Synthesis and characterization of stable blue light‐emitting poly(spirobifluorene) derivatives containing alkoxy group

Polymers containing alkoxy‐substituted spirobifluorene have been prepared from nickel(0)‐mediated coupling or palladium‐catalyzed Suzuki coupling. The polymers were characterized using various spectroscopies, such as ¹H‐NMR, FT‐IR, and elemental analysis. The high glass transition temperature and high decomposition temperature suggested that the resulting polymers possessed a high thermal stability. The obtained polymers possessed weight average molecular weight of 4500–33,000 with polydispersity index of 1.1–1.9 and good solubility. The low onsets of the oxidation potential suggested that the polymers containing alkoxy substituted spirobifluorene possessed a good hole injection property. The photoluminescence and electroluminescence of the polymers containing alkoxy substituted spirobifluorene showed stable blue color by suppressing the excimer formation due to intermolecular interaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2316–2324, 2005     

Synthesis of regio- and stereoselective alkoxy-substituted spirobifluorene derivatives for blue light emitting materials

Three new octyloxy substituted spirobifluorenes, 2,7-diphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DPBSBF, 1a), 2,7-dibiphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DBBSBF, 1b) and 2,7-diterphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DTBSBF, 1c) were prepared. All the compounds had been fully characterized by ¹H and ¹³C NMR, UV-Vis, DSC, mass spectrometry and gave satisfactory elemental analyses. They possessed good solubility in common organic solvents and good homogeneous film formation. The optical energy band gap of DBBSBF was 3.27 eV between the HOMO energy level, 5.85 eV, measured by UPS and the LUMO, 2.58 eV, calculated from absorption spectrum. A blue organic light emitting diode (OLED) based on the structure of ITO/TPD (60 nm)/DBBSBF (40 nm)/Alq₃ (20 nm)/LiF (1 nm)/Al (100 nm) showed good performance. The luminance of 3125 cd/m² was observed at a drive voltage of 12.8 V and the colour coordinate in CIE chromaticity was (0.14, 0.12). The external quantum efficiency was obtained to be 2.8% at 100 cd/m².     

Synthesis of amphiphilic poly(para‐phenylene)s by Suzuki polycondensation

1,4‐Dibromobenzenes carrying nonpolar hexoxy and polar oligo(ethylene glycol) side chains were subjected to Suzuki polycondensation with a benzene‐1,4‐bisboronic acid ester to produce high‐molar‐mass poly(para‐phenylene)s. The molar masses were determined with size exclusion chromatography with conventional polystyrene and universal calibration. These novel amphiphilically equipped rigid‐rod polymers have the potential to segregate lengthwise into polar and nonpolar domains, a property that has only rarely been described, and promise to exhibit novel interesting supramolecular properties. The oligo(ethylene gylcol) side chains terminate with a silyl‐protected alcohol group, and its deprotection on the polymer was proven to proceed quantitatively. This not only led to a further polarity increase but allows us to attach even more polar (e.g., charged) units in future projects. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2879–2889, 2003     

Synthesis and properties of new poly(terfluorene) derivatives containing spirobifluorene and electron transport groups for stable blue electroluminescence

We have synthesized three new blue‐emitting poly(terfluorene) derivatives containing spirobifluorene and electron transport groups (quinoline or oxadiazole). The strategy is to connect the monomers via positions 2 and 2′ of spirobifluorene, which significantly restricts the interchain interaction and effectively adjusts the conjugation length. The incorporation of electron‐deficient units (quinoline or oxadiazole) into the positions 7 and 7′ of spirobifluorene tunes the emission band and reduces the lowest unoccupied molecular orbital energy level. Blue electroluminescence with narrow emission was achieved in the devices of ITO/PEDOT/polymer/Ca/Al. The maximum luminances are in the range of 102–235 cd/m² and the maximum photometric efficiencies are in the range of 0.17–0.21 cd/A. All the polymers show good spectral stability, and are promising for use as stable blue‐emitting or electron‐transport/injection materials in polymeric light‐emitting diodes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4517–4529, 2005     

