Distribution by Scientific Domains

Kinds of Homopolymer

  • corresponding homopolymer

  • Selected Abstracts

    Thermodynamics of Phase Behavior in PEO/P(EO- b -DMS) Homopolymer and Block Co-Oligomer Mixtures under Pressure

    Shichun Jiang
    Abstract The cloud-point temperatures (Tcl's) of poly(ethylene oxide) (PEO) and poly(ethylene oxide)- block -polydimethylsiloxane (P(EO- b -DMS)) homopolymer and block-oligomer mixtures were determined by turbidity measurements over a range of temperatures (105 to 130,C), pressures (1 to 800 bar), and compositions (10,40 wt.-% PEO). The system phase separates upon cooling and Tcl was found to decrease with an increase in pressure for a constant composition. In the absence of special effects, this finding indicates negative excess volumes. Special attention was paid to the demixing temperatures as a function of the pressure for the different polymer mixtures and the plots in the T - , plane (where , signifies volume fractions). The cloud-point curves of the polymer mixture under pressures were observed for different compositions. The Sanchez-Lacombe (SL) lattice fluid theory was used to calculate the spinodals, the binodals, the Flory-Huggins (FH) interaction parameter, the enthalpy of mixing, and the volume changes of mixing. The calculated results show that modified P(EO- b -DMS) scaling parameters with the new combining rules can describe the thermodynamics of the PEO/P(EO- b -DMS) system well with the SL theory. Cloud point curves for various PEO/P(EO- b -DMS) polymer mixtures at various pressures on the T - ,PEO plane. [source]

    Scale-up development of high-performance polymer matrix for DNA sequencing analysis

    ELECTROPHORESIS, Issue 19 2006
    Fen Wan
    Abstract Linear polyacrylamide (LPA) has been widely used as a replaceable separation matrix in CE. An increase in the molecular weight of the separation medium favors the separation of larger DNA fragments. In order to obtain ultrahigh-molecular-weight (UHMW) LPA, a "frozen" method was developed to synthesize the LPA homopolymer. This approach has three major advantages when compared with other existing routes of LPA synthesis: (i),long LPA chains could be obtained easily, with their average molecular weight (MW) being in the high 10,MDa range; (ii),the desired MW could be adjusted over a broad range by controlling the temperature and the concentration of initiators during synthesis; (iii),the product solution contains only a tiny amount of impurity besides the solvent and LPA. Both static and dynamic laser light scattering measurements were carried out to characterize the synthesized LPA in the buffer solution. The DNA sequencing matrix prepared from LPA using this method was studied and the results were compared with the newly developed commercial product POP7 from Applied Biosystems. It should be noted that this approach can be applied to synthesize other water-soluble polymers, resulting in UHMW products because the chain transfer constant is smaller at lower temperatures. [source]

    Conjugated Polymer Based on Polycyclic Aromatics for Bulk Heterojunction Organic Solar Cells: A Case Study of Quadrathienonaphthalene Polymers with 2% Efficiency

    Shengqiang Xiao
    Abstract Polycyclic aromatics offer great flexibility in tuning the energy levels and bandgaps of resulting conjugated polymers. These features have been exploited in the recent examples of benzo[2,1- b:3,4- b']dithiophene (BDT)-based polymers for bulk heterojunction (BHJ) photovoltaics (ACS Appl. Mater. Interfaces2009, 1, 1613). Taking one step further, a simple oxidative photocyclization is used here to convert the BDT with two pendent thiophene units into an enlarged planar polycyclic aromatic ring,quadrathienonaphthalene (QTN). The reduced steric hindrance and more planar structure promotes the intermolecular interaction of QTN- based polymers, leading to increased hole mobility in related polymers. As-synthesized homopolymer (HMPQTN) and donor,acceptor polymer (PQTN - BT) maintain a low highest occupied molecular orbital (HOMO) energy level, ascribable to the polycyclic aromatic (QTN) moiety, which leads to a good open-circuit voltage in BHJ devices of these polymers blended with PCBM ([6,6]-phenyl-C61 -butyric acid methyl ester; HMPQTN: 0.76,V, PQTN - BT: 0.72,V). The donor,acceptor polymer (PQTN - BT) has a smaller optical bandgap (1.6,eV) than that of HMPQTN (2.0,eV), which explains its current (5.69,mA,cm,2) being slightly higher than that of HMPQTN (5.02,mA,cm,2). Overall efficiencies over 2% are achieved for BHJ devices fabricated from either polymer with PCBM as the acceptor. [source]

    B,Z DNA Transition Triggered by a Cationic Comb-Type Copolymer

    Naohiko Shimada
    Abstract The conformational transition from right-handed B,DNA to left-handed Z,DNA,the B,Z transition,has received increased attention recently because of its potential roles in biological systems and its applicability to bionanotechnology. Though the B,Z transition of poly(dG,dC),,poly(dG,dC) is inducible under high salt concentration conditions (over 4,M NaCl) or by addition of multivalent cations, such as hexaamminecobalt(III), no cationic polymer were known to induce the transition. In this study, it is shown by circular dichroism and UV spectroscopy that the cationic comb-type copolymer, poly(L -lysine)- graft -dextran, but not poly(L -lysine) homopolymer or a basic peptide, induces the B,Z transition of poly(dG,dC),,poly(dG,dC). At a cationic amino group concentration of 10,4,M the copolymer stabilizes Z,DNA. The transition pathway from the B to the Z form is different to that observed previously. We speculate that the cationic backbone of the copolymer, which reduces electrostatic repulsion among DNA phosphate groups, and the hydrophilic dextran chains, which reduce activity of water, cooperate to induce the B,Z transition. The copolymer specifically modified the micro-environment around DNA molecules to induce Z,DNA formation through stable and spontaneous inter-polyelectrolyte complex formation. [source]

