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Synthesis, electropolymerization, and electrochromic performances of two novel tetrathiafulvalene–thiophene assemblies

  • Yuhao Li , Shixiong Deng , Pengfei Cai , Chenyun Wang , Han Wang and Yongjia Shen EMAIL logo
Published/Copyright: July 20, 2020
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e-Polymers
From the journal e-Polymers Volume 20 Issue 1

Abstract

6,7-Bis(hexylthio)-2-[(2-hydroxyethyl)thio]-3-methylthio-tetrathiafulvalene (TTF-2) is coupled with thiophene-3-carboxylic acid and thiophene-3,4-dicarboxylic acid by Steglich esterification, respectively, to afford 2-((4′,5′-bis(hexylthio)-5-(methylthio)-[2,2′-bi(1,3-dithiolylidene)]-4-yl)thio)ethyl thiophene-3-carboxylate (TTF-Th) and bis(2-((4′,5′-bis(hexylthio)-5-(methylthio)-[2,2′-bi(1,3-dithiolylidene)]-4-yl)thio)ethyl)thiophene-3,4-di-carboxylate (DTTF-Th). Their structures were characterized by ESI-MS, 1H NMR, and elemental analysis. Electropolymerization of TTF-Th and DTTF-Th was conducted with 0.1 M n-Bu4NPF6. The results indicated that both assemblies could rapidly form polymers via electrochemical deposition. In addition, their electrochromic performances illustrated that the color of P(TTF-Th) could switch from orange-yellow to dark blue, while P(DTTF-Th) changed its color from orange in the neutral state to dark blue in the oxidation state. Moreover, the electrochromic performances of P(DTTF-Th) were better than P(TTF-Th) due to the introduction of one extra TTF unit.

Keywords: electrochromic; electropolymerization; polythiophene; tetrathiafulvalene; selective esterification

1 Introduction

Among all electrochromic materials, conjugated conductive polymers have drawn a great deal of attention during the past few decades due to their structural controllability, high coloration efficiency (CE), fast response time, low cost, and various color changes (1,2). Polythiophene is one of the most common conducting electrochromic polymers, owing to the ease of electropolymerization, stable electrochromic performance, significant color contrast, and considerable conductivity (3).

Compared with inorganic materials, the main drawbacks of conducting electrochromic polymers are the stability of oxidized state and machinability (4). For example, the oxidized unsubstituted polythiophene is unstable in air because of its high oxidation potential. β-Substituted polythiophene could have much lower oxidation potential when electron donors were introduced (4). Thus, numerous novel poly(3-substituted thiophenes) and poly(3,4-sunbstituted thiophenes) have been synthetized and studied, among which poly(3,4-(ethylenedioxy)thiophene) exhibited some extraordinary properties (5,6,7,8). Also, the introduction of long alky chains could improve the solubility of polymer to enhance the machinability.

Tetrathiafulvalene (TTF) and its derivatives with unique electron structure can be reversibly oxidized to radical monocation and dication, which are both thermodynamically stable and aromatic. TTF, as an outstanding electron donor, has generated considerable interest in optoelectronic materials, such as fluorescence probe (9), dye-sensitive solar cell (10), and light-sensitive ambipolar (11). It has also been reported to participate in the construction of conducting polymers in backbone or side chain (12,13,14,15,16).

TTF–thiophene assembly and its polymer were first reported in 1991 by Bryce et al. (17). In the later decades, the electrochromic properties of TTF–thiophene polymers were studied (18,19). In our previous work, TTF derivatives with long alky chains had been developed to form various polymers (15,20,21,22,23), especially TTF–EDOT polymers. The patterns of TTF–thiophene polymers are shown in Figure 1.

Figure 1 Patterns of some TTF-thiophene polymers (15,17,18).
Figure 1

Patterns of some TTF-thiophene polymers (15,17,18).

We found that the intermolecular electron transfer between TTF and EDOT was not significant (23). Hence, TTF moiety was directly introduced to thiophene in this study. Moreover, we decided to attach different numbers of TTF units to thiophenes. By comparing the experimental results of different polymers, we can make a clear understanding of the influence of TTF numbers on electrochromic properties, which is the aim and the innovation of this study.

