Synthesis and Characterization of a Block Copolymer Containing Regioregular Poly(3‐hexylthiophene) and Poly(γ‐benzyl‐L‐glutamate)

Poly(3‐hexylthiophene)‐b‐poly(γ‐benzyl‐L ‐glutamate) (P3HT‐b‐PBLG) rod–rod diblock copolymer was synthesized by a ring‐opening polymerization of γ‐benzyl‐L ‐glutamate‐N‐carboxyanhydride using a benzylamine‐terminated regioregular P3HT macroinitiator. The opto‐electronic properties of the diblock copolymer have been investigated. The P3HT precursor and the P3HT‐b‐PBLG have similar UV–Vis spectra both in solution and solid state, indicating that the presence of PBLG block does not decrease the effective conjugation length of the semiconducting polythiophene segment. The copolymer displays solvatochromic behavior in THF/water mixtures. The morphology of the diblock copolymer depends upon the solvent used for film casting and annealing results in morphological changes for both films deposited from chloroform and trichlorobenzene.

     

Photoluminescence Study on Charge Transfer Behavior of Poly(3‐hexylthiophene) and PCBM Blends

Charge transfer behavior of Poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl eser (PCBM) in solutions and in films were examined by photoluminescence (PL) spectroscopy. PL study in solutions indicated that separation distance between P3HT and PCBM affected charge transfer efficiency more seriously than the interface area issue between P3HT and PCBM. P3HT/PCBM film showed very effective photo‐induced charge transfer before post‐thermal annealing on the bi‐layer P3HT/PCBM film. Charge transfer efficiency was gradually diminished by the annealing‐induced phase separation between P3HT and PCBM as revealed by increasing PL emission intensity of P3HT.     

New Strategy for Enzymatic Synthesis of High‐Molecular‐Weight Poly(butylene succinate) via Cyclic Oligomers

Summary: High‐molecular‐weight poly(butylene succinate) (PBS) is prepared by the lipase‐catalyzed polymerization of dimethyl succinate and butane‐1,4‐diol via the formation of cyclic oligomers as a new strategy for the green production of bio‐based plastics. The cyclic oligomer is first produced by the lipase‐catalyzed condensation of dimethyl succinate and butane‐1,4‐diol in a dilute toluene solution using lipase from Candida antarctica, followed by the ring‐opening polymerization of the cyclic oligomer in a more concentrated solution or in bulk with the same lipase to produce PBS with an of 130 000. On the other hand, PBS is produced with an of 45 000 by direct polycondensation.

The lipase‐catalyzed preparation of PBS by two routes.     

Poly(3‐hexylthiophene) films prepared using binary solvent mixtures

Binary solvent mixtures were routinely used to induce the hierarchical assembly of poly(3‐hexylthiophene) (P3HT) in the liquid phase. This technique has garnered a lot of interest as a route to well‐organized films and composites, but, to date, the impact that the attributes of the liquid‐phase aggregates and solvent mixtures have on the organization of the films have only been partially scrutinized. The molecular weight and concentration dependence of P3HT assembly in three binary solvent mixtures containing chloroform and acetonitrile, n‐hexane, or dichloromethane were studied using ultraviolet/visible absorbance spectroscopy and dynamic light scattering techniques. Films drop cast under slow and rapid evaporation conditions were observed using optical and atomic force microscopy. In general, there is no evidence that the characteristics of the liquid phase P3HT aggregates impact the structures of the films, but films cast from these solvent mixtures under rapid evaporation conditions exhibit an array of disparate morphologies and mesoscale patterning. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 624–638     

Poly(3‐hexylthiophene) aggregation at solvent–solvent interfaces

The aggregation behavior of P3HT is investigated at the interface of orthogonal solvents for P3HT. The changeable characteristics of P3HT aggregate dispersions, for example, extent of aggregation and intrachain order, are studied by varying (1) the interfacial area, (2) the poor solvent used to induce aggregation – dichloromethane (DCM), hexane (HEX), and acetonitrile (AcN) – and (3) the relative composition of the good solvent, chloroform (CF), and poor solvents. The results are compared to those observed using rapid injection of the solvent. Miscibility gap values (Δδ) provide a reasonable justification of the assembly behavior of P3HT in the solvent mixtures in terms of the kinetics of polymer aggregation and the kinetics of solvent mixing at the interface. Atomic force microscopy (AFM) is used to analyze the morphology of films processed from dispersions with disparate characteristics, but having the same solvent composition, for example, 70:30 CF:HEX or 60:40 CF:DCM. Based on the disparity of the kinetics and miscibility gap values, the prevalence of specific structural motifs in the films, for example, spheroids (globules) and fibers, is effectively rationalized in terms of the structural attributes of the aggregates in the liquid phase rather than the evaporation rate (boiling point) differences of the solvents in the mixture. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 999–1011     

