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1.
Two electroactive polystyrene derivatives para‐ substituted with π‐conjugated oligothiophene, poly(5‐hexyl‐5″‐(4‐vinylphenyl)‐2,2′:5′,2″‐terthiophene) ( PH3TS ), and poly(5‐hexyl‐5″″‐(4‐vinylphenyl)‐2,2′:5′,2″:5″,2″′:5″′,2″″‐quinquethiophene) ( PH5TS ) have been successfully synthesized via the Stille coupling reaction between tributyltin postfunctionalized poly(4‐(2‐thiophenyl)styrene) ( PTS ) and bromo‐oligothiophene. The effect of the chain length of the pendant oligothiophenes on properties of the resulting polymers including solubility, thermal stability, optical absorption, and electroactivation energy levels has been studied by using a variety of techniques such as thermogravimetric analyzer, differential scanning calorimetry, UV–Vis, Fluorescence, and cyclic voltammetry. With shielding of the hexyl terminal groups attached to the pendant oligothiophene units, no obvious chain aggregation was observed for both PH3TS and PH5TS even in a poor solvent environment. When compared with conventional linear conjugated polymer systems, the concept of grafting electroactive units as pendant side chains via postfunctionalizing aliphatic polymers might offer a strategy to precisely synthesize new electroactive polymer materials for a number of organic electronic applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

2.
The effect of the presence of hexyl group in thiophene on the photophysical and electrochemical properties of poly[(9,9‐dioctyluorene)?2,7‐diyl‐alt‐(4,7‐bis(3‐hexylthien‐5‐yl)?2,1,3‐benzothiadiazole)?2′,2″‐diyl] (F8TBT) is investigated. The copolymers present electron donor–acceptor architecture and are synthesized by Suzuki coupling reaction. The UV/Vis spectra show absorption maximum in the wavelength range of blue and orange, which are associated with different segments of the polymer backbone. Addition of hexyl substituent groups has a positive effect on the molar absorptivity and increases the emission and absorption intensities due to fluorene and thiophene‐benzothiadiazole‐thiophene (TBT) units, although an increment in the bandgap is observed. Cyclic voltammetry study of the polymer films reveal irreversible reduction and oxidation processes of the TBT units in the polymer chain and the HOMO and LUMO energy levels suggest ambipolar character for the polymers, while the electrochemical bandgaps are consistent with the absorbance measurements. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1975–1982  相似文献   

3.
The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu3)2 (C?C? C6H4? C6H4? C?C? )]n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR 31P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007  相似文献   

4.
A mechanistic study of the trans?cis isomerization of the azobenzene moiety in a side‐chain liquid‐crystal polymer system was carried out with six liquid‐crystalline polymethacrylates in which different electron‐withdrawing substituents were attached to the para‐positions of the azobenzene chromophores. Compared to the non‐nitro‐substituted azo polymers, the nitro‐substituted azo polymers exhibited two quite different behaviors: an extraordinarily high reaction rate of the thermal cis–trans isomerization and an unexpected composition of cis–trans isomers obtained from the photochemical trans–cis isomerization process. A potential energy profile for the isomerization process was established on basis of the structures of the proposed transition states and was employed to elucidate the reaction mechanism. The results confirmed that the nitro‐substituted azo polymer system proceeded via a rotation mechanism in either direction of the trans?cis isomerization reaction, whereas the non‐nitro‐substituted species were more likely to follow an inversion mechanism. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2296–2307, 2001  相似文献   

