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981.
Keiji Ogata Yuushou Nakayama Hajime Yasuda 《Journal of polymer science. Part A, Polymer chemistry》2002,40(16):2759-2771
1‐(2‐N,N‐Dimethylaminoethyl)‐2,3,4,5‐tetramethylcyclopentadienyl‐chromium dichloride ( 1 ), (2‐N,N‐dimethylaminoethyl)cyclopentadienylchromium dichloride ( 6 ), and (2‐N,N‐dimethylaminoethyl)indenylchromium dichloride ( 7 ) in the presence of modified methylaluminoxane exhibit high catalytic activities for the polymerization of ethylene with random copolymerizations of ethylene with propylene, ethylene with 1‐hexene, and propylene with 1‐hexene. These initiators conduct polymerizations to give high molecular weight polymers with low polydispersities. However, the stereoregularities are very poor in these reactions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2759–2771, 2002 相似文献
982.
Jean-François Côté Gérald Perron Jacques E. Desnoyers George C. Benson Benjamin C.-Y. Lu 《Journal of solution chemistry》1998,27(8):685-705
The association theory based on the Bjerrum model, which had been developed for the treatment of apparent and partial molar volumes of electrolyte solutions, is extended to apparent molar relative enthalpies L
2,. Experimental enthalpies of dilution for tetrabutylammonium bromide in acetonitrile, propylene carbonate, and -butyrolactone and for lithium perchlorate and sodium thiocyanate in acetonitrile were obtained and analyzed with this model. Literature data for various electrolytes in water, acetonitrile, and n-propanol were also reanalyzed. Through the Bjerrum equations, enthalpies of dilution can be extrapolated to infinite dilution and reliable L
2, obtained for associated electrolytes. The model can be used to estimate the association constant K
A of the electrolyte and these K
A are compared with literature values (generally obtained from conductivity). Considering the difference in the concentration ranges investigated in L
2, and measurements, K
A extracted from L
2, generally fall within an expected range of deviation from the ones obtained by conductivity, provided that no specific interactions are present in solution. 相似文献
983.
George Z. Papageorgiou George P. Karayannidis Dimitris N. Bikiaris George Litsardakis 《European Polymer Journal》2006,42(2):434-445
The multiple melting behavior of poly(1,3-propylene terephthalate) (PPT) samples after isothermal crystallization from the melt was studied. The step-scan temperature-modulated differential scanning calorimetry (TMDSC) and high rate DSC were used to investigate this behavior in conjunction with standard DSC, wide-angle X-ray diffraction (WAXD) and polarizing light microscopy (PLM). The effect of PPT average molecular weight on the melting was also examined. In general multiple endotherms after isothermal crystallization of PPT were attributed to a continuous crystal perfection process during the subsequent heating scan via melting-recrystallization-remelting. Multiple melting behavior was more pronounced for the low molecular weight PPT. Step-scan TMDSC showed that extensive recrystallization occurs in PPT samples, especially after rapid isothermal crystallization. In fact two recrystallization exothermic peaks were observed. High rate DSC revealed the initial morphology generated during the isothermal step and showed that the low and middle peaks are associated with melting of primary crystals while the high temperature peak should be attributed to melting of recrystallized material. 相似文献
984.
V. La Carrubba V. Brucato S. Piccarolo 《Journal of Polymer Science.Polymer Physics》2002,40(1):153-175
Reliable experimental data for semicrystalline polymers crystallized under pressure are supplied on the basis of a model experiment in which drastic solidification conditions are applied. The influence of the pressure and cooling rate on some properties, such as the density and microhardness, and on the product morphology, as investigated with wide‐angle X‐ray scattering (WAXS), is stressed. Results for isotactic polypropylene (iPP) samples display a lower density and a lower microhardness with increasing pressure over a wide range of cooling rates (from 0.01 to 20 °C/s). Polyamide‐6 (PA6) samples exhibit the opposite behavior, with the density and microhardness increasing at higher pressures over the entire range of cooling rates investigated (from 1 to 200 °C/s). A deconvolution technique applied to iPP and PA6 WAXS patterns has allowed us to evaluate the final phase content and to assess the crystallization kinetics. A negative influence of pressure on the α‐crystalline phase crystallization kinetics can be observed for iPP, whereas a slightly positive influence of pressure on the crystallization kinetics of PA6 can be noted. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 153–175, 2002 相似文献
985.
