Surface morphology evolution of poly (styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film

Well-ordered nanostructured polymeric supramolecular thin films were fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA). A depression Of cylindrical nanodomains was formed by the block of P4VP(H+) and PMCMA associates surrounded by PS. The repulsive force aroused from the incompatibility between the block of P4VP(H+) and PMCMA was varied through changing the molecule weight (M-w) of PMCMA, the volume fraction of the block of P4VP(H+), and annealing the film at high temperature. Increasing the repulsive force led to a change of overall morphology from ordered nanoporous to featureless structures. The effects of solvent nature and evaporation rate on the film morphology were also investigated. Further evolution of surface morphologies from nanoporous to featureless to nanoporous structures was observed upon exposure to carbon bisulfide vapors for different treatment periods. The wettability of the film surface was changed from hydrophilicity to hydrophobicity due to the changes of the film surface microscopic composition.

Motion of integrated CdS nanoparticles by phase separation of block copolymer brushes

A new method of reversibly moving US nanoparticles in the perpendicular direction was developed on the basis of the phase separation of block copolymer brushes. Polystyrene-b-(poly(methyl methaerylate)-co-poly(cadmium dimethacrylate)) (PS-b-(PMMA-co-PCdMA)) brushes were grafted from the silicon wafer by surface-initiated atom transfer radical polymerization (ATRP). By exposing the polymer brushes to H2S gas, PS-b-(PMNlA-co-PCdNlA) brushes were converted to polystyrene-b-(poly(methyl methacrylate) -co-poly(methacrylic acid)(CdS)) (PS-b-(PMMA-co-PMAA(CdS))) brushes, in which US nanoparticles were chemically bonded by the carboxylic groups of PMAA segment. Alternating treatment of the PS-b-(PMMA-co-PMAA(CdS)) brushes by selective solvents for the outer block (a mixed solvent of acetone and ethanol) and the inner PS block (toluene) induced perpendicular phase separation of polymer brushes, which resulted in the reversible lifting and lowering of US nanoparticles in the perpendicular direction. The extent of movement can be adjusted by the relative thickness of two blocks of the polymer brushes.

Development of nanodomain and fractal morphologies in solvent annealed block copolymer thin films

We have systematically studied the thin film morphologies of asymmetric polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer subjected to solvent vapors of varying selectivity for the constituent blocks. Upon a short treatment in neutral or PS-selective vapor, the film exhibited a highly ordered array of hexagonally packed, cylindrical microdomains. In the case of PEO selective vapor annealing, such ordered cylindrical microdomains were not obtained. instead, fractal patterns on the microscale were observed and their growth processes investigated. Furthermore, hierarchical structures could be obtained if the fractal pattern was exposed to neutral or PS selective vapor.

One-pot synthesis of polyimides via Ni-catalyzed coupling of bis(chlorophthalimide)s

A one-pot synthesis method for the preparation of polyimides containing biphenyl units was developed via nickel-catalyzed coupling reaction of bis(chlorophthalimide)s which were prepared from chloroplithalic anhydrides and diamines in xylene. The resulting polyimides had inherent viscosities of above 0.60dL g(-1). In the meantime, the copolymerizations from a mixture of three isomeric bis(chlorophthalimide)s gave the polymers with inherent viscosities of 0.36-0.55 gdL(-1). The solubility and film formability of the copolymers were better than those of homopolymers from bis(4-chlorophthalimide). The 10% weight loss of these polyimides was between 470 and 531 degrees C.

Synthesis and characterization of novel sulfonated polyimides from 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid

A novel sulfonated diamine monomer, 1,4-bis(4-aminophenoxy)-naphthyl-2,7-disulfonic acid (BAPNDS), was synthesized. A series of sulfonated polyimide copolymers were prepared from BAPNDS, 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and nonsulfonated diamine 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and mechanically strong membranes were obtained. The membranes displayed slightly anisotropic membrane swelling. The dimensional change in thickness direction was larger than that in planar. The novel SPI membranes showed higher conductivity, which was comparable or even higher than Nafion 117. Membranes exhibited methanol permeability from 0.24 x 10(-6) to 0.80 X 10(-6) cm(2)/s at room temperature, which was much lower than that of Nafion (2 x 10-6 CM2/s). The copolymers were thermally stable up to 340 degrees C. These preliminary results have proved its potential availability as proton-exchange membrane for PEMFCs or DMFCs.

