Doping the Backbone of π‐Conjugated Polymers with Tricoordinate Boron: Synthetic Strategies and Emerging Applications

The doping of π‐conjugated organic compounds with trivalent boron atoms produces materials with intriguing properties and functions that result from the interaction of the π‐electron system with the vacant p orbital on boron. This offers unique opportunities in various applications such as organic (opto)electronics, biomedical imaging, and sensors for physiologically relevant anions or amines, as demonstrated by numerous examples on the molecular scale. Recently, the B‐doping strategy has been expanded to polymer chemistry with a view to benefit from the best of both worlds. Herein, recent advances in the synthesis of π‐conjugated polymers doped with tricoordinate boron in the backbone are reviewed. Selected applications are described where these functional materials have already been successfully implemented.     

Interactions Between Polymers and Nanoparticles: Formation of “Supermicellar” Hybrid Aggregates

Abstract

When polyelectrolyte‐neutral block copolymers are mixed in solutions to oppositely charged species (e.g., surfactant micelles, macromolecules, proteins, etc.), there is the formation of stable “supermicellar” aggregates combining both components. The resulting colloidal complexes exhibit a core‐shell structure, and the mechanism yielding to their formation is electrostatic self‐assembly. In this contribution, we report on the structural properties of “supermicellar” aggregates made from yttrium‐based inorganic nanoparticles (radius 2 nm) and polyelectrolyte‐neutral block copolymers in aqueous solutions. The yttrium hydroxyacetate particles were chosen as a model system for inorganic colloids, and also for their use in industrial applications as precursors for ceramic and opto‐electronic materials. The copolymers placed under scrutiny are the water‐soluble and asymmetric poly(sodium acrylate)‐b‐poly(acrylamide) diblocks. Using static and dynamical light‐scattering experiments, we demonstrate the analogy between surfactant micelles and nanoparticles in the complexation phenomenon with oppositely charged polymers. We also determine the sizes and the aggregation numbers of the hybrid organic–inorganic complexes. Several additional properties are discussed, such as the remarkable stability of the hybrid aggregates and the dependence of their sizes on the mixing conditions.     

Oligo‐ and poly(fullerene)s for photovoltaic applications: Modeled electronic behaviors and synthesis

The atom transfer radical addition polymerization (ATRAP) of fullerene to give poly(fullerene)s (PFs) for organic electronics is explored. Quantum chemistry maps the expected electronic behavior of PFs with respect to common electron acceptors, namely fullerene, phenyl‐C₆₁‐butyric acid methyl ester and its bis‐adduct, and mono‐ and bis‐indine‐fullerene derivatives. Surprisingly, it is found that PFs should demonstrate electron affinities and LUMO energy levels closer to the bis‐derivatives than the mono‐adducts, even though only one C₆₀ double‐bond is used in PF chain formation. A self‐consistent library of PFs is synthesized and a correlation between structural characteristics and molecular weights is found. While comonomers with –OC₁₆H₃₃ linear side‐chains lead to the highest known ATRAP molecular weights of 21000 g mol ^{? 1}, like‐for‐like, branched side‐chains permit syntheses of higher molecular weights and more soluble polymers. Of the series, however, PFs with ‐OC₁₂ side‐chains are expected to be of the greatest interest for opto‐electronic applications due to their ease of handling and highest regioregularity. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1345–1355     

Improvement of thermoplasticity for s‐BPDA/PDA by copolymerization and blend with novel asymmetric BPDA‐based polyimides