    Perpendicularly Aligned, Size-and Spacing-Controlled Nanocylinders by Molecular-Weight Adjustment of a Homopolymer Blended in an Asymmetric Triblock Copolymer

    U. Ahn
    Abstract Perpendicularly arrayed and size-controlled nanocylinders have been prepared by simply blending an asymmetric polystyrene- block -polyisoprene- block -polystyrene triblock copolymer with polystyrene (the minority component) homopolymers of different molecular weights. The preference for perpendicular orientation or hexagonal ordering of the nanocylinders over a large area in the asymmetric block copolymer can be controlled by adjusting the molecular weight of the blended homopolymer, and the perfection of hexagonal ordering of the perpendicular cylinders can be tuned by using a substrate whose surface tension is much different from that of the majority component of the block copolymer. Such highly controlled nanostructured block-copolymer materials, which have been obtained by a simple method independent of film thickness and interfacial tension between the blocks and the substrates, have wide-ranging commercial potential, e.g., for use in membranes and nanotemplates with size-tunable pores, bandgap-controlled photonic crystals, and other nanotechnological fields demanding a specific nanosize and nanomorphology. [source]

    Cover Picture: Structural Modifications to Polystyrene via Self-Assembling Molecules (Adv. Funct.

    Abstract The cover shows tensile failure of a sample of pure polystyrene (left), and a polystyrene sample with greater impact strength containing 1% by weight of dispersed nanoribbons (right), as reported in work by Stupp and co-workers on p.,487. The nanoribbons are formed by self-assembly of molecules known as dendron rodcoils (DRCs) in styrene monomer, resulting in the formation of a gel. This gel can then be polymerized thermally. We have previously reported that small quantities of self-assembling molecules known as dendron rodcoils (DRCs) can be used as supramolecular additives to modify the properties of polystyrene (PS). These molecules spontaneously assemble into supramolecular nanoribbons that can be incorporated into bulk PS in such a way that the orientation of the polymer is significantly enhanced when mechanically drawn above the glass-transition temperature. In the current study, we more closely evaluate the structural role of the DRC nanoribbons in PS by investigating the mechanical properties and deformation microstructures of polymers modified by self-assembly. In comparision to PS homopolymer, PS containing small amounts (,,1.0,wt.-%) of self-assembling DRC molecules exhibit greater Charpy impact strengths in double-notch four-point bending and significantly greater elongations to failure in uniaxial tension at 250,% prestrain. Although the DRC-modified polymer shows significantly smaller elongations to failure at 1000,% prestrain, both low- and high-prestrain specimens maintain tensile strengths that are comparable to those of the homopolymer. The improved toughness and ductility of DRC-modified PS appears to be related to the increased stress whitening and craze density that was observed near fracture surfaces. However, the mechanism by which the self-assembling DRC molecules toughen PS is different from that of conventional additives. These molecules assemble into supramolecular nanoribbons that enhance polymer orientation, which in turn modifies crazing patterns and improves impact strength and ductility. [source]

    Preparation of novel polyindene/polyoxymethylene blends and investigation of their properties

    Tenzile Zilhan Cabuk
    Abstract In this study, the conducting homopolymer of indene was synthesized by a chemical polymerization method in a nonaqueous medium, and polyindene (PIn)/polyoxymethylene (POM) blends were prepared. The physical, chemical, thermal, and spectral properties of the synthesized homopolymer and their blends were investigated. The conductivities of PIn and the PIn/POM blends were measured with a four-probe technique. The conductivity of PIn was determined as 1.16 10,5 S/cm, whereas the conductivities of the PIn/POM blends were determined to be in the range 3.16 10,6 to 9.8 10,6 S/cm. From Gouy scale magnetic susceptibility measurements, we found that PIn and the PIn/POM blends had polaron natures. The amount of Fe (milligrams per gram) in the PIn and PIn/POM structures were determined by inductively coupled plasma,optic emission spectrometry. Fourier transform infrared spectra were taken to analyze the structural properties of PIn and the PIn/POM blends. The thermal properties of PIn and PIn/POM blends were investigated with thermogravimetric analysis and differential scanning calorimetry analyses, and we found that they showed adequate thermal stability. According to the initial decomposition temperature among the blends, the blend including 16% PIn had the highest decomposition temperature with 244C. The morphological structures of the PIn, POM, and blends were clarified with scanning electron microscopy. 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source]

    Preparation and properties of organic,inorganic hybrid composites based on polystyrene and an incompletely condensed polyvinylsilsesquioxane oligomer

