Synthesis and characterization of polyesters containing heterocyclic thiaxanthone units

Several polyesters containing thiaxanthone rings were prepared from 2,7-dichloroformylthiaxanthone-5,5′-dioxide ( IVa ), 2,8-dichloroformylthiaxanthone-5,5′-dioxide ( IVb ), and bisphenols by solution polycondensation. The 2,8-diethoxycarbonylthiaxanthone-5,5′-dioxide ( V ) was prepared and characterized by spectral methods to confirm the formation of 2,8-thiaxanthonedicarboxylic acid-5,5′-dioxide ( IVb ). Prior to polymer synthesis two model compounds,2,7-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-1) and 2,8-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-2), were synthesized and characterized by spectral methods. The polyesters were obtained in 62–78% yield and had inherent viscosities in the range 0.42–0.90 dL/g. The effect of thiaxanthone rings on solubility, crystallinity, and thermal stability of the polyesters are also discussed. The polyesters have decomposition temperatures in the range 372–438°C.     

Synthesis and characterization of polyamides containing heterocyclic thiaxanthone units

Novel polyamides containing heterocyclic thiaxanthone units were prepared by condensing 2,7-dichloroformylthiaxanthone-5,5′-dioxide and 2,8-dichloroformylthiaxanthone-5,5′-dioxide with various aromatic diamines, under low temperature solution polymerization conditions in DMAc. The model diamide, 2,8-ditolylcarbamylthiaxanthone-5,5′-dioxide was synthesised and characterized by spectroscopic methods. The polyamides were prepared in 70–80% yield and had inherent viscosity in the 0.36–0.73 dL/g range. The poyamides have decomposition temperatures in the 425–510°C range in nitrogen. The effect of thiaxanthone rings on polymer backbone on solubility, crystallinity, and thermal stability is also discussed.     

Preparation and properties of polybenzimidazoles containing cardo groups

Several polybenzimidazoles containing cardo groups were prepared: A cardodicarboxylic acid, 9,9-bis(4-carboxyphenyl)fluorene, and two cardotetramines, 9,9-bis(3,4-diaminophenyl)fluorene and 9,9-bis(3,4-diaminophenyl)10-anthrone. The cardodicarboxylic acid was condensed with aromatic tetramines and the cardotetramines were condensed with aromatic dicarboxylic acids. Prior to polymer synthesis two model compounds, 9,9-bis[4,(2-benzimidazolyl)phenyl]fluorene and 2,2′-diphenyl-5,5′-(9,9-fluorenediyl)-bibenzimidazole were prepared and characterized by spectral methods. The polymers were obtained in 60–70% yield and showed reduced viscosity in the range of 0.7–1.1 dL/g. They were soluble in dimethyl formamide (DMF) and chlorinated solvents like tetrachlorethane. The thermal stabilities of these cardopolymers were superior to noncardopoly-benzimidazoles.     

Preparation and properties of some cardopolyamides containing phenoxathiin-10,10-dioxide and phenoxaphosphine units

Several new cardopolyamides containing phenoxathiin-10,10-dioxide and phenoxaphosphine units were prepared by condensing 3,3-bis(4-aminophenyl)-phthalide (PDA), 9,9-bis(4-aminophenyl) fluorene (FDA), and 9,9-bis(4-aminophenyl)-10-anthrone (ADA) with 2,8-dichloroformylphenoxathiin-10,10-dioxide (PDC) and 2,8-dichloroformyl-10-phenylphenoxaphosphine-10-oxide (PPDC) in DMAc. A low temperature solution polycondensation technique was employed throughout. The cardopolymides were obtained in 80–92% yield and showed inherent viscosities in the range 0.41–0.6 dL/g. All the polymers were characterized by IR spectra, density, solubility, crystallinity, and thermal analysis.     

