Synthesis of sulfonated poly(arylene-co-naphthalimide)s as novel polymers for proton exchange membranes

A series of novel sulfonated poly(arylene-co-binaphthalimide)s (SPPIs) were successfully synthesized via Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and bis(chloronaphthalimide)s. Bis(chloronaphthalimide)s were conveniently prepared from 5-chloro-1,8-naphthalic anhydride and various diamines. Tough and transparent SPPI membranes were prepared and the electrolyte properties of the copolymers were intensively investigated as were the effects of different diamine structures on the copolymer characterisitics. The copolymer membrane Ia-80, with an ion exchange capacity (IEC) of 2.50 meq g(-1), displayed a higher proton conductivity, i.e. 0.135 S cm(-1) at 20 degrees C, as compared to Nafion 117 (0.09 S cm(-1), 20 degrees C).

Critical behavior of brittle-ductile transition of polymers

We report that the brittle-ductile transition of polymers induced by temperature exhibits critical behavior. When t close to 0, the critical surface to surface interparticle distance (IDc) follows the scaling law: IDc proportional to t(-v) where t = 1 - T/T-BD(m) (T and T-BD(m) are the test temperature and brittle-ductile transition temperature of matrix polymer, respectively) and v = 2/D. It is clear that the scaling exponent v only depends on dimension (D). For 2, 3, and 4 dimension, v = 1, 2/3, and 1/2 respectively. The result indicates that the ID, follows the same scaling law as that of the correlation length (xi), when t approach to zero.

Blue electroluminescent polymers with dopant-host systems and molecular dispersion features: polyfluorene as the deep blue host and 1,8-naphthalimide derivative units as the light blue dopants

We developed a series of highly efficient blue electroluminescent polymers with dopant-host systems and molecular dispersion features by selecting 1,8-naphthalimide derivatives as the light blue emissive dopant units, choosing polyfluorene as the deep blue emissive polymer host and covalently attaching the dopant units to the side chain of the polymer host. The polymers' EL spectra exhibited both deep blue emission from the polymer host and light blue emission from the dopant units because of the energy transfer and charge trapping from the polymer host to the dopant units.

Highly efficient red electroluminescent polymers with dopant/host system and molecular dispersion feature: polyfluorene as the host and 2,1,3-benzothiadiazole derivatives as the red dopant

By selecting polyfluorene as the polymer host, choosing 2,1,3-benzothiadiazole derivative moieties as the red dopant units and covalently attaching 0.3 mol% of the dopant units to the side chain of the polymer host, we developed a novel series of red electroluminescent polymers of dopant/host system with molecular dispersion feature. Their EL spectra exhibited predominant red emission from the dopant units because of the energy transfer and charge trapping from the polymer backbone to the dopant units. The emission wavelength of the polymers could be tuned by modifying the chemical structures of the dopant units.

Synthesis and characterization of color-stable electroluminescent polymers: Poly(dinaphtho [1,2-a : 1 ',2 '-g]-s-indacene)s

Two new stepladder conjugated polymers, that is, poly(7,7,15,15-tetraoctyldinaphtho[1,2-a:1',2'-g]-s-indacene) (PONSI) and poly(7,7,15,15-tetra(4-octylphenyl)dinaphtho[1,2-a:1',2'-g]-s-indacene) (PANSI) with alkyl and aryl substituents, respectively, have been synthesized and characterized. In comparison with poly(indenofluorene)s, both polymers have extended conjugation at the direction perpendicular to the polymer backbone because of the introduction of naphthalene moieties. The emission color of the polymers in film state is strongly dependent on the substituents. While PONSI emits at a maximum of 463 nm, PANSI with the same backbone but aryl substituents displays dramatically redshifted emission with a maximum at 494 nm.

Novel pH- and temperature-responsive block copolymers with tunable pH-responsive range

A series of novel pH- and temperature-responsive diblock copolymers composed of poly(N-isopropylacrylamide) (PNIPAM) and poly[(L-glutamic acid)-co-(gamma-benzyl L-glutamate)] [P(GA-co-BLG)] were prepared. The influence of hydrophobic benzyl groups on the phase transition of the copolymers was studied for the first time. With increasing BLG content in P(GA-co-BLG) block, the thermal phase transition of the diblock copolymer became sharper at a designated pH and the critical curve of phase diagram of the diblock copolymer shifted to a higher pH region.

Ion-Responsive Behavior of Ionic-Liquid Surfactant Aggregates with Applications in Controlled Release and Emulsification

We propose a simple but efficient, rapid, and quantitative ion-responsive micelle system based on counter-anion exchange of a surfactant with an imidazolium unit. The ion-exchange reaction results in the amphiphilic-to-hydrophobic transition of the imidazolium salt, leading to the destruction of the micelles, which has been successfully applied to control led release and emulsification.

3-phenylethynyl phthalimide end-capped imide oligomers and the cured polymers

In the past decades, 4-phenylethynyl phthalic anhydride (4-PEPA) has been the most important endcapper used for thermoset polyimide. As the isomer of 4-PEPA, 3-phenylethynyl phthalic anhydride (3-PEPA) has attracted our interest. In this article, 3-PEPA was synthesized and a comparative study with 4-PEPA on curing temperature, curing rate, thermal and mechanical properties of oligomers and cured polymers was presented. The new phenylethynyl endcapped model compound, N-phenyl-3-phenylethynyl phthalimide, was synthesized and characterized.