    Zhen Dai
    Abstract An incompletely condensed polyvinylsilsesquioxane (PVSQ) oligomer containing abundant silanol groups was synthesized and characterized by FTIR, 1H-NMR, 29Si-NMR, and MALDI-TOF-MS. Polystyrene/polyvinylsilsesquioxane (PS/PVSQ) hybrid composites were prepared by an in situ bulk polymerization. The hybrid composites showed higher Tg, Td, and char yield than PS homopolymer and without mechanical loss. The improvements in the properties of PS/PVSQ hybrid composites can be ascribed to the crosslinking function of PVSQ by silanol condensation in later processing. The hybrids showed different morphology from discrete microstructure to continuous network depending on the concentration of PVSQ. Because of the surface enrichment, a PVSQ protection layer was formed, which made the hybrid surface more hydrophobic. The structure and the reaction mechanism of PS/PVSQ hybrid composites were also investigated. 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source]

    Modification of cellulose acetate with oligomeric polycaprolactone by reactive processing: Efficiency, compatibility, and properties

    Szilvia Klbert
    Abstract Oligomeric polycaprolactone (oPCL) was used for the modification of cellulose acetate by reactive processing in an internal mixer at 180C, 50 rpm, 60 min reaction time, and 45 wt % caprolactone (CL) content. The product of the reaction was characterized by several analytical techniques and its mechanical properties were determined by dynamic mechanical thermal analysis and tensile testing. The synthesized oPCL contained small and large molecular weight components. The small molecular weight fraction plasticized cellulose acetate externally and helped fusion. Although composition and structure did not differ considerably from each other when CL monomer or polycaprolactone oligomer was used for modification, the grafting of a few long chains had considerable effect on some properties of the product. The large molecular weight chains attached to CA increased the viscosity of the melt considerably and resulted in larger deformability. oPCL homopolymer is not miscible with cellulose acetate and migrates to the surface of the polymer. Exuded polycaprolactone oligomers crystallize on the surface but can be removed very easily. More intense conditions may favor the grafting of long chains leading to polymers with advantageous properties. 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source]

    Raman spectroscopy for spinline crystallinity measurements.


    Abstract Online Raman spectra, obtained at different points along the spinline during the melt spinning of polypropylene homopolymer (hPP) fibers, are presented. The percentage crystallinity corresponding to each spectrum was determined from the normalized intensity of the 809-cm,1 Raman band. A calibration curve for propylene crystallinity was established offline with compression-molded films and fibers spun under different processing conditions. Several hPPs and propylene,ethylene copolymers (with 5,15% ethylene) were used to cover a wide calibration range for propylene crystallinity (9.5,60.9%) with an R2 value of 0.989. This calibration curve was subsequently used to predict the polypropylene crystallinity in the spinline as a function of distance from the spinneret. Under identical conditions of quench and throughput, at a fixed point along the spinline, the overall crystallinity developed in the fiber was found to increase with an increase in the spinning speed. As the spinning speed increased, the point of the onset of crystallization moved closer to the spinneret. The rise in crystallinity was more gradual, at 750 m/min as opposed to 1500 m/min. Increasing the throughput at constant spinning speed was found to decrease the rate of crystallization because of a decrease in the spinline stress. At a fixed distance from the spinneret under identical conditions of quench and spinning speed, fibers spun at a higher throughput showed less overall crystallinity. The onset and rate of crystallization was found to be faster in the lower melt index H502-25RG resin as compared to the 5D49 resin under the spinning conditions explored. The experimental data presented here were used to validate fundamental fiber-spinning models (see part II of this series of articles). The validated models and experimental observations can be used to guide the fiber spinning of isotactic polypropylene for rapid product development. 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source]

    Water sorption kinetics in light-cured poly-HEMA and poly(HEMA- co -TEGDMA); determination of the self-diffusion coefficient by new iterative methods

    Irini D. Sideridou
    Abstract The present investigation is concerned with the determination of self-diffusion coefficient (D) of water in methacrylate-based biomaterials following Fickian sorption by two new methods: the Iterative and the Graphical methods. The D value is traditionally determined by means of the initial slope of the corresponding sorption curve and the so-called Stefan's approximation. The proposed methods using equations without approximations and data resulting from the whole sorption range reach to accurate values of D, even when the sorption curve does not present an initial linear portion. In addition to D, the Graphical method allows the extrapolation of the mass of the sorbed water at equilibrium (M,), even when the equilibrium specimen's mass fluctuates around its limited value (m,). The test of the proposed procedures by means of ideal and Monte Carlo simulated data revealed that these methods are fairly applicable. The obtained D values compared with those determined by means of the Stephan's method revealed that the proposed methods provide more accurate results. Finally, the proposed methods were successfully applied to the experimental determination of the diffusion coefficient of water (50C) in the homopolymer of 2-hydroxyethyl methacrylate (HEMA) and in the copolymer of HEMA with triethylene glycol dimethacrylate (98/2 mol/mol). These polymers were prepared by light curing (, = 470 nm) at room temperature in presence of camphorquinone and N,N -dimethylaminoethyl methacrylate as initiator. 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source]