Asymmetric biphenyl type polyimides (PI) derived from 2,3,3′,4′‐biphenyltetracarboxylic dianhydride (a‐BPDA) and p‐phenylenediamine (PDA) or 4,4′‐oxydianiline (ODA) show higher T_gs, and much better thermoplasticity than the corresponding isomeric PIs from symmetric 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA). In addition, a‐BPDA‐derived PIs are completely amorphous owing to their bent chain structures and highly distorted conformations, whereas the PIs from s‐BPDA are semicrystalline. a‐BPDA‐derived PIs possessing these properties or the a‐BPDA monomer were used as a flexible blend component or a comonomer to improve the insufficient thermoplasticity of semirigid s‐BPDA/PDA homo polymer. The blends composed of s‐BPDA/PDA (80%) with a‐BPDA‐derived PIs (20%), as well as the s‐BPDA/PDA‐based copolymer containing 20% a‐BPDA, showed a certain extent of thermoplasticity above the T_gs without causing a decrease in T_g. In addition, these blends and copolymer provided comparatively low thermal expansion coefficient (ca. 18 ppm). The improved film properties for the blends are related to good blend miscibility. On the other hand, when s‐BPDA/ODA was used as a flexible matrix polymer instead of a‐BPDA‐derived PIs, the 80/20 blend film annealed at 400°C exhibited no prominent softening at the T_g. This result arises from annealing‐induced crystallization of the flexible s‐BPDA/ODA component. Thus, these results revealed that a‐BPDA‐derived PIs are promising candidates as matrix polymers for semirigid s‐BPDA/PDA for the present purpose. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2499–2511, 1999     

Syntheses and properties of organosoluble polyimides based on 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐4, 7‐methanohexahydroindan

A series of organosoluble aromatic polyimides (PIs) was synthesized from 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐4,7‐methanohexahydroindan (3) and commercial available aromatic dianhydrides such as 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA), 4,4′‐sulfonyl diphthalic anhydride (SDPA), or 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropanic dianhydride (6FDA). PIs (III_c–f), which were synthesized by direct polymerization in m‐cresol, had inherent viscosities of 0.83–1.05 dL/g. These polymers could easily be dissolved in N,N′‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide (DMF), pyridine, m‐cresol, and dichloromethane. Whereas copolymerization was proceeded with equivalent molar ratios of pyromellitic dianhydride (PMDA)/6FDA, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA)/6FDA, or BTDA/SDPA, or ½ for PMDA/SDPA, copolyimides (co‐PIs), derived from 3 and mixed dianhydrides, were soluble in NMP. All the soluble PIs could form transparent, flexible, and tough films, and they showed amorphous characteristics. These films had tensile strengths of 88–111 MPa, elongations at break of 5–10% and initial moduli of 2.01–2.67 GPa. The glass transition temperatures of these polymers were in the range of 252–311°C. Except for III_e, the 10% weight loss temperatures (T_d) of PIs were above 500°C, and the amount of carbonized residues of the PIs at 800°C in nitrogen atmosphere were above 50%. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1681–1691, 1999     

Synthesis and characterization of hyperbranched polyimides with good organosolubility and thermal properties based on a new triamine and conventional dianhydrides

A triamine monomer, 1,3,5‐tris(4‐aminophenoxy)benzene (TAPOB), was synthesized from phloroglucinol and 4‐chloronitrobenzene, and it was successfully polymerized into soluble hyperbranched polyimides (HB PIs) with commercially available dianhydrides: 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA). Different monomer addition methods and different monomer molar ratios resulted in HB PIs with amino or anhydride end groups. From ¹H NMR spectra, the degrees of branching of the amino‐terminated polymers were estimated to be 0.65, 0.62, and 0.67 for 6FDA–TAPOB, ODPA–TAPOB, and BTDA–TAPOB, respectively. All polymers showed good thermal properties with 10% weight‐loss temperatures (T₁₀'s) above 505 °C and glass‐transition temperatures (T_g's) of 208–282 °C for various dianhydrides. The anhydride‐terminated HB PIs showed lower T₁₀ and T_g values than their amino‐terminated counterparts. The chemical conversion of the terminal amino or anhydride groups of the 6FDA‐based polyimides into an aromatic imido structure improved their thermal stability, decreased their T_g, and improved their solubility. The HB PIs had moderate molecular weights with broad distributions. The 6FDA‐based HB PIs exhibited good solubility even in common low‐boiling‐point solvents such as chloroform, tetrahydrofuran, and acetone. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3804–3814, 2002     

