New series of AB2‐type hyperbranched polytriazoles derived from the same polymeric intermediate: Different endcapping spacers with adjustable bulk and convenient syntheses via click chemistry under copper(I) catalysis

In this article, according to the concept of “suitable isolation group,” six new AB₂‐type polytriazoles containing azo‐chromophore moieties, derived from the same hyperbranched polymer intermediate, were successfully prepared through click reaction under copper(I) catalysis by modifying the synthetic route, in which different isolation groups in different size were introduced to the periphery of the hyperbranched polymers as end‐capping moieties. With the different end‐capping groups, these hyperbranched polymers, P1 – P6 , exhibited different solubility and processability; also, their nonlinear optical properties were modified accordingly, realizing the adjustment of the properties of hyperbranched polymers through the structural design. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Polymer thermal and acoustic properties using heterodyne detected transient grating technique

We investigated the acoustic and thermal features of a polymeric system by a heterodyne detected transient grating technique. We studied two polymers characterized by different molecular weights. Transient grating experiments could reveal a reliable series of information on sound velocity, acoustic damping time, and thermal diffusion of the polymers. The temperature and molecular weight dependence of the polymer acoustic and thermal properties are reported. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Synthesis and two‐photon absorption properties of conjugated polymers with N‐arylpyrrole as conjugated bridge and isolation moieties

Three novel conjugated polymers with N‐arylpyrrole as the conjugated bridge were designed and synthesized, which emitted strong one‐ or two‐photon excitation fluorescence in dilute tetrahydrofuran (THF) solution with high quantum yields. The maximal two‐photon absorption (TPA) cross‐sections of the polymers, measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in THF, were 752, 1114, and 1869 GM, respectively, indicating that the insertion of electron‐donating or electron‐withdrawing moieties into the polymer backbone could benefit to the increase of the TPA cross‐section. Their large TPA cross‐sections, coupled with the relatively high emission quantum yields, made these conjugated polymers attractive for practical applications, especially two‐photon excited fluorescence. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

New imidazole‐functionalized polyfluorene derivatives: convenient postfunctional syntheses,sensitive probes for metal ions and cyanide,and adjustable output signals with diversified fluorescence color

Based on our previous work on the sensitive and selective conjugated fluorescent polymeric sensors toward cyanide, 2,1,3‐benzothiadiazole and 4,7‐bis(thiophen‐2‐yl)‐2,1,3‐benzothiadiazole were incorporated into the polyfluorene backbone to yield three new polymers bearing imidazole moieties in the side chains, with different fluorescence color. The fluorescence could be turned off by Cu²⁺ ions and then recovered on addition of cyanide, making them good cyanide sensors with the detection limit down to 1.9 μM. Moreover, by fully understanding this “turn off–turn on” strategy and using the cooperation of two polymers with different fluorescence color, the emission color of the mixture system of one of the imidazole‐containing polymers and one from the corresponding polymers without imidazole ones, could be adjusted by the concentrations of the added copper and cyanide ions, leading to the output fluorescent signals diversity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of helical poly(phenylacetylene)s bearing cinchona alkaloid pendants and their application to asymmetric organocatalysis

Four novel dynamic helical poly(phenylacetylene)s bearing cinchona alkaloids as pendant groups were synthesized starting from the commercially available cinchona alkaloids, cinchonidine, cinchonine, quinine, and quinidine, by the polymerization of the corresponding phenylacetylene monomers with a rhodium catalyst. These polymers exhibited an induced circular dichroism (ICD) in the UV–visible region of the polymer backbones in solution, resulting from the preferred‐handed helical conformation induced by the optically active cinchona alkaloid pendants. In response to the solvent used, their Cotton effect patterns and intensities were significantly changed accompanied by the changes in their absorption spectra probably due to the changes in their helical conformations, such as the inversion of the helical sense or helical pitch of the polymers. When these helical polymers were used as polymeric organocatalysts for the asymmetric conjugated addition and Henry reactions, the optically active products with a modest enantiomeric excess were obtained whose enantioselectivities were comparable to those obtained with the corresponding cinchona alkaloid‐bound monomers as the catalysts. However, we observed a unique enhancement of the enantioselectivity and a reversal of the stereoselectivity for some helical polymers, suggesting the important role of the helical chirality during the asymmetric organocatalysis. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and thermal crosslinking of carbosiloxane and oligo(oxyethylene) polymers

