Synthesis and properties of novel poly(aryl ether ketone)s containing imide linkages in the main chains

A new monomer containing imide linkages, bis[4-(p-phenoxybenzoyl)-1,2-benzenedioyl]-N,N,N′,N′-4,4′-diaminodiphenyl ether (BPBDADPE), was prepared by the Friedel–Crafts reaction of bis(4-chloroformyl-1,2-benzenedioyl)-N,N,N′,N′-4,4′-diaminodiphenyl ether (BCBDADPE) with diphenyl ether (DPE). Novel poly(aryl ether ketone)s containing imide linkages in the main chains (PEK-I) were synthesized by electrophilic Friedel–Crafts solution copolycondensation of terephthaloyl chloride (TPC) with a mixture of DPE and BPBDADPE. The polymers were characterized by different physico-chemical techniques. The polymers with 10–40 mol% BPBDADPE are semicrystalline and had increased T _gs over commercially available poly(ether ether ketone) (PEEK) and poly(ether ketone ketone) (PEKK) (70/30) due to the incorporation of imide linkages in the main chains. The polymers IV and V with 30–40 mol% BPBDADPE had not only high T _gs of 182–183 °C, but also moderate T _ms of 341–343 °C, having good potential for melt processing and exhibited high thermal stability and good resistance to common organic solvents.     

Metal Complexes of π-Conjugated Polymers

π-Conjugated chelating polymers such as poly(2,2′-bipyridine-5,5′-diyl), poly(1,10-phenanthroline-3,8-diyl), and salophen polymers have been prepared by organometallic polycondensations. The obtained polymers form metal complexes with various metal species such as [Ru(bpy)₂]²⁺ and CuCl₂. Metal complexes of π-conjugated ligands are also polymerized by dehalogenative organometallic polycondensations. Some of the metal complexes of π-conjugated polymers exhibit electrical conducting nature and show catalytic activity for redox reactions.     

Pendant-decorated polytriphenylamine derivative: potential blue-emitting and hole-transporting material

Using Suzuki coupling reaction, we successfully synthesized a conjugated polymer with alternating fluorene and triphenylamine as the main chain and bearing bulky (2,3,4,5-tetraphenyl) phenyl pendants: poly(9,9-dioctyl)-2,7-fluorene-co-N-4-(2,3,4,5-tetraphenyl)diphenyl-4,4′-diphenylamine (PFT-TPP). This polymer is readily soluble in common organic solvents, has good thermal stability, and readily forms thin film by solution processing. It has an optical bandgap of ca. 2.90 eV, as indicated by the UV–vis investigation. The PL emission of PFT-TPP peaks at 447 nm in dilute THF solution and at 444 nm in a solid film. PFT-TPP shows relatively high HOMO (−5.30 eV) and LUMO levels (−2.40 eV) by cyclic voltammetry, due to the high content of electron-donating triphenylamine segments in the polymer backbone.     

π-Conjugated polyphenylene gels with charge transfer structures assisted by TCNQ

The reaction of π-conjugated poly(p-phenylene)s (PPPs) consisting of 2- or 3-amino-1,4-phenylene (NH₂Ph) and 2,5-dioctyloxy-1,4-phenylene (OctPh) or 9,9-dihexylfluorene-2,7-diyl (HexFlu) rings [polymer-1: (NH₂Ph-OctPh)_n and polymer-2: (NH₂Ph-HexFlu)_n] with 7,7,8,8-tetracyanoquinodimethane (TCNQ) yielded gel-1 and gel-2. These gels were form through a charge transfer (CT) between the NH₂ group and TCNQ, causing the gels to be linked by a TCNQ dianion. ESR measurements suggest that radical species generated by CT in the gels are delocalized in the π-conjugated polymer backbone. UV–vis measurements revealed that CT between the NH₂ group and TCNQ was essential for gel formation. When a dimethyl sulfoxide (DMSO)/TCNQ solution was added to a chloroform solution of the polymers, the absorption corresponding to CT bands increased with an increasing amount of TCNQ. Photoluminescence (PL) measurements suggested that TCNQ served as a quencher for fluorescent polymer-1 and polymer-2. Quenching behavior was investigated by Stern–Volmer analysis.     

