipitation in large amounts of methanol, filtered, and dried in vacuo to constant weight. The conversion of the monomer was determined gravimetrically.

Chain extension was performed employing above ARGET ATRP technique in GVL. In a polymerization tube, 526.2 mg (51.09 μmol) of PSt macroinitiator (M n = 10,300) was dissolved in 2.73 g (26.18 mmol) of St under stirring and nitrogen atmosphere. 1.67 mg (15.71 μmol) of Na2CO3, 1.52 mg (5.23 μmol) of TPMA, 11.69 μg (52.33 nmol) of CuBr2, and 10.37 mg (52.34 μmol) AsAcNa were placed in 1.5 mL GVL in another tube under stirring. The above two solutions were mixed, bubbled with nitrogen for 15 min, and then sealed with a rubber septum. The tube was placed in an oil bath at a desired reaction temperature. After an expected time, the tube was opened to stop the reaction. The chain extended PSt was obtained after precipitation in large amounts of methanol, decanted, and dried in vacuo to constant weight.

2.3 Characterization

Monomer conversion was determined by gravimetry and number-average molecular weight (M n) and molecular weight distributions were determined by gel permeation chromatograph (GPC) on a PL GPC220 equipped with two PLgel 5 µm MIXED-C columns using a series of standard PMMA as calibrations and THF as the eluent at a flow rate of 1.0 mL·min−1 at 40°C. 400 MHz 1H NMR spectra of the samples were recorded on a Bruker Avance III 400 MHz spectrometer, with a 5 mm TIX triple resonance detection probe, in CDCl3 with tetramethylsilane (TMS) as an internal standard. A Bruker Autoflex speed mass spectrometer equipped with a 2 kHz smartbeam-II laser was used for MALDI–MS experiments. The instrument operated at an accelerating potential of 20 kV in a positive mode. Trans-2-(3-(4-tert-Butylphenyl)-2-methyl-2-propenylidene)malononitrile (DCTB) was used as MALDI matrix. Either sodium trifluoroacetate or sodium trifluoroacetate was used as a cationization agent. Typical sample preparation was performed by making stock solutions in THF of the matrix (30 mg·mL−1), polymer analyte (5 mg·mL−1), and cationization agent (2 mg·mL−1). The stock solutions were mixed in a 10/1/1 ratio (matrix/analyte/cation), and deposited onto a MALDI target plate.

3 Results and discussion

3.1 ARGET ATRP polymerization of St in GVL using AsAc-Na as regenerating system

The first ARGET ATRP polymerization of St was conducted in GVL using CuBr2 as the catalyst in the deactivated form, TPMA as the ligand, and AsAc-Na as the reducing agent in the ratio [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0 set as 200/1/0.5/1.25/1.

Table 1 shows that radical polymerization of St in GVL was successfully conducted, throughout the whole reaction, there were no phase separation in the reaction system and the St monomer as well as its polymers were well dissolved in GVL, which indicates that GVL can be used as a solvent for the ATRP reaction of St. However, the controllability of polymerization was not very good in this catalytic system, even at higher catalyst concentrations (0.25 mol% of catalyst vs monomer), providing a polymer with a broad molecular weight distribution (M w/M n > 1.35). The poor controllability of the polymerization is also evidenced by the presence of a shoulder peak in the high molecular weight portion of the GPC curve of the polymer (Figure 1) and higher values of ΔM n (the difference between M n,GPC and M n,th). The probable reason is that there are not enough deactivator species (X-Cu ii /L) in the reaction system to stabilize the free radicals, making the concentration of free radicals too high and making it easy to produce a double radical termination reaction. In the ARGET ATRP reaction, the equilibrium of activator species (CuI/L) to the deactivator species (X-Cu ii /L) in the system can be regulated by the reaction conditions through the redox reaction of the reducing agent with the high valence metal catalyst to obtain the low valence metal halide, which in turn generates the active species. The extent of the reduction reaction can be controlled by the optimization of the reaction conditions, for which the polymerization reaction at different temperatures was investigated to regulate the controllability of the polymerization reaction. As shown in Figure 1 and Table 1, under each reaction temperature condition, as the polymerization reaction temperature increased from 90°C to 120°C, the polymerization reaction could be carried out successfully (the conversion rate could reach about 50% in all cases); however, the dispersion of the polymers also increased gradually. The above results show that although lowering the temperature is favorable to improve the controllability of the polymerization reaction, the GPC curves of the polymers show shoulder peaks even at low reaction temperatures.