Reduced Graphene Oxide/Poly(3‐hexylthiophene) Supramolecular Composites

Poly(3‐hexylthiophene) (P3HT) supramolecular structures are fabricated on P3HT‐dispersed reduced graphene oxide (RGO) monolayers and surfactant‐free RGO monolayers. P3HT is able to disperse RGO in hot anisole/N,N‐dimethylformamide solvents, and forms nanowires on RGO surfaces through a RGO induced crystallization process. The TEM and AFM investigation of the resultant P3HT/RGO composites shows that P3HT nanowires grow from RGO, and connect individual RGO monolayers. Raman spectroscopy confirms the interaction between P3HT and RGO, which allows the manipulation of the RGO electrical properties. Such a bottom‐up approach provides interesting graphene‐based composites for nanometer‐scale electronics.

     

Direct Correlation Between Electric and Structural Properties During Solidification of Poly(3‐hexylthiophene) Drop‐Cast Films

Structural and electrical properties of semicrystalline P3HT cast films onto Si/SiO₂ surface are studied during the solidification under applied electric field in lateral OFET geometry. During evaporation of the solvent, the formation of P3HT crystallites is monitored simultaneously by time‐resolved X‐ray diffraction and by source‐drain current measurements. The electrical current is reaching its maximum in two pronounced regimes already before complete solidification of the polymer as detected by X‐ray diffraction intensities. The monitored complex time dependence of current and X‐ray intensities reveals a highest conducting level for the gel‐like state.     

Kumada Catalyst‐Transfer Polycondensation: Mechanism,Opportunities, and Challenges

Kumada catalyst‐transfer polycondensation (KCTP) is a new but rapidly developing method with great potential for the preparation of well‐defined conjugated polymers (CPs). The recently discovered chain‐growth mechanism is unique among the various transition metal‐catalyzed polycondensations, and has thus attracted much attention among researchers. Most progress is found in the areas of mechanism and external initiation via new initiators, but also the number of monomers other than thiophene that can be polymerized is steadily increasing. Accordingly, the variety of CP chain architectures is increasing as well, and a considerable contribution of KCTP toward more efficient materials can be expected in the future. This review critically focuses on very recent progress in the synthesis of CPs and the mechanism of KCTP, and is finally aimed at providing a comprehensive picture of this exciting polymerization method.

     

Precision Synthesis of Poly(3‐hexylthiophene) from Catalyst‐Transfer Suzuki−Miyaura Coupling Polymerization

^tBu₃ PPd(Ph)Br ( 1 )‐catalyzed Suzuki‐Miyaura coupling polymerization of 2‐(4‐hexyl‐5‐iodo‐2‐thienyl)‐4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane ( 2 ) was investigated. Monomer 2 was polymerized with 1 at 0 °C in the presence of CsF and 18‐crown‐6 in THF containing a small amount of water to yield P3HT with a narrow molecular weight distribution and almost perfect head‐to‐tail regioregularity. The values increased up to 11 400 g · mol⁻¹ in proportion to the feed ratio of 2 to 1 . The MALDI‐TOF mass spectra showed that P3HT with moderate molecular weight uniformly had a phenyl group at one end and a hydrogen atom at the other, indicating involvement of a catalyst‐transfer mechanism. Successive 1 ‐catalyzed polymerization of fluorene monomer 3 and then 2 yielded a well‐defined block copolymer of polyfluorene and P3HT.

     

Exploring the synthesis and impact of end‐functional poly(3‐hexylthiophene)

In recent years, end‐functional poly(3‐hexylthiophene) (P3HT) has proven to be instrumental in the continued development and innovation within the broad conjugated polymer arena, enabling a variety of applications, particularly in organic electronics. The availability of P3HT with controlled molecular weights, low polydispersity, and importantly, a wide range of reactive end‐groups not only serves as a key building block for the preparation of conjugated block copolymers but also facilitates the development of hybrid nanocomposite materials via inorganic surface modification strategies. This Highlight focuses on the synthetic approaches to end‐functional P3HT and the impact of these systems in emerging technologies. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 831–841     

Minimization of the auxiliary reagent loading for direct arylation polymerization (DArP) of 2‐bromo‐3‐hexylthiophene