Isomeric anthracene diimide polymers

N-type semiconducting polymers are attractive for organic electronics, but desirable electron-deficient units for synthesizing such polymers are still lacking. As a cousin of rylene diimides such as naphthalene diimide (NDI) and perylene diimide (PDI), anthracene diimide (ADI) is a promising candidate; its polymers, however, have not been achieved yet because of synthetic challenges for its polymerizable monomers. Herein, we present ingenious synthesis of two dibromide ADI monomers with dibromination at differently symmetrical positions of the ADI core, which are further employed to construct ADI polymers. More interestingly, the two obtained ADI polymers possess the same main-chain and alkyl-chain structures but different backbone conformations owing to varied linking positions between repeating units. This feature enables their different optoelectronic properties and film-state packing behavior. The ADI polymers offer first examples of conjugated polymer conformational isomers and are highly promising as a new class of n-type semiconductors for various organic electronics applications.

Two anthracene diimide (ADI) polymers with the backbone conformational isomerism, new members of aromatic diimide polymers family, have been synthesized as a class of highly promising n-type semiconductors for organic electronics.     

POLYMERS DERIVED FROM HEXAFLUOROACETONE

Abstract

The continuing demand for polymeric materials with a unique combination of properties has brought forth a sizable research effort concerning the use of trifluoromethyl substituents, particularly the 1,1,1,3,3,3-hexafluoroisopropylidene (HFIP) function derived from the incorporation of hexafluoroacetone (HFA) into the monomer. This work had its beginnings approximately 25 years ago when Rogers briefly reported in a patent the preparation of polyimides (PIs) from an hexafluoroisopropylidenebrideged diamine [1,2]. Since then numerous efforts have been made toward the synthesis, characterization, and evaluation of CF₃-containing polymers. Much of this information is found in patents, indicating the importance of these polymers to industry. At the present time, at least 11 known classes of polymers containing pendant or backbone-incorporated bis-trifluoromethyl groups have been reported. These polymers show promise as film formers, gas separation membranes, seals, soluble polymers, coatings, and in other high-temperature applications. Frequently the polymer properties imparted by the inclusion of the HFIP function encompass: increased solubility, flame resistance, glass transition temperature, thermal stability, oxidation resistance, and environmental stability; decreased color, crystallinity, dielectric constant, and water absorption.     

Synthesis of Oligothiophene‐Layered Polymers

Polymers with layered π‐electron systems comprising bithiophenes and quaterthiophenes based on a xanthene skeleton have been synthesized by an iron‐catalyzed oxidative coupling reaction. The polymers are well soluble in common organic solvents, and polymer thin films are readily obtained by a spin‐coating or casting technique. The synthesized polymers exhibit good thermal stability, and their 10% weight loss temperatures are approximately 400 °C. These behaviors of the polymers suggest that they can be used as opto‐electronic devices such as hole‐transporting materials.

     

Linking polythiophene chains with vinylene‐bridges: A way to improve charge transport in polymer field‐effect transistors

A series of novel branched polythiophene derivatives bearing different densities of vinylene‐bridges as linking chains were synthesized by a general synthetic strategy. The organic field‐effect transistors, which were fabricated by spin‐coating the polymer solutions onto octadecyltrichlorosilane‐modified SiO₂/Si substrates with top‐contact configuration, afforded a high mobility of 8.0 × 10^?3 cm² V^?1 s^?1 with an on/off ratio greater than 10⁴ and a threshold voltage of about ?3 V in saturation regime. The devices based on these polymers possessed better performance than those of polymers without conjugated bridges and polymers with longer conjugated bridges. These results demonstrated that the combination of conjugated polythiophene backbones and vinylene‐bridges would improve the carrier mobility. As an emerging class of conjugated materials, polymers with vinylene‐bridges as linking chains would open up new opportunities in organic electronics, and their applications in organic electronics are promising. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1381–1392, 2009     

Thienyl—Appended porphyrins: Synthesis,photophysical and electrochemical properties,and their applications

This review focuses on the synthesis, photophysical and electrochemical properties of thienyl porphyrins where processes such as electron transfer, energy transfer and electropolymerisation are discussed. The purpose of this review is to examine the influence of the thienyl ring, whether it be directly connected (via meso and β positions) or indirectly connected (via a covalent linker or axial coordination) on the ground and excited state electronic properties of the porphyrin macrocycle. Additionally, the importance of the electronic properties of a bridging oligothiophene between the porphyrin and another centre in supramolecular systems is discussed. Also included are applications of thienyl porphyrins in such areas as catalysis, therapeutics, (opto)electronics and electron-transfer/light-harvesting systems.     