Acyclic diene metathesis (ADMET) polymerization has been used in the synthesis of telechelic materials using alkoxy‐functionalized carbosiloxane or oligo(oxyethylene)‐based polymers, varying from internal to terminal cured materials or the combination of them. Previous investigations demonstrated that introduction of chain‐end crosslinking improves the stress–strain behavior of such materials. A series of saturated and unsaturated carbosiloxane and oligo(oxyethylene)‐based polymers were synthesized by ADMET polymerization using silacyclobutane as chain‐end, thermally induced crosslinker. The carbosiloxane derivatives presented pure amorphous behavior, whereas the oligo(oxyethylene) polymers were semicrystalline. The thermal curing process was monitored by differential scanning calorimetry via the exotherm between 160 and 210 °C. Mechanical properties on thermoset polymers were measured, where cured polymers showed moduli from 0.6 to 9.3 MPa, tensile strengths from 0.3 to 1.0 MPa, and elongations from 12 to 76%. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Bandgap engineering of indenofluorene‐based conjugated copolymers with pendant donor‐π‐acceptor chromophores for photovoltaic applications

Three narrow‐band‐gap conjugated copolymers based on indenofluorene and triphenylamine with pendant donor‐π‐acceptor chromophores were successfully synthesized by post‐functionalization approach. All the polymers have good solubility in common solvents and excellent thermal stability. The photophysical properties, energy levels and band gaps of the polymers were well manipulated by introducing different acceptor groups onto the end of their conjugated side chains. By using different acceptor groups, the band gaps of the polymers were narrowed from 1.86 to 1.53 eV by lowering their lowest unoccupied molecular orbital levels, whereas their relatively deep highest occupied molecular orbital levels of approximately ?5.35 eV were maintained. Bulk‐heterojunction solar cells with these polymers as electron donors and (6,6)‐phenyl‐C₇₁‐butyric acid methyl ester as acceptor showed power conversion efficiencies as high as 3.1% and high open circuit voltages more than 0.88 eV. The relationships between the performance and film morphology, energy levels, charge mobilities were discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of dendronized polymers through bergman cyclization of enediyne‐containing Frechet‐type dendrimers

In this article, dendronized polymers with rigid backbones were synthesized from enediyne‐containing Frechet‐type dendrimers. Two generations of dendrimers were conically incorporated with 3‐(2‐(2‐(trimethylsilyl)ethynyl)phenyl)prop‐2‐yn‐1‐ol. The trimethylsilyl protection groups of enediyne units were subsequently removed, and two types of brush polymers with rigid conjugated backbone were prepared through Bergman cyclization polymerization at elevated temperature under vacuum. The dendronized polymers were characterized with GPC, IR, UV–vis, and NMR spectroscopy. Furthermore, the morphology of the dendronized polymer was revealed by atomic force microscopy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Hydrogen‐bonded supramolecular polymers from derivatives of α‐amino‐ε‐caprolactam: A bio‐based material

Hydrogen‐bonded supramolecular polymers were prepared from the derivatives of α‐amino‐ε‐caprolactam (ACL), obtained from a renewable resource. Several self‐complimentary bis‐ or tetra‐caprolactam monomers were synthesized by varying the number of carbons of the spacer between the hydrogen‐bonding end groups. Physical properties of these hydrogen‐bonded polymers were clearly demonstrated by differential scanning colorimetry, solid‐state NMR, and X‐ray powder diffraction analyses. The supramolecular behavior was also supported by fiber formation from the melt for several of these compounds, and stable glassy materials were prepared from the physical mixtures of two different biscaprolactams. The self‐association ability of ACL was also used by incorporating ACL at the chain ends of low‐molecular weight Jeffamine (M_n = 900 g/mol) using urea and amide linkages. The transformation of this liquid oligomer at room temperature into a self‐standing, transparent film clearly showed the improvement in mechanical properties obtained by the introduction of terminal hydrogen‐bonding groups. Finally, the use of monomers with a functionality of four gave rise to network formation either alone or combination with bifunctional monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Stable and good color purity white light‐emitting devices based on random fluorene/spirofluorene copolymers doped with iridium complex

