Synthesis and characterization of naphthalene diimide/diethynylbenzene copolymers

A series of conjugated polymers has been synthesized by Sonogashira coupling of N,N′-bis(2-octyldodecyl)-2,6-dibromonaphthalene-1,4,5,8-bis(dicarboximide) and four para-diethynylbenzene derivatives: 1,4-diethynyl-2,5-dihexadecyloxybenzene, 1,4-diethynyl-2,5-bis(2-octyldodecyloxy) benzene, 1,4-bis(2-ethylhexyl)-2,5-diethynylbenzene, 1,4-diethynyl-2,5-bis(trifluoromethyl)benzene. The polymers display absorption maxima at wavelengths ranging from 530 nm to 654 nm with molar absorptivities ranging from ca. 4 to 7 × 10⁴ M^?1 cm^?1. The peak reduction potentials, determined by differential pulse voltammetry, for polymer films varied from ?0.93 to ?1.14 V vs. ferrocenium/ferrocene with the trifluoromethyl-substituted derivative being the most readily reduced. All four polymers exhibited electron transport characteristics in bottom-gate/top-contact field-effect transistors, showing average electron mobility values ranging from 1.4 × 10^?4 to 3.7 × 10^?3 cm² V^?1 s^?1.     

Synthesis and characterization of the first soluble nonracemic chiral main-chain perylene tetracarboxylic diimide polymers

The first two nonracemic chiral main-chain perylene tetracarboxylic diimide (PDI) polymers have been synthesized via acyclic diene metathesis polymerization. The use of optically pure l-α amino acids as the starting materials enables us to tune PDI π-stacking interaction in optically active polymers. The integration of π-stack tuning groups renders two main-chain PDI polymers soluble in chloroform. Spectroscopic evidences suggest that PDI π-stacks form in chloroform solutions of the two PDI polymers, even at very low concentration, probably via an intra-molecular folding process. Inside π-stacks, PDI units organize in a left-handed helical fashion. Flexible free-standing films can be cast from chloroform solution of one polymer.     

Synthesis and characterization of novel polyarylates bearing NLO moieties

A series of thermally stable second‐order nonlinear optical polyarylates containing azo side‐chain groups have been obtained by interfacial polycondensation. Theoretical calculations of the static hyperpolarizabilities, first‐ and second‐order hyperpolarizability, were carried out. The structures of the obtained monomers and polymers were confirmed by infrared, ¹H NMR and ultraviolet spectroscopies. Thermal and optical properties of the obtained polymers were evaluated. The investigations show that some of the new polymers obtained in this study may find use in optical applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2195–2201, 2006     

Synthesis of donor-acceptor poly(perylene diimide-altoligothiophene) copolymers as n-type materials for polymeric solar cells

Donor-acceptor alternated copolymers based on perylene diimide units linked in bay positions with oligothiophene units were prepared and used as acceptor material in polymeric solar cells. The copolymers have exhibited ambipolar electrochemical properties, high electronic affinities and wide electronic absorption in the visible spectrum. The spectroscopical characterization of the copolymer blends with poly-3-hexylthiophene showed evidences indicative of a charge transfer from the perylene-based copolymers to the polythiophene. All-polymeric solar cells were prepared with the blends and the photovoltaic characterization of these devices showed conversion efficiencies of 0.8% and 0.4%. The results demonstrate the potentialities of perylene-based copolymers as processable photoactive acceptor in organic solar cells.     

Synthesis and characterization of side-chain maleimide-styrene copolymers with new pendant azobenzene moieties

Four side-chain maleimide-styrene polymers have been synthesized from maleimide-alt-styrene copolymer (MASt) and some original azo-moieties using polymer analogous reactions. The structures have been obtained with good yields; remarkably, they showed a high chromophore load, up to ~100%. The polymers were characterized by means of SEC, FT-IR, ¹H-NMR, DSC-TGA, and elemental analysis. The side-chain polymers exhibited improved solubility and enhanced thermal stability up to 320oC, while their glass transition temperatures have been found to be as high as 210oC. The third-order NLO refraction (n₂) and susceptibility χ⁽³⁾ coefficients were measured by Z-scan technique. The results of Z-scan measurements showed that the polymers have only nonlinear refraction, the nonlinear absorption being negligible.     

