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1.
A convenient two‐step approach for the synthesis of ferrocenyl‐functionalized long chain branched polydienes, based on both butadiene and isoprene, respectively, is presented. Classical living anionic polymerization was used to synthesize different ABn type poly(diene) macromonomers with moderate molecular weights between 1700 and 3200 g/mol and narrow polydispersity. Quantitative end‐capping with chlorodimethylsilane resulted in the desired ABn macromonomer structures. In the ensuing Pt‐catalyzed hydrosilylation polyaddition, branched, functionalized polydienes were obtained by a concurrent ABn + AR type of copolymerization with mono‐ and difunctional ferrocenyl silanes (fcSiMe2H or fc2SiMeH). Molecular weights of the branched polymers were in the range of 10,000 to 44,000 g/mol (SEC/MALLS). Because of the large number of functional end groups, high loading with ferrocene units up to 63 wt % of ferrocene was achieved. Detailed studies showed full conversion of the functional silanes and incorporation into the branched polymer. Further studies using DSC, TGA, and cyclovoltammetry (CV) measurements have been performed. Electrochemical studies demonstrated different electrochemical properties for fcSiMe2‐ and fc2SiMe‐units. The CVs of polymers modified with diferrocenylsilane units exhibit the pattern of communicating ferrocenyl sites with two distinct, separate oxidation waves. The polymers were also deposited on an electrode surface and the electrodes investigated via CV, showing formation of electroactive films with promising results for the use of the materials in biosensors. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2518–2529, 2009  相似文献   

2.
The synthesis of arborescent polymers with poly(γ‐benzyl L‐glutamate) (PBG) side chains was achieved through successive grafting reactions. The linear PBG building blocks were produced by the ring‐opening polymerization of γ‐benzyl L‐glutamic acid N‐carboxyanhydride initiated with n‐hexylamine. The polymerization conditions were optimized to minimize the loss of amino chain termini in the reaction. Acidolysis of a fraction of the benzyl groups on a linear PBG substrate and coupling with linear PBG using a carbodiimide/hydroxybenzotriazole promoter system yielded a comb‐branched or generation zero (G0) arborescent PBG. Further partial deprotection and grafting cycles led to arborescent PBG of generations G1 to G3. The solvent used in the coupling reaction had a dramatic influence on the yield of graft polymers of generations G1 and above, dimethylsulfoxide being preferable to N,N‐dimethylformamide. This grafting onto scheme yielded well‐defined (Mw/Mn ≤ 1.06), high molecular weight arborescent PBG in a few reaction cycles, with number‐average molecular weights and branching functionalities reaching over 106 and 290, respectively, for the G3 polymer. α‐Helix to coiled conformation transitions were observed from N,N‐dimethylformamide to dimethyl sulfoxide solutions, even for the highly branched polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5270–5279  相似文献   

3.
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   

4.
New isoindigo and di(thienyl)ethylene‐containing π‐extended conjugated polymers with different branched side chains were synthesized to investigate their physical properties and device performance in thin‐film transistors and photovoltaic cells. 11‐Butyltricosane (S3) and 11‐heptyltricosane (S6) groups were used as side‐chain moieties tethered to isoindigo units. The linking groups between the polymer backbone and bifurcation point in the branched side chain differ in the two polymers (i.e., PIDTE‐S3 and PIDTE‐S6 ). The polymers bearing S6 side chains showed much better charge transport behavior than those with S3 side chains. Thermally annealed PIDTE‐S6 film exhibited an outstanding hole mobility of 4.07 cm2 V?1 s?1 under ambient conditions. Furthermore, bulk heterojunction organic photovoltaic cells made from a blend film of PIDTE‐S3 and (6,6)‐phenyl C61‐butyric acid methyl ester demonstrated promising device performance with a power conversion efficiency in the range of 4.9–5.0%. © 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015 , 53, 1226–1234  相似文献   

