Synthesis and chemical modification of new luminescent substituted poly(p-phenylene) polymers

A new acyl-functionalized poly(p-phenylene) (Ac-PPP) was synthesized by Yamamoto cross-coupling and chemically modified to obtain an anthracene-containing derivative (An-PPP). The chemical structures of the polymers were confirmed by ¹H-NMR, ¹³C-NMR, and FTIR spectroscopic analysis. They are fully soluble in common organic solvents and have number-average molecular weight of 2.70 × 10³ and 5.26 × 10³ g mol⁻¹ for Ac-PPP and An-PPP, respectively. The optical properties of the polymers were investigated by UV–visible absorption and photoluminescence spectroscopies. A green emission was observed in Ac-PPP solid thin film and a yellow one in the anthracene-containing polymer An-PPP. The optical bandgap values were 3.21 and 3.08 eV for Ac-PPP and An-PPP, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of new poly(ortho ester amidine) copolymers for nonviral gene delivery

A new type of pH-labile cationic polymers, poly(ortho ester amidine) (POEAmd) copolymers, has been synthesized and characterized with potential future application as gene delivery carriers. The acid-labile POEAmd copolymer was synthesized by polycondensation of a new ortho ester diamine monomer with dimethylaliphatimidates, and a non-acid-labile polyamidine (PAmd) copolymer was also synthesized for comparison using a triethylene glycol diamine monomer. Both copolymers were easily dissolved in water, and can efficiently bind and condense plasmid DNA at neutral pH, forming nano-scale polyplexes. The physicochemical properties of the polyplexes have been studied using dynamic light scattering, gel electrophoresis, ethidium bromide exclusion, and heparin competition. The average size of the polyplexes was dependent on the amidine:phosphate (N:P) ratio of the polymers to DNA. Polyplexes containing the acid-labile POEAmd or the non-acid-labile PAmd showed similar average particle size, comparable strength of condensing DNA, and resistance to electrostatic destabilization. They also share similar metabolic toxicity to cells as measured by MTT assay. Importantly, the acid-labile polyplexes undergo accelerated polymer degradation at mildly acid-pHs, resulting in increasing particle size and the release of intact DNA plasmid. Polyplexes from both types of polyamidines caused distinct changes in the scattering properties of Baby Hamster Kidney (BHK-21) cells, showing swelling and increasing intracellular granularity. These cellular responses are uniquely different from other cationic polymers such as polyethylenimine and point to stress-related mechanisms specific to the polyamidines. Gene transfection of BHK-21 cells was evaluated by flow cytometry. The positive yet modest transfection efficiency by the polyamidines (acid-labile and non-acid-labile alike) underscores the importance of balancing polymer degradation and DNA release with endosomal escape. Insights gained from studying such acid-labile polyamidine-based DNA carriers and their interaction with cells may contribute to improved design of practically useful gene delivery systems.     

Synthesis and characterization of poly(N-(2-(thiophen-3-yl)methylcarbonyloxyethyl)maleimide) and its spectroelectrochemical properties

A new monomer; N-(2-(thiophen-3-yl)methylcarbonyloxyethyl) maleimide (NMT) was synthesized. The chemical structure of the monomer was characterized by Nuclear Magnetic Resonance (¹H-NMR) and Fourier Transform Infrared (FTIR) Spectroscopy. Electrochemical polymerization of NMT was performed in acetonitrile (AN)/borontrifloride ethylether (BFEE) solvent mixture (1:1, v/v) where tetrabutylammonium tetrafluoroborate (TBAFB) was utilized as the supporting electrolyte. The resulting conducting polymer was characterized by Fourier Transform Infrared (FTIR) Spectroscopy, thermal analyses and Scanning Electron Microscopy (SEM). Electrical conductivity was measured by the four-probe technique. The spectroelectrochemical behavior and switching ability of P(NMT) film were investigated by UV–Vis spectrophotometry. P(NMT) revealed color changes between yellow and blue in the reduced and oxidized states respectively.     