Synthesis and characterization of poly(tetramethylsilarylenesiloxane) derivatives bearing benzodithiophene moieties

Poly(tetramethylsilarylenesiloxane) derivatives bearing benzo[1,2-b;4,5-b′]dithiophene (P1) and benzo[2,1-b;3,4-b′]dithiophene (P2) moieties were prepared via polycondensation of the corresponding disilanol monomers, that is, 2,6-bis(dimethylhydroxysilyl)benzo[1,2-b;4,5-b′]dithiophene (M1) and 2,7-bis(dimethylhydroxysilyl)benzo[2,1-b;3,4-b′]dithiophene (M2), respectively. It was deduced that P1 is a crystalline polymer while P2 is an amorphous one from the results of differential scanning calorimetry (DSC). Bathochromic and hyperchromic effects were observed in the absorption and fluorescence spectra when dimethylsilyl substituents were introduced on the benzo[1,2-b;4,5-b′]dithiophene and benzo[2,1-b;3,4-b′]dithiophene skeletons. The fluorescence quantum yields (Φ_Fs) were not improved by the introduction of dimethylsilyl groups onto the benzo[1,2-b;4,5-b′]dithiophene and benzo[2,1-b;3,4-b′]dithiophene skeletons, whereas the improvement in the Φ_Fs was remarkable in the case of poly(tetramethylsilarylenesiloxane) derivatives that possessed the corresponding fused benzene ring systems, i.e., poly(tetramethyl-2,6-silanthrylenesiloxane) and poly(tetramethyl-1,8-silphenanthrylenesiloxane).     

Synthesis and characterization of thermoresponsive diblock copolymer bearing amino acid moieties via click reaction

We report here the synthesis of well-defined thermoresponsive diblock copolymer bearing amino acid diamide derivatives, poly(N-acryloyl-l-valine N′-methylamide)-b-poly(ethylene glycol) monomethylether, via click reaction using CuSO₄/sodium ascorbate as catalyst in DMF/water mixed solvent. The effects of chain length and water volume fraction in DMF on coupling efficiency were investigated. For those reactions that both reacting polymers have short chain length, the reaction efficiency was less affected by water volume fraction and relatively high conversion was achieved. And the higher molecular weight of reactant polymer performed, the more impressive effects of water content on coupling efficiency appeared. Then, the thermoresponsive property in terms of the lower critical solution temperature (LCST) of the block copolymer was evaluated in aqueous solution by UV/vis spectroscopy. Optically active character was detected by circular dichroism instrument under temperature ranging from 1 to 30 °C, and the spectra undergo one drastic change at the temperature near LCST point.     

Synthesis and characterization of novel copolymers with acid‐labile ketal moieties derived from camphor

Novel diastereomeric acrylic ketal monomers derived from (+)‐camphor and (±)‐camphor were synthesized. To investigate the applications of the camphor derivatives on positive‐tone photoresists, the acrylic ketal monomers were copolymerized with methyl methacrylate, methacrylic acid, and n‐butyl methacrylate. The optical activities of the chiral monomers and polymers were all evaluated. After UV irradiation and postexposure baking, the optical activity of the polymers decreased because of the decomposition of the acid‐labile pendant chiral groups. The existence of alicyclic camphyl groups increased the etching resistance of the photoresists. The thermogravimetric properties of the copolymers, the exposure curves, the lithographic evaluation of the positive‐tone photoresists, and the effects of alicyclic groups on the plasma etching resistance of the copolymers were all investigated. A resolution of a line‐and‐space pattern of 0.3 μm was achieved. Acid‐catalyzed dehydration crosslinking was also found in this system. Sufficient UV irradiation and heat treatment could cause the acid‐catalyzed dehydration crosslinking of pendant carboxyl groups and thereby increase the efficiency of the thermal resistance of the polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2969–2978, 2003     

Novel amphiphilic diblock copolymers bearing acid-labile oxazolidine moieties: Synthesis, self-assembly and responsive behavior in aqueous solution