Spectral investigation and laser action in solid films of fluorene-dibenzothiophene-s,s-dioxide co-polymers

A systematic optical study of a series of 9,9–dyoctylefluorene-2,7-diyl-dibenzothiophene-s,-s-dioxide-3,7-diyl co-polymers p(F-S)y has been performed where S unit (-dibenzothiophene-s,sdioxide-3,7diyl) varied from 15 to 50 mol%. We have investigated optical absorption, steady state and time resolved photoluminescence spectroscopy at room temperature and at low temperature. The emission band for all of these materials is red shifted from that of poly(9,9-dioctylfluorene). Except for p(F-S)50 all our material show one phosphorescence band at low temperature. Dual phosphorescence is observed for p(F-S)50 that are originated from different monomer units. Drop cast film of p(F-S)50 shows amplified spontaneous emission (ASE) effect peaking at 2.66 eV with FWHM at 5 nm.     

Synthesis and photoluminescent properties of polymer containing perylene and fluorene units

A new luminescent polymer, F-PTCD, with N,N′-bis-(propenylaniline)-3,4,9,10-perylene tetracarboxylic diimide-emitting segments (PTCD) and 9,9-diphenylfluorene (DIPT) was synthesized by Heck reaction. The structures were characterized by MS, EA, ¹H NMR, IR and the photoluminescent (PL) properties were investigated by UV/vis absorption and fluorescence emission spectra. The fluorescence quantum yield was 0.453 in acetone. Thermogravimetric analysis and differential scanning calorimetry showed that the polymer is thermal stable up to 569 °C with glass-transition temperature higher than 125 °C. They are yellow-red emitting materials with the band gap of 2.33 eV estimated from the onset absorption. In addition, the emission can be quenched by both electron donor (N,N-dimethylaniline) and electron acceptor (Fullerene), where the processes followed the Stern-Volmer equation. Furthermore, the interaction between F-PTCD and carbon nanotubes (CNTs) was also studied by fluorescent quenching.     

Dependence of optical properties on the preparation methods of poly[(9,9′‐dialkylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)]

A blue‐light‐emissive fluorene‐based polyoxadiazole, an n‐type polyfluorene derivative, was synthesized by both one‐step and two‐step methods. Directly polymerized poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx‐DP) exhibited a higher molecular weight and a more efficient photoluminescence quantum yield than poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐(1,3,4‐oxadiazole‐2,5‐diyl)] (PFOx) prepared via a polyhydrazide precursor, poly[9,9′‐didodecylfluorene‐2,7‐(2,5‐dihydrazide‐ 1,3,4‐oxadiazole). Both polymers, differently prepared, showed similar photoluminescent properties in 1,2‐dichloroethane. However, in a film state, the influence of the interchain interactions on the photoluminescence of PFOx with the lower molecular weight was larger than on the photoluminescence of PFOx‐DP. The electron‐deficient property of an oxadiazole group in the polymer backbone resulted in low‐lying highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of ?6.29 and ?3.26eV, respectively, of the polymer suitable for electron‐transport/hole‐blocking layers and emissive layers in multilayer electroluminescence devices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3112–3118, 2004     

Synthesis of well-defined norbornene–lactone-functionalized polymers via ATRP

Well-defined norbornene–lactone-functionalized polymers were synthesized by atom transfer radical polymerization (ATRP) of 5-methacryloxy-6-hydroxynorbornene-2-carboxylic-6-lactone (MNL) and 5-acryloxy-6-hydroxynorbornene-2-carboxylic-6-lactone (ANL) monomers. The ATRP of MNL initiated by ethyl 2-bromopropionate (EBrP), in both N,N-dimethylformamide (DMF) and o-dichlorobenzene (ODCB) solvents was successfully carried out in the presence of CuCl/CuBr and N,N,N′′,N′′,N′′-pentamethyltriethylenetetramine (PMDETA) at 70 °C. The CuCl/ODCB catalyst system gave rise to a lower M _w/M _n (≦1.20) than CuBr/DMF catalyst system. The ATRP of ANL was feasible in the presence of CuBr and PMDETA at 70 °C but showed lower reactivity than MNL. The resulting polymers were characterized by means of gel permeation chromatography (GPC) and ¹H NMR spectroscopy.     

