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1.
Zhen Li  Jingui Qin  Anjun Qin 《Polymer》2005,46(2):363-368
A new post-functional strategy was developed to prepare polysiloxanes with the sulfonyl-indole based chromophore and carbazolyl side groups. Thus a polysiloxane (P1) with indole and carbazolyl groups as side chains was first synthesized through hydrosilylation reaction, and then the post-azo coupling of p-ethylsulfonylbenzenediazonium fluoroborate toward the indole rings afforded the multifunctional sulfonyl-indole based chromophore-functionalized polysiloxane (P2 and P3). The polymers were easily soluble in common organic solvents, and their maximum absorption appeared at 394 nm, which is about 30 nm blue-shifted compared to the corresponding chromophore with nitro acceptors, and could result in a wider transparency window. The poled films of P2 and P3 reveals a resonant d33 value of 12 and 18 pm/V, respectively, by second harmonic generation (SHG) measurements.  相似文献   

2.
Zhen Li  Jingui Qin  Zhou Yang 《Polymer》2005,46(13):4971-4978
A new post functional strategy was developed to prepare polyphosphazenes with a high density of the indole based chromophore (nitro-indole or sulfonyl-indole chromophores) and carbazolyl side groups. Thus polyphosphazene (P1) with carbazolyl and indole groups was first prepared by direct nucleophilic substitution reaction with poly(dichlorophosphazene). Then, polyphosphazenes (P2-P4) containing charge-transporting agent (carbazolyl groups) and indole azo chromophores were synthesized via a post azo coupling reaction between P1 and p-nitrobezenediazonium fluoroborate or p-ethylsulfurylbenzenediazonium fluoroborate in N-methylpyrrolindone (NMP). The structures of P1-P4 were characterized, and the poled film of P2-4 revealed a resonant d33 values in the range of 7-26 pm/V by second harmonic generation (SHG) measurements.  相似文献   

3.
A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and 1H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006  相似文献   

4.
3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene (2) was prepared by the reaction of 2‐iodoethanol with 3,4‐dihydroxy‐4′‐nitrostilbene. Diol 2 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate and 1,6‐hexamethylenediisocyanate to yield novel Y‐type polyurethanes 3–5 containing dioxynitrostilbene as a non‐linear optical (NLO)‐chromophore. Polymers 3–5 were soluble in common organic solvents, such as acetone and DMF. These polymers showed thermal stability up to 280 °C in TGA thermograms with Tg values in the range of 100–143 °C in DSC thermograms. The approximate lengths of aligned NLO‐chromophores of the polymers estimated from AFM images were around 2 nm. The SHG coefficients (d33) of poled polymer films were around 4.5 × 10?8 esu. Poled polymer films had improved temporal and long‐term thermal stability owing to the hydrogen bonding of urethane linkage and the main‐chain character of the polymer structure, which are acceptable for NLO device applications. Copyright © 2004 Society of Chemical Industry  相似文献   

5.
With the aim to control nonlinear optical (NLO) effects of polyurethanes, especially to efficiently translate the fixed μβ values of the organic chromophore to possibly higher macroscopic NLO activities of polymers, a facile synthetic strategy, consisting of the postazo coupling and esterification reactions, was developed to prepare a series of second-order nonlinear optical polyurethanes (P2-P5). And in the polymers, different isolation groups were introduced to the sulfonyl-based chromophore moieties at the acceptor side. Thus, polyurethane P1 containing aniline groups was obtained from the copolymerization of 2,4-toluenediisocyanate (TDI) and N,N-2-(2-hydroxyethyl)aniline directly; then a postazo coupling reaction of p-(2-hydroxyethyl)sulfonylbenzenediazonium fluoroborate toward the aniline ring afforded the sulfonyl-based chromphore-functionalized polyurethane P2, which underwent the subsequent esterification reactions between the hydroxyl groups in P2 and different organic acids to link different isolation spacers (changing from small groups to much larger ones such as carbazolyl groups), to the chromophore moieties at the acceptor side, to yield polyurethanes P3, P4 and P5. The polymers exhibit good solubility in common organic solvents and are thermally stable. The maximum absorption appeared at about 436 nm with a cutoff at ca. 570 nm, resulting in a wider transparency window. The tested NLO properties demonstrate that the resonant d33 values of polymers could be improved about 1.5 times by attaching isolation spacers with suitable bulkiness.  相似文献   