A novel oxazolidine based acid-labile monomer N-acryloyl-2,2-dimethyl-1,3-oxazolidine (ADMO) was synthesized and polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization using poly(ethylene glycol) based chain transfer agent (PEG-CTA). The diblock copolymers PEG-b-PADMO were composed of hydrophilic PEG with fixed length and hydrophobic PADMO with different lengths, which formed core-shell micelles in water. Morphologies and sizes of micelles were obtained by transmission electron microscopy (TEM) and dynamic light scattering (DLS), which showed that the shapes of polymeric aggregates developed from small spherical micelles, worm-like micelles to larger size of vesicles, as the length of PADMO increased. The hydrolysis kinetics of the micelles was studied using ¹H NMR, DLS and release of loaded Nile Red dye, whose rate strongly depended on pH and micellar structure. It led to the disruption of polymeric micelles and concomitant release of the guest molecules, due to the transformation of hydrophobic PADMO into hydrophilic poly(2-hydroxyethyl acrylamide) (PHEAM).     

Synthesis, characterization and photoconductive properties of optically active methacrylic polymers bearing side-chain 9-phenylcarbazole moieties

The synthesis of two novel optically active monomers containing 9-phenylcarbazole moieties, such as (S)-(+)-2-methacryloyloxy-N-[4-(9-carbazolyl)phenyl]succinimide [(S)-(+)-MCPS] and (S)-(+)-3-methacryloyloxy-N-[4-(9-carbazolyl)phenyl]pyrrolidine [(S)-(+)-MCPP], is described. Each monomer has been radically homopolymerized to afford the corresponding optically active polymeric derivatives, which have been fully characterized. Their spectroscopic, thermal and photoconductive properties were compared to those of the new achiral homopolymer poly[N-(2-methacryloyloxyethyl)-N-[4-(9-carbazolyl)phenyl]ethylamine] {poly[MCPE]}, devised as an optically inactive macromolecular model compound, as well as to analogue polymeric derivatives containing side-chain optically active carbazolyl moieties. The chiroptical properties of the chiral polymers are quantitatively higher than in the corresponding monomers. Owing to the substantially stereoirregular structure of the main chain, this suggests that the overall optical activity is mainly due to conformational dissymmetry of the macromolecules. Spectroscopic evidence suggests the presence in all polymeric derivatives of dipole-dipole interactions between the 9-phenylcarbazolyl chromophores, occurring as a consequence of their anchorage to the polymer backbone, which favours their aggregation and justifies their high decomposition temperatures.     

Synthesis and characterization of novel epoxy resin bearing naphthyl and limonene moieties, and its cured polymer

The synthesis of novel epoxy resin containing both naphthalene moiety and cycloaliphatic group by chemical bonding in the same molecule has been conducted starting from naphthol and limonene. Its chemical structure was characterized with FTIR spectroscopy, NMR, and GPC analyses. Dynamic cure behaviors with different curing agents were investigated using differential scanning calorimetry. The physical properties of the resulting polymers were evaluated with dynamic thermal mechanical spectroscopy, thermogravimetric and thermal mechanical analysis, and X-ray diffraction. Compared to that of diglycidyl ether of bisphenol A, cured polymer of the novel epoxy resin showed remarkably higher glass transition temperature (T_g), lower coefficient of thermal expansion, higher thermal stability, better moisture resistance and dielectric property.     

Synthesis and photovoltaic properties of two-dimensional conjugated polythiophene derivatives presenting conjugated triphenylamine/thiophene moieties