5.
We synthesized through‐space conjugated polymers with [2.2]paracyclophane and thieno[3,4‐b]pyrazine units in the main chain by the Sonogashira–Hagihara coupling reaction. The obtained polymers were soluble in common organic solvents, and homogeneous thin films were readily obtained from the polymer solutions by spin‐coating techniques. The polymers exhibited the extension of the conjugation length via the through‐space interaction. The polymers showed orangish‐red emission with peak maxima of around 610 nm in diluted solutions and their thin films, which were derived from the thieno[3,4‐b]pyrazine moieties. The optical and electrochemical behaviors of the polymers containing pseudo‐para‐ and pseudo‐ortho‐linked [2.2]paracyclophane were identical. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009  相似文献   

6.
Poly((2‐Alkylbenzo[1,2,3]triazole‐4,7‐diyl)vinylene)s (pBTzVs) synthesized by Stille coupling show different absorption spectra, solid‐state morphology, and photovoltaic performance, depending on straight‐chain versus branched‐chain (pBTzV12 and pBTzV20) pendant substitution. Periodic boundary condition density functional computations show limited alkyl pendant effects on isolated chain electronic properties; however, pendants could influence polymer backbone conjugative planarity and polymer solid film packing. The polymers are electronically ambipolar, with best performance by pBTzV12 with hole and electron transport mobilities of 4.86 × 10?6 and 1.96 × 10?6 cm2 V?1 s?1, respectively. pBTzV12 gives a smooth film morphology, whereas pBTzV20 gives a very different fibrillar morphology. For ITO/PEDOT:PSS/(1:1 w/w polymer:PC71BM)/LiF/Al devices, pBTzV12 gives power conversion efficiency (PCE) up to 2.87%, and pBTzV20 gives up to PCE = 1.40%; both have open‐circuit voltages of VOC = 0.6–0.7 V. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1539–1545  相似文献   

7.
AB2 monomers present opportunities to conduct one‐pot syntheses of highly branched or “hyperbranched” polymers, which are known for their distinct physical and chemical properties relative to linear polymers. This paper describes the synthesis of a deoxybenzoin‐containing AB2 monomer and its use in step‐growth polymerization to prepare branched aromatic polyesters. Highly soluble deoxybenzoin polymers were obtained with degrees of branching reaching 0.36 and estimated molecular weights approaching 20 kDa. The phenolic chain ends of the polymer allowed for post‐polymerization modification by silylation and esterification chemistry. TGA and microscale combustion calorimetry revealed these novel aromatic polyesters to possess the critically important characteristics of flame‐retardant polymers, such as high char yield and low heat release. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1765–1770  相似文献   

8.
When the flexible terminal substituent changes from butoxy to hexyloxy or longer, smectic C (SC) liquid crystalline phase was firstly reported to develop from a kind of mesogen‐jacketed liquid crystalline polymer (MJLCP) whose mesogenic side groups are unbalancedly bonded to the main chain without spacers. A series of MJLCPs, poly[4,4′‐bis(4‐alkoxyphenyl)‐2‐vinylbiphenyl(carboxide)] (nC2Vp, n is the number of the carbons in the alkoxy groups, n = 2, 4, 6, 8, 10, and 12) were designed and synthesized successfully via free radical polymerization. The molecular weights of the polymers were characterized with gel permeation chromatography, and the liquid crystalline properties were investigated by differential scanning calorimetry, polarized light microscopy experiments, and 1D, 2D wide‐angle X‐ray diffraction. Comparing with the butoxy analog, the polymer with unbalanced mesogenic core and shorter flexible substituents (n = 2, 4) keeps the same smectic A (SA) phase, but other polymers with longer terminal flexible substituents (n = 6, 8, 10, and 12) can develop into a well‐defined SC phase instead of SA phase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 505–514, 2009  相似文献   

