Synthesis and characterization of electroactive bottlebrush nano-copolymers based on polystyrene and polyaniline as side chains and poly(3-(2-hydroxyethyl)thiophene) as backbone

Abstract

Electroactive bottlebrush copolymers were synthesized via grafting of polystyrene (PSt) and polyaniline (PANI) from poly(3-(2-hydroxyethyl)thiophene) backbones by atom transfer radical polymerization (ATRP) and chemical oxidation polymerization. The bromoesters were attached to the polymer chains to afford the proper macroinitiators for ATRP of PSt branches. Likewise, some other polymer chains were functionalized with antranilic acid for chemical oxidation polymerization of PANI. Electroactivity behaviors of the synthesized bottlebrushes were approved by the cyclic voltammetry, and their conductivities were determined using the four-probe technique. Thanks to the electrical conductivity and thermal stability, the synthesized bottlebrushes can be appropriate candidates for being used in various systems such as organic solar cells.

Introduction

Bottlebrushes are the cylindrical polymers with the long polymer backbones densely grafted by the polymer side chains [1, 2]. As the backbone is longer than the side chains, a worm-like morphology could be detected in their good solvents [3, 4]. Bottlebrushes have attracted a huge attention for their compact and cylindrical structures with respect to the traditional random-coil polymers [5, 6]. The polymer bottlebrushes could be employed in the super-soft elastomers [7, 8] and molecular templates for one-dimensional nano-materials [9,10,11].

The bottlebrush copolymers could be applied in the delivery systems [12], stimuli-responsive coatings [13], photonics [14], and lithography [15]. Very recently, the well-defined conducting bottlebrushes have been introduced on the basis of electron donor poly(3-hexylthiophene) (P3HT) and norbornene end caps. It is found that the longer polythiophene chains reflected better properties and thus the higher solar cell device performances [16]. Bottlebrushes were first synthesized in early 1980s [17, 18], and the primary works focused on the development of polymer synthesis procedures. The controlled polymerization techniques enabled the development of bottlebrushes with desired lengths and structures. An overview of the latest key developments and research activities in the area of molecular bottlebrushes is also published [19]. Three main strategies of grafting through, grafting onto, and grafting from have been introduced for development of the bottlebrush polymers [20,21,22,23]. The grafting through methodology is performed by directly polymerizing the macromonomers through their terminal polymerization groups. Recently, ring opening metathesis polymerization (ROMP) has been developed as an appropriate technique to produce the well-defined bottlebrushes [24,25,26]. Radzinski et al. [27] investigated the effect of anchor groups on the rate of propagation, conversion, and the maximum obtainable degree of polymerization during ROMP grafting through polymerization. The grafting from method was originated from the situ polymerization of side chains from the backbone macroinitiator, reflecting the heterogeneity in length distribution and grafting density [28, 29]. An advantage of this procedure is the synthesis of bottlebrushes with very long backbones. The grafting density can also be tailored by co-polymerizing the two monomers during the backbone synthesis [30]. Moreover, the block copolymer side chains could be designed by the sequential polymerizations [31]. The protection/deprotection of functional groups in grafting from methodology could be considered as a disadvantage [32]. The grafting onto method is performed through attaching the end functionalized side chains onto the polymer backbone having the reactive group on each monomer unit. The charming property of this method is that both backbone and side chains can be separately prepared, inducing a good control over the structure [33,34,35].

On the other hand, electronically active polymers have attracted huge interest in distinct applications such as polymeric integrated circuits [36, 37]. In addition, their compatibility with the plastic substrates makes it feasible to produce the flexible, lightweight, and portable electronic devices [38]. The linear rod–coil block copolymers such as P3HT-g-PSt were previously applied to control the active layer morphology in the organic photovoltaics [39]. The presence of P3HT-g-PSt increased the crystallinity of P3HT regions. In this regard, we decided to synthesize the copolymers with a different structure, namely, bottlebrush architectures. In addition to the rod–coil poly(3-(2-hydroxyethyl)) (P3EtTh)-g-PSt bottlebrushes, we also synthesized the rod–rod copolymers of P3EtTh-g-polyaniline (PANI) with a bottlebrush configuration. The electroactivity of samples was investigated by the cyclic voltammetry, and the respective conductivities were determined using the four-point probe technique.

