Regio-regular structure high molecular weight poly(propylene carbonate) by rare earth ternary catalyst and Lewis base cocatalyst

Lewis base modification strategy on rare earth ternary catalyst was disclosed to enhance nucleophilic ability of active center during copolymerization of carbon dioxide and propylene oxide (PO), poly(propylene carbonate) (PPC) with H-T linkages over 83%, and number-average molecular weight (M-n) up to 100 kg/mol was synthesized at room temperature using Y(CCl3OO)(3)-ZnEt2-glycerine catalyst and 1,10-phenanthroline (PHEN) cocatalyst. Coordination of PHEN with active Zinc center enhanced the nucleophilic ability of the metal carbonate, which became more regio-specific in attacking carbon in PO, leading to PPC with improved H-T linkages.

Hot-corrosion behaviors of overlay-clad yttria-stabilized zirconia coatings in contact with vanadate-sulfate salts

A dense clad overlay with chemical inertness was achieved on top of the plasma-sprayed YSZ thermal barrier coatings by laser in order to protect them from hot-corrosion attack. The Al2O3-clad YSZ coating exhibited good hot-corrosion behavior in contact with salt mixture of vanadium pentoxide (V2O5) and sodium sulfate (Na2SO4) for a longtime of 100 h at 1173 K. The LaPO4-clad YSZ coating showed corrosion resistance inferior to the Al2O3-clad one. Yttria was leached from YSZ by reaction between Y2O3 and V2O5, which caused progressive destabilization transformation of YSZ from tetragonal (t) to monoclinic (m) phase. The chemical inertness of the clad layers and the restrained infiltration of the molten corrosive salts by the dense clad layers were primary contributions to improvement of the hot-corrosion resistances.

Synthesis and properties of soluble poly[bis(benzimidazobenzisoquinolinones)] based on novel aromatic tetraamine monomers

Four aromatic tetraamine monomers possessing flexible ether linkages were successfully synthesized by nucleophilic aromatic substitution of hydroquinone, 4,4'-dihydroxybiphenyl, 2,2'-bis(4-hydroxyphenyl)propane, and 2,7-dihydroxynaphthalene with 5-chloro-2-nitroaniline, followed by reduction, respectively. With these monomers, a new class of soluble poly[ bis(benzimidazobenzisoquinolinones)] was prepared by a one-step, high-temperature solution polycondensation. The resulting polymers were completely soluble in phenolic solvents and had high inherent viscosities ranging from 1.2 to 1.5 g dL(-1). These polymers had glass transition temperatures in the range of 427-449 degrees C. Thermogravimetric analysis showed that all polymers were thermally stable, with 5% weight loss recorded above 510 degrees C in nitrogen.

Synthesis and properties of water stable poly[bis(benzimidazobenzisoquinolinone)] ionomers for proton exchange membranes fuel cells

A novel sulfonated tetraamine, di(triethylammonium)-4,4'-bis(3,4-diaminophenoxy)biphenyl-3,3'-disulfonate (BAPBDS), was successfully synthesized by nucleophilic aromatic substitution of 4,4'-dihydroxybiphenyl with 5-chloro-2-nitroaniline, followed by sulfonation and reduction. A high-temperature polycondensation of sulfonated tetraamine, non-sulfonated tetraamine (4,4 -bis(3,4-aminophenoxy)biphenyl) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (a) or 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianydride (b) gave the poly[bis(benzimidazobenzisoquinolinones)] ionomers SPBIBI-a(x) or SPBIBI-b(x), where x refers to the molar percentage of the sulfonated tetraamine monomer. Flexible and tough membranes of high mechanical strength were obtained by solution casting and the electrolyte properties of the polymers were intensively investigated. The ionomer membranes displayed excellent dimensional and hydrolytic stabilities.

Synthesis and property of a novel sulfonated poly(ether ether ketone) with high selectivity for direct methanol fuel cell applications

Bisphenol monomer 4-carboxylphenyl hydroquinone (4C-PH) containing carboxyl groups was synthesized by diazotization reaction of p-aminobenzoic acid and 1,4-benzoquinone and subsequent reductive reaction. Copolymerization of bisphenol A, 4C-PH, sodium 5,5'-carbonylbis(2-fluorobenzene-sulfonate) and 4,4'-difluorobenzophenone at various molar ratios through aromatic nucleophilic substitution reaction resulted in a new sulfonated poly(ether ether ketone) containing pendant carboxyl groups (C-SPEEK). The structures of the monomer 4C-PH and copolymers were confirmed by FT-IR and H-1 NMR. Flexible and transparent membranes with sulfonic and carboxylic acid groups as the proton conducting sites were prepared. The dependence of ion-exchange capacity (IEC), water uptake, proton conductivity and methanol permeability on the degree of sulfonation has been studied.