Synthesis and characterization of fluorine–thiophene-based π-conjugated polymers using coupling reaction

A solution processible fluorine–thiophene-based copolymers, namely poly[2,7-bis(4-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P1), poly[2,7-bis(3-octyl-2-thienyl)-9,9-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P2), poly[2,7-bis(3,3′-dioctyl-5,5′-bithien-2yl)-9,9′-dioctylfluorene-co-alt-5,5′-(2,2′-bithiophene)] (P3) were synthesized using Suzuki and Stille coupling reaction. The polymers showed weight loss starting around 400 °C indicative of good thermal stability. UV–vis properties and photoluminescence (PL) properties were investigated in toluene. P1, P2 and P3 exhibited the absorption maximum at 450, 428 and 435 nm and their PL spectrum peaked at 587, 559 and 560 nm, respectively. And all polymers, P1, P2 and P3, showed electroluminescence (EL) spectrum peaked at 592, 595 and 607 nm in the range of orange red. The polymers were electrochemically active in oxidation regions. P3 especially showed high oxidation stabilities in 1.17 V vs. Ag/Ag⁺. And P1 and P3 showed higher crystallinity than P2, because they have a repeated unit of 3,3-dialkyl-quaterthiophene.     

Synthesis and characterization of polyamides and poly(amide-imide)s based on ether-sulfone-diamines

A series of polyamides and poly(amide-imide)s were prepared by the direct polycondensation of 4,4′-[sulfonylbis(1,4-phenyleneoxy)]dianiline or 4,4′-[sulfonylbis(2,6-dimethyl-1,4-phenyleneoxy)]dianiline with aromatic dicarboxylic acids and phthalimide unit-bearing dicarboxylic acids in a N-methyl-2-pyrrolidone (NMP) solution containing dissolved calcium chloride using triphenyl phosphite and pyridine as condensing agents. The inherent viscosities of the resulting polymers were above 0.45 dL/g and up to 1.70 dL/g. Except for the polyamides derived from terephthalic acid and 4,4′-biphenyldicarboxylic acid, all the other polyamides and all poly(amide-imide)s were readily soluble in polar organic solvents such as NMP, N, N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and m-cresol, and afforded transparent and tough films by solution-casting. Most of the polymers showed distinct glass transition on their differential scanning calorimetry (DSC) traces and their glass transition temperatures (T_g) stayed between 140–264 °C. The methyl-substituted polymers showed higher T_gs than the corresponding unsubstituted counterparts. The results of the thermogravimetry analysis (TGA) revealed that all the methyl-substituted polymers showed lower initial decomposition temperatures than the unsubstituted ones.     

Asymmetric polymerization of N-substituted maleimides with organolithium — bisoxazolines complex

Asymmetric anionic polymerizations of achiral N-substituted maleimide (RMI) (N-cyclohexyl (CHMI), N-phenyl (PhMI), N-tert-butyl (TBMI)) by n-butyllithium (n-BuLi) or fluorenyllithium (FlLi) complexes of chiral bisoxazoline derivatives in toluene gave optically active polymers ([α]²⁵ ₄₃₅− 2.9° to − 8.2°). The polymers prerared with initiator of n-BuLi – 2,2′-bis(4,4′-isopropyl-,3-oxazoline) showed negative specific rotations (poly(RMI), [α]²⁵ ₄₃₅− 5.8° to − 8.2°) which were greater than those ([α]²⁵ ₄₃₅− 2.9° to − 5.9°) with other chiral 2,2′-bis(4,4′-alkyl-1,3-oxazoline) (alkyl group = iso-butyl and benzyl). Received: 29 July 1997/Revised: 27 August 1997/Accepted: 1 September 1997     

Fluorescence study of interaction between an anionic conjugated polyelectrolyte and bovine serum albumin

The interaction between an anionic conjugated polyelectrolyte, poly[9,9-bis(3′-butyrate)fluoren-2,7-yl] sodium (BBS-PF), and bovine serum albumin was investigated by fluorescence spectroscopy. The emission of BBS-PF was effectively quenched by BSA with a quenching constant K _SV of 3.1 × 10⁷ L/mol when BSA was at nanomolar concentrations, but the emission increased when the concentration of BSA was at micromolar level. The excitation band of BBS-PF blue-shifted when the emission was quenched where the negatively charged BSA induced the aggregation of BBS-PF, yet the excitation band of BBS-PF red-shifted when the emission increased where the BSA acted as a surfactant and formed hydrophobic interaction with BBS-PF. BBS-PF could also quench BSA through energy transfer by resonance with a quenching constant K _SV of 1.1 × 10⁶ L/mol. The emission band changes of BSA reflected the conformation transitions of BSA from class II to class I and the binding of BBS-PF with BSA made the BSA more folded.     