In this work, we present a powerful set of synthetic strategies aimed at minimization of auxiliary reagent loading for direct arylation polymerization (DArP) of 2‐bromo‐3‐hexylthiophene. As such, we report efficient lowering of Pd(OAc)₂ catalyst loading as well as loading of other auxiliary reagents, such as neodecanoic acid and N,N‐dimethylacetamide. Unprecedented low loadings of catalyst down to 0.0313% (313 ppm) were achieved, while producing polymer in high yield (91% after Soxhlet extraction), with a high molecular weight (24.2 kDa) and carefully controlled chemical structure thus making the optimized DArP protocol significantly more cost‐effective, convenient, sustainable, and environmentally friendly. The resulting polymer samples were thoroughly investigated in terms of their chemical structure as well as optical, thermal, chain ordering and electronic properties using GPC analysis, ¹H NMR, MALDI, UV–vis, GIXRD spectroscopy, DSC, and SCLC hole mobility measurements. The results demonstrate that the reagent lowering strategies increase the polymer regioregularity from 94.6 to 96.5% as evidenced by ¹H NMR spectra and corroborated by GIXRD, DSC, and UV–vis measurements. Additionally, polymer samples obtained at low reagent loading are more uniformly proton‐terminated as evidenced by ¹H NMR and MALDI end‐group analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1492–1499     

Solubility characteristics of poly(3‐hexylthiophene)

Solubility data for poly(3‐hexylthiophene) (P3HT) in 29 pure solvents are presented and discussed in detail. Functional solubility parameter (FSP) and convex solubility parameter (CSP) computations are performed and the CSP and FSP results are compared to previously reported Hansen solubility parameters (HSPs) and to the parameters calculated using additive functional group contribution methods. The empirical data reveals experimental solubility parameters with substantial polar (δ_P) and hydrogen‐bonding (δ_H) components, which are not intrinsic to the structure of the P3HT polymer. Despite these apparent irregularities, it is shown that the predictor method based on the solubility function, f, does provide a reliable way to quantitatively evaluate the solubility of P3HT in other solvents in terms of a given set of empirical solubility data. The solubility behavior is further investigated using linear solvation energy relationship (LSER) modeling and COSMO‐RS computations of the activity coefficients of P3HT. The LSER model reveals that (1) the cavity term, δ_T, is the dominant factor governing the solubility behavior of P3HT and (2) the solvent characteristics that dictate the structural order (crystallinity) of P3HT aggregates do not similarly influence the overall solubility behavior of the polymer. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1075–1087     

The effect of amide solvent structure on the direct arylation polymerization (DArP) of 2‐Bromo‐3‐hexylthiophene

In this work, we investigate the influence of the amide solvent chemical structure on the properties of poly(3‐hexylthiophene) (P3HT) prepared via direct arylation polymerization (DArP). Our findings indicate that for successful polymerization the amide must possess an acyclic aliphatic structure since cyclization of an amide results in a complete shutdown of DArP reactivity as evidenced by failed polymerization in N‐methylpyrrolidone, whereas the presence of an aromatic motif renders the amide solvent susceptible to C? H activation and leads to incorporation of the solvent structure into the P3HT backbone, as demonstrated on the example of N,N‐diethylbenzamide. Additionally, we observed that the steric bulk of alkyl substituents on both the nitrogen atom and the carbonyl group within the amide structure has to be delicately balanced for optimal DArP reactivity. In the optimal cases, P3HT is obtained in high yield, with high molecular weight and contains a minimal amount of structural defects. The obtained polymer samples were comprehensively studied in terms of their chemical structure, optical, thermal and solid‐state properties in thin films using GPC analysis, ¹H NMR, MALDI, UV–vis, GIXRD spectroscopy, and DSC. We additionally note a drastic difference of the amide solvent effect between DArP and Stille polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2494–2500     

Catalyst‐Transfer Suzuki–Miyaura Condensation Polymerization of Stilbene Monomer: Different Polymerization Behavior Depending on Halide and Aryl Group of ArPd(tBu3P)X Initiator