Experimental

Materials

The 2-(3-thienyl)ethanol (3EtTh) was purchased from Aldrich, and the N,N-dicyclohexyl carbodiimide (DCC), dimethylaminopyridine (DMAP), p-anthranilice acid, and anhydrous ferric chloride (FeCl3) were prepared from Sigma-Aldrich (USA) and used without any purification. The aniline monomer (Merck; Darmstadt, Germany) was distilled twice under the reduced pressure right before the application. Ammonium proxydisulfate (APS, Merck) was purified through the re-crystallization from ethanol at room temperature. The N-methyl-2-pyrrolidone (NMP, anhydrouse grade, 99.5% Aldrich) and tetrahydrofurane (THF, Merck) were dried by refluxing and distilling. All other agents were prepared from Merck and Sigma-Aldrich and purified according to the standard procedures.

Synthesis of poly 2-(3-thienyl) ethanol (P3EtTh)

A proper reactor was filled by the 2-(3-thienyl) ethanol (1.1 g, 0.98 mmol) and 25 mL CHCl3 and then bubbled by the pure argon within 15 min. In a parallel system, 8.0 g of anhydrous FeCl3 was dissolved in 30 mL acetonitrile. The latter was slowly added to the primary system at 0 °C under an inert atmosphere for 30 min. The reaction mixture was refluxed for 1 day at room temperature and terminated by pouring the reactor content into the distilled water. The resultant material was dried in vacuum (Scheme 1).

Scheme 1
scheme1

Synthesis of P3EtTh-g-PANI

Synthesis of phenylamine-functionalized P3EtTh with p-anthranilice acid (PhAP3EtThM)

A reactor was charged with p-anthranilice acid (0.21 g, 1.58 mmol), DCC (0.652 g, 3.16 mmol), and THF (40 mL), and the mixture was subsequently bubbled by pure argon for 15 min and stirred at room temperature for 1 h. A 1.6 mmol of DMAP was then added to the reactor. The mixture was stirred for 3 days under an argon protection. Eventually, the mixture was filtered to remove the dicyclohexyl urea salts, and the THF was evaporated to afford the ultimate product. The resultant was washed with n-hexane in order to remove the DCC trace (Scheme 1).

Synthesis of P3EtTh-g-PANI

A reaction system was filled with 10 mL dimethylformamide (DMF) and 1.0 g PhAP3EtThM. The APS (0.48 g, 0.02 mmol) was parallelly dissolved in H2SO4 (0.5 M, 15 mL). The oxidant solution was added to the system, and the temperature was switched to 0 °C. In a separate container, the aniline monomer (0.1 g, 2.1 mmol) was dissolved in H2SO4 (0.5 M, 15 mL). The latter was added to the oxidant/PhAP3EtThM solution within 20 min. The mixture was stirred for 10 h at 0 °C, and, subsequently, the polymer was filtered, washed with water/methanol, and dried in vacuum at room temperature (Scheme 1).

Synthesis of 3-[1-ethyl-2(2-bromoisobutyrate)]thiophene (3EtBIBTh)

The 3-thiophene ethanol (1.2 g, 9 mmol) and triethylamine (1.2 g, 12.1 mmol) were dissolved in 50 mL CH2Cl2 and then cooled to 8 °C. The 2-bromoisobutyryl bromide (2.8 g, 12 mmol) was dissolved in 10 mL CH2Cl2 and added dropwise into the reactor during 30 min. The mixture was subsequently switched to 30 °C and kept stirring for 1 day. The mixture was eventually filtered to remove the precipitate of triethylamine hydrochloride. The filtrate was diluted with CH2Cl2 and washed with HCl, NaHCO3, and distilled water. The organic layer was also dried with MgSO4 overnight [40] (Scheme 2).

Scheme 2
scheme2

Synthesis of P3EtTh-g-PSt

Synthesis of 2,5-poly{3-[1-ethyl-2(2-bromoisobutyrate)]thiophene} (P3EtBIBTh)

FeCl3 (3.6 g, 21.7 mmol) was dispersed in 25 mL CHCl3 in an appropriate reactor. The 3EtBIBTh (1.5 g, 5.4 mmol) was then dissolved in 20 mL CHCl3 and added dropwise into the system. After 2 h, it was added into 1 L methanol and stirred for another 3 h. The solid was gathered and washed with methanol for four times. The precipitate was Soxhlet-extracted with methanol and then dried under vacuum overnight. The obtained polymer was washed three times with water to remove the residual of FeCl3 and dried under vacuum at room temperature (Scheme 2).

Synthesis of P3EtTh-g-PSt

The P3EtBIBTh macroinitiator (80 mg, 0. 24 mmol) was dispersed in toluene (20 mL) by the help of sonication. The suspension was transferred into a reactor containing CuCl (24 mg, 0.24 mmol). After pouring the PMDETA (56 mg, 0.24 mmol) and styrene (260 mg, 2.4 mmol), the system was stirred for 3 h. The reactor was subsequently switched to 75 °C under constant stirring. The solvent was evaporated after 1 day, and the product was redissolved in THF and disprecipitated in hexane. The polymer product was dried under vacuum for 2 days (Scheme 2).

Characterization

Fourier transform infrared (FT-IR) spectra of the synthesized samples were recorded on a Shimadzu 8400S FT-IR (Shimadzu, Kyoto, Japan). The proton nuclear magnetic resonance (1H NMR) spectra of polymers were measured by FT-NMR (400 MHz) Bruker spectrometer (Bruker, Ettlingen, Germany) using the deuterated chloroform (CDCl3)/dimethyl sulfoxide (DMSO-d6). The ultraviolet–visible (UV–Vis) spectra were recorded on a Shimadzu 1650 PC UV–Vis spectrophotometer (Shimadzu, Kyoto, Japan). The electrochemical measurements were done on Auto-Lab PGSTA T302 N. The conductivities were determined using a four-point probe (Azar Electrode, Urmia, Iran). The morphologies were also recorded by means of the field emission scanning electron microscope (FESEM type 1430 V, Cambridge, UK) and the atomic force microscope (AFM Nanoscope IV). The thermal decompositions were measured through the thermogravimetric analyzer (TGA-PL STA 1640, Shropshire, UK) under nitrogen atmosphere with a heating rate of 10 °C min−1. The average molecular weight values were determined by the gel permeation chromatography (GPC, Agilent, 1100) utilizing the DMF as eluent.

Results and discussion

The design of polymeric structures for various applications such as photovoltaic devices and biomedical uses is the purpose of recent researches. In the current work, the polythiophenic backbones were densely grafted with different polymers and the bottlebrush nanostructures were obtained. In upcoming sections, the synthesized polymers will be thoroughly characterized.