Polyimides based on furanic diamines and aromatic dianhydrides: synthesis,characterization and properties

Novel polyimides containing furan moieties were prepared from the resulting furanic diamine monomers with various aromatic dianhydrides including 1,2,4,5-benzene-tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, and hexafluoroisopropylidene 2,2-bis(phthalic anhydride), via a two-step process. The resulting polyimides were characterized by solubility tests, viscosity measurements, FTIR, ¹H NMR spectroscopy, differential scanning calorimetric (DSC), and thermogravimetric analysis (TGA) analysis. The polyimides with inherent viscosities in the range of 0.048–0.095 L/g showed excellent solubility in aprotic amide and organic solvents, such as N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, dimethylformamide and acetone, chloroform, etc. DSC showed glass transition temperatures (T _g) in the range of 116–143 °C. These polymers showed excellent thermal stability up to 390 °C.     

Synthesis and structural characterization of novel biologically active and thermally stable poly(ester-imide)s containing different natural amino acids linkages

Starting from the natural α-amino-acid L-tyrosine, a potentially bioactive diphenolic molecule, N,N′-(pyromellitoyl)-bis-L-tyrosine dimethyl ester (8), was prepared in three steps using protecting groups to block the NH₂ and COOH of tyrosine. A facile and rapid polycondensation reaction of diol 8 with several optically active diacid chlorides such as N,N′-(pyromellitoyl)-bis-(L-α-amino) diacid chlorides derived from L-phenyalanine, L-leucine, L-methionine, L-valine and L-alanin was developed under microwave irradiation. The polymerization reactions proceeded rapidly and was completed within 12 min, producing a series of novel poly(ester-imide)s (PEI)s in good yields and moderate inherent viscosities of 0.41–0.51 dL/g. The obtained polymers were characterized by means of FT-IR, ¹H-NMR, elemental and thermogravimetric analysis techniques. In addition, in vitro toxicity test and biodegradability behavior of the diphenolic 8 and obtained PEIs were investigated in culture media and soil burial degradation. The outcome showed that synthesized diol 8 and its derived polymers are biologically active and biodegradable under natural environment.     

Solid state electrochemistry and spectroelectrochemistry of poly(arylene bisimide–alt-oligoether)s

Two electroactive polymeric arylene bisimides, namely poly[(4,7,10-trioxatrideca-1,13-diyl)-(1,4,5,8-naphthalenetetracarboxylic bisimide-N,N′-diyl)] and its perylene analogue – poly[(4,7,10-trioxatrideca-1,13-diyl)-(3,4,9,10-perylenetetracarboxylic bisimide-N,N′-diyl)] have been synthesized and studied by cyclic voltammetry, UV–vis-NIR as well as Raman spectroeletrochemistry. Contrary to low molecular weight arylene bisimides, which show a clear two electron, double-step electrochemical reduction (neutral form to radical anion and from radical anion to dianion), in the synthesized polymers multielectron transfers are observed, accompanied with a strong electrochromic effect. However, as probed by cyclic voltammetry, their first reduction step is retarded and covers a wider potential range. We attribute this effect to macromolecular nature of the compounds being reduced and their structural inhomogeneity caused by π-stacking induced nanoaggregation of bisimide segments of the polymer chains. The second redox step seems unaffected by the polymeric nature of the electroactive compounds and yields a reduction peak similar to that registered for low molecular weight bisimides. Raman spectroelectrochemical data, combined with the established vibrational model of the perylene derivative – (poly[(4,7,10-trioxatrideca-1,13-diyl)-(3,4,9,10-perylenetetracarboxylic bisimide-N,N′-diyl)]) – enabled us to determine the mechanism of the first step of the electrochemical reduction process. The electrochemically induced shifts of the Raman bands unequivocally show that the reduction process results in the transformation of the carbonyl group into a radical anion. The surplus negative charge is delocalized on the six-member imide ring with the aromatic core very little affected.     

Synthesis and characterization of new optically active poly(amide-imide)s containing 1,3,4-oxadiazole moiety in the main chain

Six new optically active poly(amide-imide)s were synthesized by poly condensation reaction of 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole (8) with six chiral N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic)-bis-l-amino acids (3a–f) in a medium consisting of N-methyl-2-pyrrolidone (NMP), triphenylphosphite (TPP), calcium chloride (CaCl₂), and pyridine. Chiral N,N′-(bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic)-bis-l-amino acids (3a–f) were obtained by the reaction of bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (1) with two equimolar of l-alanine (2a), l-valine (2b), l-leucine (2c), l-isoleucine (2d), l-phenyl alanine (2e), and l-2-aminobutyric acid (2f) in acetic acid. The poly condensation reaction produced a series of novel poly(amide-imide)s (9a–f) in high yield and with inherent viscosities between 0.30 and 0.52 dL/g. The resulting polymers were characterized by elemental analysis, viscosity measurement, solubility testing, thermo-gravimetric analysis (TGA), ¹H-NMR, and FT-IR techniques.     

