Synthesis of optically active poly(N‐propargylsulfamides) with helical conformation

A novel chiral N‐propargylsulfamide monomer ( 1a ) and its enantiomer ( 1b ) were synthesized and polymerized with (nbd)Rh⁺B^?(C₆H₅)₄ as a catalyst providing poly(1) (poly( 1a ) and poly( 1b )) in high yields (≥99%). Poly(1) could take stable helices in less polar solvents (chloroform and THF), demonstrated by strong circular dichroism signals and UV–vis absorption peaks at about 415 nm and the large specific rotations; but in more polar solvents including DMF and DMSO, poly(1) failed to form helix. Quantitative evaluation with anisotropy factor showed that the helical screw sense had a relatively high thermal stability. These results together with the IR spectra measured in solvents showed that hydrogen bonding between the neighboring sulfamide groups is one of the main driving forces for poly(1) to adopt stable helices. In addition, copolymerization of monomer 1a and monomer 2 was conducted, the solubility of poly(1) was improved drastically. However, the copolymerization had adverse effects on the formation of stable helices in the copolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 500–508, 2007     

Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007     

Synthesis and nuclear magnetic resonance analysis of starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers

A new biodegradable starch graft copolymer, starch‐g‐poly(1,4‐dioxan‐2‐one), was synthesized through the ring‐opening graft polymerization of 1,4‐dioxan‐2‐one onto a starch backbone. The grafting reactions were conducted with various 1,4‐dioxan‐2‐one/starch feed ratios to obtain starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers with various poly(1,4‐dioxan‐2‐one) graft structures. The microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was characterized in detail with one‐ and two‐dimensional NMR spectroscopy. The effect of the feed composition on the resulting microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3417–3422, 2004     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Synthesis and light emitting properties of polyacetylenes having pendent fluorene groups

Five novel fluorene‐containing polymers, poly[(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA1 ), poly[(1‐pentyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene) ( PFA2 ), poly[1‐decyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA3 ), poly[1‐phenyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA4 ), and poly[1‐(3,4‐difluorophenyl)‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA5 ) were synthesized by the polymerization of the corresponding fluorene‐substituted acetylenic monomers ( M1–M5), using WCl₆, MoCl_5, and TaCl₅ as catalysts and n‐Bu₄Sn as a cocatalyst. The synthesized polymers were thermally stable and readily soluble in common organic solvents. The degradation temperatures for a 5% weight loss of the polymers were ∼352–503 °C under nitrogen. PFA1–PFA5 show emission peaks from 402 to 590 nm. Besides, their electroluminescent properties were studied in heterostructure light‐emitting diodes (LEDs), using PFA2–PFA5 as an emitting layer. The PFA5 device revealed an orange‐red emission peak at 602 nm with a maximum luminescence of 923 cd/m² at 8 V. A device with the ITO/PEDOT/ a mixture of PFA2 (98 wt %) and PFA5 (2 wt %)/Ca/Al showed near white emission. Its maximum luminance and current efficiency are 450 cd/m² at 15 V and 1.3 cd/A, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 519–531, 2006     

Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds

Crosslinked polymeric materials, which exhibit thermal remendability and removability through Diels–Alder (DA) and retro‐DA reactions, were obtained from using multifunctional maleimide and furan compounds as monomers. The synthesized monomers possess low melting points and good solubility in organo solvents to show excellent processing properties. The performance of DA and retro‐DA reactions were demonstrated with DSC and FTIR measurements. High performance of thermal remendablility and removability of the crosslinked materials were observed with SEM and solvent tests. These materials were applicable in advanced encapsulants and structural materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 905–913, 2006     

Highly soluble and optically transparent poly (ether imide)s based on 2,6‐ or 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and aromatic bis(ether amine)s bearing trifluoromethyl groups

Two series of novel fluorinated poly(ether imide)s (coded IIIA and IIIB ) were prepared from 2,6‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride, respectively, with various trifluoromethyl‐substituted aromatic bis(ether amine)s by a standard two‐step process with thermal or chemical imidization of the poly(amic acid) precursors. These fluorinated poly(ether imide)s showed good solubility in many organic solvents and could be solution‐cast into transparent, flexible, and tough films. These films were nearly colorless, with an ultraviolet–visible absorption edge of 364–386 nm. They also showed good thermal stability with glass‐transition temperatures of 221–298 °C, 10% weight loss temperatures in excess of 489 °C, and char yields at 800 °C in nitrogen greater than 50%. The 2,7‐substituted IIIB series also showed better solubility and higher transparency than the isomeric 2,6‐substituted IIIA series. In comparison with nonfluorinated poly (ether imide)s, the fluorinated IIIA and IIIB series showed better solubility, higher transparency, and lower dielectric constants and water absorption. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5909–5922, 2006     

Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Synthesis of TiO2–SiO2/polymer core–shell microspheres with a microphase‐inversion method

A novel microphase‐inversion method was proposed for the preparation of TiO₂–SiO₂/poly(methyl methacrylate) core–shell nanocomposite particles. The inorganic–polymer nanocomposites were first synthesized via a free‐radical copolymerization in a tetrahydrofuran solution, and the poor solvent was added slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles. The average particle sizes of the microspheres ranged from 70 to 1000 nm, depending on the reaction conditions. Transmission electron microscopy and scanning electron microscopy indicated a core–shell morphology for the obtained microspheres. Thermogravimetric analysis and X‐ray photoelectron spectroscopy measurements confirmed that the surface of the nanocomposite microspheres was polymer‐rich, and this was consistent with the core–shell morphology. The influence of the synthetic conditions, such as the inorganic composition and the content of the crosslinking monomer, on the particle properties was studied in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3911–3920, 2006     

Divinylsiloxane‐bisbenzocyclobutene‐based polymer modified with polystyrene–polybutadiene–polystyrene triblock copolymers

Divinylsiloxane‐bisbenzocyclobutene (DVS‐bisBCB) polymer has very low dielectric constant and dissipation factor, good thermal stability, and high chemical resistance. The fracture toughness of the thermoset polymer is moderate due to its high crosslink density. A thermoplastic elastomer, polystyrene–polybutadiene–polystyrene triblock copolymer, was incorporated into the matrix to enhance its toughness. The cured thermoset matrix showed different morphology when the elastomer was added to the B‐staged prepolymer or when the elastomer was B‐staged with the DVS‐bisBCB monomer. Small and uniformly distributed elastomer domains were detected by transmission electron micrographs (TEM) in the former case, but TEM did not detect a separate domain in the latter case. A high percentage of the polystyrene–polybutadiene–polystyrene triblock copolymer could be incorporated into the DVS‐bisBCB thermoset matrix by B‐staging the triblock copolymer with the BCB monomer. The elastomer increased the fracture toughness of DVS‐bisBCB polymer as indicated by enhanced elongation at break and increased K1c values obtained by the modified edge‐lift‐off test. Elastomer modified DVS‐bisBCB maintained excellent electrical properties, high T_g and good thermal stability, but showed higher coefficient of linear thermal expansion values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1591–1599, 2006