Arylidene Polymers. IX. Synthesis,Characterization, and Morphology of New Polyesters of Diarylidenecycloalkanones Containing Thianthrene Units

New polyesters containing thianthrene tetraoxide were synthesized by the interaction of 2,7-dichloroformylthianthrene-5,5′,10, 10′-tetraoxide with 2,5-bis(p-hydroxybenzylidene)cyclopentanone, 2,5-divanillylidenecyclopentanone, 2,6-bis(p-hydroxybenzyiidene)-cyclohexanone, 2,6-divanillylidenecyclohexanone, and 2,7-bis(p-hydroxybenzylidene)cycloheptanone by using the interfacial polycondensation technique. The resulting polyesters were characterized by elemental and spectral analyses. All the synthesized polymers readily dissolved at room temperature in dimethylsulfoxide. The thermal properties of the polymers were evaluated and correlated to their structural units by TGA and DSC measurements. X-ray analysis of polymers showed that all the polyesters are amorphous. Moreover, the morphology of a new high performance polyester, poly[oxycarbonyl-2,7-thianthrene-5,5′,10,10′-tetraox-idecarbonzeoxyl(2-methoxy-p-phenylene)methylidyne(2-oxo-1,3-cyclohexanediylidenemethylidyne)methylidene(3-methoxy-p-phenylene)], has been investigated by scanning electron microscopy.     

Synthesis of 3,3′-biisoxazoles from cyanogen N,N′-dioxide and trimethylsilyl enol ethers via the corresponding 5,5′-bis(trimethylsilyloxy)-3,3′-Δ2-biisoxazolines

Regioselective 1,3-dipolar cycloaddition of Cyanogen N,N′-dioxide ( 2 ) to trimethylsilyl enol ethers 3a-d, 6 and 7 gave the corresponding 5,5′-bis(trimethylsilyloxy)-3,3′-Δ²-biisoxazolines which upon short heating with 10% hydrochloric acid afforded 3,3′-biisoxazoles 5a-d , 8 and 9. Only the intermediate 5,5′-bis(trimethylsilyloxy)-derivative 4a was isolated and studied. Reaction of 2 with vinyl methyl ketone ( 10 ) gave biisoxazoline 11 which by oxidation with γ-manganese dioxide gave biisoxazole 12.     

Synthesis and investigation of polybenzimidazoles containing alkyl substituents in aromatic nuclei

Polybenzimidazoles have been synthesized from 3,3′-diamino-5,5′-dimethylbenzidine, 3,3′,4,4′-tetraamino-5,5′-dimethyldiphenylmethane, bis(3-amino-4-methylamino)phenylmethane, bis(3-amino-4-methylamino-5-methyl)phenylmethane, and diphenyl esters of adipic, sebacic, isophthalic, and terephthalic acids and 4,4′-dicarboxydiphenyl oxide by solid-phase polyheterocyclization. Properties of the polybenzimidazoles have been studied. The polymers have high thermal stability. They are soluble in a number of organic solvents and give strong, elastic films. Solubility and thermal stability of polybenzimidazoles is determined by the methyl group position in the polymeric chain. The influence of other alkyl substituents on properties of polybenzimidazoles have been investigated. The polymer structure has been studied by infrared and PMR spectroscopy and elemental analysis.     

新型磺化聚苯并咪唑的合成及性能

以对苯二酚及对氟苯甲腈为原料, 合成了1,4-二(4-羧基苯氧基)苯, 再经磺化反应合成了1,4-二(4-羧基苯氧基)苯-2-磺酸钠(BCPOBS-Na), 并以4,4'-二羧基二苯醚(DCDPE)作为非磺化二酸单体与3,3'-二氨基联苯胺反应合成了一系列磺化聚苯并咪唑(SPBI). 通过红外光谱、 核磁共振及热重分析等手段对聚合物的结构及性能进行了分析. 研究了聚合物的特性黏度、 溶解性、 成膜性及聚合物薄膜的力学性能.     