9.
New water‐soluble methacrylate polymers with pendant quaternary ammonium (QA) groups were synthesized and used as antibacterial materials. The polymers with pendant QA groups were obtained by the reaction of the alkyl halide groups of a previously synthesized functional methacrylate homopolymer with various tertiary alkyl amines containing 12‐, 14‐, or 16‐carbon alkyl chains. The structures of the functional polymer and the polymers with QA groups were confirmed with Fourier transform infrared and 1H and 13C NMR. The degree of conversion of alkyl halides to QA sites in each polymer was determined by 1H NMR to be over 90% in all cases. The number‐average molecular weight and polydispersity of the functional polymer were determined by size exclusion chromatography to be 32,500 g/mol and 2.25, respectively. All polymers were thermally stable up to 180 °C according to thermogravimetric analysis. The antibacterial activities of the polymers with pendant QA groups against Staphylococcus aureus and Escherichia coli were determined with broth‐dilution and spread‐plate methods. All the polymers showed excellent antibacterial activities in the range of 32–256 μg/mL. The antibacterial activity against S. aureus increased with an increase in the alkyl chain length for the ammonium groups, whereas the antibacterial activity against E. coli decreased with increasing alkyl chain length. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5965–5973, 2006  相似文献   

10.
Hyperbranched poly(ether nitrile)s were prepared from a novel AB2 type monomer, 2‐chloro‐4‐(3,5‐dihydroxyphenoxy)benzonitrile, via nucleophilic aromatic substitution. Soluble and low‐viscous hyperbranched polymers with molecular weights upto 233,600 (Mw) were isolated. According to the 1H NMR and GPC data, the unique polymerization behavior was observed, which implies that the weight average molecular weight increased after the number average molecular weight reached plateau region. Model compounds were prepared to characterize the branching structure. Spectroscopic measurements of the model compounds and the resulting polymers, such as 1H, DEPT 13C NMR, and MS, strongly suggest that the ether exchange reaction and cyclization are involved in the propagation reaction. The side reactions would affect the unique polymerization behavior. The resulting polymers showed a good solubility in organic solvents similar to other hyperbranched aromatic polymers. The hydroxy‐terminated polymer was even soluble in basic water. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5835–5844, 2009  相似文献   

11.
A one‐pot synthetic route based on copper‐catalyzed Huisgen reaction has been developed to functionalize a methacrylate propargylic polymer with azido‐substituted moieties. This procedure was used for the preparation of electro‐optic materials containing well‐known Disperse Red One (DR1) chromophores along with bulky adamantyl moieties (Adam). The postfunctionalization of the propargylic polymer was successfully achieved using different molar ratios of DR1/Adam. These novel polymers exhibit high glass transition temperature owing to the rigid structure of adamantyl units. Moreover, the second harmonic generation measurements demonstrated the effectiveness of adamantyl groups to act as insulating shield limiting thus the electrostatic interactions between chromophores. Indeed, higher optimal chromophore concentration (50 mol %) than in conventional DR1‐containing polymers (30 mol %) allowed us to increase the d33 coefficient up to 92 pm/V. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5652–5660, 2009  相似文献   

12.
A series of novel branched polythiophene derivatives bearing different densities of vinylene‐bridges as linking chains were synthesized by a general synthetic strategy. The organic field‐effect transistors, which were fabricated by spin‐coating the polymer solutions onto octadecyltrichlorosilane‐modified SiO2/Si substrates with top‐contact configuration, afforded a high mobility of 8.0 × 10?3 cm2 V?1 s?1 with an on/off ratio greater than 104 and a threshold voltage of about ?3 V in saturation regime. The devices based on these polymers possessed better performance than those of polymers without conjugated bridges and polymers with longer conjugated bridges. These results demonstrated that the combination of conjugated polythiophene backbones and vinylene‐bridges would improve the carrier mobility. As an emerging class of conjugated materials, polymers with vinylene‐bridges as linking chains would open up new opportunities in organic electronics, and their applications in organic electronics are promising. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1381–1392, 2009  相似文献   

13.
Four polythiophene derivatives including regiorandom polymers P1 , P2 , and P3 and a regioregular polymer P4 , containing a phenyl side chain with electron‐withdrawing carbonyl groups such as an ester and a ketone at the 3‐position of the thiophene ring, were synthesized by Stille coupling reaction. Bulk‐heterojunction polymer solar cells (PSCs) based on these polymers as p‐type semiconductors and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) were fabricated, and their photovoltaic performances were evaluated for the first time. The PSC devices based on the regioregular polymer P4 :PCBM = 1:2 (w/w) exhibited a high‐open‐circuit voltage (Voc) of 0.943 V because of the low‐lying highest occupied molecular orbit energy level of P4 . The short π–π stacking distance (0.355 nm) in the parallel direction to the substrate and “face‐on” rich orientation were observed by the grazing incidence wide‐angle X‐ray scattering experiment, which might reflect higher Jsc and FF values of the P4 :[6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) PSC device than others. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 875–887  相似文献   

