Preparation of π-conjugated polymers consisting of 2-decylbenzimidazole and thiophene units and chemical properties of the polymers

Polycondensation by Stille coupling of 2-decyl-4,7-dibromobenzimidazoles and N-methyl-2-decyl-4,7-dibromobenzimidazole with 2,5-bis(trimethylstannyl)thiophene and 5,5′-bis(trimethylstannyl)-2,2′-bithiophene gave the corresponding π-conjugated polymers, poly(2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 1b, poly(2-decylbenzimidazole-4,7-diyl-bithiophene-2,5-diyl) 1c and poly(N-methyl-2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 2b, in 98-99% yields. The polymers 1b and 2b were fully soluble in CF₃COOH, and partially soluble in DMF (about 60 and 40% for 1b and 2b, respectively) and NMP (about 70 and 40%, respectively). The NMP soluble part of 1b and DMF soluble part of 2b gave values of 0.36 and 0.24 dl g⁻¹ in NMP and DMF, respectively. The DMF soluble part of 1b, 1c and 2b showed absorption peaks at about 458, 465 and 388 nm, respectively, in DMF. In an alkaline medium the absorption peaks of 1b and 1c are shifted to a longer wavelength by 92-101 nm; the observed shifts in the acidic medium and alkaline medium were much larger than those observed with usual benzimidazoles with low molecular weights. Packing structures of 1b, 1c and 2b are discussed based on their XRD patterns.     

Preparation and properties of new π-conjugated polyquinoxalines with aromatic fused rings in the side chain

Summary New π-conjugated polyquinoxalines with aromatic fused rings in their side chain have been prepared. Dehalogenative organometallic polycondensation of 5,8-dibromo[2,3-b]-acenaphthenequinoxaline and 5,8-dibromo[2,3-b]phenanthrenequinoxaline with a zerovalent nickel complex afforded poly([2,3-b]acenaphthenequinoxaline-5,8-diyl) (P(5,8-Qx(ace))) and poly([2,3-b]phenanthrenequinoxaline-5-8-diyl) (P(5,8-Qx(phen))) in high yields. P(5, 8-Qx(ace)) had an [η] value of 0.23 dL g⁻¹ and showed absorption and photoluminescence peaks at 445 and 565 nm, respectively. (P(5,8-Qx(phen))) gave absorption and photoluminescence peaks at 400 and 514 nm, respectively. XRD data indicated formation of ordered structures of the polymers in the solid. Preparation of related copolymer with thiophene is also reported. Received: 15 February 2000/Accepted: 2 March 2000     

Preparation of poly(3,3′-dialkynyl-2,2′-bithiophene-5,5′-diyl) with high coplanarity and effective π-conjugation system

New head-to-head type polythiophenes with acetylenic -CCR side groups, HH-P3(CCR)Th (R=n-C₁₀H₂₁, n-C₆H₁₃, n-C₄H₉), were prepared by palladium-catalyzed polycondensation of the corresponding dibromo-monomers by using Me₃SnSnMe₃ as the polycondensing agent. The single crystal structure of the monomer revealed high coplanarity of the bithiophene unit, and the derived polymer showed a UV-vis absorption peak at approximately 520 nm. The λ_max position was red-shifted from those of regioregular poly(3-alkylthiophene)s (385 and 430 nm for HH- and HT-type polymers, respectively). These data indicate that the newly synthesized polythiophene with the -CCR group has a highly coplanar structure with a large effective π-conjugation system.     

Synthesis of π-conjugated polymers bearing electronic and optical functionalities by organometallic polycondensations and their chemical properties

A wide variety of π-conjugated polymers have been synthesized by using organometallic polycondensations. For instance, Ni(0) complex-promoted dehalogenative polycondensation of dihaloaromatic compounds, X-Ar-X, affords poly(arylene)s, -(Ar)_n-. Pd-catalyzed polycondensation gives alternating copolymers, -(Ar-Ar′)_n-, and poly(arylene-ethynylene)s, -(Ar-CC-Ar′-CC)_n-. These polymers show distinguishing optical and electrochemical properties and functionalities. Their well-characterized linear structures lead to molecular assembly and packing of the polymer molecules in solutions and in the solid state. In this article, we describe the synthesis of π-conjugated polymers by the organometallic polycondensations, chemical properties of the synthesized polymers, and applications of the polymers for electronic and optical devices.     