Conjugated polymers PSNFP and PSNFF based on naphthalene‐containing spirofluorene structure and 9,9‐dioctylfluorene, 2,5‐dioctylbezene were designed and synthesized for light emitting applications. These two polymers show good blue emission both in solution and thin film. Thermal gravimetric analysis reveals they have good thermal stability with the decomposition temperature higher than 400 °C. Electrochemistry characterization shows that both of these polymers have a large band gap and deep highest occupied molecular orbital, which are important features for phosphorescent host materials. White light‐emitting diodes were fabricated by using PSNFF as the host material, containing two typical phosphorescent Ir complex dopants: green emitter Ir(mppy)₃ and red emitter Ir(piq)₂. The color coordinate CIE stayed nearly constant, changed from (0.32, 0.31) to (0.28, 0.31) when the current density varied from 2 to 20 mA cm^?2. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis and photophysical properties of soluble low‐bandgap thienothiophene polymers with various alkyl side‐chain lengths

We report the facile synthesis and characterization of a class of thienothiophene polymers with various lengths of alkyl side chains. A series of 2‐alkylthieno[3,4‐b]thiophene monomers (Ttx) have been synthesized in a two‐step protocol in an overall yield of 28–37%. Poly(2‐alkylthieno[3,4‐b]thiophenes) (PTtx, alkyl: pentyl, hexyl, heptyl, octyl, and tridecyl) were synthesized by oxidative polymerization with FeCl₃ or via Grignard metathesis (GRIM) polymerization methods. The polymers are readily soluble in common organic solvents. The polymers synthesized by GRIM polymerization method (PTtx‐G) have narrower molecular weight distribution (?) with lower molecular weight (M_n) than those synthesized by oxidative polymerization (PTtx‐O). The band structures of the polymers with various lengths of alkyl side chains were investigated by UV–vis spectroscopy, cyclic voltammetry, and ultraviolet photoelectron spectroscopy. These low‐bandgap polymers are good candidates for organic transistors, organic light‐emitting diodes, and organic photovoltaic cells. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Low‐temperature side‐chain cleavage and decarboxylation of polythiophene esters by acid catalysis

Solubility switching of polymers is very useful in thin layer processing of conjugated polymers, as it allows for multilayer processing and increases the stability of the polymer. Acid catalyzed thermocleavage of ester groups from thiophene polymers carrying primary, secondary, and tertiary substituents have been examined by TGA‐MS using different sulphonic acids. A substantial lowering of the cleavage temperature is observed, and the ester cleavage can even be performed in situ on roll‐to‐roll‐coated films on polyethylene terephthalate (PET). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of poly(quinoxaline‐2,3‐diyl)s with alkoxy side chains by aromatizing polymerization of 4,5‐dialkoxy‐substituted 1,2‐ diisocyanobenzenes

Poly(quinoxaline‐2,3‐diyl)s bearing alkoxy pendants was synthesized by living polymerization of 4,5‐dialkoxy‐3,6‐dimethyl‐1,2‐diisocyanobenzenes, which were easily accessible from 3,6‐dimethylcatechol, using organonickel complexes as initiators. Thermal properties of the obtained polymers were fully determined by thermogravimetric analysis and differential scanning calorimetry, exhibiting strong dependence on their side chains. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

“Clickable” polymers via a combination of RAFT polymerization and isocyanate chemistry

We describe a facile, one‐pot, two‐step polymerization towards synthesizing block co‐polymers bearing reactive isocyanate functional groups. Reversible addition fragmentation chain transfer (RAFT) polymerization is used to mediate the co‐polymerization of isocyanate‐bearing monomers dimethyl meta‐isopropenyl benzyl isocyanate (TMI) and 2‐isocyanatoethyl methacrylate (ICEMA) with styrene and methyl methacrylate (MMA), respectively. ICEMA was incorporated into the polymer at a faster rate than TMI and its unhindered isocyanate group was found to be more reactive than the hindered isocyanate group of TMI. Both the TMI/styrene and the MMA/ICEMA systems maintain the reactivity of the isocyanate functionality, which was exploited by attaching representative hydroxyl‐bearing small and large molecules as well as solid substrates to the block co‐polymers. Thus, we demonstrate the versatility of the block co‐polymer system as a basis for forming branched polymers or as grafts for a solid substrate. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and properties of copolymers of ethylene/carbon monoxide with styrene/carbon monoxide

The terpolymerization of ethylene, styrene, and carbon monoxide was accomplished by two different palladium‐based catalysts: a phosphine‐based ligand system and a nitrogen‐based ligand system. The range of possible compositions and the composition dependence of the properties of the resulting polymers were determined. These polymers were essentially carbon monoxide versions of the ethylene styrene interpolymers recently presented by Dow. A comparison between the two families of polymers is attempted. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 752–757, 2000     

Preparation of porous crosslinked polymers with different surface morphologies via chemically induced phase separation