5.
The well‐defined azoindazole‐containing homopolymer, poly(6‐{6‐[(4‐dimethylamino) phenylazo]‐indazole}‐hexyl methacrylate) (PDHMA), and amphiphilic diblock copolymer, poly({6‐[6‐(4‐dimethylamino)phenylazo]‐indazole}‐hexyl methacrylate)‐b‐poly(2‐(dimethylamino)ethylmethacrylate) (PDHMAmb‐PDMAEMAn), were successfully prepared via reversible addition‐fragmentation chain transfer polymerization technique. The homopolymer and amphiphilic diblock copolymer in CH2Cl2 exhibited intense fluorescence emission accompanied by trans–cis photoisomerization of azoindazole group under UV irradiation. The experiment results indicated that the intense fluorescence emission may be attributed to an inhibition of photoinduced electron transfer of the cis form of azoindazole. On the other hand, the intense fluorescence emission of amphiphilic diblock copolymers in water‐tetrahydrofuran mixture was observed, which increased with the volume ratio of water in the mixed solvent. The self‐aggregation behaviors of three amphiphilic diblock copolymers were examined by transmission electron microscopy, laser light scattering, and UV–vis spectra. The restriction of intramolecular rotation of the azoindazole groups in aggregates was considered as the main cause of aggregation‐induced fluorescence emission. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.  相似文献   

6.
trans‐Poly(dimethylsilylenearylenevinylene)s (trans‐rich) and cis‐poly(dimethylsilylenearylenevinylene)s (cis‐rich) containing phenylene, biphenylene, and phenylenesilylenephenylene units were prepared by hydrosilylation catalyzed with the RhI(PPh3)3 complex. The addition of a phenylene π unit to poly(silylenephenylenevinylene) expanded the conjugation in the main chain, whereas the insertion of a dimethylsilylene σ unit in the biphenylene moiety reduced the conjugation. UV spectra of the trans‐type polymers showed redshifts and hyperchromic effects with respect to those of the cis‐type polymers, indicating wider conjugation, and the quantum yields of emission of the former polymers were much higher than those of the latter polymers. The quantum yield of the trans‐rich polymer with the biphenylene moiety reached 0.15, which was about 102 times as large as those of trans‐type polymers with phenylene (3.4 × 10?3) and phenylenesilylenephenylene (1.9 × 10?3) moieties. The effects of the geometric structure and π unit on the absorption and emission properties of these polymers were examined with molecular orbital methods. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 535–543, 2002; DOI 10.1002/pola.10139  相似文献   

7.
A strategy of the fine‐tuning of the degree of intrachain charge transfer and aromaticity of polymer backbone was adopted to design and synthesize new polymers applicable in photovoltaics. Three conjugated polymers P1 , P2 , and P3 were synthesized by alternating the electron‐donating dithieno[3,2‐b:2′3′‐d]pyrrole (D) and three different electron‐accepting (A) segments ( P1 : N‐(2‐ethylhexyl)phthalimide; P2 : 1,4‐diketo‐3,6‐diphenylpyrrolo[3,4‐c]pyrrole; and P3 : thiophene‐3‐hexyl formate) in the polymer main chain. Among the three polymers, P2 possessed the broadest absorption band ranging from 300 to 760 nm, the lowest bandgap (1.63 eV), and enough low HOMO energy level (?5.27 eV) because of the strong intrachain charge transfer from D to A units and the appropriate extent of quinoid state in the main chain of P2 , which was convinced by the theoretical simulation of molecular geometry and front orbits. Photovoltaic study of solar cells based on the blends of P1 – P3 and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) demonstrated that P2 :PCBM exhibited the best performance: a power conversion efficiency of 1.22% with a high open‐circuit voltage (VOC) of 0.70 V and a large short‐circuit current (ISC) of 5.02 mA/cm2 were achieved. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

8.
π‐Conjugated polymers, PTOTBT , PTEHTBT , and PTt‐BTBT , composed of benzothiadiazole as an electron accepting unit and terthiophene as an electron donating unit in the backbone were prepared. PTOTBT , PTEHTBT , and PTt‐BTBT contained side chain groups of n‐octyl, 2‐ethylhexyl, and t‐butyl groups, respectively. Solubility, optical and thermal properties of the polymers showed strong dependences on their side chain groups. PTEHTBT having 2‐ethylhexyl groups in the side chain exhibited absorption maximum (λmax) at longer wavelength (565 nm) than PTOTBT (534 nm) and PTt‐BTBT (495 nm). PTOTBT showed higher thermal stability than the others. The prepared polymers were employed to polymer solar cells (PSCs) with a configuration of ITO/PEDOT‐PSS/polymer: PC61BH/LiF/Al. Power conversion efficiency of the PSC‐based on PTEHTBT was 1.32%. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

