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1.
Core‐shell type hyperbranched polymers that are capable of forming unimolecular micelles and reverse micelles in aqueous and hydrocarbon medium, respectively, were synthesized via two approaches, namely AB2 + A‐R and A2 + B3 + A‐R type copolymerizations. In case of micelle‐forming polymers, an AB2 monomer carrying a decamethylene spacer was used along with heptaethylene glycol monomethyl ether (HPEG) as the A‐R type comonomer. One the other hand, for the preparation of reverse micelle‐forming polymers, an AB2 monomer containing an oligo(oxyethylene) spacer was used along with cetyl alcohol as the A‐R type comonomer. The former was readily soluble in water while the latter was soluble in hydrocarbon solvents like hexane. NMR spectral studies confirmed that both the approaches generated highly branched structures wherein about 65–70% of the terminal B groups were capped by the A‐R comonomer. Dye‐uptake measurements revealed that the polymers prepared via the AB2 + A‐R approach exhibited a significantly larger uptake compared with those prepared via the A2 + B3 + A‐R approach. This suggests that the AB2 + A‐R approach generates hyperbranched polymers with better defined core‐shell topology when compared with polymers prepared via the A2 + B3 + A‐R approach, which is in accordance with previous studies that suggest that A2 + B3 approach yields polymers with significantly lower branching levels and consequently less compact structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 80–91, 2009  相似文献   

2.
Novel liquid crystalline (LC) hyperbranched (HB) polyesters comprising phenylbenzothiazole (PBT) unit as mesogen in the interiors were prepared at various feed mole ratios (A2/B3) by solution polycondensation of a dioxydiundecanol derivative of PBT (A2 monomer) with trimesic acid trimethyl ester (B3 monomer) via A2+B3 approach and their LC and optical properties were investigated. Analogous linear polyesters containing the PBT unit in the main chains were also prepared by the solution polycondensation of A2 monomer with aromatic or aliphatic dimethyl esters. FTIR and 1H‐NMR spectroscopies indicated that the HB polyesters are produced without gelation during the polycondensation and have degree of branching (DB) of 7–46%. The structures of HB polymers changed depending on the feed mole ratios and the polymer prepared in the mole ratio of A2/B3 = 3/2 had the highest inherent viscosity and DB. Acetylation of terminal OH group‐having HB polyesters prepared in excess mole ratios of A2/B3 afforded ones bearing acetoxy groups in the terminals. DSC measurements, polarizing microscope observations of textures, and X‐ray analyses suggested that only the terminal OH group‐having HB polymer prepared in the mole ratio of A2/B3 = 3/1 form smectic C phase. In the linear polymers, the polymers derived by using the aromatic dimethyl esters had no LC melt, but those from the aliphatic dimethyl esters formed LC smectic C phase. The acetoxy group‐bearing HB polymers showed more stable smectic A or C phase than those with the OH terminals. Solution UV‐vis and photoluminescent (PL) spectra indicated that the linear and the HB polymers have analogous optical properties and display maximum absorbances and blue‐light emission on the basis of the PBT unit, where the Stokes shifts were observed because of intermolecular aggregation effects, but there is a large difference between the optical behaviors of the linear and the HB polymers in film, whose Eg values of the linear polymers decreased and those of the HB polymers vice versa. Quantum efficiencies (Φ) had a tendency of increase in the linear polymers and the HB polymers forming LC phases. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6688–6702, 2008  相似文献   

3.
New thermotropic liquid crystalline (LC) hyperbranched (HB) polyesters containing 2,5‐diphenyl‐1,3,4‐thiadiazole (DTD) unit as mesogen in the interiors were prepared at various mole ratios (A2/B3) by melt and solution polycondensations of a dioxydiundecanol of DTD (A2) and 1,2,3‐propanetricarboxylic acid (B3) via the A2 + B3 approach and their LC and optical properties were investigated. FTIR and 1H‐NMR spectroscopies indicated that all the expected HB polyesters, which show good solubilities in organic solvents, are produced without gelation during the polymerization. Among them, the HB polymer prepared in the mole ratio of A2/B3 = 3/2 by the solution polycondensation had the highest inherent viscositiy. DSC measurents, polarizing microscope observations of optical textures, and X‐ray analyses suggested that the LC properties of HB polymers depend on the polymerization methods and the feed mole ratios. In the HB polymers prepared using the melt polycondensation, only the polymer prepared in the mole ratio of A2/B3 = 3/1 formed a highly‐ordered, tilted, crystal‐like smectic phase, but all the polymers prepared by the solution polycondensation formed highly‐ordered, tilted, smectic phases. Solution and solid‐state UV‐vis and photoluminescent (PL) spectra indicated that the HB polymers show maximum absorbances and blue‐light emission on the basis of the DTD unit, where the Stokes‐shifts were observed, probably because of intermolecular aggregation effects © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2998–3008, 2007  相似文献   