Novel sulfonated poly(arylene ether ketone) copolymers bearing carboxylic or benzimidazole pendant groups for proton exchange membranes

A novel strategy in which the benzimidazole group and sulfonic group are simultaneously attached to an aromatic polymer has been reported in this paper. For this purpose, sulfonated poly(arylene ether ketone) copolymers containing carboxylic acid groups (SPAEK-x-COOH, x refers to the molar percentage Of sulfonated repeating units) are prepared by the aromatic nucleophilic polycondensation of sodium 5,5'-carbonyl-bis(2-fluobenzene-sulfonate) (SDFBP), 4,4'-difluorobenzophenone (DFBP) and phenolphthalin (PPL). Then the carboxylic acid groups attached to the SPAEK-x-COOH are transformed to benzimidazole units through condensation reactions (referred to as SPAEK-x-BI). Fourier transform infrared spectroscopy and H-1 NMR measurements are used to characterize and confirm the structures of these copolymers.

Synthesis and properties of novel soluble polyimides having a spirobisindane-linked dianhydride unit

A new synthetic procedure was elaborated allowing the preparation of semiaromatic dianhydride. N-Methyl protected 4-chlorophthalic anhydride was nitrated with HNO3 to produce N-methyl-4-chloro-5-nitrophthalimide (1). The aromatic nucleophilic substitution reaction between 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1-spirobisindane and 1 afforded spirobisindane-linked bis(N-methylphthalimide) (2), which was hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). The latter was polymerized with five different aromatic diamines to afford a series of aromatic polyimides. The properties of polyimides such as inherent viscosity, solubility, UV transparency and thermal stability were investigated to illustrate the contribution of the introduction of spirobisindane groups into the polyimide backbone. The resulting polyimides were readily soluble in polar solvents such as chloroform, THF and N-methyl-2-pyrrolidone. The glass-transition temperatures of these polyimides were in the range of 254-292 degrees C. The tensile strength, elongation at break, and Young's modulus of the polyimide film were 68.8-106.6 MPa, 5.9-9.8%, 1.7-2.0 GPa, respectively. The polymer films were colorless and transparent with the absorption cutoff wavelength at 286-308 nm.

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.

Synthesis and gas transport property of polyimide from 2,2 '-disubstituted biphenyltetracarboxylic dianhydrides (BPDA)

A series of dianhydride monomers, 2,2'-disubstituted-4,4',5,5'-biphenyltetracarboxylic dianhydride (substituents = phenoxy, p-methylphenoxy, p-tert-butylphenoxy, nitro, and methoxy) were synthesized by the nitration of an N-methyl protected 3,3',4,4'-biphenyttetracarboxylic dianhydride (BPDA) and subsequent aromatic nucleophilic substitutions with aroxides (NaOAr) or methoxide. These dianhydrides were polymerized with various aromatic diamines in refluxing m-cresol containing isoquinoline to afford a series of aromatic polyintides. The effects of varying 2,2'-substituents of the dianhydride (BPDA) moiety on the properties of polyimides were investigated. It was found that polyimides from the dianhydrides containing phenoxy, p-methylphenoxy, and p-tert-butylphenoxy side groups possessed excellent solubility and film forming capability whereas polyimides from 2,2'-dinitro-BPDA and 2,2'-dimethoxy-BPDA were less soluble in organic solvent. The soluble polymers formed flexible, tough and transparent films. The films had a tensile strength, elongation at break, and Young's modulus in the ranges 102-168 MPa, 8-21%, 2.02-2.38 GPa, respectively. The polymer gas permeability coefficients (P) and ideal selectivities for N-2, O-2, CO2 and CH4 were determined for the -OAr substituted polyimides. The oxygen permeability coefficient (P-O2) and permselectivity of oxygen to nitrogen (PO2/N-2) of the films were in the ranges 3.4-11.3 barrer and 3.8-4.6, respectively.