9.
In this article, the synthesis and the functionalization of well‐defined, narrow polydispersity (polydispersity index < 1.2) star polymers via reversible addition‐fragmentation chain transfer polymerization is detailed. In this arm first approach, the initial synthesis of a poly(pentafluorophenyl acrylate) polymer, and subsequent, cross‐linking using bis‐acrylamide to prepare star polymers, has been achieved by reversible addition fragmentation chain transfer polymerization. These star polymers were functionalized using a variety of amino functional groups via nucleophilic substitution of pentafluorophenyl activated ester to yield star polymers with predesigned chemical functionality. This approach has allowed the synthesis of star glycopolymer using a very simple approach. Finally, the core of the stars was modified via thiol‐ene click chemistry reaction using fluorescein‐o‐acrylate and DyLigh 633 Maleimide. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

10.
4‐Arm star side‐chain liquid crystalline (LC) polymers containing azobenzene with different terminal substituents were synthesized by atom transfer radical polymerization (ATRP). Tetrafunctional initiator prepared by the esterification between pentaerythritol and 2‐bromoisobutyryl bromide was utilized to initiate the polymerization of 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl methacrylate (MMAzo) and 6‐[4‐(4‐ethoxyphenylazo)phenoxy]hexyl methacrylate (EMAzo), respectively. The 4‐arm star side‐chain LC polymer with p‐methoxyazobenzene moieties exhibits a smectic and a nematic phase, while that with p‐ethoxyazobenzene moieties shows only a nematic phase, which derives of different terminal substituents. The star polymers have similar LC behavior to the corresponding linear homopolymers, whereas transition temperatures decrease slightly. Both star polymers show photoresponsive isomerization under the irradiation with UV–vis light. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3342–3348, 2007  相似文献   

11.
This article concerns the hydrosilylation polyaddition of 1,4‐bis(dimethylsilyl)benzene ( 1 ) with 4,4′‐diethynylbiphenyl, 2,7‐diethynylfluorene ( 2b ), and 2,6‐diethynylnaphthalene with RhI(PPh3)3 catalyst. Trans‐rich polymers with weight‐average molecular weights (Mw's) ranging from 19,000 to 25,000 were obtained by polyaddition in o‐Cl2C6H4 at 150–180 °C, whereas cis‐rich polymers with Mw's from 4300 to 34,000 were obtained in toluene at 0 °C–r.t. These polymers emitted blue light in 4–81% quantum yields. The cis polymers isomerized into trans polymers upon UV irradiation, whereas the trans polymers did not. The device having a layer of polymer trans‐ 3b obtained from 1 and 2b demonstrated electroluminescence without any dopant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2774–2783, 2004  相似文献   

12.
Stereochemical course of the reaction of homophthalic anhydride and N‐(1‐methyl‐1H‐pyrrol‐2‐yl‐methylidene)‐phenethylamine was studied. Mixtures of the expected trans‐ and cis‐1,2,3,4‐tetrahydroiso‐quinoline‐4‐carboxylic acids trans‐ 4 and cis‐ 4 were obtained along with by‐products 5 and 6 . The ratios of all products and the diastereomers, obtained under different reaction conditions, were established by pmr. THF as a solvent and ultrasonic treatment are applied for the first time in the reaction of this type. The reaction was made diastereoselective towards any isomer. The carboxylic group of trans‐ 4 was transformed in four steps into various cyclic amino‐methyl groups yielding numerous new tetrahydroisoquinolinones trans‐ 10a‐i incorporating a given fragment of pharmacological interest. Reduction of 10a‐i was studied.  相似文献   

13.
The photoirradiation of trans‐ and cis‐poly(dimethylsilylenephenylenevinylene)s gave cis‐rich mixtures at equilibrium states. The degree of the photoisomerization could be exactly evaluated by comparing the UV spectra of the photoirradiated solutions with those of the trans and cis polymers. The geometric configuration of the trans and cis polymers was thermally stable and hardly changed even though they were heated. The trans and cis polymers exhibited different emission properties; e.g., trans polymer: λmax = 400 nm, quantum yield = 3.4×10–3; cis polymer: λmax = 380 nm, quantum yield = 1.5×10–3.  相似文献   