4.
A novel photoactive, liquid‐crystalline, hyperbranched benzylidene polyester (PAHBP) was synthesized from a dilute solution of an A2 photoactive monomer [bis(4‐hydroxybenzylidene)‐4‐phenyl cyclohexanone] and a B3 monomer (1,3,5‐benzene tricarboxylic acid chloride) by the solution polycondensation method in the presence of pyridine as a condensing agent. PAHBP was thoroughly characterized by Fourier transform infrared, 1H and 13C NMR, ultraviolet–visible spectrometry, and gel permeation chromatography. The inherent viscosity of the polymer was 0.35 dL/g in tetrahydrofuran. The degree of branching was 0.53, which confirmed the branched architecture of the polymer. Furthermore, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy were used to examine the thermal stability and thermotropic liquid‐crystalline properties of the hyperbranched polyester. The polymer exhibited a nematic mesophase over a wide range of temperatures. The photoreactivity of PAHBP was studied by photolysis under ultraviolet light. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 53–61, 2006  相似文献   

5.
A series of photoactive liquid crystalline polyester epoxies incorporating bisbenzylidene segments as photoactive mesogenic cores were synthesized by polyaddition of diepoxy monomers and terephthalic acid/trimesic acid. To investigate the influence of structural parameters such as, molecular architecture, structural rigidity of mesogenic unit and substituents on thermal, mesogenic, and photoactive properties, the bisbenzylidene segment was incorporated into one acyclic and two cycloalkanone units with two and four substituents, respectively in both linear and hyperbranched architectures. Degree of branching of hyperbranched polymers was found to be in the range of 0.49–0.62. All polymers exhibited nematic mesophase (nematic droplets). Photo induced (2π + 2π) cycloaddition reaction, upon exposure to light at 365 nm, was examined. Inter molecular photocycloaddition was confirmed by photoviscosity measurement of UV irradiated polymer solutions. Faster photo induced reactivity of polymers in hyperbranched architecture was observed when compared to linear structure. Acyclic units facilitated photocycloaddition, and five‐membered ring showed higher photoactivity compared to six‐membered ring. The steric hindrance caused by substituents decreased the photoactivity of polymers. Refractive index change was found to be in the range of 0.015–0.024. Substantial variation of refractive index indicates that these polymers could be used for optical recording. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7637–7655, 2008  相似文献   

6.
In this paper, hyperbranched polyimides having the same repeating unit were synthesized by employing ideal A2+B3 polymerization, non-ideal A2+B3 polymerization and AB2 self-polymerization methods. The polymerization behavior, polymer properties were compared for three methods. Hyperbranched polyimides by ideal A2+B3 polymerization, non-ideal A2+B3 polymerization and AB2 self-polymerization methods show apparent difference in many physical properties, such as inherent viscosity, glass transition temperature, and film formation behavior etc. The hyperbranched polymers by the non-ideal A2+B3 polymerization are suitable for smooth, flexible and self-standing film preparation, which provides useful information for hyperbranched polymers toward self-standing materials.  相似文献   

7.
A series of blue light‐emitting hyperbranched polymers comprising poly(fluorene‐co‐dibenzothiophene‐S,S‐dioxide) as the branch and benzene, triphenylamine, or triphenyltriazine as the core were synthesized by an “A2 + A2' + B3” approach of Suzuki polymerization, respectively. All resulted copolymers exhibited quite comparable thermal properties with the glass transition temperatures in the range of 59–68 °C and relatively high decomposition temperatures over 420 °C. Photoluminescent spectra exhibited slight variation with the molar ratio of the dibenzothiophene‐S,S‐dioxide unit and the size of the core units. Polymer light‐emitting devices demonstrated blue emission with excellent stability of electroluminescence. Copolymers based on smaller core units of benzene and triphenylamine exhibited enhanced device performances regarding to that of triphenyltriazine. With the device configuration of ITO/PEDOT:PSS/polymer/CsF/Al, a maximum luminous efficiency of 4.5 cd A?1 was obtained with Commission Internationale de L'.Eclairage (CIE) coordinates of (0.16, 0.19) for the copolymer PFSO15B. These results indicated that hyperbranched structure can be a promising strategy to attain spectrally stable blue‐light‐emitting polymers with high efficiency. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1043–1051  相似文献   