    Inverse Monte Carlo procedure for conformation determination of macromolecules

    Mark Bathe
    Abstract A novel numerical method for determining the conformational structure of macromolecules is applied to idealized biomacromolecules in solution. The method computes effective inter-residue interaction potentials solely from the corresponding radial distribution functions, such as would be obtained from experimental data. The interaction potentials generate conformational ensembles that reproduce thermodynamic properties of the macromolecule (mean energy and heat capacity) in addition to the target radial distribution functions. As an evaluation of its utility in structure determination, we apply the method to a homopolymer and a heteropolymer model of a three-helix bundle protein [Zhou, Y.; Karplus, M. Proc Natl Acad Sci USA 1997, 94, 14429; Zhou, Y. et al. J Chem Phys 1997, 107, 10691] at various thermodynamic state points, including the ordered globule, disordered globule, and random coil states. 2003 Wiley Periodicals, Inc. J Comput Chem 24: 876,890, 2003 [source]

    A novel aromatic,aliphatic copolyester consisting of poly(1,4-dioxan-2-one) and poly(ethylene- co -1,6-hexene terephthalate): Preparation, thermal, and mechanical properties

    Jie Gong
    Abstract A novel multiblock aromatic,aliphatic copolyester poly(ethylene- co -1,6-hexene terephthalate)-copoly(1,4-dioxan-2-one) (PEHT-PPDO) was successfully synthesized via the chain-extension reaction of dihydroxyl teminated poly(ethylene- co -hexane terephthalate) (PEHT-OH) with dihydroxyl teminated poly(1,4-dioxan-2-one) (PPDO-OH) prepolymers, using toluene-2,4-diisocyanate as a chain extender. To produce PEHT-OH prepolymer with an appropriate melting point which can match the reaction temperature of PEHT-OH prepolymer with PPDO-OH prepolymer, 1,6-hexanediol was used to disturb the regularity of poly(ethylene terephthalate) segments. The chemical structures and molecular weights of PEHT-PPDO copolymers were characterized by 1H NMR, FTIR, and GPC. The DSC data showed that PPDO-OH segments were miscible well with PEHT-OH segments in amorphous state and that the crystallization of copolyester was predominantly contributed by PPDO segments. The TGA results indicated that the thermal stability of PEHT-PPDO was improved comparing with PPDO homopolymer. The novel aromatic,aliphatic copolyesters have good mechanical properties and could find applications in the field of biodegradable polymer materials. 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2828,2837, 2010 [source]

    Well-defined amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbone and hydrophobic poly(vinyl acetate) side chains

    Yaogong Li
    Abstract A series of well-defined amphiphilic graft copolymers containing hydrophilic poly(acrylic acid) (PAA) backbone and hydrophobic poly(vinyl acetate) (PVAc) side chains were synthesized via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization followed by selective hydrolysis of poly(tert -butyl acrylate) backbone. A new Br-containing acrylate monomer, tert -butyl 2-((2-bromopropanoyloxy)methyl) acrylate, was first prepared, which can be polymerized via RAFT in a controlled way to obtain a well-defined homopolymer with narrow molecular weight distribution (Mw/Mn = 1.08). This homopolymer was transformed into xanthate-functionalized macromolecular chain transfer agent by reacting with o -ethyl xanthic acid potassium salt. Grafting-from strategy was employed to synthesize PtBA- g -PVAc well-defined graft copolymers with narrow molecular weight distributions (Mw/Mn < 1.40) via RAFT of vinyl acetate using macromolecular chain transfer agent. The final PAA- g -PVAc amphiphilic graft copolymers were obtained by selective acidic hydrolysis of PtBA backbone in acidic environment without affecting the side chains. The critical micelle concentrations in aqueous media were determined by fluorescence probe technique. The micelle morphologies were found to be spheres. 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6032,6043, 2009 [source]

    Determination of block size in poly(ethylene oxide)- b -polystyrene block copolymers by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

    Marion Girod
    Abstract Characterization of block size in poly(ethylene oxide)- b -poly(styrene) (PEO- b -PS) block copolymers could be achieved by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) after scission of the macromolecules into their constituent blocks. The performed hydrolytic cleavage was demonstrated to specifically occur on the targeted ester function in the junction group, yielding two homopolymers consisting of the constitutive initial blocks. This approach allows the use of well-established MALDI protocols for a complete copolymer characterization while circumventing difficulties inherent to amphiphilic macromolecule ionization. Although the labile end-group in PS homopolymer was modified by the MALDI process, PS block size could be determined from MS data since polymer chains were shown to remain intact during ionization. This methodology has been validated for a PEO- b -PS sample series, with two PEO of number average molecular weight (Mn) of 2000 and 5000 g mol,1 and Mn(PS) ranging from 4000 to 21,000 g mol,1. Weight average molecular weight (Mw), and thus polydispersity index, could also be reached for each segment and were consistent with values obtained by size exclusion chromatography. This approach is particularly valuable in the case of amphiphilic copolymers for which Mn values as determined by liquid state nuclear magnetic resonance might be affected by micelle formation. 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3380,3390, 2009 [source]

    Novel temperature- and pH-responsive graft copolymers composed of poly(L -glutamic acid) and poly(N -isopropylacrylamide)