Synthesis,characterization, and electrogenerated chemiluminescence of deep blue emitting eumelanin‐inspired poly(indoylenearylene)s for polymer light emitting diodes

Deep blue emitting copolymers were synthesized by uniting the Eumelanin‐inspired indole core with fluorene and carbazole units via Suzuki polymerization. The resulting polymers, PIF and PIC, showed deep blue emission in the range of 416–418 nm and quantum yields of 0.39–0.60. Both polymers exhibited an intense and stable electrogenerated chemiluminescence. Interestingly, deep HOMO levels of −5.71 and −5.61 eV were observed for PIF and PIC, respectively. Solution processed polymer light emitting diodes (PLEDs) were fabricated using the PIF as a guest. PLEDs emitted deep blue light at 418 nm, with the luminous efficiency peaking at 1 Cd/A, given that the photopic response at that wavelength is 0.0151. The electroluminescence of PIF displayed a Commission Internationale de l'Eclairage coordinates of (0.16, 0.07) with a maximum external quantum efficiency of 1.1%. Hence, these materials prove to be promising candidates for the fabrication of deep blue PLEDs. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 125–131     

Synthesis of high-molecular-weight poly(amide-ester)s by direct polycondensation with diphenyl chlorophosphate

High molecular weight aromatic poly(amide-ester)s were prepared by the direct polycondensation reactions between aromatic dicarboxylic acids and aminophenols under mild conditions in pyridine. The condensing agents examined in this study were diphenyl chlorophosphate (DPCP), DPCP/LiCl, and DPCP/DMF. Addition time of the aminophenols, depending on their nucleophilicities, affected the η_inh values and monomer sequence of the resulting polymer. Their thermal properties were studied in terms of the sequences in the polymer backbones.     

Synthesis of poly(benzoxazinone)s by direct polycondensation of dicarboxylic acids with bis(anthranilic acid)s

A convenient method for the synthesis of poly(benzoxazinone)s of high molecular weights has been developed. These polymers were prepared readily by direct polycondensation of aromatic dicarboxylic acids containing phenyl ether structures with bis(anthranilic acid)s using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensations proceeded smoothly and were completed within several hours at 140°C to produce poly(benzoxazinone)s with inherent viscosities up to 2.6 dL/g. The synthesis of 2-substituted benzoxazinones by the reaction of aromatic carboxylic acids or dicarboxylic acid with anthranilic acid in PPMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(benzoxazinone)s showed 10% weight loss in air and nitrogen around at 440 and 460°C, respectively.     

Synthesis of poly(spiropyran)s by polycondensation and their photoisomerization behaviors

Poly(spiropyran)s were synthesized by polycondensation of a bis(indoline) monomer with bis(o-positioned formyl and hydroxy)-substituted aromatic monomers in alcoholic solvents. The structures of the products and their molecular weights were determined by the ¹H NMR and GPC measurements, respectively. Furthermore, photoisomerization behaviors of the poly(spiropyran)s were analyzed by the UV–Vis and ¹H NMR measurements of their solutions in dichloromethane upon the UV and visible light irradiations.     

Enhancement of color purity in blue light emitting poly(fluorene)s and poly(p‐phenylene)s with 2,6‐distyrylpyridine kinked segments along the backbone

2,6‐bis(4‐Distyrylpyridine) ( 1 ) was synthesized by the condensation of 2,6‐dimethylpyridine with 4‐bromobenzaldehyde. Two new series of soluble random or alternating polyfluorenes ( PF‐Py ) and poly‐p‐phenylenes ( PP‐Py ) with various compositions were prepared by Suzuki coupling utilizing 1 as a comonomer. These polymers showed optical band gaps of 3.00–3.07 eV and photoluminescence (PL) quantum yields in solution of 0.37–0.91 for PF‐Py and 0.29–0.38 for PP‐Py . Polymers PF‐Py emitted blue light with PL maximum at 410–424 nm in solution and 406–428 nm in thin films that was red shifted with increasing distyrylpyridine content. Polymers PP‐Py behaved as blue emitters both in solution and in solid state, with PL maximum at 416–436 nm. The optical properties of these polymers could be tuned by the reversible protonation–deprotonation process of the pyridine ring. The emitted color of the polymers in solution and thin film could be changed continuously between blue and green (PL maximum up to about 520 nm) by exposing the polymers to the acid or base environment. Thin films of PF‐Py displayed excellent color stability with a small red shift of 10 nm but without additional emission band in the long wave region of the spectrum, even after being annealed at high temperature for a long time. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4486–4495, 2005     