Synthesis of 2,3,5,6-tetrahydro-4H-1,4-thiazin-3-one 1,1-dioxides from methyl (styrylsulfonyl)acetate

Methyl (styrylsulfonyl)acetate ( 1 ) was shown to be a useful building block for the synthesis of 5-phenyl-2,3,5,6–4H-tetrahydro-1,4-thiazin-3-one (2), its 4-amino 3 , and 4-hydroxy 4 derivatives. Their 2-spirocyclopropanes 9, 10 , and 11 , and 2,7-diphenyl-6,7-dihydro-8H-pyrimido[5,4-b][1,4]thiazinc 5,5-dioxide ( 18 ) were also prepared from 1 .     

Synthesis and characterization of fluorine‐containing polybenzimidazole for proton conducting membranes in fuel cells

Two new kinds of fluorine‐containing polybenzimidazoles (PBI), poly(2,2′‐(tetrafluoro‐p‐phenylene)‐5,5′‐bibenzimidazole) and poly(2,2′‐tetradecafluoroheptylene‐5,5′‐bibenzimidazole), were synthesized by condensation polymerization of 3,3′‐diaminobenzidine and perfluoroterephthalic acid (or perfluoroazelaic acid), with polyphosphoric acid as solvent. Thermogravimetric analysis results show that the fluorine‐containing polymers synthesized exhibit promising thermal stability. The film‐forming properties of the fluorine‐containing polymers are improved over nonfluorinated PBI. The introduction of fluorine into the backbone of the polymers has significant positive affection on their chemical oxidation stability demonstrated by Fenton test. Compared with poly(2,2′‐(m‐phenylene)‐5,5′‐bibenzimidazole)/phosphoric acid (PA) composite membrane, the resulting fluorinated membranes with a same PA doping level exhibit better flexibility and higher proton conductivity. The maximum proton conductivity gained is 3.05 × 10^?2 S/cm at 150 °C with a PA doping level of 7. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2115–2122, 2010     

Conjugated polymers based on dicarboxylic imide‐substituted isothianaphthene and their applications in solar cells

Four new polymers containing a benzo[c]thiophene‐N‐dodecyl‐4,5‐dicarboxylic imide (DIITN) unit including the homopolymer and three donor–acceptor copolymers were designed, synthesized, and characterized. For these copolymers, DIITN unit with low bandgap was selected as an electron acceptor, whereas 5,5′‐(2,7‐bisthiophen‐2‐yl)‐9‐(2‐decyltetradecyl)‐9H‐carbazole), 5,5′‐(3,3′‐di‐n‐octylsilylene‐2,2′‐bithiophene), and 5,5′‐(2,7‐bisthiophen‐2‐yl‐9,9‐bisoctyl‐9H‐fluoren‐7‐yl) were chosen as the electron donor units to tune the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) levels of the copolymers for better light harvesting. These polymers exhibit extended absorption in the visible and near‐infrared range and are soluble in common organic solvents. The relative low lying HOMO of these polymers promises good air stability and high open‐circuit voltage (V_oc) for photovoltaic application. Bulk heterojunction solar cells were fabricated by blending the copolymers with [6,6]‐phenyl‐C61‐butyric acid methyl ester or [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM). The best power conversion efficiency of 1.6% was achieved under simulated sunlight AM 1.5G (100 mW/cm²) from solar cells containing 20 wt % of the fluorene copolymer poly[5,5′‐(2,7‐bisthiophen‐2‐yl‐9,9‐bisoctyl‐9H‐fluoren‐7‐yl)‐alt‐2,9‐(benzo[c]thiophene‐N‐dodecyl‐4,5‐dicarboxylic imide)] and 80 wt % of PC71BM with a high open‐circuit voltage (V_oc) of 0.84 V. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A two-dimension medium band gap conjugated polymer based on 5,10-bis(alkylthien-2-yl)dithieno[3,2-d:3′,2′-d′]benzo[1,2-b:4,5-b′]dithiophene: Synthesis and photovoltaic application