Table 1

Results of ARGET ATRP of St in GVL at different temperatures

Entry* T (℃) Conv. (%)a M n,GPC (×103 g·mol−1)b M n,th (×103 g·mol−1)c ΔM n%d M w /M n
1 90 40.9 10.9 8.5 22.0 1.35
2 100 53.6 15.1 11.2 25.8 1.56
3 110 61.2 18.9 12.7 32.8 1.82
4 120 60.0 16.1 12.5 22.3 1.92

*Polymerization conditions: [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0= 200/1/0.5/1.25/1 in GVL, V St = 3 mL, V GVL = 1.5 mL.

aDetermined gravimetrically. Reaction time = 3 h.

bDetermined using GPC against PMMA standard.

c M n,theo = M EBPA + [St]0/[EBPA]0 × conversion × M St.

dΔM n% = (M n,GPC – M n,th)/M n,GPC × 100%.

Figure 1 GPC traces for the polymerization of St in GVL at different reaction temperatures. Reaction conditions: [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0 = 200/1/0.5/1.25/1, t = 4 h.
Figure 1

GPC traces for the polymerization of St in GVL at different reaction temperatures. Reaction conditions: [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0 = 200/1/0.5/1.25/1, t = 4 h.

Next, the effect of reaction time on polymerization was examined, as shown in Figure 2 and Table S1. The polymerization process generally conforms to the quasi-primary kinetic polymerization characteristics, k p app ( R p = − d [ M ] / d t = k p [ P n ] [ M ] = k p app [ M ] ) , as determined from the kinetic slopes, was 8.8 × 10−5 s−1 for the polymerization with 0.1 molar ratio CuBr2 to the initiator. At the same time, an induction period of about half an hour can be noticed, probably due to the high concentration of catalyst, which does not establish the reaction equilibrium at the beginning of the reaction. The molecular weight increased with the increase of conversion; however, the dispersion of the polymer gradually increased with the increase of reaction time, and the presence of a shoulder peak and higher values of ΔM n could be observed at the late stage of the reaction (as shown in Figure 3 and Table S1), these results all indicate that a chain termination reaction has occurred.

Figure 2 ln([M]0/[M t]) as a function of time (a) and (b) number-average molecular weight (M n,GPC) and molecular weight distribution (M w/M n) versus conversion for ARGET ATRP of St in GVL at 100°C. Polymerization conditions: [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0 = 200/1/0.1/1.25/1 in GVL at 110°C, V St = 3 mL, V GVL = 1.5 mL.
Figure 2

ln([M]0/[M t]) as a function of time (a) and (b) number-average molecular weight (M n,GPC) and molecular weight distribution (M w/M n) versus conversion for ARGET ATRP of St in GVL at 100°C. Polymerization conditions: [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0 = 200/1/0.1/1.25/1 in GVL at 110°C, V St = 3 mL, V GVL = 1.5 mL.

Figure 3 GPC traces for the polymerization of St in GVL at different monomer conversions: 13.0%, 21.5%, 29.4%, 43.4%, and 53.8%. Reaction conditions as shown in Figure 2.
Figure 3

GPC traces for the polymerization of St in GVL at different monomer conversions: 13.0%, 21.5%, 29.4%, 43.4%, and 53.8%. Reaction conditions as shown in Figure 2.

In summary, the ARGET ATRP reaction of St can be successfully carried out in biomass solvent GVL; however, the polymer dispersion increases as the conversion increases, suggesting that there are not enough deactivator species (X-Cu ii /L) to stabilize the free radicals, which may be due to the fact that the deactivator species (X-Cu ii /L) are destabilized by the generation of HCl during the reaction, even with the addition of the more alkaline AsAc-Na reductant (45).