Langmuir and Langmuir-Blodgett Films of Polyfluorenes and Their Use in Polymer Light-Emitting Diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9′-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (П-A) and surface potential (ΔV-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.     

Synthesis and characterization of polyimides based on isopropylidene-containing bis(ether anhydride)s

Two bis(ether anhydride)s, 4,4′-[1,4-phenylenebis(isopropylidene-1,4-phenyleneoxy)]-diphthalic anhydride (IV _a) and 4,4′-[isopropylidenebis(1,4-phenylene)dioxy]diphthalic anhydride (IV _b), were prepared in three steps starting from the nucleophilic nitrodisplacement reaction of 4-nitrophthalonitrile with α,α ′-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene (I _a) and 4,4′-isopropylidenediphenol (I _b) in N,N-dimethylformamide (DMF) in the presence of potassium carbonate. The bis(ether anhydride)s IV _a and IV _b were polymerized with various aromatic diamines to obtain two series of poly(ether amic acid)s VI _a–g and VII _a–g with inherent viscosities in the range of 0.30∼0.74 and 0.29∼1.01 dL/g, respectively. The poly(ether amic acid)s were converted to poly(ether imide)s VIII _a–g and IX _a–g by thermal cyclodehydration. Most of the poly(ether imide)s could afford flexible and tough films, and they showed high solubility in polar solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide, and m-cresol. The obtained poly(ether imide) films had tensile strengths of 45∼83 MPa, elongations-to-break of 6∼27%, and initial modulus of 0.6∼1.7 GPa. The T_gs of poly(ether imide)s VIII _a–g and IX _a–g were in the range of 194∼210 and 204∼243 °C, respectively. Thermogravimetric analysis (TG) showed that 10% weight loss temperatures of all the polymers were above 500 °C in both air and nitrogen atomspheres.     

N-[2-(8-heptadecenyl)-4,5-dihydro-1H-imidazole-1-ethyl]-2-bromoisobutyramide as initiator for atom transfer radical polymerization (ATRP) and surface-initiated ATRP of methyl methacrylate on iron

N-[2-(8-heptadecenyl)-4,5-dihydro-1H-imidazole-1-ethyl]-2-bromoisobutyramide (IEB) was synthesized and characterized by elemental analysis, FT-IR, and ¹H NMR. It had been successfully used as a bidentate initiator for the ATRP of methyl methacrylate with CuBr/2,2′-bipyridine as the catalyst, and N,N-dimethylformamide as the solvent at 70 °C. The kinetics was first order in monomer and the number-average molecular weight of the polymer increased linearly with the monomer conversion, indicating the ‘living’/controlled nature of the polymerization. The polymerization reached high conversions producing polymers with a low molecular weight distribution ( M _w/M _n = 1.319). The obtained poly(methylmethacrylate) (PMMA) functionalized with 2-(8-heptadecenyl)-4,5-dihydro-1H-imidazoleyl and ω-Br as the end groups were characterized by FT-IR spectroscopy. They can be used as macroinitiators for chain extension reaction. Then, PMMA coatings were grafted from iron substrates by surface-initiated ATRP from a surface-bound IEB initiator. The EIS measurements confirmed the successful grafting of the polymer coatings. Greatly improved short-term anticorrosive properties for PMMA-modified electrodes were demonstrated by substantially increased resistance of the film for a period of 24 h as compared to bare iron.     

A new and efficient synthetic method of a liquid crystalline epoxy resin with biphenol and aromatic ester group

This article describes a high efficient and economical method to synthesize a liquid crystalline epoxy resin (LCER) containing biphenol and aromatic ester group, 3,3′,5,5′-tetramethylbiphenyl-4,4′-diyl bis(4-(oxiran-2-ylmethoxy) benzoate) (4). First, 3,3′,5,5′-tetramethylbiphenyl-4,4′-diyl bis(4-hydroxybenzoate) (3) was prepared by direct esterification of 3,3′,5,5′-tetramethylbiphenyl-4,4′-diol (2) with p-hydroxybenzoic acid (1) in the presence of a certain amount of p-toluene sulfonic acid (p-TSA) as catalyst. And then (4) was synthesized by the reaction of (3) with epichlorohydrin. The chemical structure, melting range, and liquid crystalline phase transition behavior of (4) were characterized by FT-IR, ¹H-NMR, ¹³C-NMR, mass spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM).