Syntheses of poly(siloxane)-supported zirconocene catalysts and application to olefin polymerizations

Poly(siloxane)s with bisindenyl, bisfluorenyl, bis(1,2,3,4-tetramethylcyclopentadienyl), bis(2,4,7-trimethylindenyl) and monoindenylmethyl side groups were synthesized by condensation of the corresponding dichlorosilanes and water. For reference, diphenylsilanediol or hydroquinone was also employed in place of water. A series of poly(siloxane)-supported zirconocene catalysts were then prepared from these precursors and applied to ethene and propene polymerizations as well as to the copolymerization of ethene with 1-octene in the presence of methylalumoxane. The polymerization activity of the new supported metallocenes depends drastically upon the substituents in the siloxane backbone. The zirconocene catalysts supported on poly(bisindenylsiloxane) and poly(bisfluorenylsiloxane) give the highest activities for ethene and propene polymerizations, respectively. The weight-average molecular weights of the polymers are also markedly dependent upon the substituents. On the other hand, the molecular mass distributions (MMD) are generally not so sharp, suggesting that the active species formed in these supported catalysts are not uniform. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 421–428, 1998     

Hydrogen Bonding Interaction of Formic Acid-, Formaldehyde-, Formylfluoride-Nitrosyl Hydride： Theoretical Study on the Geometries, Interaction Energies and Blue- or Red-Shifted Hydrogen Bonds

The hydrogen bonding interaction of formic acid-, formaldehyde-, formylfluoride-nitrosyl hydride complexes was investigated by the density functional theory （DFT） and ab inito method in conjunction with 6-311＋＋G（2d,2p） basis set. The geometries, vibrational frequencies and interaction energies of the complexes were calculated by both standard and CP-corrected methods respectively. Moreover, G3B3 method was employed to estimate the interaction energies. There are C--H…O, N--H…O, N--H…F blue-shifted H-bonds and red-shifted O----H…O H-bond in the complexes. Electron density redistribution and rehybridization contribute to the N--H and C--H blue shifts. All geometric reorganizations contribute to the N--H blue shifts and partial geometric reorganizations contribute to the C--H blue shifts. The geometric reorganizations of the complex C except ZH（5）-O（4）-C（1） contribute to the O----H red shift. For the N--H blue shifts, the effect of r（N--O） variation on the N--H blue shifts is larger than that of ZH-N-O variation. Rehybridization plays a dominant role in the degree of N--H blue shifts, whereas the electron density redistribution contributes more to the degree of C--H blue shifts than the other effects do.     

Ionic organic/inorganic materials. I. Novel cationic siloxane copolymers containing quaternary ammonium salt groups in the backbone

The synthesis and characterization of some novel cationic siloxanes copolymers containing quaternary ammonium salt (QAS) groups in the backbone is reported in this article. One cationic oligomer having QAS in the backbone and reactive groups like 2,3‐epoxypropyl and 2‐hydroxy‐3‐chloropropyl (RCO) as well as 1,3‐bis(3‐aminopropyl)tetramethyldisiloxane or α,ω‐bis(3‐aminopropyl)oligodimethylsiloxane (AP) were used as precursors for this goal. Elemental analysis, IR and ¹H NMR spectroscopy, thermogravimetric analysis, and X‐ray photoelectron spectroscopy were used to characterize the obtained copolymers. The thermal stability of the cationic siloxane copolymer increased when the siloxane oligomer having a high number of siloxane units in the chain (AP) was used as a precursor. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3570–3578, 2002     

Enhanced dielectric properties of poly(dimethyl siloxane) bimodal network percolative composite with chemically modified graphene

Bimodal network composite was prepared using a two-step method containing graphene modified by γ-(2, 3-epoxypropoxy) propyl trimethoxysilane (KH560), short chain poly(dimethyl siloxane) (C_S-PDMS) and long chain poly(dimethyl siloxane) filled with treated fumed silica (C_L-h-PDMS). A series of composites with different filler contents (including reduced graphene oxide and reduced graphene oxide grafted with KH560, referred to rGO and KrGO, respectively) were prepared to explore their percolation thresholds (fc). We discover that the dielectric constant and loss of 1.32 vol% KrGO/h-PDMS composite were 18.8 and 0.13 at 10² Hz before fc, respectively, which was 2.1 and 0.12 times that of rGO/h-PDMS, and 6.6 and 2.1 times that of pure h-PDMS. The origin is that KH560 insulting layer increases the interlayer distance of graphene sheets to cut down the leakage current. In addition, the modulus of 1.32 vol% KrGO/h-PDMS is less than 3 MPa.     