3.2 ARGET ATRP polymerization of St in GVL using AsAc-Na/Na2CO3 as regenerating system

As discussed above, ARGET ATRP of St using AsAc-Na alone as reducing agent is poorly controllable, especially at higher monomer conversion. There are a number of literature reports that the addition of base to the reaction system can improve the controllability of the reaction. Among those, the introduction of Na2CO3 has good effect on St polymerization, for this reason Na2CO3 was chosen as additive to investigate the effects on polymerization (41–44).

As shown in Table 2, the addition of Na2CO3 base not only increases monomer conversion but also improves the controllability of the polymerization reaction. With the introduction of 0.075 mol% of Na2CO3 versus monomer, the monomer conversion increased from 47% to 72.7%; meanwhile, the polymer dispersion decreased from 1.41 to 1.12, low values of ΔM n and the shoulder peak on the GPC curves disappeared as seen in Figure 4. Addition of more Na2CO3, did not further improve the monomer conversion and controllability. The above results indicate that the introduction of Na2CO3 significantly improved the controllability of ARGET ATRP polymerization of St in GVL.

Table 2

Effect of the amount of Na2CO3 on the ARGET ATRP of St in GVL

Entry* Na2CO3 T (°C) Conv.a (%) M n,GPC (×103 g·mol−1)b M n,th (×103 g·mol−1)c ΔM n%d M w/M n
1 None 90 47.0 11.6 9.8 15.5 1.41
2 0.15 90 72.7 15.7 15.1 3.8 1.12
3 0.3 90 66.3 16.1 13.8 14.3 1.33
4 0.3 110 85.6 20.5 17.8 13.2 1.46

*Polymerization conditions: [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0/[Na2CO3]0=200/1/0.1/1.25/1/x in GVL, V St = 3 mL, V GVL = 1.5 mL.

aDetermined gravimetrically, reaction time = 24 h.

bDetermined using GPC against PMMA standard.

c M n,theo = M EBPA + [St]0/[EBPA]0 × conversion × M St.

dΔM n% = (M n,GPC – M n,th)/M n,GPC × 100%.

Figure 4 GPC traces for the polymerization of St in the absence and presence of Na2CO3. Reaction conditions as shown in Table 2.
Figure 4

GPC traces for the polymerization of St in the absence and presence of Na2CO3. Reaction conditions as shown in Table 2.

Reducing catalyst usage has been a goal pursued in metal-catalyzed ATRP polymerization research, not only to reduce the cost of the polymerization reaction, but also to make polymer post-processing simpler. At the same time, lowering catalyst usage, the occurrence of side reactions can also be reduced (39). As discussed above, the controllability of the polymerization was not good when no Na2CO3 was added, and the controllability of the polymerization became worse even when the catalyst concentration was higher (Table 1). As shown in Table 3, when the catalyst concentration was reduced from 500 to 50 ppm after the introduction of the Na2CO3, the polymerization remained well controllable. Even when CuBr2 concentration reduced to 5 ppm, the polymerization conformed to the characteristics of living polymerization, although the dispersion of the polymer increased slightly, probably due to the lower concentration of X--Cu ii /L.

Table 3

Effect of the amount of CuBr2 on the ARGET ATRP of St in the presence of Na2CO3

Entry* CuBr2 Conv.a (%) M n,GPC (×103 g·mol−1 )b M n,th (×103 g·mol−1 )c ΔM n%d M w /M n
1 0.1 62.2 15.0 14.5 3.3 1.16
2 0.01 69.7 13.4 12.9 3.7 1.18
3 0.001 77.6 17.0 16.2 4.7 1.28

*Polymerization conditions: [St]0/[EBPA]0/[CuBr2]0/[TPMA]0/[AsAc-Na]0/[Na2CO3]0 = 200/1/x/0.1/1/0.15 in GVL, V St = 3 mL, V GVL = 1.5 mL.

aDetermined gravimetrically, reaction time = 24 h, T = 90℃.

bDetermined using GPC against PMMA standard.

c M n,theo = M EBPA + [St]0/[EBPA]0 × conversion × M St.

dΔM n% = (M n,GPC – M n,th)/M n,GPC × 100%.

Next, the appropriate polymerization reaction temperature at low catalyst concentration was examined, as shown in Table 4, increasing the polymerization reaction temperature, the controllability of the polymerization became poor, and the monomer conversion could only reach about 50% at a polymerization duration of 24 h at 110℃. Lowering the reaction temperature (90℃) is favorable to the polymerization reaction, and the conversion can reach about 80%, while the dispersion of the polymer is lower, indicating that the polymerization has a good controllability under this reaction temperature condition.

Table 4

Effect of temperatures on the ARGET ATRP of St in the presence of Na2CO3

Entry T (℃) Conv. (%)a M n,GPC (×103 g·mol−1)b M n,th (×103 g·mol−1)c ΔM n%d M w /M n
1 80 57.3 11.3 11.93 −5.5 1.32
2 90 77.6 17.0 16.2 4.7 1.28
3 100 74.5 18.1 15.5 14.3 1.26
4 110 46.1 6.2 9.61 −55.0 1.52

Polymerization conditions: [St]: [EBPA]: [CuBr2]:[TPMA]: [AsAc-Na]: [Na2CO3] = 200:1:0.001:0.1:1:0.15, V St = 3.0 mL, V GVL = 1.5 mL, t = 24 h.

aDetermined gravimetrically, reaction time = 24 h, T = 90℃.

bDetermined using GPC against PMMA standard.

c M n,theo = M EBPA + [St]0/[EBPA]0 × conversion × M St.

dΔM n% = (M n,GPC – M n,th)/M n,GPC×100%.

To further investigate on the ARGET ATRP of St under low catalyst usage in GVL, the kinetic experiments were carried out in different reaction times. The kinetic analysis is shown in Figure 5a, while molecular weight versus monomer conversion and M W/M n values are reported in Figure 5b. The kinetic plot using this catalyst system was almost linear starting from the origin but there was a curvature observed and conversion above 90% became very difficult. This might be due to the lack of reductant in the later stages of the reaction, leading to a decrease in the concentration of active centers in the system and a gradual decrease in the rate of the reaction. For this reason we calculated that the k p app value for the initial 5 h was 3.89 × 10−5 s−1. These results demonstrated that the concentration of propagating radicals remained constant during the reaction process and especially at the beginning of polymerization.

Figure 5 ln([M]0/[M]t) as a function of time (a) and (b) number-average molecular weight (M n,GPC) and molecular weight distribution (PDI) versus conversion for ARGET ATRP of St in GVL at 90°C. Polymerization conditions: [St]:[EBPA]:[CuBr2]:[TPMA]:[AsAc-Na]:[Na2CO3] = 200:1:0.001:0.1:1:0.15, V St = 3 mL, V GVL = 1.5 mL.
Figure 5

ln([M]0/[M]t) as a function of time (a) and (b) number-average molecular weight (M n,GPC) and molecular weight distribution (PDI) versus conversion for ARGET ATRP of St in GVL at 90°C. Polymerization conditions: [St]:[EBPA]:[CuBr2]:[TPMA]:[AsAc-Na]:[Na2CO3] = 200:1:0.001:0.1:1:0.15, V St = 3 mL, V GVL = 1.5 mL.

3.3 Analysis of chain ends and chain extensions

The 1H NMR data confirm a high degree of chain end functionality of PS synthesized in GVL solvents. As shown in Figure 6, the molecular weight calculated from the 1H NMR spectrum (M n,NMR) was 5,200 g·mol−1, which was in good agreement with M n,GPC = 4,500 indicating that the PS obtained was end-terminated by the Br atoms with high fidelity.