A two-dimension medium band gap copolymer poly{5,10-bis(4,5-didecylthien-2-yl)dithieno[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene-2,7-diyl-alt-2,5-di(3-octylthien-2-yl) thiophen-5,5′-diyl}, named as PDTBDT-T-3T, was prepared by the palladium-catalyzed Stille cross coupling reaction and characterized. The resulting polymer exhibits good solubility in common organic solvents, excellent thermal stability, and extensive light absorption from 300 nm to 650 nm with an optical band gap of 1.92 eV, the highest occupied molecular orbital (HOMO) level of ?5.03 eV and the hole mobility up to 1.92 × 10^?4 cm²·V^?1·s^?1. The power conversion efficiencies (PCEs) of 2.02%–3.19% have been achieved in the traditional PVCs for the copolymer. It should be noted that the PCEs of 4.2% for the inverted PVCs from the copolymer with PFN (poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl- fluorene)]) as cathode modifying interlayer, were similar with the PCEs of 4.39% for the inverted PVCs from P3HT:PC₇₁BM at the same condition. These results indicated that the copolymer could be used as potential candidate for P3HT.     

DFT study of the electronic and charge transfer properties of perfluoroarene–thiophene oligomers

The ground state structures of 5,5″-diperfluorophenyl-2,2′:5′,2″:5″,2‴-quaterthiophene (1), 5,5′-bis{1-[4-(thien-2-yl)perfluorophenyl]}-2,2′-dithiophene (2), 4,4′-bis[5-(2,2′-dithiophenyl)]-perfluorobiphenyl (3), 5,5″-diperfluorophenyl-2,2′:5′,2″-tertthiophene (4), 5,5′-diperfluorophenyl-2,2′-dihiophene (5), and 5,5-diperfluorophenylthiophene (6) have been optimized at the B3LYP/6-31G(d), B3LYP/6-31G(d,p), PBE0/6-31G(d), and PBE0/6-31G(d,p) level of theories. The B3LYP/6-31+G(d) and PBE0/6-31+G(d) level of theories have been applied to investigate the absorption spectra. The PBE0 functional is good to predict the C–S bond lengths while the C–F bond lengths are good envisaged with B3LYP functional. The increment of thiophene rings between two perfluoroarene rings leads to red shift in absorption spectra. The electron affinities are energetically destabilized while energetic stabilization of the radical-cation increases by decreasing the thiophene rings from four to one. The perfluoroarene rings leads to enhance the electron injection.     

New synthetic route to alternating copoly(aromatic ester–aliphatic amide)s

The preparation of three novel alternating copoly(aromatic ester–aliphatic amide)s containing the same ordered amide–amide–ester–ester (AAEE), the same para-disubstituted phenyl, and the different long methylene chain structure were described. 1,1′-(Adipoyl)bisbenzotriazole (AdBBT), 1,1′-(suberoyl)bisbenzotriazole (SuBBT), and 1,1′-(sebacoyl)bisbenzotriazole (SeBBT) were synthesized. These diacylbenzotriazoles were preferred to aminoethanol at the amino group because of the selective N-acylation of active acylamide of benzotriazole in excellent yield at room temperature to give diol monomers such as N,N′-bis(2-hydroxyethyl)adipic amide (HEAdA), N,N′-Bis(2-hydroxyethyl)subaric amide (HESuA), and N,N′-bis(2-hydroxyethyl)sebacic amide (HESeA). Polycondensation of 1,1′-(teraphthaloyl)bisbenzotrizole (tPBT) with HEAdA, HESuA, and HESeA gave the corresponding alternating copoly(aromatic ester–aliphatic amide)s: P(tPE–AdA), P(tPE–SuA), and P(tPE–SeA), respectively. The alternating copoly(aromatic ester–aliphatic amide)s were characterized by ¹H-NMR spectra. The resulting polymers have two different chain units; one is chain unit of poly(ethylene terephthalate) and the other is a chain unit of polyamide-2,6, polyamide-2,8, and polyamide-2,10; both are linked via a C? N bond.     

