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.

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.

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.

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.

Partial Evaporation of Strontium Zirconate During Atmospheric Plasma Spraying

Perovskite-type SrZrO3 has been investigated as a candidate material for thermal barrier coating application. During plasma spraying of SrZrO3, SrO volatilized more than ZrO2 and the coating composition deviates from initial stoichiometry. In this investigation, partial evaporation was investigated by spraying SrZrO3 powders into water. The influences of spraying current, distance and particle size of the powder on the partial evaporation were also investigated in a quantitative way. With optimized spraying parameters, stoichiometric SrZrO3 coating was produced by adding an excess amount of Sr in the precursors before plasma spraying to compensate for the volatilized component.

Chiral Salan Aluminium Ethyl Complexes and Their Application in Lactide Polymerization

Synthetic routes to aluminium ethyl complexes supported by chiral tetradentate phenoxyamine (salan-type) ligands [Al(OC6H2(R-6-R-4)CH2)(2){CH3N(C6H10)NCH3}-C2H5] 7: R = H ; 5, 8: R = Cl; 6, 9: R = CH3) are reported. Enantiornerically pure salan ligands 1-3 with (R,R) configurations at their cyclohexane rings afforded the complexes 4, 5, and 6 as mixtures of two diastereoisomers (a and b). Each diastereoisomer a was, as determined by X-ray analysis, monomeric with a five-coordinated aluminium central core in the solid state, adopting a cis-(O,O) and cis-(Me,Me) ligand geometry. From the results of variable-temperature (VT) H-1 NMR in the temperature range of 220-335 K, H-1-H-1 NOESY at 220 K, and diffusion-ordered spectroscopy (DOSY), it is concluded that each diastereoisomer b is also monomeric with a five-coordinated aluminium central core.

Polymerization of Lactide Using Achiral Bis(pyrrolidene) Schiff Base Aluminum Complexes

A series of aluminum ethyls and isopropoxides based on a bis(pyrrolidene) Schiff base ligand framework has been prepared and characterized. NMR studies of the dissolved complexes indicate that they adopt a symmetric structure with a monomeric, five-coordinated aluminum center core. The aluminum ethyls used as catalysts in the presence of 2-propanol as initiator and the aluminum isopropoxides were applied for lactide polymerization in toluene to test their activities and stereoselectivities. All polymerizations are living, as evidenced by the narrow polydispersities and the good fit between calculated and found number-average molecular weights of the isolated polymers. All of these aluminum complexes polymerized (S,S)-lactide to highly isotactic PLA without epimerization of the monomer, furnished isotactic-biased polymer from rac-lactide, and gave atactic polymer from meso-lactide.

The Surface Modification of Hydroxyapatite Nanoparticles by the Ring Opening Polymerization of gamma-Benzyl-L-glutamate N-carboxyanhydride

The surface modification of hydroxyapatite (HA) nanoparticles by the ring opening polymerization (ROP) of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) was proposed to prepare the poly(gamma-benzyl-L-glutamate) (PBLG)-grafted HA nanoparticles (PBLG-g-HA) for the first time. HA nanoparticles were firstly treated by 3-aminopropylthriethoxysilane (APS) and then the terminal amino groups of the modified HA particles initiated the ROP of BLG-NCA to obtain PBLG-g-HA. The process was monitored by XPS and FT-IR. The surface grafting amounts of PBLG on HA ranging from 12.1 to 43.1% were characterized by thermal gravimetric analysis (TGA). The powder X-ray diffraction (XRD) analysis confirmed that the ROP only underwent on the surface of HA nanoparticles without changing its bulk properties. The SEM measurement showed that the PBLG-g-HA hybrid could form an interpenetrating net structure in the self-assembly process.

Gold nanoparticle-based near-infrared fluorescent detection of biological thiols in human plasma

In this work, a new fluorescent method for sensitive detection of biological thiols in human plasma was developed using a near-infrared (NIR) fluorescent dye, FR 730. The sensing approach was based on the strong affinity of thiols to gold and highly efficient fluorescent quenching ability of gold nanoparticles (Au NPs). In the presence of thiols, the NIR fluorescence would enhance dramatically due to desorption of FR 730 from the surfaces of Au NPs, which allowed the analysis of thiol-containing amino acids in a very simple approach. The size of Au NPs was found to affect the fluorescent assay and the best response for cysteine detection was achieved when using Au NPs with the diameter of 24 nm, where a linear range of 2.5 x 10(-8) M to 4.0 x 10(-6) M and a detection limit of as low as 10 nM was obtained. This method also demonstrated a high selectivity to thiol-containing amino acids due to the strong affinity of thiols to gold.

Super-hydrophobicity of silica nanoparticles modified with vinyl groups

Super-hydrophobic films with vinyl-modified silica nanoparticles (V-SiOx-NPs) were successfully prepared. The rough surface, which was composed of microstructures of disordered V-SiOx-NPs and nanostructures on the surface of V-SiOx-NPs, rather than the chemical composition devoted to the super-hydrophobicity of film. The relationship between contact angle and diameter of V-SiOx-NPs was then investigated. The sessile contact angles (CA) of films with 150-1600nm V-SiOx-NPs were around 166 regardless the diameter, while the film with 85 nm V-SiOx-NPs had the lowest CA of about 158. The packing manner of V-SiOx-NPs determined the air fraction on the surface and then the CA.

Effects of polymerization conditions on hydrophilic groups in aromatic polyamide thin films

For polyamide used in reverse osmosis (RO) membranes, the content of pendant acid groups is critical to its performance. In this work, FTIR was used to analyze the acid contents in the polyamide films prepared via interfacial polymerization of trimesic acid trichloride (TMC) in hexane and 1,3-phenylenediamine (MPDA) in water, and the effects of reaction conditions, including monomer concentrations, time, and temperature, were studied. It was found that more pendant acid groups are present in the polyramide film at higher TMC concentrations or lower MPDA concentrations, and longer reaction times and lower temperatures also favor the formation of the free acids. These results can be explained by the monomer diffusion in the interfacial polymerization process. This work may help the design and fabrication of RO membranes with different hydrophilicity and target performance.