Enantiomeric PLA-PEG block copolymers and their stereocomplex micelles used as rifampin delivery

A novelty approach to self-assembling stereocomplex micelles by enantiomeric PLA-PEG block copolymers as a drug delivery carrier was described. The particles were encapsulated by enantiomeric PLA-PEG stereocomplex to form nanoscale micelles different from the microspheres or the single micelles by PLLA or PDLA in the reported literatures. First, the block copolymers of enantiomeric poly(L-lactide)-poly(ethylene-glycol) (PLLA-PEG) and poly(D-lactide)-poly(ethylene-glycol) (PDLA-PEG) were synthesized by the ring-opening polymerization of L-lactide and D-lactide in the presence of monomethoxy PEG, respectively. Second, the stereocomplex block copolymer micelles were obtained by the self-assembly of the equimolar mixtures of enantiomeric PLA-PEG copolymers in water. These micelles possessed partially the crystallized hydrophobic cores with the critical micelle concentrations (cmc) in the range of 0.8-4.8 mg/l and the mean hydrodynamic diameters ranging from 40 to 120 nm. The micelle sizes and cmc values obviously depended on the hydrophobic block PLA content in the copolymer.Compared with the single PLLA-PEG or PDLA PEG micelles, the cmc values of the stereocomplex micelles became lower and the sizes of the stereocomplex micelles formed smaller. And lastly, the stereocomplex micelles encapsulated with rifampin were tested for the controlled release application.

Synthesis and characterization of electroactive and biodegradable ABA block copolymer of polylactide and aniline pentamer

A triblock copolymer PLA-b-AP-b-PLA (PAP) of polylactide (PLA) and aniline pentamer (AP) with the unique properties of being both electroactive and biodegradable is synthesized by coupling an electroactive carboxyl-capped AP with two biodegradable bihydroxyl-capped PLAs via a condensation reaction. Three different molecule weight PAP copolymers are prepared. The PAP copolymers exhibit excellent electroactivity similar to the AP and polyaniline, which may stimulate cell proliferation and differentiation. The electrical conductivity of the PAP2 copolymer film (similar to 5 x 10(-6) S/cm) is in the semiconducting region. Transmission electron microscopic results suggest that there is microphase separation of the two block segments in the copolymer, which might contribute to the observed conductivity. The biodegradation and biocompatibility experiments in vitro prove the copolymer is biodegradable and biocompatible. Moreover, these new block copolymer shows good solubility in common organic solvents, leading to the system with excellent processibility. These biodegradable PAP copolymers with electroactive function thus possess the properties that would be potentially used as scaffold materials for neuronal or cardiovascular tissue engineering.

Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton-exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2'-bis(p-aminophenoxy)-1,1'-binaphthyl-6,6'-disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30-80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film-forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945-0.161 S/cm) at 20-80 degrees C in liquid water. The membranes exhibited methanol permeability from 9 x 10(-8) to 5 X 10(-7) cm(2)/s at 20 degrees C, which was much lower than that of Nafion (2 x 10(-6) cm(2)/s). The copolymers were thermally stable up to 300 degrees C. The sulfonated polyimide copolymers with 30-60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability.