Synthesis and properties of new sulfonated poly(p-phenylene) derivatives for proton exchange membranes. I

Several high molecular weight poly(2,5-benzophenone) derivatives were synthesized by high yield nickel-catalyzed coupling polymerization of 2,5-dichloro-4′-substituted benzophenones. The monomers were prepared by Friedel-Crafts catalyzed reaction of 2,5-dichlorobenzoyl chloride and several aromatic compounds. The resulting polymers are organosoluble and show no evidence of crystallinity by differential scanning calorimetry (DSC). The temperatures of 5% weight loss of the polymers via dynamic thermogravimetric analysis in air were above 480 °C. Sulfonation of selected polymers utilizing concentrated or fuming sulfuric acid at room temperature introduced sulfonic acid moieties to the aromatic side group. Activated fluoro aryl groups were also used to generate pendent sulfonated functionalities. The sulfonated polymers were examined for ion exchange capacities, water absorption capacities and proton conductivities. The sulfonated polymers were not good film formers, but could be demonstrated to show high values of proton conductivity in the range of 0.06-0.11 S/cm when supported on glass fabrics or via polymer blending strategies.     

Synthesis and characterization of poly(1,5-naphthylene vinylene) and its copolymers with poly(2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene)

Poly(1,5-naphthylene vinylene) (PNV) and its copolymers with poly(2-methoxy-5-(2′-ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV) were synthesized via a liquid-solid two-phase reaction. The liquid phase was a tetrahydrofuran (THF) solution of the monomers, 1,4-bis(bromomethyl)-2-methoxy-5-(2-ethylhexyloxy)benzene (MOEHODCX) and 1,5-bis(bromomethyl) naphthalene (DBMN), and contained a certain amount of tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. The solid phase was potassium hydroxide particles with diameters smaller than 2 mm. The structures of the polymers were studied by infrared and Raman spectroscopies. The solutions of the copolymers emitted green light. The UV-vis and photoluminescence spectral bands of the copolymers showed blue shifts with the increase in their PNV contents. A polymer light-emitting diode was fabricated with the copolymer prepared by copolymerization MOEHODCX and DBMN with feeding molar ratio of 1:1, and its luminescence efficiency was measured to be 0.069.     

Synthesis and characterization of organosoluble luminescent poly(amide-imide)s

Poly(amide-imide)s (PAIs) were synthesized from 9,9’-bis(4-aminophenyl)fluorene (APF) and different diimide-dicarboxylic acids (DIDA). The aromatic fluorene group is isolated by DIDA. The structure of the polymer was confirmed by ¹H NMR, ¹³C NMR, and FTIR. These PAIs were soluble in polar aprotic solvents, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide. The crystallinity of the polymers is estimated by means of wide-angle X-ray diffraction. The resultant PAIs exhibited nearly amorphous nature. Thermal stability of the PAIs was characterized by differential scanning calorimetry and thermogravimetric analysis. No obvious glass transition temperatures were detected and the 5% weight loss temperatures of the PAIs were in the range 296–453 °C in nitrogen. The optical properties were studied by Ultraviolet–visible (UV/VIS) spectra and photoluminescent (PL) in solution and film states. The results show similar absorbance and emission to those of the constituting APF monomer. The highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital (LUMO) were estimated from cyclic voltammograms. The values of HOMO and LUMO are -6.67 to -6.72, and -3.54 to -3.58, respectively. Their optical and electrochemical properties are not changed significantly by different DIDA.     

席夫碱-取代水杨醛缩氨基吡啶衍生物的合成与表征

以水杨醛与2-氨基吡啶为原料设计合成了7种席夫碱，通过元素分析、红外光谱和核磁共振氢谱分析，确定了化合物的结构，初步试验表明6种化合物具有热致变色性质。     

苯乙烯——甲基丙烯酸共聚物的合成及表征

采用简单、经济、稳定的悬浮聚合法合成了苯乙烯—甲基丙烯酸共聚物(SMAA),得率为92%左右.通过正交试验确定了最佳配方.经FT—IR、DSC、元素分析、化学滴定、GPC等测试方法表征,证实了所合成的产物为透明的苯乙烯—甲基丙烯酸无规共聚物.研究表明,SMAA的耐热性比PS好得多,其玻璃化温度随共聚物中MAA含量的增加而增大,SMAA20的Tg为138.8℃,比PS的约高40℃,在100℃时热拉伸强度保留率为72.3%.共聚物的加工性能良好,熔体指数为8.05g/10min(230℃,载荷50N),熔化特性良好.其力学性能比PS有明显提高,拉伸强度和弯曲强度分别比PS提高52.2%和43.6%.     