A novel and simple method for producing crosslinked polymers with controlled surface morphology is demonstrated in this study. The porous crosslinked polymers were made via stepwise polymerization of a mixture of epoxy resin, D.E.R. 331, and diethylene triamine in diisobutyl ketone (DIBK). Both the surface and bulk morphology of the cured polymers are dependent on the solvent fraction of the reactive solution. When the concentration of DIBK was more than about 30 vol %, chemically induced phase separation (CIPS) occurred during cure at 30 °C, and closed spherical pores, about 4 μm in diameter, appeared in the bulk of the crosslinked polymers, whose diameter increased to about 4.5 and 9 μm when the solvent was increased to 40% and 50%, respectively. The surface morphology of the epoxy networks is different from that of the bulk. Smaller pore size or dense skin was formed via the CIPS process, which can be tailored by covering the reactive solution with different contacting films during cure. The competition between the solvent‐rich and polymer‐rich phase absorbed onto the surface of contacting film could change the surface morphology. Therefore, the porous crosslinked polymers having similar bulk morphology could be prepared with a variety of surface structures. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Synthesis and postfunctionalization of well‐defined star polymers via “double” click chemistry

In this article, the synthesis and the functionalization of well‐defined, narrow polydispersity (polydispersity index < 1.2) star polymers via reversible addition‐fragmentation chain transfer polymerization is detailed. In this arm first approach, the initial synthesis of a poly(pentafluorophenyl acrylate) polymer, and subsequent, cross‐linking using bis‐acrylamide to prepare star polymers, has been achieved by reversible addition fragmentation chain transfer polymerization. These star polymers were functionalized using a variety of amino functional groups via nucleophilic substitution of pentafluorophenyl activated ester to yield star polymers with predesigned chemical functionality. This approach has allowed the synthesis of star glycopolymer using a very simple approach. Finally, the core of the stars was modified via thiol‐ene click chemistry reaction using fluorescein‐o‐acrylate and DyLigh 633 Maleimide. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Using multimodal blends to elucidate the mechanism of flow‐induced crystallization in polymers

The effect of polydispersity on the formation of flow‐induced, oriented morphology in polyolefins is investigated by polarized light imaging and small angle X‐ray scattering. A torsional shear flow was applied at different temperatures to model polyethylene blends (bimodal and trimodal hydrogenated polybutadienes) comprising of two kinds of long chains with different molecular weight (1080 and 1770 kDa) in a matrix of short chains (18 KDa), and the results were compared to those of polydisperse materials. While a single boundary associated with the threshold flow conditions for the onset of oriented morphology is observed in the bimodal blends, two boundaries corresponding to the orientation of the longest chains (1770 kDa) and next longest chains (1080 kDa) are detected in the trimodal blends. The results obtained, herein, are extended by inference to polydisperse polymers. It is demonstrated that the shear rate dependence of the critical specific work parameter for the onset of oriented morphology in polydisperse polymers is dictated by the molecular weight distribution and that the longest chains mainly control the process with some contribution from shorter chains involved in the formation of flow‐induced precursors at higher flow rates. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Latex aging: The effects of coalescing agents and thermal annealing on the morphology of composite latex particles

Many composite polymer latices are produced with nonequilibrium particle morphologies and these can be prone to structural changes with the time of storage. Here we report on the use of coalescing agents, and separately thermal annealing to follow the morphology changes with aging time. Two coalescing agents with very different water solubilities were used to plasticize the latex polymers. During months of storage time the polymer particles were analyzed via differential scanning calorimetry and transmission electron microscopy. A parallel set of aging experiments were carried out for the same latices where the change agent was simple thermal annealing. Both latex and dry polymer samples were annealed at temperatures above 100 °C and for various periods of time. Both sets of experiments lead to the conclusion that when the aging temperature is at or above the effective glass transition temperature (taking into account solvent plasticization) of the glassiest of the polymers in a two‐component latex, morphological change can be rather fast and easily characterized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1583–1589, 2011     

New moderate bandgap polymers containing alkoxysubstituted‐benzo[c][1,2,5]thiadiazole and thiophene‐based units

Alkoxysubstituted benzo[c][1,2,5]thiadiazole electron accepting units were prepared and copolymerized with various thiophene‐based electron donating monomers to produce new low bandgap polymers P1–4 . The materials showed broad absorption in the range from 300 to 700 nm with bandgaps below 2 eV in solution. Efficiencies of over 1% were obtained from photovoltaic cells using P4 with PCBM as acceptor. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011