In this study we synthesized three two-dimensional (2-D) polythiophene derivatives (PTs), namely PTBPTPA, PTStTPA, and PTCNStTPA, featuring three different conjugated units—biphenyl (BP), stilbene (St), and cyanostilbene (CNSt), respectively—in the polymer backbones and presenting conjugated triphenylamine/thiophene (TPATh) moieties on the side chains. In addition, we also synthesized three conjugated BP-, St-, and CNSt-based main-chain-type conjugated polymers (PTBP, PTSt, and PTCNSt, respectively). Incorporating the St and CNSt moieties into the polymer backbones and appending TPATh units induced high degrees of intramolecular charge transfer within the conjugated frameworks of the polymers, thereby resulting in lower band gap energies and red-shifting of the maximal UV–Vis absorption wavelengths. Moreover, the energy levels of the highest occupied molecular orbitals of the BP-, St-, and CNSt-based main-chain-type and 2-D PTs were lower than that of P3HT, implying that they would be applicable for the preparation of polymer solar cells (PSC) with greater open-circuit voltages. The photovoltaic performances of PSCs fabricated from blends of the 2-D PTs and the fullerene derivative PC₆₁BM were superior to those of PSCs based on the main-chain-type polymer/PC₆₁BM blends.     

Preparation of polyimide/nylon 6 graft copolymers from polyimides containing ester moieties: Synthesis and characterization

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ?‐caprolactam. In the graft copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. The thermal stability and chemical resistance were dramatically increased by the incorporation of only 5 wt % polyimide in the graft copolymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 309–318, 2006     

Synthesis and characterization of biodegradable and biocompatible amphiphilic block copolymers bearing pendant amino acid residues

Polylactide (PLA)-based biodegradable and biocompatible amphiphilic block copolymers bearing pendant amino acid residues were synthesized through a relatively easy and efficient way. The composition and structure of these copolymers were characterized by gel permeation chromatography (GPC) and ¹H nuclear magnetic resonance (¹H NMR) spectroscopy. The self-assembly behavior of the copolymers was investigated by fluorescence (FL), dynamic light scattering (DLS), and transmission electron microscope (TEM). It was shown that aggregates less than 100 nm in average size were formed by these copolymers, which changed from micelles to vesicles with the variation of the block length. In addition, the in vitro cytotoxicity of these copolymers was determined and compared with that of PEO-b-PLA in the presence of Bel-7402 cells. The result suggested that the block copolymers PAGE/cys-b-PLA exhibited better biocompatibility. Therefore, these PLA-based copolymers are expected to find promising applications in drug delivery or tissue engineering.     

Synthesis and properties of polymer brushes bearing ionic liquid moieties

Poly(1-ethyl 3-(2-methacryloyloxy ethyl) imidazolium chloride) (PEMEIm-Cl) brushes were grafted onto Au surface via surface initiated atom transfer radical polymerization (ATRP). The swelling/collapsed behavior of the brushes was characterized by AFM in different electrolyte solutions. These 15 nm ultrathin polyelectrolyte brushes can be used to modulate the interfacial resistance via conformational changes triggered by external electrolytes and solvent. The interfacial resistance was characterized using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) using [Fe(CN)₆]^3−/4− as the redox probe. The effects of electrolytes, the concentration and type of electrolytes and temperature are investigated in more detail.     

Synthesis and characterization of novel polyazomethines containing perylene units

Polyazomethines including perylene units in the main chain were synthesized via polycondensation of diaminoperylene with aromatic dialdehydes. UV/vis, FT-IR, ¹H NMR, ¹³C NMR and elemental analysis techniques were carried out for the characterization of the synthesized diaminoperylene, dialdehydes and polyazomethines including perylene units (PAM-PERs). The number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of PAM-PERs were determined by size exclusion chromatography (SEC). Thermal properties of PAM-PERs was determined by using TGA/DTA and DSC systems. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels, and electrochemical and optical (E_g) band gap values were calculated by using the results of cyclic voltammetry and UV/vis, respectively. Conductivity measurements of PAM-PERs were carried out with electrometer by using four-point probe technique. The conductivity was observed to be increased by doping agent iodine.     

聚苯乙烯-聚硅氧烷接枝共聚物的合成与表征

以甲基丙烯酰氧丙基聚硅氧烷大单体(PDMS-MA)与苯乙烯共聚合,制备了聚苯乙烯-聚硅氧烷梳状接枝共聚物（PSt-g-PDMS）,采用傅里叶变换红外光谱（FTIR）表征了接枝共聚物的组成,研究了聚硅氧烷大单体的相对分子质量对共聚合活性的影响,并对接枝共聚物的热性能进行了表征.结果表明,大单体PDMS-MA的共聚合活性随其相对分子质量的增大而减小,随投料比的增加,共聚合转化率下降.与纯聚苯乙烯相比,PSt-g-PDMS的热稳定性提高.而且,随着大单体PDMS-MA相对分子质量和它在共聚物中含量的增加,接枝共聚物的热稳定性增加.     