Synthesis and properties of novel fluorinated poly(phenylene-co-imide)s

A new class of high-performance materials, fluorinated poly(phenylene-co-imide)s, were prepared by Ni(0)-catalytic coupling of 2,5-dichlorobenzophenone with fluorinated dichlorophthalimide. The synthesized copolymers have high molecular weights ((M) over bar (W)= 5.74 x 10(4)-17.3 x 10(4) g center dot mol(-1)), and a combination of desirable properties such as high solubility in common organic solvent, film-forming ability, and excellent mechanical properties. The glass transition temperature (T(g)s) of the copolymers was readily tuned to be between 219 and 354 degrees C via systematic variation of the ratio of the two comonomers. The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 66.7-266 MPa, 2.7-13.5%, and 3.13-4.09 GPa, respectively. The oxygen permeability coefficients (P-O2) and permeability selectivity of oxygen to nitrogen (P-O2/P-N2) of these copolymer membranes were in the range of 0.78-3.01 barrer [1 barrer = 10(-10) cm(3) (STP) cm/(cm(2) center dot s center dot cmHg)] and 5.09-6.2 5, respectively. Consequently, these materials have shown promise as engineering plastics and gas-separation membrane materials.

Synthesis, properties, and gas permeation performance of cardo poly(arylene ether sulfone)s containing phthalimide side groups

Novel bisphenol monomers (1a-d) containing phthalimide groups were synthesized by the reaction of phenolphthalein with ammonia, methylamine, aniline, and 4-tert-butylanilne, respectively. A series of cardo poly (arylene ether sulfone)s was synthesized via aromatic nucleophilic substitution of 1a-d with dichlorodiphenylsulfone, and characterized in terms of thermal, mechanical and gas transport properties to H-2, O-2, N-2, and CO2. The polymers showed high glass transition temperature in the range 230-296 degrees C, good solubility in polar solvents as well as excellent thermal stability with 5% weight loss above 410 degrees C. The most permeable membrane studied showed permeability coefficients of 1.78 barrers to O-2 and 13.80 barrers to CO2, with ideal selectivity. factors of 4.24 for O-2/N-2 pair and 28.75 for CO2/CH4 pair. Furthermore, the structure-property relationship among these cardo poly(arylene ether sulfone)s had been discussed on solubility, thermal stability, mechanical, and gas permeation properties. The results indicated that introducing 4-tert-butylphenyl group improved the gas permeability of polymers evidently.

Efficient one-pot synthesis of highly substituted pyridin-2(1H)-ones via the Vilsmeier-Haack reaction of 1-acetyl,1-carbamoyl cyclopropanes

A facile and efficient one-pot synthesis of highly substituted pyridin-2(1H)-ones is developed via the Vilsmeier-Haack reaction of readily available 1-acetyl,1-carbamoyl cyclopropanes, and a mechanism involving sequential ring-opening, haloformylation, and intramolecular nucleophilic cyclization reactions is proposed.

Vilsmeier-Haack reactions of 2-arylamino-3-acetyl-5,6-dihydro-4H-pyrans toward the synthesis of highly substituted pyridin-2(1H)-ones

A facile and efficient one-pot synthesis of highly substituted pyridin-2(IH)-ones was developed via Vilsmeier-Haack reactions of readily available enaminones, 2-arylamino-3-acetyl-5,6-dihydro-4H-pyrans, and a mechanism involving sequential ring-opening, haloformylation, and intramolecular nucleophilic cyclization reactions is proposed.

Synthesis and characterization of blue-light-emitting poly(aryl ether)s containing oligofluorenes in the main chain

A series of blue light-emitting poly(aryl ether)s (PAEs) containing ter- or pentafluorenes in the main chain have been synthesized via nucleophilic substitution polycondensation reaction. The energy levels of the polymers were tuned by introducing hole-transporting triaryamine groups in the side chains and/or incorporating electron-transporting oxadiazole segments in the main chain. The optical properties of the polymers are dominantly determined by the well-defined oligofluorene segments, and therefore all polymers show high photoluminescence quantum yield. Differential scanning calorimeter (DSC) characterizations indicate that they are vitrified polymers with high glass transition temperature (up to 156 degrees C). The polymers comprising pentafluorenes exhibit electroluminescent properties equal to or better than fully conjugated fluorene homopolymers. With the device structure of ITO/PEDOT:PSS/polymer/Ca/Al, an external quantum efficiency of 1.4% along with Commission Internationale de L'Eclairage (CIE) coordinates of (0.17, 0.09) has

Efficient synthesis of aryl hydroxylactams by reducing imides with activated zinc dust

A series of aryl hydroxylactams (2a, 2b, 2d-2g, 2i-2k, 2m, and 2n) was synthesized by partially reducing aryl cyclic imides in moderate to excellent yields with activated zinc dust alone in acetic acid. This method was regiospecific and can be employed as an alternative for reported methods to partially reduce aryl cyclic imides.