Figure 6 1H NMR spectrum of the product obtained by reaction of St in GVL for 1 h. The solvent is CDCl3 (M n,th = 4.5 × 103 g·mol−1, M n,sec = 5.2 × 103 g·mol−1, M w /M n = 1.50).
Figure 6

1H NMR spectrum of the product obtained by reaction of St in GVL for 1 h. The solvent is CDCl3 (M n,th = 4.5 × 103 g·mol−1, M n,sec = 5.2 × 103 g·mol−1, M w /M n = 1.50).

The chain-end functionality of the synthesized polymers was also confirmed by chain extension of a PS-Br macro-initiator with St. Figure 7 shows the complete shift of the entire molecular weight curves from relatively low molecular weight PS (M n,GPC = 10,300, M w/M n = 1.21) to a higher molecular weight (M n,GPC = 27,700, M w/M n = 1.35). These results all prove the “living” character of the PS synthesized with this catalytic system.

Figure 7 GPC curves of PS (right line) before and (left line) after chain extension. Polymerization conditions: [St]:[PS-Br]:[CuBr2]:[TPMA]:[AsAc-Na]:[Na2CO3] = 500:1:0.001:1:0.1:0.3, V St = 3 mL, V GVL = 1.5 mL, T = 90°C.
Figure 7

GPC curves of PS (right line) before and (left line) after chain extension. Polymerization conditions: [St]:[PS-Br]:[CuBr2]:[TPMA]:[AsAc-Na]:[Na2CO3] = 500:1:0.001:1:0.1:0.3, V St = 3 mL, V GVL = 1.5 mL, T = 90°C.

We also performed MALDI-TOF tests on the PS samples and confirm that the structure of the PS polymers is with high fidelity. The left figure displays the MALDI-TOF data of PS-Br, with a matrix composed of DCTB + CF3OONa. The right figure is a magnified view, where red indicates low laser intensity and black represents high laser intensity. We observed a peak spacing corresponding to the repeat unit mass of PS at 104.062. Calculated for n = 50, the theoretical value for [PS-Br + Na] is 5,514.171, while the experimental value is 5,514.102. Another peak spacing at 104.062 corresponds to [M + Na + 184], similar to what was reported in the literature (46). Additionally, as the laser intensity in the mass spectrum increases, the Br at the polymer chain ends gradually disappears, while the peak of [M + Na + 184] intensifies. No new peaks emerge, indicating that the synthesized polymer chain ends are all Br-terminated (Figure 8).

Figure 8 MALDI mass spectra of PS-Br chains at different laser intensities.
Figure 8

MALDI mass spectra of PS-Br chains at different laser intensities.

3.4 Polymerization mechanism discussion

As mentioned above, ARGET ATRP of St in GVL was performed when only AsAc-Na acted as the reducing agent. It was found that the polymerization showed living polymerization characteristics, however even at high catalyst dosage, the molecular weight distribution of the polymer became broader at the later stage of the reaction, and a shoulder peak appeared in the high molecular weight portion of the GPC curves. When Na2CO3 was introduced into the polymerization system, the controllability of the polymerization reaction was significantly improved. ARGET ATRP of St consisting of Na2CO3 and AsAc-Na as reducing agents provided good yields and narrow molecular weight distributions at very low catalyst concentrations (0.001 mol% vs monomer). At the same time, the amount of catalyst is reduced while reducing the occurrence of side reactions, with higher bromine groups at the end of the polymer chain. A possible main reason for the above phenomenon is the gradual accumulation of HCl in the reaction system, which destabilizes the deactivator species (X-Cu ii /L) and leads to an increase in the probability of bimolecular radical coupling reaction in the system. The introduction of Na2CO3 quenches the acidity released during catalyst regeneration and prevent the amine ligand from being protonated and improve the stability of the catalyst (42). Another mechanism is in which Na2CO3 may act as base generating alkoxide ions which are the true reducing agents (43,44). Due to the presence of this effect, the amount of catalyst can be significantly reduced in this ARGET ATRP of St system, and effectively avoids the occurrence of the double termination reaction, although it cannot be completely avoided. At the same time, due to the lower amount of catalyst, the occurrence of β-H elimination side reactions can also be reduced. The plausible mechanism of the ARGET ATRP of St in the presence of Na2CO3 is shown in Scheme 1.