Solvent inducing aggregates of perylene tetracarboxylic diimide in polymer backbone

We have investigated the optical properties of a synthesized polymer containing perylene tetracarboxylic diimide (PDI) in different solvents. The structured absorption and photoluminescence (PL) spectra of the PDI in the polymer are sensitive to the solvents. The excited states with the PL peaks at 530 and 570 nm have the same PL excitation bands and life times, but the PL excitation band of the 625 nm excited states with long life time is different from the others. The PL bands with the peaks at 530 and 570 nm originate from the separated PDIs, whereas the 625 nm emission band is connected with the π–π stacked aggregates of the PDI in the polymer. The polymer chains become coiled to be favor of forming the π–π stacked aggregates of the PDI in weak polar solvent. The experimental results indicate that more π–π stacked aggregates are formed in tetrahydrofuran/ethanol blend solvents due to the collapsed polymer chains, but the PL intensity of the aggregates is precipitately decreased with the increase in the content of ethanol due to concentration quenching. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4113–4118, 2013     

Synthesis and characterization of hindered‐phenol‐containing amine moieties as antioxidants for polypropylene copolymers

(4‐Ethylphenyl)‐3,5‐ditertiarybutyl‐4‐hydroxybenzylamine, 1‐phenyl‐4‐(3,5‐ditertiarybutyl‐4‐hydroxybenzyl)piperazine, and 1‐(3,5‐ditertiarybutyl‐4‐hydroxybenzyl)piperidine were synthesized and characterized, and their performance in polypropylene copolymer (PPCP) was tested by multiple extrusions in a Brabender plasticorder. The thermooxidative stability of PPCP was assessed by the measurement of oxidative induction time at 200 ± 1°C, and the thermal stability was assessed by observation of the change in the melt flow rate. A comparative study of the synthesized antioxidants with the commercially available antioxidant 2,6‐ditertiarybutyl‐4‐methylphenol was made. The presence of phenolic and amino groups influenced the performance of the antioxidants. The performance of the antioxidants influenced the thermal stability of the PPCP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1097–1103, 2004     

Synthesis and photophysical properties of novel organo-soluble polyarylates bearing triphenylamine moieties

Two series of new blue photoluminescent aromatic polyesters (polyarylates) were synthesized from 4,4′-dicarboxytriphenylamine and 4,4′-dicarboxy-4″-methyltriphenylamine with various bisphenols by the diphenylchlorophosphate (DPCP) activated direct polycondensation in a medium of pyridine and lithium chloride. These polymers were amorphous and readily soluble in various common organic solvents including DMAc, THF, and chloroform, and could be cast from their chloroform solutions into transparent films due to their excellent solubility. These polyarylates exhibited moderately high T _g values (186–264 °C) and thermal stability. In THF solution, these triphenylamine-containing polyarylates showed UV-Vis absorption bands at 359–365 nm and photoluminescence peaks around 427–451 nm in the blue region. Figure Two series of new blue photoluminescent aromatic polyesters (polyarylates) were synthesized from 4,4’-dicarboxytriphenylamine and 4,4’-dicarboxy-4”-methyltriphenylamine with various bisphenols by the diphenylchlorophosphate (DPCP) activated direct polycondensation in a medium of pyridine and lithium chloride. These polymers were amorphous and readily soluble in various common organic solvents including DMAc, THF, and chloroform, and could be cast from their chloroform solutions into transparent films due to their excellent solubility. These polyarylates exhibited moderately high Tg values (186-264 oC) and thermal stability. All the PL spectra of these polymers showed a blue shift when the solvent was changed from NMP to THF or chloroform. Solvation should increase the interaction between polymer chain and solvent, which may consume certain excitation energy and lead to increase on the emission wavelength.