Characterization of P3EtTh-g-PANI

FT-IR spectra The P3EtTh was synthesized by the chemical oxidation polymerization, and the hydroxyl groups in side chains of P3EtTh were reacted with p-anthranilic acid to reach the P3EtThM macromonomer. The synthesized macromonomers were subsequently employed in the chemical oxidation copolymerization with aniline monomer to produce the P3EtTh-g-PANI bottlebrushes. FT-IR spectra of P3EtTh, P3EtThM, and P3EtTh-g-PANI are illustrated in Fig. 1a and b. FT-IR spectrum of P3EtTh demonstrated the prominent absorptions of 2-(3-thienyl) ethanol monomer. The aromatic and aliphatic –CH stretching vibrations (2800–3100 cm−1), –CH2 bending vibration (1300–1450 cm−1), C=C stretching vibrations (1530 and 1633 cm−1), and γ(C–H) in the aromatic ring (854 cm−1), hydroxyl groups (3423 cm−1) and the weak C–S stretching vibrations (675 cm−1) were detected [41]. With respect to FT-IR of P3EtTh, the most significant alterations in spectrum of P3EtThM were the appearance of –NH2 stretching vibrations (3326 cm−1), stretching vibrations of aliphatic and aromatic C–H (2800–3100 cm−1), aromatic C=C stretching vibrations (1564 cm−1), and γ(C–H) in the aromatic rings (773 cm−1). In addition, the hydroxyl stretching vibration disappeared, demonstrating that the hydroxyl groups had reacted with p-anthranilic acid. FT-IR spectra of homo-polyaniline (H-PANI) and P3EtTh-g-PANI are represented in Fig. 1b. FT-IR of H-PANI exhibited the principal absorptions for the stretching vibrations of aromatic C–H (3050–3200 cm−1), the γ(C–H) in aromatic rings (757 and 794 cm−1), the N–H stretching vibrations (3456 cm−1), the stretching vibration of the C=C in benzenoid units (1577 cm−1), the aromatic C–N stretching vibrations (1307 cm−1), and the weak aromatic and combination bands (1650–1900 cm−1) [42, 43]. FT-IR spectrum of P3EtTh-g-PANI displayed all principal bands of PANI and P3EtTh precursors. The most conspicuous alterations in these spectra included the stretching vibrations of aliphatic C–H (2800–2950 cm−1) and the N–H stretching vibrations (3326 cm−1). Notably, the other bands of P3EtTh were overlapped with the sharp PANI bands (Fig. 1).

Fig. 1
figure1

FT-IR spectra of P3EtTh and P3EtThM (a), P3EtTh-g-PANI, and HPANI (b)

1H NMR spectra The P3EtTh and P3EtThM were further characterized by means of 1H NMR spectroscopy. 1H NMR spectra of mentioned polymers are illustrated in Fig. 2a and b, respectively. In Fig. 2, the peaks of 2.88–2.97 ppm (methylene protons of the attached thiophene ring), 3.73–3.76 ppm (methylene protons of –CH2–OH), 4.28 ppm (proton of the hydroxyl group), and 6.98–7.03 ppm (proton of the β-position of thiophene ring) were detected. For the phenylamine-functionalized P3EtTh, the aromatic protons of phenyl rings and the aromatic protons of β-position of the thiophene ring appeared at 7.68–7.75 ppm. Furthermore, the chemical shifts at (5.57–5.59 ppm) and (2.72–2.78 and 4.13 ppm) were recorded because of NH2 and methylene protons of CH2–CH2–O– (labeled as a and b in Fig. 2b).

Fig. 2
figure2

1H NMR spectra of P3EtTh (a) and P3EtThM (b)

Characterization of P3EtTh-g-PSt

FT-IR spectra FT-IR spectra of P3EtTh, P3EtThBr, and P3EtTh-g-PSt are displayed in Fig. 3. In comparison with FT-IR spectrum of P3EtTh, the most significant changes in FT-IR of P3EtThM were the disappearance of –OH stretching vibrations (3423 cm−1), which approved the formation of P3EtThBr. FT-IR spectrum of P3EtTh-g-PSt represented the main absorption peaks of P3EtTh and PSt (Fig. 3). The aliphatic and aromatic –CH stretching (2800–3100 cm−1), –CH2 bending vibrations (1300–1467 cm−1), C=C stretching vibrations (1544 and 1652 cm−1), and γ(C–H) in the aromatic rings (854 cm−1) and the weak C–S stretching vibrations (675 cm−1) were also recorded.

Fig. 3
figure3

FT-IR spectra of P3EtTh, P3EtThBr, and P3EtTh-g-PSt

1H NMR spectra1H NMR spectra of 3EtThBr, P3EtThBr, and P3EtTh-g-PSt are illustrated in Fig. 4a–c, respectively. Only difference between the 3EtThBr and P3EtThBr spectra was the peak intensities and the absence of –OH groups in spectrum of P3EtThBr, which verified the synthesis of P3EtThBr. The conspicuous alteration in 1H NMR spectrum of P3EtTh-g-PSt was the detection of peaks at 0.63–1.7 ppm due to the methyn and methylene protons (–CH–CH2–) of PS and 7.23–7.58 ppm for the aromatic protons of PS and P3EtTh.