1,1-二(2-苯并咪唑基)-2-苯基乙烯衍生物荧光受体的合成与阳离子识别

合成了3种新型1,1-二(2-苯并咪唑基)-2-苯基乙烯衍生物——1,1-二(2-苯并咪唑基)-2(4-氰基苯基)乙烯(1)、1,1-二(2-苯并咪唑基)-2(4-甲氧羰基苯基)乙烯(2)和1,1-二(2-苯并咪唑基)-4-苯基-1,3-丁二烯(3),通过核磁共振氢谱和碳谱(1H、13C NMR)、质谱(MS)对它们进行了结构表征。用紫外可见吸收光谱(UV-V is)和荧光发射光谱测定了该阳离子受体与不同金属离子(Zn2 、Cd2 、Hg2 和Cu2 )的络合选择性。结果表明:该荧光受体对Zn2 、Cd2 、Hg2 和Cu2 均具有较高的选择性和荧光响应。     

Novel blue‐greenish electroluminescent poly(fluorenevinylene‐alt‐dibenzothiophenevinylene)s and their model compounds

Poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐2,8‐vinylene) (PS) and poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐5,5‐dioxide‐2,8‐ vinylene) (PSO) as well as corresponding model compounds were synthesized by Heck coupling. Both the polymers and model compounds were readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane, chloroform, and toluene. The polymers showed a decomposition temperature at ～430 °C and a char yield of about 65% at 800 °C in N₂. The glass‐transition temperatures of the polymers were almost identical (75–77 °C) and higher than those of the model compounds (26–45 °C). All samples absorbed around 390 nm, and their optical band gaps were 2.69–2.85 eV. They behaved as blue‐greenish light emitting materials in both solutions and thin films, with photoluminescence emission maxima at 450–483 nm and photoluminescence quantum yields of 0.52–0.72 in solution. Organic light‐emitting diodes with an indium tin oxide/poly(ethylene dioxythiophene):poly(styrene sulfonic acid)/polymer/Mg:Ag/Ag configuration with polymers PS and PSO as emitting layers showed green electroluminescence with maxima at 530 and 540 nm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6790–6800, 2006     

Preparation of dibenzofuran-type amorphous polyetherketone by novel etherification reaction

4-Fluorobenzophenone reacted with potassium carbonate in the presence of silica catalyst in diphenyl sulfone solvent to yield 4,4′-dibenzoyldiphenyl ether. This new etherification reaction was extended to three difluoro aromatic ketones. 4,4′-Bis(4-fluorobenzoyl)diphenyl ether ( I ) reacted with potassium carbonate to yield a crystalline poly(oxy-1,4-phenylene-carbonyl-1,4-phenylene) (PEK) and 4,4′-bis{4-[4-(4-fluorobenzoyl)phenoxy]benzoyl}benzene ( II ) gave a crystalline poly(oxy-1,4-phenylene-carbonyl-1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene-oxy-1,4-phenylene-carbonyl-1,4-phenylene-carbonyl-1,4-phenylene)(PEKEKEKK). 2,8-Bis(4-fluorobenzoyl)dibenzofuran ( III ) or 2,8-bis(4-chlorobenzoyl)dibenzofuran ( IV ) reacted with potassium carbonate to yield a poly(oxy-1,4-phenylene-carbonyl-2,8-dibenzofuran-carbonyl-1,4-phenylene) (PEKBK). The PEKBK was a noval amorphous polymer with the glass transition temperature of 222°C and it showed excellent thermal stability [T. Tanabe and I. Fukawa, Jpn. Pat., Kokai 64–74223 (1989)]. Several amorphous dibenzofuran type polyetherketone copolymers were prepared by coplycondensation of III with 4,4′-difluorobenzophenone ( V ) or 1,4-bis(4-fluorobenzoyl)benzene ( VI ) [T. Tanabe and I. Fukawa, Jpn. Pat., Kokai 1153722 (1989)]. © 1992 John Wiley & Sons, Inc.     