    Chaoliang He
    Abstract A series of novel temperature- and pH-responsive graft copolymers, poly(L -glutamic acid)- g -poly(N -isopropylacrylamide), were synthesized by coupling amino-semitelechelic poly(N -isopropylacrylamide) with N -hydroxysuccinimide-activated poly(L -glutamic acid). The graft copolymers and their precursors were characterized, by ESI-FTICR Mass Spectrum, intrinsic viscosity measurements and proton nuclear magnetic resonance (1H NMR). The phase-transition and aggregation behaviors of the graft copolymers in aqueous solutions were investigated by the turbidity measurements and dynamic laser scattering. The solution behavior of the copolymers showed dependence on both temperature and pH. The cloud point (CP) of the copolymer solution at pH 5.0,7.4 was slightly higher than that of the solution of the PNIPAM homopolymer because of the hydrophilic nature of the poly(glutamic acid) (PGA) backbone. The CP markedly decreased when the pH was lowered from 5 to 4.2, caused by the decrease in hydrophilicity of the PGA backbone. At a temperature above the lower critical solution temperature of the PNIPAM chain, the copolymers formed amphiphilic core-shell aggregates at pH 4.5,7.4 and the particle size was reduced with decreasing pH. In contrast, larger hydrophobic aggregates were formed at pH 4.2. 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4140,4150, 2008 [source]

    Synthesis and optical properties of blue luminescent poly(2,6-naphthalene)s

    Takeshi Mori
    Blue luminescent 2,6-naphthalene-based homopolymer and copolymers were synthesized by Yamamoto method using Ni(cod)2 and Pd-catalyzed Suzuki coupling, respectively. Two kinds of substituents, an electron rich 3,6,9-trioxaundecyloxy (a) and a bulky 2-isopropyl-5-methylhexyloxy (b), significantly suppressed excimeric emissions of polynaphthalenes in film states, which achieved pure blue photoluminescence. [source]

    Simultaneous reversible addition fragmentation chain transfer and ring-opening polymerization

    Maude Le Hellaye
    Abstract The simultaneous ring-opening polymerization (ROP) of ,-caprolactone (,-CL) and 2-hydroxyethyl methacrylate (HEMA) polymerization via reversible addition fragmentation chain transfer (RAFT) chemistry and the possible access to graft copolymers with degradable and nondegradable segments is investigated. HEMA and ,-CL are reacted in the presence of cyanoisopropyl dithiobenzoate (CPDB) and tin(II) 2-ethylhexanoate (Sn(Oct)2) under typical ROP conditions (T > 100 C) using toluene as the solvent in order to lead to the graft copolymer PHEMA- g -PCL. Graft copolymer formation is evidenced by a combination of size-exclusion chromatography (SEC) and NMR analyses as well as confirmed by the hydrolysis of the PCL segments of the copolymer. With targeted copolymers containing at least 10% weight of PHEMA and relatively small PHEMA backbones (ca. 5,000,10,000 g mol,1) the copolymer grafting density is higher than 90%. The ratio of free HEMA-PCL homopolymer produced during the "one-step" process was found to depend on the HEMA concentration, as well as the half-life time of the radical initiator used. 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3058,3067, 2008 [source]

    Preparation, characterization, and chiral recognition of optically active polymers containing pendent chiral units via reversible addition-fragmentation chain transfer polymerization

    Jian Wang
    Abstract Optically active polymers bearing chiral units at the side chain were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of 2,2,-azobisisobutyronitrile (AIBN)/benzyl dithiobenzoate (BDB), using a synthesized 6- O - p -vinylbenzyl-1,2:3,4-Di- O -isopropylidene- D -galactopyranose (VBPG) as the monomer. The experimental results suggested that the polymerization of the monomer proceeded in a living fashion, providing chiral group polymers with narrow molecular weight distributions. The optically active nature of the obtained poly (6- O - p -vinylbenzyl-1,2:3,4-Di- O -isopropylidene- D -galactopyranose) (PVBPG) was studied by investigating the dependence of specific rotation on the molecular weight of PVBPG and the concentration of PVBPG in tetrahydrofuran (THF). The results showed the specific rotation of PVBPG increased greatly with the decrease of the concentration of the PVBPG homopolymer. In addition, the effect of block copolymers of PVBPG on the optically active nature was also investigated by preparing a series of diblock copolymers of poly(methyl methacrylate) (PMMA)- b -PVBPG, polystyrene (PS)- b -PVBPG, and poly(methyl acrylate) (PMA)- b -PVBPG. It was found that both the homopolymer and the diblock copolymers possessed specific rotations. Finally, the ability of chiral recognition of the PVBPG homopolymer was investigated via an enantiomer-selective adsorption experiment. 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3788,3797, 2007 [source]

    Poly(triarylamine): Its synthesis, properties, and blend with polyfluorene for white-light electroluminescence