Fig. 4
figure4

1H NMR spectra of 3EtThBr (a), P3EtThBr (b), and P3EtTh-g-PSt (c)

UV–Vis spectroscopy of prepared samples

The optical properties of the synthesized P3EtTh, P3EtThBr, P3EtTh-g-PANI, and P3EtTh-g-PSt were investigated using UV–Vis spectroscopy. The spectra were recorded on the solution states of samples in DMSO. UV–Vis spectrum of P3EtTh demonstrated three electronic transitions at 257, 303, and 401 nm (Fig. 5). The peaks in question were associated with the overlap of ππ* transition for the thiophene rings of P3EtTh. Moreover, the blue shift in the case of P3EtTh-g-PANI in comparison with P3EtTh was originated from the elevated conjugation length, which was for the presence of PANIs. However, the red shift in the P3EtTh-g-PSt was resulted from a decreased conjugation length because of the non-conductive PSt chains.

Fig. 5
figure5

UV-Vis spectra of the P3EtTh (green), P3EtThBr (purple), P3EtTh-g-PANI (blue), and P3EtTh-g-PSt (orange) (color figure online)

GPC traces

The GPC chromatograms of P3EtTh, P3EtThBr, P3EtTh-g-PSt, and P3EtTh-g-PANI samples are illustrated in Fig. 6. The GPC traces confirmed that the polymeric materials were synthesized with a narrow distribution. The data details of GPC measurements are also reported in Table 1.

Fig. 6
figure6

GPC traces of P3EtTh (green), P3EtThBr (purple), P3EtTh-g-PSt (red), and P3EtTh-g-PANI (blue) in DMF as eluent (color figure online)

Table 1 The characteristics of synthesized materials by GPC

Electroactivity behaviors

The electroactivities of P3EtTh, P3EtBIBTh, P3EtTh-g-PANI, H-PANI, and P3EtTh-g-PSt were studied by the cyclic voltammetric (CV) measurements in 25 mV and scan rates of 10–50 mV s−1 in 0.1 M lithium perchlorate/acetonitrile versus the reference electrode of Ag/AgCl (Fig. 7a–j). The P3EtTh represented a redox pair with anodic and cathodic peaks at − 181, and + 1018 mV, respectively. The P3EtBIBTh also depicted the three cathodic and anodic peaks at − 504, − 220, and 946 mV. The P3EtTh-g-PANI bottlebrushes reflected the three redox pairs with the cathodic and anodic peaks at − 824, − 122, and + 825 mV. In contrast, the CVs curves of H-PANI exhibited the three cathodic/anodic peaks at − 1342, − 148, and + 781 mV. Furthermore, the CVs of P3EtTh-g-PSt bottlebrushes possessed the two redox couples with the cathodic/anodic peaks at − 438 and + 228 mV. For these samples, a shift in the anodic peaks in direction of positive potentials was detected by increasing the scan rate, indicating the reversibility of electrochemical oxidation/reduction (doping/dedoping) properties.

Fig. 7
figure7

Cyclic voltammograms of chemically synthesized P3EtTh (a), P3EtBIBTh (c) P3EtTh-g-PANI (e), H-PANI (g), and P3EtTh-g-PSt (i) samples at a scan rates of 10–50 mV s−1 and P3EtTh (b), P3EtBIBTh (d), P3EtTh-g-PANI (f), H-PANI (h), and P3EtTh-g-PSt (j) samples at constant rate 25 mV, in solution of lithium perchlorate/acetonitrile (0.1 M) between − 2 and + 1.50 V

Thermal properties

Thermal stabilities of P3EtTh, P3EtThBr, P3EtTh-g-PSt, and P3EtTh-g-PANI were investigated upon heating under nitrogen protection by means of TGA (Fig. 8). The thermal decomposition of P3EtTh commenced at 150 °C, and the weight loss increased from this temperature up to 700 °C. The residue at 700 °C for this sample was to some extent 0 wt%. In addition, the thermal decompositions of P3EtThBr and P3EtTh-g-PANI began at 200 °C and the weight losses enhanced from this temperature to 250 °C, after which the weight losses continued with the constant rates. The P3EtTh-g-PSt bottlebrushes represented a somehow similar thermal stability. The weight loss of samples between 100 and 250 °C was also attributed to the evaporation of residual water or organic solvents.

