Synthesis and thermal characterization of poly(dimethyl bicyclobutane‐1,3‐dicarboxylate) and its copolymers

Dimethyl bicyclobutane‐1,3‐dicarboxylate was synthesized. Its homopolymer (PDBD) containing exclusively cyclobutane rings in its backbone was prepared by free radical polymerization. The copolymers of this bicyclobutane monomer with methyl methacrylate were also prepared. The glass transition temperature of the homopolymer is 159°C, while those of its copolymers are 143 and 121°C with 75/25 and 50/50 of the P(DBD/MMA) composition ratio, respectively. The T_g of PDBD homopolymer is substantially higher than that of commercial PMMA homopolymer despite a lower molecular weight, and is also much higher than that of its monomethyl cyclobutanecarboxylate analogue. These DBD homopolymer and copolymers also show better thermostability than the PMMA homopolymer. The weight‐average molecular weight of homopolymer is 37,000. The polydispersities of these polymers are relatively narrow, with the range of 1.6–1.9. These polymers form clear colorless films resembling PMMA film. The DBD homopolymer film shows a very similar optical cutoff compared to PMMA. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1569–1575, 1999     

Preparation of amphiphilic statistical copolymers of 2‐hydroxyethyl methacrylate with 2‐diethylaminoethyl methacrylate,precursors of water‐soluble copolymers

Statistical copolymers of 2‐hydroxyethyl methacrylate (HEMA) and 2‐diethylaminoethyl methacrylate (DEA) were synthesized at 50 °C by free‐radical copolymerization in bulk and in a 3 mol L^?1 N,N′‐dimethylformamide solution with 2,2′‐azobisisobutyronitrile as an initiator. The solvent effect on the apparent monomer reactivity ratios was attributed to the different aggregation states of HEMA monomer in the different solvents. The copolymers obtained were water‐insoluble at a neutral pH but soluble in an acidic medium when the molar fraction of the DEA content was higher than 0.5. The quaternization of DEA residues increased the hydrophilic character of the copolymers, and they became water‐soluble at a neutral pH when the HEMA content was lower than 0.25. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2427–2434, 2002     

A novel fluorine‐containing graft copolymer bearing perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains

A series of novel graft copolymers consisting of perfluorocyclobutyl aryl ether‐based backbone and poly(methyl methacrylate) side chains were synthesized by the combination of thermal [2π + 2π] step‐growth cycloaddition polymerization of aryl bistrifluorovinyl ether monomer and atom transfer radical polymerization (ATRP) of methyl methacrylate. A new aryl bistrifluorovinyl ether monomer, 2‐methyl‐1,4‐bistrifluorovinyloxybenzene, was first synthesized in two steps from commercially available reagents, and this monomer was homopolymerized in diphenyl ether to provide the corresponding perfluorocyclobutyl aryl ether‐based homopolymer with methoxyl end groups. The fluoropolymer was then converted to ATRP macroinitiator by the monobromination of the pendant methyls with N‐bromosuccinimide and benzoyl peroxide. The grafting‐from strategy was finally used to obtain the novel poly(2‐methyl‐1,4‐bistrifluorovinyloxybenzene)‐g‐poly(methyl methacrylate) graft copolymers with relatively narrow molecular weight distributions (M_w/M_n ≤ 1.46) via ATRP of methyl methacrylate at 50 °C in anisole initiated by the Br‐containing macroinitiator using CuBr/dHbpy as catalytic system. These fluorine‐containing graft copolymers can dissolve in most organic solvents. This is the first example of the graft copolymer possessing perfluorocyclobutyl aryl ether‐based backbone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Novel thermally latent self‐crosslinkable copolymers bearing oxetane and hemiacetal ester moieties: The synthesis,self‐crosslinking behavior,and thermal properties

Novel thermally latent self‐crosslinkable copolymers ( 14 and 15 ) containing hemiacetal ester and oxetane moieties were synthesized by the radical copolymerizations of 1‐propoxyethyl methacrylate, 3‐ethyl‐3‐methacryloyloxymethyl oxetane, and/or n‐butyl methacrylate at 60 °C in the presence of 2,2′‐azoisobutylonitrile as an initiator. The obtained copolymers showed good solubility for common organic solvents such as tetrahydrofuran, chloroform, and dimethyl sulfoxide (DMSO). The thermal crosslinking behaviors were examined with several Lewis acid catalysts ( 6 ). In particular, the treatment with aluminum‐2‐ethylhexanate triethanolamine complex ( 6c ) at 160 °C was found to efficiently yield the corresponding self‐crosslinked polymers ( 14′ and 15′ ). Incidentally, the resulting products were hardly insoluble in various organic solvents, including DMSO. The thermal properties of the obtained self‐crosslinked polymers 14′ and 15′ were estimated by thermogravimetric analysis and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4260–4270, 2005     