In this study, TTF and thiophenes were connected via Steglich esterification. The synthetic route is shown in Scheme 1. The assembly, used as monomers, was transformed into polymers via electropolymerization. The results indicated that the polymers possessed electrochromic performances when different potentials were applied to them. Moreover, performances vary because of the number of TTF units.

Scheme 1 The synthetic route of P(TTF-Th) and P(DTTF-Th).
Scheme 1

The synthetic route of P(TTF-Th) and P(DTTF-Th).

2 Experimental

2.1 Instruments and materials

1H NMR was recorded on a Bruker AVANCE 400 (Bruker BioSpin AG Co.); HRMS was obtained by a MAT 8430 spectrometer (ESI; Finnigan); UV-Vis was carried out with USB 2000 miniature UV-Vis spectrometer (Ocean Optics). Cyclic voltammetry and electropolymerization were performed in CHI 620E electrochemical workstation (Shanghai Chenhua Instruments Co. Ltd).

The synthesis of the precursor TTF-1 was performed based on the literature (24). All reagents and solvents were commercially available and provided by certified manufacturers. Dichloromethane (DCM) was dried by CaH2 and fresh-distilled accordingly; N,N-dimethylformamide (DMF) was dehydrated by 4 A molecular sieve.

2.2 Synthesis

2.2.1 TTF-2

TTF-1 (0.57 g, 1 mmol) was dissolved in freshly dried DMF (30 mL). A solution of CsOH (0.19 g, 1.1 mmol) in methanol (5 mL) was added after 10 min. The mixture was stirred under nitrogen for 30 min at room temperature. After bromoethanol (0.5 mL, 7.3 mmol) was added, the mixture was stirred for another 12 h before the completion of reaction. The reaction mixture was extracted by ethyl acetate (3 × 50 mL) and washed with DI water (3 × 50 mL). The organic layer was collected and concentrated by a vacuum evaporator. The residue was purified on silica column chromatography (petroleum ether [PE]:DCM = 2:1, v/v). A total of 0.412 g (73.8%) red powder was obtained. 1H NMR (CDCl3, 400 MHz, TMS, ppm): δ = 3.74 (t, J = 12.0 Hz, 2H, –CH2O), 2.95 (t, J = 12.0 Hz, 2H, –SCH2), 2.81 (t, J = 4.0 Hz, 4H, –SCH2), 2.47 (s, 3H, –SCH3), 1.60 (t, J = 16.0 Hz, 4H, –CH2), 1.42–1.26 (m, 12H, –C3H6), and 0.86 (t, J = 16.0 Hz, 6H, –CH3).

2.2.2 TTF-Th

Thiophene-3-carboylic acid (83 mg, 0.65 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC; 143 mg, 0.75 mmol), and 4-dimethylaminopyridine (DMAP; 92 mg, 0.75 mmol) were dissolved into freshly distilled DCM (20 mL). After stirring for 30 min at 40°C under nitrogen, TTF-2 (279 mg, 0.5 mmol) was added into the reaction mixture. After stirring for 24 h at RT under nitrogen, the reaction mixture was washed with 0.1 M hydrochloric acid (3 × 30 mL) and DI water (3 × 30 mL). The organic layer was collected and concentrated by a vacuum evaporator. The residue was purified on silica column chromatography (PE:DCM = 4:1, v/v). A total of 0.115 g (34.4%) orange powder was obtained. 1H NMR (CDCl3, 400 MHz, TMS, ppm): δ = 8.12 (s, 1H, thiophene), 7.51 (d, J = 4.0 Hz, 1H, thiophene), 7.30 (s, 1H, J = 4.0 Hz, thiophene), 3.54 (t, J = 12.0 Hz, 2H, –CH2CO); HRMS (ESI): [M + Na]+ calcd for: 691.0125; found: 691.0099.

2.2.3 DTTF-Th

Thiophene-3,4-dicarboxylic acid (43 mg, 0.25 mmol), EDC (143 mg, 0.75 mmol), and DMAP (92 mg, 0.75 mmol) were dissolved in freshly distilled DCM (20 mL). After stirring for 30 min at 40°C under nitrogen, TTF-2 (307 mg, 0.55 mmol) was added into the reaction mixture. After stirring for 24 h at RT under nitrogen, the reaction mixture was washed with 0.1 M hydrochloric acid (3 × 30 mL) and DI water (3 × 30 mL). The organic layer was collected and concentrated by a vacuum evaporator. The residue was purified on silica column chromatography (PE:DCM = 4:1, v/v). A total of 75 mg (24.0%) orange powder was obtained. 1H NMR (CDCl3, 400 MHz, TMS, ppm): δ = 7.91 (s, 2H, thiophene), 4.48 (t, J = 12.0 Hz, 4H, –CH2CO), and 3; HRMS (ESI): [M + Na]+ calcd for: 1275.0262; found: 1275.0268.