6.
A series of poly(fluoroalkoxyphosphazenes) containing a mixture of 2,2,3,3,4,4,5,5‐octafluoropentoxy and 2,2,2‐trifluoroethoxy substituents was synthesized. The series included polymers with 25–94% incorporation of the trifluoroethoxy substituent, as well as single‐substituent polymers with 100% octafluoropentoxy or trifluoroethoxy side groups. Polymers were analyzed by multinuclear NMR spectroscopy, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis, and were subjected to limiting oxygen index and microtensile testing. It was found that the Tg and Td values among the cosubstituted polymers varied little with changes in composition, but the mechanical properties varied over a wide range. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2569–2576, 2004  相似文献   

7.
A new polysiloxane P1 with pendant carbazoly groups and a high density of the pentafluorophenyl azo chromophore as side chain was synthesized in moderate yield by two successive postfunctionalization reaction including Vilsmeir formylated reaction and Knoevenagel condensation. Its structure was verified by 1H NMR, IR, and UV–Vis spectra. The polymer P1 exhibited good solubility in common organic solvents and was thermally stable up to 282 °C. The maximum absorption appeared at about 407 nm for P1 in THF, which was blue-shifted about 87 nm compared to the corresponding polysiloxane P2 with a well-known nitro acceptor azo chromophore, resulting in a wider transparency window. The value of the NLO coefficient d33 of P1 thin film, measured by in situ second harmonic generation (SHG), was 11.9 pm/V. Preliminary photorefractive experiments showed that P1 obtained diffraction efficiency of 78% and a time constant of 1.19 sec.  相似文献   

8.
Effectively dispersing of carbon nanotubes (CNTs) is the key to producing high performance CNTs/poly(aryl ethers) (PAEs) composite materials. Here, a series of novel soluble carbazole‐based PAEs with different alkyl side‐chains were synthesized corresponding polymers P1, P2, P3, and P4, and characterized clearly by 1H NMR and IR. All the polymers exhibited good mechanical properties and thermostabilities (Tg ~ 128–212 °C, Td5% ~ 450–499 °C) as PAEs. Due to containing lots of large π‐conjugated carbazole derivative units and possess suitable solubility, these non‐conjugated polymers can wrap and disperse MWNTs well (238–416 mg/L) in CHCl3, and the similar work has been reported rarely. This excellent property makes these polymers become a promising and ideal type solubilizer for CNTs/PAEs composite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46250.  相似文献   

9.
Poly(amide‐imide)s (PAI) bearing azobenzene chromophore groups were prepared by allowing a hydroxyl‐containing azobenzene dye (Disperse Red 1) to react with and reactive‐terminated PAI with weight–average molecular weights ranging from ~ 1.2 to 2.0 × 104 g/mol. Such PAI were prepared by the condensation of trimellitic anhydride (TMA) and 4,4′‐methylene diphenyl diisocyanate (MDI). The final polymers presented a deep red color, with an absorption maxima in N,N‐dimethylformamide (DMF) solution at 490 nm, close to the azobenzene reactant used (Disperse Red 1) and molecular weights slightly higher than the pristine polymer, showing that the azo chromophore incorporation reaction does not lead to side reactions. The azofunctionalized polymer presented a high Tg value (170°C) that could be increased by a thermal curing process to 240°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 841–847, 2007  相似文献   

10.
Three conjugated polymers, P1–P3, with dithiafulvalene (DTF) as side chains have been synthesized. All polymers have good thermal stabilities. The DTF unit could be oxidized to DTF?+ which was observed from cyclic voltammetry and ultraviolet–visible (UV–vis) spectra, and the oxidation process was independent of the conjugated backbone of the polymer. The strong π–π* transition absorbing band of the three polymers decreases gradually as increasing oxidation, and the resulting DTF?+ species give rise to an additional band at 750–1100 nm, which can be assigned to a distinguishing feature of the cation radical species. Photovoltaic device based on the blend of P2 and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) showed the power conversion efficiency of 1.05% with a fill factor of 42.8%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41508.  相似文献   

