Femtosecond-laser-induced backward transfer of fluorinated ethylene propylene for fabrication of "lotus effect"surfaces

“Lotus effect” glass surfaces with fluorinated ethylene propylene were successfully fabricated by using a femtosecond laser-induced backward transfer(LIBT) method. By space-selectively modifying both the surface morphology and surface chemistry in a single step, LIBT provides a convenient and flexible route to fabricate superhydrophobic surfaces with ultralow adhesion. A systematic mechanism responsible for the anisotropic wetting behaviors and adhesion modulation was proposed with a combination of the Cassie and Wenzel models. X-ray photoelectron spectroscopy revealed that oxidation and defluorination were induced by laser radiation. LIBT is proved to be a promising method for programmable manipulations of functional surfaces with diverse wettability.

i-PP/EPR REACTOR ALLOY PREPARED THROUGH ETHYLENE/PROPYLENE SLURRY COPOLYMERIZATION CATALYZED BY METALLOCENE SUPPORTED iPP PARTICLES

i-PP/m-EPR reactor alloy were prepared through ethylene/propylene slurry copolymerization catalyzed by metallocene(rac-Et(Ind)_2ZrCl_2)supported on porous iPP particles.Polar monomer(dihydromyrcene alcohol)treated with triethyaluminum was added in the preparation of porous iPP particles to introduce hydroxyl groups and thus enhance the ability for chemically supporting the metallocene catalyst.The effects of MAO/Zr ratio and monomer composition in feed on the reaction activity and property of polymer were i...

COPOLYMERIZATION OF ETHYLENE AND PROPYLENE WITH (CpCH_2CH_2CH=CH_2)_2MCl_2(M=Zr,Hf)AND Cp_2ZrCl_2 CATALYSTS

(CpCH_2CH_2CH = CH_2)_2MCl_2(M=Zr, Hf)/MAO and Cp_2ZrCl_2/MAO (Cp=cyclopentadienyl; MAO=methylaluminoxane) catalyst systems have been compared for ethylene copolymerization to investigate the influence of theligand and transition metal on the polymerization activity and copolymer properties. For both CH_2CH_2CH=CH_2 substitutedcatalysts the catalytic activity decreased with increasing propene concentration in the feed. The activity of the hafnocenecatalyst was 6～8 times lower than that of the analogous zirconocene catalyst, ^(13)C NMR analysis showed that the copolymerobtained using the unsubstituted catalyst Cp_2ZrCl_2 has greater incorporatien of propene than those produced byCH_2CH_2CH=CH_2 substituted Zr and Hf catalysts. The melting point, crystallinity and the viscosity-average molecularweight of the copolymer decreased with an increase of propenc concentration in the feed. Both CH_2CH_2CH= CH_2 substitutedZr and Hf catalysts exhibit little or no difference in the melting point and crystallinity of the produced copolymers. However,there are significant differences between the two zirconocene catalysts. The copolymer produced by Cp_2ZrCl_2 catalyst havemuch lower T_m and X_c than those obtained with the (CpCH_2CH_2CH=CH_2)_2ZrCl_2 catalyst. The density and molecular weightof the copolymer decreased in the order: (CpCH_2CH_2CH=CH_2)_2HfCl_2>(CpCH_2CH_2CH=CH_2)_2ZrCl_2>Cp_2ZrCl_2. The kineticbehavior of copolymerizaton with Hf catalyst was found to be different from that with Zr catalyst.

^(13)C NMR Study of Ethylene/propylene/octene-1 Terpolymers Synthesized with TiCl_4/MgCl_2/ i -Bu_3Al as the Catalyst

The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.

