Branched polystyrene with abundant pendant vinyl functional groups from asymmetric divinyl monomer

Branched polystyrenes with abundant pendant vinyl functional groups were prepared via radical polymerization of an asymmetric divinyl monomer, which possesses a higher reactive styryl and a lower reactive butenyl. Employing a fast reversible addition fragmentation chain transfer (RAFT) equilibrium, the concentration of active propagation chains remained at a low value and thus crosslinking did not occur until a high level of monomer conversion. The combination of a higher reaction temperature (120 degrees C) and RAFT agent cumyl dithiobenzoate was demonstrated to be optimal for providing both a more highly branched architecture and a higher polymer yield.

Ethylene Polymerization of the New Titanium Complexes Bearing a Phosphine Oxide-Bridged Bisphenolato Ligand

A series of novel titanium(IV) complexes combining a phosphine oxide-bridged bisphenolato ligand TiCl2{2,2'-O=P-R-3 (4-R-2-6-R-1-C6H2O)(2)}(THF) (6a: R-1 = tBu, R-2 - H, R-3 Ph; 6b: R-1 - Ph, R-2 = H, R-3 = Ph; 6c: R-1 = R-2 = tBu, R-3 = Ph; 6d: R-1 = R-2 cumyl, R-3 = Ph; 6e: R-1 = tBu, R-2 = H, R-3 = PhF5) were prepared by the reaction of corresponding bisphenolato ligands with TiCl4 in THF. X-ray analysis reveals that complex 6a adopts distorted octahedral geometry around the titanium center. These catalysts were performed for ethylene polymerization in the presence of modified methyaluminoxane (MMAO).

Polymerization of ethylene to branched polyethylene with silica and Merrifield resin supported nickel(II) catalysts with alpha-diimine ligands

Silica and Merrifield resin were used as carriers for the support of alpha-diimine nickel(II) precatalysts for ethylene polymerization. The alpha-diimine ligands containing allyl were modified by introducing the reactive Si-Cl end-group, allowing their immobilization via a direct reaction of the Si-Cl groups with the silanols on silica surface or the hydroxyls on the ethanolamine-modified Merrifield resin. The resulting supported alpha-diimine ligands were characterized by analytical and spectroscopic techniques (NMR and Fr-IR).

Synthesis, structural characterization, and ethylene polymerization behavior of the vanadium(III) complexes bearing salicylaldiminato ligands

Vanadium(III) complexes bearing salicylaldiminato ligands (2a-k) [RN=CH(Ar0)]VCl2(THF)2 (Ar C61714, R = Ph, 2a; p-CF3Ph, 2b; p-CH3Ph, 2c; 2,6-Me2Ph, 2d; 2,6-iPr2Ph, 2e; cyclohexyl, 2f; Ar = C6H3tBu(2), R = Ph, 2g; 2,6-iPr2Ph, 2h; Ar = C6H2tBU2(2,4), R = Ph, 2i; 2,6-iPr2Ph, 2j; Ar = C6H2Br2, R = Ph, 2k) were prepared from VC13(THF)3 by treating with 1.0 equiv of (RN=CH)ArOH in tetrahydrofuran (THF) in the presence of excess triethylamine (TEA).

Synthesis and characterization of titanium complexes bearing two beta-enaminoketonato ligands with electron-withdrawing groups and their behavior in ethylene polymerization

A series of new titanium complexes with two asymmetric bidentate beta-enaminoketonato (N,O) ligands (4b-t), [RN=CCF3)CHC(t-BU)O](2)TiCl2 (4b, R = -C6H4F(o); 4c, R = -C6H4F(m);4d, R = -C6H4F(p); 4e, R = - C6H3F2(2,3); 4f, R = -C6H3F2(2,4); 4g, R = -C6H3F2(2,5); 4h, R = -C6H3F2(2,6); 4i, R = -C6H3F2(3,4); 4j, R = -C6H3F2(3,5); 4k, R = -C6H2F3(2,3,4); 4l, R = -C6H2F3(3,4,5); 4m, R = -C6H4CF3(o); 4n, R =-C6H4CF3(m); 4o, R = -C6H4CF3(p); 4p, R = -C6H4Cl(p); 4q, R = -C6H4I(p); 4r, R = -C6H4NO2(P); 4s, R = -CH2C6H5; 4t, R = -C6H11), have been synthesized and characterized.

Synthesis of magnetite core-shell nanoparticles by surface-initiated ring-opening polymerization of L-lactide

Fe3O4-polylactide (PLA) core-shell nanoparticles were perpared by surface functionalization of Fe3O4 nanoparticles and subsequent surface-initiated ring-opening polymerization of L-lactide. PLA was directly connected onto the magnetic nanoparticles surface through a chemical linkage. Fourier transform infrared (FT-IR) spectra directly provided evidence of the PLA on the surface of the magnetic nanoparticles. Transmission electron microscopy images (TEM) showed that the magnetic nanoparticles were coated by PLA with a 3-nm-thick shell.