Isomeric polyimides

This review deals with polyimides based on isomeric dianhydrides and diamines, and with chiral polyimides. First, however, a summary is presented of recent work on the synthesis of isomeric dianhydrides, the reaction of mellophanic dianhydride with diamines, and the tendency toward cyclization in reactions of some dianhydrides and diamines. Then turning to polymers, the discussion covers solubility, thermal and dielectric properties, permeability and permselectivity for gas separation, and rheology of isomeric polyimides. Several useful general rules have been found: i.e. the glass transition temperature of polyimides based on isomeric dianhydrides with a given diamine decreases in the order 3,3'- > 3,4'- > 4,4-dianhydride if the polymers are of comparable molecular weight, whereas the thermal stability and the T-beta/T-g ratio (in absolute temperatures) increase in the order of 3,3'- < 3,4'- < 4,4'-dianhydride. Polyimides from 3,3'- or 3,4'-dianhydride have higher solubility than those from 4,4'-dianhydride. Polyimides from 3,4'-dianhydrides exhibit much lower melt viscosity than those from the other isomeric anhydrides. The dielectric constants of polyimides derived from m,m'-diamines are lower than those from p,p'-diamines. Polyimides based on 3,3'- or 3,4'-dianhydrides have higher permeability and slightly lower permselectivity than polyimides based on 4,4'-dianhydrides.

Water resistant sulfonated polyimides based on 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BNTDA) for proton exchange membranes

A series of sulfonated polyimides (SPIs) were synthesized in in-cresol from 4,4'-binaphthyl- 1,11,8,8'-tetracarboxylic dianhydride (BNTDA), 4.4'-diaminodiphenylether-2,2-disulfonicacid (ODADS), and 4.4'-diamino-diphenyl ether (ODA) in the presence of triethylamine and benzoic acid. The resulted polyimides showed much better water resistance than the corresponding sulfonated polyimides from 1,4,5,8-naphthatenetetracarboxylic dianhydride (NTDA) and ODADS, which is contributed to the higher electron density in the carbonyl carbon atoms of BNTDA. Copolyimides S-75 and S-50 maintained their mechanical properties and proton conductivities after aging in water at 100 degrees C for 800 h. The proton conductivity of these SPIs was 0.0250-0.3565 S/cm at 20 degrees C and 100% relative humidity (RH), and increased to 0.11490.9470 S/cm at 80 degrees C and 100% RH. The methanol permeability values of these SPIs were in the range of 0.99-2.36 x 10(-7) cm(2)/S, which are much lower than that of Nafion 117 (2 x 10(-6) cm(2)/s).

Hydrazine-based polyimides from isomeric bis(chlorophthalimide)s

3,3-Dichloro-N,N'-biphthalimide (3,3'-DCBPI), 3,4'-dichloro-N,N'-biphthalimide (3,4'-DCBPI), and 4,4'-dichloro-N,N'X-biphthalimide (4,4'-DCBPI) were synthesized from 3- or 4-chlorophthalic anhydrides and hydrazine in glacial acetic acid. The yield of 3,3'-DCBPI (90%) was much higher than that of 4,4'-DCBPI (33%) because of the better stability of the intermediate, 3-chloro-N-aminophthalimide, and 3,3'-DCBPI. A series of hydrazine-based polyimides were prepared from isomeric DCBPIs and 4,4-thiobisbenzenethiol (TBBT) in N,N-dimethylacetamide in the presence of tributylamine. Inherent viscosity of these polymers was in the range of 0.51-0.69 dL/g in 1-methyl-2-pyrrolidinone (NMP) at 30 degrees C. These polyimides were soluble in 1,1,2,2-terachloroethane, NMP, and phenols. The 5% weight-loss temperatures (T(g)s) of the polymers were near 450 degrees C in N-2. Their glass-transition temperatures (T(g)s) determined by dynamic mechanical thermal analysis and differential scanning calorimetry increased according to the order of polyimides based on 4,4'-DCBPI, 3,4'-DCBPI, and 3,3'-DCBPI. The hydrolytic stability of these polymers was measured under acid, basic, and neutral conditions and the results indicated that the order was 3,3'-DCBPI/TBBT > 3,4'-DCBPI/TBBT > 4,4'-DCBPI/TBBT.