14.
Ethyl cyanoacrylate (ECA) was polymerized radically in the presence of small amounts of trifluoroacetic acid as effective inhibitor of incidental anionic polymerization. Methyl methacrylate and other functional vinyl monomers (e.g., 2‐chloroethyl and 2‐bromoethyl methacrylate) were copolymerized with ECA, yielding linear ECA‐rich copolymers, which could readily undergo further modifications, for instance nucleophilic substitution with azide. In the presence of a disulfide‐containing dimethacrylate crosslinker and a chain transfer agent (CBr4) during the free radical copolymerizations of ECA with methacrylates, highly branched ECA‐based polymers containing disulfide groups at the branching points were obtained prior to gelation. The polymers degraded upon addition of reducing agents. The prepared polymers, which contained peripheral (chain end) alkyl bromide groups as well as pendant alkyl chloride or bromide groups were then reacted with sodium azide, affording azide‐containing polymers that were reacted with functional alkynes under copper‐catalyzed “click” chemistry conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3683–3693  相似文献   

15.
The linear rheological responses of a series of specially designed wedge‐type polymers synthesized by the polymerization of large molecular weight monomers have been measured. These wedge polymers contained large side groups which contained three flexible branch chains per polymer chain unit. The master curves for these polymers were obtained by time temperature superposition of dynamic data at different temperatures from the terminal flow regime to well below the glass transition temperature, Tg. While these polymers maintained a behavior similar to that of linear polymers, the influence of the large side group structure lead to low entanglement densities and extremely low rubbery plateau modulus values, being near to 13 kPa. The viscosity molecular weight dependence was also somewhat higher than that normally observed for linear polymers, tending toward a power law near to 4.2 rather than the typical 3.4 found in entangled linear chains. The glassy modulus of these branched polymers is also found to be extremely low, being less than 100 MPa at Tg ?60 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 899–906  相似文献   

16.
Unprotected exo,exo‐5‐norbornene‐2,3‐dicarboxylic acid and exo,exo‐7‐oxa‐5‐norbornene‐2,3‐dicarboxylic acid were polymerized via ring‐opening metathesis polymerization. This reaction yielded polymers with molecular weights (Mn from GPC) ranging from 31 to 242 kg/mol and polydispersity indices between 1.05 and 1.12, using Grubbs' third generation catalyst. The water solubility as a function of pH value of the polymers was investigated by dynamic light scattering (DLS). DLS and acid‐base titration revealed that the oxanorbornene polymer was water soluble over a wider pH range than its norbornene analog. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1266–1273, 2009  相似文献   

17.
A series of mesogen‐jacketed liquid crystalline polymers, poly{2,2,3,3,4,4,4‐heptafluorobutyl 4′‐hydroxy‐2‐vinylbiphenyl‐4‐carboxylate} (PF3Cm, where m is the number of carbon atoms in the alkoxy groups, and m = 1, 4, 6, and 8), the side chain of which contains a biphenyl core with a fluorocarbon substituent at one end and an alkoxy unit of varying length on the other end, were designed and successfully synthesized via atom transfer radical polymerization. For comparison, poly{butyl 4′‐hydroxy‐2‐vinylbiphenyl‐4‐carboxylate} (PC4Cm), similar to PF3Cm but with a butyl group instead of the fluorocarbon substituent, was also prepared. Differential scanning calorimetric results reveal that the glass transition temperatures (Tgs) of the two series of polymers decrease as m increases and Tgs of the fluorocarbon‐substituted polymers are higher than those of the corresponding butyl‐substituted polymers. Wide‐angle X‐ray diffraction measurements show that the mesophase structures of these polymers are dependent on the number of the carbon atoms in the fluorocarbon substituent and the property of the other terminal substituent. Polymers with fluorocarbon substituents enter into columnar nematic phases when m ≥ 4, whereas the polymer PF3C1 exhibits no liquid crystallinity. For polymers with butyl substituents, columnar nematic phases form when the number of carbon atoms at both ends of the side chain is not equal at high temperatures and disappear after the polymers are cooled to ambient temperature. However, when the polymer has the same number of carbon atoms at both ends of the side chain, a hexagonal columnar phase develops, and this phase remains after the polymer is cooled. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