2.3 Electropolymeriazation

TTF-Th and DTTF-Th were electropolymerized by static-potential chronoamperometry. The initial potential and pace potential were 0 and 2.0 V, respectively. ITO glass was used as both the working and counter electrodes, and Ag/AgCl electrode was used as the reference electrode. The duration of polymerization was 600 s.

P(TTF-Th) was obtained by potentiostatic polymerization of TTF-Th. TTF-Th was dissolved in freshly distilled mixed solvent (acetonitrile [AN]:methylene chloride = 4:1, v/v). The concentration was 0.1 M; n-Bu4NPF6 (0.1 M) was used as the supporting electrolyte.

P(DTTF-Th) was afforded by potentiostatic polymerization of DTTF-Th. Other reaction conditions were the same as that used for P(TTF-Th).

2.4 Electrochromic analysis

The obtained polymer was dissolved in the electrolyte after electropolymerization. The solvent was removed by a vacuum evaporator. The solution of polymer in AN was sprayed on a piece of ITO glass. After being dried in air, the ITO glass was dipped into AN for another 24 h to remove extra n-Bu4NPF6. The film was obtained after being dried in air for 12 h. Figure 2 shows the films before and after immersion in AN.

Figure 2 Digital picture of polymer films immersion in AN: (a) P(TTF-Th) and (b) P(DTTF-Th).
Figure 2

Digital picture of polymer films immersion in AN: (a) P(TTF-Th) and (b) P(DTTF-Th).

The prepared film was placed into a cuvette with 0.1 M n-Bu4NPF6/AN, which also worked as an electrolytic bath. ITO glass was used as the working electrode. Counter electrode was the platinum wire, and Ag/AgCl electrode was used as the reference electrode.

3 Results and discussion

3.1 Electrochemical and optical properties

The electrochemical redox behaviors of TTF-Th and DTTF-Th were examined by cyclic voltammetry at a potential scan rate of 100 mV s−1. The CV curves of TTF-2, TTF-Th, and DTTF-Th are shown in Figure 3, and their oxidation peak data are listed in Table 1. All three compounds exhibited two pairs of redox peaks. With the increase of the scan speed, the current of oxidation peaks enlarged. In the meantime, the peaks migrated due to the polarization of electrodes.

Figure 3 Cyclic voltammetry curves: (a) TTF-2, TTF-Th, and thiophene; (b) TTF-Th at different scan speeds; (c) TTF-2, DTTF-Th, and thiophene; and (d) DTTF-Th at different levels of scan speed.
Figure 3

Cyclic voltammetry curves: (a) TTF-2, TTF-Th, and thiophene; (b) TTF-Th at different scan speeds; (c) TTF-2, DTTF-Th, and thiophene; and (d) DTTF-Th at different levels of scan speed.

Table 1

Oxidation potentials and migration of TTF-2, TTF-Th, and DTTF-Th

Eox11/2(V)Eox21/2(V)ΔEox11/2(mV)ΔEox21/2(mV)
TTF-20.560.91
TTF-Th0.710.9615050
DTTF-Th0.711.03150120

Among these curves, TTF-2 showed two oxidation peaks at 0.56 and 0.91 V, which correspond to the successive oxidation of TTF unit into radial monocation TTF+·and dication TTF2+. TTF-Th and DTTF-Th displayed their Eox11/2 and Eox21/2 at 0.71 V/0.96 V and 0.71 V/1.03 V, respectively. Compared with TTF-2, the first oxidation peak of two assemblies moved positively at 150 mV and the second peak moved positively at 50 and 120 mV migrations. The migration indicated that there is an interaction between TTF and thiophene. As a result, the electron density of the TTF decreased, which became harder to be oxidized.

DTTF-Th was expected to exhibit four pairs of redox peaks since there are two TTF units in this molecule. However, only two pairs appeared at the actual curve, which showed that DTTF-Th is a parallel structure. There are two chemical equivalent TTF units in DTTF-Th.

