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The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed. 相似文献
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A series of porous microspheres of linear and ethylene diacrylate (M') cross-linked copolymers of 2-vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol-acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions. 相似文献
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A modified method of preparing crown functionalized linear polysiloxane has been described.4'-allylbenzo-15-crown-5 was subjected to hydrosilylation with methyldichlorosilane,followed bypolycondensation with silanol-terminated polydimethylsiloxane to give the title crownfunctionalized linear polysiloxane. It was found that the polysiloxane could be coordinated withplatinum salt to form platinum complex, which could catalyze the hydrosilylation of olefins withtriethoxysilane efficiently. 相似文献
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共聚物铑配合物催化甲醇羰基化制备醋酸的反应动力学分析 总被引:4,自引:1,他引:4
以共聚物铑配合物催化甲醇羰基化经醋酸甲酯到醋酸的反应,具有高稳定性、高活性的特点.本文通过对作者近期研究工作的总结,绘出此催化反应全过程的循环图,并在此基础上求出有关动力学参数,结果计算值与实验值相符,证明此机理的合理性,并讨论了几种共聚物配体之间的差异. 相似文献
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采用以原子重叠及电子离域的分子轨道理论ASED MO(含原子对排斥的EHMO法)为基础的结构自动优化法,对共聚物铑配合物催化甲醇羰基化制乙酸反应速率控制步骤 氧化加成进行了理论研究.计算了不同共聚物配体形成的铑催化剂与碘甲烷的氧化加成反应途径,并得到反应活化能,分析了氧化加成反应过程中的电子转移和空间因素对活化能的影响,计算结果与实验结果是相符的,并从理论上解释了2 乙烯基吡啶形成的共聚物铑配合物催化活性高于4 乙烯基吡啶形成的共聚物铑配合物催化活性的原因. 相似文献
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The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence was determined as alternating. The copolymerization rates at different feed ratios, temperatures and in different solvents were investigated, giving evidence to the very active involvement of the CT complexes in the copolymerization. Terpolymerization with acrylonitrile also showed that the complex mechanism was a proper one for this system. 相似文献
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1,1,4,4-Tetraphenyl-1,3-butadiene (TPB) was successfully introduced into the polymer multilayerfilms by means of Langmuir-Blodgett (LB) technique. Results of UV-VIS spectra and X-ray diffractionshowed that the uniform films had a layer structure similar to the superlattice of organic multiple quantumwells. The electroluminescence (EL) devices fabricated from the doped polymer LB films emitted blue light.Compared with the casting films, the photoluminescence (PL) and EL spectra showed that the exciton energyshifts to higher and the half-width of the emission peak becomes narrower due to exciton confinement effect. 相似文献
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Urushiol polymer containing B--N bond (PUBN) was synthesized with urushiol-boronpolymer and diethylene triamine. Its structure was characterized by XPS, IR, UV, HPLC,DTA-TG and elemental analysis. The physico-mechanical and anticorrosive propertiesof the polymer were also investigated. The results show that the coating of PUBN canbe hardened in 2h at room temperaure and its film has excellent physico-mechanicalproperties and good anticorrosive properties. 相似文献
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The ~(13)C T_(1s) of --CH_3 side group in PPU/P (St-co-AA), AB-crosslinked polymers (i. e.ABCP) was studied by using high resolution solid state NMR. The rotation motion of --CH_3 sidegroup in PPU was analyzed by means of the average spectral density functions of internal rota-tion. The results showed that the rotation of the --CH_3 side group is related closely to the com-patibility between the two components. The compatibility was studied by analyzing the protonspin-lattice relaxation in rotating frame, spin-spin relaxation and spin-diffusion. The resultsshowed that the hydrogen bonds between the components play a major role in determining thecompatibility. Through spin diffusion studying, the soft phase domain size was calculated. Bystudying proton spin-spin relaxation, the content of each component in each phase and that ofeach phase in the samples can be obtained. The result shows that the content of interphase is related closely to the compatibility. 相似文献
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Yong Zhang Ze-da Xu Xing-he Fan Xiao-fang Chen Xin-hua Wan Qi-feng Zhou Department of Polymer Science Engineering College of Chemistry Molecular Engineering Peking University Beijing China 《高分子科学》2002,(4):285-290
To allow anisotropies of optical properties in a magnetic field, nitroxide radical is introduced into the ortho-position of the phenylene ring in the side chain. A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPOradical was synthesized. The polymer has a good solubility in organic solvents. The ESR spectrum of the polymer indicatedthree absorption lines characteristic of TEMPO radical. The optical phase conjugated responses (I_4) of the polymer filmswere investigated by degenerate four-wave mixing (DFWM). The experimental results showed that optical phase conjugatedresponse of the TEMPO-PAZ could be easily controlled by choosing the appropriate direction of magnetic field presumablydue to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymer investigated here, the nitroxide radicalwas introduced to increase optical phase conjugated response intensity in a magnetic field, aiming originally at searching fora new photo-active organic magnetic multifunctional materials. 相似文献