Synthesis and characterization of poly(ε-caprolactone)-containing amino acid-based poly(ether ester amide)s

A new family of biodegradable amino acid-based poly(ether ester amide)s (AA-PEEAs) consisting of three building blocks [poly(ε-caprolactone) (PCL), L -phenylalanine (Phe), and aliphatic acid dichloride] were synthesized by a solution polycondensation. Using DMA as the solvent, these PCL-containing Phe-PEEA polymers were obtained with fair to very good yields with weight average molecular weight (M_w) ranging from 6.9 kg/mol to 31.0 kg/mol, depending on the original molecular weight of PCL. The chemical structures of the PCL-containing Phe-PEEA polymers were confirmed by IR and NMR spectra. These PCL-containing Phe-PEEAs had lower T_g than most of the oligoethylene glycol (OEG) based AA-PEEAs due to the more molecular flexibility of the PCL block in the backbones, but had higher T_g than non-amino acid based PEEA. The solubility of the PCL-containing Phe-PEEA polymers in a wide range of common organic solvents, such as THF and chloroform, was significantly improved when comparing with aliphatic diol based poly(ester amide)s and OEG based AA-PEEAs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheological properties of poly(ε-caprolactone) and poly(styrene-co-acrylonitrile) blends

Summary Rheological properties of poly(-caprolactone) (PCL) and Poly (styrene-co-acrylonitrile) (SAN) blends were examined as a function of the acrylonitrile (AN) content in SAN, to systematically understand the correlation between the interaction parameter and the theological properties of miscible polymer blends. When the plateau modulus (G _N ⁰) and zero shear viscosity ( ₀) of the PCL/SAN blends are plotted against the AN content in SAN, a minimum is observed. Qualitatively, the results obtained parallel the variation of the interchain interaction with the AN content. The negative deviation ofG _N ⁰ and ₀ from linearity seems to be attributed to the increase in the entanglement molecular weight between dissimilar chains which results from the chain extension caused by interchain interaction.     

Organosoluble and colorless fluorinated poly(ether imide)s derived from a highly contorted biphenyl-2,2′-diol bis(ether anhydride) and aromatic bis(ether amine)s with trifluoromethyl substituents

A series of new fluorinated aromatic poly(ether imide)s (PEIs) were prepared from highly contorted 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and various trifluoromethyl-containing bis(ether amine)s via chemical or thermal imidization. All the PEIs showed good solubility in a variety of organic solvents and could afford flexible, colorless, and transparent thin films via solution-casting. They showed cut-off wavelengths of Uv-vis absorptions below 380 nm and very low yellowness index (b* < 7.0). They also showed high thermal stability with the 10% weight loss temperature from 503 to 585 °C of in nitrogen or air atmosphere. The glass transition temperatures (T _gs) are recorded in the range of 194–254 °C by DSC. For a comparative study, another series of non-fluorinated PEIs derived from the same biphenyl-2,2′-diol bis(ether anhydride) with various bis(ether amine)s without the trifluoromethyl substituents were also synthesized and characterized.     

Preparation and thermotropic properties of copoly(4,4′-biphenylene sebacate-co-eicosanedioate)s

Summary A series of thermotropic copoly(4,4-biphenylene sebacate-co-eicosanedioate)s were prepared by melt polycondensation of 4,4-biphenylene diacetate, sebacic acid and eicosanedioic acid. Their thermal transitions and liquid crystalline properties were investigated by DSC and polarized micrrocope. The copolyesters were found to exhibit a smectic phase, but no nematic phase was observed upon cooling. The smectic-isotropic transition temperature decreased as the content of eicosanedioate unit increased, and the corresponding transition heat did not change to a great extent. However, the crystalline-smectic transition temperature showed an eutectic behavior, and the crystalline-smectic transition heat was depressed considerably after copolymerization. The X-ray diffraction data of the copolyesters after thermal treatment were measured and compared with the thermal properties measured by DSC.     