Synthesis,Structures, and Thermal Properties of Symmetric and Janus “Lantern Cage” Siloxanes

Symmetric and asymmetric (Janus-type) new “lantern cage” siloxanes (PhSiO_1.5)₄(Me₂SiO)₄(RSiO_1.5)₄ (R=Ph or iBu) were synthesized through reaction of all-cis-[PhSi(OSiMe₂Br)O]₄ with all-cis-[RSi(OH)O]₄ (R=Ph or iBu). These precursors were obtained by facile two or three-step reactions from commercially available compounds. The spectroscopic properties of the resulting products were fully characterized and they showed high thermal stability and sublimation without decomposition. The crystal structures clearly indicated that the internal vacancy volumes of the lantern cages are considerably larger than that of octaphenylsilsesquioxane (PhSiO_1.5)₈. DFT calculations of the lantern cage showed a distinctly different electronic state from that of octasilsesquioxane. These results suggest that lantern cage siloxanes have a characteristic “field” in the molecule.     

Star‐shaped siloxane polymers with various cyclic cores: Synthesis and properties

Six new star‐shaped polydimethylsiloxane (PDMS) with various cyclic siloxane cores were synthesized by the “grafting onto” method. The polymers obtained feature low dispersity and well‐defined structures. Two of them, Q ₈ ‐PDMS and D ₁₂ ‐PDMS , have a three‐dimensional spatial structure traditional for star‐shaped polymers where the arms are arranged in all directions from the branching center. The other four polymers, D ₄ ‐PDMS – D ₈ ‐PDMS , have quite a different spatial geometry (cis‐structure) where all the PDMS‐arms are arranged on one side of the branching center plane. Such star‐shaped structures were not reported before. The structures and purity of the polymers obtained were confirmed using a set of physicochemical methods of analysis. The effect of the macromolecule structure on the properties of the target polymers was identified. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Apparent depth‐dependent modulus and hardness of polymers by nanoindentation: Investigation of surface detection error and pressure effects

Nanoindentation is a widely used technique to characterize the mechanical properties of polymeric materials at the nanoscale. Extreme surface stiffening has been reported for soft polymers such as poly(dimethylsiloxane) (PDMS) rubber. Our recent work [J. Polym. Sci. Part B Polym. Phys. 2017 , 55, 30–38] provided a quantitative model which demonstrates such extreme stiffening can be associated with experimental artifacts, for example, error in surface detection. In this work, we have further investigated the effect of surface detection error on the determination of mechanical properties by varying the sample modulus, instrument surface detection criterion, and probe geometry. We have examined materials having Young's moduli from ∼2 MPa (PDMS) to 3 GPa (polystyrene) using two different nanoindentation instruments (G200 and TI 950) which implement different surface detection methods. The results show that surface detection error can lead to apparent large stiffening. The errors are lower for the stiffer materials, but can still be significant if care is not taken to establish the range of the surface detection error in a particular experimental situation. We have also examined the effect of pressure beneath the probe on the nanoindentation‐determined modulus of polystyrene with different probe geometries. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 414–428     

HArF和HNO二聚体相互作用氢键的理论研究

The hydrogen bonding interaction of 1:1 dimer formed between HNO and HArF molecule has been completely investigated in the present study using Second-order M?ller-Plesset Perturbation (MP2) method in conjunction with 6-311+G**, 6-311++G** and 6-311++G(2d,2p) basis sets. The standard and CP-corrected calculations have been employed to determine the equilibrium structures, the vibrational frequencies and interaction energies. The interaction energies of the dimers were also calculated at G2MP2 level. Two stable structures are found as the minima. Dimer I(H···F)is a five-membered cyclic hydrogen bonded structure and is more stable than the Dimer II(H···O). The blue-shifted N-H···F hydrogen bond is confirmed with standard and CP-corrected calculations by the MP2 and DFT methods in conjunction with different basis sets. The results obtained at MP2 in conjunction with different basis sets show there is a red-shifted hydrogen bond (Ar-H···O) in the Dimer II(H···O). The topological and electronic properties, the origin of red- and blue-shifted hydrogen bonds were investigated at MP2/6-311++G(2d,2p) with CP corrected calculations. From the NBO analysis, the reasonable explanations for the red- and blue-shifted hydrogen bonds were proposed.     

Piezoelectric and dielectric properties of siloxane elastomers filled with bariumtitanate

Piezoelectric elastomers were prepared from suspensions of bariumtitanate (BaTiO₃) particles in a telechelic polydimethylsiloxane (t-PDMS) by crosslinking the t-PDMS under an electric field. Crosslinking reaction was monitored by measurement of complex dielectric constant ε′ − iε″. Dielectric constant ε′ increased with increasing BaTiO₃ content, and agreed approximately with the theoretical ε′ calculated with the Maxwell–Wagner theory. Piezoelectric constant d₃₃ of the poled elastomers was measured by application of compressions in the direction of the poling field. It was found that d₃₃ was of the order of 10⁻¹¹ C/N and increased steeply with increasing content of BaTiO₃ but became almost independent of composition in the range of BaTiO₃ content from 3 to 14 vol %. To examine the effect of electric field on the aggregation structure of the particles, we observed light scattering of the suspension under an electric field, and found that the scattering pattern became anisotropic. This indicated that the particles are connected like a pearl necklace and are stretched in the direction of the poling field. The dependence of d₃₃ on the volume fraction of BaTiO₃ was explained by a model proposed by Banno. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3065–3070, 1999