New poly (amide-imide) syntheses. IX. Preparation and properties of poly(amide-imide)s derived from 2,7-bis (4-aminophenoxy) naphthalene and various bis (trimellitimide)s

Eleven bis(phenoxy) naphthalene-containing poly(amide-imide)s IIIa–k were synthesized by the direct polycondensation of 2,7-bis (4-aminophenoxy) naphthalene (DAPON) with various aromatic bis (trimellitimide)s IIa–k in N-methyl-2-pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. Poly (amide-imide)s IIIa–k having inherent viscosities of 0.70–1.12 dL/g were obtained in quantitative yields. The polymers containing p-phenylene or bis(phenoxy) benzene units exhibited crystalline x-ray diffraction patterns. Most of the polymers were readily soluble in various solvents such as NMP, N, N-dimethylacetamide, dimethyl sulfoxide, m-cresol, o-chlorophenol, and pyridine, and gave transparent, and flexible films cast from DMAc solutions. Cast films showed obvious yield points in the stress-strain curves and had strength at break up to 87 MPa, elongation to break up to 11%, and initial modulus up to 2.10 GPa. These poly(amide-imide)s had glass transition temperatures in the range of 255–321°C, and the 10% weight loss temperatures were recorded in the range of 529–586°C in nitrogen. The properties of poly(amideimide)s IIIa–k were compared with those of the corresponding isomeric poly (amide-imide)s III′ prepared from 2,7-bis(4-trimellitimidophenoxy) naphthalene and aromatic diamines. © 1994 John Wiley & Sons, Inc.     

Enolethers. XXI. Synthesis of 5,5′-disubstituted 4,4′-bipyrimidines

1,6-Dialkoxy-3,4-diones 3 are easily accessible by acylation of enol ethers 1 with oxalyl chloride and subsequent elimination of hydrogen chloride using triethylamine. The open-chain 2,5-dimethyl derivative 3b is converted with amidines 4a-c and S-methylisothiourea (4d) , respectively, to give 2,2′-disubstituted 5,5′-dimethyl-4,4′-bipyrimidines 5a-d . The dihydrofuran and dihydropyran derivatives 3c and 3d , however, react with benzamidine (4c) in dimethylformamide only in the presence of calcium hydride as condensation agent yielding 5,5′-bis(2-hydroxyethyl)- and 5,5′-bis(3-hydroxypropyl)-2,2′-diphenyl-4,4′-bipyrimidine 6a and b.     

Parameters influencing the molecular weight of 3,6‐carbazole‐based D‐π‐A‐type copolymers

Condensation copolymerization reactions of carbazole 3,6‐diboronate with 4,7‐bis(5‐bromo‐2‐thienyl)‐2,1,3‐benzothiadiazole (DTBT) only produce low‐molecular‐weight donor (D)‐π‐acceptor (A) copolymers. High‐molecular‐weight copolymers for use in optoelectronic devices are necessary for achieving extended π‐conjugation and for controlling the copolymer processibility. To elucidate the cause of the persistently low molecular weight, we synthesized three 3,6‐carbazole‐based D‐A copolymers using copolymerizations of N‐9′‐heptadecanyl‐3,6‐carbazole with DTBT, N‐9′{2‐[2‐(2‐methoxy‐ethoxy)‐ethoxy]‐ethyl}‐3,‐6‐carbazole with DTBT, and N‐9′‐heptadecanyl‐3,6‐carbazole with alkyl‐substituted DTBT. We investigated several parameters for their influence on molecular copolymer weight, including the conformation of the chain during growth, the solubility of the monomers, and the dihedral angles between the donor and acceptor units. Size exclusion chromatography, UV–vis absorption spectroscopy, and computational studies revealed that the low molecular weights of 3,6‐carbazole‐based D‐A copolymers resulted from conjugation breaks and the resulting high coplanarity, which led to strong interactions between polymer chains. These interactions limited formation of high‐molecular‐weight‐copolymers during copolymerization. The strong intermolecular interactions of the 3,6‐carbazole moiety were exploited by incorporating 3,6‐carbazole units into poly[9′,9′‐dioctyl‐2,7‐flourene‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] prepared from 9′,9′‐dioctyl‐2,7‐flourene and DTBT. Interestingly, the number average molecular weight increased gradually with increasing 2,7‐fluorene monomer content but the number of conjugation breaks was a range of 6–7. The hole mobilities of the copolymers were studied for comparison purposes. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011