11.
A series of new polyphosphazene polymers were synthesized using three different pendant groups with the goal of probing structure–function relationships between pendant group substitution and polymer swelling/water flux through thin dense films. Formation of polymers with relative degrees of hydrophilicity was probed by varying the stoichiometry of the pendant groups attached to the phosphazene backbone: p‐methoxyphenol, 2‐(2‐methoxyethoxy)ethanol, and o‐allylphenol. The polymers in this study were characterized using NMR, thermal methods, and dilute solution light‐scattering techniques. These techniques revealed that the polymers were amorphous high polymers (Mw = 105–107) with varying ratios of pendant groups as determined by integration of the 1H‐ and 31P‐NMR spectra. Thin dense film membranes were solution‐cast with azo‐bis(cyclohexane)carbonitrile included in the matrix and crosslinked using thermal initiation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 422–431, 2001  相似文献   

12.
Acrylamide‐based, hydrophobically modified (HM) polybetaines containing N‐butylphenylacrylamide (BPAM) and varying amounts of the sulfobetaine monomer 3‐(2‐acrylamido‐2‐methylpropanedimethylammonio)‐1‐propanesulfonate (AMPDAPS) or the carboxybetaine monomer 4‐(2‐acrylamido‐2‐methylpropyldimethylammonio)butanoate (AMPDAB) were synthesized by micellar copolymerization. The corresponding control (co)polymers lacking BPAM or betaine comonomers were also prepared. The terpolymers were characterized by 13C‐NMR and UV spectroscopy, classical light scattering, and potentiometric titration. Low charge density polymers contained 3.9–8.6 mol % betaine, whereas the high charge density systems contained 17–25 mol % betaine; the HM polymers contained up to 1.0 mol % BPAM as the hydrophobe. The weight‐average molecular weights of the polymers ranged from 4.19 × 105 to 1.29 × 106 g/mol, and most HM polymers exhibited negative second virial coefficients. The pKa of the carboxybetaine moieties was found to increase with increasing levels of hydrophobic and betaine comonomer incorporation. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH and electrolyte concentration, was investigated using rheological analysis. The solution behavior of the polymers was characteristic of HM polyacrylamides and acrylamide‐based polyzwitterions. The high charge density HM polycarboxybetaine exhibited unusual solution behavior that can be explained in terms of electrostatic, hydrophobic, and hydrogen‐bonding associations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 647–657, 2004  相似文献   

13.
In this article, the imidization reaction kinetic of novel poly(ester amic acid)s with azobenzene units as side groups was studied by dynamic experiments by means of differential scanning calorimetry. Polymers differ in the number of chromophore moieties in their repeating unit and position in which azobenzene group is attached to the polymer chain. The kinetic parameters of poly(ester amic acid)s conversion to poly(ester imide)s was compared with data calculated for parent polymer, that is, without azobenzene groups. For the first time to our knowledge, the imidization kinetic of polymers with side azobenzene groups was studied. Kinetic parameters, such as the activation energy and frequency factor were estimated with the by Ozawa model [(E(O) and A(O)), respectively] and Kissinger model [(E(K) and A(K), respectively]. The values of activation energy determined with both models were in the range 167.1–198.3 kJ/mol. The lowest activation energy of imidization reaction exhibited polymer in which azobenzene units were placed between amide linkages. Polymers were characterized by FTIR, 1H‐NMR, X‐ray, and UV–vis methods. The glass transition temperature of resultant poly(ester imide)s was in the range of 217–237°C. The presence of chromophore units slightly decreased Tg and significantly improved their solubility and optical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

14.
Mixed‐substituent fluoroalkoxyphosphazene polymers bearing ~15% 1H,1H,2H,2H‐perfluorooctan‐1‐oxy or 1H,1H,2H,2H‐perfluorodecan‐1‐oxy side groups together with trifluoroethoxy cosubstituent groups were synthesized. The low reactivity of the long‐chain fluoroalkoxides and their limited solubility in organic solvents prevented higher levels of substitution. Moreover, the sodium alkoxides with two methylene residues adjacent to the oxygen proved to be unstable in solution due to elimination of NaF and precipitation of side products, and this limited the time available for chlorine replacement reactions. The resulting cosubstituent polymers were characterized by proton nuclear magnetic resonance (1H‐NMR), 31P‐NMR, 19F‐NMR, gel‐permeation chromatography, and differential scanning calorimetry. Unlike homo‐ or mixed‐substituent fluoroalkoxyphosphazene polymers, such as [NP(OCH2CF3)2]n (a microcrystalline thermoplastic, Tg ~ ?63°C, Tm ~ 242°C) or [NP(OCH2CF3)(OCH2(CF2)xCF2H)]n (PN‐F, a rubbery elastomer, Tg ~ ?60°C, but no detectable Tm), the new polymers are gums (Tg ~ ?50°C, but no detectable Tm) with molecular weights in the 105 g/mol rather than the 106 g/mol range. POLYM. ENG. SCI., 54:1827–1832, 2014. © 2013 Society of Plastics Engineers  相似文献   