Helix‐sense‐selective copolymerization of triphenylmethyl methacrylate with chiral 2‐isopropenyl‐4‐phenyl‐2‐oxazoline

The asymmetric induction leading to a one‐handed helix was investigated in the anionic and radical copolymerization of triphenylmethyl methacrylate (TrMA) and (S)‐2‐isopropenyl‐4‐phenyl‐2‐oxazoline ((S)‐IPO), and highly isotactic copolymers with a reasonable optical activity were obtained. In the anionic copolymerization, the optical activity of the obtained copolymers depended on the polarity of solvents, and a highly optically active copolymer was produced in the copolymerization in toluene. The chiral oxazoline monomer functioned not only as a comonomer but also as a chiral ligand to endow the polymer with large negative optical rotation in the copolymerization with TrMA. The copolymers with small positive optical rotation were obtained in THF, indicating that IPO unit may work only as the chiral monomer that dictates the helical sense via copolymerization with TrMA. The isotacticity of the obtained copolymers depended on the contents of TrMA units in the copolymers, but was almost independent of the solvent for copolymerization. In the radical copolymerization, the obtained copolymers exhibited small optical activities. It seemed that the chiral monomer cannot induce one‐handed helical structure of TrMA sequences even if the sequences probably have a high isotacticity. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 441–447     

Durable and refreshable polymeric N‐halamine biocides containing 3‐(4′‐vinylbenzyl)‐5,5‐dimethylhydantoin

A novel vinyl‐hydantoin monomer, 3‐(4′‐vinylbenzyl)‐5,5‐dimethylhydantoin, was synthesized in a good yield and was fully characterized with Fourier transform infrared (FTIR) and ¹H NMR spectra. Its homopolymer and copolymers with several common acrylic and vinyl monomers, such as vinyl acetate, acrylonitrile, and methyl methacrylate, were readily prepared under mild conditions. The polymers were characterized with FTIR and ¹H NMR, and their thermal properties were analyzed with differential scanning calorimetry studies. The halogenated products of the corresponding copolymers exhibited potent antibacterial properties against Escherichia coli, and the antibacterial properties were durable and regenerable. The structure–property relationships of the polymers were further discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3348–3355, 2001     

Synthesis and characterization of poly(1,4‐bis((E)‐2‐(3‐dodecylthiophen‐2‐yl)vinyl)benzene) derivatives

New amorphous semiconducting copolymers, poly(9,9‐dialkylfluorene)‐alt‐(3‐dodecylthienyl‐divinylbenzene‐3‐dodecylthienyl) derivatives (PEFTVB and POFTVB), were designed, synthesized, and characterized. The structure of copolymers was confirmed by H NMR, IR, and elemental analysis. The copolymers showed very good solubility in organic solvents and high thermal stability with high T_g of 178–185 °C. The weight average molecular weight was found to be 107,900 with polydispersity of 3.14 for PEFTVB and 76,700 with that of 3.31 for POFTVB. UV–vis absorption studies showed the maximum absorption at 428 nm (in solution) and 435 nm (in film) for PEFTVB and at 430 nm (in solution) and 436 nm (in film) for POFTVB. Photoluminescence studies showed the emission at 498 nm (in solution) and 557 nm (in film) for PEFTVB and at 498 nm (in solution) and 536 nm (in film) for POFTVB. The solution‐processed thin‐film transistors showed the carrier mobility of 2 × 10^?4 cm² V^?1 s^?1 for PEFTVB‐based devices and 2 × 10^?5 cm² V^?1 s^?1 for POFTVB‐based devices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3942–3949, 2010     

Controlled free‐radical polymerization of 2‐vinylpyridine in the presence of nitroxides