Fig. 8
figure8

TGA curves of P3EtTh (brown), P3EtThBr (red), P3EtTh-g-PSt (blue), and P3EtTh-g-PANI (green) (color figure online)

Electrical conductivity measurement

The electrical conductivities of the synthesized samples were determined using the four-point probe approach. The experimental data were repeated three times to reach the accurate results. Using the values of voltage (V), the current from outer probes (I), thicknesses (d), the volume specific resistivities (ρ, Ω cm), and subsequently, the electrical conductivities (σ; S cm−1) were calculated by the equations of ρ = (V/I) (π/ln2) d and σ = 1/ρ. The electrical conductivity results are reported in Table 2. The grafting of PANI and PS side chains onto the bottlebrush P3EtTh-g-PANI and P3EtTh-g-PSt nanostructures decreased the conductivity up to 0.05 and 0.16 S cm−1, respectively. The highest conductivity of 0.32 S cm−1 was recorded for the pristine P3EtTh backbones. The conductivity values of P3EtTh-g-PANI, and P3EtTh-g-PSt bottlebrushes were equal to 0.27 and 0.16 S cm−1, respectively.

Table 2 Electrical conductivities of synthesized samples

Morphology

So as to deeply investigate the morphology of prepared bottlebrushes, FESEM images are depicted in Fig. 9. The P3EtTh (Fig. 9a) and P3EtThBr (Fig. 9b) represented globular conformations but with different globule sizes. The fibril-like and bubble-like nanostructures were also detected for the P3EtTh-g-PSt and P3EtTh-g-PANI systems, respectively. The morphologies in question are displayed in Fig. 9c and d, respectively. Similar FESEM results were also reported in the literature [44]. The P3EtTh-g-PSt and P3EtTh-g-PANI bottlebrushes were also investigated by means of AFM, and the results are reported in Fig. 10. The polythiophenic backbones having the lengths ranged in 90–100 nm were densely covered by the PSt and PANI brushes to afford the rod–coil and rod–rod bottlebrushes, respectively.

Fig. 9
figure9

FESEM images of P3EtTh (a), P3EtThBr (b), P3EtTh-g-PSt (c), and P3EtTh-g-PANI (d) samples

Fig. 10
figure10

AFM images of P3EtTh-g-PSt (a) and P3EtTh-g-PANI (b) bottlebrushes

Conclusions

The synthesis and characterization of rod–rod and rod–coil bottlebrushes, based on the conductive PANI and non-conductive PSt side chains grafted onto the P3EtTh backbones, were performed. By comparing the electrical conductivities, the PANI grafts elevated the conductivity of bottlebrushes. Therefore, the two bottlebrush nanostructures with to some extent similar configurations possessed different electrical conductivities. The morphologies of P3EtTh-g-PSt and P3EtTh-g-PANI bottlebrushes were investigated by FESEM and AFM analyses. The polythiophenic backbones having the lengths ranged in 90–100 nm were covered by the PSt and PANI brushes to develop the rod–coil and rod–rod bottlebrushes, respectively. The P3EtTh-g-PANI reflected the three redox pairs with cathodic/anodic peaks at − 824, − 122, and + 825 mV, and the typical CVs of P3EtTh-g-PSt possessed the two redox couples at − 438 and + 228 mV. These types of nanostructures could be suitable candidates as soluble conductive polymers in several applications such as organic photovoltaics.

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Acknowledgements

Financial support from Payame Noor University is gratefully acknowledged.

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Correspondence to Raana Sarvari.

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Massoumi, B., Sorkhishams, N., Sarvari, R. et al. Synthesis and characterization of electroactive bottlebrush nano-copolymers based on polystyrene and polyaniline as side chains and poly(3-(2-hydroxyethyl)thiophene) as backbone. Polym. Bull. 77, 3707–3724 (2020). https://doi.org/10.1007/s00289-019-02936-3

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Keywords

  • Bottlebrush
  • Graft
  • ATRP
  • PSt
  • PANI