Michael S. Sevegney Rangaramanujam M. Kannan Allen R. Siedle Ratna Naik Vaman M. Naik 《Vibrational Spectroscopy》2006,40(2):246-256
Vibrational spectroscopy is used to sensitively detect specific morphologies and microstructures present in metallocene-catalyzed syndiotactic polypropylenes (sPP). Six materials, ranging in racemic triad content from 26 to 96% rr, are studied. Changes in high-resolution infrared (IR) and Raman spectra of melt-slow-cooled films are observed as the degree of syndiotacticity varies. Three different types of peak behavior are observed: splitting, wavenumber shift, and change in peak intensity. An overall trend toward greater molecular order (e.g. ordered chain conformations, increased crystallinity) is observed as syndiotacticity increases. By combining results with supporting evidence from X-ray diffraction and IR linear dichroism experiments of highly syndiotactic sPP, new peak assignments are proposed for tacticity-sensitive vibrational bands. Some very interesting spectral behavior is observed for material of intermediate stereoregularity (49% rr). Previously unobserved peaks appear in X-ray diffractograms and IR absorbance spectra, suggesting the presence of an as-yet unidentified “transitional” structure—perhaps a disordered modification of crystalline Form I. This moderate level of syndiotacticty appears to be a critical point or threshold below which sPP chains are unable to adopt characteristic helical or planar zigzag conformations. Results from this work provide a more thorough understanding of stereochemical effects on vibrational spectra, which will be very useful in the interpretation of ongoing IR linear dichroism studies of newly available semi-syndiotactic (semi-sPP) materials. 相似文献
986.
George R. Newkome Kyung Soo YooSeok-Ho Hwang Charles N. Moorefield 《Tetrahedron》2003,59(22):3955-3964
A convenient combinatorial-style route for the incorporation of multiple, differing functional groups, in a controllable ratio, onto a dendritic poly(propylene imine) scaffolding is described. Attachment of the functionality is accomplished by the connective formation of bis(2,2′:6′,2-terpyridine)Ru(II) complexes via reaction of a terpyridine-modified dendritic surface with 1→3 branched monomers each possessing a focal terpyridine moiety. This synthetic approach produces a heterogeneous surface coating that is compared and contrasted to that of analogous homogeneous surfaced constructs. UV-vis absorption and TGA data for the metallodendrimers are also reported. 相似文献
987.
A.?Sch?nhalsEmail author H.?Goering C.?Schick B.?Frick R.?Zorn 《Colloid and polymer science》2004,282(8):882-891
The glassy dynamics of poly(propylene glycol) (PPG) and poly(methyl phenyl siloxane) (PMPS) confined to nanoporous glasses (pore sizes 2.5–20 nm) investigated by dielectric spectroscopy, temperature modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature modulated DSC agree quantitatively indicating that both experiments sense the glass transition.For PPG the glassy dynamics in nanopores is determined by a counterbalance of an adsorption and a confinement effect where the temperature dependence of the relaxation times obeys the Vogel/Fulcher/Tammann (VFT-) equation. The former effect results from an interaction of the confined macromolecules with the internal surfaces which in general slows down the molecular dynamics. A confinement effect leads to an acceleration of the segmental dynamics compared to the bulk state and points to an inherent length scale on which the glassy dynamics takes place. The step of the specific heat capacity cp at the glass transition vanishes at a finite length scale of 1.8 nm. This result supports further the conception that a characteristic length scale is relevant for glassy dynamics.For PMPS down to a pore size of 7.5 nm the temperature dependence of the relaxation times follows the VFT-dependence and a confinement effect is observed like for PPG. At a pore size of 5 nm this changes to an Arrhenius-like behavior with a low activation energy. At the same pore size cp vanishes for PMPS. This points to a dramatic change in the character of molecular motions responsible for glassy dynamics and supports further the relevance of a characteristic length scale on which it takes place.Quasielastic neutron scattering experiments on PMPS reveal that the microscopic dynamics characterized by the mean square displacement depends on confinement above the glass transition. The diffusive character of the relevant molecular motions seems to disappear at a length scale of about 1.6 nm. 相似文献
988.