Mechanical and Physical properties of chitosan and whey blended with poly(ε-caprolactone)

Properties important for packaging were studied on blends of 0-15 wt% poly( l caprolactone) and chitosan and a whey-protein-isolate. The blends were obtained by solution mixing, and films were produced by solvent casting. Transparency was measured by UV/VIS spectroscopy and the printability was qualitatively estimted by using a red ethanol dye. Mechanical properties of solid films and seals were assessed by tensile tests. Stiffness and folding endurence were also measured. The blend morphology was characterized by scanning electron microscopy. It was found that all the blends were transparent. The whey-protein-isolate had the best printability properties and printability remained in the poly( l -caprolactone)-blends. Film stiffness decreased and strain at break increased strongly when the pure chitosan and the pure whey-protein-isolate were wetted. The addition of poly( l -caprolactone) to chitosan and whey-protein-isolate had only a moderate effect on the toughness properties but a strong effect on the modulus which could be predicted by the Halpin-Tsai model. The modulus of the whey-protein-isolate increased and the modulus of the chitosan decreased with the addiion of poly( l -caprolactone). It was found that it was impossible to seal chitosan with a standard heat-pulse sealing technique. The whey-protein-isolate was sealable but the strength of the seals was lower than the intrinsic strength of the pure whey-protein-isolate. The folding endurance properties of chitosan and its blends were far better than those of the whey-protein-isolate and its blends.     

Synthesis and hydrolysis of β-cyanoethyl ether of poly(vinyl alcohol)

Poly(vinyl alcohol) (PVA) was cyanoethylated by reaction with acrylonitrile in the presence of sodium hydroxide and quaternary ammonium halide. Quaternary ammonium halide, acting as a phase transfer catalyst, increases the degree of substitution (DS) of PVA. The DS also increased with increasing acrylonitrile concentration. Cyanoethylation of PVA up to 98% can be achieved under optimum conditions. The hydrolysis of β-cyanoethyl ether of PVA (CN–PVA) was studied. The rate of hydrolysis was affected by the sodium hydroxide concentration and the reaction temperature. The rheological properties of aqueous solution of hydrolysis product of CN–PVA were determined at different temperatures, and the flow activation energy was calculated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2771–2777, 1999     

Preparation of π-conjugated polymers consisting of 1-aminopyrrole and 4-amino-1,2,4-triazole units

π-Conjugated polymers based on 1-aminopyrrole and 4-amino-1,2,4-triazole were prepared. Pd-catalyzed organometallic polycondensation gave poly(arylene-ethynylene) (PAE)-type π-conjugated polymers consisting of BOC-protected 4-amino-1,2,4-triazole (Taz(BOC)) units (BOC = t-butoxycarbonyl). The number average molecular weights (M_n) were determined to be 5200–19,200 using GPC. An alternating copolymer of Taz(BOC) and bithiophene (Th–Th) units, P(Taz(BOC)-Th-Th)_n-Pd, with an M_n of 10,800 was also prepared by Pd-catalyzed organometallic polycondensation. (Taz(BOC)-Th-Th)_n-Pd showed a UV–Vis absorption peak at λ_max = 425 nm, which is reasonable for a π-conjugated five-membered ring polymer with a coplanar structure. The deprotection of the BOC group of the polymers proceeded at 200 °C; this BOC-deprotection was investigated using a model compound. The optical and electrochemical properties of the π-conjugated polymers are reported.     

Biosynthesis and chemical modification of poly(γ-glutamic acid)

Summary The water soluble poly(-glutamic acid) (-PGA) was synthetized by bacteria. A series of new, less water soluble -esters were prepared by repeated esterification.The characterization of the resulted polymers was performed by 200 MHz ¹H and 75.4 MHz ¹³C NMR spectroscopy.     

Synthesis and optical properties of π-conjugated polymers composed of diester-substituted bithiophene and dibenzothiophene or carbazole

Novel π-conjugated polymers composed of diester-subsituted bithiophene and dibenzothiophene (PDBT-DEBT) or N-alkyl carbazole (PCz-DEBT) were prepared via the Stille cross-coupling polymerization using Pd(0) catalyst. The structures of obtained polymers were confirmed by ¹H NMR and IR spectroscopies. Optical properties of the polymers were investigated by UV–vis and photoluminescence spectroscopies. The photoluminescence spectra of the polymers showed strong emission peaks in the green region.     