18.
Novel naphtho[1,2‐b:5,6‐b′]dithiophene (NDT) and diketopyrrolopyrrole (DPP)‐containing donor‐acceptor conjugated polymers (PNDTDPPs) with different branched side chains were synthesized via Pd(0)‐catalyzed Stille coupling reaction. Octyldodecyl (OD) and dodecylhexadecyl (DH) groups were tethered to the DPP units as the side chains. The soluble fraction of PNDTDPP‐OD polymer in chloroform has much lower molecular weight than that of PNDTDPP‐DH polymer. PNDTDPP‐DH polymer bearing relatively longer DH side chains exhibited much better charge‐transport behavior than PNDTDPP‐OD polymer with shorter OD side chains. The thermally annealed PNDTDPP‐DH polymer thin films exhibited an outstanding charge carrier mobility of ~1.32 cm2 V?1 s?1 (Ion/Ioff ~ 108) measured under ambient conditions, which is almost six times higher than that of thermally annealed PNDTDPP‐OD polymer thin films. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5280–5290  相似文献   

19.
Tetraphenylporphyrin‐end‐functionalized polycyclohexane (H2TPP‐PCHE) and its metal complexes (MTPP‐PCHE) were synthesized as the first successful example of porphyrin‐end‐functionalized transparent and stable polymers with a well‐controlled and defined polymer chain structure. Chloromethyl‐end‐functionalized poly(1,3‐cyclohexadiene) (CM‐PCHD) was synthesized as prerequisite prepolymer by the postpolymerization reaction of poly(1,3‐cyclohexadienyl)lithium and chloro(chloromethyl)dimethylsilane. CM‐end‐functionalized PCHE (CM‐PCHE) was prepared by the complete hydrogenation of CM‐PCHD with p‐toluenesulfonyl hydrazide. H2TPP was incorporated onto the polymer chain end by the addition of 5‐(4‐hydroxyphenyl)‐10,15,20‐triphenylporphyrin to CM‐PCHE. The complexation of H2TPP‐PCHE and Zn(OAc)2 (or PtCl2) yielded a zinc (or platinum) complex of H2TPP‐PCHE. H2TPP‐PCHE and MTPP‐PCHE were readily soluble in common organic solvents, and PCHE did not inhibit the optical properties of the H2TPP, ZnTPP, and PtTPP end groups. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

20.
Azobenzene monomeric precursors bearing piperazine as donor moiety with different withdrawing groups and derived side chain polymethacrylates have been prepared and characterized. Monomers having terminal cyano or nitro groups, and the corresponding polymers, exhibited smectic A phases. Linear and nonlinear optical properties of every monomer and thin films of the cyano polymer ( pol‐PZ‐CN ) have been also studied. UV‐vis spectroscopy revealed out‐of‐plane orientation in the as prepared films, as confirmed by waveguide refractive index measurements. Moreover, absorption spectra indicated the presence of azo aggregates in these films. The initial molecular arrangement has been modified by applying thermal annealing within the mesophase range and UV‐blue irradiation. Although thermal annealing resulted in a significant amplification of the out‐of‐plane optical anisotropy due to thermotropic self‐organization of side chain azo moieties, irradiation with 440 nm light induced some disruption of aggregates. The nonlinear optical response of Corona poled films has been studied by second harmonic generation measurements, and the influence of the molecular arrangement on the nonlinear dij coefficients has been analyzed. The more efficient poling corresponded to preirradiated films. In any case, a noticeable degree of polar order (70% of the initial d33 value) remained for several months after the poling in films kept at RT. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 232–242, 2010  相似文献   

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