The UV-Vis spectra of thiophene, TTF-2, TTF-Th, and DTTF-Th (1 × 10−5 M in DCM) are shown in Figure 4. The curve of thiophene shows a strong absorption peak at 211 nm, which refers to the characteristic absorption peak of π-conjugation thiophene ring. TTF-2 displayed a broad absorption band from 230 to 350 nm, with three fine peaks at 254, 311, and 342 nm, indicating the π–π* transition of the TTF unit. Also, the shoulder peak from 370 to 400 nm could be considered as the hydrogen bond interaction (18), which often can be observed in TTF alcohol and carboxylic acid derivatives. The absorption curve of TTF-Th looks like the combination of thiophene and TTF-2, which implies that TTF and thiophene are connected successfully. However, a 40 nm red shift of thiophene absorption peak could be observed, which indicated the intramolecular interaction between TTF and thiophene units. Like TTF-Th, the curve of DTTF-Th exhibited the similar tendency. A 50 nm red shift of thiophene absorption peak could also be observed, indicating stronger interaction between TTF and thiophene units. Compared with TTF-Th, the relative strength of absorption of TTF moiety was stronger because of the existence of two TTF units.

Figure 4 UV-Vis spectra: (a) TTF-2, TTF-Th, and thiophene; (b) TTF-2, DTTF-Th, and thiophene.
Figure 4

UV-Vis spectra: (a) TTF-2, TTF-Th, and thiophene; (b) TTF-2, DTTF-Th, and thiophene.

3.2 Electrochromic performances of the polymers

Figure 5 illustrates the electrochromic behaviors of P(TTF-Th). The wavelength range was from 350 to 850 nm because the ITO glass had influence on the absorption under 350 nm and the upper limit of detection of the instrument was 850 nm. The neutral polymer was orange with no obvious absorption between 350 and 850 nm. With the increase of the applied potential, the oxidation of the polymer film gradually happened at 0.8 V. An absorption band near 430 nm could be observed. The absorption band became stronger and stronger, which finally reached peak at 1.2 V. With increasing potential, the absorption band at 450 nm was weakened and disappeared, while a new and gradually enhanced absorption band appeared at 700 nm. The absorption maximum was observed at 1.5 V when the color of the polymer turned to blue.

Figure 5 Electrochromic curves at increasing potentials: (a) P(TTF-Th) and (b) P(DTTF-Th).
Figure 5

Electrochromic curves at increasing potentials: (a) P(TTF-Th) and (b) P(DTTF-Th).

The absorption band of P(TTF-Th) at 430 nm was considered as the absorption of oligothiophene, which was weakened due to further polymerization. The absorption band at 750 nm referred to the absorption of oxidized polymer.

Some unique electrochromic behaviors of P(DTTF-Th) were exhibited. Like P(TTF-Th), the absorption band at 450 nm appeared at a lower potential (0.6 V). With increasing potential, a new and gradually enhanced absorption band appeared at 700 nm, while the former 450 nm band was also enhanced. The absorption maximum was attained at 1.1 V, while the color of polymer turned to dark blue.

Compared with P(TTF-Th), P(DTTF-Th) was more symmetric. The absorption band of P(DTTF-Th) at 450 nm was considered as the absorption of radical cation of TTF moiety. Thus, the strength was enhanced with the increase of the applied potential. The absorption band at 750 nm also referred to the absorption of oxidized polymer. The lower response potential and the more obvious color change could be fairly attributed to the increase of TTF units.

The coloration response time of two polymers is shown in Figure 6. P(DTTF-Th) had quicker response time (2.7 s) than P (TTF-Th) (5.0 s). Optical contrast refers to the change of transmittance during coloration and bleed process. At 700 nm, the optical contrast of P(TTF-Th) could be easily calculated (16.56%). At 710 nm, P(TTF-Th) had more significant optical contrast (27.12%), which also shows the better electrochromic performance.

Figure 6 (a) The timing transmittance curves of P(TTF-Th); (b) the timing current curve of P(TTF-Th); (c) the timing transmittance curves of P(DTTF-Th); and (d) the timing current curve of P(DTTF-Th).
Figure 6

(a) The timing transmittance curves of P(TTF-Th); (b) the timing current curve of P(TTF-Th); (c) the timing transmittance curves of P(DTTF-Th); and (d) the timing current curve of P(DTTF-Th).