8.
Three new types of hyperbranched photoactive liquid crystalline siloxane polymers containing azo moieties were synthesized using click chemistry methodology. The polymers were soluble in most of the polar solvents like chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulphoxide and dichloromethane. The molecular weights of the polymers were in the range of 9000–12,000 g mol?1. The trans‐cis photoisomerization of the polymer were studied both under UV radiation and dark. The isomerization rate constants were found to be in the range of 0.7–1.4 × 10?2 sec?1 and 7.0 × ?2.5 × 10?5 sec?1. The thermotropic behavior of the polymers was studied by using polarizing optical microscopy and differential scanning calorimetry, respectively. The polymers P1 and P2 showed liquid crystalline texture characteristic of nematic phase. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

9.
A series of s‐triazine‐based hyperbranched polyethers (HBPE) have been synthesized to obtain thermostability but flexible polymers by an interfacial polycondensation of different diols as A2 and cyanuric chloride as B3 monomers using A2 + B3 approach in the presence of a phase transfer catalyst. The polymerization reaction parameters are optimized, and the results indicate that the optimum conditions for the interfacial polycondensation are a 2:3 mole ratio of cyanuric chloride to diol using butanediol, benzyldimethylhexadecyl ammonium chloride as the catalyst, dichloromethane as the organic solvent, and a three‐step procedure with keeping the reaction mixture at different low temperatures for 2h/2h/5h. Other techniques such as high‐temperature solution, one‐step polycondensation, and transesterification were also carried out to synthesize the HBPE but proved to be not suitable due to large number of side reactions. The synthesized polymers were characterized by FTIR, 1H NMR, and 13C NMR spectroscopy, hydroxyl number determination, solution viscosity measurements, and GPC analysis. The thermal behavior of the hyperbranched polymer was investigated by thermogravimetric analysis and differential scanning calorimetry. All the results were compared with those from an analogous linear polyether, obtained from 2‐methoxy‐4,6‐dichloro‐s‐triazine and butanediol by using the same polymerization technique. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3994–4004, 2010  相似文献   

10.
A series of hyperbranched poly(arylene ether phosphine oxide)s (HB PAEPOs) were prepared via an A2 + B3 polymerization scheme with tris(4‐fluorophenyl)phosphine oxide as B3, and a variety of bisphenols as A2. The effects of the reactivity of the A2 monomer, the A:B ratio, the addition mode, the solvent, and the concentration on the final molecular weight, polydispersity index (PDI), and degree of branching (DB) were studied. Soluble HB PAEPOs with weight‐average molecular weights of up to 299,000 Da were achieved. Reactions in which the A2 component was added slowly resulted in lower DBs (0.2–0.5), whereas the slow addition of the B3 component provided samples with DBs of approximately 0.75. Reactions performed under high‐dilution conditions afforded completely soluble materials with weight‐average molecular weights of 9000–12,100 Da and PDI values as low as 2.20. The molecular weights achieved under high‐dilution conditions were independent of the mode of monomer addition. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3871–3881, 2003  相似文献   

11.
A novel series of soluble hyperbranched interrupted π‐conjugated polymers (HICPs) based on complicated 9,9‐diarylfluorenes (CDAFs) branching core and end‐capped with high carrier‐mobility pyrene moieties were synthesized via the “A2 + A′2 + B3” type Suzuki coupling condensation. The new polymer architecture improves the spectrum stability than the corresponding linear and hyperbranched polymers in PLEDs. Besides, it overcomes the drawback of high driving voltage of common interrupted π‐conjugated polymers. CDAF1 exhibits excellent thermal and morphological stability with a decomposition temperature (Td) higher than 445 °C and a glass transition temperature (Tg) up to 128 °C. No obvious low‐energy green emission band at 520 nm was observed under extreme thermal annealing conditions in air at 200 °C for 12 h. The CDAF1 device shows stable blue emission with the peak at 422 and 447 nm. The Commission International d'Eclairage (CIE) 1931 coordinates is (0.18, 0.16) and the brightness reaches 1051 cd/m2 at 15.7 V. White PLED based on CDAF1/MEH‐PPV blends exhibits a low turn‐on voltage of 4.8 V with voltage‐independent CIE of (0.32, 0.32). Molecular simulations were used to investigate the conformation and interchain interaction. HICPs based on CDAFs tethered with high‐mobility moieties are promising stable blue and host materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6451–6462, 2009  相似文献   