14.
Polymerization of p‐(dimethylsilyl)phenylacetylene in toluene at 25 and 80°C using RhI(PPh3)3 as the catalyst afforded highly regio‐ and stereoregular poly(dimethylsilylene‐1,4‐phenylenevinylene)s (cis‐ 3 a and trans‐ 3 a ) containing 98% cis‐ and 99% trans‐vinylene moieties, respectively. Similarly, poly(butylmethylsilylene‐1,4‐phenylenevinylene)s ( 3 b with 91% cis‐ and 95% trans‐structures) and poly(diisopropylsilylene‐1,4‐phenylenevinylene) with 95% trans‐structure were synthesized. All polymers were soluble in common organic solvents. The trans‐type polymers showed red shifts and hyperchromic effects in the UV‐visible spectrum. The onset temperature of weight loss (T0) of cis‐ 3 a was much higher than that of trans‐ 3 a .  相似文献   

15.
Hydrogen‐bonded supramolecular polymers were prepared from the derivatives of α‐amino‐ε‐caprolactam (ACL), obtained from a renewable resource. Several self‐complimentary bis‐ or tetra‐caprolactam monomers were synthesized by varying the number of carbons of the spacer between the hydrogen‐bonding end groups. Physical properties of these hydrogen‐bonded polymers were clearly demonstrated by differential scanning colorimetry, solid‐state NMR, and X‐ray powder diffraction analyses. The supramolecular behavior was also supported by fiber formation from the melt for several of these compounds, and stable glassy materials were prepared from the physical mixtures of two different biscaprolactams. The self‐association ability of ACL was also used by incorporating ACL at the chain ends of low‐molecular weight Jeffamine (Mn = 900 g/mol) using urea and amide linkages. The transformation of this liquid oligomer at room temperature into a self‐standing, transparent film clearly showed the improvement in mechanical properties obtained by the introduction of terminal hydrogen‐bonding groups. Finally, the use of monomers with a functionality of four gave rise to network formation either alone or combination with bifunctional monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

16.
A consecutive radical addition‐coupling reaction induced by spin‐trapping agent is applied to produce degradable multisegmented polymer using α,ω‐dibromo polymer as a precursor. The macroradical generated by single electron transfer process catalyzed by Cu/PMDETA from α,ω‐dibromo polymer can be efficiently captured by 2‐methyl‐2‐nitrosopropane (MNP), which results in nitroxide radical. The in situ formed nitroxide radical immediately undergoes cross‐coupling reaction with polymeric radical, generating block polymer bridged with alkoxyamine moiety. The consecutive radical addition‐coupling reaction generates multisegmented polymer via step‐growth mechanism. Different multisegmented polymers have been prepared from α,ω‐dibromo‐PS, PtBA, and PtBA‐PS‐PtBA. The block number of multisegmented polymers can be tailored by varying the feed ratio of α,ω‐dibromo precursor to MNP. The multisegmented polymer can be degraded in the presence of hydrogen atom donor or air, and the molecular weight distribution transformed back into shape of its original precursor as it is conjugated by alkoxyamine moieties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

17.
A series of OEGylated poly(γ‐benzyl‐l ‐glutamate) with different oligo‐ethylene‐glycol side‐chain length, molecular weight (MW = 8.4 × 103 to 13.5 × 104) and narrow molecular weight distribution (PDI = 1.12–1.19) can be readily prepared from triethylamine initiated ring‐opening polymerization of OEGylated γ‐benzyl‐l ‐glutamic acid based N‐carboxyanhydride. FTIR analysis revealed that the polymers adopted α‐helical conformation in the solid‐state. While they showed poor solubility in water, they exhibited a reversible upper critical solution temperature (UCST)‐type phase behavior in various alcoholic organic solvents (i.e., methanol, ethanol, 1‐propanol, 1‐butanol, 1‐pentanol, and isopropanol). Variable‐temperature UV–vis analysis revealed that the UCST‐type transition temperatures (Tpts) of the resulting polymers were highly dependent on the type of solvent, polymer concentration, side‐ and main‐chain length. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1348‐1356  相似文献   