聚二烷基硅烷的合成及其表征

以二甲基二氯硅烷、二苯基二氯硅烷为原料，通过Wurtz还原反应合成出聚二甲基硅烷、聚二苯基硅烷，并用UV、^1H NMR、FT—IR以及GPC、DSC—TGA等方法进行了光谱分析和结构表征。     

In situ FTIR spectroelectrochemistry of poly[2-(3-thienyl)ethyl acetate] and its hydrolyzed derivatives

Poly[2-(3-thienyl)ethyl acetate] (PTEtAc) was chemically synthesized and transformed to partially hydrolyzed PTEtAc (PTEtAcOH) and poly[2-(3-thienyl)ethanol] (PTEtOH). The influence of the acetoxy and hydroxyl terminal functionalities in the side groups on the electrochemical properties of these polyalkylthiophenes was studied by cyclic voltammetry and in situ FTIR spectroelectrochemistry. The cyclic voltammograms point to a chemically reversible behaviour of the p-doping process for PTEtAc and PTEtAcOH, while for PTEtOH the redox activity of the polymer film is lost during consecutive potential scans.The attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) was used to investigate the p-doping of the three different type of thiophene polymer films. In situ FTIR spectra taken at different electrode potentials in a cyclovoltammetric scan display the doping induced changes of the polymer pattern. Important differences in the behaviour of the polymers were observed and interpreted in terms of different film structures.     

Chain helicity of a poly(phenylacetylene) with chiral centers between backbone and mesogenic groups on side chains

An optically active poly(phenylacetylene), poly{2-(R)-methyl-2-[4′-(tetradecyloxy)biphenyl-4-yloxy]propyl 4-ethynylbenzoate} (P1) is synthesized in a high yield with a high molecular weight (1.3 × 10⁶ g/mol) by [Rh(nbd)Cl]₂ catalyst. The chemical structure of the polymer is characterized by IR and NMR spectroscopies with satisfactory analysis data. The polymer is soluble in many common organic solvents. It shows circular dichroism (CD) band in the absorption region of the polyacetylene backbone, indicating that P1 is chiroptical owing to the formation of helical conformation with an excess screw sense. Combining the results of CD and light scattering experiments, we find that addition of poor solvent can induce the neighboring helical segments within a single polymer strand to become closer, resulting in exciton coupling prior to polymer precipitation. The exciton coupling can be kept in the solid state after solvent evaporation.     

Synthesis and properties of new highly soluble poly(amide-ester-imide)s containing poly(ethylene glycol) as a soft segment

In this study, a new class of highly soluble poly(amide-ester-imide)s (PAEI)s contains poly(ethyleneglycol) (PEG) as hydrophilic and soft segment were prepared. Poly(ethylene glycol)-bis-(N-trimellitylimido-4-phenyl carboxylic acid) (3) as a novel diacid monomer was synthesized via two step. The reaction of poly(ethylene glycol) (PEG 6000) with trimellitic anhydride chloride yield poly(ethylene glycol)-bis-trimellitic anhydride (1). The reaction of dianhydride 1 with p-aminobenzoic acid (2) produces novel diacid monomer 3. The direct polycondensation technique of the diacid 1 with several aromatic diamines was carried out in pyridine/N-methyl-2-pyrrolidone/triphenylphosphite/CaCl₂ as condensing agent. The resulting novel PAEIs with inherent viscosities ranging between 0.21 and 0.42 dl g⁻¹, were obtained in good yield. This group of polymers exhibit excellent solubility in a variety of organic solvents and water. All of these polymers were characterized with FT-IR spectroscopy. Thermal properties, ¹H-NMR and XRD study of these PAEIs were also reported. The results demonstrate that this polymers show crystalline structure as well as high thermal stability. In addition the effect of PEG length on solubility and thermal properties of the polymers were also studied.     

Synthesis, crystallization and tensile properties of poly(ethylene terephthalate-co-2,6-naphthalate)s with low naphthalate units content

A series of poly(ethylene terephthalate-co-naphthalate)s (PETN copolymers) with low naphthalate units content was synthesized. A melting point depression was observed, while the glass transition temperatures were slightly higher than that of Polyethylene terephthalate (PET). Crystallization rates of the copolymers decreased with increasing comonomer content. WAXD patterns showed that only PET crystals were formed. Co-crystallization behaviour was evaluated on the basis of the Wendling–Suter model. The tensile properties of the copolymers PETN 97/3 and PETN 94/6, Young's modulus yield stress and elongation at break was significantly improved compared to PET. WAXD showed that some crystalline precursor was generated during drawing of the specimens. DSC traces of the drawn specimens showed enhanced crystallization rates compared to that of the original amorphous specimens.     