Bulk free‐radical polymerization of 2‐vinylpyridine (2VP) in the presence of 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) was studied under different conditions (temperature and presence of additives). Linear poly‐(2‐vinylpyridine) with a narrow molecular weight distribution and controllable molecular weight was prepared in the presence of acetic anhydride at 95 °C up to a conversion of 66%. At higher conversions side reactions became very important (pseudoliving polymerization). By applying this procedure, well‐defined random copolymers of 2VP with styrene or tert‐butylmethacrylate as well as block copolymers of 2VP with styrene were synthesized. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2889–2895, 2001     

Stimulus‐responsive polymers based on 2‐hydroxypropyl acrylate prepared by RAFT polymerization

Homopolymerization and diblock copolymerization of 2‐hydroxypropyl acrylate (HPA) has been conducted using reversible addition fragmentation chain transfer (RAFT) chemistry in tert‐butanol at 80 °C. PHPA homopolymers were obtained with high conversions and narrow molecular weight distributions over a wide range of target degrees of polymerization. Like its poly(2‐hydroxyethyl methacrylate) isomer, PHPA homopolymer exhibits inverse temperature solubility in dilute aqueous solution, with cloud points increasing systematically on lowering the mean chain length. The nature of the end groups is shown to significantly affect the cloud point, whereas no effect of concentration was observed over the PHPA concentration range investigated. Various thermoresponsive PHPA‐based diblock copolymers were prepared via one‐pot syntheses in which the second block was either permanently hydrophilic or pH‐responsive. Preliminary studies confirmed that poly(ethylene oxide)‐poly(2‐hydroxypropyl acrylate) (PEO₄₅‐PHPA₄₈) and poly(2‐hydroxypropyl acrylate)‐ poly(2‐hydroxyethyl acrylate) (PHPA₄₉‐PHEA₆₈)diblock copolymers formed well‐defined PHPA‐core micelles in 10 mM sodium nitrate solution at 40 °C and 70 °C with mean hydrodynamic diameters of 20 nm and 35 nm, respectively. In contrast, most other PHPA‐based diblock copolymers investigated formed larger colloidal aggregates in 10 mM NaNO₃ solution at elevated temperatures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2032–2043, 2010     

Synthesis and dielectric properties of photoreactive polystyrene containing [1‐(3‐isopropenyl‐phenyl)‐1‐methyl‐ethyl]‐carbamate in the side chain

Novel polystyrene derivatives comprising [1‐(3‐isopropenyl‐phenyl)‐1‐methyl‐ethyl]‐carbamate in the side chain were synthesized as photoreactive copolymers. Poly(4‐vinylphenol) was made to react with 1‐(1‐isocyanato‐1‐methyl‐ethyl)‐3‐isopropenyl‐benzene (m‐TMI) and the unreacted hydroxyl groups were protected with acetyl chloride. The copolymers are highly sensitive to the radical photoinitiators that can be activated by irradiation of UV light (λ = 300–365 nm). FTIR spectroscopy was employed to monitor the structural changes in the copolymers exposed to UV irradiation. The dielectric properties of the copolymers were investigated by measuring the capacitance and calculating the permittivity as a function of frequency, along with the I–V characteristics. Their properties were compared with those of thermally crosslinkable poly(4‐vinylphenol) blended with poly(melamine‐co‐formaldehyde), which is frequently used as a dielectric layer in organic field‐effect transistors (OFETs). No significant dielectric dispersion was observed in the frequency range of 1 kHz–1 MHz. The dielectric constant was determined to be in the range of 4.2–6.0, which offers a potential for the application of these copolymers to OFET gate insulators. These soluble dielectrics exhibit good film uniformity and can also be patterned using a standard photolithographic technique. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1710–1718, 2008     

Synthesis and properties of fluorene or carbazole‐based alternating copolymers containing Si and vinylene units in the main chain