The synthesis of bridged ansa metallocenes usually gives a diastereomeric mixture ofracemic and meso metallocene isomers and in many cases the meso form is about 50 % ofthe product of metallocene synthesis"'. The amount of desired racemic isomer is ratherpoor and can be separated from the meso isomer by fractional crystallization'. The racemicansa-metallocene isomer acts as catalyst for propylene polylnerization to produce isotacticpolypropylene (PP) while the corresponding meso isomer gives a… 相似文献
989.
Emmerich Wilhelm E. Jimenez G. Roux-Desgranges J. -P. E. Grolier 《Journal of solution chemistry》1991,20(1):17-28
Excess molar volumes V
E
and excess molar heat capacities C
P
E
at constant pressure have been measured, at 25°C, as a function of composition for the four binary liquid mixtures propylene carbonate (4-methyl-1,3-dioxolan-2-one, C4H6O3; PC) + benzene (C6H6;B), + toluene (C6H5CH3;T), + ethylbenzene (C6H5C2H5;EB), and + p-xylene (p-C6H4(CH3)2;p-X) using a vibrating-tube densimeter and a Picker flow microcalorimeter, respectively. All the excess volumes are negative and noticeably skewed towards the hydrocarbon side: V
E
(cm3-mol–1) at the minimum ranges from about –0.31 at x1=0.43 for {x1C4H6O3+x2p-C6H4(CH3)2}, to –0.45 at x1=0.40 for {x1C4H6O3+x2C6H5CH3}. For the systems (PC+T), (PC+EB) and (PC+p-X) the C
P
E
s are all positive and even more skewed. For instance, for (PC+T) the maximum is at x
1,max
=0.31 with C
P,max
E
=1.91 J-K–1-mol–1. Most interestingly, C
P
E
of {x1C4H6O3+x2C6H6} exhibits two maxima near the ends of the composition range and a minimum at x
1,min
=0.71 with C
P,min
E
=–0.23 J-K–1-mol–1. For this type of mixture, it is the first reported case of an M-shaped composition dependence of the excess molar heat capacity at constant pressure.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60th birthday, Clermont-Ferrand, France, 17–18 May 1990. 相似文献
990.
Hui-liang Zhang Xiao-hong Sun Qing-yong Chen Min-qiao Ren Zhi-hao Zhang Hong-fang Zhang Zhi-shen Mo 《高分子科学》2007,(6):589-597
In this paper,melt blends of poly(propylene carbonate)(PPC)with poly(butylene succinate)(PBS)were characterized by dynamic mechanical analysis(DMA),differential scanning calorimetry(DSC),tensile testing,wide-angle X-ray diffraction(WAXD),polarized optical microscopy and thermogravimetric analysis(TGA).The results indicated that the glass transition temperature of PPC in the 90/10 PPC/PBS blend was decreased by about 11K comparing with that of pure PPC.The presence of 10% PBS was partially miscible with PPC.The 90/10 PPC/PBS blend had better impact ==========and tensile strength than those of the other PPC/PBS blends.The glass transition temperature of PPC in the 80/20,70/30,and 60/40 PPC/PBS blends was improved by about 4.9 K,4.2 K,and 13 K comparing with that of pure PPC,respectively;which indicated the immiscibility between PPC and PBS.The DSC results indicated that the crystallization of PBS became more difficult when the PPC content increased.The matrix of PPC hindered the crystallization process of PBS.While the content of PBS was above 20%,significant crystallization-induced phase separation was observed by polarized optical microscopy. It was found from the WAXD analysis that the crystal structure of PBS did not change,and the degree of crystallinity increased with increasing PBS content in the PPC/PBS blends. 相似文献