The synthesis and redox-induced off-on PL properties of poly(3,4-bisphenyl-N-methylferrocene-pyrrole-2,5-dione)

A novel π-conjugated polymer containing a ferrocene group was designed and synthesized from 3,4-bis(4-bromophenyl)-N-methylferrocene-pyrrole-2,5-dione by dehalogenation polycondensation with the zerovalent nickel complexes (a Yamamoto reaction). The polymer was characterized by FT-IR, ¹H NMR, gel permeation chromatography, UV, cyclic voltammetry and Fluorescence spectroscopy. The polymer has the M_w of 2620 and polydispersity index of 1.5. Also this polymer showed high solubility in common organic solvents, good film formability on the glass substrate and redox property. The fluorescence of the model compound and polymer with a diphenylmaleimide moiety is almost quenched due to the ferrocene group because of the intramolecular electron transfer. However, the model compound and the polymer showed a recovered fluorescence when a ferrocene group of them was oxidized chemically and electrochemically.     

Synthesis and properties of novel poly(tetramethylsilnaphthylenesiloxane) derivatives

Novel poly(tetramethylsilnaphthylenesiloxane) derivatives were synthesized and characterized by differential scanning calorimetry (DSC), thermogravimetry (TG), and X-ray diffraction analyses. Poly(tetramethylsilnaphthylenesiloxane) derivatives were obtained by condensation polymerization of the corresponding disilanol derivatives, i.e. 1,4-, 1,5-, 2,6-, and 2,7-bis(dimethylhydroxysilyl)naphthalenes, which were prepared by the Grignard reaction using chlorodimethylsilane and the corresponding dibromonaphthalene derivatives followed by the hydrolyses, catalyzed by palladium on charcoal. The obtained poly(tetramethyl-1,5-silnaphthylenesiloxane) was insoluble in common organic solvents; however, the other polymers exhibited the good solubility in common organic solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane, and toluene. The introduction of tetramethyl-1,5-silnaphthylenesiloxane units into the resulting polymer was confirmed by ¹H NMR spectrum of the copolymer obtained by condensation copolymerization of 1,5-bis(dimethylhydroxysilyl)naphthalene with 1,4-bis(dimethylhydroxysilyl)naphthalene. It was revealed from the DSC and X-ray diffraction measurements that poly(tetramethyl-1,5-silnaphthylenesiloxane) and poly(tetramethyl-2,6-silnaphthylenesiloxane) exhibited the crystallinity; however, poly(tetramethyl-1,4-silnaphthylenesiloxane) and poly(tetramethyl-2,7-silnaphthylenesiloxane) were amorphous. The glass transition temperature (T_g) and the temperature at 5% weight loss (T_d5) of poly(tetramethylsilnaphthylenesiloxane) derivatives with dimethylsilyl group at 1-position of the naphthylene moiety were higher than those at 2-position of the naphthylene moiety. The T_g and melting point (T_m) of the present polymers were higher than those of poly(tetramethyl-1,4-silphenylenesiloxane).     

Synthesis and properties of cyclopentadithiophene-based poly(silarylenesiloxane) derivatives

Poly(silarylenesiloxane) derivatives with 4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene moiety, bearing dimethyl- (P1), methylphenyl- (P2) and diphenyl- (P3) substituents on silyl moieties, were prepared via polycondensation of the corresponding disilanol monomers, that is, 2,6-bis(dimethylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M1), 2,6-bis(methylphenylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M2), and 2,6-bis(diphenylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M3), respectively. P1-P3 exhibited the good solubility in common organic solvents, such as benzene, toluene, chloroform, dichloromethane, THF, and so on. The glass transition temperatures (T_gs) of P1, P2 and P3 were determined by differential scanning calorimetry to be 56, 97 and 137 °C, respectively, depending on the substituent on the silyl moieties. No melting temperatures (T_ms) of P1, P2 and P3 were observed, suggesting the obtained P1-P3 are amorphous polymers. The temperatures at 5% weight loss (T_d5s) of P1, P2 and P3 were 460, 459 and 479 °C, respectively, indicating that the larger number of phenyl group on the silyl moieties resulted in the better thermostability. Bathochromic and hyperchromic effects were observed in the absorption and fluorescence spectra by introducing silyl substituents onto 4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene moiety. In addition, the bathochromic shift of the maximum absorption (λ_abs) and the increase in the fluorescence quantum yield (Φ_F) were observed by the introduction of phenyl group onto the silyl moieties.     