We report Suzuki–Miyaura coupling polymerization of tetraalkoxy‐substituted 4‐bromostilbene‐4′‐boronic acid 1 with several t‐Bu₃P‐ligated Pd initiators; this is the first example of catalyst‐transfer condensation polymerization (CTCP) of a monomer containing a carbon–carbon double bond. When o‐tolylPd(^tBu₃P)Br was used as the initiator, the o‐tolyl group was not introduced at the polymer end, but polymer with boronic acid at one end and bromine at the other was obtained. However, when we employed stilbenePd(^tBu₃P)I generated in situ from iodostilbene and Pd(^tBu₃P)G2 precatalyst, or isolated ArPd(^tBu₃P)X (Ar, X = Ph, I; o‐tolyl, I; and Ph, Br), the aryl group was introduced at the polymer end, indicating that CTCP of 1 proceeded. Therefore, the iodide and aryl group of the Pd initiator complex is crucial for CTCP of 1 . However, the molecular weight distribution of the obtained polymer was broad, possibly because coordination of the carbon–carbon double bond of 1 to ArPd(^tBu₃P)I resulted in slow initiation. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 297–304     

Regioregular Poly(3‐hexylthiophene) in a Novel Conducting Amphiphilic Block Copolymer

Regioregular poly(3‐hexylthiophene) has been successfully incorporated into a novel amphiphilic block copolymer. The amphiphilic nature of poly(3‐hexylthiophene)‐block‐poly(acrylic acid) has been investigated using spectroscopic methods and has yielded solvatochromic behavior in several solvents of varying polarity. Evidence suggests that a supramolecular, long range ordering of block copolymer occurs in polar solvents, resulting in the formation of aggregates. Despite relatively large amounts of non‐conductive blocks, the poly(3‐hexylthiophene) diblock copolymer yields a high conductivity of 1 S · cm⁻¹, and atomic force microscopy shows the formation of a highly organized nanofibrilar morphology in the solid state.

     

Synthesis of Novel μ‐Star Copolymers with Poly(N‐Octyl Benzamide) and Poly(ε‐Caprolactone) Miktoarms through Chain‐Growth Condensation Polymerization,Styrenics‐Assisted Atom Transfer Radical Coupling,and Ring‐Opening Polymerization

Star copolymers are known to phase separate on the nanoscale, providing useful self‐assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ‐star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ‐star copolymers presenting poly(N‐octyl benzamide) (PBA) and poly(ε‐caprolactone) (PCL) arms: a combination of chain‐growth condensation polymerization, styrenics‐assisted atom transfer radical coupling, and ring‐opening polymerization. Gel permeation chromatography, mass‐analyzed laser desorption/ionization mass spectrometry, and ¹H NMR spectroscopy reveal the successful synthesis of a well‐defined (PBA₁₁)₂‐(PCL₁₅)₄ μ‐star copolymer (M _n,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA₂PCL₄ μ‐star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm.

     

Design of Well‐Defined Monofunctionalized Poly(3‐hexylthiophene)s: Toward the Synthesis of Semiconducting Graft Copolymers

The post‐functionalization of poly(3‐hexylthiophene) (P3HT) via various synthetic routes is reported. Well‐defined and monofunctionalized ω‐thiol‐terminated P3HT, ω‐carboxylic acid‐terminated P3HT, ω‐acrylate‐terminated P3HT, and ω‐methacrylate‐terminated P3HT are obtained in high yields through a straightforward procedure. From those, different novel P3HT‐based graft copolymers are synthesized following two routes: “grafting onto” and “grafting through” (macromonomer polymerization) methods. The synthesis of three types of graft copolymers is described. Each one has “rod” P3HT‐grafted side chains on a “coil” main chain, which can be polyisoprene, poly(vinyl alcohol), or poly(butyl acrylate). Each copolymer is characterized by size‐exclusion chromatography and NMR.     

Hydrodynamic properties and conformation of poly(3‐hexylthiophene) in dilute solutions

Conducting polymers demonstrate low solubility in organic solvents. Introducing aliphatic substituents into polymer chains improves their solubility, but may also lead to changes in conformational characteristics of macromolecules. In the present work, the studies of hydrodynamic properties and conformational characteristics of comb‐shaped poly(3‐hexylthiophene) with aliphatic side substituents were carried out in chloroform solutions. Conformational analysis of the studied macromolecules was performed for the first time using homologous series with a wide range of molecular weights of the polymers in dilute solutions. The hydrodynamic properties of these macromolecules were interpreted using the worm‐like spherocylinder model and the straight spherocylinder model. The projection of the monomer unit in the direction of the main polymer chain λ = 0.37 nm was determined experimentally. The following parameters of poly(3‐hexylthiophene) were characterized and quantified: equilibrium rigidity (Kuhn segment length) А = 6.7 nm and hydrodynamic diameter of a polymer chain d = 0.6 nm. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 875–883