Basicity of Stereoregulating Electron-Donor Compounds in Ziegler–Natta Catalysts: A Study by Infrared Spectroscopy and Chemical Exchange Reactions

2014 ◽  
Vol 118 (49) ◽  
pp. 28572-28579 ◽  
Author(s):  
V. N. Panchenko ◽  
A. N. Goryachev ◽  
L. V. Vorontsova ◽  
E. A. Paukshtis ◽  
V. A. Zakharov
Materials ◽  
2018 ◽  
Vol 11 (9) ◽  
pp. 1667
Author(s):  
Jing Liu ◽  
Hsiang-Ching Wang ◽  
Chean-Cheng Su ◽  
Cheng-Fu Yang

An immiscible blend of poly(hydroxy ether of bisphenol-A) (phenoxy) and poly(1,4-butylene terephthalate) (PBT) with phase separation was observed in as-blended samples. The compatibilization of phenoxy/PBT blends can be promoted through chemical exchange reactions of phenoxy with PBT upon annealing. The annealed phenoxy/PBT blends had a homogeneous phase with a single Tg that could be enhanced by annealing at 260 °C. Infrared (IR) spectroscopy demonstrated that phase homogenization could be promoted by annealing the phenoxy/PBT blend, where alcoholytic exchange occurred between the dangling hydroxyl group (–OH) in phenoxy and the carbonyl group (C=O) in PBT in the heated blends. The alcoholysis reaction changed the aromatic linkages to aliphatic linkages in the carbonyl groups, which initially led to the formation of a graft copolymer of phenoxy and PBT with an aliphatic/aliphatic carbonyl link. The progressive alcoholysis reaction resulted in the transformation of the initial homopolymers into block copolymers and finally into random copolymers, which promoted phase compatibilization in blends of phenoxy with PBT. As the amount of copolymers increased upon annealing, the crystallization of PBT was inhibited by alcoholytic exchange in the blends.


Earlier work from this laboratory has concerned the possible use of phosphorus n.m.r. as a method to monitor, in a non-invasive manner, the biochemical state of the perfused heart as a function of its mechanical performance. We showed that a simulated coronary infarction could be detected by 31 P n.m.r. (Hollis et al 1978 a and that hypothermia and KC1 arrest could preserve the pH and the ATP levels at more nearly normal values than in a non-arrested heart during long periods (40 min) of ischaemia (Hollis et al . 1978 b ).More recently it was shown that multiple doses of KC1, given at intervals, were more effective in this respect than was a single dose (Flaherty et al . 1979). These studies essentially followed the kinetics of transitions of the heart between two or more distinct physiological states (i.e. normoxic and ischaemic, with or without KC1 arrest) by observation of the 31 P n.m.r. spectra at various time intervals over periods of up to 1 h. As described in detail and demonstrated in Dr Truman Brown’s contribution to these discussions, the rates of chemical exchange reactions occurring in a steady state can be measured by the techniques of saturation transfer in various biological systems, including perfused hearts.


1972 ◽  
Vol 45 (7) ◽  
pp. 1956-1960 ◽  
Author(s):  
Masaru Ichikawa ◽  
Sadao Tanaka ◽  
Shuichi Naito ◽  
Takahiro Nakamura ◽  
Mitsuyuki Soma ◽  
...  

2014 ◽  
Vol 953-954 ◽  
pp. 1246-1249 ◽  
Author(s):  
Chean Cheng Su ◽  
Chern Hwa Chen ◽  
Neng Lang Shih ◽  
Yin Shuo Li

Compatibilization via transreactions in blends of poly (butylene succinate-co-butylene terephthalate) [P(BS-co-BT)] with poly (hydroxy ether of bisphenol-A) (phenoxy) were investigated. Analyses were based on characterization using differential scanning calorimetry (DSC) and solid-state nuclear magnetic resonance (NMR). They revealed that the P(BS-co-BT)/phenoxy blend had a phase morphology that could be homogenized only following annealing at high temperatures. As-blended P(BS-co-BT)/phenoxy (50/50 composition) exhibited immiscible phases with two distinct Tgs, but the initially phase separated blends finally merged to form a homogeneous phase with a single Tgupon heating and annealing for 60 min at 280 °C. Chemical exchange reactions upon heat-annealing were likely to have caused the phase homogenization in the P(BS-co-BT)/phenoxy blend. NMR was performed on blend samples before and after they were heated to 280 °C, but the similarity of bonds made obtaining straight results difficult. Results of this study demonstrate phase homogenization can be brought only upon heat-annealing in the P(BS-co-BT)/phenoxy blend.


1968 ◽  
Vol 46 (12) ◽  
pp. 2147-2157 ◽  
Author(s):  
R. J. Gillespie ◽  
J. S. Hartman

1H and 19F n.m.r. studies of BF3 adducts of some simple methyl ketones in methylene chloride solution have led to the following conclusions. (1) Only 1:1 adducts are formed which are not appreciably dissociated. (2) The down-field shifts of the proton resonances caused by complexation with BF3 are essentially independent of the ketone and depend only on the distance of the proton from the carbonyl group. (3) BF3 exchange is rapid on the n.m.r. time scale at room temperature, but the exchange process can be slowed sufficiently by lowering the temperature that separate signals due to free and complexed species can be observed. (4) Collapse of the 10B−11B isotope shift with increasing temperature showed that a second chemical exchange process, which exchanges fluorine among boron atoms, occurs in addition to the process of rapid breaking and re-forming of donor–acceptor bonds. A possible mechanism for this fluorine scrambling reaction is discussed.


1986 ◽  
Vol 43 (2) ◽  
pp. 47-50
Author(s):  
V. G. Kalygin ◽  
V. I. Nazarov ◽  
O. S. Chekhov ◽  
B. G. Varshal ◽  
L. L. Mirskikh

2015 ◽  
Vol 2015 ◽  
pp. 1-8 ◽  
Author(s):  
F. Kooli

The thermal stabilities of polyvinylpyrrolidone-organoclays or organo-acid-activated clay composites prepared by chemical exchange reactions were assessed. The raw clay mineral was acid-activated prior to expansion by cetyltrimethylammonium surfactants. The acid activation process affected the intercalated amount of cetyltrimethylammonium cations in the resulting organoclays and, thus, the amount of polyvinylpyrrolidone in the composite. The content of cetyltrimethylammonium cations decreased with the extent of acid activation. The organophilic modification of the clay mineral was an important step in the intercalation of the polyvinylpyrrolidone molecules and, thus, in the expansion of the silicate sheets from 3.80 nm to 4.20 nm. The composites exhibited better crystalline order with intense reflections at lower angles. The thermal stability of organoclays, acid-activated clays, and composites was studied using thermogravimetric analysis andin situX-ray diffraction. The decomposition of intercalated surfactants occurred at lower temperatures relative to the neat surfactant salt, and the basal spacing of the organoclays (or acid-activated clays) shrunk to 2.0 nm at 215°C. However, the basal spacing of composites exhibited better stability and collapsed to 2.0 nm at 300°C. This type of material could offer an alternative stable product for engineering purposes in the design of new composites.


2015 ◽  
Vol 17 (37) ◽  
pp. 24193-24200 ◽  
Author(s):  
YoungAh Kwon ◽  
Sungnam Park

A chemical exchange 2DIR study of ion–molecule complexation dynamics in electrolyte solutions.


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