Synthesis of high molecular weight poly(ether ketone)s by polycondensation of activated bis(aryl chloride)s with bisphenolates

The ability to achieve high molecular weight poly(ether ketone)s from the polycondensation of bis(aryl chloride)s with bis(phenolate)s has been consistently demonstrated. The polymerizations presented here help to delineate for specific bis(aryl chloride)/bisphenolate pairs the reaction conditions required to obtain high molecular weight polymers. Polycondensation of 1,3-bis(4-chlorobenzoyl)-5-tert-butylbenzene ( 6 ) and 2,2′-bis(4-chlorobenzoyl)-biphenyl ( 15 ) with various bisphenolates as well as of 2,2′-bis(4-hydroxyphenoxy)biphenyl ( 33 ) with 4,4′-dichlorobenzophenone ( 41 ) and 1,3-bis(4-chlorobenzoyl)benzene ( 43 ) were used as representative model systems to select reaction conditions that led to high molecular weight polymers. © 1995 John Wiley & Sons, Inc.     

Poly(2,7-dibenzosilole): a blue light emitting polymer

2,7-Disubstituted dibenzosilole monomers have been prepared by the selective trans-lithiation of 4,4'-dibromo-2,2'-diiodobiphenyl followed by silylation with dichlorodihexylsilane. Suzuki copolymerization of dibromo and bis(boronate) monomers afforded poly(9,9-dihexyl-2,7-dibenzosilole) which showed better efficiency than the corresponding polyfluorene in a single layer light emitting device. Preliminary studies demonstrated this to be a promising blue light emitting polymer.     

The tenth anniversary of Suzuki polycondensation (SPC)

This article describes the successful transfer of the Suzuki cross-coupling (SCC) reaction to polymer synthesis, one of the major developments within the last decade of polymer synthesis. The polymers prepared by Suzuki polycondensation (SPC) and its Ni-catalyzed reductive counterpart are soluble and processable poly(arylene)s that, because of their rigid and conjugated backbones, are of interest for the materials sciences. Achievable molar masses easily compete with those of traditional polyesters and polyamides. This article also provides insight into some synthetic problems associated with the transfer of SCC from low molar mass organic chemistry to high molar mass polymer chemistry by addressing issues such as monomer purity, stoichiometric balance, achievable molar masses, and defects in the polymer structure. Although the emphasis of this article is synthetic and structural issues, some potential applications of the polyarylenes obtained are briefly mentioned. Together with the enormous developments in the areas of metallocene, ring-opening metathesis, and acyclic diene metathesis polymerization, the success of SPC impressingly underlines the increasing importance of transition-metal-catalyzed CC-bond-forming reactions in polymer synthesis. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1533–1556, 2001     

Synthesis and characterization of a soluble blue light emitting alternating copolymer

An alternating copolymer with monomer units of fluorene and phenylenedivinylene was synthesized by reaction between n-hexyl fluorene phosphonium salt and isophthalic aldehyde based on the Wittig reaction. The polymer solution in chloroform was made into a film with a very fine surface by spin-casting on indium-tin oxide (ITO) coated glass to fabricate a light emitting diode (LED) with an aluminum negative electrode. The optical absorption spectrum of the solid film shows a peak at 370 ran while the PL spectrum has the main peak at 560 nm with a secondary peak at 440 nm and the EL spectrum has a single peak at 560 nm showing the Stokes shift of 190 nm. The peak in the PL spectrum shifts to 420 nm with a vibronic structure at 440 nm on either dilution by chloroform or blending with polyvinylcarbazole (PVK). The emissive polymer bulk seemed to generate sites for excimers and molecular aggregates which were diminished on the dilution or blending. The peak in the EL spectrum also shifts to 440 nm on blending of 20% of the copolymer with PVK. Further dilution to 10% of the copolymer shifts the EL peak to 420 nm with the onset potential of 15 V and the highest quantum efficiency of 0.01% in this series. The concentrated channels were developed in the blends with severe phase separation to show a lower onset potential but poor quantum efficiency.     