Formation of nonextinct ring-banded textures and multistacked lamella of tetra-aniline-block-poly(L-lactide) rod-coil diblock oligomer films induced by solvent vapor treatment

The self-assembly processes of the rod-coil diblock oligomer thin film of tetra-aniline (TANI)-block-poly(L-lactide) (PLLA) with different film thicknesses induced in the coil-selective solvent of acetone vapor at room temperature were studied. The morphologies of the oligomer films were determined by the film thickness. For the thicker film (232 nm), the nonextinct concentric ring-banded textures could form. While for the thinner and appropriate film (about 6 nm), multistacked diamond-shaped appearances with the periodic thickness being about 8.5 nm(6-nm-thick extended PLLA chain and 2.5-nm-thick p-pi conjugating TANI bimolecular layer) formed. The possible formation models of those two regular morphologies were presented in detail.

Crystallization and ring-banded spherulite morphology of poly(ethylene oxide)-block-poly(epsilon-caprolactone) diblock copolymer

The crystallization behavior of crystalline-crystalline diblock copolymer containing poly(ethylene oxide) (PEO) and poly(epsilon-caprolactone) (PCL), in which the weight fraction of PCL is 0.815, has been studied via differential scanning calorimeter (DSC), wide-angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). DSC and WAXD indicated that both PEO and PCL blocks crystallize in the block copolymer. POM revealed a ring-banded spherulite morphology or the PEO-b-PCL diblock copolymer.

Syntheses and properties of soluble biphenyl-based polyimides from asymmetric bis(chlorophthalimide)s

A novel synthesis of asymmetric bis(chlorophthalimide)s (3,4-BCPIs) has been established. The polymerizations of them produced higher molecular weight (0.38-0.51 dL/g) polyimides containing biphenyl units than those of isomeric polymers derived from symmetric bis(chlorophthalimide)s (4,4'-BCPIs) and 3,3'-BCPIs. The distribution of the formed biphenyl units of head to tail, head to head, and tail to tail in the chain of the polymers was about 58.0:21.0:21.0, determined by C-13 NMR spectra of the polymers. The composition of model compounds, determined by HPLC, was well consistent with the 13C NMR spectrum result. Comparing with polymers derived from 4,4'-BCPIs and 3,3'-BCPIs, the polymers derived from 3,4-BCPIs showed better solubilities in N,N-dimethylacetamide (DMAc), N,N-dimethyl-formamide (DMF), and N-methylpyrrolinone (NMP). Flexible films could be cast from the polymer solution with the inherent viscosities of above 0.35 dL/g. The polymer derived from asymmetric bis(chlorophthimide)s gave the highest T-g among the isomeric polymers.

Synthesis and properties of novel polyimides derived from 2,2 ',3,3 '-benzophenonetetracarboxylic dianhydride

A new synthetic route to 2,2',3,3'-BTDA (where BTDA is benzophenonetetracarboxylic dianhydride), an isomer of 2,3',3',4'-BTDA and 3,3',4,4'-BTDA, is described. Single-crystal X-ray diffraction analysis of 2,2',3,3'-BTDA has shown that this dianhydride has a bent and noncoplanar structure. The polymerizations of 2,2',3,3'-BTDA with 4,4'-oxydianiline (ODA) and 4,4'-bis(4-aminophenoxy)benzene (TPEQ) have been investigated with a conventional two-step process. A trend of cyclic oligomers forming in the reaction of 2,2',3,3'-BTDA and ODA has been found and characterized with IR, NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and elemental analyses. Films based on 2,2',3,3'-BTDA/TPEQ can only be obtained from corresponding polyimide (PI) solutions prepared by chemical imidization because those from their polyamic acids by thermal imidization are brittle. PIS from 2,2',3,3'-BTDA have lower inherent viscosities and worse thermal and mechanical properties than the corresponding 2,3',3',4'-BTDA- and 3,3',4,4'-BTDA-based PIs. PIs from 2,2',3,3'-BTDA and 2,3',3',4'-BTDA are amorphous, whereas those from 3,3',4,4'-BTDA have some crystallinity, according to wide-angle X-ray diffraction.