Alternating copolymerization of 9,9‐dihexyl‐2,7‐dibromofluorene (HFl), N‐hexyl‐2,7‐dibromocarbazole (2,7‐HCz) or N‐hexyl‐3,6‐dibromocarbazole (3,6‐HCz) with Si‐containing divinyl or diallyl compounds, divinyldimethylsilane, divinyldiphenylsilane, 1,3‐divinyltetramethyldisiloxane, 1,4‐bis(dimethylvinylsilyl)benznene, diallyldimethylsilane, or diallyldiphenylsilane has been investigated using Mizoroki‐Heck reaction with a Pd catalyst. The corresponding alternating copolymers were obtained in good yield. The alternating copolymers from HFl or 2,7‐HCz showed good solubility in typical organic solvents. On the other hand, the copolymer with 3,6‐HCz became insoluble due to the crosslinking. Photophysical properties of the resulting copolymers were investigated with UV–vis absorption and photoluminescence spectroscopy. All the copolymers showed absorption peak derived from π–π* transition at around 340 nm, which was blue shifted in comparison with that of the corresponding homopolymer. Whereas emission peaks of the copolymers of the cast film were red shifted in comparison with that of the homopolymers. Multiple broad absorption peaks, which would be derived from intramolecular charge transfer through σ–π moiety, were also detected in the range from 390 to 450 nm in the spectra of the copolymers containing Si‐vinylene unit. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4513–4521, 2008     

Synthesis and characterization of fluorescent poly[fluorene‐co‐phenylene‐1‐(di‐2‐pyridylamine)] copolymer and its Ru(II) complex

2,2′‐dipyridylamine substituted poly(fluorene‐co‐phenylene) copolymers with different concentrations of dipyridylamine have been synthesized by Suzuki polycondensation. These polymers were found to be soluble in organic solvents such as tetrahydrofuran, chloroform, and dimethylformamide. The photoluminescence of the copolymer was slightly blueshifted as the concentration of dipridylamine was increased. The introduction of dipyridylamine and the ruthenium complex into the polymer significantly improved the photoluminescence efficiency. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4838–4846, 2004     

Synthesis and characterization of poly(arylene ether)s containing 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one or 6‐(4‐hydroxyphenyl)pyridazine moieties

A series of novel soluble pyridazinone‐ or pyridazine‐containing poly(arylene ether)s were prepared by a polycondensation reaction. The pyridazinone monomer, 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one ( 1 ), was synthesized from the corresponding acetophenone and glyoxylic acid in a simple one‐pot reaction. The pyridazinone monomer was successfully copolymerized with bisphenol A (BPA) or 1,2‐dihydro‐4‐(4‐hydroxyphenyl)phthalazin‐1(2H)‐one (DHPZ) and bis(4‐fluorophenyl)sulfone to form high‐molecular‐weight polymers. The copolymers had inherent viscosities of 0.5–0.9 dL/g. The glass‐transition temperatures (T_g's) of the copolymers synthesized with BPA increased with increasing content of the pyridazinone monomer. The T_g's of the copolymers synthesized from DHPZ with different pyridazinone contents were similar to those of the two homopolymers. The homopolymers showed T_g's from 202 to 291 °C by differential scanning calorimetry. The 5% weight loss temperatures in nitrogen measured by thermogravimetric analysis were in the range of 411–500 °C. 4‐(6‐Chloropyridazin‐3‐yl)phenol ( 2 ) was synthesized from 1 via a simple one‐pot reaction. 2 was copolymerized with 4,4′‐isopropylidenediphenol and bis(4‐fluorophenyl)sulfone to form high‐T_g polymers. The copolymers with less than 80 mol % pyridazinone or chloropyridazine monomers were soluble in chlorinated solvents such as chloroform. The copolymers with higher pyridazinone contents and homopolymers were not soluble in chlorinated solvents but were still soluble in dipolar aprotic solvents such as N‐methylpyrrolidinone. The soluble polymers could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3328–3335, 2006     

Synthesis via ATRP,kinetics study and characterization (molecular‐morphological) of 3‐Arm star diblock copolymers of the (PS‐b‐P2VP)3 type

The synthesis of five homopolymers (PS)₃ and the corresponding diblock copolymer 3‐arm stars of the (PS‐b‐P2VP)₃ type is reported through atom transfer radical polymerization. Such star homo‐ and copolymers are prepared without any addition of solvent (bulk polymerization). The kinetics study results lead to the ability of predicting the best polymerization time with high values of monomer to polymer conversion, sufficient polydispersity indices and average molecular weights. Molecular characterization through size exclusion chromatography, viscometry, low‐angle laser light scattering, proton and carbon nuclear magnetic resonance spectroscopy (¹H NMR and ¹³C NMR, respectively) verified the successful synthesis of both homopolymer and copolymer 3‐arm star‐like architectures. Furthermore, the morphological characterization of the final copolymers is reported through transmission electron microscopy studies verifying the self‐assembly without any indication of homopolymer or Cu(I) traces. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 23–32     

