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Progress in Chemistry 2019, Vol. 31 Issue (8): 1103-1115 DOI: 10.7536/PC190209 Previous Articles   Next Articles

Solid State Polymerization of Polythiophene and Its Applications

Ni Huang1, Feng Xu2, Jiangbin Xia1,**()   

  1. College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China
  • Received: Online: Published:
  • Contact: Jiangbin Xia
  • About author:
    ** E-mail:
  • Supported by:
    National Natural Science Foundation of China(21875173)
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Due to their good stability and easy structure tailorability, as the typical type of conjugated polymers, polythiophene derivatives have played big role in organo-electronic and renewable energy involved fields. Meanwhile, solid state polymerization attracts lots of attention from researchers because of its advantages of environment benign, large-scale producibility and so on. Thus, in this review, the progresses of thiophene derivatives monomers design and reaction mechanism are reviewed, including their application involved. Furthermore, their opportunities and challenges are discussed as well.

Key words: conjugated polythiophene and its derivatives, solid state polymerization, energy storage
Fig. 1 Typical conjugated polymers [13]
Fig. 2 Several methods for the preparation of polythiophene and its derivatives[37]
Fig. 3 Solid state polymerization of polybutylene[40]
Fig. 4 Solid state polymerization of S2N2[39]
Fig. 5 Poly (3, 4-ethoxythiophene) absorption spectra: (a) direct solid state polymerization; (b) by hydrazine hydrate treatment [41]
Fig. 6 (left) Solid phase polymerization equation of EDOT and its corresponding monomer and polymer photographs; (right) X-ray crystal structure (monoclinic) view of monomer DBEDOT [40]
Fig. 7 Possible reaction mechanism and process of solid state polymerization of DBEDOT[40]
Fig. 8 2, 5-dibromothiophene derivatives[42]
Fig. 9 Solid state polymerization process of poly 3, 4-ethylenedioxyselene (PEDOSe) [42]
Fig. 10 (a) Vertically designed PEDOT derivatives and (b)synthesis and solid state polymerization of DBProDOT monomer [44]
Table 1 Properties of DBEDTT and DIEDTT and their polymers obtained by solid phase polymerization[45]
Monomer Melting
point		 Polymerization
temperature		 Reaction
time
DBEDTT 55 40 7 d
DIEDTT 130 110 7 d
Fig. 11 Molecular structure of dibromothiophene derivatives[46]
Fig. 12 (left) Polymerization of EDTM derivatives. (right) (a) DB1 X-ray single crystal structure; (b) cell stacking diagram and the distance between adjacent Br-Br atoms [48]
Table 2 The conductivity of PEDOT derivatives prepared by SSP method[47]
Entry Polymer Polymerization method Conductivity
(S/cm)		 Reaction
temperature(℃)
1 PEDOT Oxidation 3.62 30
2 PEDOT SSP 5.91 80
3 PEDTM SSP 44.50 80
4 P1 SSP 0.31 80
5 P2 SSP 19.00 80
6 P3 SSP 1.08 80
7 P1 SSP 161.0 120
Fig. 13 EDOT parallel design strategy and related monomers [48,49]
Table 3 Effects of I2-3-alkyl-EDOT solid-state polymerization temperature (24 h) on molecular weight and PDI[50]
Temperature Yield (%) Mna (kg·mol-1) DPb PDIa
80 ℃ >90 4.40 11 2.19
90 ℃ >90 3.83 10 2.16
100 ℃ >90 3.64 9 1.94
80 ℃(3 d) >90 4.11 10 2.20
Fig. 14 An EDOT derivative of an alkyl chain of different lengths [50]
Fig. 15 Aromatic ring substituted EDOT derivative and its crystal structure [51]