18.
Three methyl end‐capped oligo(ethylene glycol) (MOEG) ethers ( 1b‐d ) and a methoxyderivative ( 1a ) of benzofulvene monomer BF3k were synthesized and induced to polymerize spontaneously by solvent removal to obtain soluble π‐stacked polymers bearing densely grafted MOEG side chains (poly‐ 1b – d ) and model polymer poly‐ 1a. The physicochemical features (e.g., solubility, NMR, MALDI‐TOF, and absorption/emission spectra, as well as MWD, conformation plot, and thermal properties) of the synthesized polymers were compared in a structure‐property relationship study. This approach afforded the following evidence. The structure of poly‐ 1a – d is very similar to that of BF3k , suggesting that the polymerization mechanism is not affected by the presence of the electron‐rich methoxy group or bulkier MOEG side chains. However, the latter appear to be capable of affecting the conformational behavior of the polymer backbone. The solubility of poly‐ 1a – d depends on the number of the oligo(ethylene glycol) monomeric units. In particular, poly‐ 1d , featuring a long MOEG side chain (n = 9), shows an amphiphilic character and is soluble in a number of organic solvents, whereas it interacts with water to give isolated macromolecules in equilibrium with nanosized water‐soluble aggregates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2446–2461, 2010  相似文献   

19.
Well‐defined azobenzene‐containing side‐chain liquid crystalline diblock copolymers composed of poly[6‐(4‐methoxy‐azobenzene‐4′‐oxy) hexyl methacrylate] (PMMAZO) and poly(γ‐benzyl‐L ‐glutamate) (PBLG) were synthesized by click reaction from alkyne‐ and azide‐functionalized homopolymers. The alkyne‐terminated PMMAZO homopolymers were synthesized by copper‐mediated atom transfer radical polymerization with a bromine‐containing alkyne bifunctional initiator, and the azido‐terminated PBLG homopolymers were synthesized by ring‐opening polymerization of γ‐benzyl‐L ‐glutamate‐N‐carboxyanhydride in DMF at room temperature using an amine‐containing azide initiator. The thermotropic phase behavior of PMMAZO‐b‐PBLG diblock copolymers in bulk were investigated using differential scanning calorimetry and polarized light microscopy. The PMMAZO‐b‐PBLG diblock copolymers exhibited a smectic phase and a nematic phase when the weight fraction of PMMAZO block was more than 50%. Photoisomerization behavior of PMMAZO‐b‐PBLG diblock copolymers and the corresponding PMMAZO homopolymers in solid film and in solution were investigated using UV–vis. In solution, trans–cis isomerization of diblock copolymers was slower than that of the corresponding PMMAZO homopolymers. These results may provide guidelines for the design of effective photoresponsive anisotropic materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

20.
Tropone‐fused, various π‐conjugated polymers ( P2 – P5 ) were synthesized by the palladium‐catalyzed coupling reaction of 1,4‐dibromo‐6,8‐dimethyl‐7H‐benzocyclohepten‐7‐one with aromatic divinyl, diboronic acid, and diethynyl compounds. The molecular orbital calculation of the model compounds was performed to discuss effective conjugation length of the repeating unit of the polymers. The absorption spectra of phenylenevinylene‐type polymers shifted to longer wavelengths than the model compounds by about 60 nm. They exhibited green fluorescence [λmax(em) = 544 and 561 nm]. The absorption spectrum of a phenylene‐type polymer blueshifted by 10 nm; however, that of a phenyleneethynylene‐type polymer redshifted by 83 nm as compared with their model compounds. They showed fluorescence with peak maxima at 457 and 489 nm, respectively. As a result, the absorption spectra of phenylene‐ and phenylenevinylene‐type polymers blueshifted, but that of a phenyleneethynylene‐type polymer redshifted by the annulation of tropone onto a benzene ring in the conjugated polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1208–1215, 2004  相似文献   

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