Synthesis and characterization of amphiphilic graft copolymers with hydrophilic poly(acrylic acid) backbone and hydrophobic poly(methyl methacrylate) side chains

A series of well-defined amphiphilic graft copolymers containing hydrophilic poly(acrylic acid) backbones and hydrophobic poly(methyl methacrylate) side chains were synthesized by successive atom transfer radical polymerization followed by the selective hydrolysis of poly(methoxymethyl acrylate) backbone. Grafting-from strategy was employed for the synthesis of graft copolymers with narrow molecular weight distributions. Hydrophobic side chains were connected with the backbone through stable C-C bonds instead of ester connections. The backbone can be easily hydrolyzed to poly(acrylic acid) with HCl without affecting the hydrophobic side chains. The amphiphilic graft copolymers can form stable micelles in water. The critical micelle concentration was determined by fluorescence spectroscopy. The micellar morphologies were found to be vesicles by transmission electron microscopy and changed to spheres with the addition of NaCl.     

Nitriles in Organic Synthesis: Synthesis of new pyridazine,pyridine and pyrazolo[3,4-b]pyridine derivatives

The reaction of diethyl monoiminomalonate with benzoylacetonitrile affords the ethyl 3-amino-4-cyanopentanoate derivative 1 a . Compound 1 a condensed with salicylaldehyde to yield the coumarin 5 and coupled with arenediazonium salts to yield the arenehydrazones 6a – c . Compounds 6a , b could be converted into the aminopyridazinium carboxylate 8a , b on treatment with aqueous sodium hydroxide. The reaction of 6a – c with hydrazine and phenyl hydrazine is reported.     

Determination of hydrazide content in poly(oxadiazole-hydrazide) copolymers by NMR and thermal analysis

A new technique based on nuclear magnetic resonance (NMR) is developed in this paper to determine quantitatively the hydrazide content in poly(oxadiazole-hydrazide) copolymers. Two-dimensional ¹H-¹³C shift correlation and ¹H NMR spectra of poly(4,4′-diphenylether-1,3,4-oxadiazole-hydrazide) copolymers with different hydrazide contents were performed to characterize these copolymers and allow for development of a NMR based quantitative correlation for hydrazide content. Thermal gravimetric measurements (TGA) were also performed in order to provide an independent data set for validation of the NMR based technique. The results obtained with the proposed NMR technique were shown to be in good qualitative agreement with the TGA results.     

Comparison of poly(ethylene oxide) crystal orientations and crystallization behaviors in nano-confined cylinders constructed by a poly(ethylene oxide)-b-polystyrene diblock copolymer and a blend of poly(ethylene oxide)-b-polystyrene and polystyrene

A poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymer with a number average molecular weight of PEO blocks, =8.8 kg/mol, and a number average molecular weight of PS blocks, =24.5 kg/mol, (volume fraction of the PEO blocks, f_PEO, was 0.26) exhibited a hexagonal cylinder (HC) phase structure. Small angle X-ray scattering results showed that the PEO cylinder diameter was 13.3 nm, and the hexagonal lattice was a=25.1 nm. The cylinder diameter of this HC phase structure was virtually the same as that in the blend system constructed by a PEO-b-PS diblock copolymer (=8.7 kg/mol and =9.2 kg/mol) and a PS homo-polymer (=4.6 kg/mol) in which the f_PEO was 0.32. The cylinder diameter in this blend sample was 13.7 nm and the hexagonal lattice was a=23.1 nm. Comparing crystal orientation and crystallization behaviors of this PEO-b-PS copolymer with the blend, it was found that the crystal orientation change with respect to crystallization temperature was almost identical. This is attributed to the fact that in both cases the PEO block tethering densities and confinement sizes are very similar. This indicates that when the of PS homo-polymer is lower than the PS blocks, the PS homo-polymer is located inside of the PS matrix rather than at the interface between the PEO and PS in the HC phase structure. On the other hand, a substantial difference of crystallization behaviors was observed between these two samples. The PEO-b-PS copolymer exhibited much more retarded crystallization kinetics than that of the blend. Based on the small angle X-ray scattering results, it was found that in the blend sample, the HC phase structure was not as regularly ordered as that in the PEO-b-PS copolymer, and thus, the HC phase structure contained more defects in the blend. This led to a suggestion that the primary nucleation process in the confined crystallization is a defect-controlled process. The mean crystallite sizes were estimated by the Scherer equation, and the PEO crystal sizes are on the scale of the confined size.