Synthesis and photophysical characterization of the free‐radical copolymerization of metaloquinolate‐pendant monomers with methyl methacrylate

A series of novel metaloquinolate [aluminum quinolate (Alq₃), zinc quinolate (Znq₂), and lithium quinolate (Liq)]‐containing copolymers were prepared. This is the first report of the synthesis of metaloquinolate‐containing polymers by free‐radical copolymerization. The structures of the metaloquinolate monomers and copolymers were characterized by ¹H NMR and Fourier transform infrared techniques. The differential scanning calorimetry and thermogravimetric analysis results showed that the copolymers were more thermally stable than the methyl methacrylate homopolymer. The copolymers (<25 wt % Alq₃, <20 wt % Znq₂, or <15 wt % Liq) could be dissolved in common solvents without crosslinking. The ultraviolet–visible absorption and photoluminescence (PL) emission properties of the copolymers were consistent with the literature data of metaloquinolate complexes. The PL efficiencies of the metaloquinolate‐containing copolymers with 25 wt % Alq₃, 20 wt % Znq₂, or 15 wt % Liq were 19.89, 13.24, and 11.82%, respectively. The experimental results indicated that these kinds of materials could be used for practical applications in organic light‐emitting diodes. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 397–406, 2005     

Temperature‐induced aggregation of the copolymers of N‐isopropylacrylamide and sodium 2‐acrylamido‐2‐methyl‐1‐propanesulphonate in aqueous solutions

A series of random copolymers of N‐isopropylacrylamide (NIPAM) and sodium 2‐acrylamido‐2‐methyl‐1‐propanesulphonate (AMPS) was synthesized by free‐radical copolymerization. The content of AMPS in the copolymers ranged from 1.1 to 9.6 mol %. The lower critical‐solution temperature (LCST) of copolymers in water increased strongly with an increasing content of AMPS. The influence of polymer concentration on the LCST of the copolymers was studied. For the copolymers with a higher AMPS content, the LCST decreased faster with an increasing concentration than for copolymers with a low content of AMPS. For a copolymer containing 1.1 mol % of AMPS the LCST dropped by about 3 °C when the concentration increased from 1 to 10 g/L, whereas for a copolymer containing 9.6 mol % of AMPS the LCST dropped by about 10 °C in the concentration range from 2 to 10 g/L. It was observed that the ionic strength of the aqueous polymer solution very strongly influences the LCST. This effect was most visible for the copolymer with the highest content of AMPS (9.6 mol %) for which an increase in the ionic strength from 0.2 to 2.0 resulted in a decrease in the LCST by about 27 °C (from 55 to 28 °C), whereas for the copolymer containing 1.1 mol % of AMPS the LCST decreased only by about 6 °C (from 37 to 31 °C) when the ionic strength increased from 0.005 to 0.3. The reactivity ratios for the AMPS and NIPAM monomer pairs were determined using different methods. The values of r_AMPS and r_NIPAM obtained were 11.0–11.6 and 2.1–2.4, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2784–2792, 2001     

Thermotropic liquid‐crystalline polyesters of 4,4′‐biphenol and phenyl‐substituted 4,4′‐biphenols with 4,4′‐oxybisbenzoic acid

A series of thermotropic polyesters, derived from 4,4′‐biphenol (BP), 3‐phenyl‐4,4′‐biphenol (MPBP), and 3,3′‐bis(phenyl)‐4,4′‐biphenol (DPBP), 4,4′‐oxybisbenzoic acid (4,4′‐OBBA), and other aromatic dicarboxylic acids as comonomers, were prepared by melt polycondensation and were characterized for their thermotropic liquid‐crystalline (LC) properties with a variety of experimental techniques. The homopolymer of BP with 4,4′‐OBBA and its copolymers with either 50 mol % terephthalic acid or 2,6‐naphthalenedicarboxylic acid had relatively high values of the crystal‐to‐nematic transition (448–460 °C), above which each of them formed a nematic LC phase. In contrast, the homopolymers of MPBP and DPBP had low fusion temperatures and low isotropization temperatures and formed nematic melts above the fusion temperatures. Each of these two polymers also exhibited two glass‐transition temperatures, which were associated with vitrified noncrystalline (amorphous) regions and vitrified LC domains, as obtained directly from melt polycondensation. As expected, they had higher glass‐transition temperatures (176–211 °C) than other LC polyesters and had excellent thermal stability (516–567 °C). The fluorescence properties of the homopolymer of DPBP with 4,4′‐OBBA, which was soluble in common organic solvents such as chloroform and tetrahydrofuran, were also included in this study. For example, it had an absorption spectrum (λ_max = 259 and 292 nm), an excitation spectrum (λ_ex = 258 and 292 nm with monitoring at 350 nm), and an emission spectrum (λ_em = 378 nm with excitation at 330 nm) in chloroform. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 141–155, 2002     