15.
Cytosolic phospholipase A2α (cPLA2α) may play a critical role in neuropsychiatric and neurodegenerative disorders associated with oxidative stress and neuroinflammation. An effective PET radioligand for imaging cPLA2α in living brain might prove useful for biomedical research, especially on neuroinflammation. We selected four high‐affinity (IC50 2.1–12 nm ) indole‐5‐carboxylic acid‐based inhibitors of cPLA2α, namely 3‐isobutyryl‐1‐(2‐oxo‐3‐(4‐phenoxyphenoxy)propyl)‐1H‐indole‐5‐carboxylic acid ( 1 ); 3‐acetyl‐1‐(2‐oxo‐3‐(4‐(4‐(trifluoromethyl)phenoxy)phenoxy)propyl)‐1H‐indole‐5‐carboxylic acid ( 2 ); 3‐(3‐methyl‐1,2,4‐oxadiazol‐5‐yl)‐1‐(2‐oxo‐3‐(4‐phenoxyphenoxy)propyl)‐1H‐indole‐5‐carboxylic acid ( 3 ); and 3‐(3‐methyl‐1,2,4‐oxadiazol‐5‐yl)‐1‐(3‐(4‐octylphenoxy)‐2‐oxopropyl)‐1H‐indole‐5‐carboxylic acid ( 4 ), for labelling in carboxyl position with carbon‐11 (t1/2=20.4 min) to provide candidate PET radioligands for imaging brain cPLA2α. Compounds [11C] 1 – 4 were obtained for intravenous injection in adequate overall yields (1.1–5.5 %) from cyclotron‐produced [11C]carbon dioxide and with moderate molar activities (70–141 GBq μmol?1) through the use of Pd0‐mediated [11C]carbon monoxide insertion on iodo precursors. Measured logD7.4 values were within a narrow moderate range (1.9–2.4). After intravenous injection of [11C] 1 – 4 in mice, radioactivity uptakes in brain peaked at low values (≤0.8 SUV) and decreased by about 90 % over 15 min. Pretreatments of the mice with high doses of the corresponding non‐radioactive ligands did not alter brain time–activity curves. Brain uptakes of radioactivity after administration of [11C] 1 to wild‐type and P‐gp/BCRP dual knock‐out mice were similar (peak 0.4 vs. 0.5 SUV), indicating that [11C] 1 and others in this structural class, are not substrates for efflux transporters.  相似文献   

16.
The synthesis of chiral side‐chain liquid‐crystalline polysiloxanes containing both cholesteryl undecylenate (MI) and 4‐allyloxy‐benzoyl‐4‐(S‐2‐ethylhexanoyl) p‐benzenediol bisate (MII) mesogenic side groups was examined. The chemical structures of the obtained monomers and polymers were confirmed with Fourier transform infrared spectroscopy or 1H‐NMR techniques. The mesomorphic properties and phase behavior of the synthesized monomers and polymers were investigated with polarizing optical microscopy, differential scanning calorimetry, and thermogravimetric analysis (TGA). Copolymers IIP–IVP revealed a smectic‐A phase, and VP and VIP revealed a smectic‐A phase and a cholesteric phase. The experimental results demonstrated that the glass‐transition temperature, the clearing‐point temperature, and the mesomorphic temperature range of IIP–VIP increased with an increase in the concentration of mesogenic MI units. TGA showed that the temperatures at which 5% mass losses occurred were greater than 300°C for all the polymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2670–2676, 2002  相似文献   