    Hung-Yi Lin
    Abstract A new high-molecular-weight poly(triarylamine), poly[di(1-naphthyl)-4-anisylamine] (PDNAA), was successfully synthesized by oxidative coupling polymerization from di(1-naphthyl)-4-anisylamine (DNAA) with FeCl3 as an oxidant. PDNAA was readily soluble in common organic solvents and could be processed into freestanding films with high thermal decomposition and softening temperatures. Cyclic voltammograms of DNAA and PDNAA exhibited reversible oxidative redox couples at the potentials of 0.85 and 0.85 V, respectively, because of the oxidation of the main-chain triarylamine unit. This suggested that PDNAA is a hole-transporting material with an estimated HOMO level of 5.19 eV. The absorption maximum of a PDNAA film appeared at 370 nm, with an estimated band gap of 2.86 eV from the absorption edge. Unusual multiple photoluminescence maxima were observed at 546 nm, and this suggested its potential application in white-light-emission devices. Nearly white-light-emission devices could be obtained with either a bilayer-structure approach {indium tin oxide/poly(ethylenedioxythiophene):poly(styrene sulfonate)/PDNAA/poly[2,7-(9,9-dihexylfluorene)] (PF)/Ca} or a polymer-blend approach (PF/PDNAA = 95:5). The luminance yield and maximum external quantum efficiency of the light-emitting diode with the PF/PDNAA blend as the emissive layer were 1.29 cd/A and 0.71%, respectively, and were significantly higher than those of the homopolymer. This study suggests that the PDNAA is a versatile material for electronic and optoelectronic applications. 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1727,1736, 2007 [source]

    Preparation and characterization of poly(butylene terephthalate)/poly(ethylene terephthalate) copolymers via solid-state and melt polymerization

    M. A. G. Jansen
    Abstract To increase the Tg in combination with a retained crystallization rate, bis(2-hydroxyethyl)terephthalate (BHET) was incorporated into poly(butylene terephthalate) (PBT) via solid-state copolymerization (SSP). The incorporated BHET fraction depends on the miscibility of BHET in the amorphous phase of PBT prior to SSP. DSC measurements showed that BHET is only partially miscible. During SSP, the miscible BHET fraction reacts via transesterification reactions with the mobile amorphous PBT segments. The immiscible BHET fraction reacts by self-condensation, resulting in the formation of poly(ethylene terephthalate) (PET) homopolymer. 1H-NMR sequence distribution analysis showed that self-condensation of BHET proceeded faster than the transesterification with PBT. SAXS measurements showed an increase in the long period with increasing fraction BHET present in the mixtures used for SSP followed by a decrease due to the formation of small PET crystals. DSC confirmed the presence of separate PET crystals. Furthermore, the incorporation of BHET via SSP resulted in PBT-PET copolymers with an increased Tg compared to PBT. However, these copolymers showed a poorer crystallization behavior. The modified copolymer chain segments are apparently fully miscible with the unmodified PBT chains in the molten state. Consequently, the crystal growth process is retarded resulting in a decreased crystallization rate and crystallinity. 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 882,899, 2007. [source]

    Latices of poly(fluoroalkyl mathacrylate)- b -poly(butyl methacrylate) copolymers prepared via reversible addition,fragmentation chain transfer polymerization

    Xiaodong Zhou
    Abstract Poly(fluoroalkyl mathacrylate)- block -poly(butyl methacrylate) diblock copolymer latices were synthesized by a two-step process. In the first step, a homopolymer end-capped with a dithiobenzoyl group [poly(fluoroalkyl mathacrylate) (PFAMA) or poly(butyl methacrylate) (PBMA)] was prepared in bulk via reversible addition,fragmentation chain transfer (RAFT) polymerization with 2-cyanoprop-2-yl dithiobenzoate as a RAFT agent. In the second step, the homopolymer chain-transfer agent (macro-CTA) was dissolved in the second monomer, mixed with a water phase containing a surfactant, and then ultrasonicated to form a miniemulsion. Subsequently, the RAFT-mediated miniemulsion polymerization of the second monomer (butyl methacrylate or fluoroalkyl mathacrylate) was carried out in the presence of the first block macro-CTA. The influence of the polymerization sequence of the two kinds of monomers on the colloidal stability and molecular weight distribution was investigated. Gel permeation chromatography analyses and particle size results indicated that using the PFAMA macro-CTA as the first block was better than using the PBMA RAFT agent with respect to the colloidal stability and the narrow molecular weight distribution of the F-copolymer latices. The F-copolymers were characterized with 1H NMR, 19F NMR, and Fourier transform infrared spectroscopy. Comparing the contact angle of a water droplet on a thin film formed by the fluorinated copolymer with that of PBMA, we found that for the diblock copolymers containing a fluorinated block, the surface energy decreased greatly, and the hydrophobicity increased. 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 471,484, 2007 [source]

    Phosphorylated copolymers containing pendant, crosslinkable spiro orthoester moieties

    J. Canadell
    Abstract The synthesis of a novel spiro orthoester containing monomer, 1,4,6-trioxaspiro[4.4]-2-nonylmethyl acrylate, is presented. This monomer was polymerized via a free-radical system to yield the homopolymer and a series of copolymers with phosphorus-containing comonomers. Diethyl vinyl phosphonate, allyldiphenylphosphine oxide, and diethyl(methacryoyoxymethyl)phosphonate were used in various feed ratios to produce copolymers with different phosphorous concentrations containing crosslinkable spiro orthoester side-chain units. The crosslinking of the polymers was performed cationically with ytterbium triflate, and in all cases, the expansion of the polymer was observed. Moreover, the incorporation of phosphorus into the copolymers increased the limiting oxygen indices, regardless of the percentage of phosphorus used. 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6728,6737, 2006 [source]