Diffusion mobility of reactants,phase equilibrium,and specific features of radical copolymerization kinetics in the nonyl acrylate/2‐methyl‐5‐vinyltetrazole system

Combined analysis of experimental data on monomer diffusion, phase equilibrium, and copolymerization kinetics in systems of monomers (nonyl acrylate and 2‐methyl‐5‐vinyltetrazole) as well as their copolymers and homopolymers was carried out. The composition of the mixture in the vicinity of the growing macroradical can differ significantly from the average composition in the whole reactor volume because of consumption of the more‐reactive reactant 2‐methyl‐5‐vinyltetrazole. Nonyl acrylate exhibited limited compatibility with copolymers enriched in 2‐methyl‐5‐vinyltetrazole and its homopolymer. Phase diagrams were obtained for the latter homopolymer. The concentration plots of the diffusion coefficients of both monomers in their copolymers of various compositions were determined. Microphase separation was observed at specific conversions in the reaction system where the composition of a copolymer and its concentration in a monomer solution approached the binodal of the phase diagram. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1383–1389, 2002     

2,3‐bis(5‐Hexylthiophen‐2‐yl)‐6,7‐bis(octyloxy)‐5,8‐di(thiophen‐2‐yl) quinoxaline: A good construction block with adjustable role in the donor‐π‐acceptor system for bulk‐heterojunction solar cells

Three 2,3‐bis(5‐hexylthiophen‐2‐yl)‐6,7‐bis(octyloxy)‐5,8‐di(thiophen‐2‐yl)‐quinoxaline ( BTTQ )‐based conjugated polymers, namely, PF‐BTTQ ( P1 ), PP‐BTTQ ( P2 ), and PDCP‐BTTQ ( P3 ), were successfully synthesized for efficient polymer solar cells (PSCs) with electron‐rich units of fluorene and dialkoxybenzene and electron‐deficient unit dicyanobenzene, respectively. All the polymers exhibited good solubility in common organic solvents and good thermal stability. Their deep‐lying HOMO energy levels enabled them good stability in the air and the relatively low HOMO energy level assured a higher open circuit potential when used in PSCs. Bulk‐heterojunction solar cells were fabricated using these copolymers blended with a fullerene derivative as an acceptor. All of them exhibited promising performance, and the best device performance with power conversion efficiency up to 3.30% was achieved under one sun of AM 1.5 solar simulator illumination (100 mW/cm²). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and photovoltaic properties of low‐bandgap 4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole‐based poly(heteroarylenevinylene)s

Three novel low‐bandgap copolymers containing alkylated 4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole (HBT) and different electron‐rich functional groups (dialkylfluorene (PFV‐HBT), dialkyloxyphenylene (PPV‐HBT) and dialkylthiophene (PTV‐HBT)) were prepared by Horner polycondensation reactions and characterized by ¹H NMR, gel permeation chromatography, and elemental analysis. The alkyl side chain brings these polymeric materials good solubility in common organic solvents, which is critical for the manufacture of solar cells in a cost‐effective manner. The copolymers exhibit low optical bandgap from 1.48 to 1.83 eV. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the copolymers were measured by cyclic voltammetry. Theoretical calculations revealed that the variation laws of HOMO and the LUMO energy levels are well consistent with cyclic voltammetry measurement. The bulk heterojunction photovoltaic devices with the structure of ITO/PEDOT‐PSS/polymer:PCBM/LiF/Al were fabricated by using the three copolymers as the donor and (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) as the acceptor in the active layer. The device based on PTV‐HBT:PCBM (1:4 w/w) achieved a power conversion efficiency of 1.05% under the illumination of AM 1.5, 100 mW/cm². © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.