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To raise the room temperature ionic conductivity and improve the mechanical strength of a PEO-based polymer electrolyte, a noncrystalline two-component epoxy electrolyte system has been prepared. The diglycidyl ether of polyethylene glycols as precursors of the system were synthesized by a two-step process. The presumed structure of the product was characterized, by ~(13)C, ~1H NMR and IR spectroscopy. It was found that a side-reaction occurred between the secondary hydroxyl group of PEG-chlorohydrin and epichlorohydrin in some degree, resulting in a by- product containing—CH_2Cl side group. By selecting a characteristic signal, which is undistorted by the increase in the length of CH_2 CH_2—O segment, a ~1H NMR approach of determining the equivalent epoxy weight (EEW) was proposed. The method is valid to specimens even though the EEW is as high as 2,000. The examination of the specimens by DSC showed that epoxidation greatly depressed the crystallinity of the PEG's, whereas the T_g was raised. 相似文献
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Polycyclotrimerization of diynes was explored as a new route to hyperbranched polymers in thisinvestigation. Polymerization of terminal diynes of 1,8-nonadiyne and 1,9-decadiyne was studied usingTaCl_5, NbCl_5, Mo(CO)_4(nbd) and [Mo(CO)_3cp]_2 as catalysts (where nbd = 2,5-norbornadiene, cp = cyclo-pentadiene). A soluble polymer was obtained when the polymerization of 1.9-decadiyne was initiated byTaCl_5 at low temperature (0℃). The polymer, however, became partially soluble after purification, possiblydue to the postpolymerization-induced crosslinking. NbCl_5-catalyzed polymerization of 1,9-bis(trimethylsilyl)-1,8-nonadiyne gave a completely soluble polymer. Soluble polymers were also obtainedfrom the polymerization of 3,9-dodecadiyne initiated by NbCl_5, Mo(CO)_4(nbd), [Mo(CO)_3cp]_2, PdCl_2-ClSiMe_3 and Pd/C-ClSiMe_3. IR, UV, and NMR spectroscopic analysis revealed that different catalysts gavepolymers with different structures, ranging from linear polyenes to hyperbranched polyphenylenes. Thepolymers absorb UV light at around 250 nm and emit fluorescence at 340 nm when they are excited at 248nm. 相似文献
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The morphological features of a side-chain liquid crystalline polymer during the mesophasetransitions were investigated by using the DSC technique. The polymer used was polyacrylate with mesogensof three benzene rings attached to the main chain through a flexible spacer. A special two-phase texture wasobserved in the transition temperature range. Similar to main-chain liquid crystalline polymers the transitionprocess of the side-chain liquid crystalline polymer was composed of an initiation of the new phase at localplaces of the old phase matrix and a growth process of the new phase domains. 相似文献
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The mechanical relaxation time of a two-component epoxy network-LiClO_4 system as a polymer electrolyte was investigated. The network is composed of diglycidyl ether of polyethylene glycol (DGEPEG) and triglycidyl ether of glycerol (TGEG), wherein LiCIO_4 was incorporated and acts as both the ionic carrier and the curing catalyst. As the relaxation time is informative to the segmental mobility, which is known to be essential for ionic conductivity, the average relaxation times of the specimens were determined through master curve construction. Experimental results showed that the salt concentration, molecular weight of PEG in DGEPEG and DGEPEG/TGEG ratio have profound effect on the relaxation time of the specimen. Among these factors , the former reinforces the network chains, leading to lengthen the relaxation time, whereas the latter two are in favour of the chain flexibility and show an opposite effect. The findings was rationalized in terms of the free volume concept. 相似文献
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A new azobenzene side-chain polymer (TEMPO-PAZ) containing TEMPO (4-hydroxy-2, 2, 6, 6-tetramethyl-piperidinooxy) radical end group was synthesized by free radical copolymerization. Photoinduced alignment was studied onthe polymer films at room temperature with linearly polarized light of 514.5 nm, The experimental results showed that themagnetic response intensity of the TEMPO-PAZ could be easily controlled by choosing the appropriate polarized lightirradiating times, presumably due to the nitroxide radical in the TEMPO-PAZ molecular structure. For the polymerinvestigated here, the photoinduced alignment technique was introduced to increase the magnetic response intensity ofpolymer under irradiation, aiming originally at searching for a new photo-active organic magnetic multifunctional materials.On the other hand, experimental results also showed that the TEMPO-PAZ can be used as a material for optical image storage. 相似文献
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The correlation between shape and size of linear chains on the simple cubic lattice is investigated using a dynamicMonte Carlo technique. A positive correlation between the asphericity parameter A and the square of the end-to-end distanceR~2, as well as that between A and the square of the radius of gyration S~2, is found for both RW and SAW chains, indicatingthat a chain conformation of small size is usually more spherical than one of large size. The result can explain why the shapeof the SAW chain deviate much more from a sphere than that of the RW chain, and can also explain the similar dependenceof size and shape on chain stiffness and on the distance of the first bead of a chain from an infinitely large flat surface. 相似文献