CE can be given by:

(1)CE=ΔODΔQ,ΔOD=logTbTc,

where ΔQ is the time integral of current on unit area. The integral can be obtained by timing current curves, and the area of electrode is provided by the manufacturer. Thus, the CE of P(TTF-Th) at 710 nm is 32.70 cm2 C−1. The value of P(DTTF-Th) is 59.31 cm2 C−1. All the electrochromic parameters are listed in Table 2.

Table 2

Electrochromic performance parameters of two polymers

Polymersλmax (nm)Tb (%)Tc (%)ΔT (%)Response time (s)CE (cm2 C−1)
P(TTF-Th)70079.2262.6616.565.032.70
P(DTTF-Th)71079.0351.9127.122.759.31

3.3 Theoretical calculations

To better understand the electron and structure properties of two polymers, TTF-Th and DTTF-Th, were theoretically calculated by the hybrid density functional theory at the B3LYP/6-31G* level of theory. The geometries and the electron simulation of HOMO/LUMO orbitals are shown in Figure 7. It can be noted that the HOMO wave functions of TTF-Th were located at the TTF unit, the electron rich part, while the electron partly spreads to the thiophene moiety in the LUMO orbital. For DTTF-Th, the HOMO and LUMO wave functions were located on the TTF donor and thiophene acceptor moiety, respectively.

Figure 7 Geometries and HOMO/LUMO orbital simulations: (a) TTF-Th and (b) DTTF-Th.
Figure 7

Geometries and HOMO/LUMO orbital simulations: (a) TTF-Th and (b) DTTF-Th.

In addition, the HOMO/LUMO orbital energies and theoretical band gaps of the polymers are listed in Table 3. The HUMO energy levels of TTF-Th and DTTF-Th were much lower than those of unsubstituted thiophene, and the values were close to the oxidation threshold (approximately −5.27 eV) (25), indicating that the synthesized polymers were resistant to oxidation in air, compared with unsubstituted polythiophene.

Table 3

Theoretical calculated HOMO/LUMO energies and band gap of TTF-Th and DTTF-Th

HOMO (eV)LUMO (eV)Eg (eV)
Thiophene−6.58−0.46−6.12
TTF-Th−5.09−1.34−3.75
DTTF-Th−5.02−1.80−3.22

4 Conclusions

Two novel TTF-thiophene assemblies, TTF-Th and DTTF-Th, were synthesized. The results of UV-Vis absorption spectra and redox showed that there was interaction between TTF and thiophene units in both TTF-Th and DTTF-Th. These two assemblies were electropolymerized to afford the corresponding polymers. P(DTTF-Th) exhibited better electrochromic properties, with lower starting and ending voltage, quicker response time, more significant optical contrast, and better CE. The number of TTF units does influence the electrochromic performances of polymers.

Acknowledgments

This study was financially supported by the National Natural Science Foundation of China (Grant No. 21576087).

Appendix

Figure A1 1H NMR of TTF-2.
Figure A1

1H NMR of TTF-2.

Figure A2 1H NMR of TTF-Th.
Figure A2

1H NMR of TTF-Th.

Figure A3 HRMS (ESI) of TTF-Th.
Figure A3

HRMS (ESI) of TTF-Th.

Figure A4 1H NMR of DTTF-Th.
Figure A4

1H NMR of DTTF-Th.

Figure A5 HRMS (ESI) of DTTF-Th.
Figure A5

HRMS (ESI) of DTTF-Th.

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Received: 2020-04-30
Revised: 2020-06-06
Accepted: 2020-06-22
Published Online: 2020-07-20