Organophosphorus Compounds in Organic Electronics

This Minireview describes recent advances of organophosphorus compounds as opto‐electronic materials in the field of organic electronics. The progress of (hetero‐) phospholes, unsaturated phosphanes, and trivalent and pentavalent phosphanes since 2010 is covered. The described applications of organophosphorus materials range from single molecule sensors, field effect transistors, organic light emitting diodes, to polymeric materials for organic photovoltaic applications.     

Polyfluorene derivatives pending iridium complexes: Improved optoelectronic properties by introducing D‐A units and altering pendent mode

To study influence of the donor(D)‐acceptor(A) units and pendent mode of phosphorescent moiety on the opto‐electronic properties for its resulting copolymers, two D‐A‐based polyfluorene derivatives ( P 1 and P 2) pending the red‐emitting iridium bi(phenylisoquilonato) (picolinato) [Ir(Piq)₂(pic)] unit and a polyfluorene derivative ( P 3) only pending Ir(Piq)₂(pic) unit were synthesized and characterized, in which the donor of carbazole, the acceptor of oxadiazole are grafted into the C‐9 position of fluorene, the Ir(Piq)₂(pic) unit is pended into either the C‐9 position for P 1 and P 3 or the end for P 2 of fluorene by unconjugated linkage, respectively. Their opto‐electronic properties were significantly influenced by the D‐A units and pendent mode of the Ir(Piq)₂(pic) unit. In the polymer light‐emitting devices with a configuration of ITO/PEDOT/polymers/LiF/Al, the P 1 showed best electroluminescent properties than the P 2 and P 3. The maximum current efficiency of 0.72 cd/A and the highest luminance of 1398 cd/m 2 were obtained in the P 1‐based device, which are 1.3 and 1.5 times higher than those in the P 2‐based device, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Vitamin C Functionalized Poly(Methyl Methacrylate) for Free Radical Scavenging

Abstract

In the present work, a strategy was developed to use mild and highly selective enzymatic methods to covalently couple the primary hydroxyl group of vitamin C with methyl methacrylate monomer, followed by a second enzymatic reaction catalyzed by horseradish peroxidase to polymerize the vinyl monomer yielding a vitamin C functionalized poly(methyl methacrylate) (PMMA). Vitamin C, L‐ascorbyl methylmethacrylate and PMMA, when used at concentrations up to 133 µM, fully scavenged 2,2‐diphenyl‐1‐picryl hydrazyl free radicals (0.2 mM). Thus, the formation of vinyl polymers with active pendent antioxidant compounds, in this case vitamin C, retained an ability to scavenge radicals while in polymeric form. The functionalized antioxidant on a PMMA backbone has implications for consumer‐related applications like foods, pharmaceuticals, and personal care products.     

Energy Transport along Conjugated Polymer Chains with Extended Radiative Lifetimes: A Theoretical Study

The ability to improve exciton diffusion lengths is a key issue in optimizing many opto‐electronic devices based on conjugated polymers. On the basis of quantum‐chemical calculations, we investigate a strategy consisting of extending the radiative lifetime of energy carriers through incorporation along the polymer backbone of repeating units with forbidden optical transition. The results obtained for poly(p‐phenylenebutadiyne), PPE, and poly(p‐triphenylenebutadiyne), PTPE, show that the larger number of hops performed by the electronic excitations during their lifetime in PTPE is compensated by the smaller hopping length (associated with the reduced conjugation length), so that similar on‐chain diffusion lengths are predicted in both polymers.     