Poly(oligothiophene-alt-benzothiadiazole)s: Tuning the Structures of Oligothlophene Units toward High-Mobility "Black" Conjugated Polymers

A series of donor-acceptor low-bandgap conjugated polymers, i.e., PTnBT (n = 2-6), composed of alternating oligothiophene (OTh) and 2,1,3-benzothiadiazole (BT) units were synthesized by Stille cross-coupling polymerization. The number of thiophene rings in OTh units, that is n, was tuned from 2 to 6. All these polymers display two absorption bands in both solutions and films with absorption maxima depending on n. From solution to film, absorption spectra of the polymers exhibit a noticeable red shift. Both high- and low-energy absorption bands or P'F5BT and PT6BT films locate in the visible region, which are at 468 and 662 nm for PT5BT and 494 and 657 nm for PT6BT.

Novel NIR-absorbing conjugated polymers for efficient polymer solar cells: effect of alkyl chain length on device performance

Three low bandgap conjugated polymers, i.e., PDTPBT-C8, PDTPBT-C6 and PDTPBT-C5, which consist of alternating N-alkyl dithieno[3,2-b: 2',3'-d] pyrrole and 2,1,3-benzothiadiazole units and carry 1-octylnonyl, 1-hexylheptyl and 1-pentylhexyl as side chains, respectively, were synthesized. These polymers show strong absorption in the wavelength range of 600-900 nm with enhanced absorption coefficient as the length of alkyl chain decreases. The film morphology of the polymers and 1-(3-methoxycarbonyl) propyl-1-phenyl-[6,6]-C-61 (PCBM) blends is also dependent on the alkyl chain length. As the length decreases, the film becomes more uniform and the domian size decreases from 400-900 nm for PDTPBT-C8 to similar to 50 nm for PDTPBT-C5.

Constructing mixed-metal coordination polymers from copper(II)-pyridinedicarboxylate metalloligands

In the mixed-metal complex catena-poly[bis[diaquasilver(I)] [bis[aquacopper(II)]-mu(3)-pyridine-2,5-dicarboxylato-2': 1: 1'kappa N-5,O-2: O-5: O-5, O-5'-mu-pyridine-2,5-dicarboxylato-2: 1 kappa(4) N, O-2: O-5, O-5'-disilver(I)-mu(3)-pyridine-2,5-dicarboxylato-1: 1': 2 '' kappa(5) O-5, O-5': O-5: N, O-2-mu pyridine-2,5-dicarboxylato-1': 20 ''kappa(4) O-5, O-5': N, O-2] hexahydrate], {[Ag(H2O)(2)][AgCu(C7H3NO4)(2)(H2O)] center dot 3H(2)O}(n), a square-pyramidal Cu-II center is coordinated by two N atoms and two O atoms from two pyridine-2,5-dicarboxylate (2,5-pydc) ligands and a water molecule, forming a [Cu(2,5-pydc)(2)-( H2O)](2-) metalloligand. One Ag I center is coordinated by five O atoms from three 2,5-pydc ligands and, as a result, the [Cu(2,5-pydc)(2)(H2O)](2-) metalloligands act as linkers in a unique mu(3)-mode connecting Ag-I centers into a one-dimensional anionic double chain along the [101] direction.

Hemoglobin conjugated micelles based on triblock biodegradable polymers as artificial oxygen carriers

An artificial oxygen carrier is constructed by conjugating hemoglobin molecules to biodegradable micelles. Firstly a series of triblock copolymers (PEG-PMPC-PLA) in which the middle block contains pendant propargyl groups were synthesized and characterized. After the amphiphilic copolymer was self-assembled into core-shell micelles in aqueous solution, azidized hemoglobin molecules protected by carbon monoxide (CO) were conjugated to the micelles via click reaction between the propargyl and azido groups. The conjugation causes an increase of the micelle's mean diameter. Maximum conjugation ratio is 250 wt% in the hemoglobin-conjugated micelles (HCMs). Oxygen-binding ability of the HCMs was demonstrated by converting the CO-binding state of the HCMs into O-2-binding state.

Synthesis of Hyperbranched Polymers with Pendent Norbornene Functionalities via RAFT Polymerization of a Novel Asymmetrical Divinyl Monomer

Hyperbranched polymers with numerous pendent norbornene functionalities have been synthesized via the radical polymerization of a novel asymmetrical divinyl monomer hearing a higher reactivity methacrylate group and it lower reactivity norbornene group. Mediated by a rapid reversible addition-fragmentation chain transfer (RAFT) equilibrium, the concentration of polymeric chain radicals is decreased, and thus the gelation did not occur until higher monomer conversions (ca. 90%). An increase in reaction temperature call also significantly promote the formation of the hyperbranched structure owing to the decreased stability of the intermediate radicals derived from the norbornene group, which was confirmed by a model copolymerization system of two single vinyl monomers with similar structures to the vinyl groups in the asymmetrical divinyl monomer. Furthermore, Tri-SEC and conventional Sin-SEC as well as H-1 NMR.

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED VINYL POLYMERS FROM RAFT POLYMERIZATION OF AN ASYMMETRIC DIVINYL MONOMER

Hyperbranched vinyl polymers were prepared by reversible addition-fragmentation chain transfer ( RAFT) polymerization of a styrenic asymmetric divinyl monomer. This was achieved by using cumyl dithiobenzoate or S-dodecyl-S'-(alpha,alpha'-dimethyl-alpha ''-acetic acid) trithiocarbonate as the chain transfer agent, 1,1'-azobis(cyclohexanecarbonitrile) or thermal initiation as a source of radicals. Cross-linking was inhibited by a rapid RAFT-based equilibrium between active propagation chains and dormant species, and thus a hyperbranched polymer with a monomer conversion as high as 80% was obtained. The hyperbranched structure and properties of the resultant polymers were characterized by a combination of H-1-NMR spectroscopy and a triple detection size exclusion chromatography (TRI-SEC). The hyperbranched vinyl polymer has a broad molecular weight distributions and a low Mark-Houwink exponent alpha value compared with the linear counterpart.