Chiral ligand 2-(2 '-piperidinyl)pyridine: synthesis, resolution and application in asymmetric diethylzinc addition to aldehydes

Chiral ligand 2-(2'-piperidinyl)pyridine 1 has been synthesized in good overall yield by sequential benzylation, hydrogenation and debenzylation of 2,2'-bipyridine. Its enantiomerically pure enantiomers have been obtained by resolution of 2-(1-benzyl-2-piperidinyl)pyridine 2 with D-tartaric acid (or L-tartaric acid) followed by debenzylation. The absolute configuration was determined by X-ray analysis of the (S)-2 D-tartrate. It was demonstrated that I can be used as an effective enantioselective catalyst in the addition of diethylzinc to aldehydes.

Syndiotactically enriched 1,2-selective polymerization of 1,3-butadiene initiated by iron catalysts based on a new class of donors

A series of phosphoryl (P=O) contained compounds: triethylphosphate (a), diethyl phenyl phosphate (b), ethyldiphenylphosphate (c) triarylphosphates (d and h-m), triphenylphosphine oxide (e), phenyl diphenylphosphinate (f) and diphenyl phenylphosphonate (g) have been prepared. Iron catalysts, which are generated in situ by mixing the compounds with Fe(2-EHA)(3) and (AlBu3)-Bu-i in hexane, are tested for butadiene polymerization at 50 degrees C. Phosphates donated catalysts have been, unprecedently, found to conduct extremely high syndiotactically (pentad, rrrr=46.1-94.5%) enriched 1,2-selective (1,2-structure content=56.2-94.3%) polymerization of butadiene.

Effect of La-Mg-based alloy addition on structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy

Effect of La-Mg-based alloy (AB(5)) addition on Structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy has been investigated systematically. XRD shows that the matrix phase structure is not changed after adding AB(5) alloy, however, the amount of the secondary phase increases with increasing AB(5) alloy content. The electrochemical measurements show that the plateau pressure Ti0.10Zr0.15V0.35Cr0.10Ni0.30 + x% La0.85Mg0.25Ni4.5Co0.35Al0.15 (X = 0, 1, 5, 10, 20) hydrogen storage alloys increase with increasing x, and the width of the pressure plateau first increases when x increases from 0 to 5 and then decreases as x increases further, and the maximum discharge capacity changes in the same trend.

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Synthesis and characterization of phenylene-thiophene all-conjugated diblock copolymers

Grignard metathesis (GRIM) polymerization for all-conjugated diblock copolymers comprising poly (2,5-dihexyloxy-1,4-phenylene) (PPP) and poly(3-hexylthiophene) (P3HT) blocks were systematically studied with LiCl as additive and 1,2-bis (diphenylphosphino) ethane nickel dichloride (Ni(dppe)Cl-2) or 1,3-bis(diphenylphosphino) propane nickel dichloride (Ni(dppp)Cl-2) as catalyst. It was found that the addition order of the monomers was crucial for the success of copolymerization. With the monomer addition in the order of phenyl and then thienyl Grignard reagents, all-conjugated PPP-b-P3HT diblock copolymers with different block ratios were successfully synthesized. In contrast, the inverted addition order only afforded a mixture containing both block copolymers and deactivated or end-capped homopolymers.

Novel spiro-fluorenes from tandem radical addition for liquid crystalline monodisperse conjugated oligomers

3'-Nonafluorobutylmethyl-4'-methyl-spiro[cyclopentyl-9,1']fluorenes were successfully synthesized via tandem radical-addition reactions between 9,9-diallylfluorenes and perfluorobutyl iodide in the presence of a radical initiator followed by reduction under mild conditions. Single crystal analysis indicates that two substituents at 3,4-positions of cyclopentane are in a maleinoid form. Accordingly, four oligo(fluorene-co-bithiophene)s with the same molecular length of similar to 10 nm (7 fluorene units and 12 thiophene units) containing one to three novel spiro-fluorene units were synthesized.

Effects of Y2O3 addition on the phase evolution and thermophysical properties of lanthanum zirconate

Lanthanum zirconate (La2Zr2O7, LZ) powders with the addition of various Y2O3 contents for potential thermal barrier coatings (TBCs) application were synthesized by solid-state reaction. The structure evolution, sintering-resistance and thermophysical properties of the synthesized powders and sintered ceramics were systematically studied. X-ray diffraction (XRD) results indicate that LZ containing 3-12 wt.% Y2O3 mainly keeps a pyrochlore-type structure, and two new phases of LaYO3 and Y0.18Zr0.82O1.91 are also detected. Raman spectra confirm that the higher the Y2O3 content, the easier is the formation of LaYO3.

Preparation and characterization of poly(piperazineamide) composite nanofiltration membrane by interfacial polymerization of 3,3 ',5,5 '-biphenyl tetraacyl chloride and piperazine

Most nanofiltration (NF) membranes are composite and have a polyamide thin film prepared by interfacial polymerization. Their performances mainly correlate the structure of the thin film and monomers used for its preparation. In this work, a novel thin-film composite (TFC) nanofiltration membrane was successfully prepared from 3,3',5,5'-biphenyl tetraacyl chloride (mm-BTEC) and piperazine (PIP) through interfacial polymerization. Attenuated reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS) were used to characterize the chemical composition of the membrane surface. The membrane performance was optimized by studying preparation parameters including monomer concentration, reaction time, and pH of aqueous phase.