Scheme 1 Possible mechanism of catalyst reactivation by AsAc-Na/Na2CO3 in the Cu-mediated ARGET ATRP of St in GVL (DHA = dehydroascorbic acid).
Scheme 1

Possible mechanism of catalyst reactivation by AsAc-Na/Na2CO3 in the Cu-mediated ARGET ATRP of St in GVL (DHA = dehydroascorbic acid).

4 Conclusions

In this article, the ARGET ATRP polymerizations of St were successfully performed by using a biomass solvents GVL. An activation and regeneration system suitable for this polymerization reaction was investigated and it was found that an activation and regeneration system consisting of Na2CO3 and AsAc-Na provided good yields and narrow molecular weight distributions at a molar ratio of CuBr2 of 0.001% (5 ppm) to the monomer (Conv. = 77.6%, M w /M n = 1.28). These results show that GVL is an excellent green solvent for the polymerization of not only acrylate monomers but also St monomers and the next work explores the application of this solvent in the industrial production of epoxy-based powder coating and chain extender materials. However, it should also be noted that it is difficult to achieve a high conversion of St monomer in this catalytic system, which may cause difficulties in the synthesis of new polymers, and the current high price compared to other solvents should be taken into account when applying this solvent in a larger scale.

  1. Funding information: This work was supported by a grant from the project of Anhui Laboratory of Clean Catalytic Engineering (LCCE-2021-03) and National College Student Innovation and Entrepreneurship Training Program (202210363062).

  2. Author contributions: Qianqian zhu: investigation, data curation, formal analysis, writing – draft; Tianchen Song: methodology, formal analysis, supervision; Jiaxin zhao: data curation, formal analysis; Gang Gao: data curation; Yixin Xiang: supervision, resources; Jiangang Gao: supervision, resources; Xianrong Shen: conceptualization, funding acquisition, resources, supervision, writing – review & editing.

  3. Conflict of interest: Authors state no conflict of interest.

  4. Data availability statement: The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Received: 2024-02-01
Revised: 2024-04-10
Accepted: 2024-04-21
Published Online: 2024-05-31

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/epoly-2024-0022
Keywords for this article
styrene polymerization; green solvent; ARGET ATRP; γ-valerolactone; living radical polymerization
Creative Commons
BY 4.0

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  64. Molecular dynamics simulation of the interaction between polybutylene terephthalate and A3 during thermal-oxidative aging
  65. Crashworthiness of GFRP/aluminum hybrid square tubes under quasi-static compression and single/repeated impact
  66. Review Articles
  67. Recent advancements in multinuclear early transition metal catalysts for olefin polymerization through cooperative effects
  68. Impact of ionic liquids on the thermal properties of polymer composites
  69. Recent progress in properties and application of antibacterial food packaging materials based on polyvinyl alcohol
  70. Additive manufacturing (3D printing) technologies for fiber-reinforced polymer composite materials: A review on fabrication methods and process parameters
  71. Rapid Communication
  72. Design, synthesis, characterization, and adsorption capacities of novel superabsorbent polymers derived from poly (potato starch xanthate-graft-acrylamide)
  73. Special Issue: Biodegradable and bio-based polymers: Green approaches (Guest Editors: Kumaran Subramanian, A. Wilson Santhosh Kumar, and Venkatajothi Ramarao)
  74. Development of smart core–shell nanoparticles-based sensors for diagnostics of salivary alpha-amylase in biomedical and forensics
  75. Thermoplastic-polymer matrix composite of banana/betel nut husk fiber reinforcement: Physico-mechanical properties evaluation
  76. Special Issue: Electrospun Functional Materials
  77. Electrospun polyacrylonitrile/regenerated cellulose/citral nanofibers as active food packagings
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