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1.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
2.
Anuj Mittal Swaminathan Sivaram 《Journal of polymer science. Part A, Polymer chemistry》2005,43(21):4996-5008
A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, CuIBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities Mw/Mn ≤ 1.23. The rate of polymerization follows first‐order kinetics, kapp = 3.4 × 10?5 s?1, indicating the presence of low radical concentration ([P*] ≤ 10?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (Mn,SEC) increased linearly with conversion and were found to be higher than predicted molecular (Mn,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (Mn = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (Mn = 10,300), which is achieved in 23 h. The plot of lnkapp versus 1/T gave an apparent activation energy of polymerization as (ΔE≠app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH0eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005 相似文献
3.
Hiroto Kudo Nobuhito Ito Keiji Nakajima Masami Ochiai Tadatomi Nishikubo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(19):4421-4429
The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (Tg's) and refractive‐indices (nD's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of Tg's and nD's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007 相似文献
4.
Chin‐Ping Yang Ruei‐Shin Chen Kuei‐Hung Chen 《Journal of polymer science. Part A, Polymer chemistry》2003,41(7):922-938
To investigate the position and amount of the CF3 group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF3 groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF3 group close to the imide group was more effective in lowering the color; this means that CF3 of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF3 groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003 相似文献
5.
In this paper we highlighted the synthesis, characterization, and practical exploitation of different types of polyphosphazenes substituted with fluorinated groups. There are several ways in which fluorine atoms can be inserted into polyphosphazenes, all of which leading to different polymers showing a wide range of characteristics. In general it is true that the insertion of fluorine atoms into phosphazene macromolecules leads to an enhancement of the thermal stability, flame resistance, low-temperature elastomericity, and chemical inertness of the phosphazenes obtained. The contribution of Italian research groups to the preparation and exploitation of organic commercial macromolecules grafted onto fluorinated polyphosphazenes is also reviewed. 相似文献
6.
Seok‐Ho Hwang Kyung Soo Yoo Charles N. Moorefield Sang‐Won Lee George R. Newkome 《Journal of Polymer Science.Polymer Physics》2004,42(8):1487-1495
A series of metallodendrimers, assembled by means of bis(terpyridinyl)Ru(II) connectivity on poly(propylene imine) dendrimer scaffolds, with homogeneous or heterogeneous surfaces, were prepared. Differential scanning calorimetry and thermogravimetric analysis were used to determine their thermal behavior, glass‐transition temperatures, and the decomposition kinetics and temperatures; no synergy effects for these properties were observed for the heterogeneously surfaced constructs in contrast to the corresponding homogeneously coated materials, which exhibited different values depending on their surface functionalities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1487–1495, 2004 相似文献
7.
The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH4 > N2 > O2 > CO2. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO2 decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO2‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004 相似文献
8.
以PCl3为脱水剂,将邻氨基硫酚与水杨酸脱水环化合成出2-(2-羟基苯基)苯并噻唑,并进一步将所得产物与乙酸锌反应合成出2-(2-羟基苯基)苯并噻唑螯合锌(Zn(BTZ)2)材料。以该配合物作为发光层制备出结构为ITO/PVK:TPD/Zn(BTZ)2/Al近白色电致发光器件,其色坐标位于白场之内(x=0.242,y=0.359),在驱动电压为16V时,亮度达3200cdm2,对应的量子效率为0.32%。进一步在Zn(BTZ)2中掺入橙红色染料Rubrene,制成ITO/PVK:TPD/Zn(BTZ)2:Rubrene/Al结构器件,实现了纯白色发光(色坐标值:x=0.324,y=0.343),非常接近于白色等能点,且量子效率达0.47%。最后对上述器件的发光和电学性能进行了深入的研究和探讨。 相似文献
9.
Bahattin Gümgüm Nermin Biricik Feyyaz Durap Ismail Özdemir Nevin Gürbüz Wee Han Ang Paul J. Dyson 《应用有机金属化学》2007,21(8):711-715
Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
10.
A method of nonaqueous capillary zone electrophoresis (CZE) has been developed to characterize block (co)polymers of poly(ethylene oxide) and poly(styrene) containing metallo bis(terpyridine) complexes as bridging units. Specific CZE separation conditions had to be applied, with barium perchlorate dissolved in N-methylformamide (NMF) as background electrolyte and OV-1701-OH deactivated capillaries. For detection UV absorption was measured at a wavelength of 316 nm. Metallo diblock polymers with molecular weights up to 30,000 Da could be analyzed by the proposed nonaqueous CZE method. Experiments performed with polymeric compounds containing Fe, Ni or Ru as central metal ions showed that their electrophoretic mobilities were independent of the type of metal ion. Therefore, the data on the size of the polymeric compounds could be obtained using just one set of calibration standards. Polydispersities of the samples calculated from the experimental results were in correlation with the polydispersities of the polymers used in the synthesis of the metallo diblock polymers. Several polymeric samples contained metallo mono(terpyridine) complexes as impurities. These by-products could be separated from the main product. With symmetrical diblock polymers only one by-product was detected, while with an asymmetric diblock polymer two types of mono-complexes were found. The amount of the mono-complexes present as impurities was dependent on the type of central metal ion (Ni > Fe >> Ru). 相似文献