© 2020 Yuhao Li et al., published by De Gruyter

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

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  15. On-demand optimize design of sound-absorbing porous material based on multi-population genetic algorithm
  16. Enhancement of mechanical, thermal and water uptake performance of TPU/jute fiber green composites via chemical treatments on fiber surface
  17. Enhancement of mechanical properties of natural rubber–clay nanocomposites through incorporation of silanated organoclay into natural rubber latex
  18. Preparation and characterization of corn starch/PVA/glycerol composite films incorporated with ε-polylysine as a novel antimicrobial packaging material
  19. Preparation of novel amphoteric polyacrylamide and its synergistic retention with cationic polymers
  20. Effect of montmorillonite on PEBAX® 1074-based mixed matrix membranes to be used in humidifiers in proton exchange membrane fuel cells
  21. Insight on the effect of a piperonylic acid derivative on the crystallization process, melting behavior, thermal stability, optical and mechanical properties of poly(l-lactic acid)
  22. Lipase-catalyzed synthesis and post-polymerization modification of new fully bio-based poly(hexamethylene γ-ketopimelate) and poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) copolyesters
  23. Dielectric, mechanical and thermal properties of all-organic PI/PSF composite films by in situ polymerization
  24. Morphological transition of amphiphilic block copolymer/PEGylated phospholipid complexes induced by the dynamic subtle balance interactions in the self-assembled aggregates
  25. Silica/polymer core–shell particles prepared via soap-free emulsion polymerization
  26. Antibacterial epoxy composites with addition of natural Artemisia annua waste
  27. Design and preparation of 3D printing intelligent poly N,N-dimethylacrylamide hydrogel actuators
  28. Multilayer-structured fibrous membrane with directional moisture transportability and thermal radiation for high-performance air filtration
  29. Reaction characteristics of polymer expansive jet impact on explosive reactive armour
  30. Synthesis of a novel modified chitosan as an intumescent flame retardant for epoxy resin
  31. Synthesis of aminated polystyrene and its self-assembly with nanoparticles at oil/water interface
  32. The synthesis and characterisation of porous and monodisperse, chemically modified hypercrosslinked poly(acrylonitrile)-based terpolymer as a sorbent for the adsorption of acidic pharmaceuticals
  33. Crystal transition and thermal behavior of Nylon 12
  34. All-optical non-conjugated multi-functionalized photorefractive polymers via ring-opening metathesis polymerization
  35. Fabrication of LDPE/PS interpolymer resin particles through a swelling suspension polymerization approach
  36. Determination of the carbonyl index of polyethylene and polypropylene using specified area under band methodology with ATR-FTIR spectroscopy
  37. Synthesis, electropolymerization, and electrochromic performances of two novel tetrathiafulvalene–thiophene assemblies
  38. Wetting behaviors of fluoroterpolymer fiber films
  39. Plugging mechanisms of polymer gel used for hydraulic fracture water shutoff
  40. Synthesis of flexible poly(l-lactide)-b-polyethylene glycol-b-poly(l-lactide) bioplastics by ring-opening polymerization in the presence of chain extender
  41. Sulfonated poly(arylene ether sulfone) functionalized polysilsesquioxane hybrid membranes with enhanced proton conductivity
  42. Fmoc-diphenylalanine-based hydrogels as a potential carrier for drug delivery
  43. Effect of diacylhydrazine as chain extender on microphase separation and performance of energetic polyurethane elastomer
  44. Improved high-temperature damping performance of nitrile-butadiene rubber/phenolic resin composites by introducing different hindered amine molecules
  45. Rational synthesis of silicon into polyimide-derived hollow electrospun carbon nanofibers for enhanced lithium storage
  46. Synthesis, characterization and properties of phthalonitrile-etherified resole resin
  47. Highly thermally conductive boron nitride@UHMWPE composites with segregated structure
  48. Synthesis of high-temperature thermally expandable microcapsules and their effects on foaming quality and surface quality of foamed ABS materials
  49. Tribological and nanomechanical properties of a lignin-based biopolymer
  50. Hydroxyapatite/polyetheretherketone nanocomposites for selective laser sintering: Thermal and mechanical performances
  51. Synthesis of a phosphoramidate flame retardant and its flame retardancy on cotton fabrics
  52. Preparation and characterization of thermoresponsive poly(N-isopropylacrylamide) copolymers with enhanced hydrophilicity
  53. Fabrication of flexible SiO2 nanofibrous yarn via a conjugate electrospinning process
  54. Silver-loaded carbon nanofibers for ammonia sensing
  55. Polar migration behavior of phosphonate groups in phosphonate esterified acrylic grafted epoxy ester composites and their role in substrate protection
  56. Solubility and diffusion coefficient of supercritical CO2 in polystyrene dynamic melt
  57. Curcumin-loaded polyvinyl butyral film with antibacterial activity
  58. Experimental-numerical studies of the effect of cell structure on the mechanical properties of polypropylene foams
  59. Experimental investigation on the three-dimensional flow field from a meltblowing slot die
  60. Enhancing tribo-mechanical properties and thermal stability of nylon 6 by hexagonal boron nitride fillers
  61. Preparation and characterization of electrospun fibrous scaffolds of either PVA or PVP for fast release of sildenafil citrate
  62. Seawater degradation of PLA accelerated by water-soluble PVA
  63. Review Article
  64. Mechanical properties and application analysis of spider silk bionic material
  65. Additive manufacturing of PLA-based scaffolds intended for bone regeneration and strategies to improve their biological properties
  66. Structural design toward functional materials by electrospinning: A review
  67. Special Issue: XXXII National Congress of the Mexican Polymer Society
  68. Tailoring the morphology of poly(high internal phase emulsions) synthesized by using deep eutectic solvents
  69. Modification of Ceiba pentandra cellulose for drug release applications
  70. Redox initiation in semicontinuous polymerization to search for specific mechanical properties of copolymers
  71. pH-responsive polymer micelles for methotrexate delivery at tumor microenvironments
  72. Microwave-assisted synthesis of the lipase-catalyzed ring-opening copolymerization of ε-caprolactone and ω-pentadecanolactone: Thermal and FTIR characterization
  73. Rapid Communications
  74. Pilot-scale production of polylactic acid nanofibers by melt electrospinning
  75. Erratum
  76. Erratum to: Synthesis and characterization of new macromolecule systems for colon-specific drug delivery
https://doi.org/10.1515/epoly-2020-0044
Keywords for this article
electrochromic; electropolymerization; polythiophene; tetrathiafulvalene; selective esterification
Creative Commons
BY 4.0