Vanadium(V) Complexes Containing Unsymmetrical N-Heterocyclic Carbene Ligands: Highly Efficient Synthesis and Catalytic Behavior towards Ethylene/Propylene Copolymerization

The highly efficient method has been developed for the synthesis of NHC·VOCl_(3) containing symmetrical or unsymmetrical Nheterocyclic carbene(NHC) ligands by the transmetallation reaction of NHC·AgCl with VOCl_(3).The total isolated yield of VOCl_(3)[1,3-(2,4,6-Me_(3)C_(6)H_(2))_(2)(NCH=)_(2)C:](V4') reached 86% by transmetallation reaction,which is much higher than that(48%) by direct coordination method.This methodology has also been used to synthesize the novel vanadium complexes containing unsymmetrical NHC ligands of VOCl_(3)[PhCH_(2)NCH=CHNR)C:](V5',R=2,4,6-Me_(3)C_(6)H_(2);V6',R=2,4-Me_(2)-6-Ph-C_(6)H_(2);V7',R=2,6-^(i)Pr_(2)-C_(6)H_(3)) with high yield,which could not be obtained by direct coordination method.The catalytic activity and copolymerization ability would be improved by introducing unsymmetrical NHC ligands due to their less steric bulky effect.The vanadium complex V5' containing unsymmetrical NHC ligand exhibits higher catalytic activity(3.7×10^(5)g_(copolymer)·mol^(-1) of V·h^(-1)) than that of V4' containing symmetrical NHC ligand.Moreover,the higher propylene incorporation ratio(45.6 mol%) in the copolymers of ethylene with propylene could be obtained by using V5' than that(39.9%) by using V4'.The results would provide a highly efficient strategy for the synthesis of early transition metal complexes containing versitile NHC ligands,affording the catalyst with both high catalytic activity and copolymerization ability for the synthesis of high performance polyolefin elastomers.

Separation of a C_(3)H_(6)/C_(2)H_(4) mixture using Pebax^(■) 2533/PEG600 blend membranes

In industry, ethylene(C_(2)H_(4))/propylene(C_(3)H_(6)) separations are usually performed by a cryogenic process,which is energy intensive. Membrane separation technology is an alternative separation process that saves energy and is efficient. In this study, blend membranes were prepared by doping polyethylene glycol(PEG600) into a poly(ether-block-amide)(Pebax^(■) 2533) matrix and were used to separate the C_(2)H_(4)/C_(3)H_(6) mixture. The PEG 600 and Pebax^(■) 2533 polymers have good compatibility because they share hydrogen bonds. The addition of PEG600 is conducive to the hydrophilicity and the free volume of blend membranes, and it is also conducive to the solubility of C_(2)H_(4) and C_(3)H_(6) in the membranes, which improves the ability of the membranes to separate this gas pair. The Pebax^(■) 2533/PEG600 blend membrane with 15%(mass) PEG600 showed the highest separation performance in our investigated membranes, with a C_(3)H_(6)/C_(2)H_(4) selectivity of 8.9 and a C_(3)H_(6) permeability of 196 barrer(1 barrer = 1.33×10^(14)m^(3)(STP)·m·m^(-2)·s^(-1)·kPa^(-1)) at 238 K and 0.2 MPa, which is higher than that of the Pebax^(■) 2533/NaY-6%(mass) membrane(α_(C_(3)H_(6)/C_(2)H_(4)) =6.5, P_(C_(3)H_(6))=211 barrer) reported in our previous work. It is confirmed that incorporating PEG600 into the Pebax^(■) 2533 matrix to fabricate blend membranes is an efficient strategy for separating light olefins.

Stabilizing MXene suspension with polyhydric alcohols

MXenes have promises in myriad applications by virtue of two-dimensional nature and adjustable functional groups.To achieve the applications,MXenes are always first prepared in the form of aqueous suspension.However,fast degradation caused by the attack of dissolved oxygen and water molecules is the main obstacle to the application of MXenes.It has come to light that the degradation preferentially takes place at defective sites and edges where defects enrich.To tackle this problem and increase the stability,herein,using Ti_(3)C_(2)T_(x)MXene as a model material,we report a simple yet efficient strategy for long term storage of MXene suspension by introducing glycerol,a typical polyhydric alcohol.The effectiveness of the strategy is evidenced by structural compositional and morphological investigations.Glycerol protects the defective sites of MXene flakes through restricting water and/or oxygen molecules from reactive sites.This is supported by ab initio molecular dynamics simulations that form hydrogen bonds between MXene and glycerol molecules just over defective sites.Following this mechanism,other polyhydric alcohols,such as ethylene glycol and propylene glycol,are also effective in stabilizing Ti_(3)C_(2)T_(x)MXene suspension.The strategy based on polyhydric alcohols has the potential to be extended to other MXenes,solving the most urgent challenge in the field of MXene engineering.