12.
Hyperbranched polyesters are among the most common hyperbranched polymers. One of the interesting features of hyperbranched polyesters is that they contain unreacted hydroxyl and carboxylic acid groups at the linear and terminal structural units, which can be postmodified to adjust thermal, solubility, or mechanical properties, or to prepare core–shell type architectures. This article reports on the synthesis of a novel class of hyperbranched polyesters via an A2 + B3 type Baylis–Hillman polymerization of 2,6‐pyridinedicarboxaldehyde and trimethylolpropane triacrylate. Baylis–Hillman polymerization generates highly functional polyesters that contain not only unreacted aldehyde and/or acrylate groups at the linear and terminal structural units but also chemically orthogonal vinyl and hydroxyl groups along the polymer backbone. Using 3‐hydroxyquinuclidine as the catalyst, hyperbranched polymers with number‐average molecular weights up to 7500 g/mol and degrees of branching up to 0.81 were obtained. To demonstrate the versatility of these hyperbranched polyesters to act as platforms for further derivatization, the orthogonal postpolymerization modification of the hydroxyl, vinyl, and pyridine functional moieties with phenyl isocyanate, methyl‐3‐mercaptopropionate, and methyl iodide is presented. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.  相似文献   

13.
A series of photoactive liquid crystalline linear and hyperbranched polyester epoxies were synthesized by polyaddition of photoactive bis benzylidene alkanone diol monomers and terephthalic acid and trimesic acid respectively with good yield. The effect of molecular architecture (linear and hyperbranched), size of mesogenic unit (cyclic and acyclic units) on the physicochemical, thermal, mesogenic, and photoactive properties of hyperbranched polymers were studied and compared. Degree of branching of hyperbranched polymers was found to be in the range of 0.46–0.49. Monomers containing cyclic moieties only exhibited nematic mesophase, while all polymers exhibited typical nematic mesophase. Intermolecular photo cycloaddition reaction was studied by ultraviolet–visible spectra (UV–vis) and NMR spectroscopy and photo viscosity measurement of UV irradiated polymer solutions. Faster photo induced behavior of hyperbranched polymers containing acyclic alkanone moiety, as compared to polymers containing cycloalkanone moieties, was observed. The change in the refractive index was found to be in the range of 0.02–0.024. Substantial variation of refractive index indicates that this polymer could be used for optical recording. All the polymers were also found to be fluorescent in nature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 552–563, 2008  相似文献   

14.
Hyperbranched polycarbonates were synthesized successfully via the A2 + B3 route by the reaction of a bis(carbonylimidazolide) with triethanolamine. These polymers containing the carbonate group as thermolabile moiety are decomposing into volatile products at around 200°C. The polymers were characterized with 1H/13C NMR spectroscopy, SEC, DSC and TGA techniques.  相似文献   

15.
Summary: We developed a facile approach to hyperbranched polymers by applying a superelectrophilic reaction within an A2 + B3 strategy. A significant reactivity difference between the intermediate and the starting material was utilized to avoid gelation in the A2 + B3 polymerization. A number of hyperbranched poly(arylene oxindole)s were achieved in a one‐step polymerization and characterized by NMR spectroscopy and gel permeation chromatography. Moreover, further modifications at the interior and exterior of the resulting polymers were explored as well.

Structure of the hyperbranched polymers produced using the A2 + B3 approach.  相似文献   


16.
New types of carboxyl-terminated hyperbranched polyesters (HBPEs) with aromatic-aliphatic structure were synthesized by single step-melt polycondensation of adipic acid (as A2 monomer) and phloroglucinol (as B3 monomer) as a core via A2 + B3 approach, at three different monomer mole ratios (A2/B3 = 1: 1, 1.5: 1, 2: 1, respectively). FTIR spectroscopy indicated that the polymers contained hydroxyl groups, ester bonds, benzene ring, methyl and methylene groups, which were in agreement with the expected HBPEs. The HBPEs have inherent viscosities about 0.24 to 0.27 dL/g. The degree of branching of the HBPEs was estimated to be 0.45–0.49% by 1H-NMR and 13C-NMR measurements. The melting temperature of HBPE-1, HBPE-2 and HBPE-3 were 154, 155 and 160°C respectively measured by differential scanning calorimetry (DSC). The synthesized polymers were thermally stable; the thermogravimetric analysis (TGA) measurement revealed that HBPEs had 10% weight loss at 310°C in nitrogen.  相似文献   