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  6. Investigation on compatibility of PLA/PBAT blends modified by epoxy-terminated branched polymers through chemical micro-crosslinking
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  12. Animal fat and glycerol bioconversion to polyhydroxyalkanoate by produced water bacteria
  13. Effect of microstructure on the properties of polystyrene microporous foaming material
  14. Synthesis of amphiphilic poly(ethylene glycol)-block-poly(methyl methacrylate) containing trityl ether acid cleavable junction group and its self-assembly into ordered nanoporous thin films
  15. On-demand optimize design of sound-absorbing porous material based on multi-population genetic algorithm
  16. Enhancement of mechanical, thermal and water uptake performance of TPU/jute fiber green composites via chemical treatments on fiber surface
  17. Enhancement of mechanical properties of natural rubber–clay nanocomposites through incorporation of silanated organoclay into natural rubber latex
  18. Preparation and characterization of corn starch/PVA/glycerol composite films incorporated with ε-polylysine as a novel antimicrobial packaging material
  19. Preparation of novel amphoteric polyacrylamide and its synergistic retention with cationic polymers
  20. Effect of montmorillonite on PEBAX® 1074-based mixed matrix membranes to be used in humidifiers in proton exchange membrane fuel cells
  21. Insight on the effect of a piperonylic acid derivative on the crystallization process, melting behavior, thermal stability, optical and mechanical properties of poly(l-lactic acid)
  22. Lipase-catalyzed synthesis and post-polymerization modification of new fully bio-based poly(hexamethylene γ-ketopimelate) and poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) copolyesters
  23. Dielectric, mechanical and thermal properties of all-organic PI/PSF composite films by in situ polymerization
  24. Morphological transition of amphiphilic block copolymer/PEGylated phospholipid complexes induced by the dynamic subtle balance interactions in the self-assembled aggregates
  25. Silica/polymer core–shell particles prepared via soap-free emulsion polymerization
  26. Antibacterial epoxy composites with addition of natural Artemisia annua waste
  27. Design and preparation of 3D printing intelligent poly N,N-dimethylacrylamide hydrogel actuators
  28. Multilayer-structured fibrous membrane with directional moisture transportability and thermal radiation for high-performance air filtration
  29. Reaction characteristics of polymer expansive jet impact on explosive reactive armour
  30. Synthesis of a novel modified chitosan as an intumescent flame retardant for epoxy resin
  31. Synthesis of aminated polystyrene and its self-assembly with nanoparticles at oil/water interface
  32. The synthesis and characterisation of porous and monodisperse, chemically modified hypercrosslinked poly(acrylonitrile)-based terpolymer as a sorbent for the adsorption of acidic pharmaceuticals
  33. Crystal transition and thermal behavior of Nylon 12
  34. All-optical non-conjugated multi-functionalized photorefractive polymers via ring-opening metathesis polymerization
  35. Fabrication of LDPE/PS interpolymer resin particles through a swelling suspension polymerization approach
  36. Determination of the carbonyl index of polyethylene and polypropylene using specified area under band methodology with ATR-FTIR spectroscopy
  37. Synthesis, electropolymerization, and electrochromic performances of two novel tetrathiafulvalene–thiophene assemblies
  38. Wetting behaviors of fluoroterpolymer fiber films
  39. Plugging mechanisms of polymer gel used for hydraulic fracture water shutoff