Novel π-conjugated organoboron polymers: Poly (ethynylene-phenylene-ethynylene-borane)s

Summary Novel poly(ethynylene-phenylene-ethynylene-borane)s were prepared by polycondensation between bifunctional lithium acetylide and aryldimethoxyborane. The polymers obtained are expected as a novel type of organoboron π-conjugated polymers via vacant p-orbital of boron atom. The polymerization between dilithium 2,5-didodecyloxybenzene- 1,4-diethynilide and tripyldimethoxyborane [tripyl=2,4,6-triisopropylphenyl] gave the corresponding polymer in 67% yield. From gel permeation chromatographic analysis (THF, PSt standards), the number-average molecular weight of the polymer was found to be 2700. In the UV-vis spectrum of the polymer (in chloroform at room temperature), an absorption maximum was observed at 397 nm. The fluorescence emission spectrum (in chloroform, room temperature, excitation wavelength at 400 nm) showed its λ_max at 456 nm in the visible blue region. The polymers obtained were very soluble in common organic solvents such as THF, chloroform and benzene. Received: 11 April 2000/Accepted: 22 April 2000     

Synthesis and characterization of polyrotaxanes comprising α-cyclodextrins and poly(ε-caprolactone) end-capped with poly(N-isopropylacrylamide)s

Biodegradable polyrotaxane (PR)-based triblock copolymers were synthesized via the atom transfer radical polymerization (ATRP) of N-isopropylacrylamide (NIPAAm) initiated with polypseudorotaxanes (PPRs) consisting of a distal 2-bromopropiomyl bromide end-capping poly(ε-caprolactone) (Br-PCL-Br) and a varying amount of α-cyclodextrins (α-CDs) in the presence of Cu(I)Br/PMDETA at 25 °C in aqueous solution. The copolymers were featured by relatively higher yields from 46.0% to 82.8% as compared with previous reports. Their structure was characterized in detail by using ¹H NMR, ¹³C CP/MAS NMR, GPC, WXRD, DSC and TGA analyses. When a feed molar ratio of NIPAAm to Br-PCL-Br was changed from 50 to 200, the degree of polymerization of PNIPAAm blocks attached to two ends of PPRs was in a range of 158–500. About one third of the added α-CDs were still entrapped on the central PCL chain after the ATRP process. Attaching PNIPAAm rendered the copolymers soluble in aqueous solution showing the thermo-responsibility as evidenced by turbidity measurements.     

Synthesis and characterization of multiblock semi-crystalline hydrophobic poly(ether ether ketone)–hydrophilic disulfonated poly(arylene ether sulfone) copolymers for proton exchange membranes

Multiblock copolymers based on alternating segments of telechelic phenoxide terminated hydrophilic fully disulfonated poly(arylene ether sulfone) (BPS100) and decafluorobiphenyl (DFBP) terminated hydrophobic poly(arylene ether ketimine) (PEEKt), were synthesized from the hydrophilic and ketimine-protected amorphous hydrophobic telechelic oligomers by nucleophilic coupling reactions. After film formation from DMSO, the copolymer was acidified, which converted the ketimine to semi-crystalline ketone segments and the sulfonate salts to disulfonic acids. A semi-crystalline phase with a T_m of 325 °C was confirmed. The semi-crystalline multiblock copolymer membranes were tough, ductile and solvent resistant. Fundamental properties as proton exchange membranes (PEMs) showed enhanced conductivities under fully hydrated and reduced humidity conditions. These multiblock copolymers exhibited low in-plane anisotropic swelling behavior, in contrast to the random copolymers.     