Surface Modification of Functional Nanoparticles for Controlled Drug Delivery

Abstract

Surface‐modified nanoparticles have received much attention as drug carriers. Natural and synthetic polymers are used as the materials to prepare nanoparticles and the properties of these nanoparticles originate with these polymeric materials. In particular, these nanoparticles are modified for specific objectives. The surface characteristics of (shell) nanoparticles are more important than those of the core, because the shell layer directly contacts body fluids and organs. Generally, the nanoparticles are coated with hydrophilic polymer to give long circulation and/or are conjugated with functional ligands or proteins for site‐specific delivery. In this review, the preparative methods and the applications of surface modification of polymeric functionalized nanoparticles for long‐circulation, site‐specific delivery, and oral delivery are discussed.     

Synthesis,Characterization, and Structure of Some 1,4‐Disubstituted Cyclopenta[d][1,2]oxazines

Oxazine‐based chemistry offers an alternative to thiophene and pyrrole semiconductors and has been largely unexplored for electronics applications. Discrete monomers or oxazine polymers could serve as an efficient hole carrier for novel devices. A series of 1,4‐disubstituted cyclopenta[d ][1,2]oxazines (R = tolyl, p‐nitrophenyl, t‐buytl, furyl, and 5‐methylthienyl) were isolated via ring closure with hydroxylamine from a 1,2‐acylcyclopentadiene precursor. The target oxazines were characterized by NMR and IR spectroscopy and direct analysis in real time (DART) MS. Single‐crystal x‐ray structure determination confirmed the identity of the tolyl oxazine, which shows a face‐to‐face stacking pattern of the heterocyclic rings.     

Polysulfide Polymers: Synthesis,Blending, Nanocomposites,and Applications

Abstract

Polysulfide polymers as an important class of polymers are used in different applications as sealants, adhesives, etc. They are usually synthesized by reaction of disodium polysulfides with dihalo compounds to yield liquid or solid polymers. Their most important advantages are excellent adhesion to different surfaces, creation of no defect in sealant under stress and pressure, resistance against to fuels and solvents, very low gas and steam permeability, and high resistance to ozone and UV. This article aims to review methods of synthesis, properties, and applications of polysulfide polymers. Also, polysulfide-based nanocomposites and blends are also briefly discussed.     

High Tg and high organosolubility of novel polyimides containing twisted structures derived from 4-(4-amino-2-chlorophenyl)-1-(4-aminophenoxy)-2,6-di-tert-butylbenzene

A series of new polyimides (PIs) containing di-tert-butyl side groups were synthesized via the polycondensation of 4-(4-amino-2-chlorophenyl)-1-(4-aminophenoxy)-2,6-di-tert-butylbenzene (3) with various aromatic tetracarboxylic dianhydrides. The introduction of the asymmetric di-tert-butyl groups and twisted-biphenyl structures is an effective way to increase the inter chain distance and decrease the intermolecular interaction and packing ability of the resulted polymers. Thus, these novel PIs exhibited low dielectric constants (2.83-3.10), low moisture absorption (0.95-1.69%), excellent solubility, and high glass transition temperatures (307-456 °C). The PIs derived from the new diamine and the rigid pyromellitic dianhydride (PMDA) were soluble in N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, tetrahydrofuran, m-cresol, and cyclohexanone. The polymers also show good retention of storage modulus at high temperature (325 °C). In addition, ¹H NMR spectrum of the diamine 3 revealed that the protons of 4-aminophenoxy moiety are not chemical shift equivalent.     

Polymeric Nanocomposites—Polyhedral Oligomeric Silsesquioxanes (POSS) as Hybrid Nanofiller

Abstract

Polyhedral oligomeric silsesquioxane (POSS), a hybrid nanostructured macromer has been used in the last decade for preparation of polymeric nanocomposites. Its versatile chemistry, which lends it for almost infinite chemical modification, sets it apart from other nanostructured fillers like nanoclays, carbon nanotubes, and carbon nanofibers. Depending on its functionality, 3‐D network, bead or pendant type‐POSS based polymeric nanocomposites can be synthesized. These have the potential to be designed for products with specific nanostructures for specific end‐use applications. This article discusses the trends in current research involving use of POSS macromers for modification of mainly thermal and viscoelastic properties of various polymers.