  40. Synthesis of flexible poly(l-lactide)-b-polyethylene glycol-b-poly(l-lactide) bioplastics by ring-opening polymerization in the presence of chain extender
  41. Sulfonated poly(arylene ether sulfone) functionalized polysilsesquioxane hybrid membranes with enhanced proton conductivity
  42. Fmoc-diphenylalanine-based hydrogels as a potential carrier for drug delivery
  43. Effect of diacylhydrazine as chain extender on microphase separation and performance of energetic polyurethane elastomer
  44. Improved high-temperature damping performance of nitrile-butadiene rubber/phenolic resin composites by introducing different hindered amine molecules
  45. Rational synthesis of silicon into polyimide-derived hollow electrospun carbon nanofibers for enhanced lithium storage
  46. Synthesis, characterization and properties of phthalonitrile-etherified resole resin
  47. Highly thermally conductive boron nitride@UHMWPE composites with segregated structure
  48. Synthesis of high-temperature thermally expandable microcapsules and their effects on foaming quality and surface quality of foamed ABS materials
  49. Tribological and nanomechanical properties of a lignin-based biopolymer
  50. Hydroxyapatite/polyetheretherketone nanocomposites for selective laser sintering: Thermal and mechanical performances
  51. Synthesis of a phosphoramidate flame retardant and its flame retardancy on cotton fabrics
  52. Preparation and characterization of thermoresponsive poly(N-isopropylacrylamide) copolymers with enhanced hydrophilicity
  53. Fabrication of flexible SiO2 nanofibrous yarn via a conjugate electrospinning process
  54. Silver-loaded carbon nanofibers for ammonia sensing
  55. Polar migration behavior of phosphonate groups in phosphonate esterified acrylic grafted epoxy ester composites and their role in substrate protection
  56. Solubility and diffusion coefficient of supercritical CO2 in polystyrene dynamic melt
  57. Curcumin-loaded polyvinyl butyral film with antibacterial activity
  58. Experimental-numerical studies of the effect of cell structure on the mechanical properties of polypropylene foams
  59. Experimental investigation on the three-dimensional flow field from a meltblowing slot die
  60. Enhancing tribo-mechanical properties and thermal stability of nylon 6 by hexagonal boron nitride fillers
  61. Preparation and characterization of electrospun fibrous scaffolds of either PVA or PVP for fast release of sildenafil citrate
  62. Seawater degradation of PLA accelerated by water-soluble PVA
  63. Review Article
  64. Mechanical properties and application analysis of spider silk bionic material
  65. Additive manufacturing of PLA-based scaffolds intended for bone regeneration and strategies to improve their biological properties
  66. Structural design toward functional materials by electrospinning: A review
  67. Special Issue: XXXII National Congress of the Mexican Polymer Society
  68. Tailoring the morphology of poly(high internal phase emulsions) synthesized by using deep eutectic solvents
  69. Modification of Ceiba pentandra cellulose for drug release applications
  70. Redox initiation in semicontinuous polymerization to search for specific mechanical properties of copolymers
  71. pH-responsive polymer micelles for methotrexate delivery at tumor microenvironments
  72. Microwave-assisted synthesis of the lipase-catalyzed ring-opening copolymerization of ε-caprolactone and ω-pentadecanolactone: Thermal and FTIR characterization
  73. Rapid Communications
  74. Pilot-scale production of polylactic acid nanofibers by melt electrospinning
  75. Erratum
  76. Erratum to: Synthesis and characterization of new macromolecule systems for colon-specific drug delivery
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