    Block copolymers by chemoenzymatic cascade polymerization: A comparison of consecutive and simultaneous reactions

    Matthijs de Geus
    Abstract The synthetic parameters for the chemoenzymatic cascade synthesis of block copolymers combining enzymatic ring-opening polymerization (EROP) and atom transfer radical polymerization (ATRP) in one pot were investigated. A detailed analysis of the mutual interactions between the single reaction components revealed that the ATRP catalyst system could have a significant inhibiting effect on the enzyme activity. The inhibition of the enzyme was less pronounced in the presence of multivalent ligands such as dinonyl bipyridine, which thus could be used in this reaction as an ATRP catalyst. Moreover, the choice of the ATRP monomer was investigated. Methyl methacrylate interfered with EROP by transesterification, whereas t -butyl methacrylate was inert. Block copolymers were successfully synthesized with this cascade approach by the activation of ATRP after EROP by the addition of the ATRP catalyst and, with lower block copolymer yields, by the mixing of all the components before the copolymerization. Adetailed kinetic analysis of the reactions and the structure of the block copolymers showed that the first procedure proceeded smoothly to high block copolymer yields, whereas in the latter a noteworthy amount of the poly(t -butyl methacrylate) homopolymer was detected. 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4290,4297, 2006 [source]

    Solid-phase incorporation of gaseous carbon dioxide into oxirane-containing copolymers

    Bungo Ochiai
    Abstract Carbon dioxide was incorporated into poly(glycidyl methacrylate- co -methyl methacrylate) by a solid-phase reaction, which transformed the pendent oxirane moieties into cyclic carbonate moieties, with quaternary ammonium halide catalysts. The incorporation of carbon dioxide into the copolymer led to soluble carbonate-containing polymers, whereas the incorporation of carbon dioxide into the glycidyl methacrylate homopolymer produced an insoluble product. The copolymer composition, reaction temperature, and catalyst amount affected the incorporation efficiency and the side reaction that caused crosslinking. Effective incorporation was achieved under the following reaction conditions: the glycidyl methacrylate content was less than approximately 50%, the temperature was greater than the glass-transition temperature, and the catalyst concentration was 1.5,6 mol %. 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3812,3817, 2004 [source]

    Synthesis and characterization of poly(methyl methacrylate)/casein nanoparticles with a well-defined core-shell structure

    Junmin Zhu
    Abstract Well-defined, core-shell poly(methyl methacrylate) (PMMA)/casein nanoparticles, ranging from 80 to 130 nm in diameter, were prepared via a direct graft copolymerization of methyl methacrylate (MMA) from casein. The polymerization was induced by a small amount of alkyl hydroperoxide (ROOH) in water at 80 C. Free radicals on the amino groups of casein and alkoxy radicals were generated concurrently, which initiated the graft copolymerization and homopolymerization of MMA, respectively. The presence of casein micelles promoted the emulsion polymerization of the monomer and provided particle stability. The conversion and grafting efficiency of the monomer strongly depended on the type of radical initiator, ROOH concentration, casein to MMA ratio, and reaction temperature. The graft copolymers and homopolymer of PMMA were isolated and characterized with Fourier transform infrared spectroscopy and differential scanning calorimetry. The molecular weight determination of both the grafted and homopolymer of PMMA suggested that the graft copolymerization and homopolymerization of MMA proceeded at a similar rate. The transmission electron microscopic image of the nanoparticles clearly showed a well-defined core-shell morphology, where PMMA cores were coated with casein shells. The casein shells were further confirmed with a zeta-potential measurement. Finally, this synthetic method allowed us to prepare PMMA/casein nanoparticles with a solid content of up to 31%. Thus, our new process is commercially viable. 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3346,3353, 2003 [source]

    Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group.


    Abstract The radical copolymerization in solution of vinylidene fluoride (VDF; or 1,1-difluoroethylene) with methyl 1,1-dihydro-4,7-dioxaperfluoro-5,8-dimethyl non-1-enoate (MDP) initiated by di- tert -butyl peroxide is presented. Six copolymerization reactions were investigated with initial [VDF]0/[MDP]0 molar ratios of 35/65 to 80/20. Both of these comonomers copolymerized in this range of copolymerization. Moreover, these comonomers homopolymerized separately under these conditions. The copolymer compositions of these random copolymers were calculated by means of 19F NMR spectroscopy, which allowed the quantification of the respective amounts of each monomeric unit in the copolymers. The Tidwell,Mortimer method was used for the assessment of the reactivity ratios (ri) of both comonomers, which showed a higher incorporation of MDP in the copolymers (rMDP = 2.41 2.28 and rVDF = 0.38 0.21 at 120 C). The Alfrey,Price Q and e values of the trifluoroallyl monomer MDP were calculated to be 0.024 (from QVDF = 0.008) or 0.046 (from QVDF = 0.015) and 0.70 (vs eVDF = 0.40) or 0.80 (vs eVDF = 0.50), respectively, indicating that MDP was an electron-accepting monomer. The thermal properties of these fluorinated copolymers were also determined. Except for those containing a high amount of VDF, the copolymers were amorphous. Each showed one glass-transition temperature (Tg) only, and with known laws of Tg's, Tg of the MDP homopolymer was assessed. It was compared to that obtained from the direct radical homopolymerization of MDP and discussed. Indeed, these two values were close (Tg = ,3 C). Thermogravimetric analyses were performed, and they showed that the copolymers were rather thermostable because the thermal degradation occurred at 280 C. 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3109,3121, 2003 [source]