Modified poly(ether–imide–amide)s with pendent benzazole structures: Synthesis and characterization

Three series of novel modified poly(ether–imide–amide)s (PEIAs) having pendent benzazole units were prepared from diimide–dicarboxylic acids, including 2-[3,5-bis(4-trimellitimidophenoxy) phenyl]benzimidazole, 2-[3,5-bis(4-trimellitimidophenoxy) phenyl]benzoxazole, and 2-[3,5-bis(4-trimellitimidophenoxy) phenyl]benzothiazole, with various diamines by direct polycondensation in N-methyl-2-pyrrolidone with triphenyl phosphite and pyridine as condensing agents. These new diimide–dicarboxylic acids containing ether linkages and benzazole pendent groups were synthesized by the condensation reaction of 5-(2-benzimidazole)-1,3-bis(4-aminophenoxy)benzene, 5-(2-benzoxazole)-1,3-bis(4-aminophenoxy)benzene, or 5-(2-benzothiazole)-1,3-bis(4-aminophenoxy)benzene with trimellitic anhydride, respectively. All of the polymers were obtained in quantitative yields with inherent viscosities of 0.39–0.65 dL/g. For comparative purposes, the corresponding unsubstituted PEIAs were also prepared by the reaction of a diimide–dicarboxylic acid monomer lacking benzazole pendent groups, namely, 3,5-bis(4-trimellitimidophenoxy) phenyl, with the same diamines under similar conditions. The solubilities of the modified PEIAs in common organic solvents and their thermal stability were enhanced compared to those of the corresponding unmodified PEIAs. The glass-transition temperature, 10% weight loss temperature, and char yields at 800°C were 19–31°C, 22–57°C and 4–8% higher, respectively, than those of the unmodified polymers. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of poly(2-pyridone-3,5-diyl)s with –(CH2)4–SO3M (M = H or Na) side chains

Poly(2-pyridone-3,5-diyl)s with –(CH₂)₄–SO₃M (M = H or Na) side chains have been prepared by nickel-complex promoted dehalogenative polycondensation. A composite film of the polymer with –(CH₂)₄–SO₃H side chains and poly(vinyl alcohol) showed a proton conductivity of 1.5 × 10^?1 S cm^?1 at 80 °C and 95% humidity. A copolymer with pyridine showed a high stability against oxidation by a Fenton reagent.     

Effect of cobalt-60 γ radiation on the physical and chemical properties of poly(ethylene terephthalate) polymer

The structural, optical, and morphological properties of Co⁶⁰ γ irradiation on poly(ethylene terephthalate) polymer samples were studied with X-ray diffraction (XRD), ultraviolet–visible spectroscopy, scanning electron microscopy (SEM), and Raman spectroscopy. The diffraction pattern of virgin sample showed that the polymer was semicrystalline in nature. However, because of irradiation, the crystallinity decreased up to a dose level of 110 kGy and increased up to 300 kGy. The crystallite size, strain, and dislocation were calculated from the XRD data, and the crystallite size decreased from 291.07 to 346.90 Å. The absorption edge shifted from 315 to 330 nm, and the band gap of the samples decreased from 3.79 to 3.66 eV. The SEM micrographs showed radial bulging along with inhomogeneous liner exfoliation, and also, a rocky shape pattern with different sizes was observed. A significant change was found in the Raman spectra of the γ-irradiated polymer at the highest dose. The results of the structural, optical, and morphological studies show recovery characteristics at the highest dose level of 300 kGy. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal properties of di- and triblock copolymers of poly(l-lactide) with poly(oxyethylene) or poly(ε-caprolactone)

High molecular weight di- and triblock copolymers of poly(l-lactide), PLLA, (80 wt%) with a crystallizable flexible second component such as poly(ε-caprolactone), PCL, or poly(oxyethylene), PEO, (20 wt%) were obtained in nearly quantitative yields by ring opening of l-lactide initiated by PCL or PEO hydroxy terminated macromers. The copolymers were characterized by ¹H NMR and FTIR spectroscopy and size exclusion chromatography and showed unimodal and narrow molecular weight distributions. X-ray diffraction measurements revealed high crystallinity (38-56%) of the PLLA blocks and gave no clear evidences of PCL or PEO crystallinity. DMTA and DSC techniques showed a melting behaviour of the copolymers (T_m=174-175 °C; ΔH_m=19-37 J/g) quite similar to that of PLLA. PCL and PLLA segments are immiscible, while PLLA and PEO segments are partially miscible in the amorphous phase. Stress-strain measurements indicated a ductile behaviour of the copolymers, characterized by lower tensile moduli (225-961 Pa) and higher elongations at break (25-134%) with respect to PLLA.