17.
New series of hyperbranched polyfluorenes containing triarylpyrazoline cores, PFZ10 , PFZ20 , PFNZ10 , and PFNZ20 , have been synthesized according to the “A2 + A′2 + B3” Suzuki coupling method. The structures and property of the monomers and conjugated polymers were characterized by elemental analysis, gel permeation chromatography, cyclic voltammetry, thermogravimetric analysis, differential scanning calorimetry, and UV–visible absorption, 1H NMR, 13C NMR, and photoluminescence spectroscopies. All these polymers exhibited good solubility in common organic solvents and good thermal stability. The long‐wavelength emission of polyfluorenes had been effectively reduced in these hyperbranched polymers. Standard polymer light emitting devices (PLEDs) from PFZ10 , PFZ20 , PFNZ10 , and PFNZ20 , with the configuration of ITO/PEDOT/polymer/TPBI/Alq3/Mg:Ag, exhibited good electroluminescence (EL) properties The PLED based on PFNZ10 emitted pure blue light with a low turn‐on voltage of 5.3 V and a high EL efficiency of about 1.93%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5296–5307, 2007  相似文献   

18.
Photoactive hyperbranched benzylidene liquid‐crystalline polyester (PAHBP) and photoactive linear benzylidene liquid‐crystalline polyester (PALBP) were synthesized by solution polycondensation with pyridine as an acid acceptor. PAHBP and PALBP were thoroughly characterized with Fourier transform infrared, 1H and 13C NMR, ultraviolet–visible spectrophotometry, fluorescent spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. Both polymers exhibited nematic mesophase. The glass‐transition temperature and liquid‐crystalline isotropic temperature of PAHBP were higher than those of PALBP. During photolysis under ultraviolet light, both polymers underwent an intermolecular photocycloaddition reaction, and the photoactivity of PAHBP was faster than that of PALBP; this was further confirmed by photoviscosity studies. PALBP and PAHBP were fluorescent in nature. An increase in the fluorescence intensity with the time of ultraviolet‐light irradiation was observed for both PAHBP and PALBP. The rate of increase in the fluorescence intensity of the linear analogue (PALBP) was higher than that of the hyperbranched polymer (PAHBP). This behavior could be attributed to the attainment of better planarity in the case of the linear one but not in the case of PAHBP because of the rapid crosslinking of PAHBP leading to an irregular architecture. This behavior was further confirmed by the calculation of the steric energy from corresponding model compounds. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3986–3994, 2006  相似文献   

19.
Self‐controlled synthesis of hyperbranched poly(ether‐ketone)s (HPEKs) were prepared from “A2 + B3” approach by using different monomer solubility in reaction medium. 1,3,5‐Triphenoxybenzene as a hydrophobic B3 monomer was reacted with commercially available terephthalic acid or 4,4′‐oxybis(benzoic acid) as a hydrophilic A2 monomer in a hydrophilic reaction medium, polyphosphoric acid (PPA)/phosphorous pentoxide (P2O5). The resultant HPEKs were soluble in various common organic solvents and had the weight‐average molecular weight in the range of 3900–13,400 g/mol. The results implied that HPEKs were branched structures instead of crosslinked polymers. The molecular sizes and shapes of HPEKs were further assured by morphological investigation with scanning electron microscopy (SEM) and atomic force microscopy (AFM). Hence, the applied polymerization condition was indeed strong enough to efficiently facilitate polycondensation via “direct” Friedel‐Crafts reaction without gelation. It could be concluded that the polymer forming reaction was kinetically controlled by automatic and slow feeding of the hydrophobic B3 monomer into the hydrophilic reaction mixture containing hydrophilic comonomer. As a result, hyperbranched structures were formed instead of crosslinked polymers even at full conversion (equifunctional monomer feed ratio). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3326–3336, 2009  相似文献   

20.
Low-viscosity liquid epoxidized aromatic hyperbranched polymers are synthesized by the reaction between epichlorohydrin (ECH) and carboxy-end hyperbranched polymers prepared from low-cost products trimellitic anhydride (B3 TMA) and dihydroxy alcohols (A2). The low-viscosity property, especially the lowest viscosity of epoxidized aromatic hyperbranched polymers is only 350 cp which has not reported among epoxidized aromatic hyperbranched polymers before, make them can be used to coatings and adhesion fields without organic solvent hopefully. The properties of the epoxidized aromatic hyperbranched polymers are measured by GPC, FT-IR and viscometer.  相似文献   

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