Fig. 16 Monomer based on EDOT-CH (R)-EDOT model [52]
Fig. 17 (a,b) absorption spectra of polymer and de-doped polymer solutions obtained from SSP. (A,B) Cyclic voltammograms of polymer films in acetonitrile solution containing 0.1 M Bu4NClO4 were measured at different scanning rates [52]
Fig. 18 Solid state polymerization of thiophene derivative monomers based on thiophene-(CH-R)-thiophene[53]
Table 4 Melting points of several monomers, starting polymerization temperatures of SSP and MSP[53]
Monomer R1 R2 Melting point SSP
Tonset/℃a		 MSP
Tonset/℃a
M1 H Ph 71 60 95
M2 H 4-Me-Ph 53 - 75
M3 H 4-OMe-Ph 72 - 75
M4 H 4-OOctyl-Ph 37 - 80
M5 H 4-N(CH3)2-Ph 118 100 118
M6 H 4-NO2-Ph 88 80 90
M7 H 4-Cl-Ph 49 - 57
M8 H 4-COOH-Ph 167 90 167
M9 H 4-COOMe-Ph 61 - 75
M10 H 1-Napth 137 75 141
M11 H n-Pr - - 55
M12 H H 54 30 54
M13 Hexyl Ph b - 80
M14 Hexyl 4-OOctyl-Ph b - 80
M15 Hexyl 4-N(CH3)2-Ph b - 100
M16 Hexyl 4-NO2-Ph b - 80
M17 Hexyl 1-naphthyl-H b - 85
M18 OHexyl Ph b - 95
M19 OHexyl 4-NO2-Ph b - 95
Fig. 19 the formula of (2R,3S)-5,7-dibromo-2,3-dimethyl-2,3-dihydrothieno[34-b][1,4]dioxine [43]
Fig. 20 Unit cell (left) and possible polymerization paths (right) [43]
Fig. 21 (a) DBProDOT crystal structure diagram; (b) DBProDOT crystal filling diagram with short contact between bromine atoms 【44]
Fig. 22 Single crystal structure and predicted polymerization route of the monomer Br2-Si-EDOT [49]
Table 5 Some important halogens/halogens and C-C spacing (?)[50,51,52]
Distance
 Br2-C-EDOT (?) I2-Si-EDOT (?) I2-P-EDOT (?) Br2-Si-EDOT (?)
shortest Hal/Hal 4.296 4.343a 4.092 4.059
2nd shortest 4.727 4.492 4.527b 5.228a
3rd shortest 4.805a 4.763 6.481 5.817
shortest C-C 3.914 5.359 3.965 5.284
2nd shortest C-C 5.414 5.676 4.234 5.416
3rd C-C distance 9.186 9.516 9.229 10.196
2rw of Halb 3.7 4.0 4.0 3.7
Longer than 2rw Halb 30.0% 8.6% 13.2% 41.3%
Fig. 23 Linear relationship between initial polymerization temperature and effective halogen distance in solid phase polymerization [55]
Fig. 24 The cyclic voltammetry curves of Pt and poly (3, 4-ethylenedioxythiophene) (PEDOT) were measured in acetonitrile solution containing 10 mM LiI,1 mM I2 and 0.1 M LiClO4[57]
Fig. 25 Schematic diagram of principle and structure of perovskite solar cell[59]
Fig. 26 Doping (a) and (b) to take off the SSP-PEDOTs powder at 800 ℃ and 2600 ℃ graphitization of XRD diagrams [60]
Fig. 27 Structure and morphology of graphite fiber [60]
Fig. 28 (A) Schematic diagram of setting of electrospinning device; (B) compression of DBEDOT/ polymer fiber pad during heating process [62]
Table 6 Thickness and electrical conductivity of PEDOT/ polymer composite films prepared by SSP method[62]
Polymer matrix DBEDOT:polymer (w/w) Thickness (μm) Conductivity
(S/cm)
PS 3∶1 19.9 2.75±0.5
- - 49.4 5.46±0.85
- - 55.2 13.24±1.00
SPS A 3∶1 17.9 13.88±1.96
SPS B 3∶1 18.2 6.75±0.32
PMMA 1∶1 25.0 0.018±0.012
- 2∶1 38.8 17.20±1.05
- 3∶1 45.0 10.73±1.23
- 3∶1 35.2 31.69±6.48
Fig. 29 Schematic diagram of making PEDOT/MnO2 supercapacitor electrode based on FTO [66]
Fig. 30 Fusion polymerization of pyrrole derivatives [67]
Fig. 31 Solid state polymerization of Br-doped conjugated polymer [63]
Fig. 32 Preparation of monolayer conjugated aromatic crystalline polymer (CAP) by interfacial polymerization on gold surface [68]
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