17.
Conjugated polymers are highly desirable for the photovoltaic applications. We report the synthesis, characterization, optoelectronic properties, and solar cell application of two polymers, namely, poly[(9,9‐didodecylfluorene‐2,7‐diyl)‐alt‐(2,2′:5′,2″‐terthiophene‐5,5″‐diyl)] (P1) and poly[(1,4‐bis(dodecyloxy)benzene‐2,5‐diyl)‐alt‐(2,2′:5′,2″‐terthiophene‐5,5″‐diyl)] (P2). The polymers were synthesized via Stille cross‐coupling reaction, and were characterized by the gel permeation chromatography, nuclear magnetic resonance, Fourier transform infrared, UV–vis, thermogravimetric analysis, and cyclic voltammetry analyses. The two copolymers are processable due to their good solubility in organic solvents (tetrahydrofuran, CHCl3, toluene, chlorobenzene, and o‐dichlorobenzene). The optical band gaps (UV–vis, film, and Egopt) of the P1 and P2 are 2.04 and 2.00 eV, respectively. The density functional theory output structures showed that S O space interaction is likely responsible for the higher planarity of P2. The polymers showed low HOMO energy levels (P1: −5.33 eV, P2: −5.05 eV). The EHOMO for P1 is close to the EHOMO (−5.4 eV) of an ideal polymer, which is an important, rare, and main origin of the observed higher Voc (801–808 mV). The onset decomposition temperatures (Td) for the P1 and P2 are 418°C and 365°C, respectively. The polymer solar cell based on the P1: C60 (1: 1) and P2: C60 (1: 1) blend showed a power conversion efficiency (PCE) of 0.94 and 0.71%, respectively. The composite polymer : PC60BM = 1 : 2 increased PCE of the P1 (1.65%) and P2 (1.09%) under AM 1.5 illumination (100 mW/cm2). The study provided important examples to design donor–donor (D–D) polymers for the photovoltaic applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42147.  相似文献   

18.
In this study, two main‐chain second‐order nonlinear optical (NLO) polyurethanes were successfully prepared with indole‐based chromophores. The introduced phenyl isolation group and the continuous zigzag polymer backbone were found to be helpful for effectively decreasing the intermolecular dipole–dipole interactions and enhancing the NLO properties of the resulting polymers. The studied polymers exhibited good optical transparency, high thermal stability, and excellent NLO effects; this indicated that the nonlinearity–stability trade‐off and nonlinearity–transparency trade‐off could be alleviated by this newly designed polymer system. Poly{4‐anilinocarbonyl[N‐ethoxyl‐5‐phenyl‐3‐azo(2′‐oxyethylene‐4′‐nitrobenzene)indole]carbonylimino} with a zigzag backbone showed a large second harmonic generation coefficient (d33) value of 88.4 pm/V. However, poly{5‐naphthyliminocarbonyl[N‐ethoxyl‐5‐phenyl‐3‐azo(2′‐oxyethylene‐4′‐nitrobenzene)indole]carbonylimino} (PUAZN) with a continuous zigzag structure exhibited a higher d33 value of 116.2 pm/V, which was attributed to the unique rigid and zigzag linkage of 1,5‐naphthalene as the isolation spacer. The enhanced NLO efficiency and relatively longer term temporal stability made PUAZN as a promising candidate for practical applications in photonic devices. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42974.  相似文献   

19.
Poly(o‐amino benzyl amine), poly(m‐amino benzyl amine), and the copolymers with aniline were synthesized in 10?4M HCl by using ammonium persulfate as oxidizing agent. The copolymers were synthesized at various feed mole fractions of comonomer diamine and characterized by elemental analysis, FTIR, 1H‐NMR spectroscopy, and electrical conductivity. The polymerization yield depended on the substituent position in the aromatic ring. Copper ion was incorporated in the polymers and the amount depended on the side groups position in the aromatic ring. The thermal stability increased when copper ions and aniline units were incorporated in the polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 31–36, 2004  相似文献   

20.
A one‐phase synthesis of AuNPs‐polymer nanocomposites using HAuCl4 as the precursor is reported in this article. A flexible polymer, poly(2‐(4‐(di(1H‐indol‐3‐yl)methyl)phenoxy) ethyl methacrylate) (PMPEM), containing indole groups on the side chain was utilized as both a reducing reagent and soft template in the system. The PMPEM‐Au nanocomposites with three different sizes of AuNPs (25–50, 2, and 5 nm) were obtained just through choosing different solvents such as toluene, tetrahydrofuran (THF), and N,N‐dimethylformamide, respectively. Nanocomposites including the size of 25–50 and 2 nm AuNPs showed strong NLO absorption and refraction behaviors. The nonlinear refractive index n2 of PMPEM‐Au nanocomposites prepared in toluene and THF were 9.35 × 10?11 and 1.85 × 10?10 m2/W, third‐order susceptibility χ(3) were 2.55 × 10?11 and 4.26 × 10?11 esu, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

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