聚芳亚胺酰胺缩聚工艺条件探索（英文）

聚芳亚胺酰胺(PAIs)是一种新型高性能聚合物.本文作者讨论了卤素单体种类、溶剂、单体浓度、反应温度、催化体系及其添加量等工艺条件对PAIs相对分子质量和相对分子质量分布的影响,得到了钯催化C-N偶联缩聚反应制备高相对分子质量PAIs的最佳条件,为该类聚合物的进一步拓展和应用提供了参考.     

Synthesis of poly(para-phenylenevinylene) rotaxanes by aqueous Suzuki coupling

PPV-based polyrotaxanes have been prepared by coupling vinyl boronic acids to aryl iodides in the presence of cyclodextrins, and the crystal structure of a [2]rotaxane of this type has been determined.     

A pure blue light emitting binaphthyl derivative：Synthesis and properties

A binaphthyl derivative with pyrene on 3 and 3＇ positions was synthesized and characterized via Suzuki coupling reaction. Emission maximum in solution was located at 390 nm with a quantum efficiency of 68% by taking 9,10-diphenyl anthracene as reference,while it is shifted to 450 nm with FWHM of 104 nm resulting from aggregation state in solid film.Glass transition temperature（Tg）and decomposition temperature were measured to be 184 and 447℃,respectively,by DSC and TGA.Unlike its photoluminescence spectrum,electroluminescent spectrum peaked at about 460 nm and shows a FWHM of 69 nm corresponding to a pure blue emission.The turn-on voltage,luminance and efficiency maximum were 5 V,2953 cd/m^2 and 1.37cd/A with CIE color coordinate of（0.16,0.15）,in the device structure of ITO/NPB（40nm）/PY-BN-PY（15nm）/BPhen（40nm）/Mg：Ag.     

Toward stable interfaces in conjugated polymers: microporous poly(p-phenylene) and poly(phenyleneethynylene) based on a spirobifluorene building block

Conjugated polymer networks based on spirobifluorene building units exhibit defined photoluminescence as well as pronounced microporosity, that is, large, stable interfaces.     

Synthesis of poly(ester amide)s by the melt polycondensation of semiaromatic polyesters with ethanolamine and their characterization

Semiaromatic poly(ester amide)s (PEAs) were synthesized by the melt polycondensation of ethanolamine (EA) derivatives with dimethyl terephthalate and ethylene glycol in the presence of tetrabutyl titanate as a catalyst, and their crystallization and thermal properties were investigated. The introduction of an amide group into a semiaromatic polyester such as poly(ethylene terephthalate) (PET) produced PEAs (EA-modified PET polymers) with an increase in the melting point. However, these PEAs were found to decompose at a lower temperature than PET on the basis of TGA. Moreover, direct pyrolysis/mass spectrometry measurements suggested that an initial step of the thermal decomposition was a β-CH hydrogen-transfer reaction via asix-member ring transition state at the ester–ethylene–amide unit, at which carbon–oxygen bond scission took place to yield carboxyl and N-vinylamide end groups. Furthermore, molecular orbital calculations using trimer models bis[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]terephthalate, N-[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]-4-[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyloxycarbonyl]benzamide, and N,N′-bis[2-[[4-(methoxycarbonyl)benzoyl]oxy]ethyl]terephthalamide strongly supported the idea that the β-CH hydrogen-transfer reaction in the thermal decomposition of PEAs might occur more easily at the methylene group next to the amide group in an ester–ethylene–amide unit rather than at the methylene group next to the ester group in an ester–ethylene–ester unit. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2184–2193, 2007