    Structure,property transition-state model for the copolymerization of ethene and 1-hexene with experimental and theoretical applications to novel disilylene-bridged zirconocenes

    Hanne Wigum
    Abstract Ethene homopolymerization and copolymerization with 1-hexene were performed with three new tetramethyldisilylene-bridged zirconocene catalysts with 2-indenyl ligand (A), 2-tetrahydroindenyl ligand (B), and tetramethyl-cyclopentadienyl ligand (C) and with methylaluminoxane as a cocatalyst. Catalysts A and B showed substantial comonomer incorporation, resulting in a copolymer melting temperature more than 20 lower than that of the corresponding homopolymer. In contrast, catalyst C produced a copolymer with a low 1-hexene content and a high melting temperature. The reduction in the molecular weight with 1-hexene addition also correlated well with the comonomer incorporation. For all three catalysts, the homopolymer and copolymer unsaturations indicated frequent chain termination after 1-hexene insertion and a high degree of chain-end isomerization during the homopolymerization of ethene. The chain transfer to Al in the cocatalyst also appeared to be important. The comonomer response could be correlated with the structural properties of the catalyst, as derived from quantum chemical calculations. A linear model, calibrated against recent experiments with unbridged (MenC5H5,n)2ZrCl2 catalysts, suggested that the low comonomer incorporation obtained with catalyst C was caused partly by a narrow opening angle between the aromatic ligands and partly by steric hindrance in the transition state of comonomer insertion. 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1622,1631, 2003 [source]

    Main-chain, thermotropic, liquid-crystalline, hydrogen-bonded polymers of 4,4,-bipyridyl with aliphatic dicarboxylic acids

    Pradip K. Bhowmik
    Abstract A series of main-chain, thermotropic, liquid-crystalline (LC), hydrogen-bonded polymers or self-assembled structures based on 4,4,-bipyridyl as a hydrogen-bond acceptor and aliphatic dicarboxylic acids, such as adipic and sebacic acids, as hydrogen-bond donors were prepared by a slow evaporation technique from a pyridine solution and were characterized for their thermotropic, LC properties with a number of experimental techniques. The homopolymer of 4,4,-bipyridyl with adipic acid exhibited high-order and low-order smectic phases, and that with sebacic acid exhibited only a high-order smectic phase. Like the homopolymer with adipic acid, the two copolymers of 4,4,-bipyridyl with adipic and sebacic acids (75/25 and 25/75) also exhibited two types of smectic phases. In contrast, the copolymer of 4,4,-bipyridyl with adipic and sebacic acids (50/50), like the homopolymer with sebacic acid, exhibited only one high-order smectic phase. Each of them, including the copolymers, had a broad temperature range of LC phases (36,51 C). The effect of copolymerization for these hydrogen-bonded polymers on the thermotropic properties was examined. Generally, copolymerization increased the temperature range of LC phases for these polymers, as expected, with a larger decrease in the crystal-to-LC transition than in the LC-to-isotropic transition. Additionally, it neither suppressed the formation of smectic phases nor promoted the formation of a nematic phase in these hydrogen-bonded polymers, as usually observed in many thermotropic LC polymers. The thermal transitions for all of them, measured by differential scanning calorimetry, were well below their decomposition temperatures, as measured by thermogravimetric analysis, which were in the temperature range of 193,210 C. 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1282,1295, 2003 [source]

    Poly(ethylene terephthalate) terpolyesters containing isophthalic and 5- tert -butylisophthalic units

    Darwin P. R. Kint
    Abstract Poly(ethylene terephthalate- co -isophthalate- co -5- tert -butylisophthalate) (PETItBI) terpolymers were investigated with reference to poly(ethylene terephthalate) (PET) homopolymer and poly(ethylene terephthalate- co -isophthalate) (PETI) copolymers. Three series of PETItBI terpolyesters, characterized by terephthalate contents of 90, 80, and 60 mol %, respectively, with different isophthalate/5- tert -butylisophthalate molar ratios, were prepared from ethylene glycol and mixtures of dimethyl terephthalate, dimethyl isophthalate, and 5- tert -butylisophthalic acid. The composition of the terpolymers and the composition of the feed agreed. All terpolymers had a random microstructure and number-average molecular weights ranging from 10,000 to 20,000. The PETItBI terpolyesters displayed a higher glass-transition temperature and a lower melting temperature than the PETI copolymers having the same content of terephthalic units. Thermal stability appeared essentially unchanged upon the incorporation of the 5- tert -butylisophthalic units. The PETItBIs were crystalline for terephthalate contents higher than 80 mol %, and they crystallized at lower rates than PETI. The crystal structure of the crystalline terpolymers was the same as that of PET with the 1,3-phenylene units being excluded from the crystalline phase. Incorporation of isophthalate comonomers barely affected the tensile modulus and strength of PET, but the brittleness of the terpolymers decreased for higher contents in 5- tert -butylisophthalic units. 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 124,134, 2003 [source]